Engineering Metallurgy

PITMAN METALLURGY
SERIES
FRANK T. SISCO, Advisory Editor
Engineering
Metallurgy
Engineering
pitman
PUBLISHING
CORPORATION
>*
Metallurgy
By
THE COMMITTEE ON METALLURGY
-4 collaborative writing group
of
metallurgy
professors.
NEW YORK
TORONTO

LONDON
Copyright
,
1957
BY
PITMAN PUBLISHING CORPORATION
All rights reserved. No part of this book
may l>e reproduced in any form without
the written permission of the publisher.
1.2
Associated Companies
Sir Isaac Pitman & Sons, Ltd.
London Mcllraurne Johannesburg
Sir Isaac Pitman & Sons (Canada), Ltd.
Toronto /
/
t &9
,
QOZAfcl-
COTA
PRINTED in the United States of America
Coauthors
Theodore Allen,
Jr.,
M.S.M.E., Associate Professor of Mechanical En-
gineering, University of Houston, Houston, Texas; Engineer Associated
with Anderson, Greenwood and Co., Bellaire, Texas
Lee L. Amidon, M.S.M.E., Professor and Head, Department of Mechani-
cal Engineering, South Dakota State College, Brookings, South Dakota
John K. Anthony.
M.S.. Associate Professor of Physical Metallurgy, Uni-
versity of Arizona, Tucson, Arizona
Robert E. Bannon,
S.M., Professor of Metallurgy, Newark College of
Engineering, Newark, New
Jersey
Francis William Brown, Ph.D., Associate Professor, Clarkson College
of Technology, Potsdam, New York
Frederick Leo Coonan, D.Sc, Professor and Chairman, Department of
Metallurgy and Chemistry, U.S. Naval Postgraduate School, Monterey,
California
Howard P. Davis, M.S., Associate Professor, Department of Mechanical
Engineering, University of Wyoming, Laramie, Wyoming
Harold Vincent Fairbanks, M.S., Professor of Metallurgical Engineering,
West Virginia University, Morgantown, West Virginia
Mars G. Fontana, Ph.D., Professor and Chairman, Department of Metal-
lurgical Engineering, The Ohio State University, Columbus, Ohio
Arthur R. Foster,
M.Eng., Associate Professor of Mechanical Engineer-
ing, Northeastern University, Boston, Massachusetts
Arthur C. Forsyth, Ph.D., Associate Professor of Metallurgical Engi-
neering, University of Illinois, Urbana, Illinois
Richard Edward Grace, Ph.D., Associate Professor of Metallurgical En-
gineering, Purdue University, Lafayette, Indiana
Leonard B. Gulbransen, Ph.D., Associate Professor, Washington Uni-
versity, St. Louis, Missouri
Joseph Gurland, D.Sc, Assistant Professor, Division of Engineering,
Brown University, Providence, Rhode Island
Walter R. Hibbard, M.S., Adjunct Associate Professor of Metallurgy,
College of Engineering, University of Bridgeport, Bridgeport, Con-
necticut
vi Coauthors
Walter M. Hirthe, M.S.M.E., Assistant Professor of Mechanical En-
gineering, College of Engineering, Marquette University, Milwaukee,
Wisconsin
Abraham Eldred Hostetter, Ph.D., Professor of Metallurgy, Kansas
State College, Manhattan, Kansas
John
J.
Kaufman, Metallurgy Department, Academy of Aeronautics,
Flushing, New York
J.
Edward Krauss, M.S., Head, Department of Mechanical Technology,
New York City Community College, Brooklyn, New York
Hollis Philip Leighly,
Jr.,
Ph.D., Chairman, Department of Metallurgy,
University of Denver, Denver, Colorado
Irving
J.
Levinson, M.S., Professor of Mechanical Engineering, Lawrence
Institute of Technology, Detroit, Michigan
Jules Washington Lindau, III, M.E., Associate Professor of Mechanical
Engineering, The University of South Carolina, Columbia, South
Carolina
James R. MacDonald, Ph.D., Chairman, Department of Mechanical En-
gineering, School of Engineering, The University of Mississippi, Uni-
versity, Mississippi
Omar C. Moore, M.S., Associate Professor of Chemical Engineering,
Alabama Polytechnic Institute, Auburn, Alabama
Don R. Mosher, B.S., Assistant Professor of Mechanical Engineering,
University of Colorado, Boulder, Colorado
Charles Arthur Nagler, Ph.D., Associate Professor, Department of
Chemical and Metallurgical Engineering, Wayne State University,
Detroit, Michigan
Richard O. Powell, College of Engineering, Tulane University, New
Orleans, Louisiana
Oran Allan Pringle, M.S.M.E., Associate Professor of Mechanical En-
gineering, University of Missouri, Columbia, Missouri
Kenneth E. Rose, M.S., Professor of Metallurgical Engineering, Uni-
versity of Kansas, Lawrence, Kansas
Philip C. Rosenthal, M.S., Professor of Metallurgical Engineering, Uni-
versity of Wisconsin, Madison, Wisconsin
Robert E. Shaffer, M.S., Associate Professor of Engineering, University
of Buffalo, Buffalo, New York
Coauthors
vii
Walter E. Short, M.S.M.E., Associate Professor of Mechanical Engineer-
ing, Bradley University, Peoria, Illinois
Floyd Sheldon Smith, M.S., Associate Professor of Mechanical Engineer-
ing, Alabama Polytechnic Institute, Auburn, Alabama
GEORGE V. Smith, Ph.D., Assistant Director for Metallurgical Engineer-
ing, School
of Chemical and Metallurgical Engineering, College of
Engineering,
Cornell University, Ithaca, New York
Sicmund Levern Smith, M.Met.E., Professor of Metallurgy, College of
Mines, University
of Arizona, Tucson, Arizona
Joseph William Spretnak, Ph.D., Professor of Metallurgical Engineer-
ing, The Ohio State University, Columbus, Ohio
Rocer Greenleaf Stevens, Ph.D., Head, Department of Chemical En-
gineering,
Southwestern Louisiana Institute, Lafayette,
Louisiana
William H. Tholke, B.S., Instructor of Metallurgy, University of Cin-
cinnati,
Cincinnati, Ohio
John Stanton Winston,
M.A., M.S., Chairman,
Department of Metal-
lurgy,
Mackay School of Mines, University of Nevada, Reno, Nevada
Preface
Engineering Metallurgy was developed to present in a concise, under-
standable manner the principles of ferrous and nonferrous metallurgy
for all engineersstudent and practicing. Both graduate and undergradu-
ate student engineers need a fundamental knowledge of the metals they
will employ in their work. The emphasis, throughout therefore, is on
metallurgical principles rather than on handbook information; however,
specific data are given so as to provide a realistic structure to reinforce
the theoretical
presentations. The practicing engineer who has had little
contact with the field of metallurgy, or who has had no formal work in
metallurgy, will find in this book a sufficiently complete summary of all
of the essentials he needs to know to obtain a broad understanding of
the field.
Keeping up with metallurgical developments in all branches of the
art, as reported in the technical literature of the world, is difficult for
those actively engaged in the manufacture, processing, or the industrial
use of engineering
metals and alloys. For the thousands of such indi-
viduals, who work with or who use metallic materials
but who cannot
possibly find time to read everything, summaries such as this book have
a well-defined place in the scheme of things.
Because metallurgy is such a dynamic and diversified art and science,
the preparation
of a definitive, up-to-date, authoritative work in this field
required
a bold approach. Forty professors actually engaged in teaching
engineering
metallurgy in universities across the country were asked to
pool their knowledge and research to produce this text. Through inten-
sive questionnaire techniques, the scope and content of the book were
first defined and outlined by the group. Once the basic content had been
selected, ideas for all chapters were channeled to experts selected to
serve on individual chapter committees. From these ideas and their own
combined
experience and research, each committee built chapter out-
lines. Overlaps and omissions were detected by the editorial staff and
referred to the committees for alteration and preparation of rough draft.
The coauthors read and checked the smoothness of presentation of the
chapter, adding to and refining the draft. Thus were built the twenty-
three chapters of Engineering Metallurgy by the forty coauthors.
Chapters
1 through
6 deal
with the general
principles of metallurgy
as they are related to engineering. Chapter 3 (Factors Affecting En-
gineering Properties) will be especially useful to the student in gaining
ix
x
Preface
an appreciation of the over-all study of engineering metallurgy. In Chap-
ter 6 (Phase Diagrams and the Simply Alloy Systems) , the student is
introduced
to basic problems of equilibrium and alloying. Chapters 7
through 10 treat of the nonferrous metals and alloys. To these important
materials, a generous amount of space has been devoted so that com-
plete coverage could be obtained. Chapters 1 1 through 20 arc concerned
with iron and steelwith special attention given to the subjects of heat
treatment and ferrous alloys. Machinability, corrosion, and the effects
of temperature are fully covered in Chapters 21 to 23.
All technical terms are defined as they are introduced, and stress is
laid upon fundamental concepts. At the end of each chapter there is
a set of questions and exercises constructed to help the student focus at-
tention on the important definitions and principles presented in the
chapter.
Principles, definitions, and illustrative examples are set down with
precision and clarity. Drawings and photographs are used without re-
serve to amplify the discussion. In certain chapters, detailed tables are
included for the convenience of the reader.
The Committee on Metallurgy is aware that the usage of this text and
developments in the field will indicate areas needing revision. Professors
and students are therefore urged to send comments on chapters to the
publisher or chapter committees so that appropriate changes may be
made in the next edition.
The Editor
Contents
Preface
v
Chapter 1. Metallurgy and Engineering 1
1.1. Metallurgy as an Art 1
1.2. Metallurgy as a Science 2
1.3. Metallurgy and Engineering 3
Chapter 2. Fundamental Structure of Metals and Alloys 5
2.1. Building Blocks of Matter 5
2.2. The Building-Up Principle 9
2.3. Types of Bonding in Solids 9
2.4. Assemblages of Atoms 11
2.5. Defects in Crystals 14
2.6. Polycrystalline Aggregates 16
2.7. Interactions in Metallic Solutions 18
2.8. Liquid Solutions 19
2.9. Solid Solutions 20
2.10. Intermediate Phases 20
Chapter 3. Factors Affecting Engineering Properties ... 23
3.1. Grain Size Control 24
3.2. Effect of Grain Size on Properties 29
3.3. Deformation of Metals 32
3.4. Slip in Single Crystals 33
3.5. Twinning
36
3.6. Deformation of Polycrystalline Metals 37
3.7. Hot Working
38
3.8. Cold Working 40
3.9. Annealing Cold Worked Metal 42
3.10. Factors Affecting Rccrysiallization Temperature and Grain
Size
45
xi
xii
Contents
3.11. Summary of Hot and Cold Working : 46
3.12. Solid Solution Effects
47
3.13. Polyphase Structures
49
3.14. Allotropic Transformation
51
3.15. Precipitation Hardening
52
Chapter 4. Static Properties of Metallic Materials ... 57
4.1. Properties of Metallic Materials
57
4.2. The Relative Standardization of Static Tests 60
4.3. Tensile Strength
61
4.4. Elastic Limit, Proportional Limit, and Modulus of Elas-
ticity
63
4.5. Yield Point and Yield Strength 66
4.6. Elongation and Reduction of Area 67
4.7. Hardness
69
4.8. Comparison of the Various Hardness Tests 72
4.9. Relation among Hardness Tests and between Hardness
and Tensile Strength for Steel 73
4.10. Relation among Hardness Tests and between Hardness
and Tensile Strength for Nonferrous Alloys .... 74
4.11. Shear, Compression, and Bend Tests 77
4.12. Sonic Testing
78
Chapter 5. Dynamic Properties of Metallic Materials . . 81
5.1. Notch Brittleness and Transition from Ductile to Brittle
Fracture
81
5.2. Value of the Notched-Bar Impact Test 85
5.3. The Mechanism of Fatigue 86
5.4. The Endurance Limit 87
5.5. Relation of the Endurance Limit to Other Properties . . 88
5.6. The Effect of Notches on the Endurance Limit .... 89
5.7. Corrosion Fatigue 92
5.8. Increasing the Endurance Limit by Shot Pcening ... 92
5.9. Significance of Endurance Data 93
5.10. Damping Capacity 94
Chapter 6. Phase Diagrams and the Simple Alloy Systems 97
6.1. Solid State Thermodynamics and Thermostatics ... 97
Contents
xiii
6.2. Concept of Dynamic Equilibrium
97
6.3. Cooling Curves
98
6.4. Solid State Mass Transfer
99
6.5. The Phase Rule
100
6.6.
Solid State Solubility
101
6.7. Binary Systems
101
6.8. Intermetallic
Compounds
106
6.9. The Peritectic
Reaction .
108
6.10. Closure
109
Chapter 7. Heat Treatment of Alloys by Precipitation
Hardening
Ill
7.1. Alloy Requirements .
Ill
7.2. Step ISolution Heat Treatment
112
7.3. Step IIPrecipitation Heat Treatment (Aging) .... 1 14
7.4. Theory of Precipitation Hardening 114
7.5. The Effect of Time and Temperature During Precipitation
Heat Treatment
117
7.6. Precipitation Hardening of Aluminum Alloys .... 119
7.7. Precipitation Hardening of Magnesium Alloys .... 121
7.8-
Precipitation Hardening of Copper Base Alloys .... 124
7.9. Precipitation Hardening in Low Carbon Steel .... 125
7.10. Strain Aging and Its Consequences in Low Carbon Steel 126
7.11. Precipitation Hardening in Alloy Steels 126
Chapter 8. Light Alloys as Engineering Materials .... 129
8.1. History of Aluminum
129
8.2. Economics of the Aluminum Industry 130
8.3. Aluminum OresOccurrence and Concentration . . . . 131
8.4. Manufacture of Aluminum
132
8.5. Physical Properties of Aluminum 133
8.6. Chemical Properties of Aluminum 134
8.7. Aluminum Alloys 135
8.8. The Wrought Alloys
136
8.9. Aluminum Casting Alloys
140
8.10. Functions of Alloying Elements 143
8.11. Cold and Hot Working of Aluminum Alloys 147
xiv
Contents
8.12. Heat Treatment of Aluminum Alloys 148
8.13. Corrosion Resistance of Aluminum Alloys 150
8.14. Joining of Aluminum Alloys 152
8.15. Magnesium and Its Alloys 155
8.16. Beryllium 158
8.17. Titanium 159
Chapter 9. Copper and Copper-Base as Engineering Materials 161
9.1. Properties and Uses of High-Purity Copper 164
9.2. Constitution of the Common Copper-Rich Alloys . . . 165
9.3. Nomenclature of the Copper-Rich Alloys 167
9.4. Characteristics and Uses of the High Brasses 168
9.5. Characteristics of the Low Brasses and the Nickel Silvers 170
9.6. Properties of the Wrought Brasses 171
9.7. Cast Brass and Cast Nickel Silver 172
9.8. The Copper-Base Bearing Metals 172
9.9- The Tin Bronzes 174
9.10. Aluminum Bronze and Copper-Silicon Alloys 176
9.11. Copper-Beryllium Alloys
177
9.12. The Copper-Rich Copper-Nickel
Alloys 184
9.13. Copper and Copper-Base Alloys in Powder Metallurgy . . 186
Chapter 10. Miscellaneous Heavy Nonferrous Metals and
Alloys
190
10.1. The White Metals
191
10.2. Lead and Tin as Engineering Materials 196
10.3. Zinc and Zinc Base Alloys as Engineering Materials . . . 197
10.4. Nickel and Nickel Base Alloys 199
10.5. Cobalt Base Alloys
201
10.6. Other Miscellaneous High Temperature Metals and Alloys 201
10.7. The Precious and Semi-Precious Metals and Alloys . . . 202
10.8. Metals and Alloys in Atomic Power Applications .... 203
Chapter 11. The Manufacture and Composition of Carbon
and Alloy Steels 208
11.1. Definitions of Ferrous Engineering Materials 210
11.2. Iron Ore and the Manufacture of Pig Iron 212
11.3. Acid and Basic Processes 216
Contents
xv
11.4. Bessemer Processes
217
11.5.
Open-Hearth Processes
220
11.6.
Manufacture
of High-Quality Steels by the Electric
Processes
226
11.7. Wrought
Iron
227
11.8.
Special Steel-making Processes
229
11.9.
Mechanical Treatment of Steel
231
11.10.
Harmful Elements in Carbon and Alloys Steels ....
233
11.11.
Manganese in Carbon and Alloy Steels
236
11.12. Carbon Monoxide, and Rimming and Killed Steels . . . 237
11.13. Silicon and Other Degasifiers
239
11.14. Other Elements
239
11.15. Low-Alloy
Steels
. . 240
11.16. High-Alloy
Steels
241
Chapter
12. The Constitution of Steel
244
12.1. The Allotropy
of Iron
244
12.2.
Iron-Carbon
Phase Diagram
245
12.3. Phase Changes and
Microstructures
of Slowly Cooled Plain
Carbon Steels
247
12.4. Isothermal
Transformation in Steel
251
12.5. The Effect of Cooling Rate Upon the Resulting
Structure 254
12.6. Effect
of Alloying Elements
Upon the Iron-Carbon Dia-
g
256
12.7. Effect of Alloying Elements on the Isothermal Transfor-
mation of Steel
257
12.8.
Effect of Hot Working on Structure
258
12.9. Effect of Cold Working on Structure
259
Chapter
13. Fundamentals of Heat Treatment
of Steel . . 263
13.1. Grain Size and Grain Growth
264
13.2. Controlling
and Classifying Grain
Size
265
13.3. Effects of Hot Working
on Grain Size
267
13.4.
Hardenability
269
13.5.
Grain Size and Hardenability
270
13.6.
Quenching and Properties of Martensite
270
13.7. The Instability of Quenched Carbon Steels
273
XVI
Contents
13.8. Retained Austenite and Cold Treatment
274
13.9. Structural and Other Changes in Tempering
274
Chapter 14. The Operations of Heat Treatment
278
14.1. Heating Cycle
279
14.2. Annealing
280
14.3. Normalizing
280
14.4. Spheroidizing
281
14.5. Quenching
for Hardening
282
14.6. Tempering
284
14.7. Isothermal Treatments
285
14.8. Case Hardening Processes
'
289
14.9. Flame Hardening and Induction Hardening 293
Chapter 15. Carbon Steel as an Engineering Material ... 297
15.1. Carbon-Steel Castings as Engineering Materials .... 298
15.2. Factors Affecting the Properties of Carbon-Steel Castings 300
15.3. Hot-Worked
Carbon Steels as Engineering Materials . . 302
15.4. Effect of Composition on Static Properties of Hot-Worked
Carbon Steels
303
15.5. Effect of Composition on Other Properties 305
15.6. Cold-Worked Carbon Steels as Engineering Materials . . 306
15.7. The Important Properties of Cold-Worked Steel ... 307
15.8. General Effects of Cold Working on Strength and Ductility 308
15.9. Variables Affecting the Properties of Cold-Worked Wire . 311
15.10. Effect of Cold-Working on Dynamic Properties . . . . 312
15.11. Heat-Treated Carbon Steels as Engineering Materials . . 312
15.12. Effect of Section Size on the Properties of Heat-Treated
Medium-Carbon Steels 315
Chapter 16. Low-Alloy Steels as Engineering Materials . . 318
16.1. Balanced Compositions in Low-Alloy Steels 319
16.2. General Effects of the Alloying Elements on Carbon Steel 320
16.3. Effects of Phosphorus, Manganese, and Silicon .... 322
16.4. Effects of Nickel and Chromium 324
16.5. Effects of the Other Common Alloying Elements .... 325
16.6. Low-Alloy Structural Steels as Engineering Materials . . 326
Contents
xvii
16.7. Composition and Properties of the Low-Alloy Structural
Steels
327
16.8. The
S.A.E. Low-Alloy Steels
328
16.9.
The S.A.E. Low-Alloy
Steels as Engineering
Materials . . 331
16.10. The New Metallurgy of Low-Alloy
Steels 333
16.11. Similarity of Properties of Heat-Treated S.A.E. Low-Alloy
Steels
334
16.12. The Engineering Properties of the S.A.E. Low-Alloy Steels 337
Chapter
17. Hardf.nability
342
17.1.
Hardness and Hardenability in Carbon Steels ....
343
17.2. Hardness and Hardenability in Low-Alloy Steels ... 344
17.3. Cooling
Rate and Hardenability
344
17.4. Time Delay and Hardenability
346
17.5. Variables
Affecting Hardenability
346
17.6. Methods of Determining Hardenability
348
17.7. The
Jominy End-Quench Hardenability Test 349
17.8. Relation of the End-Quench Test to Actual Cooling Rates
and
the Selection of Steel by Hardenability
350
17.9 Virtues and Shortcomings of the
Jominy End-Quench Test 352
17.10. Hardenability Bands
353
17.11. Relation of Hardenability to Engineering Properties . . 354
17.12.
Relation of Tempering to Hardenability
356
17.13. Fundamentals of Calculated Hardenability 356
17.14. The Accuracy of Calculated Hardenability
360
17.15. The Effect of Boron on Hardenability
361
Chapter
18. Special Purpose Steels 364
18.1. Classes of Stainless Steels
364
18.2.
Constitution of High-Chromium Steels 366
18.3.
Relation of the Constitution of High-Chromium Steels to
Their Heat Treatment
367
18.4.
Mechanical Properties of High Chromium Steels ... 369
18.5. Corrosion and Oxidation Resistance of High-Chromium
Steels
370
18.6. The Constitution of 18-8
372
18.7. The Role of Carbon in 18-8
374
xviii
Contents
18.8. Properties of 18-8 376
18.9. Recent Developments in Stainless Steels 378
18.10. Superstainless Steels 381
18.11. High-Nickel Steels and Special Iron-Nickel Alloys ... 384
18.12. Austenitic Manganese Steel 385
Chapter 19. Tool Steels, Die Steels, and Cemented Hard
Carbides
389
19.1. High-Carbon Tool Steels 390
19.2. Low Alloy Tool Steels 395
19.3. Medium Alloy Tool and Die Steels 396
19.4. High-Alloy Tool and Die Steels 397
19.5. High Speed Steels. 398
19.6. Function of Alloy Additions in Tool and Die Steels . . 402
19.7. Cast Alloys 404
19.8. Cemented Carbide Tools 405
Chapter 20. Cast Iron 408
20.1. White Cast Iron as an Engineering Material 410
20.2. Malleable Cast Iron as an Engineering Material .... 410
20.3. Engineering Properties of Malleable Cast Iron .... 410
20.4. Gray Cast Iron as an Engineering Material 412
20.5. Structure of Gray Cast Iron 414
20.6. Relation between Properties and Structure of Gray Cast
Iron 415
20.7. Effect of Cooling Rate 416
20.8. Effect of Graphite Size on Structure and Properties . . 417
20.9. Evaluation of Gray Cast Iron for Engineering Applications 419
20.10. Nodular or Ductile Cast Iron as an Engineering Material 420
20.11. Melting and Casting of Irons 422
20.12. Ternary System of Iron, Carbon, and Silicon 425
20.13. Heat Treatment of Cast Iron 430
20.14. Normal and Alloy Elements in Cast Iron 434
Chapter 21. Machinability, Wear Resistance, and Deep-Draw-
ing Properties 438
21.1. Variables Affecting Machinability 438
21.2. Evaluation of Metallic Materials for Machinability . . . 438
Contents
xix
21.S. Free Machining Steels
440
21.4. Relative
Machinability of Steel and Nonferrous Alloys . 441
21.5. Types of Wear
442
21.6. Variables Affecting
Wear Resistance
443
21.7. Evaluation of Steel for Wear Resistance 444
21.8.
Importance of Deep-Drawing Properties 445
21.9. Evaluation
of Steels for Deep Drawing
446
21.10. Yield-Point
Elongation, Stretched Strains, and Deep Draw-
ing Properties
448
21.11. Deep-Drawing
Properties of Nonferrous Alloys .... 449
Chapter
22. Corrosion and Oxidation
452
22.1.
Electrochemical
Corrosion
452
22.2.
EMF Series and Passivity
454
22.3. Uniform Corrosion
456
22.4. Galvanic or Two-Metal Corrosion
456
22.5.
Concentration Cell Corrosion
458
22.6. Pitting
459
22.7. Intergranular
Corrosion
460
22.8. Stress Corrosion
462
22.9.
Dezincification
. 466
22.10. Erosion-Corrosion
468
22.11. Methods for Combating Corrosion
469
22.12. Corrosion Testing
471
22.13.
Liquid-Metal Corrosion
472
22.14. High-Temperature
Oxidation 472
22.15. Formation of Oxides 473
22.16. Dependence of Oxides Growth upon Gas Pressure . . . 474
22.17.
Dependence of Oxide Growth
Upon Time 477
22.18. Dependence of Oxide Growth Upon Temperature . . . 479
22.19. Oxidation Prevention
480
Chapter
23. Effect of Temperature on Mechanical Properties
of Metals
485
23.1. The Importance of Creep
486
23.2. The Engineering
Significance of Creep
486
23.3. The Creep to Rupture Curve
488
xx
Contents
23.4. Determination of Creep 489
23.5. Effect of Variables on Creep 491
23.6. Fatigue and Combined Fatigue and Creep 493
23.7. Structural Changes During Creep 495
23.8. Variation of Other Properties with Temperature . . . 498
23.9. Design for Elevated Temperature Service 499
23.10. Variation Mechanical Properties at Reduced Tempera-
tures 500
23.11. Effects of Metallurgical Variables 502
23.12. Design for Low-Temperature Service .... ... 503
Index
507
Engineering
Metallurgy
CHAPTER
Metallurgy
and
Engi nee r i
ng
1
Don R. Mosher, B.S., Assistant Professor of Mechanical
Engineering, University of Colorado, Boulder, Colo-
rado
1.1. Metallurgy as an Art
METALLURGICAL knowledge had its begin-
nings in the stone age when some ancient craftsman first recognized the
difference in behavior amongst certain of the "rocks" with which he was
working. The stones familiar to this primitive artisan were hard and
brittle, and were capable of being fashioned into tools and weapons only
by tedious shaping, chip by chip. His first encounter with metal then,
undoubtedly native copper or gold, must have been an exciting exper-
ience. Here was a substance which, instead of fracturing, yielded to the
blows of his stone hammer.
Here was a material which could be formed
much more precisely, which was pleasing to the eye, which could be
worked to a keener edge, and which, moreover, somehow acquired greater
strength the more it was worked.
From the use of native metal to the deliberate reduction of an ore by
carbon is a long step, and one which is the subject of much interesting
speculation. It seems likely that the first such reduction was accidental-
possibly the result of a fortunate combination of circumstances in which
the heat of a campfire, together with carbon from the charred logs
succeeded in reducing copper ore contained in the surrounding
stones,
On other occasions the stones may have contained additional metals such
as tin, and the result was a remarkably stronger metal. In time, the rela-
tionship between the fire, the charred logs, and the particular types of
stones was recognized, and the discoverer,
the first metallurgist,
began to
produce metals at will.
He and his progeny of the next several thousand years have accumu-
lated a mass of information concerning the effects of variables in pro-
cessing upon the properties of the final product.
1
2 Engineering Metallurgy
1.2. Metallurgy as a Science
Questions concerning the reasons why these variables resulted in the
observed effects must certainly have been present in the minds of these
pioneers long before the means were available to answer them. With the
advent of the microscope and the X-ray, these inquiring minds began to
supply the answers.
The science of metallurgy really began when Sorby, a British scientist,
reported in 1864 the results of his investigations on the use of the micro-
scope to study the structure of meteoric iron. This was followed by
studies in the same general field by Martens in Germany, reported in
1878. The work of these two scientists, however, aroused little interest
at the time, and nothing further was accomplished until Sorby showed
to the British Iron and Steel Institute in 1886 some photomicrographs of
iron and steel. This aroused much interest in the internal structure of
metals, and from 1890 to 1920 many distinguished metallurgists devoted
themselves to developing a science of physical metallurgy.
The paramount early problem of metallurgy, which fairly cried for
solution, was that of the hardening of steelwhy steel containing con-
siderable carbon was soft when cooled slowly from a red heat but hard
when cooled rapidly from the same temperature. This problem occupied
most of the workers in the science of metals for more than two decades.
Despite the efforts of many brilliant minds, which resulted in a volume
of published literature that amazes present-day metallurgists, little that
was wholly decisive was accomplished until confirmatory X-ray crystal-
lography methods came into use about forty years ago. Although some
cynics say that the X-ray has created more problems than it has solved,
X-ray crystallography has been a useful tool in the study of the structure
of metals and the constitution of alloys.
In the past three decades the science of physical metallurgy has
changed remarkably. Always closely related to chemistry and physics, it
has been greatly affected by the revolution that has occurred in these
two sciences since 1920. The gap between chemistry and physics has
been largely eliminated, and, as these sciences came together, the science
of metallurgy changed from simple speculations on the structure of
metals and alloys, as affected by composition or mechanical or thermal
treatment and as observed by the microscope, to speculations which
involve such complex abstractions as spinning electrons, statistical me-
chanics, electromagnetic theory, quantum theory, wave mechanics, and
thermodynamics.
Present-day physical metallurgists are inclined to smile condescendingly
at the battles over beta iron, cement carbon, and amorphous metal which
Metallurgy and Engineering
3
filled the transactions of the metallurgical
societies forty or fifty years ago.
It is not at all certain that even broader smiles will not be in order thirty
years from now over the discussions
of free energy,
entropy, and mosaic
structure which are filling
our journals
at the present time. Especially
apropos in this connection
are the words of a venerable
man of science,
Sir Ambrose Fleming, who presented a paper to the first meeting of the
Physical Society
of London in 1873 and who, in a formal address to the
same body of scientists on "Physics and Physicists of the Eighteen
Seven-
ties,"*
summarized his seventy
years of experience by saying:
When we come to look back then on the world of physicists during
the
eighteen seventies,
what we find is that their inventions, discoveries of fact, and
ascertained principles remain
with us today of permanent
value, forming part
of our useful knowledge. But their theories and speculations
as to underlying
causes and nature have nearly all passed away. Perhaps it will also be the
same with our present-day work. If some sixty years hence a fellow of the
Physical Society gives a talk on the physics of the nineteen
thirties, he will have
to record the great additions then made to knowledge of physical facts. But he
may also have to say that our explanations
and theories concerning them have
all vanished, or at least been replaced by others also destined in turn to pass
away.
1.3. Metallurgy and Engineering
Until about forty years ago there was little need for the engineer to
know anything about metallurgy since untreated carbon steel, hot-
rolled or cold-drawn, was used for at least 95 per cent of steel structures
and machines.
The engineer was interested primarily in four properties-
tensile strength, yield point, elongation,
and reduction
of area-and in
having available an ample supply of cheap steel which, in addition to
meeting specifications for tensile properties,
would machine easily and
fabricate readily. It was considered sound engineering practice to build
machines and structures
that would carry a much higher load than was
anticipated; weight was synonymous with quality, and the heavier the
structure the better the design. High factors of safety were used; con-
sequently slight variations in quality, such as lack of structural homo-
geneity, surface
irregularities, and numerous others, made little or no
difference
in designing.
This is no longer true. Weight and the strength-weight
ratio (tensile
strength divided by specific gravity) have become very important. Under
the leadership
of the automotive
and aircraft industries
engineers have
come to realize that excess weight not only indicates
poor design but
is an inexcusable
economic loss. The experience of the automotive and
Nature, v. 143, 1939, pp. 99-102.
the aeronautical engineer in designing lightweight structures and ma-
chines stimulated similar efforts in other fields of engineering. This is
shown by the recent developments in machine tools, in lightweight rail-
way rolling stock, and even in bridge and building structures.
It is, of course, self-evident that the present-day emphasis on light
weight in engineering design as exemplified by the automobile, airplane,
and the streamlined train is directly related to the development of new
types of steels and light nonferrous alloys and to new treatments for
these materials. It is a moot question whether the metallurgist or the
engineer was responsible for most of this development. Enthusiastic
metallurgists insist that engineering progress has been the direct result
of metallurgical progress; that engineers only improved their tools, ma-
chines, and structures because metallurgical art and science had produced
new metallic materials for the engineer to use. There is no doubt that
many engineers are too conservative and that engineering progress has
at times lagged behind progress in metallurgy. On the other hand, ex-
amples could be cited where the metallurgist did not improve his product
until insistent engineering demand forced it upon him. A discussion of
whether this advance was pioneered by the metallurgist or the engineer
is as futile as arguing whether the egg or the chicken came first; the
essential fact is that important changes have taken place and that the
engineer should know something of the metallurgical progress that has
accompanied his changes in design.
It is, therefore, the purpose of this book to outline the recent develop-
ments in metallurgical art and in metallurgical science. This does not
mean that there are long descriptions of melting and refining, or of
mechanical and heat treatment, or of thermodynamics and wave me-
chanics; it does mean, however, that sufficient details of the present state
of metallurgical art and science are given so that engineers may
recognize the importance of the variables, inherent in the manufacture
and treatment of metals and alloys, that affect the engineering properties
and the suitability of these materials for engineering applications.
QUESTIONS
1. Distinguish between the art and the science of metallurgy.
2. What research tools have most profoundly influenced the development of
metallurgical science?
3. To what other sciences is metallurgy closely related?
4. How is progress in engineering and in metallurgy inter-related?
5. Why is it becoming increasingly important for engineers to understand the
fundamentals of metallurgy?
CHAPTER
Fundamental
Structure
of
Metals and Alloys
Leonard B. Gulbransen,
Ph.D., Associate Professor,
Washington University, St. Louis, Missouri
Joseph William Spretnak, Ph.D., Professor of Metal-
lurgical Engineering, The Ohio State University,
Columbus, Ohio
In RECENT
years the study of the solid state
and the application of wave
mechanics to solid state physics and metal-
lurgy has resulted in a much clearer picture of the structure
of metals and
alloys. Physical and mechanical properties of the metals, such as tensile
strength, ductility, electrical conductivity,
diffusion, etc are dependent
on structure,
sometimes to a marked degree. For this reason it is desir-
able to discuss the structure of solids, and in particular the structure of
metals and alloys.
2.1. Building
Blocks of Matter
All metals are aggregates of atoms. Atoms consist of a nucleus and one
or more planetary
electrons. In general, except for applications of the
nuclear reactions,
it can be assumed that the atomic nucleus consists of
positively charged protons, and neutrons with no electrical charge. Most
of the mass of the atom is concentrated in the nucleus and is equal to the
sum of the masses of the protons and neutrons in the nucleus. Negatively
charged electrons sufficient to balance the positively charged protons in
the nucleus,
resulting in an electrically neutral atom, are found outside
the nucleus. Electrons may be thought of as point particles, with a definite
mass and electrical charge; however, their motion must be described in
terms of an associated wave. The part of science that deals with this
problem is known as wave mechanics. The fundamental
equation de-
scribing the motion of an electron and accompanying wave is De Broglie's
equation:
A
= h/mV
where h is Planck's constant (6.62 x
10
27
erg-sec) , m is the mass of the
electron, V is the velocity of the electron, and A is the associated wave-
length. Practical use of this equation is made in electron diffraction
equipment. Application of De Broglie's equation, and Heisenberg's un-
certainty principle, which states that the position and momentum (mV)
of a particle cannot be exactly determined simultaneously, result in a
somewhat different idea of atomic structure than the classical picture of
a nucleus and planetary electrons in definite fixed orbits. Application
of the equations of wave mechanics results in a picture of the atom as a
positively charged nucleus, with electrons in discrete, but "smeared out"
orbits. The limits of the orbit can be described in terms of a probability
function, in which, the probability of finding the electron at the center of
the orbit is maximum, but finite and small probabilities exist for finding
the electron at the limits of the "smeared out" orbit. This description of
atomic structure is sometimes described as an electron cloud picture.
1 s State 2 p
State 3 d State
Fig. 2.1. Electron cloud diagrams of hydrogen atom.
In the solution of the wave equation for a given atom, the electrons are
characterized by four quantum numbers; n, I, m
t
and m
s
. The quantum
number n is called the principal quantum number, and is related to the
total energy of the electron. Number n may have any integral value from
+ 1 to infinity. The quantum number / is related to the angular mo-
mentum of the electron and may have any integral value from to (n-1) .
The quantum number m, is related to the magnetic moment of the elec-
Fundamental Structure
of
Metals and Alloys 7
tron and may have any value from to I. The quantum number m, is
related to the rotation of the electron about its own axis, and may have
values of
i/
2
. The four quantum numbers determine the energy of the
electron in various states, with the result that an atomic system may be
fully described by specifying the values for the quantum numbers for
each electron.
A further result of wave mechanics is the Pauli Exclusion Principle
which states that no two electrons in the same atom can have the same
four quantum numbers. This principle in effect restricts a given electron
to one and only one energy slate in a single atom. If then, two atoms are
brought together to form a molecule, the electrons of each atom must
occupy different energy states or energy levels. The idea of energy levels
is important with regard to molecule formation and also to the forma-
tion of the solid state.
MAXIMUM NUMBER
OF ELECTRONS
5
P
to
5s
Up
3D
Us
IS
10
6
2
"i
Fig. 2.2. Energy level diagram of an atom.
As an example of the above principles, consider the hydrogen atom.
The hydrogen atom consists of a proton, + 1 charge, and a mass of ap-
proximately one atomic unit. The hydrogen atom must then possess one
electron. In the lowest energy state, this electron would have an energy
described by the quantum numbers n =
1, / =
0, m
;
=
0, and m,
=
+
\/
2
.
The next atom in the periodic system, helium, with a + 2 charge on the
8
Engineering Metallurgy
nucleus must possess two electrons. The quantum numbers describing
these electrons, in order to fulfdl Pauli's exclusion principle, would then
be: n, =1, I, =
0, mj, =
0, m,
l
=
+ \/
z
,
and n, =
1, l =
0,
wijj =
0, and
m
sl
=
\/
z
. These two electrons have very nearly the same energy, the
only difference being related to the spin quantum numbers m, and m
tl
.
Both electrons are confined to the same major energy level with n
=
1, and
only these two electrons can occupy this level. The next atom in the
periodic system, lithium, must possess three electrons. Two of the elec-
trons have the same quantum numbers as those for helium, but the third,
n = 2, I
=
0, m = 0, and m, = + i/
2
.
A more common method of representing the electronic configuration of
an atom is to use the terminology of the spectroscopist, in which the
principal quantum number n is listed, followed by a letter designating
the quantum number /, and indicating by a superscript the number of
electrons in this particular energy state. For most metallurgical applica-
tions, the difference between energy states with different values for m
(
and
m, is so small that it may be neglected. According to this method of
representation the hydrogen atom in its lowest energy state may be
described as being in a (Is)
1
state; the helium atom in a (Is)
2
state; the
lithium atom in a (Isf (2s)

state etc. The quantum number I is desig-
nated by s for I =
0, p
for / =
1, d for / =
2, and
/
for / = 3. By applying
Pauli's exclusion principle, the s state may contain a maximum of two
electrons, the
p
state a maximum of six electrons, and the d state a maxi-
mum of ten electrons.
ATOMIC NUMBER ELEMENT ELECTIION CONFICUR ATION
1
Hydrogen (Is)
1
2
Helium (Is)'
3 Lithium (Is)' (2s)
1
i
Beryllium (Is)' (2s)
1
5 Boron (Is)' (2s)'(2p)'
6
Carbon (Is)' (2s)'(2p)'
7 Nitrogen (Is)' (2s)
'(2p)
3
fi Oxygen (Is)' (2s)'(2p)<
9 Fluorine (Is)' (2s)'(2p)
s
10 Neon (Is)' (2s)'(2
P
)
ii Sodium (Is)' <2s)'(2p) (3s)
1
12 Magnesium (Is)' (2s)'(2p) (3s)
Fic. 2.S. Table of atoms through atomic number 12 with energy states.
of
Metals and Alloys
9
2.2. The Building-Up Principle
Using the principles
outlined in the previous section, the electron con-
figuration of the elements can be determined through argon, atomic
number
18. However with the element potassium, atomic number
19,
instead of progressing from a completed
3p
energy state to the 3d state,
the next electron falls into a 4s state. Calcium follows with two electrons
in the 4s state. This discontinuity
in the building up principle results
from the fact that as electrons are added to energy levels further removed
from the nucleus a resultant shielding of the positively charged nucleus
takes place due to the intervening electrons, causing the energy of the 4s
state to actually have a lower value than that of the 3d state. Following
calcium in the periodic table, the building up of the 3d state occurs in a
normal manner, inside of a completed
Is state. The electron configura-
tion of nickel, atomic number
28, being (Is)
2
(2s)
2
(2p)
"
(3s)
2
(3p)
6
(3d)
8
(4s)
2
. The electron configuration
of element atomic number
29,
copper, then becomes normal with a completed
3d state and a (4s)
1
valence state. Elements with atomic number 21 through
28 are known as
transition elements and are characterized
by incomplete 3d energy states.
In the second long period of the periodic table a similar series of elements
occur with incomplete 4d energy states. The group of transition ele-
ments is important
to the metallurgist because it includes many of our
most important
metals, such as iron, titanium, vanadium, chromium,
manganese, cobalt, and nickel.
ATOMIC NUMBER TRANSITION ELEMENT
ELECTRON CONFIGURATION
21
Scandium
(Is)' (2s)'(2p)* (3s)'(3p)(3d)>
(4s)'
22
Titanium
(Is)
1
(2s)
2
(2p)' (3s)'(3p)(3d)
2
(4s)*
23 Vanadium
(ls)
(2s)*(2p) (3s)(3p)(3d)'
(4s)
8
24
Chromium
(Is)
1
(2s)*(2p) (3s)
2
(3p)(3d)
s
(4s)'
25 Manganese
'
(Is)' (2s)'(2p) (3s)
2
(3p)(3d) (4s)'
26 Iron
(Is)
2
(2s)'(2p)
6
(3s)'(3p)"(3d)
(4s)
2
27
Cobalt
(Is)
2
(2s)
2
(2
P)
6
(3s)
2
(3p)(3d)' (4s)
2
28
Nickel (Is)
2
(2s)*(2p) (3s)'(3p)(3d)
8
(4s)
2
Fig. 2.4. Table of atoms of the transition elements.
2.3. Types of Bonding in Solids
All solids can be classified in groups according to the bond formed
between atoms in the solid state. The four types of bonds that may be
formed in solids are:
(1)
The Van der Waal's bond
(2)
The ionic bond
(3)
The covalent bond
(4)
The metallic bond.
These various types of bonds may all be analyzed in terms of electron-
electron, electron-proton, proton-proton interaction between atoms.
Van der Waal's bonding occurs between atoms or molecules in solids
due to an induced polarity on one molecule with respect to another. This
type of bond is electrostatic in character and the binding force is relatively
weak. Solids formed by Van der Waal's bonding have low melting and
sublimation temperatures, and low strength. Solids formed by the atoms
or molecules of neon, argon, and iodine are examples of Van der Waal's
solids.
Ionic bonds can be considered to be the result of the transfer of an
electron, or electrons from one atom to another with the net result that
one atom becomes positively charged, and the other negatively charged.
On the basis of the building-up principle, such bonds should tend to
form between atoms with one or two electrons in the valence state and
atoms with one or two vacancies in the valence state. More stable elec-
tronic structures occur for completed energy levels; thus, when two
atoms such as sodium and chlorine are brought together to form a solid,
the valence electron of sodium is accepted by the chlorine atom to com-
plete the valence state of chlorine, leaving a net charge of + 1 on the
sodium atom, and resulting in a net charge of
1 on the chlorine atom.

The ionic bond is electrostatic in nature and results in a strong bond.
Examples of ionic solids are sodium chloride, magnesium fluoride,
magnesium oxide, and calcium sulfide.
The covalent bond is formed by forces arising from the sharing of
electrons between atoms. The simplest example of this type of bond is
the formation of the hydrogen molecule from two hydrogen atoms. The
lowest energy state for the hydrogen atom is the h state in which m
=
\/
2
,
and since this state can be occupied by two electrons, it follows that
if a molecule is to be formed between two hydrogen atoms, their elec-
trons must share this lowest energy level. Many elements with more than
one valence electron form crystal structures in the solid state based on
this type of electron bond. To complete an octet of electrons, required
for a stable structure, electrons are shared with 8-N neighboring atoms,
where N is the number of valence electrons in a given element. The
covalent bond is a strong bond, because of the completion of an energy
level; so that covalent solids are generally speaking hard and strong.
Examples of covalent solids are diamond, silicon, and graphite.
of
Metals and Alloys 11
The metallic bond has some of the features of both the ionic and co-
valent bond. When metal atoms are brought together to form a solid, a
broadening and possible overlapping of energy levels occurs; so that,
although a discrete number of electrons must occupy a given energy
level, according to the Pauli principle, the electrons in a given energy
level may have more freedom to move throughout the solid lattice under
an applied electric field.
Solid
Decreasing interatomic distance
Fig. 2.5. Broadening of energy levels in a solid.
The metallic state is sometimes visualized as a structure consisting of
positive ions arranged periodically in space, with a negatively charged
cloud of electrons surrounding the positively charged core. An explana-
tion of the high electrical conductivity of the metals is based on the idea
of unfilled or overlapping
broad energy levels. An applied electric field
in either
case may increase the energy of electrons in such bands and
promote them to a conduction band, resulting in a net flow of electrons
in the direction of the applied field. Insulators on the other hand are
characterized by filled and empty levels. Thus, a normal electric field
does not possess enough energy to promote electrons onto a conduction
band.
2.4. Assemblages of Atoms
Of the seven crystal systems used by the crystallographer, the two
most important to the metallurgist are the cubic and the hexagonal
systems. Nearly all of the common metals and alloys of commercial im-
portance belong to these two systems. Before discussing metal structures,
it is important to define certain terms used in describing solid structures.
The Space [.attire. A space lattice is defined as a lattice of lines divid-
ing space into equal sized prisms which stand side by side with all faces
in contact, so as to fill
space
with no voids. All of the points of a space
lattice have identical surroundings. It can be shown that there are only
fourteen possible space lattices.
The Space Group. Starting with a given space lattice, there are many
ways of building up actual crystals by placing atoms or molecules at
various points on the space lattice. Actually there are 230 such ways,
called space groups, of forming actual crystals based on the fourteen
space lattices.
The Unit Cell. The unit cell is defined as a network of lines through
the points of a space lattice, dividing it into prisms. Each unit cell in a
space lattice is identical in size, shape, and orientation with every other
unit cell. The unit cell is the building block from which the actual
crystal is constructed by repetition in three dimensions. The three most
important unit cells for the metallurgist are the body-centered cubic,
the face-centered cubic, and the hexagonal close-packed.
/'
/
7
y
y
/
\ i
/ .
f
/
/ >
/
/*
/ r
y
/
y
/

/
7
Fie. 2.6. The three unit cells.
In the cubic system all of the cube edges of the unit cell are of equal
length and stand at
90
to one another. In the hexagonal system, three
axes on the basal plane of equal length stand at
120
to one another with
the third axis of different length at
90
to the basal plane.
Special planes and special directions in crystals are of great importance
in plastic deformation of metals, hardening reactions, and other aspects
of the behavior of metal crystals; therefore, it is necessary to have some
method of describing such planes and directions.
of
The most common method is to use Miller indices and indices of direc-
tion to describe the position of a plane and its direction from a fixed
reference point. The Miller index system is based on the space lattice
and unit cell of the structure in question, and is derived from the inter-
cepts of the plane along the axes of the space lattice. The three steps in-
volved in the determination of the Miller indices of a particular plane
are as follows:
(1)
Determine the intercepts of the plane on the three-crystal axes
as a multiple or fraction of the unit cell edge.
(2)
Determine the reciprocals of these three numbers.
(3)
Reduce the reciprocals to the smallest integers that are in the
same ratio.
The three indices are then enclosed in parentheses. Planes that have the
Plane I
Intercepts x axis
=
a,,
y
axis = a
z axis
=
ao
Reciprocals x axis
= =1
y
axis
=
=
1
a
z axis 1
Plane II
x axis
=
a
y
axis = oo
z axis
= oo
x axis
=
=
1
a.
y
axis
= - =
oo
/.
axis =-r =
oo
Miller Index (111) (100)
Fig. 2.7. Determination of Miller indices.
same integers, either positive or negative, but in a different sequence
belong to the same family of planes. The planes
(010) ,
(OlO)
,
(100) etc.
belong to the same family of planes, the [100] family.
Indices of direction are derived by considering the motion that must
be imparted to a point at the origin to move it in a required direction.
The required indices are found by moving the point first along the X
axis, then along the Y axis, then along the Z axis, in terms of the unit
distance along these axes. The three smallest integers in the same ratio
that will impart die required motion to the point are the indices of
direction. Indices of direction are enclosed in square brackets. Direc-
tions having the same indices, positive or negative, but in a different
sequence belong to the same family. The indices of direction [100],
[O'TO], [001] belong to the same family of equivalent directions <100>.
Note that reciprocals are not used in finding indices of direction.
2.5. Defects in Crystals
Tn idealized representations of metal crystals, a model of perfect crystals
is generally used. In this model, a unit cell is used that possesses no
imperfections and is repeated indefinitely through space with no dis-
registry among the unit cells. Such a model clearly is not representative of
a real metal crystal. If it were, we should commonly experience tensile
strengths of the order of magnitude of millions of pounds per square
inch.
Real metal crystals and |>olycrystalline aggregates are characterized by
the presence of several types of defects. It is convenient to classify these
defects in three categories:
1. Surface imperfections
2. Line imperfections
3. Point or atomic imperfections.
Surface imperfections include the free surface of a crystal, the grain
boundary or interface between two adjoining grains in a polycrystalline
aggregate, interfaces between two solid phases, the interface of a twin and
the parent crystal, and sub-boundaries of the mosaic block
structure.
Metal crystals are made up of cubic crystallites about 10
*
cm. edge
length, called mosaic blocks. There is a slight disregistry among the
blocks, giving rise to interfaces formed by adjacent blocks.
Line imperfections are termed dislocations. There are two basic types
of dislocations, the "edge" type and the "screw" type. These dislocations
are illustrated in Figure 2.8. The dislocation concept is the basis of the
modern theories of plastic flow in metals.
Atomic imperfections include several types. The lattice vacancy is a
normal lattice point from which the atom is missing. Interstitial defects
consist of either a foreign atom in the interstitial space between normal
lattice sites, or an atom from a normal lattice site removed to an intersti-
Fundamental
Structure
of
Metals and Alloys
15
POSITIVE DISLOCATION
SCREW DISLOCATION
Fie. 2.8. Dislocations in Metals.
tial site at a considerable distance from the vacancy
so formed. Finally a
foreign atom may substitute for a host atom on a normal lattice site,
giving rise to a substitutional defect.
The defects listed above account for the flow and fracture character-
istics, electrical
properties including semi-conducting
behavior, diffusion
mechanisms, and creep characteristics of real metals and alloys. These
defects are the basis of the "prior history" effect so well known in metals
and alloys. The study of these defects by metal scientists has a two-fold
purpose; namely
(1) a better understanding
of them and how they
affect properties, and
(2)
exploration of possibilities of minimizing or
eliminating these defects. For example, metal whiskers of diameter of
about
10
'
cm. exhibit essentially theoretical
strengths and arc thought
to be free of dislocations.
Fie. 2.9. Schematic representation of crystallization. (Rosenhain)
2.6. Polycrystalline Aggregates
In technical freezing processes such as the solidification of ingots in
metal molds or castings in sand molds, many nuclei or starting sites be-
come active. A nucleus consists of a crystallite which is large enough to
be thermodynamically stable in the presence of the liquid. Each nucleus
grows until it impinges on its growing neighbors. This process is illus-
trated schematically in Figure 2.9. The impingement process yields metal
grains at the completion of freezing, since on the average, two neighbor-
ing nuclei have different orientations in space. The structure developed
is generally termed a polycrystalline aggregate.
of Metals and Alloys 17
The junction of two neighboring grains gives rise to a zone of dis-
registry termed the grain boundary. The grain boundary is a few atoms
in thickness and is essentially disordered in structure, showing viscous
properties since the atoms in this zone belong to the lattice of neither
of the two neighboring
grains. Some important manifestations of grain
boundaries are the following:
(1)
They are barriers to the propagation of slip, the basic mechanism
of plastic deformation. The smaller the grain size, the harder is the
metal.
(2)
Grain boundaries are high energy sites; thus, they are favored sites
for nucleation of solid state reactions. They may also attract solute atoms
in some cases, resulting in a segregation
of the foreign atom at the
boundary.
(3)
Diffusion is faster along grain boundaries
than in the bulk
of the grain.
(4)
At elevated temperatures, grain boundaries may contribute to de-
formation in creep by grain rotation.
The grain size range usually encountered is from 10 to 250 microns
(micron = 10*
cm.) in diameter. The grain structure is usually studied
with the aid of a microscope. In certain cases such as cast structures and
electrical sheet, grains are easily discernible by the naked eye. An ex-
ample of a polycrystalline metal is given in Figure 2.10.
Fie. 2.10. Polygonal grains of high purity iron, etched.
500x-
18
2.7. Interactions in Metallic Solutions
The initial addition of solute atoms of species B to a pure liquid or
solid metal of species A results in a liquid solution or solid solution
respectively. The solubility of B in A may be extensive or restricted.
If B is completely soluble in A, then it is said that B is completely miscible
in A. If B is not completely miscible in liquid A, then a second liquid
phase will appear. In solid metal A, limited solubility will give rise to the
appearance of a second phase, which may occur in the form of another
solid solution, or as an intermetallic compound with a characteristic
crystal structure.
Two characteristics mainly determine the miscibility of B in A, namely
the size factor and the chemical interaction among the species. The
ratio of the diameter of the solute atom B to the diameter of the solvent
atom A must be such that B can either
(1)
substitute for A at a lattice
site forming a substitutional solid solution, or
(2)
such that B ran fit in
the interstitial space of the A lattice, giving rise to an interstitial solid
solution. The size factor is illustrated in Figure 2.11.
I
. Favorable
Favorable for
for i
substitutional
interstitial i
solid solutions
solid solutions
j
i
0.59 0.85 1.0 1.15
Ratio of size of solute atom to solvent atom
Fie. 2.11. The size factor in the formation of solutions in metals.

Chemical interaction has to do with the strength of the bond between
atoms. In an assemblage of A and B atoms, the possible pairs of nearest
neighbors are A-A, B-B, and A-B. We can also refer to bond strengths by
these symbols. In solutions, three general types of behavior may be ex-
perienced: ideal solution behavior, positive deviation from ideality, and
negative deviation from ideality. In the case of ideal solution behavior,
the situation in bond strengths is A-A
B-B A-B. This is to say that
a given A atom has no preference as to an A or a B atom as its nearest
neighbor. (The number of nearest neighbors depends on the symmetry
of the space lattice, and is expressed as the coordination number. Values
for the common lattices are 12 for the face centered cubic and hexagonal
metals, and 8 for the body centered cubic) . In this case complete mis-
of
cibility in the liquid and solid state is expected, yielding the simple
A A 1 HH
isomorphous diagram. For the situation AB
> ,
positive devia-
tion is experienced,
meaning A atoms prefer to cluster with other A
atoms, and B atoms prefer to cluster with B atoms. This gives rise to the
tendency for phase separation. With increasing positive deviation, the
sequence of binary diagrams is the following:
Isomorphous
phase separation in the solid state
peritectic with a minimum

peritectic
-h> eutectic
- eutectic with a miscibility gap in the liquid region.
For the situation AB
< , negative deviation from ideality is
experienced, meaning A's and B's prefer to be associated. This leads to
the tendency for compound formation. The sequence of phase diagrams
with increasing
negative deviation is the following:
Isomorphous
ordering
compound formation.
An ordered solid solution is one in which the solute occupies specific
lattice sites and is not distributed randomly.
2.8. Liquid Solutions
The concept of liquid solutions of metals is easy to grasp since we have
common counterparts in our everyday experiences such as sugar dissolved
in coffee, salt dissolved in water. A liquid solution has some important
differences from the solid solutions. Probably the most important differ-
ence is that only "short-range order" exists. In a true solid, the crystalline
arrangement is repeated indefinitely in space giving rise to "long-range
order." When a metal melts, an increase in volume occurs (only bismuth
and gallium among the pure metals contract
on melting) . This increase
in volume is accounted for by the formation
of additional lattice vacancies
and an increase in the interatomic distances, with a loss of long-range
ordering.
It is believed that the liquid configuration is 12-15 atoms
clustered about a lattice vacancy.
As the temperature of the liquid is in-
creased, the short-range order begins to disappear and the structure ap-
proaches complete randomness.
Liquid
metals and solutions in general have no ability to sustain
shearing
stresses. The thermal and electrical conductivities are about
50%
of the values for the solid structure. The solubility of gases such as
hydrogen increases with increasing temperature. When immiscibility
occurs in the liquid region of an alloy, generally two liquid layers are
formed
because of difference in density of the two liquid phases.
20
Engineering
Metallurgy
2.9. Solid Solutions
The concept of solid solutions is somewhat harder to grasp. These
solutions are in reality solute atoms dissolved in the crystal lattice of the
host, or solvent metal. As previously mentioned, the solute atom may
substitute for a solvent atom on a lattice site, giving a substitutional solid
solution, or it may lodge in the interstitial space between the solvent
atoms, giving an interstitial solid solution. These two types of solid
solution
are illustrated schematically in a two dimensional array in
/'
7 s
s
/
y
< i
/
,
<-
'
/ } /
/
/ }
,/ /
y
2
yC
/*
yt
B
Fig. 2.12. Schematic representation of solid solution.
Figure 2.12. Solid solutions are produced either by the freezing of the
liquid solution, or by the diffusion of the solute atom into the lattice of
the solvent atom in the solid state.
The introduction of solute atoms into the lattice of the solvent metal
brings about some important changes in properties:
(1)
The electrical and thermal conductivities are reduced.
(2)
The thermoelectric power is reduced.
(3)
The strength and hardness are increased.
(4)
The ductility is decreased.
The formation of solid solutions is one of the fundamental methods of
hardening a metal.
2.10. Intermediate Phases
When the solid solubility of a solute species is exceeded, a second
phase will appear in the microstructure
of the alloy. These intermediate
phases can be classified into six categories:
(I) Intermediate solid solutions.
These solid solutions exhibit a range of composition and lie inter-
mediate to the components A and B. Terminal solid solutions, on the
other hand, start with pure A or pure B.
Fundamental
Structure
of Metals and Alloys
21
(2)
Normal Intermetallic
compounds.
These are often called valency
compounds since they show a definite
stoichiometric
ratio of A to B and a definite
chemical composition. Ex-
amples are Mg
2
Pb, Mg
3
Bi
2,
PtSn
2
, AlSb, MgTe, MnSn, and AuGa.
(3)
Electron
Compounds.
These
compounds are characterized
by a definite valence electron to
atom ratio, a definite structure,
and usually a range
of composition. The
electron/atom
ratios encountered
are
3/2, 21/13, and
7/4. A common
example of electron compounds is the Cu-Zn, or brass series of phases.
These electron compounds
are found in alloys of copper, silver, and gold.
(4)
The Sigma Phase.
The sigma phase is a hard, brittle phase found in certain alloy systems
such as for example
Fe-Cr. It has a tetragonal structure with 30 atoms
in the unit cell.
(5)
Interstitial
Compounds.
These
compounds involve
small solute atoms, usually hydrogen, nitro-
gen, and carbon, which lie in orderly
arrays between layers of the larger
solvent atoms. They are characterized
by their high melting points,
high hardness, and metallic
characteristics.
(6)
The Laves Phases.
The Laves phases are compounds which form when the difference in
atomic size between solute and solvent is intermediate.
They show the
composition
AB
2
with a size ratio of 1.2/1.
The formation
of intermediate phases is another important method of
hardening
metals. The intermediate
phases can further be classified
as to being coherent
or non-coherent.
Coherent
phases are those whose
structure is continuous
with the matrix
structure and lead to precipita-
tion hardening
(age hardening)
. Non-coherent
phases are those whose
lattice
structures are discontinuous
with that
of the matrix and are simply
mechanical
mixtures. This class of intermediate
phase leads to dispersion
hardening. The hardness
of such a mixture is mainly dependent on the
average
distance between the
precipitate particles,
or expressing
it
differently, the mean free path in the matrix.
QUESTIONS
1. Calculate the wave-length of an electron
(m =
9.1
x
10-28
grams) with a
velocity
of 1.8
X
109
cm/sec.
2. Calculate the wave-length
of a particle of mass 2000
pounds and a velocity
of
50 miles
per hour. Would it be necessary to use wave mechanics to
interpret the motion of this mass? Explain.
3. Write the electron
configuration of silver, molybdenum,
and tungsten.
4. Discuss
the difference between the ionic and Van der Waal's bond.
5. How do the metallic bond and the covalent bond differ?
6. Show how two different space groups may be constructed on a body-
centered cubic lattice.
7. Determine the number of atoms in a body-centered cubic unit cell; a face-
centered cubic cell. (Note that corner and face-centered atoms are shared
by other unit cells.)
8. Determine the Miller indices of a plane in the cubic system with intercepts
'A
a
, V-i
a, and
\i
a . (a is the length of the unit cell edge)
9. Determine the intercepts of a plane in the cubic system with Miller indices
of (235).
10. Sketch the direction [101]
in a face-centered cubic cell.
11. Enumerate the three classifications of defects encountered in real metal
crystals and give examples of each type.
12. What is the influence of these defects in metals and alloys?
13. Define a grain boundary and list some important manifestations of grain
boundries.
14. Describe the two types of solid solutions formed in metal systems.
15. What is meant by the size factor in solid solutions? Give the favorable
size factor range for the two types of solid solutions.
16. Discuss the arrangement of atoms in solid solutions exhibiting (a) ideal
behavior, (b) positive deviation from ideality, and (c) negative deviation
from ideality.
17. Give the sequence of phase diagrams expected for increasing (a) positive
deviation from ideality, and (b) negative deviation from ideality.
18. Discuss the properties of liquid solutions of metals.
19. What changes occur in physical and mechanical properties when B atoms
arc dissolved in the crystalline lattice of A, forming a solid solution?
20. Enumerate the six categories of intermediate phases and describe the char-
acteristics of each.
CHAPTER
Factors
Affecting
Engineering
Properties
3
Philip C. Rosenthal, M.S., Professor of Metallurgical
Engineering, University of Wisconsin, Madison, Wis-
consin
IF A "perfect" single crystal of metal is tested,
it is found that its strength is in the neighborhood of a million pounds
per square inch, exceeding by a hundred-fold or more the strength of the
same metal in its ordinary polycrystalline form. According to dislocation
theory, this great difference in strength between the "perfect" crystal and
the ordinary polycrystalline metal can be attributed to the presence in
the latter of dislocations within the grains, and to the grain boundaries
themselves, which in effect, represent a series of dislocations. Therefore,
the properties of polycrystalline metals are limited at the start by this
characteristic atomic disregistry; and whatever means we have available
for controlling their properties cannot eliminate this situation.
In addition to the inherent atomic imperfections that are present,
other microscopic or even macroscopic imperfections may be introduced
during the manufacture of the metal part. These are such imperfec-
tions as segregation of alloying elements, presence of non-metallic inclu-
sions, seams, porosity, voids, dissolved gas, etc., which will alter the
properties of the metal and determine its "quality." These "built-in"
factors cannot always be prevented and must be recognized as affecting
the engineering properties to a greater or lesser degree.
Starting
with a material that is already limited in its properties be-
cause of these imperfections, we can alter its properties within limits,
through the utilization of one or more of the following processes or "unit
operations" of engineering property control that are available to the
engineer for his manipulation. These are:
23
1
.
Grain size control
2. Mechanical working
3. Alloying
4. Heat treatment
5. Nuclear radiation.
The final engineering properties of a metal may therefore be thought
of as resulting from a combination of positive and negative factors. The
negative factors are the dislocations and the additional imperfections of
segregation, inclusions, porosity, and any other undesirable factors that
are picked up by the metal during the course of its preparation and that
detract from the properties of the metal. The positive factors are those
combinations of the first four of the process variables listed above that
are used to obtain the properties desired. To be most effective, any one
or combination of these operations should be performed on metal having
a "quality" consistent with the application and costs of the part.
To illustrate the extremes possible, the metal going into an ordinary
boat anchor and that going into a highly stressed landing gear of an air-
plane can be compared. In the first instance, the most important require-
ment is shape and weight, and strength is decidedly secondary. Metal
going into this part could contain a number of the imperfections pre-
viously listed without seriously detracting from its serviceability. Further-
more, no strengthening would be required by any further processing.
On the other hand, the highly stressed part of an airplane landing
gear would need to be very carefully produced to avoid any imperfections
and excessive inclusions. In addition, the metal would be alloyed and
properly heat treated and possibly mechanically worked to get the best
possible serviceability for the minimum weight of the part. Here the
negative factors would be kept at a minimum and the positive factors
derived from the processing developed to the highest degree.
While knowledge concerning the control of all the variables affecting
engineering properties is important to the engineer, it is with respect to
the processes used to manipulate the engineering properties* that he is
generally concerned and these will be discussed primarily herein. Refer-
ences to the factors affecting the "quality" of the metal will be made when
necessary.
GRAIN SIZE AND ENGINEERING PROPERTIES
3.1. Grain Size Control
Although other factors such as alloying or heat treatment may have a
more profound effect on metal properties, nevertheless control of the
The metallurgical engineer, of course, is expected to be familiar with all.

Factors
Affecting Engineering
Properties
25
Fie.
3.1. Partially
solidified iron crystals showing their dendritic appearance (Howe).
grain size of the metal can be important because such properties as
toughness,
high temperature
strength, machinability,
and formability
can vary
appreciably with the grain size. How grain size can be con-
trolled will be discussed first, following which
some of the more im-
portant
engineering
aspects of grain size control will be discussed.
Casting Process.
When metal is melted
and poured into castings,
the
metal solidifies
as a mass of interlocked grains. The way the metal freezes
and the final form it takes is related to its composition. It is not possible
to consider here all the ramifications
of solidification, and further
con-
sideration
of this point is given in Chapter
6, but those factors affecting
the final
grain size can be considered.
As the temperature
of the molten met;il is lowered
by loss of heat to the
mold walls, freezing
commences by the nucleation of solid metal grains
along
the sides of the mold. The grains so nucleated are probably
randomly
oriented but a number will be so oriented that growth inward
26
Fig. 3.2. Completely frozen gold alloy showing dendritic character of each grain and
grain boundaries. 100X.
will be favored, i.e. in the direction of the temperature gradient. At the
same time that they grow inward, these grains will also grow at lower
rates in their other dimensions as well. The growth, however, will not
be like that of an expanding block but more on the order of a growing
tree, with the main stem being represented by the growth inward and
the branches representing the lateral expansion. This tree-like structure
is related to the crystallographic structure of the metal since the lateral
growth is not random (as in a tree) but confined to definite preferred
directions. In the growing crystals illustrated in Figure 3.1, for instance,
the lateral growth in any one grain is confined to two major directions at
right angles to each other. In addition to the secondary branches, there
are also tertiary branches extending therefrom. Crystals which grow in
this manner are referred to as dendrites. The tree-like or dendritic growth
rather than a wall-like growth in these crystallographic directions is
attributed to the fact that heat can diffuse away from a protuberance
much more readily than from a flat surface; consequently, there will be a
natural tendency toward local extension of the growing interface.
The crystals in Figure 3.1 are only partially solidified. If allowed to
freeze completely, and assuming enough liquid metal available to satisfy
their needs, the grains would eventually fill out until all available space
would be occupied by solid metal and each grain would be separated from
the other by an irregular grain boundary (Fig. 3.2)
.
Factors
Affecting Engineering Properties
27
Fie. 3.3. Polygonal
or equi-axed grains of high-purity iron etched. 500
x.
If the metal is pure, the dendritic structure displayed in Figure 3.2
will not be visible, but the grain boundaries will still be present. The
dendritic structure shown in Figure 3.2 occurs because chemical hetero-
geneity is created during freezing and can be revealed by etching the
solidified alloy. Such chemical heterogeneity would not be possible in a
pure substance; therefore, evidence of the dendritic structure can only
be obtained
by draining liquid away from a partially solidified metal as
was necessary to reveal the dendrites in figure 3.1.
Whenever grains grow more rapidly in one direction than the others,
they are called columnar grains. If they grow equally fast in all direc-
tions they are called
equi-axed grains. Equi-axed grains of iron are
shown
in Figure 3.3.
The final size of these grains is dependent on two factors:
(1)
the rate
of nucleation, N, or in other words, the number of growth centers that
form in a given amount
of time, and
(2)
the rate of growth, G, of these
nuclei. It should be quite obvious that if conditions are adjusted to give
many nuclei and their growth is at a moderate rate, grain size will be
small. On the other hand, only a few nuclei, growing at an equal rate,
will produce a coarser grain structure. Both rates of nucleation and the
rates of growth can be represented by complex thermodynamic functions
involving
a number
of factors. The rate of nucleation in particular is
usually affected by impurity particles or the container walls. Practically,
however, both of these rates are dependent on the cooling rate of the
metal. As the cooling rate increases, the greater is the degree of super-
cooling of the liquid and the greater the rates of nucleation and growth.
The relative changes of these two factors, however, is such that for most
metals, rapid cooling produces a finer grain structure than slow cooling.
It is apparently impossible to repress completely nucleation in metal as is
the case for glass which represents a material which does not develop an
appreciable rate of nucleation until it is cooled to a temperature where
the rate of growth is too low to be effective and the glass remains a super-
cooled liquid.
Because nucleation of metals can be affected by impurities, some metals
can be produced in a fine grain structure by the addition of certain
nucleating or "inoculating" agents. The addition of sodium to an
aluminum-silicon alloy, for example, produces a fine grained alloy.
Mechanical vibration can also induce nucleation.
During the cooling of liquid metal in a mold other changes occur
that may have a bearing on the properties and behavior of the solid.
Most metals contract on freezing. Since this normal contractual process
occurs simultaneously with dendritic growth, interdendritic void areas
may develop that cannot be fed properly.
Also as metal cools, the solubility for certain dissolved gases or solids
may change, resulting in their precipitation and entrapment within the
grains or on grain boundaries depending on the degree and time of these
changes. These conditions affect the "quality" of the metal as discussed
earlier.
Mechanical Working. The previous section has described how grain
size of cast metals is controlled. Many metal parts, however, are produced
from metal that has been cast into an ingot and then subsequently rolled
or otherwise mechanically worked into a desired shape such as a forging,
bar stock, plate, angle or some other form. This mechanical working
can also change the grain sue of the metal.
If the working is done at an elevated temperature (hot working)
the combined effects of the heat and working action will cause recrystalli-
zation, the size of these new grains being dependent on the amount
of this mechanical action and the temperature at which it is performed.
As long as the temperature remains high enough to assure spontaneous re-
crystallization, the lower that temperature, the finer will be the grain size.
If the metal is worked at room temperature (or below for some metals)
,
the original grains are severely deformed and distorted. This is called
cold working. However, insufficient energy is available to cause this
metal to seek a new orientation (nucleate) and grow into a new set of
Factors
Properties
29
grains. By raising the temperature of the metal (annealing) , a tempera-
ture is reached where recrystallization
docs occur and a new set of
grains develops
as a result of nuclcation and growth in the solid state.
The size of these grains can be controlled, as described later in this
chapter.
Powder
Metallurgy. Metal powders
can be produced by reducing
oxides or other
compounds, by electro-deposition, grinding,
or by other
means. If these are subsequently compressed
and heated (sintered) a
metallic
compact is produced
by interdiffusion
of atoms between the
particles, producing
ultimately a metallic mass composed of grains having
a grain size that is determined by the processing
variables involved.
Allotropic
Transformation. In metals which undergo an allotropic
transformation
in the solid state a new set of grains is produced as a
result of the transformation.
Thus, in iron, which is the best example
of this situation, cooling it from the high
temperature face-centered cubic
form to the room temperature
body-centered structure results in nuclea-
tion and growth of the body-centered structure
from the original face-
centered
structure. The size of the grains is again determined by the
relative rates at which
nucleation and growth occur. Slow rates of cooling
promote large grain size.
Other Methods
for Controlling Grain Size. In addition to the fore-
going methods, it is also possible to produce
a solid metal of a certain
grain size by deposition
from a vapor
or by electrodeposition from a
solution. In the latter case the characteristics
of the plating bath deter-
mine the grain
size of the deposited metal.
3.2. Effect of Grain Size on Properties
Table
3.1 gives selected values showing
the influence
of grain size on
the strength and ductility
of pure iron.
Table 3. 1
.
Effect of Grain Size on Tensile Properties of Iron.
*
Grain Size, Grains Tensile Strength
Yield Strength Elongation in 2 in.
per sq. mm.
psi
ps;
m
2.5 to
9.7 23,900 to 33,700 5,900 to 6,500 28.8 to 35.3
35.6 to 77.5
38,200 to 41,600 8 , 300 to 20 , 200 44.8 to 50.7
109 to 135
42,200 to 43,300 15,100 to 22,200 42.8 to 45.3
Metals Handbook,
ASM, 1948 ed., p. 433.
These data show that there is a substantial increase in strength as a
result of decreasing grain size, with an accompanying rise in ductility.
However, once the grain size reaches approximately 100 grains per sq.
mm. little additional change in properties is apparent.
Since metal failure usually occurs by a process of slip (described later)
along certain crystallographic planes of the grains, followed by eventual
fracture, the effect of decreasing grain size is to cause interference to
slip among the many grains composing a fine-grained material thereby
raising its strength and altering the ductility, as compared to coarse
grained metal where each individual grain is freer to slip and distort with
less interference from neighboring grains.
Figures 3.4 and 3.5 show further examples of the effect of grain size
on the strength and ductility of metals. In the case of pure copper, very
little change in properties is evident, but for the 65-35 Cu-Zn brass the
strength and ductility are noticeably affected by grain size. In this case,
the strength decreases and ductility increases with increase in grain size.
In addition to affecting strength and ductility, grain size is also im-
portant in forming operations. Table 3.2, for example, shows the appli-
cations for brass of various grain sizes. The coarser grained material is
more readily deformed but gives a rougher surface than the fine-grained
material. Similar effects are noticed in deep-drawing of low-carbon steel
where grain size in excess of about 0.0012 inches average diameter may
lead to a surface roughness after drawing referred to as an orange peel
effect (Figure 3.4) . On the other hand, extremely fine-grained or annealed
low-carbon steel may show another type of defect after deep-drawing
called stretcher strains. This defect is characterized by fine wavy lines
that appear on the surface of the part after the deformation (Figure
3.5) . Also, a grain size that is too small is likely to make deep-drawing
difficult because of high strength and low ductility.
Table 3.2. Grain Size of Cold Worked and Annealed Copper Alloys.
*
Nominal Grain Size, mm. Typical Use
0.015 Slight forming operations.
0.025 Shallow drawing.
0.035 For best average surface combined with drawing.
0.050 Deep drawing operations.
0. 100 Heavy drawing on thick gages.
Loc, cit.
Factors
Properties
31
Fie.
3.4. Microstructure
and surface structure of a fine-grained steel (A) and a
coarse-grained steel (B). Orange-peel eficct is revealed
in (B) after Erichsen cupping
tests. (F
.
Korber, Staht & Eisen, v, 47, 1927, p. 1158).
Machining
operations are also influenced by grain size. Coarse-grained
steels, for example, allow for higher cutting
speeds, but if finish is im-
portant a fine-grained steel is recommended.
Metals under
stress at elevated temperatures tend to elongate slowly
with time (creep)
.
This behavior is associated
with grain boundary
movement,
hence where resistance to stress at high temperatures is im-
portant, a coarse-grained
metal will be superior to a fine-grained metal.
The tungsten
filament in a lamp bulb,
for example, is produced
as a
coarse-grained wire because of its better life. In other high temperature
applications, such
as turbines, jet engines, etc, the grain size of the metal
composing the high temperature components
will be a factor in determin-
ing its resistance to creep. This is discussed in Chapter 23.
32
Eiigineering Metallurgy
Fie. 3.5. Stretcher strains in low-carbon steel. % actual size (1955 Supplement
to Metals Handl>ook).
EFFECT OF MECHANICAL WORKING ON ENGINEERING
PROPERTIES
In a previous section the effects of mechanical working on grain size
were described. In addition to these effects there are other important
effects of mechanical working on the engineering properties that should
be considered. Before these can be discussed, however, it is necessary
to review briefly the principles dealing with the deformation of metals
because some knowledge of this subject is helpful for an understanding
of the engineering applications of metal working.
3.3. Deformation of Metals
When a stress of a magnitude to cause only temporary displacement
is applied to a metal, the resultant strain is termed elastic strain. If the
stress exceeds the limiting stress for elastic behavior, the permanent
strain resulting is termed plastic strain. With increased application of
stress beyond the elastic limit, metals continue to deform until they fail
by fracturing. Most nonmetals and occasionally some metals are totally
lacking in this plasticity and fail by fracturing with no permanent de-
formation. This is referred to as brittle fracture. Metals, in fact, are
unique among structural materials in their ability to be deformed and
it is only under special circumstances that they display a brittle fracture.
Demonstrations of elastic and plastic behavior in tensile testing will be
given in Chapter 4.
From an atomistic viewpoint, a stress that causes elastic strain results
in a temporary and small displacement of atoms from their normal posi-
Factors
33
Fig. 3.6. An octahedral or (111) plane. Eight such planes can be constructed in a
given cube.
tions in the lattice so that the lattice is slightly distorted. Release of the
stress causes the atoms to return to their normal positions and the lattice
regains its original shape.
In the case of plastic strain, two basic processes of atomic movement
are possible$/'/>
and twinning. These deformation mechanisms are dis-
cussed in the following sections, first with respect to single crystals and
then with respect to polycrystalline metal. It will be impossible to cover
all phases of this subject here, but the interested reader can find good
discussions of this topic elsewhere.
3.4. Slip in Single Crystals
In plastic strain there is a permanent displacement of the atoms,
the atoms moving from one atomic position in the lattice to another.
The particular crystallographic structure of a single crystal restricts the
movement
occurring during this straining to certain preferred planes.
In the face-centered
cubic metals such as copper, aluminum, or nickel the
preferred.
plane for straining by slip is normally the
(111)

plane. This
is the octahedral
plane that cuts diagonally through the unit cell as
illustrated in Fig. 3.6. When this plane is viewed from a position at right
angles to it, the atoms are close-packed much in the manner shown in Fig.
3.7b. On the other hand, it should be apparent from the left-hand illus-
tration in Fig. 3.7 that other planes such as those parallel to the faces of
the cube have a lower atomic density. Because of its high atomic density
A system of crystallographic indexing which indicates displacement of unity in
the three crystallographic directions as measured from a reference point.
V
\
(111) plane
\
(III) plane
-^\
(a)
Fig. 3.7. Arrangement of atoms in the octahedral plane of the face-centered cubic
unit cell as viewed from the side of the cube (left) and perpendicular to the face of
the plane (right).
the octahedral plane has the greatest interatomic attraction and there-
fore is said to be a strong plane. As a consequence, slip occurs parallel to
this plane rather than along some intersecting plane of lower atomic
density. For slip to occur along a plane of lower atomic density would
require that the stronger interatomic attraction existing on the octa-
hedral planes would have to be overcomean unlikely situation.
The direction of slip is likewise limited. These directions are shown by
the arrows in Fig. 3.7 and correspond to the directions parallel to the
lines of greatest concentration of atoms, and the lines of least resistance to
movement of one row of atoms past another. Any other directions within
the octahedral planes would require a greater disturbance of atoms since
the direction of movement would be tangent to some atoms but pass
directly through others.
The combination of slip planes and slip directions constitutes the
slip system. In face-centered cubic metals, four slip planes are possible as
mentioned in Figure 3.6, each having 3 slip directions. There are there-
fore 12 slip systems. Since slip depends on exceeding a critical resolved
shear stress that is specific for a given metal, metals crystals will not flow
or deform by slip unless the applied force can be resolved into shear
stress parallel to a slip plane and in one of the slip directions. This is
always possible in face-centered cubic crystals; therefore flow always
precedes fracturing in these crystals (unless a unique condition of equal
triaxial stresses exists)
.
A hexagonal close-packed metal such as zinc or magnesium can slip
only on the basal or
(0001)
plane. This plane represents the plane of
greatest atomic density in this type of crystal. As in the face-centered
metals, there are also three directions of slip. In fact, there is nothing to
Factors Affecting Engineering Properties
35
distinguish the basal plane of a hexagonal close-packed metal in atomic
arrangement from the octahedral plane of the face-centered cubic metals.
The differences come in the way atoms in adjacent planes are stacked
above or below the reference plane. Because it has only the one slip
plane and three slip directions, a hexagonal close-packed crystal has only
three slip systems, and it is possible to orient such a crystal with respect
to the applied load so that the slip planes are perpendicular or parallel
to this load. In such cases, no flow occurs and a brittle failure ensues.
Only when the basal plane is so oriented with respect to the applied
load that a shear stress can be resolved in one of the slip directions can
flow occur. Metals having this crystallographic structure, therefore, are
not so ductile as the face-centered cubic type.
The slip planes in body-centered cubic metals are not so well defined
as in the preceding two cases, and one of several possible planes can
represent the plane of major slip. The slip direction, however, is always
the close-packed direction represented by the cube diagonalsfour in
number. Around each of these four directions there are arranged 12
possible slip planes; consequently, 48 slip systems exist in these metals.
Although this represents a comparatively large number of slip systems,
each system is less regular and less densely packed than those of the
face-centered cubic metals. In general, then, the body-centered cubic
metals require somewhat higher resolved shear stresses to initiate slip,
and less permanent deformation is possible in advance of fracture.
Manifestation
of
Slip. The visual evidence of slip is the appearance
of numerous slip lines or slip bands upon microscopical examination of a
polished metal surface after the specimen has been deformed plastically.
These slip bands represent a permanent displacement of one part of a
metal crystal with respect to the rest of the crystal. The resulting micro-
scopical difference in elevation accounts for the appearance of lines
traversing
the crystal faces when viewed under a microscope. Repolishing
and etching will remove this evidence of slip because the surface displace-
ment which produced the slip lines is now removed thereby. In cases of
severe distortion, however, the disturbance is so great that slip will be
evident even though the distortion preceded the polishing and etching.
This is demonstrated by the cold worked brass in Fig. 3.1 1.
Strain Hardening.
The amount of stress required for slip increases
with an increase in the amount of prior deformation. In other words,
a strain-hardening
action occurs which lends to retard or restrict further
slip on a given slip plane. As the stress increases, slip is transferred to
other slip planes. This is the basis for hardening metals by cold work-
ing as described later. This mechanism is unique to metals and
36
represents one of its outstanding characteristics. Putty or clay, for ex-
ample, is readily deformed and worked, but no hardening action occurs.
Although much has been written about this hardening action and many
theories proposed to explain it, the theory of dislocations is generally
accepted today as offering the best explanation for the relatively low
stress required to initiate slip and increased resistance to the slip as
deformation proceeds. The low stress required to start slip is explained
on the basis of a wave-like movement of a small dislocation "zone" across
the crystal rather than a block-like displacement of the entire grain. The
increased resistance to slip as deformation progresses is attributed to an
interaction between dislocations created during the slip process. Since
the dislocation theory is still in the formative stage, any explanation of
strain hardening based on this theory is still somewhat speculative.
The theory does, however, offer the best overall explanation for metal
behavior yet available.
3.5. Twinning
Another mechanism accounting for plastic deformation of metal
crystals is twinning. This process has certain features similar to those of
slip and other features which are dissimilar.
Like slip, twinning occurs on certain crystallographic planes and
in certain directions, but the planes and directions are not necessarily
the same as those for slip. Also like slip, a certain level of shear stress is
required.
Twinning differs from slip in that the atomic movement is not from
one atom position to the next but rather a fractional atomic distance.
This results in a new orientation in part of the grain. This orientation is
such that the atoms in the area undergoing twinning present a mirror
image of those in the original part of the grain when viewed along the
plane dividing the twinned area from the untwinned region as shown
in Fig. 3.8. Although the figure depicts an atomic movement which in-
creases the greater the distance from the twinning plane, in reality the
movement, of any one atom need only be less than one atom spacing with
respect to a neighboring atom in order to accomplish the repositioning
necessary for twinning.
Twins produced by mechanical action as just described are referred to as
mechanical twins. Cold worked metals that are annealed also will exhibit
annealing tivins which probably originated from mechanical twins.
Mechanical twins are usually narrow and may be confused with slip lines.
Slip lines should appear on an unpolished surface that has been strained;
whereas, twin lines are usually evident only after etching. Furthermore,
37
Twinning plane*
Original lattice of face-centered cubic metal as
viewed parallel to twinning plane
(111).
Mirror image lattice as
created by atomic move-
ment shown by arrows.
Fig. 3.8. Diagram showing atomic movement required for twinning.
repolishing and etching would destroy a slip line but a twin would re-
appear. Slip usually shows up as lines; whereas, twins normally appear as
bands.
Twinning is not capable of contributing as much permanent deforma-
tion as slip. In face-centered cubic metals, therefore, it represents only
a small part of the total deformation. On the other hand, in hexagonal
close-packed metals, twinning is important not because of the deforma-
tion it permits but because twinning facilitates slip by aligning more
slip planes in a favorable direction.
3.6. Deformation of Polj crystalline Metals
The metals used in engineering are, of course, polycrystalline rather
than single crystals. The mechanisms previously described apply to each
of the single crystals composing the aggregate. However, the extent of
the movement is governed by the presence of the surrounding grains.
Consequently, the situation is a good deal more complex than in the ideal
case of a single crystal.
Cold working or stressing a polycrystalline aggregate composed of
randomly oriented grains causes slip to occur in the most favorably
oriented grains and on the most favorably oriented slip planes. As the
stress increases, additional grains less favorably oriented are similarly
deformed. Severe distortion in one direction will cause the following
effects in addition to the slip and twinning.
1. The lattice of each grain that is deformed tends to rotate into the
direction of the applied load.
2. In addition, the constraint by surrounding grains may cause the
lattice to be bent.
3. Deformation bands representing different degrees of orientation
within a grain appear in the microstructure.
4. A preferred orientation of the grains develops. This is sometimes
referred to as crystallographic fibering. The type of fibering that
develops depends on the metal being worked and the nature of the
stress system that is operating. This effect is of importance in the
cold working processes applied to metals, because the properties
are similarly rendered anisotropic and when the metal is recrystal-
lized by annealing (discussed later) a "recrystallization texture,"
which is also of a preferred orientation, may develop.
3.7. Hot Working
If metals are mechanically worked at a high enough temperature,
they do not strain harden, but simply recrystallize into new sets of
grains. When this occurs the working is referred to as hot working.
Hot working temperatures depend on the characteristics of the metal
being worked. Thus, lead is essentially hot workable at room tempera-
ture because it will recrystallize during the working operation. Steel, on
the other hand, must be heated to above a red heat before the operation
can be classified as hot working. In either case recrystallization occurs
simultaneously with the mechanical working, and the properties, with
the exceptions noted in succeeding paragraphs, are not changed much.
During the working process, the shape of the metal part is usually
changed drastically. As an example, in forming bar stock, the metal starts
out as a bulky ingot and ends up as an elongated bar. The same relative
changes occur to a greater or lesser degree in forming the many other
wrought shapes by rolling, forging, extruding, or by other metal working
processes. The coarse ingot structure is refined by this operation and
voids and porosity that might have been present in the original ingot are
largely eliminated, but the heterogeneity originally existing in the ingot
as a result of the changes occurring during freezing is not completely
irradicated. In fact, the metal working tends to elongate areas showing
chemical segregation, and the inclusions are also strung out in the rolling
direction. This has a tendency of producing a fiber-like structure in the
metal so that the properties when tested in the direction of rolling will
not be the same as those obtained from tests made at right angles to the
rolling direction. This type of directionality developed by the rolling
39
>
n*
-'
iMMH
Fig.
3.9 Elongated slag inclusions in rolled steel, uneiched. IOOX.
Fie. S.10. Elongated sulfide inclusions in steel and evidence of chemical segregation
in the region of these inclusions, etched. 100X.
process is sometimes referred to as mechanical fibering to distinguish it
from the preferred orientation effect which may occur as the result of cold
working and referred to as crystallographic
fibering. Examples of the
elongation of inclusions and evidence of chemical segregation are given in
Fig. 3.9 and Fig. 3.10.
The principal effect of this directionality
is to lower the ductility and
toughness in the transverse direction as compared
to the direction of
rolling. The data in Table 3.3 illustrates how the V-notch Charpy impact
values (which serve as a measure of toughness) vary with the selection of
the test piece. .Similar differences but not so pronounced are also en-
countered in the reduction of area values obtained in tensile testing.
TABLE 3.3. Influence of Directional Effects on V-Notch Charpy Impact Values at
70-F. (9).
Nature of Steel Tensile
Strength
Specimen Transverse
to Principal
Rolling Direction
Specimen Parallel
Principal
Rolling Direction
137,500 psi. 34-34 ft-lb. 67-64 ft-lb.
Straightaway 142,000 36-37 70-71
rolled steels* 134,000 43-44 75-76
Cross rolled 132,000 54-49 62-61
steels* 155,000 44-47 46-45
Cast steel, as-cast 110,000 53-56 ft-lb.
Same steel forged
*
*
110,000 102-122 ft-lb.
*
Notch parallel to plate surface.
**
From 2 x 3}^ in. section to
X
A
in. square bar.
Outside of the effects previously noted, hot working does not alter the
tensile properties of metals appreciably, particularly when compared to
the effects of cold working, which can effect a substantial change in
properties.
3.8. Cold Working
Cold working results in a distortion of the grain structure as depicted
in the series of photomicrographs of Fig. 3.11. Beginning with the hot
worked or soft tempered metals containing equi-axed grains, the succes-
sive stages of cold reduction produce increasingly greater distortion and
elongation of the grains and generation of slip lines. Because of the grain
fragmentation and disturbance of the lattice, there is an accompanying
hardening action as shown by the accompanying Rockwell B hardness
values. Tensile strength increases in about the same manner as hardness,
and there is a simultaneous decrease in ductility and toughness. Changes
in the tensile properties of brass and copper with percentage reduction in
drawing are shown in Fig. 3.12. This hardening action is attributed to
internal barriers to flow such as precipitated particles, impurity atoms,
etc., to interactions between dislocations moving on different slip sys-
tems, and to formation of subboundaries within the grains (polygoniza-
tion)
.
Factors Affecting Engineering Properties 41
ml&E&fmii
fe
s& m
M
i
,
- '-'
- 1*3;
S .a.
.-=H
:
'-
:i
----.
::
-J
-

-^- ;*- <
Fie. 3.11. Microstructure of 70% Cu-30% Zn sheet brass of various tempers.
Soft temper: 47 Rockwell B; i/
4
hard: 73 Rockwell B;
i/
2
hard: 82 Rockwell B; hard:
89 Rockwell B; spring temper: 94 Rockwell B. (Courtesy
of R. A. Ragatz, University of
Wisconsin)
Cold working therefore provides a means for hardening pure metals
or alloys. It is a particularly useful process where the composition is
such that hardening by heat treating cannot be used. The terminology
used in Fig. 3.11 (such as quarter hard, half hard, "spring temper") are
commercial expressions for the degree of cold reduction obtained. De-
pending upon the final finishing processing operations required, a metal
hardened by cold working can be ordered from the mill in any one of the
"tempers" indicated. Where heavy subsequent forming operations are
intended, the annealed or partially hardened metals are specified. But
if little further forming is to be done and a metal of high hardness and
strength desired, the full hard or spring tempers can be specified. The
actual hardness and strength for each of the tempers would vary depend-
ing on the base metal used.
42
Q.
O
O
Q
140
120
t 100
c
Soft 10 20 30 40 50 60 70 80 90
Percentage Reduction by Drawing
Be. 5.12. Eircct of cold reduction on the tensile properties of copper and brass.
(ASM Handbook.)
Steel can also be cold worked, and cold finished steel has certain
advantages not obtainable by other means. For example, not only does
cold finishing provide a smooth, oxide-free finish, but the metal itself is
readily machinable due to the increased brittleness induced by the rolling
action. This effect makes chip formation easier as compared to a steel of
the same hardness obtained in other ways.
3.9. Annealing Cold Worked Metal
Because of its strained condition, cold worked metal can be re-
crystallized by reheating or annealing. In practice, this probably should
be considered as essentially a fabrication procedure inasmuch as the
accompanying recrystallization and softening may be necessary to allow
further forming operations on the metal, but it produces properties con-
trary to the usual requirements of engineering materials. However, it is
important to be acquainted with the principles of annealing cold worked
metals because this knowledge is necessary wherever cold working is
used for fabrication.
As cold worked metals are heated, eventually enough energy is supplied
to form nuclei for recrystallization. These nuclei grow at the expense of
the deformed metal until the entire structure is composed of a new set of
grains. It is convenient to separate the process into three distinct stages:
(1)
Recovery,
(2)
Recrystallization, and
(3)
Grain growth.
Recovery. Recovery represents a relief of internal stress and a decrease
in thermelectromotive force and electrical resistivity. Internal stresses
Factors
43
c
CO
QJ
.**
co
.c
D
>~
CD
Wmm^/AalS^^^r^
Rtcot/cry
'Recrysloll'
I notion
I
Groin
G'owin
Annealing Temperature
Fin. S.13. Schematic changes in recovery, strength and recrystallization on annealing
cold worked metal. (ASM Handbook)
were originally developed during the cold working process. They repre-
sent a balance of compressive and tensile stresses within the metal. Their
magnitude and distribution are determined by the degree and type of
cold working treatment used. These stresses are detectable only indirectly
through the distortion that accompanies annealing or in the loss in
"spring-back" tendencies. "Spring-back" is the increase in diameter of a
roll of strip after it has been removed from a mandrel around which it was
held. The presence or absence of internal stress is one of the factors
that an engineer must constantly bear in mind in design, and these stresses
may be beneficial or harmful depending on how they occur within a part.
For example, shot peening a helical spring can markedly improve its
service life, i.e., its resistance to fatigue failure. Distortion occurring after
machining a cold-worked metal is an example of the harmful effects of
residual stresses.
Fig. 3.13 shows schematically what happens to residual stress, strength,
and grain size when a metal is heated in the recovery range.
Recrystallization. When the metal is heated sufficiently high, recrystal-
lation occurs. As shown by Fig. 3.14 this results in a rapid decrease in
strength
and increase in ductility. This process is both temperature and
time dependent, but the former variable has the more potent effect.
BO
._... > Lokt T.P.
, a Pnoipnorued
Elee T.P wornc
Anneolinq Temperature,
deq Fohr
200 HOC 600 800 1000 1200 1400
vr
I. *-jt ^ Contract-. at A'CQ
rr.Trrytr**.,'
^.l
,-
70
6
SO
40
30
10
(Of -j
0.10
014
0i2
OlO
06
?
3
006
J
E
o
5 S
004 O IS
J
f
0.02 25
?;"
1. 65 ?
S5
(00 ?00 300 4O0 tOO 600 700 800
Annealing Temperature,
deq Cent
Fic. 3.14. Elfect of annealing on tensile properties and grain size of four commercial
grades of copper. (ASM Handbook)
Grain Growth. Once a new set of grains is established, the growth of
these grains will continue if the temperature is raised or the time of heat-
ing prolonged. The effect on the mechanical properties as well as on grain
size is shown for copper and brass in Figs. 3.14 and 3.15.
140
Annealing Temperature, deg Fahr
ZOO 600 1000 1400
Grain
Site-
4Q
20
63XHard- in
43%Hard
24%Hord
70 .g
CM
60
g
50
.
,
so Ci
Hard ZOO 400 600 800
Annealing Temperature, deg Cent
Fic. 3.15. Effect of annealing on tensile properties and grain size of yellow brass
wire. (ASM Handbook)
Factors
Affecting Engineering Properties 45
3.10. Factors Affecting Recrystallization Temperature and Grain
Size
There are a fairly large number of variables affecting the recrystalliza-
tion temperature and the grain size after recrystallization, and since these
effects may be encountered in the engineering utilization of metals it is
important that they be recognized.
800 1200
i-00 400 600 800
Annealing Temperature, deg Cent
Fig. 3.16. Influence of the amount of prior cold work on the recrystallization
temperature of high-purity copper. Annealed one hour at temperature. (Koster, ASM
Handbook)
Percentage
of
Cold Work. Increasing the percentage of cold work
lowers the recrystallization temperature. This is more apparent in Fig.
3.16 than in Fig. 3.15. Increasing the percentage of cold work also de-
creases the size of the new grains (Fig. 3.17) . There is, however, an
intermediate amount of deformation as illustrated by Fig. 3.17 that will
lead to excessive grain growth. Apparently, this amount of deformation
restricts nucleation to but a few sites, and these nuclei therefore grow to
large grains. In an actual part where a variation in the amount of cold
working might be experienced, annealing could result in a region of ex-
g
E
in
.c
I
i
f-iq. 7
77 %JWOTTO
20 40 60 80
Degree of Deformation,
%
Fic. 3.17. Influence of degree of deformation on the grain size developed at 950 C
(1742 F) in low-carbon steel. (Hanemann, ASM Handbook)
cessively large grains which would effect the properties adversely. A cold
punching operation would be a good example of a situation where this
could occur. If annealing is required, its temperature should be con-
trolled to keep it below the recrystallization of the less severely worked
metal but above that of the more severely deformed areas to avoid large
grains in the regions of critical deformation.
Composition. The actual temperature at which recrystallization occurs
depends on the composition. Thus some metals like zinc may recrystalli/.e
by working at room temperature. Other alloys such as those used in high
temperature applications may not recrystalli/.e even when heated to 650C
(1200F) or above.
Annealing
Temperature,
deg Fohr
J00 400 500
too iso koo eso soo
Fie. 3.18. Effect of annealing lime on the softening of copper wire reduced 93%
by cold drawing. (Alkins & Cartwright, ASM Handbook)
Effect of
Time. Time-tern (jerature relations for the annealing of copper
previously cold reduced 93% are shown in Fig. 3.18. This shows that
increasing time lowers the recrystallization temperature.
Effect of
Initial Grain Size. The larger the original grain size, the
greater the amount of cold deformation to give equivalent recrystalliza-
tion temperatures and time.
3.11. Summary of Hot and Cold Working
Hot working is used primarily for fabrication purposes and does not
cause a large change in tensile properties. A directionality or fibering
effect is introduced, however, which has a tendency to reduce ductility
and toughness when tested transversely to the rolling or forming direc-
tion.
Cold working raises strength and hardness and lowers the ductility. It
offers an important method for hardening alloys that cannot be hardened
otherwise or as an auxilary treatment along with other hardening
processes. The effects of the cold rolling can be removed by annealing or
tempering and can only be reintroduced by additional cold rolling. The
combination of cold rolling and annealing has an effect on the re-
crystallizcd grain size of the metal, and the various factors affecting the
grain size and recrystallization temperature must be recognized for a
proper utilization of this process.
EFFECT OF ALLOYING ELEMENTS ON ENGINEERING
PROPERTIES
When one or more metals are added to another metal in the liquid
state, it is found that upon solidification the atoms of the added ele-
ments will either be a part of the lattice structure of the base metal as a
solid solution or another phase will appear in the microstructure. Either
of these effects will alter the engineering properties of the base metal;
therefore, alloying represents one of the important methods for con-
trolling them. Frequently, the effects of alloying are combined with those
of heat treatment to further influence the properties.
3.12 Solid Solution Effects
A binary alloy that exists as a solid solution has grains containing
atoms of two sizes in the lattice structure. This strains the lattice and in-
creases resistance to deformation, thereby serving to strengthen and
harden the alloy. For two metals that are completely soluble in each other
in the solid state, the maximum hardening occurs at about 50 atomic
percent of each. Coppernickel alloys are good examples of this case
and Fig. 3.19 shows how several properties of these alloys change with
composition. Although the maximum strength occurs at about
70%
nickel, the maximum hardness (not shown) occurs close to 50 atomic
percent (48 wt.%) nickel.
In addition to the mechanical properties, other physical properties are
altered by solid solution alloying. Fig. 3.20, for example, illustrates how
electrical resistivity and the the temperature coefficient of electrical re-
sistance vary with nickel content in copper-nickel alloys. This illustrates
the important principle that the maximum heat and electrical conduc-
tivity are obtained from pure metals and that the presence of alloys
(impurities in this case) is definitely detrimental in those instances where
high conductivity is desired.
Other alloy systems may have only limited rather than complete solid
solubility of the alloying element in the base metal. Such is true for many
of the copper-base alloys, for example. In these alloys the solid solution
hardening action increases with the amount of the alloy up to the limit
of solid solubility, following which the properties are affected by the
presence of another phase in the microstructure as described in the next
40 60 80
Nickel, percent
Etc. 3.19. Effect of nickel on the mechanical properties of copper-nickel alloys.
(Wise)
. 40 60
Nickel, per cent
Fie. 3.20. Effect of nickel on the electrical properties of copper-nickel alloys. (Wise)
Factors
Properties
49
section. The degree of hardening is usually inversely
proportional to the
range of solid solubility,
so that those alloys of very limited solubility
exhibit the greatest percentage-wise influence
on the properties. As an
illustration
of this point, it takes 0.6% Sb, 4.6% Si, 4.7% Al, 12.1 % Zn
or 13.2% Ni to increase the hardness of pure copper by an increment of
14 Vickers
DPH. (diamond pyramid hardness
number) . The order in
which these elements are listed is also the order of increasing solubility of
these elements in copper.
Besides the aforementioned effects, it might also be mentioned that
during the free/ing of alloys that exist as solid solutions at room tempera-
ture, there is a tendency for chemical segregation
to occur within the
growing dendrites as freezing progresses. Also, voids or a general porosity
may develop
or inclusions may segregate between or within grains. If
the metal is further processed by working, the segregation and porosity
are fairly well eliminated and the inclusions more or less uniformly
distributed and broken. If the metal is retained in the cast condition,
however,
these imperfections may have some bearing on the properties of
the casting. These are examples of some of the factors affecting the quality
of the metal.
3.13 Polyphase Structures
If an alloy is prepared which exceeds the limits of solid solubility at
room temperature,
the second phase may appear as:
1. The second component in essentially
pure form. Alloys of aluminum
and silicon are of this type, with the silicon
phase interspersed in
the aluminum
phase. The effect of silicon on the properties of
Al-Si alloys, is shown in Fig. 3.21.
2. An intermetallic
phase, in itself a solid solution, interspersed in the
original
solid solution. Copper-zinc
alloys, with zinc exceeding
about
38%, illustrate this behavior. The
alloy at room temperature
consists of separate grains of alpha brass, the original solid solu-
tion, and beta brass, an intermetallic phase containing
about
45%
Zn. (In the absence of the alpha phase, the beta phase can range in
composition
from about 45 to 50% Zn., which indicates its solid
solution
characteristics)
.
3. An intermetallic phase which is essentially an intermetallic com-
pound. Carbon in steel precipitates as the compound Fe.-,C so that
at room temperature
steel consists
of a mixture or iron and iron
carbide.
No matter what these extra phases are, they will influence the engineer-
ing properties. There is a tendency to generalize by staling that the effect
4 6 8 K)
% Silicon
Fie. 3.21. Effect of silicon content in annealed and hard rolled aluminum-silicon
alloys. (ASM Handbook)
of the second phase is proportional to the amount present, the properties
consequently being determined by the properties and amounts of the
individual phases present. This is only true if the second phase is rather
uniformly distributed in the parent phase; however, there are so many
exceptions to this rule that it is perhaps better to generalize that the
effects of the second phase are determined by
(1)
its properties,
(2)
the
amount present, and
(3)
its distribution. As will be learned when con-
sidering steel, for example, the way the iron carbide is distributed will
have a profound effect on the properties of the steel. Present as a net-
work, around the grains it can lead to brittleness and poor machinability.
Finely distributed throughout the steel, it contributes to high strength
and toughness.
Occasionally, a very small quantity of a given phase can be very harm-
ful to properties due to the fact that it may be distributed in a manner to
produce extreme brittleness. Examples of these effects are found with
bismuth in copper, iron sulfide in steel, and graphite in cast iron. In the
latter case, whether the graphite is distributed as essentially spherical
particles or as elongated shapes referred to as flakes will determine
whether the metal is strong and ductile or weaker ami brittle.
There are so many different possibilities that it is impossible here to
cover each of the situations that may be encountered. However, it can
be stated that the presence of a second phase can produce a decided
strengthening effect or can be decidedly harmful depending on the three
factors listed previously. In any event, by alloying to produce a second
Factors Affecting E?igineering Properties 51
phase we have available to us another method for controlling engineering
properties, and in succeeding chapters, examples will be given to illustrate
its importance.
To have
a full understanding of the consequences of alloying it
is necessary that one become familiar with the principles of alloying
as enunciated in Chapter 6.
EFFECT OF HEAT TREATMENT
ON ENGINEERING
PROPERTIES
The use of heat treatment to alter mechanical properties depends
upon:
1. An allotropic transformation as in the case of steel, or
2. A decrease in solid solubility of a second phase with decrease in
temperature as exemplified by a fairly large number of binary sys-
tems having copper, aluminum, magnesium, iron, or a number of
other metals as the base metal. Heat treating based on this effect is
referred to as age hardening or precipitation hardening.
3.14. Allotropic Transformation
Iron undergoes an allotropic
transformation from face centered cubic
to body centered cubic structure at 910C (1670F). When iron
is alloyed with carbon up to about 0.8%, this transformation is depressed
to lower temperatures and occurs over a temperature range. The normal
product on slow cooling steels in this range of carbon content is a mixture
of iron
(ferrite) and a product referred
to as pearlite which is actually a
mixture of ferrite and iron carbide. Rapid cooling, however, tends to
retard or repress this transformation with the result that other micro-
structural
products are produced, and in the instance of very rapid
cooling a new metastable phase called martensite is produced instead of
iron and pearlite. This phase is the hardest product obtainable for a
given carbon content. It is fairly brittle as produced and is usually
softened and toughened by a subsequent tempering treatment: the
higher the temperature of tempering, the softer and tougher the resultant
structure.
Utilization of the various heat treating possibilities based on
the allotropic transformation
in iron produces a variety of microstruc-
tural products and properties. Hence, heat treatment represents a basic
method for controlling the properties of steel. Inasmuch as this subject is
discussed fully in subsequent Chapters 12, 13, and 14, no details need be
presented here.
However,
it should be pointed out that in addition to the operation
of heat treatment,
the engineer also has at his disposal the benefits avail-
able from alloying so that in steel we are usually utilizing a combination
of alloying and heat treatment. For example, by varying the carbon
content (alloying) the base hardness of the steel can be changed; whereas,
varying some of the other alloying elements will alter its susceptibility to
heat treatment. Combinations of these effects, therefore, provide a
degree of control and versatility not obtainable by either method alone.
Superimposed on these effects of alloying and heat treatment are those
resulting from the quality of the metal as originally produced in the ingot
and from the mechanical processing the steel may have had. These mat-
ters must also be kept in mind when designing a part.
a'
68
|
.
-
105 F
1
/
/OT___
t
CHANCE
IN SCALE
-J75
I
1
;
'
140 F
.
^
VVL /
F
1
32 F
1
r~
210 F-'
P
'
'0
10 20 30 40 SO 60 75 100 ZOO
Time al Aging Temperature. hours
Fig. 3.22. Quench-aging of a 0.06% carbon steel. Hardness after quenching from
717C (1325 K) and aging at indicated temperatures. (ASM Handbook)
3.15. Precipitation Hardening
The principles of precipitation hardening are discussed in Chapter 7
and will therefore not be considered in detail here. The process involves
heating an alloy of selected composition to a temperature where it is a
single phase and then cooling it rapidly to a temperature where it
normally would be a two-phase structure as a result of solubility changes
with temperature. The rapid cooling, however, retains it as a single phase
metal. It is then subsequently "aged" at room temperature or above to
initiate a start toward the equilibrium two-phase structure. As a result
of the atomic adjustments that occur during this treatment, certain
alloys can be hardened appreciably. This hardening action is a function
of time and tem|>eraturc as illustrated by Fig. 3.22. The maximum hard-
ness reached is decreased as the aging temperature is raised. Also, the in-
crease in aging temperature results in a rapid drop off in hardness which
is referred to as overaging. Fig. 3.22 illustrates the fact that even in iron-
carbon alloys, which were previously used to describe the principle of
hardening by allotropic transformation, age-hardening can also be en-
countered. This aging effect depends on a slight solubility of carbon in
body-centered cubic iron. This solubility increases with increasing tem-
perature. Consequently the necessary {but not exclusive) condition for
age hardening is present.
In addition to the hardness change illustrated by Fig. 3.22, there are
also corresponding changes in strength, inverse changes in ductility and
toughness, and changes in electrical conductivity and other properties.
Aging may also be combined with metal working treatment to provide
additional control over engineering properties.
EFFECT OF NUCLEAR RADIATION
For materials going into the construction of nuclear reactors, it is
necessary to know about their relative absorption coefficient for neutrons.
Materials with low neutron absorption coefficients are necessary where
neutron passage is desired, or in other words, where the maximum utiliza-
tion and minimum waste of neutrons is desired. On the other hand, a
high coefficient is necessary for shielding or control purposes. The
absorption coefficient, then, is one of the engineering properties that must
be established. As examples, elements like boron, cobalt, and cadmium
have high absorption coefficients, but elements such as beryllium, sodium,
magnesium, aluminum and zirconium have low coefficients. The property
of neutron absorption plus related properties of strength, formability.
UNIT
CELL OF URANIUM WITH PERTINENT PLANES INDICATED
PREDOMINANT PLANES
PREDOMINANT PLANES
""*
'
EFFECTS OF PREFERRED ORIENTATION ON DIMENSIONAL STABILITY
OF URANIUM DURING IRRADIATION
Fic. 3.23. Effect of nuclear radiation on 'growth" of a nuclear fuel material.
(Courtesy of General Electric Co. Hanford Works)
corrosion resistance, heat resistance, etc. must be evaluated for the design
of nuclear reactors, and the metallurgy of the
materials used to construct
the reactor is therefore a very vital part of design.
Besides the aforementioned requirements, it is also necessary that the
susceptibility of the metal to radiation damage be known. Fig. 3.23 shows
what happened to a nuclear fuel material exposed to an intense neutron
atmosphere. The original smooth cylindrical specimen increased in size
or elongated and warped depending on crystal orientation. Proper
metallurgical treatment can considerably improve resistance to this type
of deterioration.
Structural metals subjected to neutron radiation are hardened or
strengthened and sometimes embrittled by such treatment. It has been
found that the face-centered metals are least damaged by such exposure,
whereas the hexagonal and body-centered cubic metals tend to become
brittle. Raising the temperature causes less damage. Heat treating by
annealing can be used to eliminate the embrittlement.
SERVICE
FACTORS
In the preceding sections the factors affecting the engineering properties
have largely been those concerning the processing and preparation of the
metal for service. There are, however, additional effects that may have
an influence after the part is placed in service.
Lack, of attention to the problem of residual stresses as briefly dis-
cussed under cold working could lead to a premature failure of a part of
fatigue. Besides originating from cold working, these stresses can also be
thermally induced as by welding or heat treating. Without going into the
details of this point, since it requires a knowledge of the static and
dynamic properties as discussed in Chapters 4 and 5, it should be em-
phasized nevertheless that the stress distribution created by design or
metallurgy is unfortunately often overlooked and that many of the failures
which have been recorded can be attributed to this omission.
Another service factor of extreme importance to be covered in Chapter
22 is corrosion. It should be quite obvious that when a part is designed
for corrosive conditions the properties of that part will deteriorate in
time and cause failure unless a sufficiently resistant material is used or it
is replaced frequently enough to avoid damage. By the same token, un-
expected corrosion can seriously detract from the load-carrying ability
of a part in service and possibly cause premature failure. These are addi-
tional factors, therefore, that the engineer must observe.
SUMMARY
There is a very close relationship between the structure and properties
of metals. Part of the structure is established during the manufacture of
the metal, and this can carry over in part at least to affect the final
properties. Most of the structural modifications, however, depend on
subsequent processing, and such operations as grain size control, metal
working, alloying, heat treatment, and/or nuclear radiation are available
to the engineer for controlling the properties. In certain applications,
these operations may continue while the part is in service as for example,
at high temperatures or under corrosive conditions. Then it is necessary
for the engineer to recognize the effect this will have during the service
life of the part. It can be said, therefore, that unlike gases and liquids,
the properties of solid metals depend on past history, rather than on the
variables existing at the moment.
In order to gain an appreciation of the relationships and interrela-
tionships involved in producing a given set of properties, it is necessary
for the engineer to learn about the fundamental structure of metals as
discussed in Chapter 2, about the measurements of behavior as discussed
in Chapters
4 and
5,
and about the principles of alloying and heat treat-
ment as discussed in succeeding chapters.
With the exception of corrosion behavior which is dependent on surface
conditions and chemical reactions, the behavior of a metal is governed
by its internal structural condition.
QUESTIONS
1. What are the processes available to the engineer for controlling metal
properties?
2. How does the factor of metal "quality" enter into the problem of property
control?
3. Describe the freezing of a dendrite.
4. Why is the dendritic structure absent on etched surfaces of pure metals?
5. What two factors affect the final grain size of a freezing metal?
6. How arc these two factors affected by cooling rate and what additional
variables beside cooling rate may be used to control grain size?
7. Beside the growth of dendrites, what additional changes take place during
freezing that may affect the quality of a metal?
8. Describe several ways besides the casting process which can be used to
control the grain of metals.
9. Of what practical importance is grain size control? Cite a number of
examples.
10. Compare the slip behavior in the face-centered
cubic, hexagonal close-
packed and the body-centered cubic crystals.
56
11. How does the twinning mechanism differ from the slip mechanism and in
what respects is it similar?
12. Why is the twinning mechanism important in some metals?
IS. Describe a number of the structural changes accompanying cold working of
polycrystalline metal.
14. Compare the effects of cold working and hot working on such factors as
(a) tensile strength, (b) directionality of properties, (c) toughness, and (d)
ductility.
15. Suggest possible applications for hard or spring temper brasses.
16. Why is the relief of internal stresses during the recovery period when
annealing cold worked metal of industrial importance?
17. Why is annealing a cold-worked metal sometimes considered a fabrication
procedure?
18. What damage may result from annealing at too high a temperature for a
metal that has experienced a wide variation in the amount of cold work?
19. What are the possible effects on properties when one metal is added to
another to (a) form a solid solution? (b) cause another phase to appear?
20. What basic ways are available for altering mechanical properties by heat
treatment?
21. Explain how design for nuclear reactors involves factors not encountered
in other types of applications.
CHAPTER
Static
Properties
of
Metallic Materials
Lee L. Amidon, M.S.M.E., Professor and Head, Depart-
ment of Mechanical Engineering, South Dakota State
College, Brookings,
South Dakota
Walter E. Short, M.S.M.E., Associate Professor of
Mechanical Engineering, Bradley University, Peoria,
Illinois
4.1. Properties of Metallic Materials
I HE properties of metallic materials are com-
monly divided
into three general classes:
(1)
physical constants,
(2)
electrical
and magnetic properties, and
(3)
engineering properties.
The first class includes elastic constants, density and related properties,
thermal expansion, vapor pressure, emissivity, and thermal conductivity.
The thermal properties are affected by temperature and phase changes.
Dimensions change and heat is absorbed or discharged at such times.
Problems in heat-treating
operations may be anticipated as a result.
These properties
are of interest to the physicist as well as to the metal-
lurgist. Usually, however, they are of interest to the physicist as a step
in his study of theories of matter rather than as properties of metallic
materials. Some of the physical constants are of interest to the engineer:
the elastic constants surely are, because they are important in the design
of structures; density is of interest if the strength-weight ratio must be
considered, as in aircraft
construction, high speed railway trains, and
motor-haulage vehicles; thermal expansion and thermal conductivity
may be of importance for some engineering applications and of none for
others. The essential fact for the engineer to know about the physical
constants
as a group is that in general they are determined by standardized
methods that yield fairly precise, readily reproducible values that can
be used in engineering design without trepidation regarding their mean-
ing and accuracy. Values for the constants are well established and can
be obtained in handbooks of physical tables.
57
58
Electrical and magnetic properties include thermoelectric properties,
resistivity, magnetization, induction, permeability, and coercive forces.
These properties vary widely between different metals and their alloys
and must be investigated thoroughly before making final selection for
any given service. Aluminum on a weight basis may be a better conductor
than copper and cheaper as well, but its tensile strength may not be
sufficient to make it safe for the long spans desired on high-tension trans-
mission lines so we compromise by using a steel core to provide strength
and the result is an efficient carrier at low cost. Table 4.1 gives typical
values of resistivity and the manner in which these values will change
with temperature. The resistor elements for a dynamometer will call
for a material with great resistance to the flow of electricity while in a
Table 4.1. Resistivity of Typical Metals and Alloys
Material
Copper
Aluminum
Iron
Constantan (55% Cu, 45% Ni)
.
Nichrome
(80% Ni, 20% Cu) . .
transmission line the 1
2
R loss should be as near zero as possible.
Magnetic properties are essential in the design of motors, generators,
transformers, metering equipment, and huge lifting magnets. The
magnetic properties are the result of the plus and minus magnetic fields
set up by the electrons whirling in their orbits. Ferromagnetic materials
such as iron, nickel and cobalt exhibit this property to the greatest extent.
Single atoms will not form a permanent magnet but several atoms
grouped together will form a magnetization unit. This small group is
known as a domain. There will be several domains in one metal grain.
Ordinarily the domains of a metal bar will have random orientation in
which case the bar will not be magnetic. An external magnetic field will
align the orientations found in the many domains and the bar is mag-
netized. If upon removal of the external field, the domains remain
oriented we have a hard permanent magnetic substance. On the other
hand if they tend to lose orientation then we have a soft or temporary
magnetic substance.
Resistivity at
20
C.
Microhm-cm.
Temperature Coef.
Increase per

C.
1.7241 .00393 (0-100
C)
2.654 .00429 (20
C)
9.8 .0056 (0-100 C)
-19
.0002 (20-100 C)
107.9 .0019 (20 C)
Static Properties
of
Metallic Materials 59
Temperature
has a very decided influence on ferromagnetic materials.
Increase in temperature causes the magnetization to decrease and finally
to disappear altogether at what is known as the Curie temperature. This
temperature is 1414F for iron, 2039F for cobalt, and 665F for nickel.
The domains disappear at these temperatures, which for iron is below the
point at which it becomes austenitic. These temperatures may be altered
drastically by small additions of alloying elements or impurities.
Electric properties are extremely important to the electrical engineer,
and the methods for their determination are precise; but because of their
limited application to general engineering, further discussion is beyond
the scope of this book.
From the standpoint of engineering in general and of those fields of
engineering which deal specifically with the design, erection, and main-
tenance of structures and machines, the last class, engineering properties,
is of vital importance. For convenience, they may be divided into three
classes: static mechanical properties, dynamic mechanical properties, and
miscellaneous properties. There is a very close relationship between the
engineering properties and the metal lographic structure, which will be
made clear in later chapters of this book. Because of this relationship
between micro-structure and physical properties, metallic materials are
structure sensitive. In other words, they are affected by changes in the
structure even though the chemical composition is unchanged. As we
learn how to produce space lattices which are undistorted during the
mechanical processing of our materials, much improvement in strength
and physical properties may be anticipated.
Precise instructions for the physical testing of engineering materials
have been established by the American Society for Testing Materials and
summarized in the Handbook of the American Society for Metals. It
must be understood that the properties established
by these tests are use-
ful primarily in maintaining uniformity of material once a satisfactory
design has been established. The most useful form of testing is that made
upon a completed structure under actual service conditions. Time and
cost usually limit this procedure; therefore, the following pages will
evaluate the advantages and shortcomings of the various tests of a given
material for use in engineering machines and structures.
It cannot be emphasized too strongly that the data from a small test
specimen should be accepted with caution unless it is certain that the test
piece is representative of the entire lot of material whose properties are
being determined. A large number of specimens reduce the chances for
error of even the most accurate and reproducible tests. The shape of the
designed part may determine to a large extent the distribution of stress
in a given cross-section. The presence of stress raisers (holes, sharp
changes in cross-section, scratches, inclusions) may increase the stress 3 to
5 rimes the average value. Ductile materials under static loading will yield
and little harm will be produced. However brittle materials and parts
under repeated or reversed loading will start to tear and fatigue failure
of the part thus ultimately occurs.
Many of these stress concentrations can be readily corrected by prop-
er design changes. Frequently the magnitude of stresses at concentra-
tion points cannot be readily determined by analytical methods. The use
of brittle lacquers applied to the structure under simulated service con-
ditions will reveal trouble spots which can then be corrected or eliminated.
This design technique known as stress coating will supplement the
standard test data. The use of strain gages in a similar manner will
determine the location, direction, and magnitude of the unit strain at
locations where stress concentrations are suspected. The unit strain can
then be used to calculate the actual stresses rather than the average stress
that might be determined by the ordinary methods of design. Another
method of determining stress concentrations is based on the optical
properties of transparent materials. Some of these materials are optically
isotropic when in an annealed condition, but become optically aniso-
tropic when subjected to external stress. This method requires a plastic
model, which, of course, limits its use to a certain degree. Hidden stress
raisers such as blow holes, slag inclusions, malformed space lattices or
grain structures may be revealed by sonic testing described later in this
chapter. Other methods frequently used to determine surface and hidden
defects are radiography and magnetic particle detection. All of the above
mentioned methods have the advantages of being non-destructive tests.
Physical properties, then, must always be considered in relation to the
structure itself and sound engineering judgment used in its selection,
considering always the limitations of the material for a given service or
condition.
4.2. The Relative Standardization of Static Tests
Static mechanical properties, which are a measure of the resistance of a
material to a steadily applied load, include tensile strength, compres-
sive strength, torsional strength, bending strength, hardness, and their
related properties, such as yield strength, elongation, and others deter-
mined incidentally to the first named. The determination of some of
these properties has been given considerable attention by testing societies
in the principal metal-using countries with the result that methods and
specimens are fairly well standardized.
Static Properties
of Metallic Materials
61
The most important and the two most common tests for the evaluation
of the static properties of metallic materials are tensile and hardness
tests. The former is well standardized throughout the world. If the
tensile strength of a certain steel is reported as 60 kg. per sq. mm. in
Germany, it is certain that a standard specimen of the same steel will
have a strength of about 85,000 lb. per sq. in. in the United States and
that either value represents accurately the stress necessary to break a
i/4-in. specimen of that particular steel. The tensile strength of a steel of
certain composition, made by a particular process, and of otherwise satis-
factory quality can be used in the design of a bridge in Japan, even if
the steel was made and the strength determined in France. Because hard-
ness tests are made rapidly and cheaply and because they do not destroy
the material, they are used widely. That hardness is not a definite prop-
erty but a combination of several properties makes the interpretation of
some of the tests difficult. Hardness tests are not standardized, although
the measure of a specific kind of hardness, namely, resistance to indenta-
tion, is in a fairly advanced state of development. Hardness tests took
on added importance during the war years as new and untried low-alloy
steels were substituted freely for some of the older alloy steels on the
basis of the hardness of an end-quench hardenability test.
Static tests used less frequently, and for which standardization has
not proceeded so far, include compressive, torsion, and bend tests. None
of these is used
so widely as are tensile or hardness tests, although the
transverse
test, a form of bending, is the most widely used and is prob-
ably the most valuable single test for the evaluation of gray cast iron as
an engineering
material. With this one exception, none of these tests is
standardized, and it is not always easy to interpret the values obtained or
to apply them to the design of engineering structures.
4.3. Tensile Strength
The commonly determined tensile properties, including tensile
strength,
yield strength, proportional limit, elongation, and reduction of
area, are obtained
on a single test specimen (see Fig.
4.5) . The accuracy
and reproducibility of the results depend upon the dimensions of the
specimen, the sensitivity of the machine, the alignment of the specimen
in the machine, and above all on how accurately the specimen represents
the whole section. Considerable attention has been paid to these factors
by the testing societies and the builders of machines in all countries,
with the result that reported values are about as accurate as for any
engineering
property.
17.000
16.000
15.000
14,000
13,000
12,000
11,000
10.000
TS
9000
o
:8O0o
|
7000
ta
6000
5000
4000
3000
2000
1000
c 0.002
/ ^
y
/'
/
/
c
/ hn
/,
/
/
1
1
/
1
1
1
p
I
Is
1/"
1/
1
1
i
i
r
1
1
1
_i
A ^
/
1
1
1
1
0.004 0.006 0.002
St rain, inch per inch
0.004 0006
Fie. 4.1. Stress-strain curves in tension for (A) annealed low-carbon steel and (B)
cold-worked low-carbon steel.
As is well known, the tensile strength of a specimen is the maximum
load before rupture (point C, Fig. 4.1 A) divided by the original cross-
sectional area. It is reported in pounds per square inch, tons per square
inch (England) or kilograms per square millimeter (continental
Europe)
. Specimens and other variables have been standardized by the
American Society for Testing Materials *so that further discussion is
unnecessary.
Owing to the inherent variations in structural constituents and in
composition which may cause variations in tensile strength of as much as
1,500 lb. per sq. in., there is a growing tendency to test full-sized struc-
tural members with large machines. This type of test is especially valu-
able for structures that are riveted or welded.
If a tensile test is made on a larger or a smaller specimen than is com-
monly used (0.5 in.) , the tensile strength may be considerably higher or
lower than that obtained on the standard bar. For ductile materials,
which include most rolled, forged, or heat-treated carbon and alloy
A. S. T. M. Standards, 1955.
Static Properties
of Metallic Materials 63
\
STRAIN HARDENING BEGINS
Fic. 42. Greatly enlarged view of stress-strain diagram in region near yield point.
steels, the error is not great; for a brittle material, such as cast iron, the
variation in strength may be considerable if differences in cooling rates
of cast specimens of various sizes result in differences in structure.
For a number of years, structural design has been based on either the
tensile strength or the yield strength with the use of appropriate factors
of safety. For example, a working stress for carbon steel may be of the
order of
18,000 psi. although the yield point of this material may be ap-
proximately twice this value. It might be noted that the portion of the
stress strain curve shown in Fig. 4.1 A at point B would have a consider-
ably different appearance if the curve were plotted with a different scale.
It will be noted from Fig. 4.2 that a large amount of yielding at a rela-
tively constant stress will occur before strain hardening begins. This
phenomenon is the basis of recent work in the field of plastic design.
4.4. Elastic Limit, Proportional Limit, and Modulus of Elasticity
There is occasionally
confusion among engineers and steel men con-
cerning the meaning of the terms Elastic Limit, Proportional Limit, Yield
Point, and Yield Strength.
The elastic limit is the maximum stress that
a material withstands without permanent set. Although it is practically
impossible to determine the true elastic limit experimentally, it is pos-
sible with present-day extensometers to detect a relatively slight vari-
ation from
Hooke's law,* and by careful testing the point of this variation
can be fixed with considerable exactness on the stress-strain diagram
(point P, Fig. 4.1A) . The load which this point represents, divided by
Hooke's law states that in clastic materials stress is proportional to strain. It is
generally held that in metallic materials the application of stress, within the range
where deformation is elastic, actually produces some plastic deformation. The amount,
however, is so small that for all practical purposes, and especially for engineering
design, Hooke's law is valid.
0.004 0.012 0.016 0.020
Strain, in./in.
0.024 0.032
Fic. 4.3. Stress-strain diagrams of common metals. (H. W. Gillett, Batelle Memorial
Institute, "The Behavior of Engineering Metals," p. 15.)
the cross-sectional area, is the proportional limit. It is frequently deter-
mined in testing laboratories but is seldom used in the design of struc-
tures. In most annealed and heat-treated carbon and low-alloy steels, the
proportional limit is practically identical with the elastic limit and, as
Fig. 4.1 A shows, is slightly below the yield point. If the proportional
limit of such steels is found to be much below the yield point, it is likely
that internal stresses are present. The determination of proportional
limit is frequently made to detect the presence of such stresses.
Modulus of elasticity in tension is the ratio of stress to strain with-
in the elastic range. It is given by the slope of the stress-strain curve
(see Fig. 4.1 A) up to point P. For carbon and low-alloy steels of any
composition and treatment, the value is approximately 29,000,000 lb.
per sq. in.; for aluminum alloys, the modulus in tension is about
10,000,000 lb. per sq. in.; for copper and copper alloys, about 15,000,000
lb. per sq. in. Modulus of elasticity may be determined in compression as
well as in tension; values are about the same for either method. Another
important quantity is the shear modulus, or modulus of rigidity, which
is invariably smaller than the modulus of elasticity (Young's modulus)
.
Static
Properties
of
Metallic
Materials
65
-*
A!
KM^se-r'*
0.002 0.004 0.006
Strain, in. per in.
0.008
Fig.
4.4. Stress-strain curves for two gray cast irons tested in tension.
(/. W. Bolton,
Ptoc. Am. Soc. Testing Materials, v. 32, 1932, II, p. 477)
The modulus of elasticity is a measure of the stiffness of the metal.
It is not appreciably affected
by heat treatment.
A part too springy in
the annealed state will not have the condition improved by hardening.
The modulus
decreases with increases in temperature moderately
at first,
but may change very rapidly when some specific high temperature is
reached. The rate of change varies with the alloy
chosen. Some typical
values of stress-strain
diagrams and moduli of elasticity are shown in Fig.
There are some metallic materials-gray
cast iron and austenitic alloy
steels are outstanding
examples-which
when tested
in tension have a
stress-strain
curve that is curved from
the origin (Fig.
4.4) . Such ma-
terials have no readily
determinable
proportional limit and yield point.
Moreover, they have no true modulus of elasticity;
reported moduli are
arbitrary values
that measure the relative
stiffness under
specified
conditions
of loading,
usually with a stress equivalent
to 25 per cent of
the tensile strength.
4.5. Yield Point and Yield Strength
Engineering structures and machines subject to static loads are designed
on the assumption that the stresses that must be withstood will not cause
appreciable plastic deformation (permanent set) . As plastic deformation
probably starts in a large number of independent locations, it is difficult
to determine where it actually begins. Plastic deformation does not be-
come measurable until a large part of the section has been affected, and
even then very sensitive equipment is necessary to locate this pointthe
proportional limit. Fortunately, practical experience has shown that, at
ordinary temperature, the limit of usefulness of a metallic material is that
stress which produces a plastic deformation that is readily detected.
Higher stresses than this may cause considerable damage; with lower
stresses the damage is negligible. This stress is the yield point. In ductile
materials, it is indicated by a marked elongation of the specimen with
no increase in load. It is readily detected with a pair of dividers or by the
drop of the beam of the testing machine. The yield point is of con-
siderable value to engineers in the design of structures, but it has the
disadvantage that it is not well marked in hard materials, some of which
have no true yield point. To overcome this disadvantage the American
Society for Testing Materials recommends the use of yield strength in-
stead of yield point.* This is the maximum stress that produces a
specified set, usually 0.1 or 0.2 per cent of the gage length. In hard
materials, the point can be readily determined from the stress-strain
curve (point B, Fig. 4. IB); in soft materials, it corresponds closely to
the yield point determined by drop-of-beam. The yield strength is an
important and readily determinable value and should replace the yield
point in all reports of tensile properties.
The value for yield point is affected by the rate of strain, that is, by
the speed of the cross head of the machine. Generally, however, the error
is not great for the speeds used in testing to determine whether a ma-
terial is within specifications. For example, increasing the rate of strain
tenfold, as from 0.2 to 2 per cent per min., increases the yield point only
about 2,000 lb per sq. in. The American Society for Testing Materials
specifies that the cross-head speed should not exceed
i/
8
in. per min. for a
2-in. gage length.
Very soft materials, especially annealed low-carbon sheet, frequently
have two yield points: an upper point, at which there is
a
decrease in
stress (A in Fig. 4.1 A) marked by a sudden drop of the beam of the test-
ing machine, and a lower yield point (B in Fig. 4.1 A) , where strain
1
Static Properties
of
Metallic Materials
Radius not less U
gj
.'
than'/
8
"
\|
Parallel section
Nole:
-
The gage length,
parallel sect/on, and
fillets shall be as
shown, but the ends
may be ofany shape
to fit the holders of
the testing machine
in such a way that the
load shall be axial
67
o
fiO.Ol"
-
,k
2"i0.00S"A
Gage length
for elongation
after fracture
h- ?gm/h mgnps-*^*-
3f
mih between grips >j<- 2g/n/ningrips-
"1
w+0.003to0.0OS"
(See Note!
w
<
=o.soo"io.o/o" I
^r
,
, .
x to +0.003 to 0.005
1
Zj mm.
>-}
\ ,
Ifeducedsection
6'min.
''Radius
0.5"to3"
.
-t
t
=
Thickness ofmaferial
Note: Gradual taper from ends ofreducedsection to middle.
Allmachining dimensions are shown below andtestingdimensions above specimen
Fig.
4.5. Standard round and flat tensile specimens. (AS.TM. Standards E8-46)
hardening begins and where additional stress is necessary to produce
further strain. The difference between
the upper and the lower yield
point is considered to be an indication
of the deep-drawing
capacity of
annealed low-carbon
sheet.
4.6. Elongation and Reduction of Area
In the United States, the standard round tensile-test specimen has a
diameter
of 0.505 in. (cross-sectional area 0.2 sq. in.) in a gage length
of
2 in. (Fig. 4.5 top)
. Elongation
values determined on round speci-
mens larger or smaller than the standard are directly
comparable with the
standard if it has a gage length equivalent to
G =
4.5vT
where
G is the gage length
and A the cross-sectional
area in square
inches.
Unfortunately,
since the standard tensile specimens used in
Great Britain,
Germany, and France have a different relation between
gage length and cross-sectional area from that expressed by the above
formula, values obtained in those countries,
while always reproducible
where determined, cannot be compared directly with elongation values
determined
in the United States.
68
Fie. 4.G. BrineU hardness machines: left, hand-operated laboratory model; right,
high-speed production testing model. (Courtesy
of
Tinius Olsen Testing Machine
Company)
For some products, especially for plate and thin sheet, specimens are
used that may differ in size and shape from the standard (Fig. 4.5 bot-
tom) . Gage lengths for tensile specimens of such products vary from 2
to 10 in., depending upon the material and its size. As elongation is re-
ported as a percentage of the original length, the percentage elongation
of a given material is higher the shorter the gage, owing to the fact
that most of the elongation takes place in the "necking-down" that occurs
at the point of fracture. When tensile properties are determined on speci-
mens that differ in dimensions from the standard, the gage length is
always given. Even if a standard specimen is used, most metallurgists
report the gage length
(2
in.) so that there will be no misunderstanding.
Reduction-of-area values are always reported as a percentage of the
original area so that values for this property should be comparable.
Static Properties
69
Elongation and reduction
of area give a rough,
but usually
a fairly
clear, idea
of the ductility of the metal tested. Although engineers
gen-
erally demand a relatively high elongation,
metallurgists place more
emphasis on reduction of area as a criterion of ductility and believe that
the importance of elongation
is usually overemphasized.
It is doubtful if
there are any applications for which an elongation
of more than 8 or 10
per cent in
2
in. is needed. As an example
of the exaggerated
importance
sometimes given to ductility, the crankshaft
of the internal-combustion
engine
may be cited. For years crankshafts
were made from highly
alloyed
steels which were carefully heat treated so that they would be
as ductile as possible coincident with the high hardness required.
The
cast-iron
crankshaft now used successfully in some automotive engines
shows very little elongation in the tensile test and has practically
no
resistance
to single-blow
impact.
It is generally true that in carbon steels and many nonferrous
alloys
high strength values
are accompanied
by low values of elongation and
reduction
of area and vice versa. This general relation does not always
hold for alloy steels.
One of the principal reasons why alloy
steels are
used in place of carbon steels is that
a better combination
of yield
strength and ductility-as shown by elongation
and reduction of area
(and impact resistance) -justifies
their higher
cost for many applications.
4.7. Hardness
Physicists
do not recognize
hardness
as ordinarily
determined as a
fundamental
property of matter; to engineers it is a property of great
importance.
Everyone thinks
he knows what hardness is, but no one
has been able to define it satisfactorily.
Probably
as good a definition
as
any is that hardness
is resistance
to permanent
deformation. Hardness
is complex. First and most important,
it is the resistance
of a material to
indentation.
It is also the resistance
to cutting with a tool, which involves
resistance
to indentation
plus tensile strength and toughness.
It is also
resistance to abrasion, which
likewise involves
indentation resistance,
strength,
and toughness.
There are at least
eight methods for the determination of hardness, of
which
two-Brinell
and Rockwell-are
the more frequently used. The
literature on hardness testing is extensive. Since
standards for making
Brinell and
Rockwell tests have been set up by the American Society for
Testing
Materials,*
the methods
for making these tests can be dismissed
with a few words.
*
A. S. T. M. Standards,
1955.
Fie. 4.7- Rockwell hardness lesliug machine. {Courtesy of Wilson Mechanical In-
strument Company)
In the Brinell test, a definite load is applied to the piece to be tested
by means of a hardened steel (or tungsten carbide) ball. The diameter
or the depth of the resulting impression is measured, and the Brinell
hardness number is calculated by dividing the load applied (in kilo-
grams) by the area of the impression (in square millimeters) , which is as-
sumed to be spherical. Owing to a slight deformation of the steel ball
and to the fact that the impression is not truly spherical, the hardness
number varies somewhat with the load applied and with the diameter
of the ball. These have been standardized in this country: a 10-mm. steel
ball and a load of 3,000 kg. are used for steel and a few nonferrous alloys;
and the same ball and a load of 500 kg. are used for soft materials. The
load is applied for 20 to 30 sec, the diameter of the impression varies
from about 6 mm. for soft materials to about 2.5 for hard materials and
is measured with a micrometer microscope. The Brinell machine is shown
in Fig. 4.6.
Static Properties
of
Metallic
Materials 71
The Rockwell hardness machine (Fig.
4.7) is designed to test materials
of widely varying
hardness by interchangeable indenters.
For hard ma-
terials, a diamond
cone is used; for softer metals and alloys,
y16
-in. and
l/g-in.
hardened steel balls are employed. In the Rockwell test, a minor
load of 10 kg. is applied to force the penetrator below the surface of the
material. The major load is then applied. The hardness, which is in-
versely
proportional to the depth of penetration, is read directly on a
scale, several of which are used.*
A Rockwell hardness number is mean-
ingless unless the scale symbol
accompanies the value. Loads and scales
used with the Rockwell machine are as follows:
Scale
Pencirator
Major
load,
kg-
Materials tested
A
B
C
D
E
Diamond
cone
Hi-in. ball
Diamond cone
Diamond cone
H-in. ball
60
100
150
100
100
Tungsten carbide and other very hard materials.
Thin, hard steel, such
as razor blades, nitrided
steel, and the like
Soft steels, hard nonferrous alloys
Steels of 90,000 to 350,000 lb. per sq. in. tensile
strength
Materials with thin, hard surface layer; case-
hardened and nitrided steel
Soft materials, aluminum alloys, bearing metals,
and the like
There is a third
hardness test, which is coming
into relatively wide
use, especially in the laboratory;
this is the Vickers
test in which a dia-
mond
pyramid is pressed into the surface of the material. Other hardness
tests include the scleroscope,
now rarely used, which determines hard-
ness by measuring
the rebound
of a diamond-pointed
weight falling from
a fixed height; and a number
of scratch tests in which needles of definite
hardness
or diamond or sapphire points are dragged over the polished
surface. Scratch
tests are sometimes useful in the research labora-
tory to detect
differences in the hardness of the various constituents
in
an alloy
but are rarely
used industrially.
A new laboratory hardness tester
has been recently
developed
by Frederick
Knoop at the National Bureau
of Standards.
A carefully
prepared diamond
pyramid is forced into a
There
are a number
of other scales in addition to the ones listed in the table
which are used with i/
e
-, i/
4
-, and i/
2
-in. ball indenters;
these are used occasionally for
special hardness
determinations.
There is also available a special Rockwell
machine
for the determination of superficial hardness. All of these are discussed in A. S. T. M.
Standards,
F.18-42.
polished metal surface and the dimensions of the resulting impression
are read with a microscope. The Knoop tester is flexible and apparently
gives precise results, but at present it is adapted only to the laboratory.
A practical qualitative method widely used for the determination of the
hardness of steel is the file test. In the hands of an experienced man,
relatively slight differences in hardness can be detected by rubbing the
material with a file of known hardness. Thus, a steel with a Rockwell C
hardness of 54 can be differentiated from one which has a Rockwell C
hardness of 60. Obviously, too much depends upon the personal equa-
tion for the file test to be useful except in the hands of an experienced
man.
4.8. Comparison of the Various Flardness Tests
In making hardness tests by any method a number of precautions are
necessary. In the first place, the specimen must be rigidly supported,
and the load must be applied perpendicularly. In the second place, the
surface tested must be flat and relatively smooth, and any surface scale
or decarburized areas must be removed. In the third place, specimens
must be thick enough so that the material of the anvil on which the
specimen rests does not affect the indentation in the specimen. In general,
hardness impressions on thin sections are not accurate unless the material
has a thickness equivalent to 10 times the depth of the impression.
All tests for hardness by indentation cause strain hardening to some
degree. The Brinell test is as close to an ideal test as possible as it distrib-
utes strain hardening over a relatively wide area, but it lias the dis-
advantage that the amount of strain hardening may not be uniform and,
further, that the method is too restricted in application. With a 500-kg.
load, the Brinell test is quite satisfactory for aluminum alloys and for
brass and bronze; with a 3,000-kg. load its use is restricted to steels with a
tensile strength between 45,000 and 250,000 lb. per sq. in. When the test
is used on steels that are harder than 500 Brinell (tensile strength greater
than 250,000 lb. per sq. in.) , there is likely to be some permanent defor-
mation of the steel ball that causes all subsequent hardness determina-
tions made with this ball to be inaccurate. For steels with high hardness
a special tungsten carbide ball is used.
The Rockwell machine is designed to overcome some of the limitations
of the Brinell test. It is flexible and can be used for hard materials, it
makes a small impression that is not likely to spoil the appearance of the
piece, and it can be used to measure the hardness of relatively thin sec-
Static Properties
of Metallic Materials 7:5
20
Scleroscope hardness
24 30 40 50 60 70 80 90 100
100
150
200
60
'.on
250
\
k
j\j
300
N
^
120
350
\
WO
160
Iftfl
^
L_
400
\
\
an
m
c
1
S450
240
V\0
<u
MU
260
c
550
ftYl
\
\
280
650
700
750
800
\
f
SO
340
V
\
-10
10 20 30 40 50 60 70
Rockwell C hardness
Fie. 4.8. Relation
of hardness values to
each other and to tensile strength for carbon
and low-alloy steels. (French and Sands)
accurately. The Vickers test, ideal
as a
so well adapted to routine testing as the
tions. For example, on steel of
150,000 lb. per sq. in. tensile
strength the minimum thickness
that can be tested accurately by
the Brinell method is 0.15 in.;
with the Rockwell diamond cone
(C scale), it is 0.06 in. The
Rockwell machine also has the
advantage
that hardness num-
bers are read directly from the
scale; it is unnecessary to meas-
ure the width of an impression.
The Rockwell machine is, there-
fore, widely used for routine
testing and for the inspection of
heat-treated parts.
The Vickers hardness test,
which is rapidly becoming stand-
ardized, is the most flexible of
all hardness tests and can be
used without change of pene-
trator on materials of widely
varying hardness by varying the
load applied. The impression is
small and, owing
to its diamond
shape, can be measured
very
laboratory
tool, at present is not
Rockwell.
4.9. Relation
among Hardness Tests and between Hardness and
Tensile
Strength for Steel
All indentation
hardness
methods fail to measure the hardness of the
undeformed metal. An exact mathematical correlation
of the various
hardness numbers is therefore impossible as the amount of strain harden-
ing varies from test to test and, furthermore, varies from metal to metal.
A large amount
of time and effort has been expended in studying the
relation among the hardness numbers as obtained by the Brinell,
Rock-
well, Vickers,
and scleroscope
machines. One of these correlations for
carbon and low-alloy steels is shown in Tig.
4.8*
A word of caution is
H.
J.
French and
J.
W. Sands (editors), Nickel Alloy Steels, The International
Nickel
Co., Inc., New York, 1934.
necessary concerning such a correlation. Brinell values may be converted
to Vickers or Rockwell C values, or vice versa, with an expected error of
not more than 10 per cent, except for hardness numbers over 500 Brinell
where the uncertainty becomes greater. The error in converting Brinell
or Rockwell to scleroscope may be considerably greater than 1 per cent.
The most recent conversion table and probably the most accurate for
carbon and low-alloy steels was compiled by a committee of the Society
of Automotive Engineers and the American Society for Testing Mate-
rials.* These values are reproduced in part in Table 4.2.
The resistance to indentation is directly related to compressive strength.
For most carbon and low-alloy steels there is a fairly close relation be-
tween compressive strength and tensile strength; hence, indentation
hardness values for such steels can be converted into tensile strength
with reasonable accuracy. Results of a large number of investigations on
this relation indicate that the ratio of tensile strength (in units of 1,000
lb. per sq. in.) to Brinell hardness number varies from 0.45 to 0.58, and
heat treatment apparently has no effect on the ratio. The ratio obtained
most frequently is 0.47 to 0.50. Thus, if the Brinell hardness number is
given, tensile strength can be calculated by multiplying the hardness
number by 480; the result should be accurate within =p 5,000 lb. per sq.
in. The relation between the various hardness numbers and the tensile
strength for carbon and low-alloy steels is shown in Fig. 4.8 and in Table
4.2. Although this relation is fairly accurate, there may be considerable
variation in individual specimens. The actual ratio depends upon struc-
ture, with composition a possible complicating factor, and although in
most cases the conversion may be made with an error of 5,000 lb. per
sq. in., errors as great as 12,000 lb. per sq. in. may be encountered.
4.10. Relation among Hardness Tests and between Hardness and
Tensile Strength for Nonfcrrous Alloys
In contrast to carbon and low-alloy steels, which all harden approxi-
mately the same amount when cold worked (strain hardened) and which
show, therefore, a fairly close relation among hardness tests and between
hardness and tensile strength, the nonferrous alloys differ considerably
in their capacity for strain hardening and no such relation can be worked
out for these materials as a class. For example, a high-strength duralumin
that has been heat treated will have a tensile strength of around 70,000
lb. per sq. in. and a Brinell hardness (500 kg.) of 115; whereas a cast
manganese bronze containing 55 to 60 per cent copper and 38 to 42 per
cent zinc will have a tensile strength of 90,000 lb. per sq. in. and a Brinell
1
Static Properties
75
Table 4.2. Approximate Hardness Conversion Numbers for Steel
Brinell. 10 mm. ball, Rockwell hardness nun ber
1
3,000-kg. load
Vickers
dlamond- Approxi-
mate
1 pyramid
hardness
number
Sclero-
Diameter A-scale.
B scale.
100-kg. C-scale. D-scale.
scope
hardness
tensile
strength.
of Hardness 60-kg. load. 150kg. 100 kg. (DPH) number lb. per
impression number load. Hi-in. load, load.
*,
sq. in.
mm. diamond ball diamond diamond
2.40 653
*
81.2
60.0 70.7 697 81
wn
2.45 627

80.5 58.7 69.7 667 79 323,000
2.50 601

79.8
57.3 68.7 640 77 309,000
2.55 578
*
79.1
56.0 67.7 615 75 297,000
'JfWUf
2.60 555
*
78.4 54.7 66.7 591 73
285,000
2.65 534
*
77.8 53.5 65.8 569 71 274,000
'>--
2.70 514

76.9
52.1 64.7 547 70 263,000
2.75 495
'
76.3 51.0 63.8 528 68 253,000
-
2.80 477 75.9 50.3 63.2 516 66 247,000
***/tf
2.85 461 75.1 48.8 61.9 495 65 237,000
2.90 444 74.3 47.2 61.0 474 63 226,000
3.00 415 72.8
44.5 58.8 440 59 210,000
'-
3.10 388 71.4 41.8 56.8 410 56 195,000
3.20 363 70.0 39.1 54.6 383 52 182,000
3.30 341 68.7 36.6 52.8 360 50 170,000
3.40
321 67.5 34.3 51.0 339 47 160,000
3.50 302 66.3
32.1 49.3 319 45 150,000
3.60 285
65.3 29.9 47.6 301 43 141,000
3.70 269 64.1 27.6 45.9 284 40 133,000
3.80 255
63.0 25.4 44.2 269 38 126,000
3.90 241 61.8 100.0 22.8 42.0 253 36 118,000
4.00 229
60.8 98.2 20.5 40.5 241 34 111,000
4.10 217 96.4 17.5 228 33 105,000
4.20 207
94.6 15.2 218 32 100,000
'0*i</'
x
.
4.30
197 92.8
207 30 95,000
4.40 187
90.7 196 28 90,000
4.50 179
89.0
188 27 87,000
4.60 170
86.8
178 26 83,000
4.80
156 82.9
163 24 76,000
5.00 143
78.7
150 22 71,000
*
By tungsten carbide ball.
hardness
of less than 100. Copper hardened with arsenic, in the cold-
rolled (hard) condition, will have a Rockwell B hardness of 95 to 100
and a tensile strength of about
60,000 lb. per sq. in.; whereas admiralty
metal containing
71 per cent copper, 28 per cent zinc, and 1 per cent
tin and of the same Rockwell B hardness will have a tensile strength of
95,000 lb, per sq. in. or higher.
The only nonferrous alloy for which hardness conversions have been
worked out is cartridge brass. Some of these values are collected in
Table 4.3.*
All the thousands of other alloys, with the possible exception
of the high-nickel alloys, which apparently harden much like steel, are
quite evidently a law unto themselves, and each must be considered
as a special case.
Table 4.3. Approximate Hardness Conversion Numbers for Brass (70 Per Cent
Copper, 30 Per Cent Zinc)
Brinell, 10-mm. ball Rockwell hardness number
Vickcrs
diamond
pyramid
hardness
number
(DPH)
Diameter
of
impres-
sion,
mm.
Hardness number
B scale.
100-kg.
load,
F scale.
60-kg.
load,
Tscale.
t
30-kg.
load, 3,000-kg. 500-kg.
load* load Ke-in. ball Ho-in. ball Hs-in. ball
2.00 158 91.0 108.0 75.5 183
2.10 143 85.5 105.5 72.5 165
2.20 130 79.5 102.5 69.5 149
2.30 119 74.0 99.0 66.0 135
2.40 653 109 68.5 96.0 62.0 123
2.50 601 100 63.5 93.5 59.0 113
2.60 555 93 59.0 91.0 55.5 105
2.70 514 86 54.0 88.0 52.5 98
2.80 477 80 47.5 84.4 48.0 90
2.90 444 74 40.0 80.0 43.0 82
3.00 415 69 33.5 77.0 38.5 77
3.10 388 65 28.7 74.0 34.0 73
3.20 363 61 18.5 68.5 29.0 66
3.30 341 57 12.5 65.0 23.0 62
3.40 321 53 61.0 18.0 58
3.50 302 50 56.5 12.0 54
3.60 285 48 53.5 52
3.70 269 45 47.0
48
3.80 255 42 40.0 45
3.90 241 40
43
*
For steel, included for comparison.
t
Rockwell superficial hardness: initial load 3 kg.; major load 30 kg.
If the proper precautions are observed, indentation hardness tests are
accurate and readily reproducible; and if judgment is used, the tests
give a reasonable approximation of the tensile strength and a rough idea
of machinability and wear resistance for most steels but not for most
Static Properties
77
nonferrous
alloys. Their greatest value lies in their speed and cheapness,
which make them ideal
for checking uniformity
of heat treatment and
as an acceptance test for hardened steels, especially tools and dies, and
for a number
of other metallic
materials.
4.11. Shear, Compression,
and Bend Tests
The
determination
of the resistance of a material to failure by shear
or torsion is
important for many engineering applications,
especially for
shafts subjected
to twisting, for rivets holding two plates together, for
keys in shafts,
and the like. Neither specimens
for such tests nor the
methods of making
the tests
are standardized.
Stress-strain diagrams
may be plotted
from a torsion
test, from which the maximum
torque
(torsional
or shearing strength)
,
yield point or proportional limit, and
the modulus
of elasticity
in shear (modulus
of rigidity)
may be deter-
mined.
There is no accurate
relation between torsional strength and
tensile strength, but for carbon
steels, the torsional strength is generally
about
75 per cent of the tensile strength.
Compressive
strength can be determined accurately
on brittle mate-
rials that fracture;
on ductile materials,
which flatten without fracturing,
it can be
determined only when a limiting
amount of deformation is
specified.
Compressive
strength is a common test for cast iron, as this
metal
is frequently
used in compression, but is rarely made on steel. The
compressive
strength of cast iron is 3 to 4 times its tensile strength.
Bend tests are becoming
increasingly valuable
for some of the new
low-alloy steels.
These steels are used in structures primarily
to save
weight, and the bend test is useful to determine the relative stability of
these materials
under load. When ductile materials are tested, the speci-
men does not fracture when bent; hence, the test can also be used to
detect
deep-seated flaws and other internal defects
or to discover brittle
areas in and around a weld. A variety of the bend test-the transverse
test-is a useful
measure of the quality of cast iron and has been used so
widely
for this purpose that virtual
standardization
has been effected.
Transverse tests of cast iron are made on standardized
bars. As dis-
cussed in Chap.
20, the results
are reported as the load necessary
to
fracture a specimen
of definite
diameter held on supports a specified
distance apart. In the United States this is usually
reported as transverse
strength in pounds; abroad, and to some extent in the United States, it is
reported as modulus of rupture in pounds per square inch. The test is
usually
made on a cast bar without
machining; removing
the surface
layers
of the bar may cause a slight change in values. The deflection in
inches (that is, how
much the bar bends before breaking)
is also re-
78
Fie. 4.9. Oscillograph screen showing diagram obtained by sonic tester.
ported. The transverse test gives an indication of toughness, flexibility,
surface condition, and even machinability and is the most valuable single
test for cast iron.
4.12. Sonic Testing
Large forgings, castings, and weldments are inspected for hidden flaws
by x-ray radiography. Recently the sonic tester has been developed for
non-destructive testing of all types of machine elements. This apparatus is
portable and can be used on a part even when it is completely assembled
in the machine. This makes possible inspection during manufacture, but
it also can reveal fatigue cracks and defects in highly stressed machine
parts after the machine has been placed in service.
High-frequency compression waves are produced by a quartz crystal
placed directly on the work surface or the crystal may be carried on an
oil film. The beam of vibrations flows through the metals and are re-
flected back from the bordering surfaces. The reflections are then record-
ed on an oscilloscope, A on Fig. 4.9 being true top surface reflection and
C the bottom surface reflection. An internal crack would also send back
a reflection as shown by the pip at B. Location of the defect can also be
determined from die oscillograph. The length from A to C represents the
work depth. AB is then the distance from top surface to defect on the
same scale. This ability to measure depth makes it possible to gage the
Static Properties
of
SEARCH
UNIT
AT POSITION
1
SEARCH UNIT
AT POSITION 2
Fro. 4.10. Surface Wave Testing of a Shaft. (Courtesy Sperry Products, Inc.)
progress of corrosion in piping and pressure vessels even when filled with
fluid.
The majority
of ultrasonic testing is done by x-cut quart/, crystals which
send waves directly through the specimen. However,
Y-cut crystals or
plastic wedges may be used to propogate surface waves which
can follow
curved surfaces and thus reach otherwise inaccessible locations. Fig. 4.10
shows this technique being used to check the fillet areas of a shaft for
fatigue cracks, such a crack being revealed by the surface wave unit in
position 2.
QUESTIONS
1. Define static
mechanical properties. What are the five most useful static
properties? What engineering property
is standard throughout the world?
2. What materials, because of their magnetic properties, are most useful in
the design of motors, generators, and transformers?
Define domain. Define
Curie temperature. What happens to the domain when this temperature is
reached?
S. How accurate is the tensile strength of a metallic material as usually deter-
mined? What variables affect this accuracy? What factor is most important
in using tensile-test data in engineering design?
4. What are the advantages and disadvantages of testing a completed structure
under actual service conditions?
5. Discuss the use of aluminum as an electrical conductor.
6. Distinguish between elastic limit and proportional limit. What is modulus
of elasticity, and what does it represent? Can proportional limit and
modulus of elasticity be readily determined on all metallic materials? Give
the reason for your answer.
7. Give approximate values of modulus of elasticity for (a) steel, (b) aluminum
alloys, (c) copper.
8. Describe three methods of testing which will allow the designer to deter-
mine the location and magnitude of stress concentration in a given speci-
men or structure.
9. What modulus is a measure of the stillness of a metal. Can a metal part
which is not stiff enough in the annealed state be improved by hardening?
10. What is the difference between yield point and yield strength? What is the
importance of these values to engineers? How does the speed of testing
affect the yield point?
11. What phenomenon occurs on the stress-strain curve which has developed
into a new science known as plastic design?
12. Define elongation and reduction of area. How are these values determined?
What is the effect of gage length on elongation?
13. What properties are components of hardness? What precautions are neces-
sary in the accurate determination of hardness?
14. Describe briefly the method of determining hardness by the Brinell, Rock-
well, and Vickers machines, and give the principal advantages and dis-
advantages of each.
15. When a part is so designed that stress concentration is present, how will a
ductile material react as compared with a brittle material? What will be the
reaction if the stress is released and then reapplied?
16. Convert a hardness of 40 Rockwell C to Brinell and Vickers values and to
tensile strength. How accurate are these conversions? If the tensile strength
of an annealed carbon steel is 85,000 lb. per sq. in., what are its approxi-
mate Brinell, Vickers, and Rockwell C hardness values?
17. What do we mean when we say a material is structure sensitive?
18. What hardness tests are commonly used for nonferrous alloys? Why is it
impossible to convert hardness values to tensile strength for most non-
ferrous alloys?
19. What is the value of the shear test? What is the value of the bend test (a)
for ductile materials? (b) for brittle materials? What is the relation be-
tween the strength of a metallic material in torsion and in tension?
20. How docs the sonic tester function? What is the advantage of this method
of testing as compared with x-ray analysis? How is a defect in the specimen
located?
CHAPTER
Dynamic
Properties
of
Metallic Materials
Oran Allan Pringle, M.S.M.E., Associate Professor of
Mechanical Engineering, University
of Missouri,
Columbia,
Missouri
iHE design of engineering structures and
machines that are subject to static loads is based upon tensile strength
and yield strength with an ample factor of safety. Few failures of such
structures
and machines occur. This, however, is not the case with moving
parts of machines which fail so frequently that it has been estimated that
95 per cent of all metal failures are caused by dynamic loads. For this
reason, metallurgists and engineers are now paying more attention than
ever before to the resistance of ferrous and nonferrous materials to
dynamic stresses and to methods of determining
the dynamic properties.
The principal dynamic properties
impact resistance, endurance
(fatigue) strength, and damping capacitymeasure the ability of the
material to withstand suddenly applied or pulsating loads. Endurance
strength has been the subject of much study and in some respects might
even be called a standardized property. Impact resistance and damping
capacity are not standardized; hence, the values obtained by impact and
damping tests may mean very little unless the method and the specimen
used are known. Such tests are more valuable as a method of comparing
various materials or various grades of the same material than as a means
to obtain values which can be used in design.
5.1. Notch Brittleness and Transition from Ductile to Brittle
Fracture
In applications involving impact loads it is necessary to know the in-
fluence of speed of loading or strain rate on the mechanical properties of
81
. , Stress
Stress
atMN
M-,
Fie. 5.1. Typical notches or stress raisers occurring in machines and structures.
(Moore)
the materials. According to present knowledge, there is always a con-
siderable increase in yield strength of metals at high strain rates; for
example, over a range of strain rates from
10
3
to 10
2
in. /in. per sec.
the yield point for mild steel increases by as much as 100 per cent. The
ultimate strength also increases at high strain rates but to a lesser
degree, and at very high strain rates the yield point of mild steel ap-
proaches the value of the ultimate strength. These considerations might
lead one to conclude that there is less likelihood of failure under impact
loads than static loads. Unfortunately however, it is now well known that
some commonly ductile materials can fail in a brittle fashion when sub-
jected to certain insidious combinations of high strain rates, low tempera-
tures, and notch effects.
A ductile fracture is preceded by a considerable amount of plastic
deformation; since the force required for fracture thus acts through a
comparatively large distance, a relatively large amount of energy is
absorbed. A brittle fracture is preceeded by little or no plastic deforma-
tion; therefore very little energy is required to produce this type of
fracture. Some materials, like glass, always fracture in a completely
brittle manner. On the other hand, a few metals, among them the plain-
carbon and low-alloy steels, behave in a ductile manner under some con-
Dynamic Properties
83
Charpy Impact specimen
-?--
Y-45"
/--
0. J/5" ^0.01-Bad.
ajs.*'
Alternate Charpy
impact specimen
*SM
-o.OOO-
-l.l024~iO.OI9P
0.3I5~0.00I- '-O.OI'Rad.
.
0.395?'
1 0.001\
)
Izod impact specimen
Fie.
5.2. Standard impact specimens. (American Society of Testing Materials)
ditions, such as in the ordinary tensile test; however, they can break in an
almost
completely brittle manner under certain other conditions. The
three most important conditions which tend to bring about this transi-
tion from ductile to brittle behavior are high strain rates due to shock
loads, low temperatures, and the presence of notches (Fig. 5.1). Thus
a certain steel part may bend without breaking under a static load at room
temperature if smooth, but may snap with a brittle fracture if a sharp
notch is located in the region of stress, and/or the load is suddenly ap-
plied, and/or the temperature
is sufficiently lowered.
In testing, it is often convenient to hold constant the notch condition
and strain rate and to use the temperature zone or transition temperature
at which ductile behavior ceases as an index of the susceptibility of the
material to brittle fracture. Many different types of tests and specimens
have been used. The Charpy and Izod tests are common in the United
States. The specimens used are shown in Fig. 5.2. The pendulum of the
testing machine falls from a definite height and breaks the specimen at
the notch. The energy absorbed during fracture is measured from the
backswing of the pendulum. Typical results are shown in Fig. 5.3. It
can be seen that a drastic decrease in ability to absorb impact energy
occurs when the temperature is below the transition
range.
In order to understand how brittle fracture can occur in ordinarily
ductile materials, it must be realized that several entirely different
mechanisms can cause fracture. The brittle type of fracture occurs when
the highest tensile stress reaches a critical value, and is almost indepen-
84
-I7S
70 r
1
Temperature, deg.C.
-150 -I2S -100 -75 -50 -25
tJ ,J 1 A, !_,
I '
+25
-300 -250 -200 -150 -100 -50
Temperature, deg. F.
+50 +100
Tig. 5.3. Transition temperature curves for various steels: (A) 18-8 austenitic
stainless steel; (B) annealed low-carbon 3.5 per cent nickel steel; (C) annealed low-
carbon 13 per cent chromium steel; (D) normalized 0.35 per cent carbon, 15 per cent
nickel, 0.6 per cent chromium steel; (E) annealed 0.35 per cent carbon steel; and (F)
normalized 0.35 per cent carbon steel. Specimens for steels B and E had keyhole notch;
others had V notch. (The International Nickel Company)
dent of other types of stress. On the other hand, the ductile type of
fracture occurs only after plastic yielding has taken place, which begins
when the maximum shear stress reaches a critical value. As the load on a
ductile material is increased, the critical value of shear stress is ordinarily
reached before the critical value of tensile stress, consequently plastic
deformation and ductile fracture result. If by some means the critical
shear distress could be raised so high that the critical tensile stress
were reached first, brittle fracture would occur. This is exactly what
happens at high strain rates, since increasing the strain rate raises the
yield strength. Low temperatures have a similar effect, since the yield
strength of most metals increases by a factor of around 2 as the tempera-
ture is lowered from room temperature to the boiling point of hydrogen.
The brittle tensile strength is also affected by strain rate and temperature,
but to a lesser degree.
Since brittle fracture results from exceeding a critical tensile stress
and ductile fracture from exceeding a critical shear stress, any means by
Dynamic Properties
which shear stress in a part is reduced or suppressed will tend to promote
brittle fracture. This is what is accomplished by notches. Consider a
cylindrical tensile specimen with a circumferential
notch or groove. As
the load is increased, the first effect of the notch is to produce elastic
stress concentration at the root of the notch. With further increase in
load, the elastic limit is reached, and plastic yielding relieves the stress
concentration.
As the core of the circumferential notch undergoes plastic
elongation, it must also contract in a transverse direction, pulling in on
the metal surrounding the notch. The surrounding metal then pulls
back out on the notch core, subjecting it to biaxial tension in the trans-
verse direction. Actually, however, the notch core is in a state of triaxial
tension, as the external axial load on the specimen is still acting. In a
system of equal triaxial tensions, the shear stress is zero. Thus the effect
of the notch is to suppress all or part of the shear stress which would
ordinarily be present in the tensile specimen, leaving the way open for the
tensile stress to become sufficiently high to exceed the critical value for
brittle fracture. This effect of the notch is called plastic constraint.
In addition to high strain rates, low temperatures, and notches, numer-
ous other factors tend to a lesser degree to promote the transition from
ductile to brittle fracture. Some of these factors are: increased size of
part, large grain size, pearlitic rather than martensitic microstructure,
certain deoxidation practices, and prior cycles of fluctuating load.
Although the ferritic steels are the most important alloys which exhibit
the phenomonon of a transition from ductile to brittle fracture, other
metals, such as zinc alloys, tin alloys, and magnesium have been shown to
behave similarly. On the other hand, aluminum, copper, nickel, and
austcnitic steels (Fig. 5.3) have thus far failed to show a transition tem-
perature.
5.2. Value of the Notched-Bar Impact Test
It is evident from the foregoing discussion that the chief value of the
notched-bar
impact test is in classifying materials according
to their
tendency toward brittle fracture. It is rapid and
cheap and gives informa-
tion that no other test gives at present, provided that common sense and
experienced judgement are used in its evaluation. In the present state
of development it has a number of disadvantages.
Transition tempera-
tures obtained with one type of specimen and machine cannot be directly
correlated with values obtained
with different
specimens and machines;
similarly,
test results cannot be directly correlated with results on full size
parts under service conditions. Furthermore, it is not a reliable test for
inherently brittle materials like cast iron and hardened tool steels. De-
Fig. 5.4. Typical fractures of fatigue specimens with unclistortcd area (A) in center
(Moore) and (B) at side. (Johnson)
spite these disadvantages, the engineer and metallurgist have found the
notched-bar impact test to be a valuable tool. It is used primarily as an
exclusion test to detect steels with high tendency toward brittle fracture.
In industry it is used by manufacturers of ordnance, aircraft, and auto-
mobiles, who have found as a result of experience, that steel which ex-
ceeds a certain minimum impact resistance in the laboratory gives satis-
factory service in applications where low temperatures and shock loads
are encountered.
5.3. The Mechanism of Fatigue
Ever since man has used metal for moving parts, he has noticed that
after a period of satisfactory service such a part would sometimes fail
even though the stresses were relatively low. Usually the failure would
be sudden: an axle that had been forged from steel of excellent ductility
would snap off short as if it were brittle. Examination of the fracture
would show a dull area usually surrounding an oval-shaped area of bright
crystals (Fig. 5.4)
.
Although all details of the mechanism of fatigue failure are not
thoroughly understood, the main events which occur during this pro-
gressive type of failure may be summarized. Under
repeated stress the
metal yields at one or more local areas of weakness, usually
at some surface
defect where elastic stress concentration occurs. Eventually the atomic
bonds are broken, resulting in submicroscopic cracks at the ends of which
Dynamic Properties
87
I'io.
5.5. R. R. Moore
high-speed machine for rotating-hcam
fatigue testing.
there may be high
concentrations of stress. As the stress on the piece is
repeated,
the crack
or cracks spread. After a time there is so little sound
metal left that the normal
stress on the piece is higher than the strength
of the remaining
material, and complete fracture occurs.
The appearance
of a typical fatigue fracture is explained by the fact
that as failure proceeds the severed
surfaces rub and crush each other and
produce
a dull appearance;
while the remaining unfractured
portion
preserves the normal grain structure up to the moment of fracture.
5.4. The Endurance Limit
Fatigue is perhaps not the best word to use in referring
to the type of
failure under discussion,
but it is too firmly entrenched
in metallurgical
and engineering
terminology
to be dislodged.
The term endurance
is
also commonly used.
The endurance
limit of a metal or alloy is the stress below which the
material
will not fail if subjected
to an infinitely large number of cycles
of stress. It is determined in a number of ways, the most common of which
is by alternate flexure,
usually known
as the rotating
beam method. A
polished
specimen of suitable size, which is rotated in a specially de-
signed
machine (Fig.
5.5) ,
is subjected by dead weights to alternate
tensile
and compressive stresses.
A number of identical specimens
are prepared from a single material.
I he first is run at a stress which is considerably
higher than the expected
endurance limit, and the number
of cycles causing failure is noted. The
stress is reduced
for the next specimen;
this process is continued until,
for steel, there is no fracture after 10
7
cycles of stress. The stress
(S) for
88
'104
105 106
I0
1
108
Cycles
Flo, 5.6, Typical S-N curves for carbon steels. (Moore and Kommcrs)
each number of cycles (N) is plotted; the result is the S-N diagram
(Fig.
5.6) . The value for S which the horizontal portion of the curve
represents is the endurance limit.
Although steels have a definite endurance limit, it is doubtful if the
same is true for most nonferrous alloys. At any rate, the S-N diagram for
nonferrous alloys usually does not show an abrupt knee at the endurance
limit, but rather consists of a gradual curve with the portion at lower
stresses becoming approximately horizontal only at a very large number of
cycles of stress. In reporting results of fatigue tests on nonferrous alloys
the endurance strength (or fatigue strength) corresponding to a certain
number of cycles of fatigue life, such as 500,000,000, is usually given, since
a well denned endurance limit is not found.
The importance of determining the endurance limit or endurance
strength, even though the test takes a long period of time, is evident when
it is recalled that airplane propellers, turbines, etc. may easily run a
billion cycles during their useful life.
5.5. Relation of the Endurance Limit to Other Properties
If the endurance limit is determined by the rotating-beam method
using carefully polished specimens of proper design, the value obtained
for most carbon and alloy steels is about one-half the tensile strength
(Fig.
5.7) . As there is a fairly close relation between tensile strength and
hardness, it follows that there is also a close relation between endurance
limit and hardness; the former is about 250 times the Brinell hardness
number (Fig. 5.7) . There seems, however, to be no correlation between
endurance limit and any other property of ferrous alloys.
Dynamic Properties
of
Brinell hardness number
,,0 100 200 300 400 500 600
20 40 60 80 100 120 140 160 180 200 220 240 260 280
Tensile strength, thousand lb per sq. in.
Fig. 5.7. Relation of endurance limit of steel to tensile strength and Brinell hard-
ness. (Moore)
The above relations among endurance limit, tensile strength, and
hardness hold for carbon and alloy steels of any composition and heat
treatment except those treatments which produce very high hardness,
and may be used as approximations in design. For refined design, how-
ever, the actual endurance limit of the material must be determined, as
this may in individual cases vary between 35 and 65 per cent of the
tensile strength. Cast steel (not heat treated) has an endurance limit
of about 0.4 times the tensile strength, somewhat below the average for
wrought steel. Cast iron has a ratio of 0.3 to 0.35. Attempts to correlate
endurance strength of nonferrous alloys with tensile strength are not very
successful; the endurance strength may be less than 25 per cent or more
than 50 per cent of the tensile strength.
5.6. The Effect of Notches on the Endurance Limit
The endurance limit of a carefully polished specimen may be reduced
as much as 50 per cent by a notch. In actual machines and structures
notches of some sort are almost invariably present in some form such as
rough surfaces, tool marks, holes, screw threads, keyways, fillets, inclu-
sions, gas cavities, etc. (Figs. 5.1, 5.8) . The effect varies with the kind of
Fie. 5.8. Failure of a crankshaft starting in a sharp fillet. The crack started in the
fillet about \/
2
in. above and to the left of the arrow.
notch, its location, and the notch sensitivity of the material. For hard
steels the effect of the notch can be approximately predicted by the elastic
stress concentration as calculated by mathematical theory or as determined
by photoelastic studies. For ductile steels the effect of the notch is usually
less severe. The effect of a number of different surface conditions is shown
in Fig. 5.9.
As a general rule the damaging effect of a notch in carbon and alloy
steels and in some nonferrous alloys increases with its sharpness, that is,
with increase in the ratio of its depth to the radius of its root. Usually a
notch becomes harmful of this ratio exceeds 28 or 30. When shallow
notches are present, hard steels with their relatively high endurance limits
are superior to low strength steels. On the other hand, with sharp notches
present, a soft steel with low notch sensitivity may be superior to a
high-strength high-endurance steel with high notch sensitivity. Gray cast
Dynamic Properties
of
IC
GO
Tens
80
le strength .thousand lb. per sq
100 120 140 160
' 1 1 1
in.
180 200
i_
a-
b
20
t
in
c
\
s s
d
*40
J
P<0
\
s
\
S.
-
\e
5
i
"fin
\f
1
o 70
. 9
B
o
flO
V- notch
"
-
y\l
O.lmm.
-
7.5mm.tj>
1 1 1
so
inn
i 3 4 i i J 6 i i
Tensi
i) a
e str<
3 9>
ngth
3 K
kg.p
j
er sq.
15
mrn.
D E 3 U > m
Fig.
5.9. Decrease in endurance limit for carbon and low-alloy steel specimens
having the following surfaces: (a) polished, (b) ground, (c) roughened, (d) circum-
ferential
V notch, (e) decarburized, (f) corroded in tap water, and
(g)
corroded in
salt water. (Z. Ver. deut. Ing., v. 77, 1933)
iron, although
inherently brittle, is relatively insensitive to notches.
Another important fact to remember is that a decarburized surface, while
not acting as a notch, lowers the endurance limit of the whole section to
that of a steel whose
carbon content is the same as the surface layer,
since fatigue failure usually originates at the surface. As Fig. 5.9 shows,
the effect of a decarburized surface may be greater than the effect of a
sharp notch.
Chafing or fretting
the polished surface of steel or nonferrous alloys,
a form of wear which occurs in parts which are intended to fit tightly
but which slip slightly under fluctuating loads, reduces the endurance
limit.
92
5.7. Corrosion Fatigue
If a polished metal specimen becomes corroded before testing, the en-
durance limit is lowered somewhat, an effect which would be expected in
view of the roughening of the surface. On the other hand, if a polished
specimen is corroded simultaneously with the application of repeated
stress, the endurance limit is lowered to a much greater degree. As a mat-
ter of fact, there is probably no true endurance limit in corrosion fatigue,
since with sufficient time the corrosion alone would produce failure even
at very low stresses. Some data indicate that carbon and low-alloy steels
subjected to simultaneous reversed stress and corrosion will fail at stresses
as low as 5000 lb. per sq. in. if they are run long enough (100,000,000
cycles or more) . The data given in Fig. 5.9 indicate that a combination
of corrosion and fatigue causes a loss of about 50 per cent of the endurance
limit if the tensile strength is low, and a loss of about 90 per cent if the
strength is high. The corrosion fatigue strength of most nonferrous alloys
is likewise only a small fraction of their endurance strength in air.
For high resistance to corrosion fatigue a material must have an oxide
skin which is tightly adherent and at the same time flexible enough to
withstand
repeated stressing without breaking. Among ferrous alloys, only
the high-chromium stainless steels normally have such a skin. Corrosion
of carbon and low-alloy steels results in corrosion products which, being
brittle, fracture readily and expose the underlying surface to further
attack. Since all ferrous materials, except some highly alloyed steels, are
reduced by simultaneous corrosion and repeated stressing to a common
low level of resistance, there are only two things to be done in such appli-
cations: use a stainless steel, or protect the surface by plating with some
metal that will form a continuous corrosion-resistant coating. According
to present knowledge, electroplated zinc or cadmium coatings are best.
5.8. Increasing the Endurance Limit by Shot Peening
Shot peening, if properly controlled, can increase the endurance limit
or fatigue life 25 to 100 per cent or more. Shot peening consists of sub-
jecting the surface of a finished metal part to a hail of metallic shot that
has been released
by the blades of a revolving wheel or by an air blast.
The shot, in striking the surface with force, cold work the outer layer,
increasing the strength and hardness and decreasing the ductility of this
region. At the same time, the cold working introduces longitudinal com-
pressive stresses near the surface. Surface-rolling is an alternate method
that produces the same effects.
The resulting increase in endurance limit is due to two factors:
(1)
the
increase in strength of the surface layer due to the cold work; and
(2)
Dynamic Properties
the residual
compressive stresses set up in the surface layer. Opposed to
these favorable circumstances, however, are the roughening of the surface
and the formation of a large number of shallow pits that may cause
localized stress concentration.
If the shot peening is carefully done and
if the size of the shot and the velocity of impact are controlled, the net
result of the operation is a marked increase in endurance limit or fatigue
life. Shot peening is now used regularly by some automotive and aircraft
manufacturers
for improving the life of crankshafts,
camshafts, connect-
ing rods, steering knuckles, transmission
shafts, gears, and other parts.
5.9. Significance of Endurance Data
Endurance limits that have been obtained under controlled laboratory
conditions
on carefully
designed polished specimens are valuable in the
design of machines and structures subject to repeated stresses, but they
should
be used only with full realization
of their somewhat limited signi-
ficance. Such endurance data give information of one kind only; condi-
tions in service are rarely
so simple that these data can be used without
considering
other factors.
Most structure and machine parts are subjected to more or less random
fluctuations
of load; however, most fatigue tests are run under conditions
of constant
maximum and minimum stress. At the present time there is
no completely satisfactory
method of correlating the behavior of a speci-
men under cycles of varying
stress amplitude and the behavior of another
specimen under
cycles of constant stress amplitude. It is certain, how-
ever, that the endurance limit of a specimen may be affected by its stress
history.
If a specimen is understressed,
or subjected to a few million
cycles of a stress slightly lower than its ordinary endurance limit, its final
endurance
limit as determined
later will be considerably
increased. If
a repeated stress slightly above the endurance limit is applied for a
small number of cycles, an improvement similar to that produced by
understressing is sometimes observed. On the other hand, higher values
of repeated stress and larger number of cycles may damage the material,
and its endurance limit as subsequently determined will be reduced.
Another important factor is surface condition. Parts in actual service
are rarely as highly
polished as most laboratory fatigue specimens, and
full consideration
should be given to the character of the surface, includ-
ing the
possibility of corrosion and accidental defects, and to how much
a roughened surface may reduce the endurance limit.
All in all, a great
many
complicating factors including surface condition,
variable stresses,
external and internal stress raisers both intentional
and unintentional,
notch sensitivity,
possible decarburization during heat treatment, residual
Cast iron
mmmtmHmmmmi
Carbon s+eel
Aluminum alloy
Fie. 5.10. Damping curves for cast iron, carbon steel, and an aluminum alloy.
(Pohl)
stresses, and combined stresses must be considered in problems involving
fatigue.
5.10. Damping Capacity
If a metal or alloy bar is supported at one end and if the free end is
struck with a hammer, the bar will vibrate for varying lengths of time
depending upon the composition, the stress imposed, and other factors,
but at a uniformly decreasing rate owing to the internal friction of the
material which dissipates the energy as heat and sound. The dissipa-
tion of energy per unit volume of the material for one cycle of stress is
the damping capacity. It may be reported as inch-pounds per cubic inch,
or as centimeter-kilograms per cubic centimeter, per cycle. Damping
capacity is usually measured by the area of the stress-strain hysteresis
loop. The ratio of this value to the work of deformation is the damping
ratio. This increases with the capacity of the material to damp out
vibration.
There is apparently no direct relation between damping and any other
mechanical property. In most cases the ability of a steel to damp vibra-
tion decreases as the tensile strength increases. Of ferrous materials, the
strong alloy steels usually have the lowest, and cast iron and low-carbon
steels the highest damping capacity. There are, however, many excep-
tions to this generality as steels of the same composition and tensile
strength may have very different damping capacities. Typical curves
Dynamic Properties
95
showing free vibrations clamped only by internal friction are shown in
Fig. 5.10 for cast iron, carbon steel, and duralumin.
It has been suggested that the endurance limit might be predicted from
damping capacity, although attempts
to correlate the two have not been
successful. There is, however, some evidence that damping capacity is
related to notch sensitivity. For, example, cast iron has a high damping
capacity and is relatively insensitive to notches; duralumin, with a high
notch sensitivity, has a very low capacity to damp vibrations. There is no
question, however,
that the damping capacity of a material is an im-
portant
criterion for its usefulness in many applications. For example, in
crankshafts in internal combustion engines resonant vibrations fre-
quently
occur. If a material with high damping capacity is used, the
energy of vibration
is dissipated by internal friction
and the peak
amplitude of the vibratory stresses is held to a low level, thus minimizing
the
possibility of fatigue failure.
QUESTIONS
1. Define the terms notch brittleness and notch sensitivity.
Give an example
to illustrate
the importance
of each of these properties in engineering.
2. What is the chief value of the information
gained from notched-bar im-
pact tests?
3. What are some disadvantages
of the common methods of notched-bar im-
pact testing?
4. Why is a fatigue fracture usuallv characterized
by a bright area surrounded
by a dull area?
5. Define the terms endurance limit and endurance strength.
6. Sketch typical S-N curves for a steel and an aluminum alloy.
7. How many cycles of testing arc usually necessary to determine (a) the en-
durance limit of a steel, and
(b) the endurance strength of an aluminum
alloy?
8. A recent expedition exploring
Greenland experienced considerable difficulty
with breakage of almost new vehicle tracks. What was the probable cause
of these failures?
9. What is the approximate
endurance limit of (a) quenched and tempered
alloy steel with a tensile strength of 150,000 psi and a ground surface, (b)
ultra-high
strength steel with a tensile strcngdi of 280,000 psi and a ground
surface,
and (c) annealed steel with a Brinell hardness of 200 and a V-
notch?
10. If a suspension
spring on your automobile breaks after 60.000 miles of
service, what is the most probable cause of failure?
11. What is the approximate endurance limit of a steel having a tensile strength
of 140,000 psi if the surface is (a) ground, (b) heat treated with a smooth
but decarburized
surface, and (c) heat treaded with a rough, pitted,
oxidized surface?
96
12. The gear teeth of an automobile transmission may fail in fatigue. Assuming
that the endurance limit of the steel lias been determined on a rotating*
beam testing machine, what factors would you consider in deciding upon
a suitable operating stress in the gear teeth?
13. During preliminary testing of a crankshaft, fatigue failure occurs at an
abrupt fillet. Due to dimensional restrictions it is undesirable to increase
the fillet radius. Can you suggest another method by which the fatigue-
strength of the fillet may be substantially increased?
14. What advantage would gray cast iron have over other materials for use as
a frame for a precision machine tool?
15. Railroad car axles are frequently surface-rolled over the region where the
wheel is pressed on. What benefit may be gained by this operation?
16. The elastic stress concentration factor of a notch or similar discontinuity
can frequently be determined by photoclastic studies of plastic models. To
what extent can information of this type be used in predicting fatigue
behavior of metal parts with similar discontinuities?
17. Although fatigue data for standard specimens of many different materials
are available, fatigue testing of actual parts under simulated service condi-
tions is widely practiced. Can you suggest some reasons for this?
18. Under what conditions might there be no advantage in using a high-
strength steel for a part, even though it is heavily loaded?
19. For certain applications, such as bridge cable and helical springs, cold-
drawn steel wire strengthened by work-hardening is preferred over steel
wire strengthened by quenching and tempering. Why?
20. Why can the shank area of a bolt be turned down to considerably less dian
the root area of the threads without decreasing die strength of the bolt
under fluctuating loads?
CHAPTER
Phase Diagrams and
the Simple Alloy Systems
Theodore Allen,
Jr.,
M.S.M.E., Associate Professor of
Mechanical Engineering, University of Houston, Hous-
ton, Texas; Engineer Associated with Anderson,
Greenwood and Co., Bellaire, Texas
John K. Anthony, M.S., Associate Professor of Physical
Metallurgy, University of Arizona, Tucson, Arizona
6.1. Solid State Thermodynamics and Thermostatics
1 HE study of physical metallurgy would hardly
be complete without the mention of solid state physics; indeed, it is just
a small portion of that vast field. For reason of simplicity the metallurgist
often refers to a "system." A system may be defined as an arbitrary por-
tion of matter which has been isolated from the rest of the universe by
prescribed boundaries. The system is merely separated by these bound-
aries from its environment for the purpose of analysis. A phase may be
defined as a portion of homogeneous matter in a system. When a system
undergoes a phase change, this change must take place at a rate which is
infinitesimally slow, or equilibrium can not be maintained during the
change. This is not novel, for thermodynamic processes which are
reversible necessarily require the state point to pass through a series of
quasi-static or quasi-equilibrium states. In this sense, then, reversible
or equilibrium changes should be classified as thermostatics while actual
changes which proceed at a finite rate are truly thermodynamic changes
of state. The study of metallurgy includes such non-equilibrium phase
changes as those that produce coring, segregation, and other irreversible
processes as well as those processes which are carried out slowly enough
to produce a "near equilibrium" change of state.
6.2. Concept of Dynamic Equilibrium
From what has been said in the preceding paragraph, one might infer
that this concept of equilibrium is a static sort of thing; such is not the
97
98
Engineering
Metallurgy
case. From a macroscopic
point of view this assumption
would be toler-
able, but from the microscopic point of view the picture is a dynamic one.
To be specific, two phases of a pure substance may be in equilibrium
with one another, and the molecules of one phase may be escaping into
the other phase, while those of the second phase are escaping into the
first, ff this exchange were taking place so that the net transport of mass,
momentum, and energy is zero, then the two phases would be in equili-
brium. It is a well established fact (the Second Law of Thermodynamics)
that nature tends to equalize its potentials;
a system, then, would be in
equilibrium if no unbalanced tendency existed which would bring about
a change of state provided this tendency was active.
With respect to the escaping tendency of a component from one phase
to a second phase in chemical equilibrium
with the first, it may be said
that the fugacity
of a component in one phase must be equal to the
fugacity of that same component in the second phase for
equilibrium to
persist.
6.3. Cooling Curves
Useful in equilibrium studies are cooling curves. These curves present
the temperature history
of a system while it is being heated or cooled.
Consider the cooling of liquid H
a
O. The (temperature-time) curve
for it, starting from some arbitrary temperature, say 80F, is a line with
a negative slope. The temperature decreases with time until a tempera-
ture of approximately 32
F (corresponding to standard pressure of
14.696 psi, abs.) is reached. At this point the formation of another phase
(ice) occurs. The cooling curve is then a horizontal line until all of the
liquid is frozen (the delay is explained by the phase rule in section 6.5
of this chapter)
. Upon completion of solidification, further cooling re-
sults in a drop in temperature with time. Such a cooling curve is the
simplest possible because only one component, H,0 is present in the sys-
tem.
The concentration
and nature of a component is required to specify
the composition of a phase. In the above example, there was one phase
(liquid, composed of 100% H
a
O) at the start of cooling. Next, two
phases coexisted (liquid and solid, each composed of 100% H,0) . Finally,
a single phase (solid, composed of 100% FLO) existed. Frequently a
system may contain two or three components. Such systems are referred
to as binary and ternary systems, respectively. The number of com-
ponents is not limited to three or any number in particular.
Suppose the water had been cooled very rapidly from SOT. Chances
are very good that ice would not have formed at 32F, but at a somewhat
Phase Diagrams and the Simple Alloy Systems 99
lower temperature. It is possible to cool the water below 32F without the
formation of ice. However, the addition of a small crystal of ice to serve
as a nucleus causes solidification. Freezing can also be brought about by
disturbing a super-cooled liquid. Super-cooled liquid water in this state
is not characterized by stable equilibrium. This illustration serves to
point out the influence of cooling rate on equilibrium. The only way to
freeze liquid water at exactly 32F (if this be the "absolutely correct"
freezing point) is to cool it infinitesimally slowly; otherwise the solidifi-
cation will begin at a temperature lower than 32F, the amount of de-
parture being a function of the cooling rate. The depression of the freez-
ing point is brought about because of time necessary for solidification to
begin after the freezing point is reached. The student of thermodynamics
will again recognize the influence of time on the irreversibility of proces-
ses.
When ice is melted, the melting begins at a temperature slightly
above 32 F if the heating rate is greater than zero. A way frequently
employed to determine the "correct" freezing or melting point is to
construct a heating and a cooling curve based on a minimum rate of
temperature change and to interpolate between the "depressed" freezing
point and the "elevated" melting point.
Cooling curves for alloy systems can be determined experimentally for
various concentrations of the components, and these curves may be used
to construct equilibrium or constituent diagrams such as presented in
Section 6.7 of this chapter.
6.4. Solid State Mass Transfer
The rate of mass transfer or diffusion, as it is commonly referred to,
is given by Fick's Law in the following fundamental form
m=-DA^
ax
in which m is the mass transfer rate, ? is the change of concentration
dx
in the direction of the diffusion path, per unit of path length, A is the
cross sectional area of the path (this area is normal to the path) , and D is
a coefficient of mass diffusivity. The minus sign indicates that the mass
transfer takes place in the direction of decreasing concentration. It is
through the process of diffusion that a solid solution of several metals may
be homogenized. If a large concentration of one component exists in a
localized form in a solid solution, it will diffuse. The concentration pro-
vides a gradient which gives rise to the mass transfer.
100
The process of diffusion is very slow for solids at ordinary room
temperatures. However,
the coefficient of mass diffusivity varies ex-
ponentially with the absolute temperature of die material being diffused.
Because of this increase in diffusivity at elevated temperatures, a con-
centration is diffused in a matter of minutes at 1500F that would prob-
ably take several centuries at room temperature. For this reason, alloys
which are heterogeneous because of rapid and irreversible cooling are
homogenized at elevated temperatures in annealing ovens.
By the process of dilfusion (a "self-homogeni/.ing action") solid aggre-
gations become homogeneous (and thence become phases)
.
6.5. The Phase Rule
In the latter portion of the nineteenth century, the phase rule was
advanced by
J.
Willard Gibbs. It is largely because of the work of Gibbs
that our knowledge of phase equilibria is as advanced as it is today. The
following
is a short explanation of how the phase rule may be derived.
Equilibrium
is assumed; therefore, the fugacity of a component in
one phase is equal to the fugacity of the same component in any other
phase. If there are N
p
phases in the system, then equilibrium provides
(N
p
-1) equations per component. In a system of N components, there
are N
c
(N
p
-1) fugacity equations. The concentration of all the com-
ponents in a particular phase must sum to unity. This fact provides N
p
independent equations. The number of variables that are independent,
(also called degrees of freedom) N
f
are then equal to the difference be-
tween the total number of variables and the number of independent
equations
relating these variables. The total number of variables are N
c
N due to composition plus any two thermodynamic coordinates. It fol-
lows then that
N
r
= [N
c
N
p
+ 2]
[N. (N
p
-1) ]
N
or
N
f
=N-N + 2
This is the phase rule of Gibbs. By way of illustration, attention is
again directed to the freezing of the water. When two phases of the one
component
were coexistent, the phase rule indicates that there was only
one independent variable. This is evidenced by the fact that once the
pressure (a thermodynamic coordinate which was arbitrarily taken as
14.696 psi, abs.) is independently chosen, the temperature
is fixed.
(in this case at 32F) for two phases and one component.
Upon com-
pletion of freezing, one phase existed. Now there are two variables that
are independent according to the phase rule. After solidification is
complete, the temperature varies although the pressure has been arbi-
trarily selected.
To examine further application of the phase rule, the following ques-
tion is advanced. Can three phases of a single component exist simul-
taneously?
The phase rule indicates that this is possible, but that there
would be no independent variables. This means that the state where the
three phases coexist is fixed
(
that is, there is a definite temperature and
pressure for a given component where triple phase coexistence can mani-
fest itself)
.
The temperature and pressure are not arbitrary once the
component (the system in this case) is selected. The reader will recog-
nize this concept as the "triple point" in physics.
The phase rule is a valuable tool in the field
of experimental metal-
lurgy. It is useful in predicting the phase equilibria once the system is
fixed. The phase rule does not apply to the prediction of state configura-
tions that result from non-equilibrium effects, nor is the rule applicable
to a vacuum. The phase rule is based on the assumption of equilibrium
and the existence of a system.
6.6. Solid State Solubility
Solid phases form solutions as do liquid and gaseous phases. The
mechanism
of explanation
here is much the same as that for the familiar
liquid solutions.
Solid solutions can be formed by atoms of the solute
replacing
atoms
in the crystalline structure of the solvent. This type of
solid solution
is referred to as a substitutional solid solution. Another
common
type of solution is the interstitial solid solution,
in which the
atoms of the solute locate in the interstices of the crystallographic planes
of the solvent. Iron,
iron-carbide alloys are examples of this type of
solution. The smaller atoms of carbon are the solute. Carbon is referred
to as a metalloid, since it has metal as well as nonmetal
characteristics.
One of its predominant
nonmetallic properties is its negative temperature-
resistance slope.
Section
6.7 shows equilibrium diagrams of some binary systems with
varying degrees of solubility between
components.
It is possible to have
supersaturated
solutions in the solid state; martensite is a common ex-
ample of a solid solution containing an excess of carbon.
6.7. Binary
Systems
The constitution of metallic alloys is studied by preparing a series of
high-purity alloys ranging in composition from
100% of one constituent
or component
to 100% of the other component. Suitable specimens of
these alloys are subjected to treatments
that produce
a state of equili-
brium. This step is followed by studying the changes in length, electric
resistivity,
microscopic structure, atomic structure,
absorption or libera-
102
CC
=
alpha solid solution of Cu+Ni
Cu
,
f
Ni
0%N; 25%Ni
50% Ni 75% Ni lOOZNi
100% Cu 75% Cu 50%Cu 25% Cu 0%Cu
Composition (by wt.)
M.P. of
Ni
Fig. 6.1. Equilibrium diagram for the Cu-Ni system.
tion of heat (thermal analysis) , and other changes that occur when the
alloy is heated or cooled to room temperature or sometimes to the melting
point and above. The temperatures at which the changes occur are
plotted against the composition; the result is an equilibrium diagram
(also called a constitution or phase diagram) of the series. A diagram
showing changes between two metals is called binaiy equilibrium diagram.
Solid Solution Alloys. A few binary alloys exhibit complete solubility
or miscibility in all proportions and temperatures in the solid state.
These are called solid-solution alloys. Typical of this type is the Cu-Ni
system. Development of an equilibrium diagram for Cu-Ni by thermal
analysis is shown in Fig. 6.1. (The cooling curves shown have been
previously discussed in Section 8 of this chapter)
.
The line, 1-2-3-4-5,
is the liquidus line, and everything above this line
is liquid or melt (also indicated as m)
.
The line, l-2'-3'-4'5, is the solidus line, and everything below this line
is solid solution or alpha (also, indicated as <x
)
.
(The various solid phasesnot necessarily only solid solutionsof an
equilibrium diagram are generally shown by letters of the Greek alphabet
starting from the extreme left of the diagram
(
a.
, /?,
, etc.) .
To trace the cooling of an alloy of Cu-Ni, refer to Fig. 6.2. Here alloy
"A" was chosen, containing 63% Ni and 87% Cu, which represents ap-
proximately the composition of Monel metal (shown by the vertical
dotted line)
.
\rm
Tc-
_ftrja
Td
Cu
Ni
Composition
Fig. 6.2. Equilibrium diagram for 63% Ni and 37% Cu.
The following stages on cooling may be noted (cooling must be slow
enough so that equilibrium conditions prevail) :
1. At temperature Tm, the alloy is completely molten.
2. The alloy stays molten until the temperature reaches Ta.
3. At Ta, the first crystals of solid solution appear and will have the
composition as shown at a' (by drawing a horizontal line from a
until it intersects the solidus line) . The composition may be read by
dropping a vertical line from a' to the composition axis.
4. On further cooling to Tb, more solid solution crystals appear, with
the composition changing along the solidus line from a' to b', and
the composition of the remaining melt is shown by dropping a
vertical line from b on the liquidus line to the composition line.
5. Thus, on cooling between Ta and Td, the composition of the melt
will become richer in Cu from a to d and the composition of the
solid solution crystals will vary from a' to d'.
At any temperature, Tc, between Ta and Td, the relative amounts of
solid and melt may be calculated
as follows:
Let Wt = total weight of alloy,
Wm = weight of melt,
Ws = weight of solid.
Then, Wt = Wm
+ Ws, (or) Ws = Wt Wm.
[6.1]
And, Wt
X %
Cu in the original alloy will represent the total amount
of Cu present.
Wm
x %
Cu
m
will represent the amount of Cu present in the melt.
Ws
X %
Cu, will represent the amount of Cu present in the solid.
(Cu
n, & Cu represent the composition of the melt and solid re-
104
spectively as read by dropping vertical lines from c & c', where
the horizontal line at temperature Tc intersects the liquidus and
solidus lines.
Then: Wt
X %
Cu
=
Wm
X %
Cu
m
Ws
X %
Cu
100 100
+ "
100
By substituting the value of Ws from Equation 6.1 in 6.2, Ws is elimin-
ated and Equation 6.2 becomes:
Wt
X %
Cu
=
Wm
X %
Cu
n
, Wt
X %
Cu,
_
Wm
X %
Cu
,
100
100
+ "
100 100
(or)
Wt
x %
Cu- Wt
X %
Cu
8
= Wm
X %
Cu
m
-Wm
X %
Cu
s
Wt
(%
Cu _
%
Cu
B
)
= Wm
(%
Cu
ra
-
%
Cu
8)
At temperature Tc, the composition of the original alloy is still
37%
Cu,
and the composition of the melt is 54% Cu,
and the composition
of the solid is 28% Cu.
Let
100# represent the total weight of the original alloy; then,
100 (37-28) = Wm (54-28)
;
Wm
=
1Q0X9
=34.5# or 34.5%;
26
.".
Ws =
65.5# or 65.5%.
The Lever Principle. Since the length of the horizontal line is pro-
portional to the composition, the above problem may be solved by the
so-called lever principle.
Illustration
The length of the line c-Tc-c' is 26 units
The length of the line c-Tc is 17 units
The length of the line Tc-c' is 9 units
Therefore,
%
of solid = -1^-
X
100 =
65.5%
.
X
100,
26
'
c-Tc-c
7
q
Tc-c'
and
%
of melt =
-^ X
100 =
34.5%
=
X
100.
*6
c-Tc-c'
The ratio for the melt is the distance from the nominal analysis
(fulcrum of the lever) to the solidus line over the total distance between
the lines. The ratio for the solid is the distance from the nominal
analysis to the liquidus line over the total distance.
The lever principle may be used to determine the relative amounts of
each phase when two phases are present (both phases may be solid)
.
The total horizontal distance is always measured between the two
boundary lines of the two phases present, and the fulcrum is taken at
the nominal analysis of the binary alloy.
Application of the phase rule shows that a one-phase region, such as
the cc or m areas, is trivariant: i.e.. there are three degrees of freedom.
N + N
f
= N + 2
1 +N
f
= 2+2
N
f
= 3
One degree of freedom is used in selecting a pressure of one atmos-
phere, the second degree is used in selecting a temperature which will
locate the vertical position, and the third is used in selecting the composi-
tion, which locate the lateral position. Thus, the three degrees are
utilized in fixing the position of any point in the single phase area.
When two phases are coexistent, as in the m + <x region, there are two
degrees of freedom.
N
p
+ N
f
=
N
c
+ 2
2 + N
f
= 2 + 2
N
f
= 2
One degree of freedom is used in fixing the pressure at one atmosphere.
Therefore,
if the remaining
degree of freedom is used in fixing the
temperature (vertical position) it follows that the compositions
of the
two phases are then fixed; or, if the compositions
are selected first, then
the temperature
becomes fixed.
Binary Eutectic Alloys. When two metals arc soluble in all proportions
in the liquid state but only partially soluble in each other in the
solid state, a eutectic will be formed between the limits of solid solubility.
A binary eutectic is a finely divided mechanical mixture of two solid
phases and will exhibit a definite composition and definite melting point.
Cu-Ag form alloys of this type as shown in Fig. 6-3.
Consider an alloy containing
6% Cu and
94% Ag. On cooling from
some temperature above the liquidus line, the first phase change will
occur when the temperature reaches the liquidus line. At this point, a,
crystals of alpha solid solution will start to separate, with an initial
composition as shown by drawing a horizontal line until it intersects the
solidus line at point b. On further cooling, the composition of the alpha
will change along the solidus line and the composition of the remaining
melt will change along the liquidus line; with more and more alpha
crystallizing out and, consequently, less and less of the melt remaining.
At point c the last of the melt will crystallize and the alloy will consist
of solid alpha. On further cooling to the solubility line at point d, beta
solid solution will start to precipitate from the alpha as the solubility of
X
1200
1000
800
600
Solvus (or)
solubility
line
400
Ao
108.1
Solvus (or)
solubility
line
10 20 30 40 50 60 70 80 90
Wt. % Cu
Cu
Fig. 6.3. Equilibrium diagram for the Ag-Cu system.
beta in alpha decreases with a decrease in temperature as shown by the
shape of the solubility line.
Consider an alloy containing 20% Cu and 80% Ag. Again alpha starts
to crystallize at the liquidus line. On further cooling, the composition of
the melt approaches the eutectic composition. When the temperature has
dropped to the eutectic, the remaining melt will have reached the eutectic
composition. At this point, and on further extraction of heat, the melt
will crystallize isothermally to Eutectic.
Therefore, the various areas may be described as follows:
Area 1. Two phases consisting of alpha plus precipitated beta.
Area 2. Two phases consisting of alpha plus eutectic.
Area 3. Two phases consisting of beta plus eutectic.
Area 4. Two phases consisting of beta plus precipitated alpha.
Area 5. A single phase consisting alpha solid solution only.
Area 6. A single phase consisting of beta solid solution only.
Since the eutectic is a finely divided mechanical mixture of both alpha
and beta, the combined area
(1, 2, 3, 4)
can be designated as consisting
of alpha plus beta, but they will be in different physical states as described
above.
The precipitation of one solid phase from a solid solution is a very
important factor in the heat treatment of alloys such as those of Al, Mg,
10
Atomic % Ca
20 30 40 50 60 70 60 90
Fie. 6.4. Equilibrium digram for the Mg-Ca system.
and Gu. This type of treatment is known as "aging" or precipitation
hardening and will be discussed in more detail in Section 6.8.
Application of the phase rule will show why the eutectic reaction must
occur at a constant temperature.
N
p
+ N
f
=
N +2
3 + N, = 2 + 2
N, = 1
Again, one degree of freedom is used in fixing the pressure at one
atmosphere; therefore, neither the temprature nor the composition of any
of the phases can change during the course of the eutectic reaction under
equilibrium conditions.
6.8. Intermetallic Compounds
Many alloy systems will exhibit one or more intermetallic compounds.
This type of compound is generally very hard and brittle, and, under
proper conditions, may impart additional strength ami hardness to an
alloy. Therefore, intermetallic compounds are very important industri-
ally. Compounds of this type have a definite chemical formula, eg. Cu
s
Al,
and have a definite melting point that shows as a maximum on the
liquidus line (Fig. G.4) . This melting point may sometimes be higher
than the melting point of either component.
Phase diagrams of this type may be conveniently studied by considering
them as two-part diagrams, i.e. the system Mg-MgXa and the system
108
a
^=^-
\
I
7s
i
e
*/
< i
' i
!
is the solidus line.
be is the CuAl
a
solubility line.
2 3
4-56
%Cu
Fig. 6.5. Al.-rUh end of Cu-AI phase diagram.
Mg
2
Ca-Ca. ]Jy this method the diagram simplifies itself into two eutectic
types.
Fig. 6.5 represents the Al rich end of the Cu-AI phase diagram.
If an alloy containing
2% Cu is heated to temperature T, and held for a
sufficient length of time, the alloy will become a homogeneous solid sol-
ution. Rapid quenching will then retain the alloy in this condition at
room temperature. This is known as solution treatment. On reheating
this alloy up to temperature T,, (below the solubility line be) , the inter-
metallic compound, CuAl
2
, will precipitate from the solid solution. The
amount of this precipitation will depend on time, temperature, and solu-
bility. This step in the heat-treatment is known as aging or precipitation
hardening.
The physical properties of certain alloys may be markedly changed
by the heat-treatments described above.
6.9. The Peritectic Reaction
The peritectic reaction may be called an inverse or fake eutectic re-
action, wherein a liquid and a solid react isothermally to form a new
solid. By examining Fig. 6.6, it will be noted that alloys of Li and Mg
lying between the points a & P will first contain alpha solid solution
and melt after crossing the liquidus line on cooling. At the peritectic
temperature all of the melt will react with some of the alpha to form the
new solid, beta solid solution. Between points P and b and at the
Peritectic temperature all of the alpha will react with some of the melt
to form beta. If an alloy were chosen such that its composition was ex-
40 50 60
% Wi of Li
Fig. 6.6 Equilibrium diagram for the Mg-Li system.
acily as shown at the peritectic point P, then, on cooling to the peritectic
temperature, all of the solid, alpha, would react with all of the melt to
form beta.
6.10. Closure
In recent years considerable progress has been made in the field of
solids, and these achievements are reflected in no small measure in the
science of metallurgy as well as in other subdivisions of solid state physics.
New developments include transitors, transducers, solid rocket fuels,
high temperature sealants, metal production technology, "light weight"
radiation shields, and a host of other innovations.
The salient feature of the real progress in all of these fields is that
success was accomplished by thorough consideration of the fundamental
nature of the problem. The metallurgist of the future should be well
versed in such items as quantum theory, radiation, and fundamental
rheology. The physicist has helped the engineer to understand aspects
of the solid state phenomena, but there is a need for further investigation
by the research engineer.
110
QUESTIONS
1. With reference to the "lever principle", would such a rule apply to a two
phase region in any plane where extensive properties were used as co-
ordinates? Assume equilibrium exists and recall that an extensive property
of a multiphase system is the sum of that extensive property for all phases
of the system.
2. It is known from thermodynamics that constant pressure boiling of a pure
substance (one component) takes place at constant temperature as long as
the vapor is in contact and in equilibrium with the liquid. Explain this.
S. Can the "triple point" referred to in paragraph 6.5 ever appear as an area
on a plane of thermodynamic properties? Explain.
4. During a certain experiment, pertinent to cooling a binary system, a speci-
men was "isolated" and observed to contain five phases, apparently co-
existing. Give several conclusions and substantiate.
5. With reference to the lever principle in paragraph 6.7, how was equilibrium
assumed or implied in the derivation?
6. Using the law of mass transfer as given in paragraph 6.4, derive the partial
differential equation for three dimensional, unsteady state diffusion.
7. Using the equilibrium diagram for copper and nickel calculate the pro-
portions of solid and liquid for an alloy containing 30% Ni. at a tempera-
ture of 2200 deg.F. What are the concentrations of each component in the
liquid and the solid?
8. Compute the volume of a unit mass of mixture containing 80% (by mass)
water vapor and 20% liquid water in equilibrium with the vapor. The
pressure of the mixture is 50 pounds per square inch absolute. Reference
to vapor tables will be necessary here. Was the so called "lever principle"
employed in the above computation? HINT: See Problem 1 above.
9. For copper-silver phase equilibria discuss the transformations taking place
upon cooling for the following alloys: 5% copper, 20% copper, and the
eutectic composition.
10. Some binary alloys exhibit a characteristic such that there exists a composi-
tion that has a lower melting point than cither pure component. Show
that this point is a point of tangency for the liquidus and solidus. Would
the common tangent to both curves at the above point be a horizontal
line on the equilibrium diagram? Substantiate your answer.
1 1. Can water exist in more than one solid phase? Discuss.
12. How many degrees of freedom exist for the following situations:
(a) A diatomic gas.
(b) A pendulum swung by an elastic and extensible cord.
(c) A locomotive making a run between two cities on a specified track.
CHAPTER
Heat Treatment
of
Alloys
by Precipitation Hardening
Harold Vincent Fairbanks, M.S., Professor of Metallur-
gical Engineering, West Virginia University, Morgan-
town, W. Va.
Arthur R. Foster, M.Eng. Associate Professor of
Mechanical Engineering, Northeastern University,
Boston, Massachusetts
X RECIPITATION hardening, sometimes
called dispersion or age hardening, is the most important method of
strengthening
nonferrous metals through heat treatment. This treatment
has been
used very effectively with the light alloys of aluminum and
magnesium. It has also been applied to a number of heavy alloys of
metals such as copper, iron, nickel, silver, and lead. The susceptibility
of an alloy to precipitation hardening depends upon the manner in which
its component metals combine rather than upon the properties of the
dominant metal.
The process of precipitation hardening consists essentially of two steps.
In the first step, an unstable condition is produced in the alloy structure
through the formation of a supersaturated solid solution. This step is
called solution heat treatment and produces a comparatively soft, ductile
state for the alloy.
The second step requires a certain degree of precipitation of the super-
saturated phase to impart the increased hardness and strength to the
metal. If this step is carried out at room temperature,
the process re-
quires several hours or days and is sometimes called age hardening. On
the other hand, if an elevated temperature is employed, the process re-
quires much less time and is called the precipitation heat treatment.
7.1. Alloy Requirements
There are two main requirements
for alloys to be heat treated by
precipitation hardening. The first requirement is that the solubility of the
HI
112
dissolved constituent decreases with decreasing temperature. The second
requirement is that there be some coherency between the precipitating
phase and the matrix phase. It is this coherency or lattice conformity
between
the two phases which brings about the internal crystal stresses
required for strengthening of the alloy.
Another influencing factor which governs the degree of hardening is
the quantity of available material for precipitation. The slope of the
solid solubility curve (solvus line) and the composition of the precipitat-
ing phase determines the amount of material available for precipitation.
The closer the precipitating phase is to the solid solubility curve on the
phase diagram, the more the material that is available for precipitation.
Also, the greater the decrease in the solubility with decreasing tempera-
ture, the larger will be the amount of material available for precipitation.
The precipitating material may be either a solid solution or some inter-
mediate phase or compound.
However, it must be remembered that a large quantity of material
available for precipitation does not insure that heat treatment of the alloy
by precipitation hardening is possible. In the Mg-Pb system, magnesium
can dissolve 46 percent lead at the eutectic temperature and only 2
percent lead at room temperature. This alloy shows but little strengthen-
ing effect of precipitation hardening due to the small amount of co-
herency of the precipitated phase with the matrix material.
7.2. Step I
Solution Heat Treatment

The process of precipitation hardening is divided into two steps: first,
the solution heat treatment, and second, the precipitation heat treatment.
A schematic representation for the process of precipitation hardening is
given in Fig. 7. 1
.
The alloy to be solution heat treated must have a composition that
meets two requirements:
(1)
that at an elevated temperature
a solid
solution is formed, and
(2)
that the solid solution can be retained upon
rapid cooling to room temperature. A typical alloy used for precipitation
hardening is shown as alloy N in Fig. 7.1.
The process for solution heat treatment has two parts:
(1)
heating, and
(2)
quenching.
In heating, the alloy is heated to a temperature above the solvus line
but below the solidus line. The alloy is held at this temperature for a
sufficient period of time to produce a solid solution. For some alloys the
temperature range is fairly narrow between the solvus and solidus lines.
It is very important not to heat above the solidus line as incipient melt-
ing of the alloy will take place destroying the dimensions of the fabricated
Heat Treatment
of
Alloys by Precipitation Hardening 113
PHASE DIAGRAM
PRECIPITATION
HARDENING
Temp.
Composition
Tlmt -
Kic.
7.1. Schematic representation for the process of precipitation hardening.
part. Also, too high a temperature can produce excessive grain growth.
On the other hand, the temperature should be above the solvus line in
order to take advantage of the material available lor precipitation harden-
ing and to produce as homogeneous a solid solution as possible.
In quenching, the heated alloy is cooled to room temperature rapidly
enough to retain the solid solution. The alloy at room temperature is now
in a state of nonequilibrium
as only the supersaturated solid solution
phase is present.
The retention of the potential precipitating phase in solid solution is
the prime requirement of quenching to room temperature. It is im-
portant that the alloy be quenched as uniformly as possible as uneven
quenching forms areas of high stress in the alloy which will produce
soft spots in the subsequent hardening treatment. The stressed areas
will harden first and then become softer during the subsequent heat
treatment which is necessary for the main body of the material to obtain
maximum hardness.
The result of the solution heat treatment is a supersaturated solid
solution condition in the alloy. The alloy in this state may be softer
than in the annealed condition, but generally it is found to be harder than
the annealed
state for the alloy, as shown in Fig. 7.6. However, the ma-
terial after solution heat treatment is still ductile and may be cold worked.
Some alloys start to harden upon standing at room temperature. Any
deformation required after solution heat treatment for these alloys should
be done immediately
before the hardening begins. In order to arrest this
hardening action, the metal may be placed in a deep freeze which lowers
the rate of atomic diffusion due to thermal activity. This fact was made
use of in the storage of aluminum rivets for assembling of airplane parts
during World War II. However, most alloys are fairly stable at room
temperature after solution heat treatment.
7.3. Step IIPrecipitation Heat Treatment (Aging)
The second step in the process of precipitation hardening brings about
the hardening and strengthening of the alloy. This is achieved by re-
heating the unstable solution heat treated alloy to some temperature be-
low the solvus line, but sufficiently above room temperature to allow
mobility of the atoms held in supcrsaluration.
This precipitation temperature is held for a definite period of time
until the hardness of the alloy has reached the maximum or desired value,
and then the alloy is either quenched or air cooled to room temperature.
Once the alloy has reached room temperature, it will retain the desired
properties due to the lack of mobility of the atoms in the crystals to
migrate.
Attention must be paid to the proper temperature and to the time at
temperature in order to insure maximum hardness and strength. Too
high a temperature and too long a time will cause softening of the alloy,
and the advantages of this method of heat treatment will be lost.
For some alloys the entire second step is carried out at room tempera-
ture. This is only possible when the mobility of die atoms in the alloys
are sufficient at room temperature to cause the desired hardening and
strengthening of the alloy.
7.4. Theory of Precipitation Hardening
The heat treatment of alloys by the precipitation hardening process
depends upon obtaining an unstable state for the alloy by solution heat
treatment, and then controlling the degree of approach toward the stable
state for the alloy during the precipitation heat treatment. The maxi-
mum hardness and strength are obtained before the equilibrium or stable
state for the alloy is reached.
The actual hardening and strengthening of the alloy occurs during the
precipitation heat treatment step. The mechanism involved may be di-
vided into three stages: (I) the pie-precipitation stage,
(2)
the inter-
mediate precipitation stage, and
(3)
the equilibrium precipitate stage.*
Fig. 7.2 shows sketches of the various stages in precipitation.
*
For an excellent discussion on Precipitation see "Report on Precipitation" by H.
K. Hardy and T.
J.
Heal in "Progress in Metal Physics", edited by Bruce Charles and
R. King, Interscience Publishers, Inc., Vol. 5. pp.
143-278. 1954.
Heat Treatment
of
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B. Pit -precipila'e
c hlttrmtdletc precipitate D. Equilibrium prtcipitote
solution
Fig. 7.2. Sketches showing the various stages in precipitation. Open circles represent
matrix atoms. Filled-in circles represent solute atoms.
In the pre-precipitation stage, the solute atoms segregate along specific
crystallographic planes of the matrix phase in preparation for nucleation.
These clusters of atoms are called knots or Guinier-Preston Zones, having
been detected by Guinierf and Preston;}; with X-rays.
In the intermediate precipitate stage, nucleation is taking place and
the resultant new lattice of the precipitating phase is present. This new
lattice is in the form of thin plates from 2 to 50 atoms thick and 20 to
several hundred atoms long or wide. There is a lattice coherency present
between the precipitated phase and the matrix phase which results in a
highly stressed area in the matrix surrounding the intermediate precipi-
tate.
In the third stage, the precipitate has grown to such a size that the
coherency forces between the two adjacent crystal lattice systems are over-
come and the precipitate becomes its own independent crystal entity.
This relieves the major stresses in the area and softens the metal.
It is during the second stage in which the intermediate precipitate is
formed that maximum hardening and strengthening of the alloy occurs.
This is due to the fact that a flexible dislocation cannot move easily
through the regions of localized stresses. The greater the number of
these localized stresses per unit volume of material the greater is the
strengthening of the metal due to the increased force required to push the
dislocations through the many stress barriers.
fCuinier, A., Nature 142 (19S8) 569.
j
Preston, G. D., Nature 142 (1938) 570.
116
This precipitation process is one of nucleation and growth of the
solute phase from a supersaturated solution. The driving forces involved
for the diffusion of the solute atoms include:
(1)
thermal energy,
(2)
the
supersaturated condition of the matrix phase, and
(3)
stresses which
were developed due to quenching in the solution heat treatment step.
The nucleation throughout the alloy does not necessarily start at the
same time in the alloy during the precipitation heat treatment. There-
fore, it is the statistical average effect which is produced at a given time
for a given temperature. There are undoubtedly particles in all three
stages at the same time.
Fie. 7.3. Structure of an alloy containing 3.94 per cent copper, 0.02 per cent silicon,
0.02 per cent iron, and remainder aluminum. (A) as cast,
100x;
and (B) quenched,
500x;
etched. (Courtesy
of Aluminum Research Laboratories)
If the temperature of the alloy is maintained sufficiently low, even
the first stage cannot take place. On the other hand, if the temperature
for the precipitation heat treatment is too high, only the third stage may
prevail. This is called overaging. The alloy becomes softer and loses
its strength. It may become as soft as in the annealed state. Photomicro-
graphs showing microstructure of an aluminum alloy with various treat-
aents are shown in Fig. 7.3.
Heat Treatment
of
Optimum tamp.
Strength
-Tim e
Fie.
7.4. Effect of precipitation heat treatment temperature and time on the
strength of the alloy.
7.5. The Effect of Time and Temperature During Precipitation
Heat Treatment
Both the temperature at which the precipitation heat treatment is
carried out and the length of time at temperature are important. As the
temperature is increased the mobility of the atoms in the supersaturated
lattice structure increases.
This means that the growth' of the unstable
submicroscopic
platelets in the transition phase is speeded up. This also
means that they will attain the critical size at which they shear away
from the parent alpha phase sooner. The result of this is that optimum
hardness and strength are attained more quickly. This is shown in Fig.
7.4. Increasing the time of treatment causes the growth of stable pre-
cipitated particles of the second phase with marked losses in the strength
and hardness of the alloy along with other changes in the properties of
the alloy as shown in Fig. 7.5.
If the precipitation temperature is lowered, the diffusion of the solute
atoms is impeded. In an extreme case this may mean that it is completely
suppressed
and no increase in hardness or strength can occur. In other
cases the improvement is less than the optimum amount.
The temperature
which is required to prevent hardening of the solu-
tion treated metal varies with the alloy. Some aluminum alloys must be
stored at sub-zero temperatures to suppress hardening, but beryllium
copper, after solution treatment, remains soft at room temperature in-
definitely.
Some data on hardness of 24S aluminum is included in Fig. 7.6. This
graph indicates that increased temperatures will speed the rate of harden-
ing. At 240F it shows that little overaging occurs in a week. It is
Tentile Strength
Propertie*
Log Time
Fie. 7.5. Effect of precipitation heat treatment time on alloy properties-
interesting to note that the furnace cooled specimen is much softer than
the solution treated material. This indicates that the alloy in the solu-
tion treated condition where the solid solution is maintained, is not as
soft as the equilibrium structure which contains relatively large particles
of hard, brittle second phase. This is because, in the case of 24S, the copper
is still in the solid solution with the aluminum in the solution treated
specimen. Since the atoms of copper are of
a
different size than those of
aluminum, the movement of dislocations along the various planes in the
lattice structure is impeded. This results in greater strength and hardness.
Both the temperature and the length of time at the chosen temperature
must be specified if satisfactory results are to be obtained in the precipi-
tation hardening process. It may be possible to shorten the time in the
heat treating furnace by raising the temperature. Care should be taken
that proper temperature and time be selected from published data or, if
this information is not available, that they be established experimentally.
It can be seen from Fig. 7.4 that although higher than optimum tempera-
tures may reduce the attainable strength slightly, the shortened time may
reduce the heat treating costs sufficiently to justify the slight reduction in
physical properties.
Heat Treatment
of
80
70
60
SO
C0
4Q
20
10
1
240 F aging temp.
r~~
75 F aging temp.
J
f
/8 F agina
temp
1
Fu noce coo led to re*om temp.
I ?
3 4 5 6 7
Time, days
Fie. 7.6. Rockwell B hardness vs. time for 24S. Solution treated 1 hour at 970 K.
Furnace cooled specimen cooled very slowly. Other specimens water quenched prior
to precipitation hardening.
7.6. Precipitation Hardening of Aluminum Alloys
Extensive use is made of precipitation hardening with many alloys of
aluminum. Wrought alloys may be strengthened by either cold work or
precipitation hardening. The latter usually results in a smaller decrease
in ductility for a similar or even greater increase in strength. In castings,
precipitation hardening is especially useful since no cold working can be
performed.
The binary phase diagrams for Al-Cu, Al-Mg, Al-Si, and Al-Zn all show
the characteristic decrease in the solubility of the alloying element in the
aluminum rich alpha phase as the temperature decreases. Few com-
mercial alloys are true binary alloys, but the phase diagram for aluminum
and the major alloying element usually points the way to possible success-
ful heat treatment.
120
700
SO SO 10
Copper, per cent
Fie.
7.7. The aluminum-copper phase diagram: inset, the aluminum-rich portion.
{Dix and Richardson)
The Al-Cu phase is shown in Fig. 7.7. Wrought alloys 1 IS, 14S, 17S,
and 24S all contain 4.0 to 5.5 percent copper plus minor amounts of
silicon, magnesium,
manganese, lead, and bismuth, while casting alloys
such as No. 108, 112, 142, 195 and 212 contain 4 to 8 percent copper as the
major alloying element. In alloys containing up to 5.5 percent copper all
the theta phase should go into solid solution with the alpha phase on
heating to about 1000F. A casting alloy such as No. 212 containing
8 percent copper, 1.2 percent silicon, and 1 percent iron cannot dissolve
all the theta phase when solution treated as the alpha phase when heated
to just below the eutectic temperature can hold only 5.5 percent copper.
However,
this alloy can be hardened just as the other Al-Cu alloys and
the undissolved hard, brittle theta particles will serve to improve the
machineability of the alloy. In the presence of magnesium and silicon,
other intermetallic
compounds which are susceptible to age hardening
may be formed such as Mg,Si, AlXuMg, or AlCuMgSi.
The Al-Mg phase diagram shown in Fig. 7.8 is of interest as it shows
the type of partial solubility required for precipitation hardening at
each end of the diagram. The magnesium rich end of the diagram will
be treated in Section 7.7. It can be seen from the phase diagram that
aluminum can dissolve 16 percent magnesium at the eutectic tempera-
ture of 844F and very little at room temperature. On slow cooling of
the alpha phase alloys to room temperature, the beta phase which is an
intermetallic compound of Mg
2
Al
3
precipitates. Casting alloy No. 220
containing 10 percent magnesium has the best physical properties of any
Heat Treatment
of
of the aluminum base casting alloys. Its major disadvantage is its poor
capability which requires
special foundry techniques and inhibitors to
prevent deep surface defects.
The Al-Si phase diagram shows a decreasing solubility of silicon in
aluminum as the temperature is lowered. However, the amount of the
silicon rich beta phase which is suppressed upon solution treatment is
not great enough to produce a commercially important improvement
in physical properties. Silicon rich casting alloys are used extensively,
but not in the heat treated state.
When silicon and magnesium are used together in an aluminum alloy,
an intermetallic compound of Mg
2
Si is formed which allows effective
heat treatment. The solubility of this compound in aluminum increases
from 0.27 percent at 390F. to a maximum of 1.85 percent at 1100F.,
which is the eutectic temperature. Silicon in excess of the amount form-
ing Mg
2
Si does not affect the solubility of the compound in aluminum,
but an excess of magnesium does reduce its solubility. Therefore, it is
necessary to be sure no excess magnesium is present.
Wrought alloy
SIS (l%Si, .6%Mg, .25%Cr) is of this type. 61S is
slightly
more complex (.6%Si, l%Mg. .25%Cu, .2r,%Cr) in that it con-
tains copper, which further complicates the mechanism of precipitation
hardening
by increasing the number of intermetallic
compounds which
form. The small amount of chromium added to both alloys tends to
offset the ill effects of iron which is present as an impurity. Casting
alloys
132, 355, and 356 are heat treatable Al-Si-Mg
alloys. They have
considerably
higher silicon contents (5-12%) than the wrought alloys
just mentioned.
This improves their
ratability.
Although a high
percentage of zinc can be dissolved in aluminum at
elevated temperatures
(82.8 percent at 720F. compared with
5 percent
at 248F.) alloys of these elements show only limited response to pre-
cipitation hardening.
With the addition of magnesium, compounds such
as MgZn
2>
MgZn, and AlMgZn are formed and these alloys will respond
very well to precipitation hardening. The wrought alloy 75S containing
5.6 percent zinc, 2.5 percent magnesium, 1.6 percent copper, 0.3 percent
chromium and 0.2 percent manganese is essentially
a Zn-Mg alloy. It
develops
the best mechanical properties of any of the commercial
aluminum alloys.
7.7. Precipitation Hardening of Magnesium Alloys
Precipitation hardening is especially useful with magnesium base alloys
since the close packed hexagonal crystal lattice structure will allow only
limited amounts
of cold work. The major alloying elements are alu-
10 20 30
Atomic Per Cent Al
40 50 60 70 80 90
"C
i i 1 1 1 ' i 1 1
600
500
ruA
*36
*
463"
./
451"
/ ..
400
Si
5
6
, Mg/I, \
t.V
1II
300
/
fi
200
_ i i i '
I .1 -L 1
10 20
H
40 50 60
Weight Pet Cent AL
70 80 to
Fie. 7.8. Aluminummagnesium phase diagram.*
By permission from Structure 8c Properties of Alloys, Brick & Phillips, McGraw-

Hill Book Company, Inc., 1949.
minum, zinc and manganese. The manganese strengthens the alloys by
going into solid solution with the magnesium while both the aluminum
and the zinc show the decreasing solubility required for successful pre-
cipitation hardening. Fig. 7.8 shows that 12.6 percent aluminum is
soluble in magnesium at the eutectic temperature of 815F. while less
than 2 percent is soluble at room temperature. Zinc shows virtually no
solubility in magnesium at room temperature and has a maximum of 8.4
percent at 646F. The precipitating phase is an intermetallic compound
MgZn.
Many alloys contain substantial amounts of both aluminum and zinc
so that a ternary diagram is necessary to show the phase relationships in
these alloys. The change in solid solubility and the identity of the phase
or phases in which precipitation is suppressed by solution treatment is
indicated in Fig. 7.9. On this diagram, it can be seen that casting alloy C
containing 9 percent aluminum, 2 percent zinc, and 0.2 percent man-
ganese should precipitate only
Mgi
7
Al
12>
but alloy H containing 6 percent
aluminum, 3 percent zinc, and 0.2 percent manganese also precipitates
some Mg
3
Zn
2
Al
8
. These are the two most commonly used casting alloys.
Solution treatment not only improves the strength of the alloys but also
Heat Treatment
of
%i<\
Fig. 7.9. Section of ternary diagram for Mg-Al-Zn system. Isothermal lines show
the limits of solid solubility at the various temperature levels. To the left of the
dashed line the structure consists of solid solution and MgAl. The solid dot shown
on the diagram represents the composition of Alloy C which shows this type of
microstructure. To the right of the dashed line the structure will consist of solid solu-
tion, Mg
1T
Al
M,
and Mg
3
7.njAlj. Alloy H whose composition is represented by the small
circle on the diagram is an alloy of this type.*
improves the ductility considerably, because the brittle interdendritic
eutectic compounds are dissolved. The precipitation treatment reduces
the ductility, but leaves enough for most applications. It causes a marked
increase in yield strength with little change in tensile strength.
Of the wrought alloys only 0-1 containing 8.5 percent aluminum, 0.5
percent zinc, and 0.2 percent manganese, and ZK-60 containing
5 percent
zinc, 0.7 percent zirconium have enough alloy content to be effectively
precipitation hardened. Extrusions and forgings are usually worked at
high enough temperatures and cool fast enough in the atmosphere to be
effectively solution treated. Thus, they need only to be precipitation
hardened after fabrication is completed.
The precipitation of a second phase with its different crystal lattice
dimensions results in the growth of the piece during precipitation harden-
ing. If such dimensional instability cannot be tolerated at the service
Busk and Miranda Trans. AIME. IG6. 346. 1946.

temperature, a stabilization heat treatment is required. Stabilizing con-
sists of heating to a temperature somewhat higher than the usual precipi-
tation hardening temperature to allow partial precipitation of the
second phase. The degree of transformation is greater than will occur at
the service temperature, and, therefore, there is no further tendency for
precipitation while the part is in use. This is essentially ovei aging and
causes some loss in physical properties. This type of heat treatment may
be applied to other precipitation hardening alloys as well as the mag-
nesium base alloys discussed here.
C Atomic Percentage Beryllium
5, 10 15 SO IS 30 35 40
1000
700
600
500
300,
-
(600
1200
- 1000
Co I B 3 5 6 7 8 9 10
Weight Percentage Beryllium
Fig. 7.10. Copper-rich portion ot the copper-beryllium phase diagram. (H. F.
Silliman)
7.8. Precipitation Hardening of Copper Base Alloys
Precipitation hardening is not used as extensively with copper base
alloys as it is with the aluminum and magnesium alloys, but there are
several alloys with which it may be used very effectively.
Commercial beryllium-copper alloys contain from 1 to 2-\/
A
percent
beryllium plus
\/
A
percent nickel to inhibit excessive grain growth at the
solution treatment temperatures. The phase diagram shown in Fig. 7.10
indicates a maximum solubility of 2.1 percent beryllium at 1590T. The
figures given in Table 7.1 indicate that precipitation heat treatment is
extremely effective with these alloys and that when combined with cold
Heat Treatment
of
working, tensile strengths approaching 200,000 psi may be obtained.
The usual heat treating cycle consists of solution treatment at 1450F.
followed by a water quench and reheating to 480 to 620F. for 2 to 3
hours. The high strength, corrosion resistance, and fatigue resistance of
these alloys recommend their use for springs, diaphragms, and non-spark-
ing tools.
Moncl metal which contains 67 percent nickel and 30 percent copper
plus small amounts of iron and manganese forms a single homogeneous
solid solution
as do all the alloys in the binary Cu-Ni series. However,
if
3
percent aluminum
is added producing K-Monel or 4 percent silicon
is added producing
S-Monel, the metal is responsive to precipitation
hardening.
Tin bronzes show little tendency towards precipitation hardening
although
the phase diagram indicates that it is possible. The low tem-
peratures at which the alpha
phase becomes unstable which is 570F.
for
5 percent tin and 95 percent copper prevents
any appreciable pre-
cipitation of the delta phase. The addition of up to 8 percent nickel,
however,
promotes the precipitation of a Ni-Sn rich constituent which
improves the physical
properties considerably beyond those of the ordi-
nary tin bronzes. The data in Table 7.2 indicates the effectiveness of
precipitation
hardening on a commercial alloy of this type.
7.9. Precipitation
Hardening in Low Carbon Steel
In Chapter
12 where the fundamental structure of carbon steels will be
discussed, ferrite is defined as alpha iron holding in solution small
amounts
of silicon, phosphorus, carbon, and other elements. Of the ele-
ments which may be in solution in very small quantities in alpha iron,
three: carbon, oxygen, and nitrogen can, under suitable conditions, cause
precipitation
hardening. Fig. 7.11 shows the approximate solubility of
these in iron. It will be noted that the slope of these
curves resembles the
slope
of the solubility
curves of the other alloy systems discussed in
this chapter.
Precipitation
hardening in carbon steel is a phenomenon that is com-
mon only in the low carbon grades. Since these steels are used rarely in
the quenched conditions,
precipitation hardening due to iron carbide or
iron nitride retained in solution by quenching, followed by slow spon-
taneous
precipitation
at room temperature or more rapid precipitation
at slightly
elevated temperature is seldom encountered. It is, however,
possible, by quenching a steel containing 0.04 to 0.10 percent carbon
and by precipitation
treatment at 140F. for 10 to 15 hr. to increase the
Brinell hardness from 120 to 160.
126
Oxygen, percent
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.05 ./<? . .>
Carbon, percent
.01 .02.05
Nitrogen, per cent
Fig. 7.11. Iron-rich portions of the (A) iron-carbon, (15) iron-oxygen, and (C) iron-
nitrogen phase diagrams, showing changes in solubility of carbon, oxygen, and nitrogen
with temperature. (Epstein)
7.10. Strain Aging and Its Consequences in Low Carbon Steel
There is another variety of precipitation hardening in low carbon
steels known as strain aging. If steels susceptible to aging are strained by
cold working, a hardening constituent, probably iron carbide, iron oxide,
or iron nitride, precipitates during straining and for some time afterward.
This is accompanied by increased hardness and strength and by de-
creased impact resistance. The effect of the precipitation can be detected
by cold working a rimming steel and a deoxidized steel of the same com-
position and by testing a sample of each immediately and at intervals of
several weeks or months.
Strain aging frequently has undesirable consequences. Low carbon
sheet for automobile bodies and fenders are given a light final cold work-
ing after hot rolling to prevent stretcher strains. This produces conditions
ideal for precipitation of the hardening constituent. Unless the sheet is
deep drawn immediately, the loss of ductility may be so great that the
steel will not withstand the drawing operation successfully. Strain aging
has been known to cause failures in boiler plate in the strained areas
around rivet holes.
7.11. Precipitation Hardening in Alloy Steels
Of the large number of common low alloy steels, only those con-
taining about 1 percent copper are subject to precipitation hardening.
The solubility of copper in alpha iron increases from about 0.4 percent
at room temperature to 1.4 percent at 1525F. Low carbon steels con-
taining 0.7 to 1.5 percent copper can be hardened by a heat treatment
causing precipitation of the hardening constitutent. This treatment con-
sists of heating to If>50F., cooling to room temperature, and reheating
Heat Treatment
of
for
3 or 4 hr. at 930F. Precipitation hardening increases the tensile
strength and yield strength about 20,000 psi. Ductility is decreased, but
the precipitation hardened copper steels are not brittle.
A number of investigations have been concerned with the precipita-
tion hardening of highly alloyed steels which contain 2 or 3 percent
titanium and also with stainless steels containing tungsten.
Table 7.1 Typical Properties of Beryllium-Copper Alloy 0.032"
Thick Strip
2% Be,
0.25% Co (or 0.35% Ni).*
Tensile Yield
Rockwell
Condition Strength Strength Elongation Hardness
(psi) (psi)
(%)
Number
Solution treated 72,000
25,000 50 B 60
Precipitation hardened 175,000 80,000
5 C 41
Solution treated and cold rolled
37.1%
107,000 70,000 6 B 97.5
Solution treated cold rolled
37.1 %and precipitation
hardened
195,000 110,000 3 C 42.5
*
Metals Handbook, 1948 Edition, p. 934.
Table 7.2 Properties of Type A Ni-Vee Bronze (88% Cu, 5% Ni, 5% Sn, 2% Zn)
Property
As Cast Heat Treated*
Tensile Strength, psi
50,000
85,000
Yield Strength, psi
22,000 55, 000
Percent Elongation
40 10
Brinell Hardness Number
85 180
*
Heated 6-10 hours at 1400F., water quenched, and reheated 6-10 hours at 500F.
Courtesy
of
the International Nickel Co., Inc.
QUESTIONS
1. Define precipitation hardening. Why is it sometimes called age hardening?
2. Discuss the characteristics that an alloy must possess to be precipitation
hardened.
3. Discuss what happens if too high a temperature is used during: (a) the
solution treatment,
(b) the precipitation heat treatment.
4. Discuss what happens if the alloy is held for too long a time at temperature
during: (a) the solution treatment,
(b) the precipitation heat treatment.
5. Discuss the constitutional changes which take place during precipitation
hardening.
128
6. How does precipitation hardening effect an alloy in regard to the following
properties: (a) tensile strength, (b) yield strength, (c) hardness, (d) elonga-
tion, (e) electrical resistance, and (f) corrosion resistance.
7. Discuss the effect of precipitation hardening on the movement of disloca-
tions within the metal.
8. Explain why alloys arc sometimes precipitation hardened at temperatures
higher than the temperature at which optimum strength occurs.
9. Explain why wrought magnesium alloys may be precipitation hardened
directly after fabrication without a formal solution treatment?
10. What is meant by: (a) overaging, (b) strain aging, (c) stabilizing? What
use is made of each?
11. If an alloy were to contain 4% aluminum, 2% zinc and 94% magnesium,
what phases would be present in the slowly cooled state at room tempera-
ture?
12. What alloying element added to the following materials will make them
susceptible to precipitation hardening? (a) tin bronze, (b) monel, (c) low
alloy steel.
13. List four elements whose solubility in aluminum decreases with tempera-
ture. Can all of them be used effectively as binary precipitation hardening
alloys with aluminum?
14. Why is a moderate amount of Mg used with the major alloying element Zn
in 75S?
15. What alloying clement produces the strongest commercial casting alloy of
aluminum? What is its major drawback?
16. What three alloying elements present in a plain carbon steel may cause it
to respond to precipitation hardening?
17. Is precipitation hardening used extensively with low carbon steels? Explain.
18. List some practical applications for precipitation hardening.
CHAPTER
8
Light
Alloys
as
Engineering
Materials
Francis Wii.uam Brown, Ph.D.,
Associate Professor,
Clarkson College of Technology, Potsdam, New York
8.1. History of Aluminum
ALUMINUM was first made in 1825 by a
Danish scientist named Oersted by means of a reaction between aluminum
chloride with a potassium-mercury
amalgam. In 1845 Henri Sainte-Claire
Devilie produced
globules of aluminum meta] by heating sodium metal
with anhydrous
aluminum chloride; later this method was improved by
using
cryolite as the flux. The very nature of these raw materials indicates
the large amounts of energy that are required to make aluminum and why
this metal under these processing conditions was very costly. Aluminum
was produced
by Charles M. Hall, in 1886, by the electrolytic decomposi-
tion of anhydrous
aluminum oxide (alumina) dissolved in molten
cryolite. This process has continued since 1886 to the present as the
only economical process for the manufacture of aluminum.
The first major industrial demand for aluminum
was in the aircraft
field because of aluminum's unusual
combination of lightness and
strength. The discovery
of the aluminum-copper
alloy duralumin and
its heat treatment
by Wilm in Germany
stimulated the use of aluminum.
Wilm's early work was done in connection with
Zeppelin's development
of the dirigible. Prior to the First World War, the Aluminum Company
of America supplied
the U.
S. Navy with duralumin
sheet for the Navy's
dirigible. The aircraft industry was primarily interested in the strength-
weight
ratio of the high-strength
aluminum alloys; whereas, most other
industries
were concerned primarily with the cost. It was only about
twenty-five
years ago that these alloys were considered
seriously for auto-
mobile, truck, and bus construction and for railroad rolling stock; their
consideration
for bridge and building construction
is even more recent.
129
8.2. Economics of the Aluminum Industry
For about thirty years after aluminum metal was first produced (1825) ,
it was a laboratory curiosity worth about $100 per pound. In 1857,
Sainte-Claire Deville, as the result of research supported by Napoleon
III, succeeded in bringing the price down to S25; two years later, to $17
per pound. Despite the fact that alumina was a very abundant oxide and
could be produced economically in pure form, cheap aluminum was im-
possible because of the high cost of metallic sodium and the aluminum
chloride. By 1886, the cost price of aluminum was reduced to $8 per
pound, still too high for common use.
The electrolytic reduction process developed by Charles M. Hall in
1886 brought the price down to $1 per pound. In 1943, the price for
aluminum ingots reached $.15 per pound. A question that might readily
arise here is, "can this cost be cut drastically so that aluminum and steel
are on an equal price basis?"
In 1893, less than 100 tons were produced in the United States; ten
years later domestic annual production increased to 3,000 tons. In 1915,
world production was 85,000 metric tons; in 1939 this had increased to
675,000 tons, of which the United States and Germany each were respon-
sible for 175,000 to 200,000 tons. The peak world production of aluminum
during the Second World War, in 1943 was 2,176,000 net tons, of which
considerably more than half was produced in the United States.
This country's consumption of aluminum in 1952 was distributed over
the following fields:
32% Transportation 10% Consumer Durables
15% Building Construction 6% Chemical Uses
14% Miscellaneous 6%
Machinery & Equipment
13% Electrical
4%
Packaging
It is interesting to note that, despite the fact that during the war
the output of aluminum expanded very much more than iron and steel,
the total production of primary aluminum in the United States for the
year 1943 was approximately equivalent to the average amount of steel
ingots produced in 3 working days during the same year. Reasons for this
great difference in production and cost may be deduced by
comparing
the properties of the high grade ores of each of these metals.
Aluminum Iron
Name b Source of Main U. S. Ore Bauxite (Arkansas) Hematite (Minn.)
Secondary ore Cryolite (Greenland) None
Combined water
<%)
25%
None
Combined metal
(%)
32% 50%
Density of ore
2.55 4.90
Light Alloys as Engineering Materials
131
The transportation
costs for the aluminum ores are higher due to the
greater distances involved and their higher bulking values. The aluminum
ores have specific gravity values near to that of the siliceous gangue
(2.2
2.3); this means gravity
concentration of the ore is difficult. The ship-
ping costs of bauxite are decreased by calcination of the bauxite to remove
water and other volatile matter. The lower percentage of aluminum in
the ore is another factor that leads to higher processing costs. A compari-
son of the Hall Process and the Blast Furnace Process will further bring
out the comparative
economics of these two commercial metals. A com-
parison of the costs of aluminum and steel should be made on the basis
of the finished
article and not on the relative price per pound of ingot
metal. Because the specific gravity of aluminum is approximately
one-
third that of steel, less aluminum by weight will be used. In addition
there are economies
that result from the unique
combination of the
properties
of aluminum,
namely,
(1) ease of fabrication,
(2)
good
machinability,
(3)
good surface color and polish,
(4)
low maintenance
costs,
(5)
low cost of distribution, and
(6)
high scrap value.
8.3. Aluminum
OresOccurrence and Concentration
Although
aluminum
occurs in nature in a higher percentage than iron,
the major
share exists in the form of clay. Bauxite, the principal ore of
alummum,
consists of a mixture of the mono- and tri-hydrate
of aluminum
oxide. Bauxite
has been formed in nature by the weathering of clay;
bauxite
deposits are found primarily in warm countries because high
temperatures and rainfall
accelerate this hydrolytic
degradation
of the
clay. The
main source of supply of high grade ore (50-65% alumina) in
this country is from Arkansas;
in South America
it is found in the
Guianas.
The impurities in bauxite
ore are the oxides of iron, silicon,
and titanium.
Since these impurities
are difficult to separate physically,
it is evident that
high-grade
deposits are very desirable.
Aluminum
is more
chemically reactive
than iron and silicon; therefore
it is difficult
and costly to remove these undesirable
impurities from
the crude
metal.
The Bayer
process is the most commonly
used process for the concen-
tration and
purification
of bauxite.
The fundamental
principle involved
in this process is "that alumina differs from these other oxides in being
amphoteric,
i.e., weakly acidic and basic."
Alumina will dissolve
in hot
concentrated
alkali but is insoluble
in cold dilute alkali. The steps in this
process are as follows:
(1) high-grade bauxite
is finely ground;
(2)
ore
is digested with hot, concentrated
sodium hydroxide
(caustic soda) to
form the soluble sodium
aluminate;
(3) the insoluble
(red mud) oxides
of iron, silicon, and titanium are filtered off;
(4)
the hot sodium alumin-
ate is diluted with water, seeded with crystals of alumina hydrate, and
allowed to cool;
(5)
pure hydrated alumina settles out; it is filtered off
and calcined to form alumina,
(6)
the filtrate is concentrated by evapora-
tion and used over again.
8.4. Manufacture of Aluminum
The electrolytic reduction process for the manufacture of aluminum is
dependent on the fact that anhydrous alumina dissolves in molten cry-
olite to give an ionic solution of high electrical conductivity. The passage
of direct current through this molten electrolyte deposits aluminum at
the cathode and oxygen at the anode. Since iron and silicon are objec-
tionable impurities, the iron cell must be properly lined with a material
of high purity and of a conducting nature so as to function as the cathode.
The anodes must likewise have similar properties. Ordinary carbon fulfills
the conductivity requirement but not the purity one. The lining of the cell
and the anodes are made from fabricated parts of petroleum coke. The
oxygen formed at the anode combines with the carbon to form carbon
dioxide gas; therefore, the cost of these electrodes is an important eco-
nomic factor.
When metals are manufactured by an electrolytic process, the weights
of the metals deposited are proportional to their equivalent weights.
The ratio of weights of some common industrial metals deposited by the
same amount of current vary in order listed: aluminum 9, magnesium
12.1, iron 18.6 and copper 31.8. It is evident that the economical manu-
facture of aluminum necessitates large amounts of low cost electrical
energy. Aluminum plants are therefore located near hydroelectric plants.
A measure of the relative manufacturing problems of iron and aluminum
is indicated by the listed data.
Aluminum Iron
(Hall process) (Blast furnace)
Type of operating unit Small, semi-batch large, continuous
Capacity of unit, per day 1000 lbs. 700-1500 tons
Lining of unit Petroleum coke Refractory bricks
Temperature of operation lOOO'C IfiOO'C
Weight of metal per lb. ore 50 lb. .63
II).
Weight of carbon per lb. metal. . . .75 lb. 8"i ll>.
Value of gaseous by-product . . . none 85 Btu/cu. ft.
Agent used to remove impurities. . . Caustic Soda Air, iron oxide
(Bayer Process)
Electrical Energy Requirements per
lb. metal 12 KWHr.
Energy requirements ratio
(theory) 5 1
Light Alloys as Engineering Materials 133
The aluminum produced by the Hall process consists of
99%
(mini-
mum) aluminum, the major impurities being iron and silicon. Aluminum
of high purity
(99.99%) may be obtained by an electro-refining process.
The cell used in the Hoopes process consists of three molten layers, the
bottom anodic layer of crude aluminum-copper alloy, the intermediate
layer of salts, and the top cathodic layer of pure aluminum.
8.5. Physical Properties of Aluminum
The most generally recognized physical characteristic of aluminum is its
low density. The lightest metal, magnesium, is two-thirds as dense as
aluminum (sp. gr. 2.70); whereas, iron and steel are three times as dense.
The density of most aluminum alloys range 2.70-2.80, which means that
aluminum and its alloys roughly weighs .1 lb. per cubic inch. The low
density of aluminum can be attributed to its low atomic weight
(27)
and its great chemical reactivity. These two properties in addition gener-
ally indicate such thermal properties as low melting point, high specific
heat, high heat of fusion, and high coefficient of thermal expansion.
The melting point (1220T.) and heat of fusion (94.6 cal.) are slightly
higher than corresponding properties of pure magnesium. Its very high
specific heat and its linear coefficient of thermal expansion are second
to magnesium. The high solidification shrinkage
(6.6%)
as well as its
"hot shortness" make the casting of pure aluminum rather unsatisfactory.
The electrical conductivity of metals, in decreasing order, are silver,
copper, gold, and aluminum. Pure aluminum has 64% of the electrical
conductivity of copper on an equal-volume basis but has a 212% value
on an equal-weight basis. It is therefore the best commercial electrical
conductor on the latter basis. The best thermal conductors, in decreasing
order, are silver, copper, gold, and aluminum; aluminum is the best
conductor on an equal-weight basis.
This parallelism between electrical and thermal conductivity is ex-
pressed by the Wiedemann-Franz law. Another relationship that appears
to be indicated is that these two physical properties are related to crystal
structure since all four of these listed metals have a face-centered crystal-
line structure.
The low density and melting point of aluminum are related to its prop-
erties of being soft (Brinnell Value
16)
and relatively low tensile strength
(8,500 psi).
In view of its low melting point and "hot shortness," the tensile
prop-
erties of aluminum rapidly decrease with a rise of temperature; therefore,
aluminum and many of its alloys are not well suited to elevated tempera-
ture applications. Aluminum and all of its alloys become stronger and
tougher at subnormal temperatures.
Aluminum is a very malleable and ductile metal; in fact, it is second
best of the commercial structural metals. These properties are related to
its face-centered cubic crystalline structure, for we note that copper,
silver and gold are very malleable and ductile and have face-centered
cubic structure. Under standard testing conditions, pure aluminum will
stretch 60 per cent of its length before breaking. With the combination of
high ductility, malleability, and strength, aluminum and its alloys are
adapted to working by most methods of forming and fabrication.
Due to the high degree of plasticity and relative chemical inertness to
normal conditions, aluminum can be easily finished to a high polish.
The brilliance of aluminum paint is due to the high reflectivity of the
finely divided flat flakes.
Aluminum is an excellent reflector of radiant energy of all wave lengths.
The high durability of aluminum paint is largely due to the efficient re-
flection of the ultraviolet rays; ultraviolet rays destroy the oil film in
paints and lead to loss of adhesion. Aluminum is used as thin films on the
reflectors of the most modern telescopes. Aluminum foil is important in
the thermal insulation field because of its high reflectivity of infrared
radiation.
Three important requirements of a molten metal for satisfactory casting
arc low surface tension, high fluidity, and relative chemical inertness.
Molten aluminum has a surface tension of 520 dynes per centimeter which
is one third that of molten iron, both at their respective melting temp-
eratures. Pure molten aluminum has a fluidity 50 per cent that of molten
tin; the normal impurities of commercial aluminum increase this value
to 70 per cent. Molten aluminum is protected from oxidation by a thin
oxide film; excessive agitation must be avoided to
prevent the removal of
this oxide film. Two other properties of molten aluminum contribute to
its poor castability, firstits reactivity with moisture to form aluminum
oxide and hydrogen, secondthe high selective solvency for hydrogen gas
which leads to high-porosity cast metal.
8.6. Chemical Properties of Aluminum
The very high solution potential of aluminum demonstrates that it is
the second most chemically active structural metal. In spite of this great
activity, aluminum offers great resistance to normal weathering. This
relative inertness can be attributed to the presence of a thin protective
and adhering oxide film. Other outstanding features of this oxide film
are its chemical inertness, water insolubility, ability to mend itself, and
its electrical and thermal insulation properties.
The chemical inertness of this film is indicated by fact that aluminum
tanks are used for storage and shipment of concentrated acetic acid,
dilute and concentrated nitric acid, and strong hydrogen peroxide.
When the oxide film, is removed, the active nature of the metal as-
serts itself; for example, caustic soda and strongly alkaline solutions
readily attack aluminum. When alkaline degreasing solutions are used to
clean aluminum, a corrosion inhibitor such as silicate of soda is added.
Aluminum in contact with mercury or its salts will show accelerated cor-
rosion due to the removal of the oxide film.
In the melting of aluminum and subsequent handling operations,
precautions should be taken to avoid, as much as practicable, contact with
moisture, water vapor, or other materials that will react with aluminum
to form hydrogen gas. The amount of dissolved gas can be kept at a low
amount by using a low temperature, short operating time, minimum agi-
tation, and low absolute humidity of the atmosphere.
The great affinity of aluminum for oxygen is illustrated in its use in
the steel industry. The amount of aluminum required for the deoxidation
of molten iron and steel is usually less than 1 lb. per ton. When 1-1
1/
2
lbs.
are used, the excess aluminum functions in another manner: it leads to
the subsequent formation
of a fine-grained
steel.
A similar deoxidation reaction is involved in the thermite welding and
repairing of large ferrous alloy sections, railway and street car rails,
etc. Thermite consists of a mixture of granulated aluminum and mill
scale. It is ignited by means of flashlight powder or another primer, which
leads to localized melting of the aluminum, followed by a violent reaction
to form aluminum oxide and molten iron. The excessively high tempera-
ture (4500F.) is due to the great heat of reaction, the low specific heat
of iron, and the absence of any volatile product. A modified thermite re-
action is often used in the manufacture of pure high-melting metals as
vanadium, chromium,
molybdenum, and manganese.
Atmospheric nitrogen is a very inert gas but will react with aluminum
and chromium, at elevated temperatures, to form metallic nitrides. The
presence of .851.2% aluminum in the nitralloy steel plays an important
role when being surface hardened by nitriding. The stainless steels and
other chromium alloy steels do not require aluminum for this purpose.
8.7. Aluminum Alloys
The important alloying elements used in the manufacture of aluminum
alloys are copper, manganese, magnesium, zinc, nickel, chromium, and
silicon. In special purpose alloys the elements titanium, tin, lead, and
bismuth are intentionally added. For example, lead and bismuth are
added to the extent of .5% each in the free machining alloy; those metals
are insoluble in aluminum and are therefore present as a colloidal
dispersion which functions as a lubricant.
The total alloy content of the wrought and casting alloys are usually
7%
and 16% maximum, respectively. The three main important strength-
giving elements in the wrought and cast alloys respectively are copper-
magnesium-manganese and
copper-magnesium-silicon. Silicon also plays
a very important role in the castability of alloys.
The individual alloys are designated by numbers, the wrought alloys as
a four digit number, and the cast alloys as a two- or three-digit number.
Two high-strength wrought alloys are 5056
(5%
Mg) and the 7075
(5%
Zn) ; the alloys that have excellent castability are 43, 355, 356.
There are two classes of wrought aluminum alloys:
(1)
alloys that are
not heat treated and that owe their properties to
strain hardening by
cold work,
(2)
alloys whose strength may be improved by heat treatment
and whose properties may be altered still more by cold deformation.
8.8. The Wrought Alloys
The various tempers of commercial wrought aluminum alloys until
recently have been designated by a system of numbers and letters. The
new temper designation consists of a letter indicating the basic temper
which may be more specifically defined by the addition of one or more
digits. The letter F means "as fabricated," O
"annealed, recrystallized,"
and H"strain hardened." The latter may be modified by numbers to
give a detailed meaning as per follows:
Strain hardened onlyHI, plus one or more digits.
Strain hardened and then partially annealed112, plus one or more
digits.
Strain hardened and then stabilized-H3, plus one or more digits.
In dealing with the heat-treatable type of alloys, the letter T
following
the alloy number signifies that it has been hardened by solution treatment.
The specific combination of basic operations is indicated by a number:
6061-T5 means that alloy 60G1 has been hardened by heat treatment
and
artificially aged. The various basic operations are as follows:
T2 Annealed (cast products only).
T3 Solution heat treated and then cold worked.
T4 Solution heat treated and naturally aged to substantially stable
condition.
T5 Artificially aged only.
137
Table
8.1 Temper Designations for Strain
Hardened Wrought
Aluminum Alloys
I hat Arc Not Heat
Treatable (*)
New Temper Designation({)
Strain Hardened
Strain Hardened
Old Temper
Strain Hardened
and then
and then
Destîahon
only
Partially Annealed
Stabilized
(Alloys 1100 and 3003)
14
H
-H12
-H22
'/2
H
-H14
_H24
*A
H
-H16
-H26
H
-H18
-H28
Extra Hard
(Not Standard)
-H19
(Alloys 3004, 5052,
5056J)
#{J
-HS2
% -H34
^
H
-H36
Extra Hard
(Not Standard)
H39
(
#
)
Alloys listed also available in -O and F tempers,
(t)
The tempers shown
are standard for the alloys listed.
(t)
The alloys
3004, 5052 and 5056 may also be obtained in the -HI and
-H2 type
Conditions.
'~
T6 Solution heat treated and then artificially

aged.
T7 Solution heat treated, then stabilized.
T8 Solution heat treated, cold worked and then artificially aged.

-T9 Solution heat treated, artificially
aged and then cold worked.
T10 Artificially aged and then cold worked.
W
Solution heat
treated-unstable temper.
In Tables
8.2 and 8.3 there are listed the important wrought
alloys in
order of their increasing
tensile properties,
together with other im-
portant physical
properties.
The number
of alloying
elements and total
alloy
percentage for the nonheat-treatable
are less than the heat-treat-
able alloys.
The
principal characteristic
of the wrought alloys, especially the heat-
treatable type, is their high strength-weight
ratio. The typical mechanical
properties of the annealed and fully hardened
alloys are listed in Tables
8.2 and
8.3. These
properties are applicable to room temperature
but are
satisfactory for the range from
about
0
to 150F. All of the aluminum
alloys become
stronger and tougher
at subnormal
temperatures.
Due
to the fairly rapid
decrease in tensile
properties, and
sometimes the de-
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velopment of hot shortness and/or excessive oxidation, all aluminum
alloys are not well suited for high temperature application.
The Brinell hardness of the wrought alloys (500-kg. load, 10-mm. ball)
varies from approximately 30 to 85 for untreated alloys and from 30 to
120 for the heat-treated material, depending upon the temper. Even the
hardest aluminum alloys are much softer than the softest steels. En-
durance limits (based on 500 million cycles) are low; the endurance ratio
is highest for the annealed alloys and is only about 0.25 for heat-treaied
high-strength sections. It is characteristic of the annealed alloys that the
endurance limit is higher than the yield strength.
The modulus of elasticity for tension or compression, measured in kips
per square inch, ranges from 10,000-10,600, except wherein the high
silicon
(12%)
increases it to 11,400. The values for the annealed and
hardened form of a particular alloy is the same. The modulus of elasticity
for shear, measured in kips per square inch, ranges from 3, 800-4000, the
high silicon alloy value being 4300.
The thermal and electrical conductivity of the wrought alloys are less
than the pure metal, the higher the alloy content the greater the lower-
ing. An annealed alloy has higher values than the strain hardened and/or
heat-treated alloy. The thermal coefficient of expansion per degree
Fahrenheit at room temperature is almost the same for most wrought alloy
varying from 124-135 x
10",
the only marked exception being when very
high silicon
(12%)
is present, when the value is 108 x
10-
7
. The cold
working of alloys does not appreciably change these values; whereas, heat
treatment makes an increase of several per cent.
The resistance to corrosion of aluminum alloys is usually very satis-
factory, the strain-hardening type alloys being generally superior to the
heat-treatable
type. The presence of relatively large amounts of coppcr
or zinc reduces the over-all resistance to surface attack. The resistance
to high temperature oxidation is best insured by the presence of the
alloying element nickel.
Maximum resistance to corrosion of the heat-treatable alloys is depen-
dent on the solution heat treatment being followed by a very rapid
quench; therefore, thick sections arc not as resistant as thin sections due
to their slower rate of quench. Artificial aging usually effects a marked
improvement in resistance to corrosion.
Some sheets, plates, and tubes arc produced with a surface coating of
pure or low-alloy aluminum that are metallurgically bonded to the core
during hot working. These coatings offer electrolytic protection to the
core against corrosion. This protection includes cut edges and areas
where the coating may be scratched or abraded.
8.9. Aluminum Casting Alloys
The casting alloys are designated by a number of two or three digits. In
some instances the number is preceded by a letter, which indicates a slight
variation in composition. For example, the three casting alloys 214,
B214, and F214 contain 3.8% magnesium but differ in the silicon content.
Casting alloys may be of two types:
(1)
the nonheat-trcatable alloys, and
(2)
the heat-treatable alloys. The condition of heat treatment is designed
by appending some symbol, as 195-T4.
The elements used in aluminum casting alloys are primarily copper,
silicon, and magnesium. The minor alloying elements are zinc, nickel,
manganese, iron, and tin. The requirements for the sand, permanent
mold, and die castings arc not necessarily the same, although many of the
alloys are used for both sand and die. The
5% binary silicon alloy is the
only listed alloy that is used for all three types of castings.
Aluminum finds little use in the production of castings because of its
low strength and inferior casting qualities. Two exceptions are the induc-
tion motor rotors and cable clamps, which require the higher electrical
conductivity of aluminum.
The commercial casting aluminum alloys and their important proper-
ties are listed in Table 8.4. Note that the total percentage of alloying ele-
ments is generally greater than that of the wrought alloys. Some of the
important characteristic properties of molten casting alloys such as good
fluidity, low surface tension, and low pouring temperature necessitate
a high percentage of alloying elements. The low temperature of solidi-
fication leads to low gas solubility and porosity, and fine grain structure.
The important casting characteristics for a sand and a permanent
die casting are
(1)
freedom from hot shortness,
(2)
low shrinkage
tendencies, and
(3)
pressure lightness. Low gas absorption is a very
important property for a sand-casting alloy. A die-casting alloy should
have freedom from hot shortness and mold-filling capacity.
Sand castings of almost unlimited size and shape can be made from
scores of aluminum alloys, each having unique properties or foundry
characteristics. Where only a few castings are required, or where the cast-
ing is relatively large, sand castings are indicated. On the other hand,
when large numbers of relatively small parts are required, or if a smooth
surface and a minimum amount of machining are desired, permanent-
mold or die castings are to be preferred. Some typical permanent-mold
castings are shown in Table 8.4. The method of casting, too, affects the
properties to be expected from a given composition, permanent-mold and
die castings usually having a somewhat higher strength than sand castings.
In general, when the number and the size of the castings to be made would
Light Alloys as
Engineering
Materials
141
justify the use of any of the three
methods, die castings
are the
cheapest
and can be cast to the
closest tolerances,
while sand castings
will cost the
most and will require the broadest
tolerances.
A comparison of the
mechanical and tensile
properties
of the sand
permanent
mold, and
die castings
is best made by listing the typical
values
for alloys
43.
Permanent
Sand
Mold
r)ie
Tensile strength
19,000
23000
Tensile yield strength
8,000
9 000
Elongation
(%
in 2")
8
'
10
Compressive
yield strength
9,000
9,000
30,000
16,000
10
9
Brinell
hardness
10
45
19,000
Shearing
strength
14,000
16,000
Although
the casting alloys
have a greater
alloy content than the
wrought, the
improvement
as compared with pure aluminum
is primarily
greater in the casting
properties rather
than the mechanical properties.
The
maximum
tensile strength
of the commercial
aluminum alloys in
the "as-cast"
condition for the sand,
permanent mold, and die castings are
approximately
27,000, 35,000, and
46,000 psi. respectively.
The
tensile
properties
of some casting
alloys are further improved by
solution heat
treatment.
This type of alloy contains
at least one con-
stituent whose solid
solubility is substantially
greater
at elevated
tempera-
tures than at room
temperatures.
The usual amount
of this alloying
element
,s such that it is completely
soluble
near the melting
point of
the alloy. Heat
treatment finds
limited
application
with die castings be-
cause
of blistering
and
possible loss in dimensional
accuracy.
The yield strengths
in tension
and compression
for the cast alloys are
practically
equal. The yield
strength
in compression
is very important
in the
design of some aircraft
structural
members. Some
special treat-
ments
are available
that raise the compressive
yield strength
to a value
almost
as high
as the tensile
strength.
For example,
sand casting alloy
*LZ
,
T6 3nd T62
condition
hav
*
ê respective
tensile
strengths
36,000 and
40,000 psi; the
compressive
yield strengths
under these condi-
tions are
respectively
25,000 and
38,000 psi.
The modulus
of elasticity of most aluminum
casting alloys is approxi-
mately
10,300 kips; therefore
this property
is about
one third
that of steel
The Brinell
hardness
of "as-cast" alloys range 40-70
(500-kg. load, 10-mm.
ball)
;
whereas,
for the
heat-treated
alloys the
hardness value is 75-100
The endurance
limits for the alloys
range
5,500-9,500 psi.
This gives an
endurance
ratio
of .25-.38 for cast alloys
and .17-28 for the
heat-treated
142
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143
alloys, based on a rotating-beam
test of 500 million cycles. These ratios
are one third to one half of those usual for carbon and low-alloy steels.
Inasmuch
as the total
percentage of alloying
elements is usually greater
in casting
alloys than wrought,
the melting point,
and the thermal
and
electrical conductivity,
are much lower for the former class. The melting
range and the specific gravity range
(2.66-2.92) are wider
for the casting
alloys because
of their higher alloy content. The
specific gravity and the
thermal
and electrical conductivity
values are lower for the die castings
than the sand and permanent
mold casting alloys.
Centrifugal
castings have been very
popular for many ferrous and non-
ferrous alloys because the molten metals and alloys are cleansed of oxides
and inclusions by the centrifugal
action thereby improving the mechanical
properties. The small differences in the specific gravity between
the usual
oxides and inclusion present in molten aluminum alloys makes this type of
casting of a limited advantage.
8.10.
Functions of Alloying
Elements
The advantages
and limitations
of commercial aluminum as a wrought
and cast metal
may be
summarized
as follows.
Its advantages as a
wrought
metal are high
electrical and thermal conductivity,
excellent
malleability and ductility,
excellent formability,
good machinability,
and
unusual
resistance to normal corrosion.
The limitations include low
tensile
properties,
poor high-temperature
tensile
properties, and high
temperature
brittleness. Molten
aluminum has the desirable properties
of low surface tension and good fluidity, the undesirable
properties are
high selective
hydrogen gas solubility,
high solidification
shrinkage, and
great
chemical
reactivity towards
air and moisture.
The cast metal has
the unsatisfactory
properties of high thermal
coefficient of expansion, hot
shortness, gas porosity,
and coarse grain structure.
The addition of the alloying
elements is primarily
to increase
the
tensile properties
and improve certain
fabricating
qualities of the
wrought
metal; they function
to increase
tensile strength and castability
of the alloy casting. Such alloying
always results
in the improvement
of some
properties and in the further
limitation of others. The changes
involved
depends upon the type and amount of alloying
elements, the
resulting
grain structure, size and distribution
of insoluble
constituents,
homogeneity,
etc.
Copper.
The most important
and commonly
used alloying element is
copper.
The intermetallic
compound CuAU
forms a eutectiferous
series
with aluminum;
the eutectic alloy contains
33% copper and melts at
548C. The maximum solubility
of copper in solid aluminum at elevated
temperatures is 5.65% and less than .25% at room temperature. The
copper content of the high-strength wrought alloys usually ranges between
4-4.5% copper. Although tensile properties increase progressively above
this range, higher copper alloys are not commercially practicable because
of difficulty in working. The high-strength alloys of this type include
alloys 2011, 2017, and 2024.
The electrode potentials of commercial aluminum and the intei metallic
compound CuAl
2
are .84 and .53 volts respectively. This relatively
great difference means that the corrosion resistance of the copper alloys is
much less than those of the other alloying elements. Improper heat treat-
ment of the copper-aluminum alloys can further decrease their resistance
to corrosion.
Copper used as an alloying element in the casting alloys leads to in-
creased fluidity and decreased surface tension of the molten metal. The
cast metal is improved by the freedom from hot shortness, decreased
porosity, increased tensile properties, and finer grain structure.
Silicon. The second most important alloying element in aluminum al-
loy is the metalloid silicon. It differs from the other soluble alloying ele-
ments in not forming an intermetallic compound with aluminum. It
forms a eutectic having the composition of 11.6% silicon by weight and
melts at 577C, The solubility of silicon in solid aluminum at the
eutectic and room temperatures are 1.65% and less than .05%. Although
silicon is a rather hard constituent, it is evident that due to its low
solubility and inability to form an intermetallic compound, the binary
silicon alloys are not markedly strong. A comparison of the strength
giving properties of silicon and copper is given by the tensile yield
strength values of the sand casting alloys #43
(5%
Si) and #195 (4.5%
Cu) , namely 8,000 and 34,000 psi respectively.
Silicon plays an extremely important role in the casting alloys. Its im-
portant contribution to the molten alloy are very high fluidity and
low solidification shrinkage. The shrinkage of an
8%
silicon-aluminum
binary alloy is 5.6%; the 11.6% silicon-aluminum alloy (eutectic) is
3.8%. The presence of silicon influences the properties of the solid cast
metal in having a lower coefficient of thermal expansion, absence of hot
shortness, and a lower degree of porosity. An unusual property of silicon
in a casting is to form a sound outer layer or skin which leads to pres-
sure tightness. The silicon alloys 43, 355, and 356 give excellent sand and
(>ermanent mold castings. The two die-casting silicon alloys, #13 and
#360 are very satisfactory.
The ability of silicon alloys to "undercool" leads to the modification
of the normal eutectic composition and its properties. In 1921 A. Pacz
145
discovered that very rapid cooling or the addition of .05%
metallic
sodium (or sodium fluoride) results in the formation of eutectic alloys
containing as high as 14%
silicon, having a freezing point 10-15 degrees
lower than normal. This modified alloy has a finer grain structure; it is
stronger and more ductile than the eutectic alloy.
The silicon content of wrought alloys is usually less than 1%: one
exception is the forging alloy 4032. The presence of silicon in the heat
treatable wrought alloys generally increases their response to artificial
aging.
The presence of silicon in aluminum alloys does not materially decrease
its corrosion resistance, probably due to the formation of a protective
siliceous film. The 5%
binary casting alloy #43 and wrought alloy
4032 resist atmospheric weathering, chemicals and food acids. Inasmuch
as silicon and aluminum are both amphoteric, this type of alloy is not
very resistant to alkaline conditions and solutions.
The strength and corrosion resistance of silicon-aluminum alloys
are markedly increased by the presence of magnesium due to the forma-
tion of the intermetallic compound Mg^.Si.
Magnesium. The eutectic of magnesium and aluminum contains ap-
proximately
33%
magnesium and the melting point is 451 C. The
solubility of magnesium in solid aluminum at the eutectic and room temp-
eratures is 14.9% and less than 4%
respectively. This variation in the
solid solubility with temperature renders some of the alloys susceptible to
improvement in tensile properties by heat treatment.
The electrode potential of 4% magnesium-aluminum solid solution is
approximately equal to that of aluminum; therefore this type of alloy
shows excellent corrosion resistance. In addition, these alloys show the
highest resistance to alkaline corrosion, such resistance increasing with
magnesium content.
Binary alloys containing more than 4.5% magnesium are susceptible to
stress-corrosion cracking particularly when they are in the cold worked
condition. This corrosion is due to the fact that the insoluble phase is
highly anodic to the
4%
magnesium-aluminum solid solution. The
electrode potentials of the two components are respectively 1.07 and
.87 volts. This stress corrosion is prevented by the addition of small
amounts of manganese and chiomium.
Magnesium is second to silicon in effectively increasing the fluidity of
molten alloys. The fluidity of the binary
6%
magnesium alloy is approxi-
mately the same as the binary
5%
silicon alloy.
Magnesium is a more reactive metal than aluminum; therefore it reacts
more readily with air and moisture. Molten casting alloys of magnesium-
aluminum form considerable dross, a tendency that increases with mag-
nesium content. Alloys containing 5% or more magnesium cast in ordi-
nary green sand molds show surface discoloration and porosity, particu-
larly when thick sections are involved. High magnesium-aluminum
should be heat treated in a controlled atmosphere or for a minimum of
processing time so as to avoid surface oxidation.
Magnesium ir Silicon. The magnesium silicide forms an eutectic with
aluminum containing
13% Mg
2
Si and melts at 595C. When an excess of
silicon (over that required to form the magnesium silicide) is present, a
ternary eutectic of aluminum, Mg
L
.Si and silicon results, melting point
550C. The composition of this ternary eutectic is approximately 13%
silicon,
6% magnesium and 81%
aluminum.
The Mg,Si constituent in the binary alloy has a maximum solubility in
solid aluminum of 1-85% at the eutectic temperature and less than .2%
at room temperature. These alloys have the ability to respond to heat
treatment and have tensile properties comparable with those of the heat-
treated
4%
copper alloys.
The corrosion resistance of this type of alloy is very satisfactory be-
cause the electrode potential of Mg
2
Si (.83 volt) is almost the same as
aluminum. Alloys of this type, such as alloys 6053, 6061 and 6151, differ
from most other heat treatable alloy in showing no appreciable decrease
in corrosion resistance after heat treatment.
Manganese. Manganese and aluminum form an eutectic containing
2.2% manganese by weight and melting at 657C. The intermetallic com-
pound of these metals has the formula MnAl
e
. The solubility of man-
ganese in the solid aluminum at eutectic and room temperatures is .65
and less than .1 respectively.
This low solubility indicates that the most common manganese alloy
3003 (1.25% Mn) is a non-heat-treatable alloy. The electrode potential
of this intermetallic compound is the same as aluminum, therefore this
alloy has exceptional corrosion resistance. Inasmuch as manganese and
its compounds are not toxic, this alloy is used in equipment for preparing
and processing of foods. It is also used extensively for the manufacture
of cooking utensils, conduit and pipes, pressure vessels, architectural ap-
plications and builders hardware.
Nickel. Nickel forms an eutectic: with aluminum which contains 6.5%
nickel and melts at 640C. The composition of the intermetallic com-
pound is NiAl
t
. The solubility of nickel in solid aluminum at the
eutectic and room temperatures is .06%, and less than .04% respectively.
The addition of nickel to the copper-aluminum type alloys definitely
improves the high temperature properties and retains the high thermal
properties. The forging alloys 2018, 2218 and 4032 are ternary alloys
of aluminum, copper and nickel. Their uses are for forged cylinder heads
and pistons, jet engine impellers and compressor rings and other applica-
tions wherein high strength at elevated temperatures is necessary.
Zinc. Aluminum and zinc form an eutectic consisting of 95% zinc and
5%
aluminum, melting point 440C. The solubility of zinc in solid
aluminum at the eutectic and room temperatures is
70%
and
18% respec-
tively.
Zinc is a low melting and highly volatile metal. One important limita-
tion of binary and complex zinc-aluminum alloys is their great loss in
strength at elevated temperatures. For example, castings made from A612
and C612 are not recommended for use at temperatures greatly in excess
of 200F.
These casting alloys have the marked advantage that without heat
treatment they have tensile properties comparable with the aluminum-
copper and aluminum-silicon heat treated alloys. They offer the advan-
tage that they can be heated to the temperature required for brazing
and will regain their original properties after a few days. The zinc
wrought alloy 7075 has very good strength and good resistance to cor-
rosion. This wrought alloy in the T6 condition in extrusions has a tensile
and yield strength of 88,000 and 80,000 respectively.
8.11. Cold and Hot Working of Aluminum Alloys
The purpose of cold working in the fabrication
of sheet, rod, wire,
tubing, extrusions, and like basic products are
(1)
increased tensile
properties,
(2)
grain refinement,
(3)
improvement in surface appearance,
and
(4)
improvement of dimensional properties.
Aluminum and its alloys on cold working undergo strain hardening.
The tensile properties increase with the amount of work, in some in-
stances almost proportional to the fractional reduction of the initial
Alloy
3003-O
3003-H-12
3003-H-I4
3003-H-16
3003-H-18
Alclad
202-1
-T4
2024-T3
2024-T36
2024-T81
2024-T86
Elongation
Tensile Strength Yield Strength
%
in 2 in.
1G.0OO 6,000 30
19,000 17,000 10
21.000 19,000 8
25,000 22,000 5
29,000 26,000 4
64.000
42.000 19
64.000
44,000 18
67.000
53,000 11
65,000 60,000 6
70,000 66,000 6
148
cross section. The elongation decreases with increasing amount of cold
work. As a general rule the initial cold work produces a relatively greater
effect than subsequent reductions of equal amounts. The effect of cold
work is listed for the two types of wrought alloys.
The degree of strain hardening in aluminum and its alloys has an im-
portant effect on their temperature of recrystallization. It is usual to make
50% or higher reduction in cross-sectional area between annealing or heat
treating operations in order to prevent the development of excessively
large grain structure.
In the fabrication of the commercial basic products there is an improve-
ment of the surface properties due to tool surface and shape, lubricants
used, and the burnishing effect obtained by the cold work. The greater
the degree of reduction and the inherent hardness of the alloy, the
brighter the surface.
Straightening
and flattening operations are performed cold and are
usually conducted so as to introduce a minimum of strain hardening.
Plate, rod and bar are hot worked nearly to the desired thickness, followed
by cold work to obtain greater dimensional accuracy.
The cast aluminum ingots are hot worked to convert them to wrought
structures. Hot working is carried out during the manufacture of extru-
sions and forgings. The hot working of aluminum alloys require about
30-40% more power than for steel. Extrusions are made in the shape of
rods, bars, and complicated cross sectioned materials. The extruded
section is highly fibrous in structure which is parallel to its direction of
extrusion, therefore the tensile properties are often much higher than
other hot- or cold-worked products of same alloy.
Another difference between aluminum and steel is that aluminum does
not form scale during heat treatment; therefore a suitable lubricant
should be used during hot rolling. Die lubricants are generally used
during hammer and pressing forging; extrusions usually do not require
lubrication.
8.12. Heat Treatment of Aluminum Alloys
The three basic types of thermal processing that are commonly applied
to aluminum alloys are
(1)
annealing,
(2)
solution heat treatment, and
(3)
precipitation heat treatment.
The strain-hardening which results from cold working of the aluminum
alloys may be removed by annealing. The annealing process likewise re-
moves most of the temper resulting from solution heat treatment. This
thermal treatment permits recrystallization to take place; the higher the
temperature used, the greater the rate. The rate of recrystallization is
also dependent upon the alloy involved and the severity of the cold work.
Complete annealing is almost instantaneous
for alloys 1100 and 5052 at
650F., and for alloy 3003 at 750F. The rate of cooling thereafter is not
critically important although rapid cooling may lead to some distortion.
The temperature used for annealing the heat-treatable type of aluminum
alloy must be carefully controlled and as low as practicable so as to
prevent the dissolving of the intermetallic compound. Castings of non
heat-treatable alloys are often annealed for the purpose of relieving in-
ternal strains, increasing their ductility and shock resistance.
Some alloys are improved in strength and hardness by heating in the
range of 900-1000F., given a rapid quench, and then aged at room temp-
erature and/or
at slightly elevated temperatures. The alloy after quench-
ing has fair ductility and malleability and is subjected as soon thereafter to
forming or other fabricating processing. Some alloys spontaneously in-
crease in tensile properties within a short period of time; other alloys age
so slowly that they are artificially aged by heating in the range 250-400F.
Such heat-treatable alloys contain a principal alloying constituent
that has a marked increase in solid solubility at elevated temperature.
In most instances this alloying constituent is an intermetallic compound.
The 4i/
2%
copper-aluminum alloy 2024 has CuAlj as its hardening
agent; its solid solubility at room and elevated temperatures is
.25% and
5.65% respectively.
All this intermetallic
compound goes into solid
solution at elevated temperatures and continues to remain in solution
after rapid quenching
due to the marked decreased mobility of the sys-
tem. This unstable supersaturated solution has good ductility and mal-
leability; therefore it is formed into proper shape as soon as practicable.
During the next few hours fine precipitation of submicroscopic particles
of this hard intermetallic compound takes place, progressively increasing
the tensile properties.
Other heat treatable alloys such as 6061 undergo a similar transition
during heat treatment and quenching, but differ in the respect that the
rate
of precipitation of submicroscopic
particles is extremely slow at
room temperature, therefore it is artificially aged by heating in the range
of 250-400F. The alloys normally hardened
by room temperature aging
may be further increased
in tensile properties
by this artificial aging.
The time required to reach the maximum strength by artificial aging
decreases as the aging temperature is raised; the value of the maximum
strength, in turn, decreases. The precipitation of the hardening con-
stituent from solid solution that results from artificial aging is accom-
panied by small changes in specific gravity and therefore dimensional
properties. The
5%
and
6%
copper-aluminum
alloys after artificially
150
aging show a decrease in length of approximately .01% and .15%
respectively.
The response to artificial aging for alloy 2024 is greatly enhanced if
the material is strain hardened after solution heat treatment and prior
to precipitation heat treatment. In this instance the increase in tensile
and yield strengths is more than doubled by a reduction of 6% by cold
working prior to artificial aging.
The percentage of alloying elements in casting alloys is higher than
for wrought alloys, therefore the solution heat treatment time for cast-
ing is much longer. The greater uniformity and the finer grain structure
of wrought alloys results in a greater degree of improvement in tensile
properties by heat treatment for the wrought alloys.
The solution heat treatment of alloys containing high amounts of
magnesium should be done with proper atmosphere control so as to
prevent possible oxidation along the grain boundaries. This oxidation
condition is manifest by minute surface blisters, decreased tensile prop-
erties and embrittlcment. The time of solution heat treatment of clad
alloys should be kept at a minimum so as to prevent changes in composi-
tion and electrode potential properties of the surface coating due to alloy
diffusion from the core.
The cooling rate during quenching is often critical. The alloy 2024,
improperly quenched, forms a non-uniform precipitation of microscopic
and larger size particles of AIXu which makes the alloy susceptible to
localized corrosion.
8.13. Corrosion Resistance of Aluminum Alloys
The excellent corrosion resistance of aluminum and its alloys is due
primarily to the adhesion and chemical inertness of the oxide film.
Inasmuch as this aluminum oxide is a nonconductor of electricity it
differs from iron rust (cathodic) in not causing galvanic corrosion.
Galvanic or "battery action" type of corrosion is encouraged wherein
the alloying metals or their intermetallic compounds have electrode
potentials much different than the base metal. The solid solutions and
the insoluble intermetallic compounds of manganese, chromium, mag-
nesium and MgoSi have electrode potential values almost equal to alu-
minum; therefore alloys involving these constituents show good corrosion
resistance. The solid solutions of copper, and the insoluble constituents
FeAl
s
, NiAl
3
, CuAl
2
and Si, have much lower solution potentials than
aluminum, therefore alloys of these constituents show only fair resistance
to corrosion.
The poor corrosion
resistance of the improperly quenched
aluminum
copper alloys is due to its heterogeneous nature. Alloy 2024 on solution
heat treatment and properly quenched consists of a uniform supersatu-
rated solid solution; its homogeneous nature makes it very resistant to
corrosion. The subsequent aging of the alloy leads to the uniform precipi-
tation of submicroscopic intermetallic
compound which also shows good
resistance to corrosion. When the alloy is quenched slowly, the CuAL
precipitates
out at the grain boundaries as non-uniform microscopic and
larger sized particles. The phase adjacent to the cathodic intermetallic
compound consists of areas of depleted solid solution (anodic). The
localized corrosion that lakes place in this alloy is termed intergranular
corrosion.
When a mild quench is necessary, the resistance to corrosion
may be
increased if the alloy is subsequently artificially aged. In the case of thick
sections, the rate of cooling, even by immersion in cold water, is often
not great enough to produce material
completely free from susceptibility
to this
intergranular attack. This condition
may also be discouraged
by the use of alclad materials.
One of the most effective methods for increasing corrosion resistance
of
an aluminum
alloy is to use alclad material or by applying a surface
coating of pure or low alloy aluminum.
The surface layer must be
anodic to the base metal, hence the protection is both mechanical and
electrolytic. The present products available with this type of cladding
are sheet, tube and wire. One limitation
of this type of product is that
during heat treatment,
temperature and time should be very carefully
controlled
so as to avoid excessive alloy diffusion into the clad layer,
thereby decreasing its effectiveness in protecting the core from corrosion.
Alclad 2024 sheet improperly heat treated should be checked by proper
tests for excessive
"copper diffusion."
Another commercial
process used to protect aluminum alloys from
corrosion is by the surface oxidation by electrolytic
means. The process
is known as anodization
because the aluminum is made the anode and
the iron tank the cathode, the processing
solution being dilute sulphuric
or chromic acid. The anodic film is thicker
and more uniform than the
natural oxide film; therefore it has increased
corrosion resistance, electri-
cal insulation,
abrasion hardness and chemical inertness. An unusual prop-
erty of the anodic film, especially right after its formation, is its great
power of adsorption. The excellent
anchorage power of anodized alu-
minum for paint films and dyes is dependent
upon this great power of
adsorption.
Chromic acid dip treatment, anodi/ation, painting with zinc chromate
primer, and other like processing and treatments of aluminum alloys are
based on the passivation action of chromic acid and chromates, and
their adsorption in the oxide film. When an aluminum alloy in use
shows excessive corrosion, this condition may be stopped by cleaning
area, painting with chromic acid solution, drying and then painting.
It is important that aluminum assemblies should consist as much as
possible of the same alloy or alloys of like solution electrode potential.
Rivets should be of the same alloy as the base metal, and if different,
should be of an alloy that lias a slightly lower potential so that the
rivets would be cathodic.
Galvanic corrosion can be markedly retarded
if the rivets can be electrically insulated by anodic treatment. Welding-
rods should likewise be of the same alloy or of slightly lower potential
than the base metal. Inasmuch as brazing and soldering involves foreign
metals, adjacent areas must be carefully protected from galvanic corrosion.
When two metals are involved that have marked difference in potential,
it is good practice to coat one with a metal intermediate in electrode
potential value. The steel cable used in aluminum cable for transmission
of electric current is plated with zinc to discourage galvanic action.
8.14. Joining of Aluminum Alloys
Aluminum and its alloys are usually joined by fusion and electric-
resistance welding, brazing and riveting. Brazing differs from welding
in that the filler material has a much lower melting point that that of the
parent material so that the latter does not melt.
The common types of fusion welding are the gas and the arc processes.
The three brazing processes are classed by the methods used in applying
the brazing heat, namely, furnace, torch, and dip brazing. The electric
resistance welding is classified as spot, seam, and flash.
The main difference in the welding technique and procedure of alu-
minum and its alloys as compared to the iron alloys is primarily due to the
very high thermal coefficient of expansion and high temperature oxida-
tion of aluminum, and thermal and electrical insulating pro]>erties of its
oxide coating.
The high thermal expansion of aluminum and its alloys necessitates
the use of properly designed parts and carefully prepared joints so as to
minimize buckling and distortion. The filler rod and the base metal
are both provided with a flux coating to maintain an oxide-free metal
surface during the welding process. The commercial flux materials
consist of mixtures of saline chlorides-fluorides. -Proper ventilation must
be provided in the welding area because the fumes of the flux are both
153
disagreeable
and irritating to the welder and highly corrosive to nearby
metal structures and materials. The welded part must be given a mechani-
cal cleaning or chemical pickle treatment so as to completely remove
residual saline material due to its toxic and corrosive character.
Gas welding
involves the use of oxyhydrogen and oxyacetylene torches,
the flames in both instances being neutral in character.
The gas welding
has its main application with materials ranging from .0401 inch in thick-
ness.
The main arc
processes include metal, carbon, atomic hydrogen, and
tungsten
arcs. The metal-arc is particularly suitable for heavy material;
thicknesses up to
21/g
inches have been welded satisfactorily. Difficulties
are experienced when the metal-arc is used with material less than 5/64
inch thick. The carbon-arc is used for manual and automatic welding;
the produced welds are comparable in structure and appearance to gas
welds but with less distortion. The atomic hydrogen process is applied
in much the same manner as gas welding but differs in the respect that it
is possible to control the heated zone by moving the torch away from or
towards the work. One limitation of the atomic hydrogen-arc process
is the difficulty of removing the residual flux from the welded assembly.
The tungsten
arc uses an inert gas shield to protect the arc and the weld
area; this method has two advantages:
(1)
satisfactory
welds can be
made with equal facility in vertical, flat, and overhead positions, and
(2)
no flux is required.
All commercial alloys are not readily adaptable to fusion or electric-
resistance welding.
The alloys that are commercially fusion welded are
1100, 3003, 5052, 6053, and 6061. In some instances the welding is
difficult and/or costly. One limitation
of the heat-treatable type of alloys
is that the high temperature of welding tends to decrease the mechanical
strength and the corrosion
resistance.
The proper choice of welding
rod is very important particularly when
dealing with alloys having large amounts of alloying elements.
The two
most weldable alloys 1100 and 3003 use 1100 welding rod. The high-
strength alloys
5052, 6053, and 6061, fairly difficult to weld, are welded
with
5%
silicon-aluminum
alloy filler
rod. This 4043 alloy rod has a
melting point much lower than pure aluminum, excellent fluidity and
wetting properties, and low shrinkage contraction, thereby insuring a
minimum
of shrinkage stresses and cracks.
One of the important
applications of fusion welding
is the salvaging
of aluminum alloy castings that have foundry defects, and the repairing
of cracked or broken castings. Castings should be preheated in a furnace
to approximately
800F. This thermal treatment avoids thermal stress,
reduces the welding time and amount of welding gas required. It is
important that careful temperature control is maintained during this
preheat treatment so as to avoid "burnt" material and possible collapse
of the casting.
The areas adjacent to the welded sections of the strain-hardened alloys
are annealed by the welding heat. The weld metal has tensile properties
almost equal to the annealed metal but lower in ductility. Assemblies of
heat-treatable alloys should be welded prior to heating or given a reheat
treatment so as to improve the tensile and corrosion resistance properties.
Electric-resistance welding has been a large factor in reducing the cost
of making joints, improving products, and speeding up production.
This type of welding is usually applied to strain-hardened type of alloys,
but is often used with the heat-treatable alloys particularly of the alclad
type.
The technique and equipment employed for the resistance welding of
aluminum and its alloys is considerably different than that used for steel.
In addition the electrical capacity required for aluminum is several
times greater. The three types of equipment are classified on the basis
of the electrical system used for supplying the welding current, namely,
(1)
alternating current,
(2)
magnetic energy storage and
(3)
condenser
energy storage. The proper choice of electrode shape and its proper
maintenance is very important in obtaining high quality and strength
spot welds. The welding electrode must have high electrical and thermal
conductivity and fairly good strength; electrodes are usually made of
copper-silver alloys. Weld pick-up and the softening of the tip are pre-
vented by having cold water circulating through the electrode. Some
machines use refrigerated water circulating at a rate of 2 gallons per
minute and to within 3/8 inch or closer of the tip face.
The material to be welded must first be freed of oil and grease, dirt,
and surface oxidation because these substances have electrical insulating
properties. The surface contamination may be removed by an alkaline
degreasing bath whereas the oxide coating necessitates mechanical abra-
sion or chemical etch methods. The metal must be spot welded within
a few hours of chemical etch because the oxide film will reform.
Bra/ing has been used in production on certain alloys such as 1 100 and
3003, and to lesser degree on the heat treatable alloys 6053 and 6061.
The copper-aluminum alloys and 5056 show poor workability during
brazing operations; the resulting joints and adjacent areas have decreased
tensile strength and corrosion resistance. The advantages of brazing as
compared to gas and arc welding are as follows:
(1)
it can be used with
thinner material,
(2)
the costs are lower, and
(3)
the surface appearance
155
is superior. The torch-brazed joint has the tensile strength comparable to
a weided joint and has almost the same degree of corrosion resistance.
Riveting is the most commonly used industrial method of joining the
structural aluminum alloys, particularly the heat-treatable type. The
rivets are made of commercial aluminum, the magnesium-silicon alloys
6053 and 6061, and the copper alloys
2017, 2024, and 2117. All except the
first are received from the manufacturer in the hard, heat-treated condi-
tion. Rivets of 2017 and 2024 are solution heat treated, quenched, and
driven as quickly as possible; whereas, the other type of rivets are driven
"as received."
It is advantageous
from a strength point
of view to use rivets having
about the same mechanical properties as the base metal; whereas, from
the driving standpoint it is usually advisable to have the rivets somewhat
softer. From the corrosion resistance angle it is advisable
to have the
rivet of the same composition or electrode potential as the material in
which it is driven. For example, alclad sheet alloys are usually riveted
with 6053 or 6061 because of their excellent corrosion resistance and
nearness to aluminum in their electrode
potential value.
Rivets that are solution heat treated prior to driving arc generally
processed in large quantities, quenched in cold water, washed with
alcohol, and placed in refrigerated cabinets. Solution
heat treated 2017
and 2024 alloy rivets harden at room temperature over a two-hour period,
making them unsuitable
for driving thereafter. The rivets will remain
soft for
36 hours if kept
at 32F., or lower, after
quenching. Small in-
sulated
boxes of cold rivets are kept in refrigerated
cabinets near the
individual work areas.
Large rivets
of 2017 alloy are usually driven in the hot condition. They
are solution heat treated
at 930-950F. for approximately fifteen minutes,
inserted in the hole and driven. The relatively cold driving tools and the
base metal function
as quench. Steel rivets in aluminum-alloy
structures
are driven hot in the customary fashion;
they are heated to I800F. and
driven as quickly as possible.
When the service conditions
are severe or dissimilar metals are in-
volved, special
treatments should be applied to prevent corrosion. Vari-
ous methods are used, such as application
of zinc chromate primer prior
to assembly,
use of good grade of joint compound before assembly, use
of anodized aluminum alloy rivets; and if steel rivets are involved,
they
are metallized
with aluminum or zinc after driving.
8.15. Magnesium
And Its Alloys
Magnesium is a very
unusual metal: its
properties do not run parallel to
any other commercial
metal, and its behavior is not as predictable.
Mag-
nesiuni holds the unique position among the structural metals in having
the lowest density, the highest machinability, and has an inexhaustible
source of supply.
The low specific gravity of magnesium
(1.74) means that it is 2/3 as
dense as aluminum and
1/4
that of iron and steel. The cutting speed for
magnesium and its alloys is twice that of free-cutting brass and four times
that of cast iron. Seawater contains 1 part in 770 of magnesium therefore
one cubic mile of seawater could produce nine million tons of magnesium.
There is also a vast supply of magnesium in magnesite and dolomite.
Magnesium is similar to aluminum in its low melting point, high
solidification shrinkage, hot shortness, low tensile strength near the melt-
ing temperature, good thermal and electrical conductivity, low density,
high strength-weight ratio, and non-magnetic and non-sparking prop-
erties. From a chemical point of view these two metals have low atomic
and equivalent weights, and high electrode potentials. It markedly
differs from aluminum in its crystal structure, (H. C. P.) , fair malleability
and ductility, fair cold workability, poor notch sensitivity, non-protective
oxide coating, and lower corrosion resistance. Magnesium is much more
chemically reactive than aluminum due to the physical and chemical
nature of its oxide coating.
The manufacturing procedures and processes of magnesium are very
much like that of aluminum in the respect that fl) the impurities must
be removed from the ore rather than from the produced metal,
(2)
re-
quires large amounts of energy,
(3)
requires high temperatures, and
(4)
reduction involves nonaqueous reactions.
The most important commercial process for making magnesium is by
the electrolytic reduction of molten solutions of magnesium chloride.
The formed molten magnesium floats on the surface and must be pro-
tected by an inert atmosphere since it chemically absorbs both oxygen
and nitrogen. Another limitation of this (Dow) process is that the
chlorine constitutes a health and corrosion hazard.
Two lesser important processes are the chemical reduction of mag-
nesium oxide by carbon and silicon respectively. In the carbothermic
(Hansgirg) process, briquets of magnesium oxide and carbon are
heated at 2000C. to form magnesium vapor and carbon monoxide gas.
This reaction mixture on cooling would reverse to the original raw
materials; this is prevented by rapidly cooling and diluting with natural
gas or other inert gases. The fine magnesium powder that results by this
"shock" action must be purified by distillation. The Pidgcon process
depends on the fact that silicon in the form of ferrosilicon will remove
the oxygen from magnesium, that the formed silicon dioxide is a non-
157
volatile material, and metallic
magnesium under reduced pressure can
be distilled
at 1150C. The Hansgirg
and Pidgeon
processes are more
expensive than the Dow process, but have the advantage of not depending
on electric
power.
The
improvement
of magnesium
by addition of alloying elements is
not very great. The main alloying
elements are aluminum,
zinc, and
manganese.
Zinc is more effective than aluminum in the improvement
of mechanical properties
but offers the disadvantage of decreasing its
corrosion
resistance.
A compromise is often made by using both. The
alloy
AZ-63 consists of
6% aluminum and
3% zinc. The main function
of manganese
is to increase
the corrosion
resistance.
The minor alloying elements
are beryllium,
calcium, cerium, silicon,
tin, and zirconium.
Beryllium decreases
the tendency
of burning during
the melting
and casting.
Calcium reduces oxidation during melting and
heat treatment, and increases the reliability
and formability
of mag-
nesium sheet.
Cerium increases
the high temperature strength. The
main function
of silicon is to increase the fluidity of molten magnesium
and to decrease the hot shortness and cracking tendencies of the solid
metal. Tin increases ductility,
and zirconium
leads to grain refinement.
The very
undesirable
elements and
their approximate
maximum tolerance
are copper
(.1%),
nickel
(.01%) , and iron
(.005%)
.
Magnesium
alloys are
somewhat difficult to roll; therefore structural
members are usually extruded.
Cold working, bending,
and deep drawing
can be satisfactorily
accomplished
under carefully
controlled conditions
and with frequent
annealing.
Most mechanical processing is done at
temperatures
above
225C.
Pure
commercial
magnesium sheet in the annealed and hard-rolled con-
ditions have the respective
tensile strength values of 27,000 and 33,000
psi. Most magnesium
alloys have tensile strength in the range of 40-50
thousand psi, and the maximum
of sixty thousand. Special costly alloys
containing
3%
silver
or
6% cerium have tensile strength of sixty-five
thousand.
The
heat-treatment
processes of magnesium alloys is similar to that of
aluminum
except the
temperatures involved are
considerably lower. The
readiness
with which magnesium
oxidizes
in the air means that special
precautions
and new techniques
are involved.
Although aluminum
and
its alloys
may be heat treated in molten sodium nitrate baths, violent ex-
plosions
may take place with the alloys of magnesium.
One
outstanding
advantage of magnesium and its alloys is its excellent
machinability.
Cutting fluids are used primarily
as a coolant to prevent
the magnesium
from catching
on fire. The turnings from machining
158
operations also represent a potential fire hazard. Dry sand should be
available in these areas because water or the common fire extinguishers
are unsatisfactory for putting out magnesium fires.
The casting of magnesium likewise requires special conditions.
Molten magnesium is usually protected by an inert atmosphere of sulphur
and sulphur dioxide. Green sand castings can not be used unless inhibitors
are present; otherwise the magnesium will react with the moisture. The
subsequent finishing of the casting involves metallic dust that represents
a fire hazard.
The corrosion resistance of magnesium and its alloys under normal con-
ditions is very satisfactory. Under highly humid conditions and other
severe conditions, magnesium and its alloys should have a protective film
or coating. Magnesium alloys prior to fabrication are usually shipped
with a film of oil or a chrome pickle treatment coating. The chrome
pickle is superior to the oil film for protection, but the former is easier to
remove prior to spot welding.
Magnesium alloys may be joined by gas and arc welding, electric-resist-
ance welding, and by riveting. Most of the wrought alloys can be joined
by gas welding using neutral flames of oxyhydrogen, oxyacetylene and
oxycarbohydrogen
.
The filler rod should have the same composition as the parent metal
or have a lower melting point. A flux must be used during welding due
to the ease of oxidation of magnesium. Magnesium alloy sheet, extru-
sions, forgings, sand and permanent mold castings are often welded by
using an inert gas-shielded arc method. These alloys may be resistance
welded after they have been cleaned of surface contamination and oxide
coatings. Magnesium may be riveted by the most conventional methods.
Magnesium-alloy rivets cannot be used because of their rapid work
hardening at room temperature. The rivets generally used are the
5%
magnesium-aluminum alloy 5056, which has a like electrode potential.
Most processed magnesium alloy parts and assemblies that will be used
where corrosion is greater than normal are given a final chromate treat-
ment. The chromate treatment results in the removal or passivation of all
foreign metals and produces an adhering protective coating. This coating
offers good anchorage for a paint film.
8.16. Beryllium
Beryllium resembles magnesium in its low density
(1.84) , its hexagonal
close-packed crystalline structure, and its poor cold workability. Its
similarity to aluminum is shown by its low equivalent weight, its ampho-
teric properties, and the refractory and protective nature of its oxide film.
The outstanding property of beryllium is its great power of producing
159
hardness and strength in other metals; it suffers the two great limitations
of high cost and toxicity. Its cost is high because
(1)
its ores are not
common,
(2)
the concentration
of beryllium in the ores is often less
than
4%
average,
(3)
its manufacture by the modified thermite or Gold-
schmidt process is a costly one.
The most important alloy of beryllium is the beryllium-copper alloys,
which have high fatigue and corrosion resistance, good electrical and
thermal properties, and are virtually non-sparking. The
2% alloy on
heat treatment, quenching, and aging develops a hardness equal to Rock-
well C-40.
Amounts
in the order of .01% beryllium in molten aluminum and
magnesium decrease their oxidation and combustibility markedly, and
reduce their viscosity, particularly in the case of aluminum. Small amounts
of beryllium
may be used to case-harden iron and steel.
The
vapors and powdered beryllium are very toxic and give rise to lung
diseases that are often fatal. Beryllium is available commercially in the
form of
12% beryllium-copper
alloy.
8.17. Titanium
Titanium in one of the most abundant metals in the earth's crust, the
main ores being ilmenite
(iron titanate) and rutile (titanium oxide)
.
It is made by the modified thermite
or Goldschmidt process.* The very
important
properties of titanium as a structural metal are its high melting
point
(1820C.)
,
its high tensile strength
at ordinary and elevated temp-
eratures, its relatively low density
(4.5) , and its high resistance to ordinary
corrosion. In the annealed and cold-worked
(60% reduction) condition
the commercial
metal has the respective tensile strengths
78,700 and
111,500 psi. Exposure to accelerated corrosion tests using salt spray for
30 days has little effect on commercial titanium.
Titanium,
like magnesium
and beryllium,
has the hexagonal close-
packed
crystalline
structure; therefore its workability likewise at ordinary
temperatures
is poor. When titanium
is heated to 875C, it undergoes
a transition
to an body-centered
cubic structure; hence its workability
markedly
increases at this
temperature. There is a 5.5% volume change
during this allotropic
transformation.
One limitation
of titanium is
that it will readily
unite with and burn in oxygen
at 600C. and with
nitrogen
at 800C. At elevated
temperatures titanium will likewise unite
with carbon and hydrogen.
Titanium is a very important
additive element in the steel industry.
The great affinity
of titanium
for carbon is taken advantage of and
carbide
precipitation avoided in 18-8
stainless steel by the presence of
titanium,
the amount being about five times that of the carbon content.
* And now produced widely by the Kroll process.
The presence of .5-1% titanium in 17-7 stainless steel leads to a ferritic
structure. The grain refinement of aluminum and its alloys by the
presence of small amounts of titanium is due in part to its great affinity
for dissolved oxygen, nitrogen and hydrogen. Titanium acts likewise as a
scavenger for oxygen and nitrogen in steel.
QUESTIONS
1. What is the .most abundant metal in the earth's crust? What is the metal
that is inexhaustible in its supply?
2. Magnesium oxide has been reduced industrially by the action of carbon
to form metallic magnesium. Why cannot aluminum be economically made
in the same manner?
3. What impurity as a metal oxide, if present in bauxite ore, could not be
removed in the Bayer Process?
i. Aluminum is often melted in iron pots which are usually protected by a
coating of whiting or other insulating material. Why is this protective coat-
ing important?
5. The general rule regarding gases is "they decrease in solubility in liquids
with rise of temperature." How would you explan why the solubility of
hydrogen increases with rise of temperature when present in molten
aluminum?
6. Accurate control of temperature is very important during the solution heat
treatment of aluminum alloys. What are the relative advantages of a molten
bath and an air furnace?
7. What test solution would you use on a large assembly to determine whether
it was an aluminum alloy or a magnesium alloy?
8. What are the main obstacles of manufacturing aluminum from clay?
9. Excessive rates of heating metal lead to cracking. In view of the fact that
aluminum alloys are good conductors of heat and that the nitrate bath is a
fair conductor, why is the heating in this bath still rather slow? (What in-
sulation film is involved?)
10. The processing room wherein the Hall process is conducted must be pro-
vided with good ventilation. What gas and vapor must be conducted away?
11. Why does the presence of high silicon in aluminum alloys lead to superior
fluidity? To lower degree of contraction?
12. How do you explain why magnesium has the highest machinability among
the commercial metals? Why arc its turnings so much more combustible
than those of aluminum?
13. Why should the heat treatment of magnesium be made in an air furance
rather than a molten nitrate bath?
14. Aluminum sheet arrives at the plant with fine (tissue) paper between each
sheet. Give three reasons why this has benefical results.
15. After aluminum has been anodized, and then given cold and hot rinses, it
should be painted within one hour thereafter. Why should this time be
important?
16. What precaution should be made regarding machining or processing of
beryllium alloys?
17. How do you account for the fact that titanium has high strength at elevated
temperatures?
18. Chlorine gas is passed into molten aluminum on two occasions. What are
two conditions that are eliminated by this action. Give reasons for both.
CHAPTER
Copper and Copper -Base
Alloys as Engineering
Materials
Waiter R. Hibbard,
M.S., Adjunct Associate Professor
of Metallurgy, College of Engineering, University of
Bridgeport, Bridgeport,
Connecticut
Roger Greenleaf Stevens, Ph.D., Head, Department of
Chemical Engineering, Southwestern Louisiana Insti-
tute, Lafayette, Louisiana
1 HESE metals are such an integral, but com-
monly unnoticed, part of our daily life that even the housewife in the
kitchen and the clerk in the store would find it difficult to establish a
new routine of existence if copper suddenly disappeared from the world.
Judged solely from the standpoint of absolute value to mankind, copper
and its common alloys, the brasses and the bronzes, cannot compete with
carbon steels, but each is of vital importance to our civilization and
could hardly be eliminated without destroying or at least seriously
crippling most branches of industry.
It has been said with justification that electricity is the elixir vitae of
machine civilization.
It is difficult to conceive of an electrical industry
if copper and its ores had never been known, unless nature had provided
man with a substitute of equal conductivity, plasticity, and cost. Second
only to high conductivity in importance is the resistance of copper and
some of the copper-rich alloys to corrosion in certain environments,
especially sea air and sea water.
The average automobile
uses 45 lb. of copper and its alloys, the
average steam locomotive 4,500 lb., and the modern steamship more than
3 million lb. as castings, in pipes and tubes and in electrical equipment.
No metal has proved so suitable for steamship propellers as manganese
bronze; four of these, weighing
37 tons each, drove the Queen Mary
across the Atlantic Ocean in four days.
With two or three exceptions, the copper and copper-rich alloys dis-
cussed in this chapter have been important engineering
materials for
161
'62
years and, unlike some of the light alloys discussed in the previous
chapter, are covered by specifications of the American Society for Test-
ing Materials.* In addition, most of them also conform to specifications
adopted by the Society of Automotive Engineers, the Association of
American Railroads, the American Society of Mechanical Engineers
(Boiler Construction Code)
, the American Standards Association, the
U.S. Navy, and the U.S. Army, and to general federal specifications.
These standardsespecially those issued by A.S.T.M. -should be con-
sulted for exact chemical composition and for minimum mechanical-
property and other requirements which must be met before the material
can be considered to be of good commercial quality.
Although copper is present in the earth's crust to the extent of only
0.01 per cent, ore deposits of commercial importance are fairly wide-
spread. Compared with iron ores, copper-ore deposits of commercial
quality are lean. The ores of the United States contain on an average
somewhat less than 2 per cent copper. In the important ores, copper
occurs as the oxide, carbonate, silicate, and sulphide, of which the last
named is the most abundant. In some parts of the world, notably in the
vicinity of Lake Superior, long weathering of copper ores followed by
reduction of the resulting oxide or the carbonate, or the deposition of
copper from solution, has produced large deposits of relatively pure
native metal, which was distributed far to the south by the glaciers.
Native copper was the only metal (except small quantities of meteoric
iron) used by the American Indians for tools and weapons until the
white man arrived.
The production of high-purity copper from lean sulphide ores is a
complex process, but copper exceeding 99.9 per cent purity can be pro-
duced cheaply. In brief, the process consists of concentrating and roast-
ing the complex sulphide ore (copper, plus iron, plus other metals) to
form oxides and to eliminate some of the sulphur and arsenic as the
oxide. The roasted concentrate is smelted with coke and a flux in a
reverberatory furnace to remove part of the iron. The copper and iron
sulphides fuse into a matte containing about 40 per cent copper. This
matte is charged into a Bessemer converter and is blown in a manner
similar to the refining of pig iron to produce Bessemer steel. The copper
and the remaining iron sulphides are oxidi/ed, and the iron oxide com-
bines with silica to form a silicate slag. The result of these reactions is
"blister copper" containing 95 to 97 per cent copper and considerable
copper oxide.
'Sec A. S. T. M. Standards, Part 2, 1955.
Copper and Copper-Base Alloys 163
In addition to copper oxide, blister copper generally contains small
amounts
of sulphur, iron, lead, arsenic, antimony, selenium, tellurium,
nickel, and other elements, usually including some gold and silver. In
some ores, in fact, the silver and gold are worth so much that the copper
could be called a by-product of the refining of the more precious metals.
Although
the amount varies, a typical anode melted from blister copper
frequently
contains 30 oz. of silver and nearly i/
2
oz. of gold per ton.
The final step in refining is melting and casting the blister copper into
blocks which
are electrolyzed.
Electrolytic copper contains 99.95 per
cent or more copper, with sulphur as the principal impurity. About 25
per cent of the electrolytic
copper produced is used for making copper-
base alloys; the remainder is melted in a large reverberatory
furnace,
oxidized to remove sulphur, and then "poled." This consists of inserting
green wood poles beneath the surface
of the molten metal. In the re-
action between
the wood and the molten copper oxide enough oxygen
is removed so that the remainder, 0.03 to 0.04 per cent, when evolved
during
solidification,
exactly balances the normal shrinkage of the metal.
Poled copper is known as "tough-pitch."
Its density in the cast condition
is approximately
8.5 gm. per cu. cm., compared with 8.94 for the pure
metal. Tough-pitch
copper is used for wire for electric
conductors, for
sheets, and for many other purposes.
Lake (Superior)
copper, which constitutes
about 15 per cent of the
commercial copper in the United States, is-as previously
mentioned-a
high-purity
native copper and does not usually need electrolytic refining.
It differs from electrolytic
copper in that it may contain a small amount
of silver (which does not affect conductivity)
and from 0.002 to 0.04
per cent or even more arsenic, which, in the higher
amounts, may reduce
relative conductivity
as much as 40 per cent.
A recent development
in copper refining is the production of oxygen-
free copper.
Oxygen in tough-pitch copper is present as cuprous oxide
particles,
which are almost completely insoluble
in the solid metal. For
most purposes this oxide
is not harmful, but if extremely high ductility
is essential,
the copper should be practically free from oxygen. The oxide
is also harmful if the copper is heated in an atmosphere
containing hy-
drogen
as this gas diffuses
into the metal, reacts with the oxide, and
causes
brittlencss. There are two types of oxygen-free copper. The more
common
one is produced
by deoxidizing
the molten metal with phos-
phorus or some odier element having
a high
affinity for oxygen. The
residual
phosphorus,
although only about 0.02 per cent is present, reduces
the electric conductivity
as much as 20 j>er cent. To produce high-con-
ductivity
oxygen-free
copper (known
as OFHC) , very pure copper is
164
melted and cast in an atmosphere free from oxidizing gases. A recent
innovation
consists of granulating brittle copper cathodes, which have
been deposited electrolytically and which are free from oxygen, followed
by "coalescing" these in a press at high temperatures, which welds the
particles together and extrudes the metal as a solid bar.
Copper is malleable and is hot and cold worked into sheet, plates,
tubes, and a variety of other shapes. As in the case of most other metals
and alloys, cold working increases strength and reduces ductility.
9.1. Properties and Uses of High-Purity Copper
Copper has the highest electric conductivity of all the common metals.
On a strength basis, its conductivity is more than twice that of high-
purity aluminum. About one half of the 800,000 tons of copper consumed
in the United States in the average peacetime year is used for electrical
equipment and for wire in light and power lines. When annealed, high-
purity copper has a conductivity of 100 per cent according to a standard
set up in 1913 by an international commission. Recently improved
methods of purification have resulted in conductivities as high as 102
per cent.
Copper is also the best heat conductor of any of the commercial metals,
which makes it (and its alloys) useful as cooking utensils and as radi-
ators and other heat-dissipating apparatus. In general, copper and the
copper-rich
alloys have excellent resistance to corrosion by the atmos-
phere and by water. Owing to this corrosion resistance and to a reason-
able price, copper and some of its alloys are widely used by the building
industry for roofing, down-spouts, gutters, screens, drainage and water
pipes, and for hardware and interior fixtures. When exposed to the
atmosphere for long periods, copper oxidizes and forms a green patina
which is ornamental in addition to being adherent and protecting the
underlying metal from further attack. Approximately 10 per cent of the
copper consumed annually is used by the building industry.
Copper and copper-rich alloys have a wide range of mechanical prop-
erties. Annealed high-purity copper has a tensile strength of approxi-
mately 30,000 lb. per sq. in., an elongation in 2 in. of about 60 per cent,
and a reduction of area of as much as 90 per cent. It is, therefore, weaker
and more ductile than high-purity iron. At the other extreme, precipita-
tion-hardened copper-beryllium alloys may have a tensile strength of
190,000 lb. per sq. in. with accompanying low ductility.
The tensile strength of high-purity copper may be increased to 65,000
or 70,000 lb. per sq. in. by drastic cold working; elongation is lowered
Copper and Copper-Base Alloys
165
to about
5 per cent. According to Gillett,* the endurance limit of an-
nealed
tough-pitch copper is approximately
10,000 lb. per sq. in., and
cold working
increases it to as much as 20,000 lb. per sq. in. The modulus
of elasticity is approximately
16 million lb per sq. in. The damping
capacity is almost
as high as that of cast iron.
For some applications
the low strength of high-purity
copper wire is
a distinct disadvantage.
Unfortunately,
most alloying elements added
to increase strength reduce conductivity to a fraction of the value for
high-purity copper. A satisfactory compromise
between increase in
strength and decrease in conductivity
results from the addition of small
amounts of cadmium.
1100
40 50 60
Zinc,
per cent
%
V
100
Frc. 9.1. The copper-zinc phase diagram. (A. Phillips and R, M.
BricKft
9.2. Constitution of the Common Copper-Rich
Alloys
None of the four series of important binary copper-rich alloysnamely,
copper-zinc, copper-tin,
copper-aluminum,
and copper-nickel-can be
heat treated in the sense that sterling silver or many of the aluminum-
rich alloys can be heat treated.
Sections of the copper-zinc
and the
copper-aluminum
diagrams arc given in Figs. 9.1 and 9.2. Most of the
useful alloys of copper
with zinc (brass) and of copper with aluminum
H. W. Gillett, Metals and Alloys, v. 3, 1932, p. 200.
\
Metals Handbook, American Society for Metals, Cleveland, 1939,
p. 13G7.
166
(aluminum bronze) contain less than 40 per cent zinc and less than 10
per cent aluminum respectively and are, consequently, ductile single-
phase alloys consisting of a solid solution of zinc or of aluminum in
copper. If the zinc in brass exceeds about 35 per cent, beta phase
appears, reducing ductility and impact resistance. Only one such alloy,
Muntz metal, containing -10 ]>er cent zinc, is used widely, and in this
the amount of beta is so small that ductility is not seriously affected.
Similar to conditions in the copper-zinc system, most of the wrought
aluminum bronzes are single-phase alloys containing 5 to 9 per cent
aluminum (see Fig. 9.2) . If the alloy contains more than 9.5 per cent
aluminum, beta phase appears, reducing the ductility. Although the beta
phase cannot be retained in solution by quenching, there is the possibility
of securing transition structures by quenching a wrought alloy containing
10.5 to 1 1 per cent aluminum. The result is a tensile strength of 100,000 to
110,000 lb. per sq. in. and an elongation of 10 to 15 per cent, as com-
pared with 65,000 to 85,000 lb. per sq. in. and 35 to 50 per cent elonga-
% Atomic Percentage Aluminum
_5 K> JS 20 2S SO
Weight Percentage Aluminum
Fig. 92. The copper-rich portion of the copper-aluminum phase diagram.t (W. L.
Fink, L. A. Willey, and C. S. Smith)
ilbid., 1948, p.
1160.
167
tion for the alpha-phase alloy. No precipitation hardening is possible
in the binary copper-rich copper-aluminum alloys.
The principal commercial copper-tin alloys are alpha-phase alloys
and contain 1 to 10 per cent tin and usually also zinc, lead, or both. The
only important binary alloy is phosphor bronze which contains 4 to 10
per cent tin and which is deoxidized in melting with a small amount
(less than 0.5 per cent) of phosphorus. Tin increases the hardness and
strength
of copper. A cold-rolled phosphor bronze used for springs has a
tensile strength of about
100,000 lb. sq. in. with 5 per cent tin; this
increases to 120,000 lb. per sq. in. with 10 per cent tin. No heat treatment
is possible with commercial copper-tin alloys.
Copper and nickel form a continuous series of solid solutions free from
any phase change. The strength of the solid solution of nickel in copper
increases with the nickel from about 35,000 lb. per sq. in. for very low
nickel
to 80,000 for 60 per cent nickel; elongation decreases from 70 to
45 per cent in
2 in. There are a large number of important copper-nickel
alloys which, owing to their controllable color, to their corrosion resist-
ance, or to their thermoelectric
properties, are used for coinage, orna-
mental metal work, ship construction
(
especially in parts exposed to salt
water)
,
thermocouples, and in other special applications. An alloy higher
in nickel, Monel metal-containing
65 per cent nickel and 35 per cent
copper-is widely used because of its high resistance to many corrosive
mediums.
9.3. Nomenclature
of the Copper-Rich Alloys
Although the copper industry is no worse than the steel industry in
the use of trade names and in confused nomenclature, so many mis-
named alloys are commonly used that some attention to this subject
seems advisable.
The most common examples of confused nomenclature
are calling a copper-zinc alloy bronze if it has a color resembling that of
the copper-tin alloys
and calling a copper-zinc-nickel
alloy nickel silver
if it has a silvery-white
color. This confusion is regrettable, but in most
cases nothing can be done about it, as the names are firmly fixed by
years of usage. The important fact to remember about the copper-rich
alloys is that the name may be more descriptive of color than of composi-
tion, and that a "bronze" may contain
no tin and may even be a brass;
likewise, nickel silver contains no silver.
The usual name and the typical compositions
of some common copper-
rich alloys are given in Table 9.3. It is evident that manganese bronze
(item
43)
,
hardware
bronze (item
19) , and commercial bronze (items
9
and
10) are in reality brasses. The only true bronzes given in Table
168
9.3 are items 49 to 59, which are copper-tin alloys deoxidized by phos-
phorus. Nickel silver, formerly known as German silver, is the name
of a group of brasses, containing 17 to 42 per cent zinc, in which a con-
siderable part of the copper is replaced by nickel. The composition of
four of these alloys is given in Table 9.3. Another example of confused
nomenclature is the casting alloy containing 85 per cent copper and 5
per cent each of zinc, tin, and lead. As this alloy contains 5 per cent
tin, it is as much of a bronze as it is a brass, but it is called red brass*
and is, consequently, sometimes confused with wrought red brass which
contains 85 per cent copper and 15 per cent zinc.
9.4. Characteristics and Uses of the High Brasses
As shown by the diagram in Fig. 9.1, 39 per cent zinc dissolves in
copper at room temperature. Alloys containing less than this percentage
of zincwhen in a state
of equilibriumare, therefore, single-phase solid
solutions and are known as alpha brasses. As shown also by Fig 9.1,
alloys containing about 36 to 39 per cent zinc may have a duplex structure
if heated to a high temperature but should be single phase at room
temperature. Actually, however, owing to a phenomenon known as cor-
ing, cast alloys usually have a duplex structure if the zinc is higher
than 31 or 32 per cent. A zinc content of 35 per cent is about the maxi-
mum for an alloy that is to be fabricated as a single-phase material.
Although there is a continuous series of alpha brasses containing from
5 to 39 per cent zinc, these alloys are commonly and arbitrarily divided
into two classes: high brass, containing 30 per cent or more zinc, and
low brass, containing approximately 25 per cent zinc or less (Table 9.3)
.
Since zinc is cheaper than copper, it follows that high brass is used as
widely as possible, and that the zinc content is usually close to the upper
limit, which is about 35 per cent.
Although the alpha brasses can be hot worked commercially if they
are free from lead, they are not so plastic at elevated temperatures as
the beta alloys. In common with most solid solutions they are, however,
plastic at room temperature and can be readily drawn, rolled, or spun
into a variety of shapes. In fact, these alloys combine a degree of plas-
ticity, strength, ductility, corrosion resistance, pleasing color, and low
cost unattainable in any other material of engineering importance. Alloys
13, 14 , 2 9 are used for a large variety of cast and wrought sections,
especially hardware and pipe fittings, for tubes and pipe, for ornamental
The casting alloy containing 85 per cent copper and 5 per cent eacli of tin, zinc,
and lead is also known as composition metal and in many foundries as ounce metal
because the composition corresponds approximately to 1 lb. of copper. 1 oz. of tin.
1 oz. of zinc, and 1 oz. of lead.
169
sections and building trim, for cartridge
cases, automobile radiator cores,
grillwork,
springs, screens, and tor many kinds of nails, screws, and
rivets.
Many
copper-zinc alloys are used because of their color, as stated
previously.
They change from warm red copper color of copper to com-
mercial
bronzes (Tables
9.3 items 9 and
10) which have a bronze color to
red brass (item
11) which is reddish hence its name. Some of these alloys
in the above range
duplicate the color
of gold alloys and are used for
manufacture of gold filled metals. Then comes low brass (item
12)
whose
color is pinkish, to cartridge brass (item
13) which is yellow, to
yellow brass (items
14 and
15) which are greenish-yellow
and finally to
Muntz metal (item
16) which has the color of cast statuary bronze.
Muntz metal and its modification,
manganese bronze (item 16 and 48,
Table
9.3)
,
usually contain beta phase at room temperature
(see Fig.
9.1)
,
which
reduces plasticity when the alloys are cold. These materials
are, however,
characterized
by extreme plasticity
at a red heat and can
readily
be extruded or rolled.
Owing to their resistance to atmospheric
and water
corrosion,
these two alloys, especially manganese bronze,
are used extensively
for extruded or hot-rolled pipes and condenser
tubes.
Muntz metal is now being
replaced, particularly
for condenser
tubes in marine equipment,
by a brass known as admiralty metal. This
contains
not less than
70 per cent copper, 1 per cent tin, and the re-
mainder zinc.
Other than for
condenser tubes, admiralty metal,
so
called because it was developed
by the British Admiralty, is used for
preheaters,
evaporators,
air-conditioning
equipment, and in other appli-
cations where high
resistance to salt water, fresh water, oil, or steam is
required.
Admiralty
metal is an alpha-phase
alloy and is not so easily
hot worked
as Muntz
metal and manganese
bronze, but it is readily
worked when cold.
In genera],
the machinability
of the annealed,
non-leaded
brasses is
about
the same as that of low-carbon steel, in other words, they are too
soft and gummy to be cut readily.
Cold working, however, improves
ma-
chinability,
which is also greatly
improved by adding lead. Item 29
(Table
9.3) can be machined
readily in automatic
machines. If this
alloy is given a machinability
rating of 100, the same brass containing
only
1
per cent lead
will have a rating of 70 (determined
under the same
conditions),
and item H without
lead-will have a rating
of only 30.
However,
lead reduces
the yield strength; it also makes the brass more
difficult to deform
cold and makes it virtually
impossible
to work the
alpha-phase
alloys
at elevated
temperatures.
170
9.5. Characteristics of the Low Brasses and the Nickel Silvers
As the amount of zinc in brass is reduced, the yellow color changes to
red. Items 8, 9, 10, 11, and 12 (items 9 and 10 are called bronzes
because of their color) are used for hardware, ornamental and architec-
tural sections, wire for screens, and for costume jewelry, in addition to
being used for tubes, pipe, radiator valves, and other fittings for low-
pressure water and steam. An advantage of the low brasses is that, when
the copper exceeds 80 per cent, the alloy is not subject to "season crack-
ing," a phenomenon prevalent in the high brasses when they are exposed
to a combination of corrosion and stress. Season cracking is the spon-
taneous failure of the stressed material after a considerable time in a
corrosive environment, especially in atmospheres containing ammonia.
The time element depends upon the severity of the stress and the severity
of the corrosion. Stress caused by cold working, or applied externally, is
necessary for failure of this type.
The low brasses, like the high brasses, are readily deformed cold pro-
vided the lead content is low. Also like the high-zinc alpha brasses, they
are difficult to hot work although commercial bronze (item 9, Table
9.3) can be rolled or pierced and, to a limited extent, pressed or ex-
truded, provided that more than traces of lead are absent.
Most nickel silvers have a copper content of 45 to 65 per cent. A
fairly common alloy is the one containing 75 per cent copper, 20 per
cent nickel, and 5 per cent zinc, usually sold under the trade name
Ambrac. All the nickel silvers can be classed as low brasses containing
nickel. If the copper plus nickel exceeds 63 per cent, the alloys contain
only alpha phase. They can be hot worked readily only if the zinc is
about 40 per cent or less than
10 per cent, but they can be
cold worked easily.
Nickel silvers are valuable
because of their white color, a
corrosion resistance that is
generally superior to that of
the common brasses, good
mechanical properties, and
moderate cost. The effect of
composition on color is shown
by Fig. 9.3. The nickel silvers
are used chiefly for ornamen-
tal work as a base for silver-
and gold-plated ware.
f
* *
Nickel.per cent
Fig. 9.3. Effect of composition on the color
of nickel silver. (Kihlgren)'
171
9.6. Properties of the Wrought Brasses
Some typical tensile properties of wrought brass and nickel silver are
collected in Table 9.3. As the commercial copper-zinc alloys do not
respond to heat treatment, variations in properties are obtained by cold
working and annealing which results, as in the case of some of the alumi-
num alloys, in various tempers, ranging from soft to half-hard, to hard,
and to spring temper. With the possible exception of manganese bronze
and nickel silver, the tensile strength of all the annealed brasses is very
similar to that of annealed or hot-rolled low- or medium-carbon steel,
but the yield strength is much lower. As the brasses cost five to ten times
as much as low-carbon steel, the chief justification
for the widespread
use is, of course, then ease of working cold, their pleasing color, and
their corrosion resistance, especially to water and steam. In general, the
low brasses are more corrosion-resistant
than the higher zinc alloys,
especially in impure water and in salt water. The high brasses, in addi-
tion to being subject to season cracking
are also subject to "dezincifica-
tion," or removal of the zinc, when the alloy is exposed to impure water
or salt water. The action is apparently
electrolytic and leaves a spongy
mass of copper.
Dezincification can cause failure in a relatively short
time. Alloys containing
20 per cent or less zinc are not usually subject
to this form of corrosion.
Manganese bronze has high resistance to salt
water but
may be subject to season cracking
and dezincification.
The endurance limits
of the brasses are low, ranging between 10,000
and 20,000 lb. per sq. in. for 100 million cycles, which is equivalent to
an endurance ratio of 0.20 to 0.35, or about half that of steel. Annealed
brasses have a definite yield point (as evidenced by the drop of the
beam) but cold-worked
alloys have not. Values for yield strength reported
in the literature are usually the stresses causing an extension
of 0.5 per
cent under load. These values are usually much lower than the yield
strength of steel which
corresponds to a permanent elongation of 0.2
per cent of the gage length. The modulus of elasticity
(secant modulus,
see
p. 65) varies from 15 million lb. per sq. in. for the copper-zinc
alloys and for manganese bronze to about 19 million lb. per sq. in. for
nickel silver. The
mechanical properties of brass and of nickel silver
are affected
by grain size which, in the case of worked material, depends
on annealing
temperature. Material with large grains has lower strength
and higher
elongation than fine-grained
material (except in very thin
strip)
.
T. E. Kihlgren,
Metals Handbook,
American Society for Metals, Cleveland 1939
pp.
1443-1445.
9.7. Cast Brass and Cast Nickel Silver
There are at least a thousand varieties of brass that are melted and
poured into sand molds. Most of these, however, fall into the nine gen-
eral classes of alloys for which specifications have been issued by the
American Society for Testing Materials, the Society of Automotive En-
gineers, or by the United States government. Some typical compositions
and properties of the most commonly used alloys are collected in Table
9.1* The properties of cast brass are determined on test bars cast
separately from the same metal (A.S.T.M. specification B208-46T) and
tested either with or without machining their surface.
As shown by the data in Table 9.1, the cast brass, with the exception
of manganese bronze, are relatively weak and ductile and have a very
low yield strength. Nickel silver has better properties than the copper-
zinc alloys containing no nickel, and when the zinc is omitted completely,
as in the case of cupronickel, the properties are even better. The nickel
silvers are, however, considerably more costly than the other brasses.
The cast brasses are easily machinedespecially when they contain
considerable lead, as most of them doand have a high resistance to
corrosion in many environments. They are, therefore, widely used for
architectural and ornamental castings, especially hardware and statuary;
fittings and other parts exposed to sea, air, and water or steam; plumbing
fixtures for water; valves and other parts in chemical equipment; laundry
and dairy equipment; and many others. Nickel silver is a favorite casting
alloy for automobile and household hardware and for industrial use
where alkaline waters or chemicals are encountered.
9.8. The Copper-Base Bearing Metals
The principal copper-base bearing metals (bearing metals are dis-
cussed more fully in Chapter 10.) are those in Class C of Table 10.2.
On a tonnage basis this group is more widely used than the others.
According to Clamer.t about 10 million lb. of alloy CI (either deoxi-
dized, or not, with less than 1 per cent phosphorus) is used annually in
the United States. The leaded bronzes, alloys CI to C5 and C8 and C9,
are employed by the railroads and the automotive industry; alloys C2
and C3 are suitable for small bushings and bearings; others are better
Cast Metals Handbook, American Foundrymen's Association, Chicago. 3rd ed,,
1914,
pp.
604-648.
t G. H. Clamer, Metals Handbook, American Society for Metals, Cleveland, 1939,
pp.
1428-1429.
173
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fitted for general-service bearings; alloy C5 is suitable for high speeds
and low bearing loads, and CI for moderate speeds and heavy loads.
The properties of the copper-tin-lead alloys vary with composition.
At room temperature, the property ranges for alloys CI to CIO, inclusive,
are as follows:
Property
Range
of values
Tensile strength, lb. per sq. in
28,000 to 40,000
Yield strength, lb. per sq. in
14,000 to 18,000
Elongation in 2 in., per cent
1 to 20
Compression, lb. per sq. in., for a deformation of 0.001 in 10,000 to 13,000
Brinell hardness (500 kg.)
55 to 75
The hard bronzes (alloys C6 and C7, and alloy CI as well) are used
in castings for movable bridges and turntables which act as bearings
subject to slowly or intermittently applied heavy loads. Most of the
alloys in group CI to C7 are used as large bearings ("brasses") in loco-
motives. Alloys CI, C8, and C9 are used extensively by the automotive
industry.
The high-lead alloys C10 and Cll are a fairly recent development and,
as steel backed, are used in internal-combustion engines for aircraft and
automobiles, trucks, and tractors. These alloys are inferior in tensile
properties to the other copper-rich alloys: tensile strength varies from
12,000 to 22,000 lb. per sq. in.; yield strength from 5,000 to 10,000 lb.
per sq. in.; elongation from 5 to 12 per cent; and Brinell hardness
(500
kg.) from 25 to 40. In general, however, they are superior to the white
metals; their melting temperatures are much higher, and their properties
are not so much affected by temperature. They are also resistant to re-
peated flexure which is important with present-day engine speeds. Most
important, if lubrication fails momentarily, the heat generated by the
friction sweats out a film of lead which acts as a lubricant and prevents
seizure.
The railroads were the first to use the high-lead alloys on a general
scale, adopting alloy C5 for a large number of bearings. In airplane
and automobile engines, these alloys are now used for crankshaft, drive-
shaft, and connecting-rod bearings. The most recent development is the
addition of 1 to 2 per cent nickel, or up to 1.5 per cent silver, for con-
trolling segregation and sweating of the lead, which is insoluble in copper
both in the molten and the solid state.
9.9. The Tin Bronzes
The most important industrial copper-tin alloys are the phosphor
bronzes which contain from as little as 1 per cent to as much as II per
175
cent tin. All wrought phosphor bronzes are alpha-phase alloys, deoxi-
dized by adding enough phosphorus to remove all but a trace of oxygen.
The two most commonly used of these alloys (items 51 to 57, Table
9.3)
are the ones containing
approximately. 5 and 8 per cent tin; another
popular alloy contains about 10 per cent tin. Owing to their high re-
siliency and endurance limit, these bronzes are used for springs and
diaphragms.
Phosphor bronze is hot worked with difficulty, but cold working is
easy and the alloys are available in six tempers. These, and the range of
tensile strengths for each temper and each alloy, are given in Table
9.2. The actual tensile strength
depends on the thickness of the sheet.
Elongation
(in 2 in.) varies from 40 to 60 per cent for soft sheet to less
than
10 per cent for the harder tempers. The endurance limit in the
hard temper is approximately
25,000 lb. per sq. in., and the modulus of
elasticity is
15 million lb. per sq. in., about the same as that of other
copper-rich
alloys.
Table 9.2. Tensile Strength of Phosphor-Bronzc Sheet
Temper
Reduction
by cold
rolling,
per cent
Tensile-strength range, lb. per sq. in.,
for bronze containing
5% tin
8% tin 10% tin
Soft
Half-hard...
Hard
Extra hard .
.
Spring
Extra spring
.
20.7
37.1
50.0
60.4
68.6
40,000 to 55,000
55,000 to 70,000
72,000 to 87,000
84,000 to 98,000
91,000 to 105,000
96,000 to 109,000
53,000 to 67,000
69,000 to 84,000
85,000 to 100,000
97,000 to 112,000
105,000 to 118,000
110,000 to 122,000
58,000 to 73,000
76,000 to 91,000
94,000 to 109,000
107,000 to 122,000
115,000 to 129,000
120,000 to 133,000
Another important copper-tin
alloy-which is used in the cast condi-
tion-is one containing
a small amount
of zinc. This alloy, known vari-
ously
as government bronze, zinc bronze, or more commonly as gun
metal (in the late Middle Ages it was used for casting cannons) , contains
88 per cent copper,
10 per cent tin, and 2 per cent zinc-or 88 per cent
copper,
8 per cent tin, and 4 per cent zinc. It is cast 'readily in the
foundry, has a red color, and combines fine grain with considerable
strength, toughness,
and resistance to salt-water corrosion. Gun metal is
used for joints and fittings, bolts, nuts, valve and pump parts, bushings
and bearings for steam lines, and especially in naval construction. The
tensde
strength of cast and unmachined
specimens varies from 30,000 to
45,000 lb. per sq. in., the yield strength from 13,000 to 15,000 lb. per sq.
176
in., and the elongation (in 2 in.) from 15 to 40 per cent. Impact re-
sistance is high. The modulus of elasticity is 15 million lb. per sq. in.
9.10. Aluminum Bronze and Copper-Silicon Alloys
The copper-rich copper-aluminum alloys combine the strength of a
medium-carbon steel with high resistance to corrosion by the atmosphere,
by salt water, by a large number of neutral and acid salts of low con-
centration, and by sulphuric acid. They are more resistant than manga-
nese bronze to salt water and have good strength and ductility. The
single-phase commercial alloys contain 10 per cent or less aluminum. It
was noted in
9.2 that, if the aluminum is higher than this, the structure

and properties can be changed by thermal treatment. This is also true of
the complex alloys containing 5 to 10 per cent aluminum and several
per cent of iron, nickel, or manganese. By controlling the composition
and by heat treatment the tensile strength of the wrought alloys can be
varied from 65,000 to 125,000 lb. per sq. in., with elongations varying
inversely with the tensile strength from 5 to 70 per cent. The composi-
tion and typical properties of alloys in common use are given in Table
9.3, items 60 to 63.
Aluminum bronze is hard to handle in the foundry. The alpha-phase
alloys can be hot and cold worked readily, but they are hard to machine.
Owing to its corrosion resistance, its strength and toughness, and its low
coefficient of friction against steel, aluminum bronze is used for gears,
valve stems, bolts and nuts for propellers, and for various small parts;
as cast, it is used for gun mounts, gears, bearings, propellers, pump parts,
and ornamental pieces, especially for service in salt air and salt water.
The copper-silicon alloys, usually known as bronzes, of which some 20
to 25 are available under such brand names as Duronze, Olympic, Ever-
dur, Herculoy, and others, contain 90 to 98 per cent copper, 1 to 4.5 per
cent silicon, and small amounts of zinc, iron, or manganese, orif easy
machinability is desired0.25 to 0.50 per cent lead. Strictly speaking,
the copper-silicon alloys are copper strengthened
by 1 to 5 per cent of
other elements. The strength and ductility of these alloys are approxi-
mately the same as those of low-carbon steel, and the corrosion resistance
and ease of hot and cold working are about the same as those of copper.
Strength as well as ductility increases as the silicon increases up to about
4 per cent. This is shown by the typical properties in Table 9.3 (items
66 to 69) . Thermal conductivity and electric conductivity are 8 to 10
per cent of the corresponding values for copper, and the modulus of
elasticity is 15 million lb. per sq. in.
The principal advantage of the copper-silicon alloys is their corrosion
resistance in both marine and industrial atmospheres, in sea water and
in many industrial waters, in sulphuric and hydrochloric acids, sulphates
and chlorides, and in most alkalies and alkali salts. They are also re-
sistant to alcohol and to many organic acids but are readily attacked by
nitric acid and other strong oxidizing agents. The alloys can be used for
working stresses up to 10,000 lb. per sq. in. at temperatures of 250F.
(120C.) or below, and they can be readily welded by oxyacetylene,
metallic-arc,
and resistance methods.
The copper-silicon
alloys are now used extensively for bolts, screws,
rivets, boilers, tanks, equipment for laundries and sewage disposal, parts
for fans, ducts, and other ventilating and air-conditioning
equipment,
chemical and electrical equipment, containers for gases and chemicals,
and for many other purposes.
9.11. Copper-Beryllium Alloys
Copper-beryllium alloys are a development of the past twenty-five
years. Their strength and endurance limit, after age hardening, are high
when compared with other copper-rich alloys. This, combined with a
corrosion resistance that is practically the same as of high-purity
copper,
and comparatively
high electric conductivity, would be responsible for
fairly extensive use if the cost were lower. Beryllium metal, which cost
$1,000 a pound in 1927, had been reduced to less than $40 by 1937, and
it is estimated that the price could be lowered further to S5 to $10 a
pound if there would be more demand for the metal. Assuming, how-
ever, that the cost of beryllium
is $15 a pound, an alloy of 97.5 per cent
copper and 2.5 per cent beryllium would cost between $0.55 and $0.75
a pound in ingot form, which is still too high for extensive commer-
cial use.
At present,
copper-beryllium alloys contain 1.85 to 2.25 per cent
beryllium.
To some 0.35 per cent nickel
or cobalt is added to refine the
grain. The alloys can be hot and cold worked,
but not easily, and are
available as sheet, rods, wire, and tubes. As indicated,
they respond to
precipitation-hardening
treatments. If hot worked or welded, they are
given a solution
treatment by heating to 1425 to 1475F.
(775 to 800C.)
for
30 min., followed by quenching in water. The alloys are usually cold
worked after the solution treatment.
They are aged at about 600F.
(315C.) for
1 to 4 hr. depending upon the properties desired. Typical
properties are as follows:
Table 9.3. Composition, and physical
NOTE: The tabulated values arc average and, because of manufacturing limitations, should not be utei for
petiftcation purpoui. Within manufacturing limitations and when o tpceifitd, these products will
be manufactured to applicable current ASTM Specifications.
|s
l!
Nominal Composition, per cent
Item Name
No.
Copper Zinc Tin Lead
Alumi-
num
Phos-
phorus
Man-
ganese Others
<
C0PPER8
1. Electrolytic Tough Pitch Copper-100 99.9+
99.9+
99.9
99.
9
99.68
99. JO
99.00
20
20
20
20
20
80
80
0.02
3. Silver Bearing Coppcr-112
10 to IS oz. Silver
per Tont
25 to 30 ot. Silver
Pit Ton'
Arsenic, 0.30
Tellurium, 0.50.
.
4. Silver Bearing Copper-113
6. Phosphorlzed Arsenical Copper-108 0.02
8. Tellurium Copper-127
1.00
BRASSES
8. Oilding-4 95.00
90.00
87.50
85.00
80.00
70.00
66.00
63 00
60.00
5.00
10. 00
12.50
15.00
20.00
30.00
34.00
37 00
40.00
20
20
20
30
10
30
30
40
40
14. Yellow Brass-59
LEADED BRASSES
17. Leaded Commercial llronzo-201 90.00
88.50
85.00
66.50
66.50
(10.50
66.00
65.00
64.50
04.50
64.00
62.50
61.50
61.50
9.50 0.50
2.25
1.75
0.25
0.50
1.60
1.00
0.25
0.50
1. 00
2.00
2.50
3.25
1.80
0.60
1.00
2.00
2.50
50
9.25
90
19. Hardware Bronze-267 13.25
33.25
33.00
31.90
33.00
34.75
35.00
34.50
34.00
35.00
35.25
.SvTil
90
SO. Leaded Tube Brass-220
50
21. Leaded Tube Brass-218
60
22. Fre- Cutting Tube Drass-282
90
70
23. Leaded Tube Brass-257
24. Threading Brass-223
50
60
70
20. Medium-Leaded Brass-229
27. High-Leaded Brass-235
80
28. Extra-lllgh-Leaded Hrass-238
100
29. Freo Cutting Brass-271
100
30. High-Leaded Brass-243
90
60
70
31. Leaded Muntz Metal-274 60.00 39 in
32. Free Cutting Muntz Metal-293 60.00
60.00
56.00
39.00
38.00
41.50
33. Forging Brass-2S0
80
34. Architectural Bronce-280
80
1 0.034 to 0.051% Silver. 0.085 to 0.102% Silver.
NOTES
The values given are to be considered only as a general guide, and variations In properties due to manufacturing variables
must bo expected.
Higher values for strength and hardness arc obtained by a greater amount of cold working but are limited In general to rela-
tively narrow sheet, small-diameter rod and wire, and smalt-diameter thin-wall tubo. Wide sheet and plate, large-diameter
rod, and large sizes of wire and tube have. In general properties between those given for hard and soft tempers,
(a) These relative vbIucs are given in comparison with Free Cutting Brass-271, arbitrarily given a value of 100, and are
only an approximate Indication, there being no ready means for accurately comparing the machinablllty of metals.
They arc a reasonable guide to relative tool life and amount of power required for cutting.
properties of standard copper alloys
179
=
o
>.
3^-
Elongation, Yield Strength
> .
5fc
5*> Tensile
% in 2 In.
@ 0.5 % elon- Rockwell r, g ^
Form
(b)
Applicable
ASTM
Specifi-
Strength, psi.
( Unless
othe wise
noted)
gation under
load, ]>si.
Hardness
No.
1
O <5 o
ciZ-n
cations -
-;==
l8 9
o
a
5
i
iz v a.
13
1
Mis?
Hard
(c)
Soft Hard
(c)
Soft Hard
(c)
Soft Hard
(c)
Soft
mi
(Sheet
JRod
iWire
B152 4fi. 000 33,000 8 35 40,000 10,000 B51 F35)
B124, B133
BI. B2, B3
45.000
66,000
32,000
35,000 1(e)
45
35(e)
40.000 10.000 B50 F35 ! 1083 0.322 .000009b 101. c 226
B42, B75
'
1
'
(Tube
Sheet
B88, Blll.lt
B302
B152
45,000 35,000 10 45 40.000 10,000 B50 F40 1083 0.323 .0000098 85.0 197
46,000 33,000 5 35 10,000 10,000 B51 F3 I 1083 0.322 .0000098 100.5 223
Sheet B152 46,000 33,000 5 351 40,000 10.000 B5I F35 1083 0.322 .0000098 100. f 223
Tube
Rod
B75. Bill
B301
45,000 35,000 10 45 40,000 10,000 B50 F40 1080 0.323 .0000098 45.0 112
45,000 32, 000 18 45 40,000 10.000 B50 F35 1070 0.323 .0000098 90.0 215
Rod 45,000 32,000 12 45 40,000 10.000 B50 F35 1079 0.323 .0000098 99.0 222
Sheet B36 55,000 35,000 6 38 44,000 11.000 B61 F45 1065 0.320 .0000101 56 139
/Sheet
\WIrc
B36, B130 62.000 37.000 6 40 47,000 12,000 B70
,
B,
.|
B3
B134 80, 000 38, 000 J(e) 40(e)
1045 0.318 .0000101 43.0 108
Sheet
(Sheet
65.000 38,000 r. 42 50,000 13,000 B73 1035 0.317 .0000102
40.0 100
B36 69,000 40,000 7 45 55,000 15.000 B76| B5
|
(Wire B134 88,000 42,000
Kc)
10
42(c)
50
(Tube B-13.
Bill,
B135
69,000 40.000
55,000 15,000
B76 1)5
j
1025 0.316 .0000104 37.0 92
(Sheet B36 73,000 43,000
8 50 00,000 16,000 B81 B10
IWiro B134 100,000 47,000 1(e) 45(e)
f
iooo 0.313 .0000106 32.5 81
(Sheet B19, B36 76,000 47.000 10 65 62,000 17,000 B83
'B20i
(Wire 1)131 110.000 50,000 1(e) 50(e) 1
955 0.308 .ooooiii 27 70
.Tube B135 76,000 47.000 10 60 62,666 17.000 B83 B20
Sheet
(Rod
(Wire
B36 73,000 45,000 10 60 60,000 17,000 BS0 BIS 930 0.306 .0000112 26.0 69
65,000 46,000 20 60 50,000 17,000 B75 B20'
B134 105,000 50,000 1(e) 50(e)
920 0.305 .0000114 26.0 69
Sheet
54.000 45 20,000 B' 905 0.303 .0000116 28.4 73
Sheet
Rod
B121 62,000 37,000 6 40 47,000 12,000 B70 Bl 1045 0.318 .0000101 42.0 104
B140 51,000 37.000
IS 40 45,000 12,000 B58 Bl 1040 0.319 . 0000102 42.0 105
Rod BI40 52.000 40,000 20 45 43.000 15,000 B.V, B5 1025 0.317 .0000104 311.0
28.0
93
Tube
Tube
B135 73.000 45,000 10 55 60,000 17.000 B80 B15 935 0.307 .0000112
68
B135 73,000 45.000 10 55 60.000 17.000 B80 1)1.'
935 0.307
, , v
Q] | g 26.0
26.0
68
Tube
Tubo
Sheet
Sheet
B135 73.000 45.000
60,000 17,000 B80 B15 935 0.308 0000113 68
73,000 45,000 9 55 60,000 17,000 B80 B15 935 0.307 0000112 26.0 68
iii2i
" 73,000 45,000 10 55 60,000 17,000 B80 B15 930 0.306 0000113 20.0 68
73,000 45.000 9 55 60,000 17,000 B80 B15 925 0.300 0000113 26.0
26.0
68
Sheet
Sheet
Sheet
B121
B121
73,000 45,000 S 55 60.000 17.000 B80 B15 923 0.306 on mis 68
i3.Wl
45,000 8 52 60.000 17.000 B80 B15 920 0.307 00OO1I3
26.0 68
3121 73,000 45,000 / 50 60,000 17,000 B80 B15 905 0.307 0000114 26
68
Rod B16 58,000 47,000 18 60 42,000 18,000 B70 B20 895 0.307 0000114 25.5
26.0
62
Sheet
Sheet
B121 73,000 45,000 7 50 60,000 17,000 B80 B15 908 0.305 0000113 68
B171
B13S
B124
54,000
54,000
.... 45
40 6o,'66o'
20,000
20.000 B86
" B45
B45
900
900
0.304
0.304
0000116
0000116
20.0
26.0
Tube
Rod
Rod
80.666 1
68
68
J
54,000
Ml rm
45
25
20.000 BI5
B65
895
884
0.305 0000115 26.5 82
1
0.305 0000116 28.0 7i
Courtesy American Brass Co.
NOTES (Continued)
(b)
SS&r ?SSm ES&VSST
Sl"*t
"
'M0 ta" thleki Rod' '" ia' dlttraeter: wlro
'
008 ta- d,ametcr; Tub,,
'
'
"'
(c
>
grantsERRsrâwasss
ssr
-
*
reduowi about 37% in thioknoss by m rm
^-
and
r< J:!
PClrlc
?
1 conductivity: given for soft annealed metal; in hard temper conductivity Is slightly lower.
(e) Klongation of wire, percent in 10 in.
--..
YOUX 1'S MODULUS OF ELASTICITY for copper is about 10,000,000 psl. The addition of zinc to copper reduces the
modulus, to about 14,000,000 psl. for Yellow Brass. Pot most bronzes, the value is about fWOOO0"
TheEdition of nickel
to copper Increases the modulus, Cupro Nickel, 30%-702 showing about 20.000,000 psi.
>">
""
"
>
Table 9.3
Continued.
NOTE: The tabulated values are average and, because of mnnhctoring limitations, should not be used tor
specification purposes. Within manufacturing limitations and lehen so specified, these products will
>
Nominal Composition, per cent 11
$9
Item
No. Name
Copper
Zinc Tin Lead
Alumi-
num
Phos-
phorus
Man-
ganese Others
SPECIAL BRASSES
94.97
90.25
88.00
85.00
82.00
81.00
77.00
71.00
70.00
60.00
60.00
60.00
60.00
58.50
4.00
0.90
10.00
14.00
17.00
18.00
20.98
27.96
29.00
39.25
39.25
38.55
37.60
39.25
1.00
1.75
0.03
0.10
20
36. High Strength Commercial Bronze-
286
37. Ambronze-421
Nickel, 1.00 80
20
38. Manganese Red Brass-507
1.00 30
39. Silicon Red Hrass-1027
40. Trumpet Brass-435
41. Ambraloy-927 (Aluminum -Brass).. .
1.00
2.00
Silicon, 1.00
Arsenic, 0.04
30
30
30
42. Arsenical Admlralty-439 1.00 30
1.00 30
44. Naval Brass-450 0.75
0.75
0.75
0.75
1.00
30
45. Tobin Bronze"-452
30
6.70
1.76
50
47. Leaded Naval Brass-612
80
0.25 Iron, 1.00 30
PHOSPHOR BRONZES
49. Phosphor Bronze-356 98.70
98.24
95.95
95.75
95.17
94.75
93.90
93.20
91.75
89.75
87.90 4.00
1.25
1.75
4.00
4.00
4.00
5.00
5.00
6.50
8.00
10.00
4.00
0.05
0.01
0.05
0.25
0.08
0.25
0.10
0.30
0.25
0.25
0.10
20
50. Phosphor Bronze-361 20
51 . Phosphor Bronze, (A )-302 20
52. Phosphor Bronze, (A j-303
20
S3. Phosphor Bronze-314
0.25 Iron, 0.50 20
54. Phosphor Bronte, (A)-351
20
65. Leaded Phosphor Bronze, (B)-379. . .
.
1.00 SO
20
57. Phosphor Bronze, (C)-353 20
58. Phosphor Bronze, (D )-354
4.00
20
59. Free Cutting Phosphor Bronze-610. .
.
90
ALUMINUM IBRONZE8,
60. Ambraloy-901 95.00
92.00
89.25
82.00
5.00
8.00
9.26
9.50
20
61. Ambraloy-928
20
62. Avlalitc'-915
63. Ambraioy-917
0.40
1.00
Nickel, 0.50;
Iron, 0.60
Nickel, 5.00;
Iron, 2.50
20
20
'
Trade-Mark Reg. V. S. I'at. Off. t
1.25" and over.
NOTES
The values given are to be considered only as a general guide, and variations In properties due to manufacturing variables
must be expected.
Higher values for strength and hardness arc obtained by a greater amount of cold working but arc limited in general to
relatively narrow sheet, small-dlamcler rod and wire, and small-diameter thin-wall tub*;. Wide sheet and plate, large-diam-
eter rod, and large sizes of wire and tube have, In general, properties between those given for hard and soft tempers,
(a) These relative values are given in comparison with Free Cutting Druss-271, arbitrarily
rfiven a value of 100, and are
only an approximate Indication, there being no ready means for accurately comparing the machinabllity of metals.
They are a reasonable guide to relative tool life and amount of jwwer required for cutting.
181
= ~Q
5%
i?*^

3h
Tensile
% In 2 In.
@ 0.5 % elon- Rockwell 5

Applicable Strength, psl. (Unless gation under Hardness
1
^S-c
Korm ASTM otherwise loud, psl. No.
ii 1
..a
8*jn
(b) Specifi-
noted 1 J3

J.
E = S
cations
a.
fi
KM*
_M R
S
1
a
CO i
fcji
Hard
(0)
Sort Hard
(e>
Sod Hard
(c)
Soft Hard
(o)
Soft
*3
2
>S ttti
Sheet no, ooo 40,000 6 40 50,000 15,000 B70 BS 1060 0.320 .0000101 38.0 95
Rod 70,000
12 60,000 B80 0.320
0.316
32.0
27.0
81
69
Tube 46,000 58 20,666 B15 1030 .0000102
Sheet 69,666 40,000 1 7 46 55,000 15,000 B76 135 1015 0.316 .0000104 22.0 57
Sheet 90,000 55,000
48,000
52,000
8 60 50,000 20,000 BOO B35
B25
B30
990
1005.
970
0-310
.0.313
0.301
.0000105
. 11000 10S
.0000108
14.7
27.5
22.6
39
70
58
Tube
BUI
80,000
85,000
10
10
60
65
Tube
60,000 20,000 B85
(Sheet
\Tube
B171
Bill
48,000
86, 000 52, 000 io
65
65
18,000
20,000
B25\
B30I
935 0.308 .0000112 24.7 64
Sheet B291 7(1,000 47,000 10 65 62,000 17,000 B83 B20 945 0.308 .0000111 16.0 43
1 Sheet
I
Rod
B171
B21. B124 63.000
56,000
56,000
22.000
22,000 B65
B501
B50f
885 0.304 .0000119 25.8
30 40 35.000
67
Rod B21, B124 63,000 56.000 35 45 35.000 22.000 B65 BSD 885 0.304 .0000117 25.8 67
Rod B21 63.000 56,000 28 38 35.000 22,000 B6S B50 890 0.305 .0000119 26.0 67
Rod B2I, B124 63,000 56,000 2i 35 35.000 22,000 B66 B50 l 890 0.305 .0000118 26.0 67
Rod B124, B138 75, 000 60,000 20 30 45,000 30.000 B85 890 0.302 .0000119 23.0 58
Sheet 65,000 40,000 6 48 50.000 14,000 B75 F60 1075
1070
0.321
0.321
.0000099
.0000099
43.0
37.8
126
85
Wire BIOS 105,000 45,000
UO 40(c)
Sheet moo 80,000 48,000 8 SO 65.000 20,000 B86 B28 1050 0.320
.0000099
18.4 47
Tube 70,000 48,000 15 50 58,000 20,000 B80 B2S 1050 0.320 .0000100 18.0 47
Rod B139 (15,000 48,000 30 50 55,000 20,000 B75 B28 1055 0. 322 .000010 16.4 44
[Sheet 11103 80,000 48,000 8 50 65.000 20,000 B86 B281
{Rod B139 65,000 48,000 30 50 55,000 20,000 B75 B28} 1050 0.320 .0000099 18.0 47
(Wire III.'.9
110.000 52,000 1(e) 40(c)
1
Rod B139 65.000 48.000 25 40 55,000 20.000 B75 B25 1050 0.322 .0000099
18.4 48
Wire 120,000 57,000 He)
10
40(e)
65
1040 0.319 .0000100 12.0 33
(Sheet B103 93,000 00,000
68,000 24,000 B94 B50
Rod B139 80,000 60,000 30 AS
24,000 BflOl 1025 0.318 .0000101 13.0 30
iwire B159
B103
130,000
102,000
62,000
06. 000
He)
12
40(c)
65
Sheet
[Rod
70,000 28,000 B98 B55
B139 85,000 65,000 25 65 1000 0.317 .0000102 11.0 29
.Wire B159
B139
145.000
60,000
68,000 He)
20
40(c)
1000 0.320 .000010 12.2
Rod
45,000 B76
33
Sheet B169 92,000 55,000 7 65 65,000 22,000 B92 B3.il
Rod 55,000
60,000
65.000
65
60
22,000 B35j 1060 0.295 .0000099 17.0 46
Tube
Sheet
Bill
BI69 105,000 7 60
65.000 25,000 BM BSOl
Rod BI24, B150 80,000 65,000 30 65 50,000 25.000 B50!
101(1 0.281 .0000099 14.8 41
Rod 1)124, B150
B171
B124, B150
95,000
ios.ooo
80,000
90,000
16
12
22
12
55.000 40,000 1042
1055
0.274
0.274
.0000094
.000009
12.8 85
(Plate
Rod
1
60.000 BIOS
}
7.S 22
NOTES (Continued)
(b) Form for which properties are given: Sheet, 0.040 in. thick; Rod, 1 in. dlumeter; Wire, 0.080 in. diameter; Tube, 1 In.
diameter x 0.065 In. wall thickness.
(c) Hani temper: values arc for soft sheet that has been subsequently reduced about 37% In thickness by cold rolling; and
for Rod, wire and Tube of commercial hard drawn temper.
(d) Electrical conductivity: given for soft annealed metal; in hard temper conductivity is slightly lower.
(e) Elongation of wire, per cent In 10 in.
YOUNG S MODULUS OF ELASTICITY for copper is about 16,000,000 psl. The addition of zinc to copper reduces the
modulus, to about 14,000,000 psi. for Yellow Brass. For most bronzes, the value is about 15,000,000. Tho addition of nickel to
copper Increases the modulus, Cupro Nickel, 30%-702 showing about 20,000,000 psl.
182
Table 9.3
Continued.
NOTE. The tabulated values are average and, because of manufacturing limitations, should not he met lor
specification purposes. V Itliin manufacturing limitations and when so specified, these products will
22
Nominal Composition, per cent
II
Item Name
No.
Copper Zinc Tin
Lead Nickel
Alumi-
num Silicon
Man-
ganese Others
M
CADMIUM BRONZES
64. Hltenso'-901 99.00
98.60
Cadmium, 1.00...
Cadmium, 0.80.
20
20
66. 11 ltenso--965
0.60
COPPER-SILICON ALLOYS
66. Everdur"-1010
95.80
95.60
98.25
90.75
3.10
3.00
1.60
2.00
1.10
1.00
0.26
30
60
30
60
67. EvordurM012
0.40
68. Everdur'-1015
69. Evcrdur'-IOM
7.25
CUPRO NICKELS
70. Cupro Nickel, 10%-755 88.35
68.90
10.00
30.00
0.40
0.60
Iron, 1 25 20
20
71. Cupro Nickel, 30%-702
Iron. 0.50
NICKEL SILVERS
72. Nickel Silver, 10%-76I 65.00
64.50
55.00
45.00
25.00
17.50
27.00
42.00
10.00
18.00
18.00
10.00
20
73. Nickel 8llver. 18%-719
20
20
74. Nickel Silver, lS%-724
7S. Leaded Nickel Sliver, 10%-25
1.00
2. CO
60
8PECIAL ALLOYS
76. Calsun Bronze*-951
95.50
99.05
2.00
2.50
20
20
77. Chromium Copper-999
0.10 Chromium, 0.85.
.
Trade-Mark Reg. \>. 8. Pat. Off.
NOTES
The values given are to be considered only as a general guide, and variations In properties due to manufacturing
variables
Higher values for strength and hardness are obtained by a greater amount of cold working but are limited In general to
SSfSR SfEZi SS H&t^fffiS ^""f
"** ft
1
d srooll-dlamcter thin-wall tube. Wide sheet and plate largeân,
eter rod, and large sizes of wlro and tube have. In general, properties between those given for hard and soft tempers
(a) These relative values are given in comparison with Free Cutting Brass-271, arbitrarily given a value of
100,'
and are
only an approximate indication, there being no ready means for accurately comparing the macliinabllity of metals
They are a reasonable guide to relative tool life and amount of power required for cutting.
183
i
"3 JSd"-
6
"31*.
2---
Tensile % in 2 in.
@
0.5 % elon- Rockwell
o
i.
*
Applicable
Strength, psi. (Unless gation under Hardness
S.
= 2 IS
form ASTM
otherwise loud, psl. N0. a
w;
(1)) Specifi-
noted) o
JS
SS
o' 3
S~
cations & -#=K _
6fi
C
>,
Hard Soft Hard Soft Hard Soft Hard Soft
"3
s Q <3wS.
St"*
(c)
(c) (c) (o)
IShcet
\Wirc B105
B105
55.000
90.000
95,000
37,000
40.000
42. 000
1(e)
1(c)
50
40(e)
40(e)
48.000 12,000 B65 F471
1076
1070
0.321
0.321
.0000098
.0000098
87.0
60.0
199
Wire
13S
Sheet 1)96, B97 95.000 58,000 7 60 60,000 22,000 B92 B35'.
Rod B98, B124 90,000 58.000 18 70 60,000 22,000 B90 B35 1019 0.308 .0000100 6.5 19
Wire B99 145.000 60.000 Me) 50(e)
I
Rod B98 90.000 18 60,000 1)90 1019 0.308 .0000100
6.5 IS
Sheet B97 65,000 40,000 8 46 50.000 15.000 B77 F55
Rod B98 70,000 40.000 IS 50 55,000 15,000 1)80
F55
'
Wire B99, BIOS 122,000 42,000 Ke) 40(c)
1055 0.316 .00000911
11.0 31
Tube
65,000 40.000 8 50 50,000 15,000 B71 F55
Rod BJ24, BlW
95,000 25 53.000 B87 1005
0.278 .000010 9.2 as
Tube Bill 60,000 44,000 15 40 57,000 22,000 BOS B25 U45 0.323 .0000093 9.2 26
1 Sheet
Rod
1 Wire
B122, B171 77,000 55, 000 5 40 70,000 22,000 B84 B35
70, 000 55, 000 25 40 60,000 22.000 B80 B35
BUI
95.000
70.000
58,000
55,000
Ke)
10
35(e)
45
B80 B35.
1225 0.323 .0000090 4.6 17
iTuhe
60,000 22, 000
Sheet B122 88,000 55,000 7 42 70.000 20,000 B87 B30 1010 0.313 .0000091 8.4 27
Sheet B122 85.000 58,000
4 40 70.000 B85 B40
Rod lll.il 70.000 58,000 20 45 22.000 B40 1110 0.316 .0000090 6.0 IB
Wire B206 110.000 60,000
Ke) 40(C)
Sheet B122 99,000 00,000 4 45 75,000 22,000 B93 B45
Rod B151 80,000 60,000 20 45 60. 000 22,000 B85 B45 1055 0.314 .0000093 5.3 17
Wire B206 130, 000 65,000 Ke) 40(0)
Rod 70,000 IS 40,666 B70
925 0.303 .000011 7.0 21
Wire B105 135, 000 52, 000
Ke) 40(e)
1054 0.308 .0000099 19.0 50
Rod
\Rod (()
02, 000 35, 000
72,000
03.000
20
25
40
25
57,666
61,000
15.000
45.000
B70
B77
Fgq
B65
1075
1075
0.321
0.321 .0000098
40.0 u
80.0 187
NOTES (Continued)
(b) Form for which properties are given: Sheet, 0.040 in. thick; Rod, 1 in. diameter; Wire, 0.080 in. dia ncter; Tube, 1 In.
diameter x 0.065 in. wall thickness.
(c) Ilard lemper: values arc for soft sheet that has been subsequently reduced about 37% in thickness by cold rolling; and
for Rod, \\ Ire and Tube of commercial hard drawn temper.
(d) Electrical conductivity: given for soft annealed metal; In hard tempor conductivity is slightly lower.
(e) Elongation of wire, per cent in 10 In.
(f) Properties after heat treatment (alloy 77).
YOUN'O'S MODULUS OF ELASTICITY for copper is about 16,000,000 psi. The additon of line to copper reduces the
modulus, to about 14,000,000 psl. for Yellow Brass. For most bronrts, the value Is about 15,000,000. The addition of nickel to
copper increases the modulus, Cupro Nickel, 30%-702 showing about 20,000,000 psi.
Typical Propcrlics of Copper-Beryllium Alloys
Condition
Tensile
strength, lb.
per sq. in.
1
Yield Elongation
strength, lb. in 2 in.,
per sq. in. per cent
Brincll
hardness
Soft
Average treatment
Maximum treatment ....
70,000
175,000
193,000
31,000
134,000
138,000
45
6.3
2.0
110
340
365
The endurance limit is usually between 35,000 and 45,000 lb. per sq.
in. depending on the treatment. The endurance ratio varies from approxi-
mately 45 per cent for the unhardened alloy to about 20 per cent for fully
hardened material. The modulus of elasticity averages 18 million lb. per
sq. in. In these properties the copper-beryllium alloys are far superior to
any other copper-rich alloy. They also have relatively high wear resistance
and corrosion resistance and are superior to phosphor bronze in resisting
metal-to-metal wear when run against steel. At present they are used
to a limited extent for springs, gears, diaphragms, bearings, and for
other small parts in the electrical and the aircraft industries.
Chromium copper (Table 9.3, item
77) is a heat-treatable alloy
which is extensively used for welding electrodes, grid support rods,
and for lateral wires in electronic vacuum tubes.
A copper-silver-iron alloy containing 6 per cent silver, 1 per cent
iron, copper remainder, is also a heat-treatable alloy used by the Signal
Corps of the U. S. Army for field telephone wire during the Korean war.
9.12. The Copper-Rich Copper-Nickel Alloys
Copper and nickel dissolve in each other in all proportions in the solid
state, and their alloys are free from phase changes. Some of the most
widely used industrial alloys contain from 2 to 30 per cent nickel (the
cupronickels) or 45 per cent nickel (Constantan) . Of the important
nickel-rich alloys, the best known is Monel, containing 68 per cent nickel.
This group is discussed briefly in the next chapter.
Nickel increases the tensile strength, the yield strength, and the en-
durance limit of copper, as shown for annealed alloys in Fig. 9.4.
Even the strongest alloys are ductile and have an elongation of 45 to 50
per cent in 2 in. As noted in the discussion of nickel silvers, the addi-
tion of increasing amounts of nickel to copper changes the red color
to white. A 15 per cent nickel alloy has a faint pink tinge, and a 20 per
cent nickel alloy is practically
white. The five-cent coin of
the United States, the
"nickel," is an alloy of 75 per
cent copper and 25 per cent
nickel.
The most common indus-
trial alloys contain 15, 20, and
30 per cent nickel. The 15 and
20 per cent alloys are used for
bullet jackets and for a large
variety of parts in which the
white color, high ductility,
and corrosion resistance are of
value. They were formerly
used for condenser and other
tubes for marine engines and
oil refineries, but in these ap-
plications they have largely
been replaced by the 30 per
cent alloy. This material can
readily be hot and cold
worked and can be soldered,
brazed, and welded. It is one
of the most resistant of the
copper-base alloys to salt
water and to many of the cor-
rosive solutions of the chemical industry. The cupronickels are generally
resistant to the atmosphere, to industrial waters, and to many acids and
alkalies. The
30 per cent alloy, containing also 1 per cent manganese
and
1 per cent iron, is cast into a large variety
of couplings, ells, tees,
and other fittings for valves, pumps, and other similar applications.
The
cupronickels do not respond to heat treatment.
As in the case of
most solid-solution
alloys, high strength can be attained only by cold
working with
concomitant loss of ductility. Cold working with
a reduc-
tion of
60 per cent increases the tensile strength of a 30 per cent nickel
alloy from
50,000 to 85,000 lb. per sq. in. and reduces the elongation from
50 to 4 per cent in 2 in.
Some of the copper-nickel alloys have important electric properties.
As shown by Fig 9.5, the electric resistance is at a peak and the tem-
40 SO
Nickel, per cent
Fig. 9.4. Effect of nickel on the mechanical
properties of copper-nickel alloys (Wise)
186
perature coefficient of resistance is practically zero in the alloy contain-
ing 45 per cent nickel. This alloy, known as Constantan, has high and
uniform thermoelectric force against copper and iron and is used ex-
tensively for thermocouples for the accurate measurement of tempera-
tures below 1800F. (985C.)
.
40
Nickel, per cent
Fie. 9.5. Effect of nickel on the electrical properties of copper-nickel alloys. (Wise)
It should be evident from the discussion in this chapter that the en-
gineer has available a wide variety of wrought and cast copper-rich alloys
for use in his structures and machines. There are so many of these alloys
that an intelligent choice of a specific one is sometimes difficult, espe-
cially in view of the fact that a large number of them are proprietary
alloys for which extravagant claims are occasionally made.
9.13. Copper and Copper-Base Alloys in Powder Metallurgy
Powder metallurgy is a very old art and a very young science. Sponge
iron was formed into weapons a thousand years ago, but when man dis-
covered how to melt steel, he discarded the more cumbersome method
of powder metallurgy, and the art was lost until relatively recently. With
the exception of filaments for the electric-light bulb, which have been
187
made by powder-metallurgy
methods
for fifty years, and the perfection
of hard carbide tools twenty-five years ago, most of the development in
powder metallurgy has come in the past fifteen years.*
The process underlying
the production of powder compacts is well
known and need not be reviewed here. Broadly it consists or preparing
metal or nonmetal powders of the proper size and physical character-
istics, forming them into the desired shape, compacting under high
pressure
(10 to 100 tons per sq. in.), and sintering at the proper tem-
perature.
Close tolerances can be maintained and no machining of the
finished
part is ordinarily
necessary. Despite the high cost of the equip-
ment for carrying on the various operations, great savings result in many
applications,
especially for a large number
of identical parts that are
difficult or expensive to machine
from solid metal.
The properties
of a part made from powder depend on the character
of the raw material and upon the pressing and sintering-in
other words,
on the homogeneity
and the absence (or presence) of voids in the finished
part-and
they range from about
50 per cent to practically
the same
as for the solid metal or alloy. One of the great advantages
of powder
metallurgy
is that dissimilar
metals, or metals and nonmetals, that
do not alloy in melting
can be readily combined into an article having
unique and often very desirable
properties. Of the several million
pounds of copper, for example, that are compacted
by the methods of
powder metallurgy a large proportion
goes into porous "oilless
1
or "self-
lubricating"
bearings for electrical machinery,
automobiles,
machines,
and household
appliances. More than a billion such bearings are in use.
The most common oil less bearingf is made by compacting 87.5 to 90.5
per cent copper powder,
about 9 per cent tin powder, and about 1.5 per
cent graphite.
These bearings are made with
a controlled
number of
voids (by regulating
the density)
, so that, when installed,
they contain
15 to 35 per cent impregnated
oil; they are, therefore,
both bearing
and
lubricant
and, if properly made, will function
as such for the life of the
machine.
Sometimes
3%
lead is added for improved
properties.
'The first general
technical meetings in the field were held at Massachusetts
Inst.ti.te of Icchnology in 1940 ami 1941. The papers
presented were published in
,Lo !L
Urgy'" edited by John Wu,ff
'
Am"i(an Society for Metals, Cleveland
1942, 622
pp.
The first conference
of the Powder Metallurgy
Committee of the
foTT^K
In* titute of Mini
"S
a"* Metallurgical
Engineers was held in February,
1944. The
12 papers
presented were published in Trans.
Am. Inst. Mining Met
Engrs.,
y.
161, 1945.
pp.
524-634.
See also Seminar on Theory
of Sintering" and other
papers in rrans. Am Inst. Mining Mel. Engrs., v 166,
1946, pp. 474-587.
See also
Proceedings
of Com. B-9 of A.S.T.M.
fA^.T.M. specifications
B202-51T.
188
Copper and copper-base alloys compacted with graphite are also used
successfully
for brushes and other parts of motors and generators, to
take advantage of the antifrictional character of the graphite and the
current-carrying capacity of the copper. Depending on the strength re-
quired, the amount of graphite may be 50 per cent or more. Thousands
of contacts for making and breaking electrical circuits are produced by
compacting copper and refractory metal, such as tungsten or molyb-
denum or the carbides of these metals.
The principles underlying the art of producing powder compacts are
not simple. Not only must such variables as particle size, pressure, and
sintering temperature be controlled carefully to secure the density, hard-
ness, and strength desired (all of which arc directly related) , but struc-
tural changes resulting from diffusion must also be taken into account.
The structure should resemble that of the solid metal or alloy, the grain
size should be fine, and the voids (if present) should be uniform in
size and distribution. Powders of an alloy may, when compacted, have
a structure and properties different from those resulting when the pow-
ders of the metals are used and alloying is accomplished during sintering.
On the other hand, prealloying may cause increased resistance to com-
pression and result in less dense compacts. Whether the compact is pre-
pared by hot or cold pressing, whether the powders contain gas, whether
they oxidize easilyall of these are important factors and none has been
thoroughly studied.
In general the metallurgy of producing metal parts from powder is in
its infancy and considerable advance can be expected in the next few
years. Other than for the manufacture of hard carbide tools, discussed
in a subsequent chapter, the process has been used successfully in produc-
ing parts of iron, steel, iron phis graphite, steel plus copper, stainless
steel, copper and copper-base alloys, aluminum and aluminum-base al-
loys, and iron-nickel alloysand the list is growing rapidly. Where
economic factors are favorable the future of powder metallurgy seems
secure.
QUESTIONS
1. What are the properties of copper that make it useful commercially?
2. What are the composition and properties of common brass?
3. What is Muntz metal? Commercial bronze?
4. Name two methods for making copper alloys free-machining.
5. Define dezincification.
6. What are nickel silvers and their most valuable property?
7. What is intended when the term "high brass" is used in the brass industry?
8. Give the eutectic composition of the copper-zinc alloy system.
9. What is red brass? Admiralty metal?
10. What is manganese bronze, and what is its principal use? Is it a true bronze?
11. Compare the composition and properties of cast brasses, cast nickel silvers,
and cast manganese bronze.
12. What are the principal metals in the copper-base" bearing alloys? Name
some of their principal characteristics and uses. What are the uses for high-
lead, copper-base alloys? Mow do those compare as bearings with the white
metals?
13. What is the effect of phosphorus on the properties of copper-tin bronzes?
What arc the phosphor bronzes? Name the properties and some uses of phos-
phor bronzes.
14. What is the effect of varying amounts of cold working and varying amounts
of tin on the tensile strengths of phosphor bronzes? What is the approxi-
mate composition of gun metal? What are the properties and uses of gun
metal?
15. What is the general composition of aluminum bronze? Indicate some of its
characteristics and uses.
16. Indicate the approximate composition and some of the applications of
copper-silicon alloys.
17. Indicate the approximate composition, properties before and after precipita-
tion-hardening, and applications of the copper-beryllium alloys. What is the
reason for their limited use?
18. What is the effect of increasing amounts of nickel on the tensile properties
and endurance limit of copper? What are the properties of copper-nickel
alloys? Name some of the copper-nickel
alloys.
19. What general classes of materials may be combined by powder metallurgy
methods? Name and give the properties of some articles made by powder
metallurgy methods from copper combined with other materials.
20. How are metal-powder compacts made? What variables determine the prop-
erties of articles made by the methods of powder metallurgy?
CHAPTER
10
Miscellaneous
Heavy
Nonferrous Metals and Alloys
William H. Tholke, B.S., in Metallurgical
Engineering,
Instructor of Metallurgy, University of Cincinnati,
Cincinnati, Ohio
1
HE preceding chapters on the light metals,
copper,
and copper base
alloys have dealt with the two largest nonferrous
metal industries.
Before taking up the complex field of iron-carbon alloys,
alloy steels, cast irons
and the metallurgy associated with the working
and
manufacturing
of these materials, it would be well to look briefly
at the remaining
commercial nonferrous
metals and their alloys, how they
are used, and the part they play in the overall
metals picture.
In terms of density or specific gravity most of these metals are heavier
than iron. Table 10.1 lists these metals in alphabetical order with their
respective
specific gravities. Some categorizing may be done in terms of the
physical
characteristics
of the metals, and the metal elements with which
they are alloyed. Some of these metals such as Pb, Sn, Sb, Bi, Cd, and In
have low melting
temperatures.
The alloys of Pb and Sn are often re-
ferred to as the white
metals. Then, there are those metals which have
high melting
temperatures as well as good corrosion resistance. These are
the metals Ni, Cr, Co, W, Mo, and Re and their alloys. A third group
comprises those metals and alloys which by virtue of scarcity of supply
are known as the precious and semi-precious metals. These arc the metals
Ag, All, Pt, Pd, and Rh. And, lastly, a new. group which has come into
prominence through the
development of atomic energy. These are the
elements Th, Tm, U, and Zr.
190
Miscellaneous Heavy Nonjerrous Metals and Alloys 191
Table 10.1. Miscellaneous Nonfcrrous Heavy Metals and their Specific Gravities
Specific Melting
Specific Melting
Gravity Temp. F.
Gravity Temp. "F.
Antimony
(Sb) 6.62 1167 Nickel
(Ni) 8.9 2651
Bismuth (Bi) 9.80 520 Palladium (Pd) 12.0 2830
Cadmium (Cd) 8.65 610 Platinum (Pt) 21.5 3224
Chromium
(Or) 7.19 3430 Rhenium
(Re) 20.0 5740
Cobalt
(Co) 8.90 2725 Rhodium (Rh) 12.4 3570
Columbian
(Cb) 8.57 4380 Silver (Ag) 10.5 1761
or Niobium (Nb)
Copper
(Cu) 8.96 1981 Tantalum (Ta) 16.6 5425
Gold
(Au) 1 9 . 32 1945 Thorium (Th)
11.5 3300
Indium (In)
7.31 314 Thulium (Tm) 9.35
Iridium
(Ir) 22.5 4450 Tin (Sn) 7.30 449
[Iron
(1*0 7.87 28021 Tungsten (VV) 19.3 6170
Lead (Pb) 11.34 621 Uranium (U) 18.7 2065
Vanadium
(V) 6.0 3150
Mercury
(Hg) 13.6 -38
Zinc
(Zn) 7.13 787
Molybdenum
(Mo) 10.2 4760 Zirconium
(Zr) 6.7 3353
LOW MELTING METALS AND ALLOYS
10.1. The While
Metals
The term "white metals" is usually reserved
for alloys of lead and
tin in which one or both of these metals may comprise the major per-
centage of the total
alloy content. The remaining alloying elements
present
may be one or more or the following: antimony, arsenic, bismuth,
cadmium, copper, indium, silver, and zinc. The white metal alloys are
often more commonly
known by their trade names such as pewter, terne
plate, babbits, and silver solders. Their applications find greatest usage
in the fields of
(1)
bearing materials,
(2)
type metals, and
(3)
low-melt-
ing fusible alloys such as the solders and safety fuse plugs.
The bearing metals must meet many requirements before they can
qualify as a good bearing
material.
These
may be divided into three principal classes. First in importance
is proper structure,
that is, a soft
matrix with sufficient plasticity to con-
form to slight irregularities in the machining and
alignment of the shaft,
to allow any abrasive particles in the lubricant
to become embedded in
the bearing metal (to prevent
scoring of the steel journal)
, and to retain
oil (to prevent mctal-to-metal
contact)
, combined with a number of
uniformly
distributed particles which resist wear. Some metallurgists,
however, now claim that wear-resisting
particles are not necessary for
good bearings and that the structure is of minor
importance. Such claims
are strongly supported by the successful use of the steel-backed silver
bearings and by the cadmium bearings.
Second, the mechanical properties must be satisfactorily balanced. The
bearing must resist the shock of impact loads, and it must have sufficient
strength, ductility, and resistance to compression not to crack or to
squeeze out under heavy loads, especially at the operating temperatures,
which may be 200 to 300F. (95 to 150C.) and in the modern airplane
even higher.
The third requirement is easy melting and casting and, most important,
good bonding properties. In other words, when cast in a strip as thin as
0.01 in., the metal must adhere firmly to the steel or bronze piece used
as a backing and should not spall off or separate from the backing during
operation. For some purposes, especially for large railroad bearings, it
must be possible to remelt and recast the bearing metal without exces-
sive loss by oxidation.
In addition, the bearing metal should have high thermal conductivity,
resistance to corrosion by the lubricants used, and it should be cheap.
There are four classes of bearing metals. Typical compositions of some
common alloys in these different classes, with the specification numbers
adopted by the American Society for Testing Materials and the Society
of Automotive Engineers, are given in Table 10.2.
The white metals include the tin-base (class A, Table 10.2) and the
lead-base (class B) alloys. The 14 alloys in these two groups and the
numerous unimportant modifications that have been advocated from
time to time are old and well known. The tin-base alloys, commonly
called babbitts, are widely used in automobile engines and in a large
variety of machines where speeds are high and loads are light or at most
only fairly heavy. Lead, added (alloys A4 and A5) primarily to reduce
the cost, is objectionable if operating temperatures are high as it forms
a fusible eutectic with tin and lowers the temperature at which incipient
melting takes place. The following illustrates the effect of lead: the tem-
perature at which alloy A5 (18 per cent lead) is completely liquid is
about 565F. (295C.) ; the corresponding temperatures for alloys Al
and A2 (no lead) are 680 and 670F. (360 and
355
C).
The properties of the tin-base alloys vary somewhat with composition
but are usually within the following ranges:
Properly Range of values
Tensile strength, lb. per sq. in., at 70"F. (20C.) 12.800 to 17,500
Tensile strength, lb. per sq. in., at 200F. (95C.) 6,700 to 10,000
Yield strength, lb. per sq. in., 70F. (20C.) 4300 to 6500
Yield strength, lb. per sq. in., at 200F. (95C.) 2.100 to 3,200
Brincll hardness (500 kg.) at 70F. (20"C.) 17 to 27
Brincll hardness (500 kg.) at 200-F. (95C.) 8 to 14
Miscellaneous Heavy Nonferrous Metals and Alloys
193
Table 10.2. Typical Compositions of Some Common Bearing Mclals
Specification
Nomina] composition,
percent
Class A.S.T.M. S.A.E. Sn Sb Pb Cu Zn Cd Others
Al B23-46T1 10 91 4.5 4.5
2 2 110 89 7.5 3.5
3 3 83.3 8.3 8.3
4 4 75 12 10 3
5
5 65 15 18 2
6 11 87 6.8 5.7
Bl B23-46T6 20 15 63.5 1.5
2
7 14 10 15 75
3 8 5 15 80
4 10 2 15 83
S 11 15 85
6 12
10 90
7 15 15 1
15 84
8
19 5
9 86
CI B144-46TA 792 10 10 80
0.0 to 0.9 P
2 B 7 7 83 3
3
C 5 9 85 1
4
D 7 15 78
5
E 5
25 70
6 B22-46TA
19
80 0.0 to 0.9 P
7
B 16 83
0.0 to 0.9 P
8
791 4 4 89 3
9 793 4
8 85 3
10
48
30 70
n
480
35 65
Dl
2
17P*
99.75+ Ag
17C*
1
98.50+ Ag
3
1
17R*
99.75+
Ag
18
98.5
+
1.2 Ni
5
6
180
0.6 98.3
+ 0.7 Ag
98
+
t
*
17P is plated,
17C is cast, and 17R is rolled,
t 0.5% Ca, 0.5% Na, 0.1
% Li + Al.
In the case of these alloys, the "tensile strength" is the stress producing
a deformation
of about 25 per cent, and the "yield strength" is the stress
producing
an elongation of 0.125 per cent of the gage length.
The lead-base white metals (class B, Table
10.2) are cheaper than the
tin-base alloys but are not so satisfactory for operation at high speeds and
194
medium loads. They are used extensively by the railroads for freight- and
passenger-car bearings, in electric motors, and in some machines. Alloys
B2 and B4 are used in a number of bearings in automobiles. The proper-
ties of this group of alloys also vary with composition, usually within the
following ranges:
Property
Range of values
Tensile strength, lb. per sq. in., at 70"F. (20C.) 12,800 to 15,500
Tensile strength, lb. per sq. in., at 200F. (95C).
.'
5.00 to 8,000
Yield strength, lb. per sq. in., at 70-F. (20"C.) 2,800 to 3.800
Yield strength, lb. per sq. in., at 200F. (95-C.) 1,200 to 2.000
Brinell hardness
(500 kg.), at 70F. (20"C.) 15 to 22
Brinell hardness (500 kg.), at 200F. (95C.) 6 to 11
It is evident from these values that the lead-base alloys are inferior in
properties to the tin-base metals.
As the temperature increases above 200F., the tensile and the yield
strength of the white metals decrease still more; values of 2,000 to 4,500
lb. per sq. in. are common for tensile strengths at 300 F. (150C.)
.
Elongation and reduction of area increase with temperature as, for ex-
ample, from 15 to 30 per cent and from 18 to 40 per cent respectively.
The constitution of the white-metal alloys is complex and is imperfectly
known. Essentially, the structure (Fig. 10.1) consists of a solid-solution
matrix in which needles or. cubes of a hard constituent, probably an inter-
metallic compound such as SbSn, are embedded.
Considerable work has been done recently to determine the effect of
small amounts of cadmium on the tin-base alloys. Apparently, 1 per cent
cadmium increases the tensile strength and hardness 10 to 20 per cent at
normal temperature and at 200 to 300F. (100 to 150"C.)
.
The copper base bearing materials as listed in class
G
of Table 10.2
have found wide application particularly in the automotive and other
transportation fields. The leaded bronzes (alloys of copper, tin, and
lead) in general are slightly superior to the white metals; their melting
temperatures are much higher and their properties less affected by the
operating temperature range encountered by bearings of this type. They
also have better fatigue life which is affected by repeated flexure.
Recent trends in bearing materials have been in the direction of silver
or cadmium based alloys, the oilless bearing as made by powder metal-
lurgy, and aluminum base alloys with tin as one of the principle alloying
elements. For a more complete picture of bearing alloys, their composi-
tion and properties, the reader is referred to the ASM Metal's Handbook.
The type metals are a series of lead based alloys with minor amounts of
tin and antimony which arc used in the printing industry. The choice of
Miscellaneous Heavy
Nonferrous Metals and Alloys 195
Fie
10.1. Structure of tin-base bearing metals (A) containing 86 per cent tin,
6 per cent antimony, and 8 per cent copper; and (B) containing 82 per cent tin, 10
per cent antimony, and
8 per cent copper: etched.
150x-
(Courtesy
of O. W. Ellis)
alloy depends on the printing
method used. In linotype machines it is
advantageous to have an alloy that freezes at nearly a constant tempera-
ture, hence the use of the ternary eutectic mixture of 84% lead,
12%
antimony, and
4%
tin. This alloy freezes at 462F. and makes possible
close
temperature control as well as good delineation of the type charac-
ters in the cast strip. In other printing methods a harder alloy may be
necessary and this may be obtained by adding copper in small amounts
to the type metal
or by solution heat treating and precipitation harden-
ing an alloy which has the necessary amounts of tin and antimony.
The artificial
aging operation often times can be accomplished in one
hour at 185F. or 1 minute at 212F.
These alloys are ideal for these applications since they must have
(1)
low melting temperatures,
(2)
low cost, and
(3)
good casting charac-
teristics.
Tin imparts
to the alloy fluidity which makes for ease of casting,
and the antimony increases the hardness and decreases contraction during
freezing. Both elements together lower the melting point of the alloy
and makes possible precipitation
hardening if needed.
The
fusible alloys are those which are noted principally
for their
low melting
temperatures usually
in the range of 125 to 450F. The
solders, which are primarily
mixtures of Pb and Sn, could be included
196
in this category; although their melting range is usually considered as
being from 360 to 570F. However, when alloying elements such as
antimony bismuth, cadmium, and Indium are alloyed with lead and
tin, the melting temperature of the resulting alloy may be as low as 1 I7F.
These alloys are used in the vital parts of safety mechanisms in fire and
explosion safety equipment. They are alloyed to melt or yield at
specified temperatures thus releasing fire doors or sprinkling equipment.
However, caution should be exercised in using these alloys where static
tensile loads are applied. Since these alloys have low melting tempera-
tures, they similarly have low recrystallization or cold working tempera-
tures. Hence, most of these alloys will under go creep at room tempera-
tures under static loading. Other uses for these alloys include patterns in
precision casting methods, forming dies for aluminum and magnesium,
filler material inside thin walled tubes during forming operations, cores
and forms on which other metals may be electroplated, and safety plugs
in tanks and cylinders of compressed gas.
10.2. Lead and Tin as Engineering Materials
While the preceding discussion has dealt with the alloys of lead and
tin, both metals are used in considerable quantities in commercially pure
form.
Lead is a soft metal (tensile strength of 2,000 psi) which is easily
formed by most fabricating methods. Part of this ease of fabrication re-
sults from the crystal structure of the metal which is face centered cubic,
and part from the fact that it will recrystallize at room temperature.
Thus all forming operations at room temperature results in hot working
the lead. Aside from its formability, lead is primarily noted for its cor-
rosion
resistance both to atmospheric conditions and to the acids sulphuric
and hydrofluoric. As such it is used in relatively pure form as sheet and
pipe in plumbing and building applications, in acid plants, and in the
handling of chemicals. Lead or its alloys is rarely used in strength appli-
cations where static loads exist, since it will undergo creep at room
temperatures. The principal uses for lead are
(1)
in storage batteries
(2)
as tetraethyl lead in gasolines
(3)
as a cable sheathing material
(4)
as
alloying element in solders and
(5)
as a building material. This is in the
order of the total yearly amounts used. Lead may be strengthened by
alloying with small amounts of cither antimony or calcium which pro-
duces a precipitation hardenablc alloy. The resulting room temperature
tensile strengths are as high as 12,000 psi.
Terne Plate, which is a lead based alloy containing 15 to
25%
tin hot
dipped onto sheet steel, is a competitor to zinc-coated products. It has
Miscellaneous Heavy
197
the good corrosion resistance of both lead and tin and the bright ap-
pearance and formability
of tin plate at a much lower
cost than tin plate.
Tin in the commercially pure form has essentially only one application,
the tin can. This involves depositing a thin layer of tin uniformly over
a steel sheet by either hot dipping or electroplating. The latter, while
more expensive,
has helped
conserve tin by producing
a thinner coat.
Tin has good corrosion resistance
particularly to foods and fruit juices
hence its use in the packaging
and canning industries.
However, on
steel the coat must be continuous to be protective. Otherwise an electro-
lytic cell would be established and the steel would corrode preferentially.
10.3. Zinc and Zinc Base Alloys
as Engineering
Materials
Zinc may also be considered
as one of the low melting point metals,
having a melting temperature
of 787F. This plus its good atmospheric
and salt water corrosion
resistance are the
characteristics which gives
zinc its place in the metals industry. The largest use of commercially pure
zinc is in the galvanic protection
of steel products-ga/wmzzmg
sheet,
tube,
and wire.
The protective
coat is applied either by hot dipping
the steel in molten zinc or
by electroplating.
The latter produces a
thicker coat providing longer
protection and without forming a brittle
intermetallic
compound
at the interface
between the zinc and the steel
which will crack and flake off when the product is bent. In recent years,
over
40%
of the zinc used in the United States has gone into galvanized
products.
Second, in importance in the use of zinc is the die casting industry.
Here, zinc alloys containing
up to a combined
6% of aluminum, copper,
and magnesium
are used. An increase in strength is achieved by this
alloying
and some dimensional
stability is attained in those alloys con-
taining
copper. The die casting alloys have a characteristic of shrinking
in size apparently
due to some phase change which
occurs upon aging.
Approximately
two-thirds of the total shrinkage
occurs in the first month,
and this is often times made to occur at an accelerated
rate by heating the
parts
3
to
6
hours
at 212F. The automotive
industry is probably the
largest user of zinc die castings.
Many of the accessories,
functional parts,
and decorative trim are produced by this method. It is an easy and eco-
nomical way of producing precision
parts which need little in the way of
finishing
operations.
Quite often they will
be chrome plated to enhance
their
appearance. The other
applications where zinc die castings are
used
are in household
appliances, office
equipment,
radios, toys, and
telephone
apparatus.
198
The mechanical properties of the zinc and zinc base alloys are
similar to those of aluminum and magnesium. Pure zinc has a tensile
strength of about 20,000 psi. The high strength die casting alloy has
a tensile strength of approximately 52,000 psi. However, this is not
meant to imply that zinc may be used for strength purposes. For at
room temperature, zinc and its alloys undergoes creep at loads exceeding
6,000 psi. This is as may be expected from its low melting temperature.
The fatigue strengths for these metals are of the same order being from
700 to 8500 psi depending upon the alloy.
The fabricating characteristics of zinc are good considering this metal
has a hexagonal close packed crystal structure. Some of the ease of fabri-
cation arises from the fact that pure zinc is hot worked when fabricated
at room temperature. Zinc and its alloys may be fabricated by practically
all of the known methodsrolled, drawn, spun, extruded, and cast. Some
difficulties are encountered in the joining of zinc, but with proper techni-
ques it may be gas welded or soldered.
Other uses for zinc include
(1)
use as an alloying element in brasses,
(2)
in photoengraving plates,
(3)
dry batteries,
(4)
weather stripping
and building materials, and
(3)
more recently as expendable anodes for
cathodic protection of underwater steel structures.
HIGH TEMPERATURE METALS AND ALLOYS
The early use of metals for high temperature usage was in steam
power generation and in the petroleum industry. In these applications
the operating temperatures were in the range of
1000
to 1200F. Other
uses at slightly higher temperatures were in ore roasting furnaces. How-
ever, in these applications corrosion resistance and economy are of pri-
mary consideration while mechanical strength of secondary importance.
More recently with the development of the gas turbine, jet engines, and
atomic energy, the operating temperatures have been edging upward and
the emphasis is more on mechanical strength along with corrosion re-
sistance. The early high temperature metals and alloys involved the
alloy steels and the nickel base alloys. As temperature and strength re-
quirements have increased the trend has been toward nickel, cobalt and
chromium based alloys. With the development of the cermets a new
approach to high temperature alloys has been made. In cermets, the
high temperature strength is attained from an intermctallic compound
usually a carbide of tungsten, titanium, chromium, tantalum, or noibium
embedded in a matrix of cobalt or nickel. Other examples involve
metal oxide embedded in a metallic matrix. The problem here is one
of improving the creep resistance of the metal or alloy. To do this it is
Miscellaneous
Heavy Nonferrous Metals and Alloys 199
necessary to produce a continuous matrix or network which has very
good strength
and corrosion resistance,
hence the carbides or metal
oxides. This then is surrounded
by a metal which has good oxidation
and corrosion resistance.
10.4. Nickel and Nickel Base Alloys
The metal nickel is in many respects similar to iron.
Its mechanical
properties, modulus of elasticity, and atomic diameter are quite similar.
Hence it will alloy with many of the same elements found in steels. It
differs principally in its corrosion
characteristics. It resists oxidizing
conditions
very well but will be susceptible to attack in reducing condi-
tions particularly
if sulfur is present. It resists atmospheric corrosion
quite well and often, where price will permit it, is used as a cladding ma-
terial on other metals for this purpose. Nickel is also often used as an in-
termediate layer in the chrome plating of steels.
Nickel Alloys. As aforementioned, nickel will alloy with many of the
other metal elements. It forms a continuous
series of solid solution alloys
with copper. It has a high solubility for such other metals as Co, Cr, Fe,
Mn, Mo, Ta, W, and Zn. The elements
Al, Be, Si, and Ti have only
limited solubility
and alloys of Ni containing small quantities of these
metals often exhibit precipitation
hardening characteristics.
Some of the
better known
nickel base alloys are as follows:
Monels
are a series of nickel-cop[>er base alloys containing approxi-
mately
65% Ni and
30% copper with small amounts of silicon, aluminum,
manganese
and sulfur. The Monels are primarily noted for their strength
and corrosion resistance.
The
Inconels contain appreciable quantities
of chromium and iron with
smaller
amounts of titanium,
aluminum, and niobium. These alloys
find application where high temperature
corrosion and oxidation re-
sistance is
important.
The Nimonic alloys were developed as a series which
had high strength
at high temperatures.
An early alloy containing
80% Ni and
20% Cr had
been used quite successfully as a heating element in electric furnaces and
appliances.
Modifications
of this alloy gave rise to the present Nimonic
series. The latest developments
in this series has large
quantities of
cobalt in place of the nickel
and small amounts of molybdenum, titanium,
and aluminum.
The Hastelloys are another series of high temperature
alloys developed
by the Haynes Stellite Company
and originally
were nickel base alloys
containing
appreciable
quantities of molybdenum and iron. However,
the newer alloys showed
decreases in the iron content with this being
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Miscellaneous
Heavy
Nonferrous
Metals and Alloys
201
replaced
by larger amounts
of chromium,
tungsten,
and cobalt. Some
precipitation
alloys
have been made containing
small amounts
of
titanium
and aluminum.
The Hastelloys
are fabricated
by the normal
working
methods but due to their high strengths
and good oxidation
and corrosion
resistance
require heavier
fabricating
equipment or higher
temperatures
to obtain the desired
deformation. Table
10.3 lists some of
the typical alloys falling
in these various categories.
They find applica-
tion where
operating
temperatures
are in the range of 1300 to
1800F.
10.5. Cobalt Base Alloys
The element
cobalt finds its greatest
application in alloy form. It is
used in other
metal systems
to increase
strength and corrosion
resistance
and, combined
with chromium
forms a series of alloys known as Stellites.
The
stellites will have cobalt
contents ranging from
67% down to
37.5%,
and with chromium
contents ranging
from 20 to
27%. The remaining
elements
present will consist
of varying
amounts of the following ele-
ments, Ni, W, Mo, Nb, Ti, and Fe. In addition to the above
elements,
these alloys will all contain carbon
percentages
from 0.1 to
0.5%, and the
carbon will be present in carbide form
making these alloys very hard and
brittle.
As such, with one or two
exceptions, these
alloys are usually
cast directly
to their final shape. By virtue
of their physical
properties
they are primarily
used where high
strength and abrasion
resistance is
required at high
temperatures.
Their
normal operating
temperature
range
,s from
1350 to 1800F. Other
uses for cobalt are in magnetic
materials
where it is alloyed
with Al, Fe, and Ni in "Alnico,"
and Fe plus
V in Vicalloy.
r
10.6. Other
Miscellaneous
High
Temperature
Metals and Alloys
Recent
experiments
have
indicated
the direction in which future re-
search
must
be aimed
in the development
of alloys for future higher
temperature
applications
in the range of 1800 to 2000F. Some of these
metals and
alloys will only be mentioned
briefly
here but will serve to
show
possibilities
and
shortcomings.
Recent work with alloys of iron,
chromium
and aluminum;
or iron,
molybdenum,
and aluminum
whose
alloys are
known as "Ironals"
have shown
promise as good high tempera-
ture alloys.
It is important
that little or no carbon be present.
Operating
temperatures
will be limited
to approximately
2100 to 2300F. Chromium
base alloys
are also possibilities,
but chromium
is difficult
to melt due to
its high vapor
pressure
and is very
reactive with oxygen
and nitrogen
which
makes
the alloy
very brittle.
Experimentation
with the
metals
molybdenum,
niobium,
rhenium,
tantalum
and vanadium
all of which
have high melting temperatures, as can be seen in Table 10.1, are for
the most part limited in use at high temperatures due to their oxidation
reactions. The oxides of Mo, V, and Re all volatilize at temperatures
below 1200F., while Ta and Nb form spongy oxides quite rapidly at or
above this temperature. It therefore appears that if these are to be used
for high temperature applications they will have to be clad with another
metal or ceramic which will keep oxygen away from the base metal.
OTHER METALS AND ALLOYS
10.7. The Precious and Semi-Precious Melals and Alloys
The metals and alloys which find themselves in this group are here by
virtue of their scarcity in nature and their usage as coinage and jewelry.
They are the metals silver, gold, platium, and the allied platium group-
palladium, iridium, osmium, rhodium, and ruthenium. Most of the
metals are found in nature in the metallic form or alloyed with the ores
of copper, lead, nickel, or zinc. Usually they are present in very minor
amounts and thus are obtained as by-products and only when the eco-
nomics of the operation make it worth while.
Silver. The element silver in the pure form is a soft white metal with
good corrosion resistance and high electrical conductivity. Since it is
quite soft, it is rarely used as a pure metal except perhaps as a plating
on jewelry items. When used as a base metal, it is alloyed with copper,
the common alloys being with 10% copper in coinage, and with
7.5%
copper as sterling silver. The silver solders have still higher copper con-
tents. Silver is also used in an amalgam in dental alloys and is combined
with tungsten and molybdenum by powder metallurgy for use as heavy
duty electrical contacts. As aforementioned, it is used rather widely in
electroplating of hardware, light reflectors and costume jewelry. The
amounts used here are quite small and their cost is negligible. However,
they add materially to the eye appeal and reflectivity of the base metal
and improve the oxidation resistance of the part.
Gold, like silver, is quite soft and corrosion resistant. Similarly, it
is rarely used in pure form due to its softness, the one exception being
as gold leaf in sheet form with a thickness of approximately 0.00005
inches. In this form it can be used in lettering, display, and decorative
applications. More often it is alloyed with copper, silver, or platium for
jewelry applications. When alloyed with platinum, palladium, and nickel
it takes on the characteristic white color and becomes white gold. Gold
can also be plated on jewelry either by dipping on the molten metal or
by electroplating. The latter yields heavier coats. Still thicker coats are
Miscellaneous Heavy Nonferrous Metals and Alloys 203
obtained by cladding with sheet material by rolling, soldering or brazing
the sheet to the base metal. The other application for gold is as a
medium of exchange on an international basis, for it is accepted through-
out the world.
The platinum metals while better known for their jewelry applications,
in actuality, find greater application in commercial uses such as cata-
lysts, high temperature corrosion resistant materials, electronics, and
the chemical industry. With the exception of palladium, the other metals
platinum, iridium,
osmium, rhodium, and rutheniumall cost more per
ounce than gold. Of this group, only platinum is used in pure form. The
others being used as alloying elements in platinum. Platinum is used in
making chemical and medical apparatus usually as an alloy containing
iridium. In pure form, platinum wire is used for a platinum-rhodium
alloy wire as a high temperature thermocouple. This couple readily
resists the high temperatures and oxidizing atmospheres that cause other
metals to fail rapidly.
Rhodium is sometimes used as a replacement for
silver on plated articles which will be subjected to sulfur atmospheres.
Rhodium has a silvery
appearance but will not tarnish under these con-
ditions.
10.8. Metals and Alloys in Atomic Power Applications
While considerable
interest has been
shown in recent
years in the
application of atomic energy for power purposes, much of the information
has of necessity
been withheld due to security reasons. However, the
part metals play in this new industry can be broken down into four fields:
(1)
as fuel elements,
(2)
as structural materials
or moderators,
(3)
as
control materials,
and
(4)
materials which can be irradiated and ber
come gamma ray emitters.
In the first category,
as fuel elements, it is necessary that the material
undergo atomic fission. While
many of the elements high in the period
table in terms of atomic number are radioactive, only uranium and per-
haps thorium
may be used as fuel elements.
It is necessary that the fuel
material
be rather
plentiful in nature
and undergo fission at a rapid
enough rate to make it economically
feasible as a source of energy. In
the second category, the structural
materials in an atomic reactor
should
be able to withstand the temperatures
involved, should not trap or absorb
neutrons, and should have
good corrosion
resistance. The metals which
meet these requirements
are aluminum,
beryllium,
and zirconium.
Zirconium seems
to be the preference particularly
where high tempera-
tures are
encountered.
In the third category are those metals which actually control the fission
rates in a reactor. The boron steels are the materials commonly used by
virtue of availability and ease of fabrication. Hafnium, which has a
greater capture cross section than the steels, is not as prevalent in nature
and hence is not as widely used. However, this is a field which is being
thoroughly investigated and other alloys will in all probability be de-
veloped.
In the fourth category are the metals cobalt, cesium, thulium, and
iridium. These metals when irradiated become radioactive and isotopes
of these metals are used as gamma ray emitters. The metal isotopes and
their halflife periods are listed in Table 10.4.
Tablc 10.4 Radioactive Isotopes
Isotope Av. Energy* Radiation Output mr/hr* Half Life
Cesium 137 670 KV 3750 27 yrs.
Cobalt 60 1200 KV 14000 5.3 yrs.
Iridium 192 375 KV 5950 75 days
Approximate
**Milli-roentgcns per hour at a distance of 12 inches.
These metals find wide usage in radiographic examination of metal
parts for internal defects. In many applications they have advantages
over x-rays. In general they are less costly, have greater portability, and
can be used in smaller places. The gramma ray source usually is smal-
ler than a cube 14 inch on each side. Exposure times for the radio-
graphic films are about the same as for high voltage x-rays.
QUESTIONS
1. List five metal elements which are noted primarily for their low melting
temperatures?
2. What are the "white metals," and for what are they principally used?
3. What are the principal requirements of a bearing alloy?
4. Why is a eutectic alloy used in linotype machines?
5. How does tin and antimony affect the casting characteristics of alloys con-
taining these elements?
6. What are the principal uses of lead, tin, and zinc?
7. Which of the metal elements do we consider as being high-temperature
materials
8. What is a cermet? How is strength at high temperatures attained in a
cermet?
Miscellaneous
Heavy
205
9. What are the
better known nickel-base
alloys, and what are the principal
alloying
elements in them?
10. In what ways is the element cobalt like nickel? What other uses is made of
cobalt?
11. Many of the elements have
high-melting
temperature; why can they not
be used as high temperature
metals or alloys?
12. Why are the metals gold, silver, platinum, palladium,
etc. so expensive?
13. What are the four categories for metals with respect to atomic energy?
14. What are the requirements of metals that arc used as fuel elements
in
atomic reactors?
15. Why is it important
that the structural materials
in atomic reactors
not
absorb neutrons?
How do they differ from the control materials?
16. Which of the elements are commonly
used as gamma ray emitters in radio-
graphic
examination?
17. How do gamma rays differ from x-rays?
Manufacture
of Metals
207
CHAPTER
The Manufacture and
Composition
of
Carbon
and Alloy Steels
11
Howard P. Davis, M.S., Associate Professor, Depart-
ment of Mechanical Engineering, University of
Wyoming, Laramie, Wyoming
Floyd Sheldon Smith, M.S., Associate Professor of Me-
chanical Engineering, Alabama Polytechnic Institute,
Auburn, Alabama
MAN has been using iron for at least 5,000
years. For almost half of this time he used it as a precious metal which
came from heavenas meteoritesand which was seized when found and
laboriously worked into jewelry, charms, and amulets. These he wore for
personal adornment or to ward off the evil spirits that harassed him daily.
For the last 2,500 years, he has had terrestrial iron, reduced from its ores,
and it is characteristic that the first use he made of it was to fashion
weapons. Damascus swords, made by the Moslems in the Middle Ages
from steel imported into the Near East from India, and by the famous
families of Japanese sword makers between a.d. 500 and 1500, are the
finest specimens of the early steelmakers' art which have come down to us.
They were made by welding alternate strips of high- and low-carbon steel
into a bar, forging out this composite material, doubling it over and re-
forging again and again until a laminated strip of the finest quality re-
sulted. This was drawn out into a sword or dagger blade, heat treated,
sharpened, and finally etched with a dilute acid to bring out the lamina-
tions. Such a blade is shown in Fig. 11.1, in which the blade and scab-
bard are photographed against a background of the damask pattern near
the dagger point, magnified eight times. Man's next use of iron was to
fashion tools, so that he could make life easier for himself.
Since the beginning of large-scale manufacture about 1870, steel pro-
duction has increased greatly each decade; by 1953 the world was using
over 258 million tons a year. Of this the steel industry of the United
States has been producing about 100 million tons annually.
208
The
Manufacture and Composition
209
Fie. 11.1. Damascus steel dagger. The background is a photograph of the etched
damask pattern of the blade.
8x-
(Ziegler, Mining and Metallurgy, v. 20, 1939, p. 69)
The use of chemical analysis for determining the composition of steel
and cast iron did not become general until about seventy years ago,
more than a decade after large-scale steelmaking
by the Bessemer and
the open-hearth processes had been introduced.
For many years the analysis
of steel and cast iron consisted of the
determination of carbon,
manganese, sulfur and phosphorus, silicon, if
present, and alloying elements when these were specially added.
Only in
210
the past few years has it been realized that these common elements tell
only a part of the story of the composition and that in addition some ten
or twelve other metals, metalloids, and nonmetals may be present. As a
result, the chemical composition of unalloyed steel is no longer as simple
as it seemed thirty years ago; on the contrary, it is very complex and
worthy of considerable attention.
Despite the fact that commercial carbon steels and cast irons contain
many other elements in addition to carbon, metallurgists look upon them
as alloys of the metal iron and the metalloid carbon because carbon has
the greatest effect on their structure and properties.
Commercial carbon steels contain, in addition to carbon, varying
amounts of manganese, silicon, sulfur and phosphorus, and small per-
centages of oxygen, nitrogen, and hydrogen. Occasionally they also con-
tain small amounts of copper, nickel, chromium, molybdenum, lead,
arsenic, aluminum, and tin. Some of these are added intentionally to
improve the quality, but most of them are picked up from the raw
materials used in the various processes. Steel men commonly divide these
elements into three classes: harmful, beneficial, and neutral.
11.1. Definitions of Ferrous Engineering Materials
For many years committees of metallurgists in English-speaking
countries have been trying to define carbon steel, alloy steel, cast iron,
pig iron, wrought iron, and other products of the industry precisely and
concisely, but with little success.
It would be a waste of space, and probably even confusing, if the
complex definitions for the numerous products of the iron and steel
industry were all set down at once.
Carbon steel may be defined as a commercial alloy of iron and carbon
containing less than 2.0 per cent carbon, less than about 1.30 per cent
manganese, less than 0.5 to 0.6 per cent silicon, small amounts of ad-
ventitious elements, and no intentionally added special element. If the
alloy contains more than 2.0 per cent carbon and is poured direct from
the blast furnace into cast iron molds of uniform
size, or is used in the
molten condition as an intermediate product, it is called pig iron; and if
this pig iron (usually with the addition of scrap) is remelted and poured
into a sand mold, thereby assuming the desired shape of the finished
section, it is known as cast iron. This means that whether an iron-carbon
alloy containing more than 2.0 per cent carbon is called pig iron or cast
iron depends upon whether the material is an intermediate product or a
finished product.
The Manufacture and Composition
211
Pig iron and cast iron have been differentiated here chiefly to indicate
some of the necessary distinctions in formulating definitions of ferrous
products. Pig iron is of little interest to the engineer; cast iron is an
important engineering material and is discussed in some detail later.
Ingot iron is a commercially pure iron. It contains between 99.75
and 99.90 per cent iron. The common elements, carbon, manganese,
silicon, sulfur, and phosphorus, account for about half the impurities;
the occasional elements make up the other half. Ingot iron resembles
carbon steel in that it is melted and refined by the basic open-hearth
process, but it is lower in carbon (about 0.02 per cent) than the lowest
carbon steels made industrially, which range from 0.04 to 0.08 per cent.
Ingot iron is used chiefly in the form of galvanized and enameled sheet.
Wrought iron is a low-carbon material and is no longer widely used.
The nature of the refining is such that this material contains a larger
proportion of solid nonmetallic inclusions than low-carbon steel made
by the usual processes. Owing to the nature of the process and the com-
position of the inclusions, wrought iron when rolled has relatively low
strength but is ductile and tough, and is easily welded. It is used for
staybolts, rivets, some grades of pipe, boiler tubes, and especially for
heavy chains and hooks. Wrought iron has well-marked directional
properties.
There is no precise and concise definition of alloy steel, but practically
there is seldom any difficulty in distinguishing between carbon and alloy
steels. The practical criterion is: if an element, not used primarily for
deoxidation
or degasification, is added to carbon steel or is present ad-
ventitiously in the amount required to produce a desired specific effect,
the resulting
material is an alloy steel.
It may be asked legitimately why the dividing line between carbon
steel and cast iron is placed at exactly 2.0 per cent carbon. Although this
percentage is fixed primarily for convenience, it has considerable scientific
justification. The 2.0 per cent carbon concentration marks the maximum
solid solubility of carbon in iron at very high temperature, and below
this concentration graphite
a common form of carbon in cast ironis
not ordinarily present under normal conditions of treatment.
For convenience, the commercial iron-carbon alloys may be divided
into four classes:
Low-carbon steel
Less than 0.25 per cent carbon
Medium-carbon steel
0.25 to 0.65 per cent carbon
High-carbon steel
0.65 to 1.70 per cent carbon
Cast iron and pig iron 2.50 to 4.50 per cent carbon
212
WOT
800'f
11.2. Iron Ore and the Manufacture of Pig Iron
The four essential raw materials of the iron and steel industry arc iron
ore, coke and coal, limestone, and scrap steel and scrap cast iron. The iron
ore used in the United States is chiefly hematite, an impure ferrous oxide
(Fe
2
O
g)
containing between 45 and 55 per cent metallic iron and be-
tween 20 and 35 per cent earthy matter, known as gangue, which is made
up of silica, alumina, calcium oxide, magnesium oxide, and water, plus
varying small amounts of phosphorus and occasionally sulfur. Hematites
and other usable iron ores are widespread throughout the world; the com-
mercial ores in the United States are
estimated at more than 10 billion tons,
of which 90 per cent is located near
Lake Superior and in Alabama. Iron ores
are graded by phosphorus content into
Bessemer and non-Bessemer (basic)
ores. As phosphorus is not removed in
the blast furnace, the ore must not con-
tain more than approximately half the
amount of this element permitted in
Bessemer steel.
Iron ore is reduced by coke in the
blast furnace, limestone being used to
flux the gangue and the ash of the coke.
The raw materials, in the approximate
ratio of 2 tons of ore (frequently includ-
ing some scrap steel or cast iron) to 1
ton of coke and
i/
2
ton of limestone, are
charged into the top of the furnace, and
air, preheated to
1000
F. (540C.) or
above, is blown into furnace through
a number of nozzles (called tuyeres)
near the bottom. The blast furnace,
shown in cross section in Fig. 11.2,* is a
steel shell lined with firebrick; 90 to
100 ft. high, 17 to 20 ft. in diameter at
the top, and 24 to 28 ft. in diameter
at the bosh (just above the tuyeres)
.
Operation is entirely continuous: The
raw materials, carefully weighed and
analyzed, are charged into the top at
*
Based on
J.
M. Camp and C. B. Francis, The Making, Shaping and Treating
of
Steel, Carnegie Steel Co., Pittsburgh, 5th cd., 1940,
p. 288.
Fig. 11.2. Cross section of a
modern blast furnace showing tem-
perature and chemical reaction
levels. (Based on Camp and Fran-
cis)
213
Row ,
materia!^
Limestone 774
Coke 1954 't5fi8
B^^3gfi
Ore, elc. 3925
Air 8500+
5000
Products <
10000
Sasesl2,000
_]
Kj
Slag 867
Ftc. 11.3. Relative proportions by weight of the raw materials and products of
the modern blast furnace. (Boylston)
frequent intervals and slowly settle to the bottom, the downward pressure
being slightly greater than the upward blast pressure plus the friction of
the burden on the walls of the furnace.
As the charge settles, the temperature increases (Fig. 11.2) until near
the bosh the iron ore is practically all reduced and the spongy iron is
heated to incandescence. Here it starts absorbing carbon, which lowers
the melting point. The iron then becomes pasty, absorbs carbon more
rapidly, and finally melts, trickling down over the remaining unburned
incandescent
coke into the hearth. The calcium oxide in the limestone
forms a fusible slag that is much lower in specific gravity than the iron
and that floats on top of the molten metal in the hearth from where it is
drained at regular intervals. The molten high-carbon iron is drained from
the hearth into ladles every 5 or 6 hr. and then
is either poured into
molds to solidify as pig iron or used in the molten condition in the
manufacture of Bessemer or open-hearth steel. A modern blast furnace
produces between
800 and 1 ,200 tons of pig iron every 24 hr. and, barring
shutdowns for economic conditions, will operate continuously for years.
The average proportion of the raw materials entering the blast furnace
and of the resulting products is shown graphically in Fig. 11.3.*
The slag
is mostly waste and must be disposed of, a considerable problem in some
plants. As Fig. 1 1.3 shows, an enormous volume of gas is given off. This
gas, which totals more than 100 million cu. ft. a day for a single furnace,
contains 20 to 25 per cent carbon monoxide and has a heating value
of
H. M. Boylston, Iron and Steel,
John Wiley & Sons, Inc., New York, 1935, p. 71.
214
90 to 100 B.t.u. per cu. ft. It is, consequently, used to heat the blast and
to generate power. Thermally the iron blast furnace is not efficient.
Owing, however, to the value of the gas as a by-product and to the
operation of large units, the over-all efficiency is relatively high, and pig
iron is made cheaply.
Chemistry
of
the Blast Furnace. The preheated air, which is blown
into the furnace under a pressure of 15 to 20 lb. per sq. in., comes into
immediate contact with incandescent coke forming large volumes of
carbon monoxide gas. This gas, together with the carbon in the coke,
reduces the iron oxide by two general reactions:
Fe
2
O
s
+ 3 CO * 2 Fe -f 3 C0
2
,
(1)
Fe
2
O
s
+ 3 C * 2 Fe + 3 CO.
(2)
Both reactions are reversible and may proceed in either direction de-
pending upon the temperature and other conditions prevailing at the
various levels in the furnace. The net result, however, is reduction of the
oxide to metallic iron. Both reactions are progressive: the Fe
2
O
s
is reduced
first to Fe
3 4
, then to FeO, and finally to Fe. Reaction
(1)
predominates
in the upper part of the furnace (see Fig. 11.2) , beginning at a tempera-
ture of about 400F. (210C.) ; reaction
(2)
begins at a temperature of ap-
proximately
1200F. (650C.) and continues until the iron oxide is com-
pletely reduced in the zone of the bosh.
The chemical reactions in the blast furnace are essentially reducing
so that any easily reducible oxides in the iron ore or the coke (in addition
to the iron oxide) are also reduced. Thus, all the phosphorus and most
of the manganese will be found in the iron. Oxides of silicon and sulfur
are more stable but are partially reduced. The remaining oxidesof
calcium, magnesium, and aluminumare very refractory and are not
acted upon by the carbon or carbon monoxide even at the highest
temperature of the furnace. To flux these refractory oxides, the necessary
amount of limestone (CaCO.,) must be charged. The limestone calcines in
the upper part of the furnace and, together with the calcium and mag-
nesium oxides in the ore, combines chemically with the alumina and with
part of the silica to form a fusible slag composed of calcium, magnesium,
and aluminum silicates.
The pig iron, tapped from the furnace, contains about 4 per cent
carbon, all the phosphorus, and most of the manganese in the raw ma-
terials. The amounts of silicon and sulfur in the iron are controlled to
some extent by a careful selection of raw materials but chiefly by regu-
lating the chemical characteristics of the slag, that is, by controlling the
proportion of calcium oxide to silica, and by controlling the tempera-
215
ture. The latter depends upon the amount of coke, the temperature
of the blast, the amount of water vapor in the blast (the humidity)
,
and other variables. The operation
of a modern blast furnace and the
production of cheap pig iron of satisfactory quality is an art which de-
mands long experience and skill of a high order.
Operation and Use
of
the Cupola. The cupola is a vertical, cylindrical
type of furnace, consisting of a steel shell lined with firebrick. Usually
the charging door is located 10 to 25 feet above the bottom of the furnace.
Air enters the cupola through the tuyeres, located
near the lower end of
the cupola. Fuel, metal, and flux enter the cupola through the charging
door. The initial charge of coke is known as the "bed charge." The
metal is deposited on the coke. Then alternate layers of coke and iron
are added. Generally
a limestone flux is charged
on the coke. The pur-
pose of the flux is to form a slag with the dirt, impurities in the metal,
and the coke ash.
The metal charge ordinarily consists of local gray iron scrap, purchased
gray iron scrap, pig iron, and steel scrap, where increased strength is
desired.
The proportions of various metals in the charge are governed by
the type of castings desired. The base of the charge is pig' iron. Since
the pig iron
is of known composition,
the greater the amount of pig iron
and the smaller the amount of scrap, the more uniform will be the
composition
of the resulting
castings.
For high grade castings, such as
automobile
cylinders, the percentage of pig iron will range from 25 to 50
per cent of the charge, while for low grade castings, almost no pig iron
will be used. Fluorspar, soda ash, and a number of proprietary fluxes are
sometimes
used in combination with
the limestone to thin the slag and
also to aid in the removal of sulphur.
Air is introduced
into the cupola
to aid in the combustion
of the
coke, which in turn melts the metal.
Under ordinary conditions the blast
pressure will range from 8 to 20 ounces per square inch, depending on the
height of the cupola
and the number and character
of the metal charges.
The ratio
of the coke and metal charges are ordinarily
one pound of
coke to eight
pounds of iron. The charges are very carefully weighed.
As the metal charge becomes molten it trickles down through the bed
charge of incandescent
coke and is collected in the crucible zone of the
furnace.
The liquid slag which collects above the molten metal is drawn
off through
the slag notch located just below the tuyeres. The molten
iron is drawn off through the tap hole, located at the bottom of the
cupola, into crucibles and
poured into sand molds to form gray
cast
iron castings.
11.3. Acid and Basic Processes
The reduction of iron ores and the manufacture of steel are chemical
processes and are unique in large-scale industrial operations in that the
chemical reactions involved take place at high temperatures, nearly al-
ways above 2000F. (1100C.) and usually in the range 2500 to
3500F. (1370 to 1925C). Few refractory materials withstand such
temperatures. The only ones that are available cheaply arc the oxides
of silicon, calcium, and magnesium. These are relatively inert at normal
temperatures but become active chemically at steelmaking temperatures:
silica (Si0
2)
becomes an active acid, and calcium and magnesium oxides
become active bases, reacting at high temperatures; thus,
CaO
+ SiO
s
- CaSiO
s , (3)
MgO + Si0
2
-> MgSi0
3
.
(4)
It is characteristic of silicates such as these that they fuse at temperatures
much lower than the fusing temperatures of the oxides.
Molten metals are refined by slags which are essentially silicates of
calcium, magnesium, and iron and are formed by a reaction between
definite amounts of a basic oxide and the acid oxide silica. Depending on
whether the basic or the acid constituent is in excess, the slag will have
a basic or an acid reaction at steelmaking temperatures. The character
of the refractories used in the furnacewhich is decided by economic
considerationsdetermines the character of the slag and thus determines
whether the process is basic or acid.
It is obvious that, if a furnace has an acid lining, the slag must be acid
in character or it would attack and destroy the furnace lining. Thus, in
an acid process the slag must contain an excess of silica, and in a basic
process, where the lining is magnesium oxide, the slag must contain an
excess of calcium oxide. The advantages of acid and basic steelmaking
processes may be summed up as follows:
Advantages
of
Acid Process. Acid slags contain less free oxide than
basic slags. Consequently, if all other things are equal, acid steels will be
cleaner and of higher quality than basic steel. Acid refractories are much
cheaper than basic refractories.
Advantages
of
Basic Process. The basic slags will remove phosphorus
and sulfur from the steel. Therefore, lower priced scrap and pig iron
can be used since it is not necessary to avoid small amounts of phos-
phorus and sulfur.
Fluxing materials used in the steelmaking process are classified as
basic, acid, or neutral according to their chemical activity at elevated
temperatures. Silica is the only substance that is classified as a strictlv
The Manufacture and Composition 217
acid fluxing material. Sand, gravel, and quartz are available in large
amounts and in sufficiently pure state to be used as acid fluxing materials,
but normally they are not used because the lining of the furnace will
furnish all that is required. In basic processes, silica might be used as a
flux if excess lime has been charged or where the raw materials are too
low in silicon.
Iron and manganese oxides act as basic materials when present in acid
processes, but they are not normally added for this purpose and therefore
are not classified as fluxing materials. The most common basic fluxing
materials are limestone and dolomite, limestone being mostly CaO, while
dolomite is a double oxide of calcium and magnesium. "Burnt" lime,
a calcined limestone, is usually added in the basic open hearth when more
than the amount furnished by charged limestone is found to be needed
at a later stage of the heat.
In order to make the slags less viscous without changing their acid,
basic, or oxidizing properties, a neutral substance with a low melting
point such as flourspar (mostly CaF
2
)
is most commonly used.
11.4. Bessemer Processes
Forty years ago, 25 to 30 per cent of the so-called tonnage steels were
made in the Bessemer converter. The price differential in favor of
Bessemer steel, averaging S2 to $4 a ton, disappeared some years ago owing
to the increasing scarcity and higher cost of low-phosphorus ores. This
condition, coupled with the disadvantage that Bessemer steel containing
more than about 0.20 per cent carbon is considered by many metallurgists
to be inferior in quality to steel of comparable carbon content made
by the basic open-hearth process, has resulted in the decline of Bessemer-
steel production to about 3 to 4 per cent of the total. During the past
15 years it has leveled off to between 3 to 6 million tons per year.
The Acid Bessemer Process. The acid Bessemer converter is a pear-
shaped steel vessel lined with silica brick and mounted on trunions by
which it can be tilted 180 degrees. The bottom contains a large number
of tuyeres to admit the blast. In making steel by the Bessemer process
the converter
is tilted forward, and 15 to 25 tons of molten pig iron are
poured into the belly of the vessel. It is then turned upright, and at the
same moment the blast is turned on. Refining begins immediately. No
external source of heat is needed as sufficient is generated, by the reaction
of oxygen with the carbon and other elements in the pig iron, to raise the
temperature several hundred degrees.
The blast of air entering the converter forms large volumes of iron
oxide as soon as it strikes the molten metal, which immediately oxidize
218
Fie. 11.4. Bessemer converter in operation. (Courtesy o\ Jones and Laughlin Steel
Corporation)
the manganese and silicon. The phosphorus is oxidized; but as there is
no excess of lime, stable phosphate is not formed, and none of this ele-
ment is removed from the metal. Sulfur is also unaffected.
The progress of the chemical reactions is followed by observing the
color and length of the flame shooting from the mouth of the vessel.
Refining is complete in 10 to 15 minutes when the manganese, silicon, and
carbon in the pig have been reduced to a low percentage, after which the
converter is tilted forward and the metal is poured into a ladle from
which it is poured into ingot molds. Harmful oxides are eliminated as
far as possible, and the proper amounts of carbon and manganese are
secured by adding an alloy of iron, manganese, and carbon to the ladle as
the contents of the converter are transfered to the ladle.
No slag-making materials are added; the slag formed is composed
of compound silicates of iron and manganeseoxidized from the pig
ironplus some silica eroded from the lining. It is acid in character.
Owing to the rapidity with which die reactions occur and to the large
volume of iron oxide formed, acid Bessemer steel usually contains more
dissolved iron oxide than basic open-hearth steel. The production
from a Bessemer plant of three vessels is 5,000 to 6,000 tons in 24 hours.
To produce the same tonnage of basic open-hearth steel, a battery of
twenty 100-ton furnaces is needed.
For many years, the Bessemer process has been important in the steel
industry, but, in contrast to the open-hearth process, little attention has
been paid to the chemistry or metallurgy of refining. In 1940, however,
some of the larger plants making Bessemer steel instituted a study of the
process, and some noteworthy developments resulted.*
A photo-electric
cell is now being used to determine precisely the end of the blow, and a
process has been developed for removing phosphorus by treating the
molten metal in the ladle. Very recently a method has been worked out
for deoxidizing
Bessemer steel, so that it is apparently equal in quality
to open-hearth steel of approximately
the same composition, with the
object of using this deoxidized material for seamless tubes and pipes.
The Basic Bessemer Process.
This process is not used in the United
States, mainly because the iron ore being used, and consequently the pig
iron being produced
from it, is not suitable for this process. It is
necessary that there be at least
2%
phosphorus present in the pig iron
in order that the oxidation
of the phosphorus during the
afterblow can
maintain the temperature of the bath high enough
to prevent solidifica-
tion. The silicon content must be low in order that the expensive basic
lining last as long as possible.
The operation of the basic process is similar to that of the acid process
except that lime is added, so the slag formed is basic and the phosphorus
will be removed. After the manganese, silicon, and carbon have been
oxidized
out there is the additional afterblow
during which the phos-
phorus is oxidized out of the steel.
These developments in Bessemer steel arc described in papers by Graham. Work.
McGinley and Woodworth, Yocum. lulton. Bowman, Wright, and Dunkle in Transac-
tions, Iron and Steel Division, American Institute ot Mining and Metallurgical En-
gineers, 1941, 1942, 1944. 1945.
The cost of the basic process is higher than the acid process due to the
higher cost and shorter life of the basic refractory lining, the longer
blowing time and the fact that lime has to be added to the process. In
Europe, where this process has been used with success, the high phos-
phorus ores necessary are available, and there is also a market for the
slag as a fertilizer, which helps overcome the higher cost of the process.
Fie. 11.4A Cut-away model of a modern open-hearth furnace showing roof con-
struction (upper left), bottom and port construction (lower left), cutaway checker
chamber showing brick construction (lower center), and stack (right). (Courtesy
H. W. Graham, Jones and LttUgMitt Sled Corporation)
11.5. Open-Hearth Processes
Description
of
the Modern Plant. The typical open-hearth furnace has
a capacity of 100-150 tons, with the largest furnace in the United States
having a capacity of 350 tons. The furnace is a chamber about 80 ft.
long and 18 to 20 ft. wide. The hearth is shaped like an elongated saucer,
the inside dimensions being about 40 ft. long, 14 to 18 ft. wide, and
20 to 30 in. deep at the center. The hearth lining consists of a mixture of
burned magnesite and basic slag sintered into place. The furnace is fired
tesy
ftC, I1.4B Pouring molten
blast-furnace iron into the open-hearth furnace. (Coxr-
\y of Carnegie-Illinois
Steel Corporation)
with gas, oil, tar, or powdered coal, using preheated air, and if a lean gas
is used, this is also pre-heated. At the center of the back wall is the tapping
hole,
8
in. in diameter, in such
a position that when opened it will drain
all the steel from the hearth into the ladle. There is a hole for the slag
runoff at the top level of the hearth and toward one end of the furnace.
The walls are made of silica brick, 13i/
in. thick, and extend 8 ft. above
the charging floor level. The charging doors make up most of the front
wall of the furnace and are lined with silica brick and have water cooled
frames, the bottom of the doors being just a few inches above the slag line.
The arched roof is 12 in. thick, made of silica brick, and is built in-
dependent of the walls so that it can be replaced without completely
rebuilding the furnace.
To attain the high temperature necessary to make steel, the regenera-
tive principle is used. White-hot exhausi gases from the furnace are led
through a series of brick checker-work chambers on the way to the stack.
After about 15 minutes, these exhaust gases are diverted to another set of
checker chambers at the other end of the furnace, and the cold air is led
through the heated checkers on the way to the furnace. The direction
of the exhaust and incoming gases is reversed every 15 minutes initially,
and the time interval is reduced as the temperature of the furnace ap-
proaches the tapping temperature. The reversal of the gases is automatic-
ally controlled depending on the temperature of the checkers and the
furnace. The regenerative process makes it possible for the gases to
attain a temperature of approximately 3500F. (1925C.) as they sweep
across the hearth, in addition to creating a saving in the amount of fuel
used in the furnace.
A hot metal mixer is usually located in the same area with the bank
of open-hearth furnaces. It is a large refractory-lined vessel capable of
storing as much as 1500 tons of molten metal from the various blast
furnaces until it is needed in the open hearth. Some are equipped with
heating devices but mostly they depend on the heat from the hot iron as
it comes from the blast furnace to maintain a molten condition in the
mixer. The mixer makes it possible to have a molten metal with a more
consistent chemical composition available to the open hearth, so that a
wide variation in the charge is not necessary, and also to decrease the time
from charge to tap of the furnace, because of the retained heat. This also
tends to cut down on the fuel used.
Operation
of
the Process: Charging. The order of charging the ma-
terials into the furnace is quite important. The limestone is charged first
in order that it will not enter into the slag reaction until the desired
time. Any ore charged into the furnace is placed on top of the limestone.
The limestone and ore protect the hearth from damage during the
charging of the scrap iron which follows immediately. II the scrap is
light and bulky it may be necessary to melt part of it down in order to
charge the rest into the furnace. When the furnace reaches a temperature
somewhat higher than the melting point of the pig iron, the molten
iron is poured into the furnace from a ladle, using a spout placed in
one of the charging doors.
The ratio of the amount of steel scrap to pig iron in the charge
varies according to the price of the scrap. When the price of scrap is low,
223
the charge might consist of 75% or more scrap and
25% or less pig iron,
but if the price of scrap is high, then a charge of
25% scrap and
75%
pig
iron is possible.
Melting the Charge. As soon as the steel scrap is charged into the
furnace, it is heated with a hot oxidizing flame that will cause the scrap
to melt and become oxidized. This oxidized material later becomes in-
strumental
in the purification of the pig iron by oxidizing out the
impurities. If enough oxides are not provided by the oxidation of the
scrap, additional oxidation is obtained by the ore that is charged in on
top of the limestone in the charge. This oxidation usually takes place
for about two hours after the start of charging, when at that time the
hot metal is added to the furnace.
The Ore Boil. As soon as the hot pig iron is added to the furnace the
oxides present begin to react with the impurities in the iron. First to be
removed are silicon and manganese, forming
SiO
a
and MnC) which, along
with FeO, combine to form the early slag. At the same time the oxygen
is combining with the carbon in the pig iron to form CO which, when
escaping, causes the slag to "froth" and increase in volume to such a
degree that
a considerable amount will overflow
through the slag run-
off hole.
In this manner much of the silica that would have to be
neutralized
by the limestone is eliminated, requiring less limestone to be
charged into the furnace. It is interesting to note that a good deal of iron
is lost here (as FeO in the slag) , and that sometimes this slag is re-
charged into the blast furnace
to recover both the iron and the man-
ganese from
their oxides.
The Lime Boil. After the ore boil has subsided, the temperature of the
furnace has reached the point where limestone will calcine, giving off large
volumes of
C0
2
. This characterizes
the "lime boil," which is much more
violent
a boil than the "ore boil." At the same time the lime formed by
calcination rises from the bottom of the hearth and replaces
the iron and
manganese oxides in the slag, with any excess of lime tending to make the
slag more basic. The basic property of the slag makes
it more capable of
retaining
phosphorus
in the slag as a phosphate.
This lime boil also
tends to mix thoroughly the contents of the hearth so that the chemical
composition and the temperature are more uniform
from top to bottom.
The Working Period. During
the working period there are several
specific aims. These include: (a) lowering of the phosphorus and sulfur
content
below the maximum values specified,
(b) eliminating
the silicon
and manganese residue
not oxidized out during the melting
period, (c)
eliminating
the excess carbon
as quickly as possible,
(d) conditioning
the slag so that it will be of the proper viscosity and have a basic chemical
224
composition, and (e) raising the temperature of the bath to approxi-
mately 150F. above the melting point of the steel to be tapped.
Tapping the Heat. When the carbon content has been reduced
to the desired amount and the temperature of the steel has been raised to
the tapping temperature, the heat is ready to tap. The clay plug and a
portion of the dolomite that fills the taphole is removed. The rest of the
dolomite is burned out with an oxygen torch, and the taphole is cleared by
using tapping rods from the front of the furnace. The center of the ladle
is placed off center in order to cause a swirling action and to insure rapid
melting and good mixing of the ladle additions.
Ladle Additions. Usually included in the ladle additions are alloys
of manganese to remove oxygen and sulfur, alloys of silicon that also
remove oxygen, and aluminum which is added to further the deoxidizing
process and also to control the grain size. In order to increase the carbon
content of the steel after tapping, some carbon is recovered from the
manganese alloys, and if more is needed it can be obtained by adding
ground anthracite coal to the ladle. Other intentionally added elements
may be added either in the furnace or in the ladle. All ladle additions
should be added before any slag comes from the furnace, otherwise they
become mixed with the slag causing high alloy losses and a possible
phosphorus reversion. By using varying amounts of these alloying ele-
ments, high quality steel of any desired carbon and manganese content
can be made.
Chemistry
of
the Basic Process. The basic open-hearth is an oxidation
process. Oxygen in the air or in some form of iron oxide (iron ore)
is used to oxidize the carbon, silicon, manganese, phosphorus, and part
of the sulfur in the charge.
In the basic open-hearth process limestone (CaCO
s)
is charged with the
scrap and pig iron; and when the metal is melted, this limestone, calcined
to lime (CaO) by the heat, rises to the top of the molten bath to form
slag. Iron oxide in the form of iron ore is added to augment the iron
oxide which, in the form of rust, was on the scrap and pig iron. The
iron oxide oxidizes the silicon and manganese first, according to the
reactions
Si + 2 FeO
'-*
SiO
a
+ 2 Fe,
(5)
Mn + FeO -> MnO + Fe,
(6)
MnO
+
Si0
2
- MnSiOg, (7a)
FeO + SiO, -* FeSiO.,. (7b)
The manganese and iron silicates, of low melting point and low specific
gravity, rise to join the slag. The phosphorus is then oxidized:
2 P 4- 5 FeO
-
P
a 8
+ 5 Fe, (8a)
P
a 5
+ 3 FeO - (FeO)
a
P
3 B,
(8b)
(FeO) ,P
a
O
B
+ 3 CaO - (CaO)
3
P
s
O., + 3 FeO. (8c)
The iron phosphate formed by reaction (8b) is unstable, but in the
presence of an excess of lime, reaction (8c) takes place, and the more
stable calcium phosphate is formed and also leaves the metal and joins
the slag.
Reactions
(5)
to
(8)
are exothermic and take place at relatively low
temperatures, as the charge is melting or just after melting is complete.
The oxidation of carbon,
C + FeO - CO + Fe,
(9)
by reaction
(9)
is endothermic and takes place only at high temperatures.
When all the impurities have been eliminated as far as possible or
desirable, the molten metal usually contains less than 0.10 per cent
carbon, less than 0.20 per cent manganese, less than 0.01 per cent silicon
and usually less than 0.03 per cent phosphorus. Sulfur drops from
above 0.04 or 0.05 to 0.025 or 0.035 per cent. As the result of these oxidiz-
ing reactions the molten metal also contains a relatively large quantity of
dissolved iron oxide which, as discussed in Section 11.10, is harmful.
It also contains too little manganese to combine with the sulfur. To
remove harmful oxide and to ensure the presence of sulfur as manganese
sulfide, manganese is added to the molten metal in the furnace or as it
is tapped from the furnace. This reacts with dissolved iron oxide,
Mn + FeO - Fe + MnO,
(10)
to form manganese oxide which is insoluble in the molten metal and
which rises to the top to join the slag.
The Acid Open Hearth Process. The open-hearth used in the acid
process is similar to that used in the basic process except that it is usually
smaller, and since the slag is acid, the lining of the furnace hearth is made
of acid material also. The initial charge consists of cold pig iron and
scrap. No ore is added because the iron oxide is basic and would react
with the lining of the hearth. For this same reason scrap alone is not
used as a charge, for it would oxidize and have the same detrimental
effect on the furnace lining. Only manganese, silicon, and carbon can
be removed readily; therefore a premium grade of pig iron and scrap
that is low in both phosphorus and sulfur is necessary. This tends
to increase the cost of acid steel over the basic type. The acid slag tends to
be less oxidizing than the basic slag, and for this reason there are fewer
oxide inclusions in the steel when it is poured, resulting in a "cleaner"
steel. The acid steel is usually tapped at a higher temperature, in
order that the steel may stand in the ladle for 30 minutes or more, thus
226
Fig. 11.5. Heroult electric furnace tilted for tapping, showing arrangement of
electrodes (Courtesy
of
American Bridge Company)
giving what inclusions are present a chance to rise to the surface and
enter the slag.
11.6. Manufacture of High-Quality Steels by the Electric Processes
High-quality carbon and alloy steels are made by the acid open-hearth
and the acid and basic electric process (Table 11.1). Most carbon tool
steels and special alloy steels are made in the basic-lined electric furnace.
Selected steel scrap is melted in an arc or induction furnace. The arc
furnace, shown in Fig. 11.5, produces most of these materials in lots of
5 to 70 tons; the induction furnace, with a capacity up to 5 tons, is used
chiefly to melt high-alloy steel scrap without loss of costly alloying metals.
The large arc furnaces are used chiefly for the production of low-alloy
steels by duplexing, that is, by refining further a charge of molten steel
that has been partly refined by the acid Bessemer or the basic open-hearth
process.
If the scrap contains too much carbon and phosphorus, these elements
are oxidized together with the silicon and manganese, under conditions
similar to those outlined for the basic open-hearth process on
p.
224.
When oxidation is completed, the slag is removed and a new one is
added, composed of lime, fluorspar, and silica sand or crushed ferro-
silicon. This slag, which consists principally of calcium silicate when
melted, is deoxidized, and strongly reducing conditions are established
in the furnace by scattering powdered coke or ferrosilicon over the sur-
face. Since slag and metal tend to be in equilibrium, eliminating iron
oxide from the slag also deoxidizes the metal. Furthermore, a strongly
reducing slag will remove sulphur almost completely from the metal.
Owing to the complete deoxidation of the slag and to the absence of
oxidizing gasesa condition attained only in the basic electric process-
much sounder steel can be made by this process than by either the acid
Bessemer or the basic open-hearth process where gases and slag are
strongly oxidizing at all times.
The acid electric process combines the nonoxidizing character of arc
heating with the lining and slag of an acid process. Acid electric steel is
usually not so well deoxidized as basic electric steel, but it is cheaper.
The small acid electric furnace is especially suitable for intermittent
operation and, owing to the high temperatures of the arc, is widely used
for melting steel for small high-grade castings.
The acid process is also used to produce ingots, high-quality forgings,
ordnance and alloy steel. The furnace charge is usually all scrap, and
practically the same purifying procedure is used as in the acid
open-hearth. The steel can be more thoroughly deoxidized since the
oxidizing effect of the furnace gases on the slag is eliminated. The
process is used mainly to melt and refine carefully selected scrap low in
phosphorus and sulfur, as the process will remove neither.
The general features of the various steelmaking processes arc sum-
marized in Table 11.1.
11.7. Wrought Iron
Wrought iron is a ferrous material of highly refined iron incorporated
with 1 to 4 percent of a ferrous silicate slag. Two primary methods are
228
Engineering
Metallurgy
used in its manufacture:
(1)
the puddling process, and
(2)
the Aston or
Byers process.
In the puddling process, a charge, weighing about 600 pounds, of iron
scrap, pig iron, iron ore, and mill scale are melted and refined in the
puddling furnace. The fuel used for heating and refining the charge is
bituminous coal burned on grates at one end of the furnace. After the
charge is molten, it is mixed by the operator, using the puddle bar. Dur-
ing the refining period, the oxidization of the carbon, silicon, and man-
ganese is brought about by reaction with the iron oxide. As the refining
progresses, the melting temperature rises, so the temperature within the
furnace is not sufficiently high to keep it molten, and it becomes a plastic
mass known as a puddle ball. The puddle ball is then removed from the
furnace, squeezed and rolled into bars to eliminate much of the en-
trained slag. The bars, known as "muck" bars, are cut into short lengths,
fastened together in piles, reheated to a welding temperature and rolled.
If this process is repeated a second time, the product is known as
double-refined iron.
The Aston or Byers process consists of melting Bessemer grade pig iron
in a cupola and refining it in a Bessemer convenor until the carbon,
silicon and manganese are removed. At the same time, an iron silicate
slag of the same composition as that produced in the puddling operation
is prepared in an open-hearth furnace.
The refined metal is poured at a predetermined rate into a ladle, called
a thimble, containing the molten slag. The temperature of the metal is
higher than that of the slag and the former rapidly solidifies. Gases are
liberated during the solidification period and the metal disintegrates into
small globules sinking to the bottom of the thimble to form a spongy
mass. This operation is known as shotting. The excess slag is then poured
off and the solidified ball of metal, containing slag, is transferred to the
squeezer and rolls where the same procedure follows as in the case of
puddled iron. Wrought iron is a highly ductile material and is used for
pipe and pipe fittings, bolts, sheets, bars, and plate.
11.8. Special Steel-making Processes
The Duplex Process. The acid Bessemer and the basic open-hearth
are used in succession. Most of the carbon and all of the silicon and
manganese are oxidized in the converter and then the metal is transferred
to the basic open-hearth where the phosphorus, sulfur, and the remainder
of the carbon are removed. Under good conditions an open-hearth may
produce up to twice the tonnage per week by the duplex process.
230
The Super-refining Process. This is a special duplex process in which
purified basic open-hearth metal is transferred to a basic electric furnace,
deoxidized, and finished into high-quality electric steel. Care is taken
to have the residual manganese as high as possible in the open-hearth
product. Carbon is added to bring this component near the required
finishing range. Since no further oxidation is required the basic carbide
slag is immediately charged, and dcoxidation and de-sulfurization are
carried out by the carbide and the residual manganese in the metal.
The Triplex Process. This process is carried out in two ways:
(1)
a
combination of the acid Bessemer and two open-hearths in succession, or
(2)
a combination of the duplex and super-refining process. The first
is used when pig iron is very high in phosphorus. The open-hearth is
tapped and charged into another open-hearth where a new slag is built
up and the rest of the phosphorus and carbon removed.
The Talbot Process. This is a process that results in a very large
tonnage of metal in a very short period of time. The increase in capacity
is obtained by using a bath of metal forty or more inches in depth. The
first charge, usually consisting of pig and scrap, is worked down to the
desired composition, and about one third of the metal is tapped. Ore
and limestone are added to the bath to produce a very basic oxidizing
slag. Molten pig iron, equal to the metal tapped, is poured through the
slag. The reaction is so rapid that the silicon, manganese, and most of the
phosphorus is removed. The charge is then worked down to the required
carbon and phosphorous content as the temperature is raised. For a period
of from 3 to 6 hours, the bath is purified, and another heat is tapped
The slag is reoxidized, more pig added, and the procedure repeated. At
the end of a week the furnace must be drained and the lining patched,
making the process very expensive.
The Duplex Talbot Process. This process is a combination of the
Talbot and Duplex processes. Metal from the Bessemer converter, free of
carbon, silicon and manganese, is poured through the oxidized slag, the
phosphorus being removed almost immediately. The addition of pig iron
raises the carbon content and aids in deoxidation.
The Monell Process. Limestone, ore, and sometimes steel scrap, are
charged upon a basic hearth and heated until pasty. Molten pig iron is
then added. The low temperature will remove the phosphrous very
rapidly with a violent reaction. The silicon, manganese, and carbon is
worked down in the usual manner.
The Campbell Process. A charge of pig and scrap is melted in a Camp-
bell tilting basic furnace and the phosphorus, silicon, manganese and
part of the sulfur are removed. The furnace is tapped and the metal
charged into an acid open-hearth furnace. An acid slag is built up and
the heat is finished by the usual acid procedure.
The Crucible Process. The crucible process consists of melting properly
proportioned scrap, fcrro-manganese and charcoal in a closed crucible.
This is primarily a mixing and refining process. Each crucible holds 50
to 100 pounds of metal, which is heated in a gas fired regenerative
furnace for approximately four hours for complete refining.
11.9. Mechanical Treatment of Steel
Ingot molds: Types, Sizes, Shapes. Most of the steel made in the
United States is cast into ingot molds of one type or another, irrespective
of the type of steel, for further fabrication into desired shapes. This is
done, rather than casting into desired shapes directly, because of the
better physical properties obtained, and because it can be done much
more cheaply. Two general types of ingot molds are used in the United
States: the big-end-up and the big-end-down. As their names imply, the
big-end-up mold is larger at the top, and the big-end-down is larger at
the bottom.
Most steel is solidified in the big-end-down type mold, since it is suit-
able for the cheaper semi-killed steels and for the rimming-type steels.
These steels avoid shrinkage or actually increase in volume in the molds
by the evolution of gases on cooling, thereby avoiding the formation of
"pipe." By the use of a "hot-top," a refractory collar added to the mold,
killed steels may be poured into big-end-down molds because the steel
in the hot-top section is kept molten and will fill any cavity produced by
shrinkage.
Big-end-up molds tend to produce less pipe since there is a larger
volume of steel at the top of the ingot, and it remains molten longer.
However, when used with killed steels, a hot top is generally used.
Big-end-up ingot molds are more costly and are generally reserved for
high-quality and alloy steels.
Bottom-poured ingots are those in which the metal is introduced from
the bottom, usually into big-end-up molds with refractory hot-tops. Due
to the complicated arrangement for pouring, they are more expensive and
are usually reserved for high-quality and high-alloy killed steels.
Hot Working. After the ingot has solidified, it is transferred to a
soaking pit or heating furnace to equalize the temperature and to heat
it to a temperature at which the steel is very plastic. It is then hot
worked by rolling, pressing, or forging it into a finished or semifinished
product. A few special carbon and alloy steels used in very heavy sec-
232
tions, such as large guns, axle shafts, armor plate, and the like, and a few
tonnage products are worked from the ingot directly into the finished
section. It is, however,
considered better practice, whenever the size
of the finished product permits, to reduce the ingot to a section known
as a bloom, slab, or billet, which is reheated, either with or without
intermediate cooling and inspection, and is rolled into finished products.
These may be rails, structural shapes, plates, sheets, strip, pipe and tubes,
bars, or rods of a wide variety of sizes and forms. Finished sections from
the large rolling mill, especially bars and rods, may be fabricated further
into a multitude of small articles.
Hot working has two primary objects:
(1)
to produce various shapes
and sizes economically, and
(2)
to improve the structure and properties
by breaking up the coarse crystal structure of the ingot.
Cold Working. A large tonnage of hot rolled bars, rods, sheets, pierced
tubing, and other hot rolled products are worked at room temperature.
This operation is known as cold working. Cold working is a finishing
operation and the articles coming to this stage have been roughly shaped
by hot working. The general methods of cold working are cold rolling,
cold drawing, cold pressing, or stamping. Hot rolled shapes are finished by
cold rolling and cold drawing processes to produce smooth surfaces, ac-
curate dimensions, and increased strength. The drawing of hot rolled
rods through dies is used principally in making wire and in finishing
seamless steel tubing. In the cold pressing or stamping process, plate and
sheet for various purposes are often shaped between dies by means of a
heavy hydraulic press.
Cold working also has two primary objects:
(1)
to produce sections,
sizes, and shapes that cannot be produced economically by any other
method, and
(2)
to produce certain combinations of properties, especi-
ally very high strength accompanied by considerable ductility, that also
cannot be secured economically by any other process.
The mechanical treatment of steel is an art that has been perfected
mechanically until it is now in a relatively high state of development.
Hundreds of millions of dollars have been invested in rolling mills and
forging plants that are marvels of mechanical efficiency and low-cost
production. Modern rolling mills, such as the recently developed con-
tinuous strip mill, are, in fact, such marvels of costly perfection.
Although the mechanical equipment used and the methods of hot and
cold working
are a fascinating field for discussion, they are of little con-
cern to the engineer who uses steel and who does not care whether strip
is rolled on a continuous or a hand mill so long as it has the properties
he requires and is cheap enough for him to use economically. The effect
of hot and cold working on the structure and properties, a subject of great
interest to most engineers, is given more consideration elsewhere in this
book.
Steel and other metallic materials that have been hot or cold worked
(or, in some instances, cast) frequently must be joined together to form
the finished structure. The principal methods of joining are welding and
riveting. The equipment and the methods used for joining are of much
interest to engineers but are hardly wilhin the scope of a book on ele-
mentary metallurgy and are, therefore, not discussed further here.
11.10. Harmful Elements in Carbon and Alloys Steels
The five so-called harmful elements present in all steels in varying
amounts, but mostly in small fractions of 1 per cent, are phosphorus,
sulfur, oxygen, nitrogen, and hydrogen.
Phosphorus. In the amounts usually present in carbon and alloy steels
phosphorus is combined with the iron as iron phosphide (Fe
3
P) , which
dissolves in solid iron as sugar dissolves in coffee. Although metallurgical
opinion is not wholly unanimous, most available data, plus many years of
experience with acid steels containing 0.07 to 0.12 per cent phosphorus,
indicate that this element makes steel cold short, in other words, brittle
when cold, particularly in its resistance
to impact. This brittleness is more
marked in high-carbon steels than in low-carbon grades and is apparent
if the amount of carbon plus phosphorus is above 0.30 per cent. The
static ductility is not appreciably affected.
Because of the brittleness caused by phosphorus, the maximum amount
permitted is usually given in engineering specifications. This varies from
a maximum of 0.10 to 0.12 per cent in low-carbon acid Bessemer steels
to a maximum of 0.045 per cent in rails and railway materials, structural
shapes, sheet, strip, and other products of the basic open-hearth process.
In tool steels and other high-grade high-carbon and alloy steels, the
maximum permitted is usually 0.03 and occasionally even 0.02 per cent.
The average amount of phosphorus in various grades is shown in
Table 11.1.
Despite the fact that, in general, phosphorus has a bad name and for
nearly a hundred years has been considered a nuisance that should be
kept as low as possible, it has been discovered lately that it has its good
points.
It raises the tensile and the yield strength and improves
other
proj>erties, including the resistance of steel to some varieties of corrosive
attack. Some of the new low-alloy high-strength steels contain about
0.10 per cent phosphorus used together with small
amounts of copper,
nickel, or chromium. The carbon, however, is low.
234
Sulfur. In a manner analogous to that of phosphorus, sulfur will com-
bine with iron to form iron sulfide (FeS), which dissolves in molten iron.
However, manganese, if present, having an affinity for sulfur which it
does not have for phosphorus, will rob the iron of its sulfur to form
manganese sulphide (MnS) . This compound is almost completely insolu-
ble in solid iron. Consequently, when the iron solidifies, manganese sul-
fide is present in the mass of metal as discrete particles. These particles,
together with oxides and silicates, are known to the metallurgist as solid
nonmetallic inclusions or, more simple, as inclusions, and to the man in
the mill by the more expressive term dirt. If insufficient manganese is
present, some of the sulfur remains as iron sulfide. This compound melts
at a temperature lower than the usual temperatures for rolling or forging,
with the result that the steel is likely to crack during hot working. This
brittleness or fragility at elevated temperatures is known as hot shortness.
Practically all commercial steels contain plenty of manganese, so that
engineers who use steel at elevated temperatures need not worry about
hot shortness caused by sulfur. Of much more interest to engineers is
the fact that manganese sulfide particles are always present and that
they may be present in large amounts if the sulfur is high. If these
particles segregate in vital areas, they may have a deleterious effect on the
ductility of the steel; in fact, impact resistance may be greatly reduced.
Any particle of dirt in the metal, if large enough, if the shape is favorable,
and if it is strategically located, may act as a stress raiser and cause
failure, especially by fatigue, much sooner than would normally be
expected.
Sulfur has few virtues when present in steel. Compared with phos-
phorus, it is a real nuisance and is, therefore, kept as low as possible.
Its only benefit, so far as is known now, is that, if the manganese sulfide
is present in the proper amount and is well distributed, it makes the
steel easier to machine. Steels that are machined automatically at high
speeds and that are used for parts that are not subject to high impact
stresses contain 0.080 to 0.150 per cent, or even more, manganese sulfide.
With higher sulfur percentages the manganese is frequently increased
from the usual amount in low-carbon steels, namely 0.30 to 0.60 per cent,
to O.fiO to 1.65 per cent to ensure that no iron sulfide is present. The
average sulfur percentages for various grades of steels made by the
different processes are shown in Table II. 1. In general, the higher
amount of the range is the maximum permitted by the usual specifica-
tions.
Oxygen. All steel, except that made by some special variants of the basic
electric process, is melted and refined by gases and slags that are essen-
tially oxidizing. At the high temperatures used, oxygen combines avidly
with iron, carbon, manganese, silicon, and some other elements that may
be present, forming a variety of gaseous or liquid oxides. Some of these
dissolve in molten steel and are thrown out of solution when the steel
solidifies, others are deoxidized by later slags or by alloys added especially
for this purpose. The result of these deoxidizing reactions, which are
more effective in some processes than in others (see Table 11.1), is to
produce a steel which is more or less free from oxygen and its reaction
products. Even under the best conditions, however, the steel is never
wholly cleansed; hence, all steels when solid contain a larger or smaller
quantity of gas cavities or solid inclusions bearing oxygen in some form.
These oxides or combinations of oxides (silicates) form, together with
sulphides, the most common source of the solid nonmetallic inclusions or
dirt found in commercial' steels. Like sulfide inclusions, oxides and
silicates, if segregated or if present in large particles, may act as stress
raisers or as loci of weakness where, under favorable conditions, failure
may start.
Inclusions that are entrapped in the steel ingot (or casting) when it
solidifies arc usually in the form of small rounded particles varying in
size from those which are submicroscopic to those which can be seen
on a polished surface with the unaided eye. At high temperatures most
of the inclusions are plastic. Consequently, when the ingot is rolled or
forged, they elongate into stringers or threads. It should be emphasized
that inclusions, once they are entrapped in the steel, may be distorted,
elongated, or otherwise changed in form by hot or cold work, but they
cannot be removed or even diminished in amount by any treatment. No
commercial carbon or alloy steel is wholly free from dirt. The amount
present and the degree of dispersion of the particles depend to a con-
siderable extent upon the nature of the melting process. As indicated in
Table 11.1, basic electric steel is inherently the cleanest, acid electric steel
ranks next, and acid Bessemer steel ranks lowest. The process itself is,
however, not the only factor. Also important are quality of the raw
materials used and the skill
of the man who makes the steel.
It has been well known for many years that most ferrous materials
exhibit directional properties, that is, some properties, notably impact
resistance, are lower if determined on a specimen cut at a right angle
to the direction of rolling than if determined on a specimen taken longi-
tudinally. Elongated inclusions are an important factor in causing this
difference in properties.
Owing to the impure raw materials available to the iron and steel
industry and to the necessity of using-except in a few restricted cases-
236
oxidizing reactions to get rid of these impurities economically, one of the
chief problems of steel men has been to eliminate the harmful effects of
oxygen and its compounds by deoxidizing as thoroughly as possible. For
more than sixty years one of the principal tenets of metallurgists has been
"the more complete the deoxidation, the better the steel." Within the
past twenty or twenty-five years, however, it has been found that the
phrase "for certain steels" should preface this doctrine of deoxidation.
McQuaid, Bain, and other investigators in this field have shown that
a certain degree of oxidation may be very desirable in some carbon and
alloy steels in which a control of the grain size is advantageous.
The amount of oxygen in solid steel varies from a trace to as much
as 0.02 per cent: few steels contain less than 0.005 per cent; the average
amount in commercial carbon steels is probably between 0.01 and 0.015
per cent, with the higher amounts found normally in the lower carbon
grades. Most of the oxygenprobably all of it in most steelsis present
as an oxide or silicate. Small amounts of oxygen are difficult to deter-
mine accurately by chemical analysis, and it is even more difficult to
determine in what form it exists in the metal.
Nitrogen and Hydrogen. Although the mechanism is not well under-
stood, it is generally conceded that the presence of either nitrogen or
hydrogen in carbon and alloy steels will tend to increase their brittle-
ness.
11.11. Manganese in Carbon and Alloy Steels
Manganese is an essential and a beneficial element in nearly all
grades of steel because it performs a vital dual role: It combines with
sulfur to form manganese sulfide, a less obnoxious impurity than iron
sulfide; and, as noted previously, it deoxidizes the .metal by reacting
with oxygen to form an oxide which is less soluble in molten steel than
iron oxide and which, therefore, will leave the metal more readily. The
amount used varies with the grade of steel and with the amount of
oxidation in melting; enough is added to most steels so that, after its
purifying action has been completed, 0.30 to about 0.75 per cent, occa-
sionally as much as 1.00 per cent, will be left in the metal.
A small amount of manganese also increases the strength of steel.
Either alone or, preferably, in combination with relatively small amounts
of other alloying elements, it produces such a favorable combination of
properties that the so-called intermediate-manganese alloy steels are
finding increasing use in some fields of engineering, especially for rail-
road rolling stock and in bridges. They were also widely used during
the war as a substitute for low-alloy steels containing considerable nickel.
The amount of manganese in these steels ranges from about 1.00 to 1.90
per cent. There is considerable confusion, even among metallurgists,
about the dividing line between these steels and carbon steels as some
steels that are made and used as intermediate-manganese alloy materials
may contain 1.00 per cent or even less, and a few steels that have for
years been classed as plain carbon steelsrails are an examplecontain
as much as 1.00 per cent or even more manganese. If carbon steel and
intermediate-manganese steel cannot be differentiated by their manga-
nese content, they can sometimes be classed according to the industrial
application for which they were made. This is a glaring example of the
slipshod terminology that has grown up over the years in the iron and
steel industry and that confuses maker and user, metallurgist and engi-
neer, alike.
11.12. Carbon Monoxide, and Rimming and Killed Steels
As a result of the reaction between oxygen and carbon in the molten
metal large volumes of carbon monoxide gas are formed. Most of this
gas is given off during refining; some of it, however, remains entrapped
and, unless removed
by silicon or other degasifier as described in

11.13,
will be still in the metal when it starts to solidify.
Most of this remaining
carbon
monoxide escapes during solidification. Owing, however, to the
viscosity
of the metal just before it solidifies, some of the gas remains
entrapped to form
cavities of varying size in the ingot or casting. These
cavities-blow
holes as they are commonly called-will usually weld in
rolling or forging, especially in low- and medium-carbon
steels, and will
disappear. If, however, the inner surface
of the cavity becomes oxidized,
which frequently happens in heating for rolling when the cavity is near
the surface or if the steel is high in carbon, the surfaces of the cavity do
not weld and the result is a defect
known as a seam (Fig. 1 1
.6). Seams
are usually located on the surface of
the rolled section where they can be
detected and removed by machining,
chipping,
or grinding;
but they may
be internal,
and if so they may, like
inclusions, act as loci where premature
failure will start.
Carbon steels are frequently classi-
fied
according to the method of re-
moving
gas cavities
or rendering them
Kic. 11.6. Scams on the surface of a
innocuous,
as killed, or rimming
shaft.
2x-
types.
238
Killed steels, which nearly always contain more than 0.25 or 0.30 per
cent carbon, are those which must be thoroughly sound and free from
gas cavities. The descriptive adjective comes from the action of the
molten metal when poured into the ingot mold: it lies perfectly quiet
with no evolution
of gas; there is neither bubbling nor churning of the
upper surface of the metal. Killed steels are degasified by silicon, alumi-
num, or other degasifiers. All plain carbon forging steels, all rails, all
high-carbon tool and spring steels, and all alloy steels are thoroughly
killed.
Rimming steelso called from the rim
of solid metal next to the mold wall
(Fig. 11.7)is low-carbon basic open-
hearth steel in which deoxidation is partly
completed in the furnace or in the ladle
but which is not degasified. When the
steel is poured into the ingot mold and
begins to solidify, there is a brisk but
controlled evolution of gas which results
in an ingot having a sound gasfrec surface
and in locating the blow holes so far be-
low the surface that there is no danger of
their becoming oxidized when the ingot is
heated for rolling (Fig. 11.7). The blow
holes will weld completely in rolling, and
the result is a material with a clean sur-
face free from seams. Rimming steels are
especially suitable for sheet and strip,
notably for thin, deep-drawing stock used
in large tonnages for automobile bodies
and fenders. Close control of the slag
composition (particularly the amount of
iron oxide) , slag viscosity, and the pouring
temperature, is necessary to produce a
steel that rims properly when it solidifies.
Most basic open-hearth steels contain-
ing less than 0.15 per cent carbon are
made so that they rim; steels containing
Fig. 11.7. Cross section of an in-
0.15 to about 0.25 per cent carbon, used
got of rimming steel about one-
jd , f structural shapes and plate,
twentieth natural size. (Courtesy
of
' <
"
'
American Rolling Mill Company)
are killed or are partly killed.
11.13. Silicon and Other Degasifiers
Like manganese, silicon is beneficial and is added to carbon steel as
a purifier and, in larger amounts, as both purifier and alloying element.
It is effective in removing oxygen and is, therefore, added to those grades
of steels (usually containing more than 0.30 per cent carbon) in which
gas cavities do not weld readily or are otherwise harmful. Silicon is so
used in a fe"' medium-carbon and high-carbon basic open-hearth steels
(for example, rails) , in practically all acid open-hearth and acid electric
steels, and in all basic electric steels. It is added rarely to such low-
carbon basic open-hearth steels as structural material, wire, sheet, plate,
and strip or to those low-carbon Bessemer steels which are used for
pipe and tinplate. The reaction product of silicon with carbon monoxide
gas is silica (Si0
2),
which reacts readily with manganese oxide and iron
oxide, forming silicates. These are insoluble in the molten metal and are
of such low specific gravity that they readily leave the steel. Silicon thus
carries deoxidation farther than manganese and is in addition an effective
degasifier. Enough is added to complete the purifying reactions and leave
0.10 to 0.40 per cent in the finished steel.
There is occasionally some confusionbut not so much as in the case
of manganese
in distinguishing between a silicon-treated carbon steel
and a silicon alloy steel. Some specially deoxidized open-hearth steels
used in bridge construction,
containing around 0.25 per cent silicon, have
been and still are termed silicon steels by civil engineers. This is un-
fortunate, and it is hoped that the tendency to call a material silicon
steel only if the silicon is 0.50 per cent or more will become more wide-
spread. Steels containing 1.50 to 2.25 per cent silicon and about 0.75
per cent manganese are used widely for springs, and steels containing
0.5 to 5.0 per cent silicon and small amounts of other elements are used
in the construction of dynamos and other electric apparatus.
Small amounts of aluminum and titanium are added to some grades of
carbon steel as final deoxidizers and degasifiers. It has been discovered
recently that aluminum, probably through the agency of minute alumi-
num oxide particles, can be used to control the grain size of carbon and
alloy steels. As this is one of the major recent developments in ferrous
metallurgy, it receives detailed attention elsewhere in this book. Both
aluminum and titanium are also used, in much larger amounts than is
necessary for deoxidation and degasification,
as alloying elements.
11.14. Other Elements
Since the introduction
of alloy steels some fifty years ago there has
been a gradually increasing contamination
of carbon steel by nickel.
240
copper, and other alloying elements owing to the inadvertent mixture of
alloy-steel scrap with the other scrap. In the case of elements that oxidize
readily, for example, chromium, vanadium, aluminum, titanium, and a
few others, the contamination is not serious, as they are largely oxidized
and removed
during melting and refining, leaving usually not more than
traces in the steel. In. the case of such alloys as nickel and copper, which
do not oxidize, the amounts present will normally increase slowly over a
period of years. The amount of these elements in the scrap is not of
such serious consequences for steels made by a process that uses also a
large proportion
of pig iron, which is normally free from nickel and
:opper, as it is in steel made using a large percentage of scrap (Table
11.1). In the latter the scrap may contain an unsuspected 0.10 to 0.25 per
cent nickel and 0.05 to 0.10 per cent copper, sometimes even enough to
affect the properties materially.
A recent development in free-machining steels is the addition of lead
to low-carbon material. This element is insoluble in carbon steel, but by
special methods of addition to the molten metal it may be incorporated
as a suspension so finely disseminated throughout the metal that it is not
easily visible in an unetched section with the microscope. These sub-
microscopic particles of lead apparently act as an internal lubricant and
in addition cause the chips to break up readily. Recently reported data
indicate that a lead content of 0.10 to 0.25 percent greatly increases ease
of machining
but has no appreciable effect on mechanical properties.
Carbon steel may be contaminated with small amounts of arsenic, tin,
and antimony, traces of which may be present in iron ores and may
persist through melting and refining. These metals may also be picked
up from scrap containing bearing metals or tin cans. The amounts present
are small, rarely exceeding 0.05 per cent. Very little is known about the
effect of small amounts of most of these adventitious elements. According
to the present state of our knowledge, their effect, with the possible
exception of that of antimony, which is assumed to be harmful, may
be called neutral. During the war, when some detinned scrap was used
in the manufacture of open-hearth steel, considerable attention was given
to the effect to tin. It was found that small amounts of this metal do not
cause hot shortness in rolling; they do, however, increase hardness and
reduce toughness. Tin, therefore, may be considered definitely harmful
in some grades of steel, especially in those used for deep drawing.
11.15. Low-Alloy Steels
A large number of metals (and some metalloids and nonmetals) have
been alloyed with carbon steel, either alone or in various combinations,
and the resulting properties have been studied more or less completely.
These include manganese, silicon, nickel, chromium, vanadium, tung-
sten, molybdenum, copper, and phosphorus as the more common alloy-
ing elements and cobalt, aluminum, zirconium, titanium, nitrogen, lead,
boron, and selenium as the less frequent additions. Steel may also be
coated or plated with zinc (galvanizing) , tin, lead, chromium, or nickel,
but such products are not classed as alloy steels.
There are two general classes of alloy steels:
(1)
the low-alloy engi-
neering steels and
(2)
the high-alloy tool and die steels, corrosion- and
heat-resistant steels and special-purpose alloys. In tonnage, the first class
is the more important; in value to man, both are probably of equal im-
portance, for both have played a vital role in the development of our
present-day machine-age civilization.
Before World War II there were several hundred low-alloy engineering
steels, of which some 70 to 80 were considered as standard by the Society
of Automotive Engineers. These steels were divided into eight main
classes: intermediate-manganese, silicon-manganese, nickel, nickel-chro-
mium, molybdenum (including chromium-molybdenum and nickel-mo-
lybdenum), chromium, chromium-vanadium, and tungsten steels. There
were also a large number of low-alloy structural steels, most of them
developed between 1933 and 1939, that contained small amounts (usually
less than 1 to 1.5 per cent) of nickel, copper, chromium, manganese,
silicon, phosphorus, and molybdenum in various proportions and com-
binations. These were developed to satisfy a demand for a material of
better properties than carbon steels but cheaper than the S.A.E. grades.
These have been nicknamed "Irish stew steels" by Gillett, a happy and
accurate designation.
11.16. High-Alloy Steels
There are almost as many varieties of the high-alloy steels as there are
of the low-alloy grades. These special materials can be divided into three
classes. The first includes the well-known high-speed steels and the
closely allied die and valve steels. The primary requirement is hardness,
especially at elevated temperatures, which is attained by large amounts
(10
to 25 per cent) of tungsten, chromium, and occasionally cobalt, plus
smaller amounts of vanadium, molybdenum, or silicon, together with
relatively high carbon percentages.
The second class includes all the highly alloyed steels used primarily
because of their corrosion resistance or scale resistance at normal and
at high temperatures. The basic element in these steels is chromium, in
amounts ranging from 10 to 35 per cent, either alone or together with
varying amounts of silicon, manganese, nickel, copper, or molybdenum.
The best known steels of this group are the cutlery steels, containing
242
about 0.35 per cent carbon and 14 per cent chromium, and the soft
stainless steels, containing low carbon, 15 to 25 per cent chromium, and
6 to 20 per cent nickel, which are used widely for building trim, hardware
and fixtures on buildings and automobiles, various kinds of utensils and
more recently, in the construction of railroad equipment and aircraft.
Not so well known but just as important are the highly alloyed steels
containing nickel, chromium, molybdenum, cobalt, and other alloying
metals, used in steam plants, oil refineries, gas turbines, including jet
engines, and in other applications where high stresses and high tempera-
tures are encountered.
Also in this second class are the alloys containing
up to 65 per cent nickel, 15 to 20 per cent or more chromium, the re-
mainder being iron. These are the heat-resistant alloys of high electric
resistivity that are used for the heating elements of all our domestic
and industrial heating appliances.
The third class includes a large number of alloys of highly specialized
but important uses. They arc the steels with special magnetic and electric
properties, alloys with special expansion characteristics, steels with ex-
ceptional wear resistance, and many others. Although these materials
are not manufactured in large tonnages, some are of such importance
that by means of them the communication and other industries have
experienced a veritable revolution in the past twenty or twenty-five years.
Nearly all the high-alloy materials are made in electric arc or induction
furnaces. Alloy steels are much more costly than carbon steels so that
care is exercised to keep the quality as high as possible. Selected scrap is
used, deoxidation is carried farther, and sulfur and phosphorus are usually
required to be lower than in carbon steels.
QUESTIONS
1. Name the four principal raw materials of the iron and steel industry. Name
the two main classes of final products.
2. What are the general principles underlying the reduction of iron ore in
the blast furnace? Name the two principal reactions in the blast furnace,
and give the approximate temperatures at which each reaction takes place
most readily.
3. In the manufacture of pig iron, describe how the amounts of phosphorous,
sulfur, and silicon are controlled in the product.
4. What is blast furnace slag, and where does it come from? What are its
principal (unctions?
5. Describe the acid Bessemer process. What are die raw materials used? De-
scribe the principal oxidizing reactions. How does the cost and quality of
the Bessemer process compare with
the basic open hearth?
6. Sketch briefly the general features of the basic open-hearth process, and
compare it with the acid open-hearth process in (a) raw materials, (b)
slags, (c) chemical reactions, (d) general quality of the product.
7. Give two advantages of acid open-hearth steel production over basic open-
hearth production. Give two advantages of basic open-hearth production
over acid open-hearth production.
8. Describe the regenerative principle of the basic open hearth. Give two
reasons for its use.
9. Differentiate between the "ore boil" and the "lime boil" by describing the
reactions in each.
10. Describe how the impurities, such as phosphorous, sulfur, manganese,
silicon, and carbon are eliminated in the basic open hearth.
11. Give four advantages of the electric processes for making steel. Do they
have any disadvantages?
12. Describe the manufacture of wrought iron. What are its uses? How does
wrought iron differ from ingot iron?
13. What stcelmaking process would you recommend for the production of
steel for the following: (a) wire for suspension cables? (b) sheet steel for
tin cans? (c) alloy-steel crankshafts for airplane engines? (d) rails for
mainline railway track? (e) armor plate for a battleship? (f) small high-
strength castings?
(g)
tools for machining automobile connecting rods?
14. Compare the usual amounts and the principal effects of sulfur and phos-
phorous in carbon and alloy steels.
15. Describe the principal functions of manganese and silicon when added to
carbon steel. Why is manganese a valuable alloying element?
16. Describe the essential differences between rimming and killed steels. How
do these two classes ordinarily differ in carbon content?
17. Give a practical definition of low-alloy steels. Define high-alloy steels and
give the characteristic property of the classes of high-alloy materials.
CHAPTER
12
The
Constitution
of
S tee I
Hollis Philip I.eighly,
Jr.,
Ph.D., Chairman, Depart-
ment of Metallurgy, University of Denver, Denver,
Colorado
John Stanton Winston, M.A., M.S., Chairman, Depart-
ment of Metallurgy, Mackay School of Mines, Univer-
sity of Nevada, Reno, Nevada
1
HE most common group of alloys in use today
are those referred to as steels. These alloys consist primarily of iron plus
carbon in varying amounts, to which may be added various alloying ele-
ments to achieve the desired properties. Steel is used in tremendous
quantities to produce necessities and luxuries; without steel our civiliza-
tion would be quite primitive. It is not intended to indicate, historically
speaking, that steel is a new material. On the contrary, steel was pro-
duced as early as 1200 B.C. However, it is only within the past century
that methods have been developed to produce steel in large quantities
cheaply enough to make it a material of very common usage.
12.1. The Allotropy of Iron
The effects of carbon additions to iron are intimately associated with
the allotropy of iron. In the process of freezing and cooling to atmospheric
temperature, iron undergoes two allotropic transformations. Upon solidi-
fication at 2802F. (1539C.) iron assumes a body-centered cubic struc-
ture
(8
Fe). At 2552
C
F. (I400C.) this structure transforms into a face-
centered cubic structure
(y
Fe). This structure persists clown to 1670F.
(910C.) where it transforms back to the body-centered cubic structure
(a
Fe). Actually,
8 and
a iron are the same form of iron. They are often
regarded, however, as distinct modifications because of the two ranges in
temperature in which the body-centered cubic structure is stable.
The transformations of iron from one crystal structure to another are
accompanied by changes in various properties; such as, density, electrical
conductivity, and thermal change. The thermal change consists of an
244
The Constitution
of
Steel
1
245
Time
Fig. 12.1. Cooling curve for pure iron.
absorption of heat during heating and an evolution of heat during cool-
ing. Fig. 12.1, the cooling curve for pure iron, illustrates how the measure-
ment of the changes in a given property at transformation
may be used
for determining the temperature of transformation.
12.2. Iron-Carbon Phase Diagram
In the previous chapter it was shown that iron is reduced from its
ore by means of carbon and that the resulting product,
pig iron, contains
approximately
4%
carbon. Two effects of the carbon immediately evident
are that it lowers the melting point of the iron and makes the resulting
alloy brittle. It was also shown diat the chief function of the steel making
process is to lower the carbon content to the proper level in order to
obtain
a certain combination
of desired properties. The effects of carbon
are so strong that its content
is specified in hundreths
of a per cent.
The best approach to understanding
the nature
of the iron-carbon
alloys is to study the phase diagram
of the system shown in Fig. 12.2.
In pure iron-carbon alloys, the carbon not in solid solution usually occurs
as cementite
(Fe
3
C)
,
which contains 6.68 per cent carbon by weight.
Although
cementite is metastable and decomposes, given sufficient time
at elevated temperature,
into iron plus graphite, conditions are generally
such that in steels and pure iron-carbon alloys the carbon is present as
cementite.
Therefore the phase diagram chosen for study concerns the
equilibria
between iron and cementite;
and thus, in reality, is the iron-
iron carbide diagram. Although this diagram covers a small proportion
of
the possible combinations of iron and carbon, it includes the entire range
of commercial iron-carbon
alloys (plain carbon
steels and cast irons)
.
246
Atoms per cent, carbon
4 6 8 10 12 14 16 IS 20
\"Hypoeutectoid\Hyptreutectoid
/rons-r* Stee/s
Fie. 125. Iron-carbon equilibrium diagram.
Carbon is soluble to a limited extent interstitially in each of the allo-
tropic forms of iron. Inspection of the iron-iron carbide diagram shows
that a-iron can dissolve a maximum of 0.025 per cent carbon, y-iron up to
2 per cent and 8-iron up to 0.1 per cent. These solid solutions of carbon
in alpha, gamma, and delta iron are named ferrite, austenite and l-ferrite,
respectively. The greater solubility of carbon in face-centered gamma iron
than in body-centered alpha or delta iron is probably due to the larger
size and more favorable location of the interstices in the face-centered
structure.
Since delta iron has little to do with the final microstructure of iron-
carbon alloys, transforming as it does to austenite, it will not be con-
sidered further. It should be noted, however, that in alloys between 0.1
and 0.5 per cent carbon content austenite is formed by a periiectic re-
action.
Alloys whose compositions fall between 0.5 and 2 per cent carbon
solidify as austenite. For those alloys containing more than 2 per cent
carbon a eutectic reaction occurs producing austenite and cementite.
The typical eutectic structure which forms is known as iedeburite. Alloys
containing this brittle structure cannot be hot- or cold-worked but must
be cast, and are therefore known as cast irons.
The Constitution
of
Steel 247
All alloys with compositions between 0.025 and 6.68 per cent carbon
undergo a eutectoid reaction at 1333F. (723C.) when austenite con-
taining 0.8 per cent carbon decomposes, at constant temperature, into
pearlite, an intimate mixture of ferrite and cemcntite (Figs. 12.3F and
12.4) . A plain carbon steel of this composition is called a eutectoid steel.
Steels having less carbon or more carbon than this are called hypoeute-
rtoid and hypereutectoid respectively.
From the cooling curve for pure iron (Fig. 12.1) it is evident that
arrests are experienced when the transformations occur. Such arrests
are also present in the cooling curves for iron-carbon alloys. The tempera-
tures at which these transformations in the solid state occur are called
critical temperatures or critical points. The loci of these points (lines)
on the phase diagram are given symbols. In hypoeutectoid alloys, A
3
and
Aj are the upper and lower critical temperatures (lines GS and PS
Fig. 12.2); in the eutectoid alloy and hypereutectoid alloys, A.
t
and A,
coincide (line SK Fig. 12.2) and, therefore, is designated A
ll3
. The zone
between A
3
and A, is known as the critical range.
Some of the other lines appearing on the phase diagram have also been
given symbols. The curve separating the fields austenite and austenite
plus cementite (line SE) is designated A,., and the line of temperatures of
transformation of B-iron to y-iron (line
AHJB)
is called A^.
An understanding of the phase relationships shown by the iron-iron
carbide diagram and the final microstructures attained is best obtained by
following the process of solidification and subsequent cooling of several
representative alloys of the system.
12.3. Phase Changes of Slowly Cooled Plain Carbon Steels
At the completion of solidification all steels consist of austenite while
at atmospheric temperature they consist of ferrite and cemcntite. Their
microstructure depends upon the relative amounts of ferrite and cement-
ite and the way in which these are arranged. This, in turn, depends
upon the carbon content.
The phase changes in carbon steels cooled slowly from a high tem-
perature can be illustrated by three steels containing (A) 0.30 per cent
carbon, (B) 0.80 per cent carbon, and (C) 1.30 per cent carbon. These
are indicated in Fig. 12.2 by lines xx', yy' and zz'.
At 2820F. (1550C), the first steel (xx') is a solution of carbon in
molten iron. Upon slow cooling, there is no change until the solidification
temperature
2768F. (1520C.) is reached. Here solidification of S
iron
begins and progresses with further cooling until at 2720F. the peritectic
reaction
of S + liquid - austenite occurs with an excess of liquid in this
case. Further cooling causes ihe liquid to disappear so that at 2687F.
248
Engineering
Metallurgy
Fig. 12.3. Microstructures of slowly cooled iron-carbon alloys: (A) low-carbon iron;
(B) 0.20 per cent carbon steel; (C) 0.40 per cent carbon steel; (D) 0.80 per cent carbon
steel; (E) 1.3 per cent carbon steel; (F) pearlite at high magnification; etched. A to
E, lOOx: F,
1.000X-
The Constitution
of
Steel 249
(1475C.) solidification of austenite is complete. The white-hot steel,
which consists wholly of a solid solution of carbon in gamma iron, cools
unchanged until a temperature of 1512F. (822C.) is reached. At this
point on line A
3
(GOS) , the austenite is saturated in iron (ferrite) . If the
temperature falls slightly, the excess iron is precipated in the form of
alpha phase. Since the austenite loses no carbon during the process,
the loss of some iron as alpha phase by the austenite is
equivalent to in-
creasing the carbon content of the austenite. As the temperature contin-
ues to fall, precipitation of alpha iron and increase of carbon content of the
austenite (since there is progressively less austenite for a
constant amount
of carbon) occur continuously. When the temperature reaches that of the
A
i
(PSK) , the austenite is saturated with carbon. Further cooling results
in simultaneous precipitation of alpha iron and carbon (as iron carbide)
.
This process goes to completion, which is to say that the austenite dis-
appears completely.
If the cooling is very slow through the temperature interval from line
A
s
(GOS) to just below line A
x
(PSK), the excess ferrite which is first
formed assumes the shape of discrete polyhedral grains, and the remain-
ing austenite, containing 0.80 per cent carbon, transforms to the pearlite
aggregate in which the ferrite and cementite particles are in the form
of relatively large laminated plates. The structure of the slowly cooled
steel consists of 36 per cent pearlite and 64 per cent excess ferrite.*
If a piece of slowly cooled carbon steel is polished and etched with
dilute acid and examined with the microscope, the relation between the
carbon content and the amount of free ferrite (etches light) and pearlite
(etches dark) is clearly evident. This relation is shown in Fig. 12.3.
Micrograph A shows the structure of iron containing practically no
carbon; it consists wholly of polyhedral grains of ferrite. In B, the steel
containing 0.20 per cent carbon, the dark grains of pearlite are numerous,
and in C, the material containing 0.40 per cent carbon, they are still more
numerous. The parallel plates of cementite and ferrite making up the
pearlite aggregate are shown clearly at high magnification in micrograph
F, and when viewed by the electron microscope, as is evident from Fig.
12.4.
Referring again to Fig. 12.2 (line
yy'), at 2820F. (1550C.) a steel
containing 0.80 per cent carbon is a solution of iron carbide in molten
iron. As the molten metal cools, it is unchanged until a temperature of
2670F. (1468C.) is reached where solidification of the austenite be-
gins. This is not complete until a temperature of 2520F. (1380C.) is
0.30 per cent carbon is equivalent to 4.5 per rent Fe

3
C. Since 1 part of Ke
a
C is
associated with 7 parts of ferric to form pearlite. 4.5 per cent Fe,C plus 31.5 per cent
ferrite form 36 per cent pearlile.
250
reached. It will be noted that with higher carbon the solidification range
is wider.
After the steel has solidified completely, the solution of cementite
in gamma iron cools unchanged until a temperature of 1333 (723C.)
is reached. Owing to the fact that the steel contains 0.80 per cent carbon
and, therefore, the exact amounts of cementite
(12
per cent) and iron
(88
per cent)
to form the aggregate pearlite, there will be no preliminary
precipitation
of alpha iron from the saturated austenite, as was the case
with the 0.30 per cent carbon steel described in the previous section.
As the steel cools through the A
x
temperature of 1333F. (723C.)
,
the austenite undergoes precisely the same change as was described for
the last stage of transformation of the 0.30 per cent carbon steel, that
is, simultaneous precipitation of alpha iron and iron carbide. There is
no further structural change as the steel cools from A
x
to room tempera-
ture, and if cooling through the A
x
temperature is slow, the cementite
and ferrite form well-defined plates as shown in Fig. 12.3D and, at high
magnification,
in Figs. 12.3F and 12.4.
In the case of a steel containing 1.3 per cent carbon (19.5 per cent
cementite), represented by line zz' in Fig. 12.2, the changes taking place
during slow cooling are fundamentally analogous to those taking place
in a 0.30 per cent carbon steel. The essential difference is (in addition
to a wider solidification range) that the A
cm
line marks the preliminary
separation of excess iron carbide rather than excess alpha iron. When a
steel containing 1.3 per cent carbon cools slowly, at 1640F (893C.)
the austenite is saturated with carbide. Further cooling results in pre-
cipitation of this excess carbide from the saturated austenite, which
continues as the temperature falls from 1640F. to 1333F. (the A
x
tem-
perature) . The remaining austenite, which now contains 0.80 per cent
carbon
(12 per cent cementite) , here transforms
to pearlite, as in the
preceding case. At room temperature, the structure is made up of grains
of pearlite (etches dark) with a network (or needles) of excess carbide
(light) . This structure is shown in Fig. 12.3E.
The discussion to this point has all been concerned with slow cooling.
In heating carbon steels, the reverse changes take place. For example,
a 0.30 per cent carbon steel that has been cooled slowly consists at
room temperature of a structure of 36 per cent pearlite and (>4 per cent
excess ferrite. If this steel is heated slowly, no change takes place until a
temperature of 1333F. (723C.) is just exceeded. Here, the alpha iron
of the pearlite transforms to gamma iron and the cementite goes into
solution. As heating is continued, the excess alpha iron changes to gamma
The Constitution
of
Steel 251
Fie. 12.4. Electron micrograph of pearlite in eutectoid steel. Polystyrene-silica rep-
lica.
20,000x.
etched. Approximately i/
A
in. on the micrograph = i micron = 0001
mm. (Courtesy
of C. S. Barrett)
iron and is absorbed by the austenite. At 1512F. (822C.) , these
changes are complete, and the steel, now a solid solution of 4.5 per cent
cementite in gamma iron, remains unchanged to the melting point.
12.4. Isothermal Transformation in Steel
Considerable work has been done in studying the effect of continuous
cooling upon the structure and properties of steels. The effect of the
various alloying
elements was known in a rather general way, however,
no good explanation was available. In 1930, Davenport and Bain
#
pre-
sented a paper describing the results of a study of the isothermal transfor-
mation of steel. This paper resulted in a further extensive study of many
iron-carbon
alloys, which gave a better understanding of the mechanism
of austenite decomposition
and the part played by the alloying elements.
The results of these studies are published in the Atlas
of
Isothermal
Transformation Diagrams.^
E. S. Davenport and E. C. Bain, Trans. Amer. Inst. Min.

& Met. Eng V 90 1930
p.
117-154.
t
Atlas of Isothermal Transformation Diagrams, U. S. Steel Corp., 1951.
252
1 1 1 1
Avsrtvit aunt
. _
A, TCMPOIAIVfiC
jurtrmre
t
A
is
-
V
"
- -
\ \
-
\
\
WLHSTC W*J \
1
I [.....!._..
-
130000 ICCOO00
10OMITHMIC TIUC I
Fig. 12.5. Schematic Drawing of a Typical Isothermal Transformation Curve Re-
vealing Significant Features.
The results of isothermal transformation studies are presented in the
form of diagrams such as the one in Fig. 12.5. These are usually referred
to as TTT curves (time-temperature-transformation) with time as the
abscissa and temperature as the ordinate. The left curve indicates the
beginning of transformation with the right curve showing the completion.
In the case of high or low carbon steels, the formation of the pro-eutectoid
cementite or ferrite is usually indicated on the diagram as an additional
feature.
To construct a TTT curve, it is necessary to heat thin specimens of the
desired steel into the austenite region for sufficient time to obtain a
homogeneous structure. The specimens are then quenched into a pot of
molten lead or salt which is maintained at some constant temperature, i.e.,
isothermal, below the austeniti/.ing temperature. These specimens are
kept in the molten bath for varying time intervals from 1 second to as
much as 10
5
seconds or longer. At the end of the desired time interval,
the specimen is quenched into cold water causing the isothermal trans-
formation to be- terminated. Any austenite not transformed isothermally
is transformed by quenching to martensite. The specimens quenched
isothermally
at a particular temperature are prepared metallographically
and etched. Microscopic examination will reveal that the isothermal
transformation product appears as dark areas in a white field. The
The Constitution
of
Steel 253
<
el
'
I
Fie. 12.6. Micrograph of coarse pcarlitc formed by isothermal transformation at
I275F. 600X. (left)
Ftc. 12.7. Fine pcarlitc formed by isothermal transformation at 1200F. 600X.
(right)
Fig. 12.8. Nodular pearlitc formed by isothermal transformation at 1100F. This
specimen is only partially transformed. 600X. (left)
Fig. 12.9. Bainite formed by isothermal transformation at 850F. This specimen
is only partially transformed. 600 X. (right)
254
white field represents the untransformed austenite prior to water quench-
ing. The time associated with the specimen showing the smallest amount
of dark area is assumed to be the time lor the beginning of isothermal
transformation at the particular temperature while the end of transfor-
mation is determined by the specimen showing a completely darkened
surface. By repeating the experiment at several different temperatures,
enough data are obtained to make possible the construction of a diagram
similar to that shown in Fig. 12.5.
The transformation products obtained arc a function of the transforma-
tion temperature. Near the eutectoid temperature very coarse pearlite
forms as is shown in Fig. 12.6 while finer pearlite forms as the tempera-
ture is reduced (see Fig. 12.7) until at the "nose" of the curve a very fine
pearlite forms in nodules giving nodular pearlite, Fig. 12.8. Below the
temperature of the nose, a product forms, which only occurs during
isothermal transformation, bainite, Fig. 12.9. The exact nature of this
material is not well understood but it appears to be some sort of very
fine mixture of fcrrite and cemeiuite. The above description applies to
those alloys which do not yield a pro-cutectoid constituent. Pro-eutectoid
ferrite or pro-eutectoid cementite forms before pearlite is formed.
12.5. The Effect of Cooling Rale Upon the Resulting Structure
In the previous section, the isothermal transformation of steel was
discussed. However, during the heat treatment of most steel parts, it is
not possible to remove the heat within the extremely short time as is done
for obtaining a TTT diagram. As a result, the surface may be very
severely quenched whereas the interior may cool very slowly. Such varia-
tion in cooling rate will certainly result in different structures.
It was observed that isothermal transformation just below the austen-
itizing temperature caused the austenite to transform very slowly into
coarse pearlite. As the temperature was reduced, the transformation was
more rapid and the pearlite became finer. In Fig. 12.10 there is shown a
schematic drawing of a portion of an isothermal diagram with some
typical continuous cooling curves. Curve A shows very slow cooling, such
as might be expected in furnace cooling. The austenite exists until the
curve reaches the beginning of transformation at which lime coarse pearl-
ite begins to form. It continues to form until the transformation is com-
plete. Now curve B shows moderately slow cooling that might be ex-
pected in still air cooling of steel. Austenite exists until the curve meets
the beginning of the transformation curve at which time medium pearlite
begins to form and continues to form until the transformation is com-
plete. The specimen cooled as shown by curve C would have still finer
The Constitution
of
Steel 255
i
4vsr/riir StablC
1
r
. *00
"\
_-A_. _i
\ \ *l ItltPCHASVBj
400*
--*.
-\

I \ / \r/stc
-
w
\
\
Itf^Rtfl
w
-
*"%^
OC*
- -
400"
-
00
.
i i r I
-
IMMITHMIfi IIMt ** SCO*DS
Fig. 12.10. Schematic Representation of an Isothermal Diagram and Various Con-
tinuous Cooling Curves.
pearlite. The critical cooling rate as shown by curve D shows that the
austenite would transform into martensite without any pearlite form-
ing. Martensite begins to form at the temperature shown as M
3
and in-
creases as the temperature is reduced. Any cooling rates more rapid than
D will result in complete transformation into martensite, Fig. 12.11.
- w
'
-* *-..
.
\f
1
......
--"'
Fie. 12.11. Martensite formed by water quenching after austenitizing.
600x-
256
12.6. Effect of Alloying Elements Upon the Iron-Carbon Diagram
In Section 12.2, the iron-carbon phase diagram was discussed in detail.
Now, the effect of the common alloying elements upon the eutectoid
temperature and composition will be discussed as well as the effect of the
alloying elements upon the physical properties of steel. Alloying ele-
ments tend to divide themselves into two groups: those that widen the
range of gamma stability by increasing the S-y transformation tempera-
ture and lowering the
y
transformation temperature and those that
narrow the range of gamma stability by lowering the 8-y transformation
temperature and raising the
y
transformation temperature. The com-
mon gamma stabilizers are manganese, nickel, cobalt, copper, nitrogen
and carbon, while the common alpha stabilizers are silicon, chromium,
tungsten, molybdenum,
phosphorus, vanadium, titanium, aluminum,
boron and sulfur. Nickel and manganese are such strong gamma stabi-
lizers that it is possible to have stable austenite at room temperature such
as occurs in the austenitic stainless steels and Hadfield steel respectively.
Certain of the alpha stabilizers reduce the gamma region to a narrow
loop and may result in ferrite existing continuously from the liquidus
temperature to room temperature.
By an element being an alpha or gamma stabilizer means that it either
raises or lowers the eutectoid temperature respectively. As was indi-
cated previously, nickel and manganese are gamma stabilizers and thus
reduce the eutectoid temperature, nickel being a bit more effective than
manganese. The other gamma stabilizers have a similar effect however
rather reduced. By the same token the alpha stabilizers raise the
eutectoid temperature, thereby reducing the region of gamma stability.
Titanium has the greatest effect in raising the eutectoid temperature
followed by molybdenum, tungsten, silicon and chromium in decreasing
order.
Most alloying elements have an effect in reducing the carbon content
necessary for the eutectoid composition. This results in a completely
pearlitic alloy with less carbon than indicated by the iron-carbon diagram.
Again, titanium has the greatest effect in reducing the eutectoid carbon
content with molybdenum, tungsten, silicon, manganese, chromium, and
nickel in descending order. This effect reduces the amount of cementite
and causes the steel to be softer and less brittle.
Most alloying elements have a useful effect upon the heat treating of
steel; certain alloying elements have other useful properties. One of the
properties is the ability of strengthening the ferrite to obtain sheet
and plate materials for the fabrication of high strength, lightweight ob-
jects such as pressure vessels, railroad cars, truck bodies, etc. These are
The Constitution
of
Steel 257
usually referred to as high-strength, low-alloy steels being sold under
several trade names. They rely on the fact that phosphorus, manganese,
copper, titanium and silicon form solid solutions with ferrite and thereby
strengthen it. Nickel, molybdenum, and aluminum are mild strength-
ened.
Another property that alloying elements have is their ability to
form carbides. These carbides may have a grain refining action on the
austenite during heat treatment to prevent excess grain growth. They
also may help block creep in high temperature applications. In the case
of certain types of stainless steel, columbium and titanium are used to
form a more stable carbide than chromium and thus enhance the
corrosion resistance of the steel. Columbium, titanium, zirconium, vana-
dium, tungsten, molybdenum, and chromium are considered as strong
carbide formers while manganese is only moderate. Phosphorus, nickel,
sulfur, cobalt, and copper have no effect in the formation of carbides
while aluminum and silicon tend to cause the carbides to decompose,
precipitating graphite.
12.7. Effect of Alloying Elements on the Isothermal
Transformation
of Steel
Referring back to Fig. 12.5, we see that there are regions on the diagram
labeled pearlite and bainite. By comparing this figure with Fig. 12.10, it
is apparent that if thick sections are to be completely hardened, it will be
necessary to displace the curve to the right, thus requiring a longer time
to elapse before the beginning of transformation. This is precisely the
effect of alloying elements on the TTT curve. By suitable selection of
alloying elements, it is possible to displace the curve enough to permit
complete hardening of quite large pieces by air cooling.
Usually the effect of an alloying element is determined as a function
of its ability to displace the pearlite or bainite region to the right. In the
case of the pearlite region, manganese, molybdenum, phosphorus,
and chromium have the greatest effect in that order, while silicon, nickel,
and copper have much smaller effects. The displacement of the bainite
region to the right is greatest with manganese, phosphorus, and chromium.
Silicon, nickel, and copper have reduced ability while molybdenum has
no effect on the bainite region. It is interesting to note that sulfur has a
slight tendency to displace the curve to the left. By careful selection of
proper alloying elements, the beginning curve for transformation can be
displaced considerably to the right. It should be noted that small addi-
tions of several alloying elements are more effective than one large addi-
2 J
tion. This is evident in the alloys that have been developed recently
with their multi-element additions.
The addition of alloying elements has another effect in the thermal
treatment of steel. In Fig. 12.5 it can be seen that there is
a horizontal
line labeled M
s
. This is the temperature at which martensitc begins to
form. It continues to form as the temperature is reduced. Most of the
common alloying elements tend to reduce the M, temperature, carbon
being
quite strong in its ability. The other elements reduce the M, in the
following order; manganese, vanadium, chromium, nickel, copper, molyb-
denum, tungsten. Silicon has no effect while aluminum and cobalt tend
to raise the M
5
. Alloy additions may lower the M, to such an extent that
complete transformation of austenite to martensite mav not be possible
by quenching to room temperature. It may require subatmospheric
cooling in order to form martensite.
12.8. Effect of Hot Working on Structure
So far, the discussion in this chapter has been confined to the phase
and structural changes in carbon steels when they are heated or, more
important, cooled at varying rates between the temperature where aus-
tenite is stable and room temperature. It was stated that there is no
change in the austenite if it is heated or cooled between the transforma-
tion temperature and the melting point. This is true. There is no change
in the internal structure of the austenite grains, but there may be a great
change in the size of the grains. If carbon steel is heated above the trans-
formation temperature, the austenite grains grow, and the higher the
temperature the larger the grains.
Small-grained steels are generally considered to have better properties
than coarse-grained material of the same composition. Since grain size at
room temperature depends largely upon the grain size of austenite when
it is ready to transform, the grain size of austenite should be small. One
of the important factors affecting the grain size of austenite, and of
pearlite and ferrite, is mechanical working.
When molten steel cools, solidification usually begins by crystallization
at the wall of the mold, and if the temperature of the steel is high when
it is poured, and if the ingot or casting is large and of favorable shape,
these crystals may become very large (Fig. 12.12). Hot rolling or forging,
which is ordinarily carried out at temperatures at which the metal is
plastic, breaks up the large crystals and elongates the fragments in the
direction in which the work is applied. These elongated grains, together
with elongated inclusions, give carbon and many of the alloy steels their
directional properties.
The Constitution
of
Steel
259
FIG. 12.12. Large columnar crystals in a steel ingot, natural size. (Hanemann and
Schroder, Atlas Metallographiats, Berlin, 1927)
Austenitc grains, even when plastically broken and deformed, have
the tendency to grow together again. This tendency is the greater the
higher the temperature. Hence, if the finishing temperature of hot work-
ing is much above the transformation temperature, grain growth may
occur while the steel is cooling to the transformation temperature, espe-
cially if the section is so large that cooling is slow. For this reason, if hot-
rolled or forged steels are to be used without subsequent heat treatment,
and if a fine grain is desirable, the hot-working temperatures and the
amounts of reduction are controlled so that the finishing temperature
will not be much above the transformation temperature. Thus, the steel
will cool below this teni]>erature before appreciable grain growth has
taken place. The effect of hot working in breaking up the coarse grain
structure of cast 0.20 per cent carbon steel is shown in Fig. 12.13B.
12.9. Effect of Cold Working on Structure
Cold working is usually defined as mechanical deformation of steel at
temperatures below the transformation temperature. In practice it is
260
Fig. 12.13. Structure of a 0.20 per cent carbon steel: (A) as cast, and (B) as hot
rolled; etched.
100x-
generally carried out at room temperature. If steel is plastically deformed
at these low temperaturesas in drawing wire, cold rolling or extruding
bars, or cold rolling sheetthe pearlite and ferrite grains are elongated
in the direction in which work is applied. This mechanical distortion
results in rapid increase of hardness and brittleness.
At atmospheric temperature, the rigidity of the steel is so great that
the distorted grain fragments cannot rearrange themselves by recrystal-
lizing into their normal equiaxed shape. Hence, if cold working is con-
tinued, the hardness and brittleness accompanying the fragmentation of
the grains will increase with the amount of deformation until soon, unless
the steel is annealed, it will fail. The amount of cold deformation that
steel will stand depends upon its ductility, which, in turn, is related
directly to chemical composition and prior heat treatment. Thus, an-
nealed low-carbon wire will withstand more reduction by drawing before
failure, or before reheating for recrystallization becomes necessary, than
annealed medium- or high-carbon wire.
The unstable structure of cold-worked steel* and its accompanying
hardness and brittleness
are caused by the distortion of the ferrite and
pearlite grains and not, as in quenched steel, by the presence of sub-
microscopic particles of carbon in a distorted alpha-iron lattice. But, as
The structure of severely cold-worked steel is unstable in that the fragmented

grains will recrystallize if given the opportunity; that is, if the steel is heated to the
proper temperature, which is considerably below the A
x
transformation. Actually,
however, owing to the rigidity of the material at room temperature, the fragmented
grain structure will persist indefinitely.
The Constitution
of
Steel
261
Fig. 12.14. Structure of a 0.20 per cent carbon steel (A) as cold-worked and (B)
as cold-worked and annealed; etched. 500
X-
the stability of quenched steel can be increased by tempering (see Chap.
13), so can the stability of structure of cold-worked steel be increased by
reheating below the transformation temperature. This is known as process
annealing.
Structural
changes which occur when cold-worked steel is reheated
are not gradual. Cold-worked steel is softened by heating to 800 to
1200F.
(425 to 650C), the exact temperature depending on the com-
position, si/e of the section, and the amount of cold work. Reheating at
the proper temperature effects complete recrystallization
and restoration
of the original structure and properties. The material can then be cold
worked again until grain distortion and its accompanying
brittleness
have again become so serious that another reheating is necessary. The
effect of cold working on the structure of a 0.20 per cent carbon steel
(whose structure as hot-worked is shown in Fig. 12. ISA) is illustrated in
Fig. 12.14A. The effect of reheating on the distorted grain structure is
shown in Fig. I2.14B. Note that after annealing the grains are equiaxed,
and all indication of distortion has disappeared.
QUESTIONS
1. Describe the changes taking place in cooling from 3,000F., iron-carbon
alloys having the following carbon contents, 0.3%, 0.8%,
1.5%, 3.0%, 4.3%
and
5.0%. When crossing
a two phase field, indicate how each phase
changes in quantity and composition.
2. Using the lever rule, give the composition and amounts of the phases
present in the above alloys at the following temperatures,
2,500F 2 000F
1,500F., and 1,000F.
3. Describe the crystal structures of delta iron, austenite, and ferrite. What is
the crystal structure of pearl ite? How does it differ from the previous men-
tioned phases?
262 Modern Metlallurgy jor Engineers
4. Give the range of carbon contents for steel and cast iron. From the iron-
carbon diagram, give one reason that cast irons frequently have limited
ductility.
5. Describe in detail, the method of constructing a TTT diagram. What is the
white constituent which is present in specimens which are only partially
transformed? Where does it originate?
6. Sketch the TTT curve from Fig. 12.5. Superimpose on this diagram curves
representing your opinion of the transformation curves for alloys contain-
ing manganese, silicon, phosphorus, nickel, copper, chromuim, and molyb-
denum. Sketch the position of the M, also.
7. Sketcli the iron-carbon diagram from Fig. 12.2. Superimpose on this dia-
gram, the position of the eutectoid temperature and composition for alloys
containing, titanium, molybdenum, tungsten, silicon, manganese, chromium,
and nickel.
8. Define the term carbide former. Give several examples of carbide formers.
Define alpha and gamma stabilizer. Give examples, why gamma stabilizers
are important.
9. What are columnar crystals and how are they formed? What is the effect of
hot working on the crystals? Why should the finishing temperature of hot
working be just above the transformation temperature?
10. What is cold working? How docs it affect the structure and properties of
hot worked steel? What happens to die structure and properties when cold
worked steel is reheated to 800 to 1,200F.?
11. Define the terms, hypoeutectoid, hypereutectoid, and eutectoid as used in
steel. Describe the difference that will occur when such steels are slow
cooled from the austenite region.
12. Sketch the unit lattice cells for austenite and ferritc. Point out the differ-
ences. Which is the closest packed cell? Since carbon is an interstitial atom,
indicate where it fits in the austenite unit cell.
13. From the iron-carbon diagram in Fig. 12.2, point out the various reactions
which occur. Indicate the reactants and products.
14. From the iron-carbon diagram, indicate the amount of pearlite present in
alloys containg 0.3%, 0.8%, 1.2%, and 1.9% carbon. What is the other
constituent in each of the alloys?
15. Cast iron is quite extensively used and is rather inexpensive as compared
with
cast steel. From the material presented in this chapter, give reasons
to explain this situation.
10. Describe the changes that take place during the solidification and sub-
sequent cooling of molten pure iron. Compare these charges with those
that occur in copper.
17. Define the term ferrite strcngthener. Why are these important? Give ex-
amples of ferrite strengtheners.
18. Describe the formation of martensite. Upon what variables is martensite
formation dependent?
19. When steel is cold worked, how arc the mechanical properties affected?
De-
scribe applications where cold worked steel is superior to annealed steel.
20. Describe the solidification of steel in a large ingot mold. Consider the
differences which would occur at the surface and interior of the ingot.
CHAPTER
Fundamentals
of
Heat Treatment
of
Steel
13
Abram Eldrkd HoSTETTER, Ph.D., Professor of Metal-
lurgy, Kansas State College, Manhattan, Kansas
JL HE process of quenching and tempering
steel to improve its hardness and wear resistance has been used for at least
3,000 years. Some of the early tools and weapons testify to the skill of the
early metal smiths. Little was known, however, regarding the nature of
the changes taking place in the steel during heal treatment, and the suc-
cess of these early metal workers is a tribute to their patience and persist-
ence in developing the art of heat treating. Medieval literature is filled
with the magic heat-treating processes developed by these early iron
workers, especially for the treatment of swords. The Spanish swords of
Toledo, for example, gained world renown because of the supposedly
mysterious properties of the water in which they were quenched;
the famous swords of Damascus were heated to the color of the rising sun
and were quenched by plunging them into the belly of a fat Nubian slave.
A favorite quenching medium was urine, and this is understandable since
we know that chloride brines and other salt solutions extract heat from
red-hot steel 10 to 20 percent faster than water alone.
Today our approach to the heat treatment of steel is somewhat more
scientific. Much has been learned about the complex reactions taking
place during the heat treatment of steel and various factors such as alloy
content, cooling rate, tempering temperature, etc. are much better under-
stood today. Our knowledge of the structural changes taking place in
metals is by no means complete, but with the knowledge we have, heat
treatment processes can be prescribed to give desired properties with a
minimum of "trial and error" procedure.
263
264
1650'
F
1530 K
0.6 0.8
Per cent carbon
Fig. 13.1. Schematic representation of the grain size of carbon steel as affected by
heating. (Stoughton)
13.1. Grain Size and Grain Growth
There are two means by which the grain size of carbon steel can be
changed. The first is by cold working the metal and annealing it at a
temperature below the critical range. This is called process annealing.
The grain size thus produced depends mainly on the extent of cold work-
ing and the annealing temperature. The second method is by heating
the metal above the critical range where, as described in Chapter 12,
austenite is produced. With the formation of austenite, recrystallization
takes place, resulting in a fine grain structure (Fig. 13.1)
.
In Fig. 13.1 the change in grain size with raising temperature is
indicated by varying sizes of circles. If a coarse-grained hypoeutectoid
steel is slowly heated, grain refinement starts at the lower critical range
(1330F.) and gradually proceeds throughout the critical range. Grain
refinement is then complete at the upper critical temperature. This is
not a reversible process however. That is, on cooling, the grain size does
not revert back to the original large grain size, but remains the maximum
size reached while above the critical range. On cooling, the austenite
grains convert to ferrite and pearlite or martensite, depending on the
cooling rate. In either case the grain size observed at room temperature
reflects the prior austenitic grain size. In the case of eutectoid and
hypereutectoid steels, grain refinement takes place at the eutectoid tem-
perature as shown in Fig. 13.1. In case a steel has a fine grain at room
Fundamentals
of
Heat Treatment
of
Steel 265
temperature there will be little or no change in grain size when it is heated
through the critical range.
If a steel is heated to produce fine-grain austenite and then heating
is continued several hundred degrees higher, the fine grains of austenite
grow to a larger size as shown in Fig. 13.1. Time also plays a part in
determining the final grain size. At higher temperatures the grain
growth is rapid, while at temperatures just above the transformation
range, there is little tendency for grain growth. The eventual grain size
of steel therefore depends on both the temperature to which it is heated
and the time it is held at this temperature.
The effect of temperature on grain growth is shown in Fig. 13.2. Two
pieces of steel containing
.40% carbon were heated above the critical
range and cooled slowly. Sample A was then heated to 1550F. (in the
fine grain range Fig.
13.1) and held there for 30 minutes, and sample
B
was heated to 1900F for 30 minutes. The samples were cooled slowly,
well below the critical cooling rate, and as a result, both samples are soft
and consist of grains of ferrite and pearlite. The grain size of sample B,
however, is much larger then that of sample A because of the grain
growth at 1900F.
When austenite is cooled to room temperature, the hardness and the
resulting structure is dependent on the cooling rate, as indicated in
Chapter
12. If cooling is slower than the critical cooling rate, pearlite
would be produced, and if quenched faster than the critical cooling
rate, martensite is produced. The grain size in both cases, however, is the
same if they were heated to the same temperature. Thus the grain size
depends on the temperature to which a steel is heated, but the hardness
depends on the cooling rate and is quite independent
of the grain size.
Steel may be hard or soft, depending on the cooling rate, and be fine or
coarse grained,
depending on the temperature to which the steel was
heated.
13.2. Controlling and Classifying
Grain Size
When steel is gradually heated above the critical range, there is a
certain range of temperature (Fig. 13.1) where there is little tendency for
gram growth. Above this range, grain growth becomes more and more
apparent as the temperature rises. It has been found, however, that by
adding
definite small amounts
of aluminum or other deoxidizers to
carbon and alloy steels, the tendency for grain growth at elevated tem-
peratures can be controlled.
That is, the fine-grain
temperature range
(Fig.
13.1) is broadened so that a carbon steel containing the proper
amount of aluminum
can be heated to 1830F. and still remain fine
grained, whereas a similar steel without the aluminum would quickly
become coarse grained at this temperature.
The research work of McQuaid and Elm, along with other investiga-
tors, has served to emphasize the importance of grain size in the heat
treatment of steel. For many years a coarse-grained structure was con-
sidered to be undesirable and every precaution was taken in hot working
and heat treatment to avoid it as far as possible. This idea is now known
to be wrong in some cases. Coarse-grained steels machine more easily and
harden more deeply than fine-grained steels. On the other hand, fine-
grained steels do not crack so readily when
quenched and in general
have greater toughness at low temperatures.
The grain size of steel can be classified in terms of a standard scale
established by the American Society for Testing Materials. The grain-
size class are numbered 1 to 8. In this system the number of grains per
square inch at 100X is
2"1
where n is the grain-size numbers. Photo-
graphs of each of the grain-size classes are available in metallurgical hand-
books, and the grain size of a sample is readily obtained by
comparing
the grain size of these photographs with that of the sample when viewed
or photographed at 100X. Table 13.1 lists the ASTM grain-size numbers
and the corresponding grains per square inch. Three different grain
sizes are shown in Fig. 13.3 as they appear at 100X.
Table 13.1. A.S.T.M. Grain-Size
Numbers
A.S.T.M. Grain-Size Number
Grains per Sq. In. at 100X
Average
Range
1
2
3
4
5
6
7
8
1
2
4
8
16
32
64
128
1
J/
or less
lj^to 3
3 to 6
6 to 12
12 to 24
24 to 48
48 to 96
96 or more
Another system for classifying grain size is the Shepherd fracture
standards. This set consists of ten broken steel specimens graded from fine
to coarse grain. The grain size of a sample is then determined by break-
ing it and
visually matching its grain size with one of standard
specimens.
This method is especially useful where metallographic facilities are not
Fundamentals
of
Heat Treatment
of
Steel
MM
267
5&isik;i"i^jj
Fie. 135. Structure of 0.40 per cent carbon steel (A) heated just above the trans-
formation temperature and slowly cooled and (B) overheated and slowly cooled;
etched. IOOx-
available. The fracture standards are prepared by hardening and then
breaking them. The sample being tested or compared to the standards
must also be in the hardened condition to get a valid comparison.
It must be remembered that the grain size referred to above the trans-
formation temperature is austcnitic grain si/e. In most carbon steels, how-
ever, little austenite is retained at room temperature, except in highly
alloyed steels, and at room temperature we are concerned with grain size
of the transformation product on cooling (martensite, ferrite, pearlite,
bainite etc.)
. By proper polishing and etching of martensite, the previ-
ous austenitic grain size is revealed since the grain size of the martensite
follows that of the previous austenitic grain size. Steel in the martensitic
condition may also be notched and broken to display the grain size.
The broken surface consists of many small facets. The facets follow the
fracture planes through the grains and thus their size gives an indication
of the martensitic grain size. On slow cooling hypoeutectoid steel, the
austenitic grain size is reflected in the grain size of the ferrite and
pearlite since the proeutectoid ferrite forms at the austenitic grain bound-
aries and the pearlite forms in the body of the parent austenitic grain
as shown in Fig. 13.2b.
13.3. Effects of Hot Working on Grain Size
When steel is hot worked at temperatures around 2000F., the grains
are broken up into finer grains. This fragmenting process keeps the grain
Fig. 13.3. Typical structure of slowly cooled carbon steel having (A) grain size 2:
(B) grain size 5; and (C) grain size 8; etched.
100X-
size fine even though there is a great tendency for grain growth at this
temperature. The two factors thus offset each other, and the grain struc-
ture remains fine during the hot working. If, however, the hot working
is stopped and the metal held at the hot working temperature for a
short time, grain growth takes place rather fast, and after cooling to room
temperature, the grain would be coarse. In this case the steel should
be reheated to a temperature above the critical range in order to refine
the grain. Hot working may be continued as the temperature falls to a
point just above the critical range. In this case there is little chance for
grain growth, and the grain remains fine. When steel is cast as an ingot,
the grain size is very large and columnar. Hot working is employed
to break up this coarse condition and produce a fine grain structure and
thus greatly improve the physical properties.
T
Fundamentals
of
Heat Treatment
of
Steel 269
1600
1400
1200
1000
si
800
600
400
200
Q-
E
K
vV"
VK
K^
V
\
MS
l)
X
\
Mf
1600.
1400
(200
1000
Time
A
-T
800
o.
E
*
600
400
200
\
\
,
\
f
CV
\
1
x\
\
Ms\
*)
N
\
\
\
;
Mf .
'
Time
B
Fig. 13.4. A. The TTT curve for a typical carbon steel. B. The TTT curve for an
alloy steel. Cooling curve O represents the cooling rate on the outside of a bar. Cool-
ing curve C represents the cooling rate in the center of a bar.
13.4. Hardenability
If a one-inch bar of carbon steel containing .70% carbon is quenched in
brine, the outside of the bar will be hard (close to Rc65) while the center
of the bar %vill be only Rc30 to 35. Such a steel is said to have low harden-
ability. The structure on the outside would be martensite because the cool-
ing rate on the outside portion of the bar was faster than the critical cool-
ing rate as shown in curve
O, Fig. 13.4A. The structure of the center of the
bar would be pearlite since here the cooling rate is much slower than the
critical cooling rate as shown in curve C, Fig. 13.4A. How deep the outside
hardened shell will be depends upon the critical cooling rate since all of
the steel that is cooled at the critical cooling rate or faster will be hard.
If a one-inch bar of an alloy steel is quenched, as just described for a
carbon steel, the bar will be hardened to the center, and only martensite
would be observed. Such a steel has high hardenability
(hardens deeply).
The actual cooling rate of the two steels at a given distance from the
surface is essentially the same, but the TTT curve for the alloy steel
plots to the right as shown
in Fig. 13.4B. In this case the cooling rate
represented
by curves O and C are both faster than the critical cooling
rate because the TTT curves plots sufficiently
far to the right. Thus a
comparison
of the relative
position of the TTT curve for various steels
on the time scale affords a quick qualitative
means of comparing their
relative hardenability. The role of alloying elements in determining
the position of the TTT curve has been covered in Chapter 12.
There are applications in industry where only surface hardness is
needed and high hardenability is not important. For such applications it
usually is good economy to use carbon steels. For certain uses, however,
such as aircraft parts, uniformly high strength and hardness is generally
required through the part. In these cases it becomes necessary to use an
alloy steel such as S.A.E. 4140 in order to have sufficient hardenability.
When a steel has high hardenability, a slower quench (oil quench) can
be used to obtain full hardness in a rather large section. Since this is
the case, it is unwise to use a brine quench because such a quench is much
faster than necessary and greatly increases the chances of cracking the part.
Such steels are referred to as oil hardening steels, and steels with low
hardenability arc called water hardening steels.
13.5 Grain Size and Hardenability
When carbon steel is heated to a temperature just above the critical
range and quenched in brine, very shallow hardness is obtained. If, how-
ever, the same steel is heated high enough to produce a coarse grain before
quenching, the hardness is much deeper. The increased depth of hardness
indicates a slower critical cooling rate as explained earlier. 1 his would
mean that an increase in grain sizes makes the
transformation more slug-
gish, and transformation is slower in starting at a given temperature. The
TTT curve is thus moved to the right when the grain size is increased,
which is the same effect observed when certain alloying elements are
added to the steel.
Because of the shallow hardening feature of fine-grained carbon steel,
a somewhat coarser grain may be desirable even though coarsening of the
grain may induce some brittleness. The actual grain size desired in carbon
steels may therefore be a compromise of moderately fine grain in order to
avoid the severe brittleness associated with a very coarse grain and
not have the low hardenability associated with the very fine grain. In
alloy steels, however, this dilemna is not encountered since hardenability
is afforded by the proper alloying elements.
13.6. Quenching and Properties of Martensite
As discussed in chapter 12, increasing progressively the speed of cooling,
up to a certain rate, lowers the A,
transformation temperature progres-
sively from
1333 F. (723C.) to approximately 1020F. (550C.) .
While
this increase in rate affects the speed with which the gamma iron trans-
forms, it does not affect the completeness of the transformation. The
Fundamentals
of
Heat Treatment
of
Steel 271
increased cooling rate causes the pearlite lamella to become finer. If,
however, the cooling rate is increased still more, an important phenom-
enon occurs. The transformation temperature is suddenly depressed
to 480F. (250C.) or lower, and the steel, especially if it contains more
than about 0.30 per cent carbon, becomes very hard and brittle. The
rate of cooling that is just fast enough to suddenly depress the A^ tempera-
ture to
480F. is known
as the critical cooling rate and is attained by
quenching
a high-carbon steel in water or an alloy steel in oil.
The changes taking place when high-carbon steel is cooled at the
critical rate or faster are in general simple, although some of the details
are not wholly understood. In brief the mechanism of quenching is as
follows: At a temperature above
1333F. (723C.) , the structure is
austenite, the solid solution of carbon in gamma iron. In cooling more
slowly than the critical rate, the face-centered gamma iron changes to
body-centered alpha iron and the carbon is thrown out of solution as iron
carbide. If cooling is faster than the critical rate, the change of face-
centered gamma iron to body-centered
alpha iron is arrested and an in-
termediate crystal structure, the body-centered
tetragonal, is formed. The
carbon, instead of being wholly expelled from solution, is entrapped in
the tetragonal lattice as a supersaturated solution. The result is a highly
strained, very unstable crystal structure
containing a multitude of en-
trapped submicroscopic
particles.
Steel fails under stress by slipping or gliding along crystallographic
planes of relative weakness; these submicroscopic
particles act as keys
and help to prevent easy slip (Fig. 13.5). The result is much higher
strength and hardness, accompanied,
however, by increased brittleness.
The sudden lowering
of the transformation temperature
to about
480F.
(250C.) and the increased hardness and strength are accom-
panied by the formation of a structural constituent known as martensite,
characterized by an angular, needlelike
appearance (Fig. 13.6). The
A
B
n
-^CF
J3T
C^
:cc
h
=D=
<)
\=Q-r^^^6\
-Or
Q.
0=
Fie. 13.5. Schematic representation of a crystal containing (A) no hard panicles.
(B) one large particle, and (C) many small particles.
needlelike formation, while common in rapidly cooled high-carbon steels
of small cross section, is by no means universal. Martensite is a transition
constituent; its composition, hardness, and appearance under the micro-
scope depend primarily upon the amount of carbon, the size of the sec-
tion, and the quenching treatment. Depending upon the carbon content,
the strength of steels which are chiefly martensitic in structure may vary
from 150,000 to more than 350,000 lb. per sq. in., and such steels may
be as brittle as glass or may show considerable toughness.
Metallurgists are generally agreed that the primary cause of the hard-
ness of martensite (and drastically quenched medium- and high-carbon
steels) is the precipitation of submicroscopic particles of carbon or iron
carbide from the gamma solid solution and the retention of these particles
as a supersaturated solution in the tetragonal alpha-iron lattice, where
they act as a multidude of keys effectively preventing slip. Some authori-
ties, thinking that this explanation does not account for all the hardness,
have postulated lattice distortion, internal strain, and the fine grain size as
important contributing causes.* The internal structure of martensite and
Fig. 13.6. Structure of martensite in high-carbon steel quenched in iced brine.
(A) 500x:
(B)
3,000x;
etched.
A complete and wholly satisfactory explanation of the hardness of martensite will

not be available until more is known about the atomic forces that hold the crystal
lattice together and about the nature and magnitude of the strains produced by an
entrapped stranger atom in a lattice.
Fundamentals
of
Heat Treatment
of
Steel 273
the causes of its hardness are of much interest to the physical metallurgist
but are of only passing interest to the engineer who wants a basic knowl-
edge of heat treatment. Far more important is a realization of the insta-
bility of structure that results from quenching.
13.7. The Instability of Quenched Carbon Steels
When carbon steel is cooled slowly through the transformation tem-
perature, all phase changes take place and the carbon is completely
precipitated as large particles of iron carbide (cementite) , resulting in a
structure, laminated pearlite, that is very stable. If, however, the steel
is cooled very rapidly, phase changes are arrested before completion, the
carbide is entrapped in the crystal lattice as exceedingly minute particles,
and the lattice is strained, resulting in a structure, martensite, which is
very unstable.
As is characteristic of an extremely unstable condition, there is a very
strong tendency for quenched steel to become more stable under the
slightest provocation. Re-
heating to 500F. (260C.)
or above will give the atoms
enough mobility so that in-
stability and the strained
structural condition are re-
lieved more or less com-
pletely, depending on the
temperature and the time.
The instability after
quenching is accompanied
by high internal stresses, so
high that frequently a small
piece of water-quenched
high-carbon steel, though
undisturbed, will crack (Fig.
13.8) or will, occasionally, go
to pieces with explosive
violence hours or even days
after quenching. To relieve
these stresses and to produce
at the same time a more
F.G. 13.7. Quenching cracks in the spline end
Stable ural condition,
of a shaft, natural size, etched.
quenched steel is always re-
heated. This Is known as tempering or, colloquially and somewhat in-
accurately, as drawing*
13.8. Retained Austenite and Cold Treatment
When steel is quenched, the cooling must be continued to the M
a
temperature before austenite will start to transform to martensite and be-
fore complete conversion takes place the temperature must lower to or
below the M
f
temperature (Fig. 13.4). If cooling stops between these
temperatures only part of the austenite transforms giving rise to what is
called retained austenite.
The temperature level of the M, and M
t
are both lowered by the addi-
tion of alloying elements and increase of carbon content as indicated in
Chapter 12. If the M
f
temperature is below room temperature then
quenching to room temperature will result in only part of the austenite
being transformed and the remainder being retained as austenite. If
however the steel is quenched and then cooled by refrigeration well below
the M
r
temperature the transformation of the austenite
to
martensite can
be made fairly complete.
Since martensite is much harder than austenite the hardness, strength
and wear resistance of steel can be improved by eliminating the retained
austenite by cooling the steel down to about minus 100F. This can easily
be done by placing dry ice in a container of acetone and using this as the
cooling medium.
This kind of cold treatment is often used to reduce the retained austen-
ite particularly in the case of tool steels where alloy content encourages
retained austenite and hardness and wear resistance must be especially
high or in steel gages where dimensional stability is important.
13.9. Structural and Other Changes in Tempering
When a drastically quenched high-carbon steel is reheated, two things
happen: The unstable tetragonal crystal structure of the martensite trans-
forms to the more stable body-centered cubic lattice of the ferrite, and
at the same time internal stresses are relieved. To produce such changes,
it is only necessary to reheat to about 200 to 400F. (100 to 200C.)
;
for some steels the temperature of boiling water is sufficient. Tempering
at these low temperatures produces only a very slight mobility of the
iron and carbon atoms, and it is likely that the only effect, in addition
to relief of stresses, is the escape of the carbon atoms from the tetragonal
lattice as it changes to body-centered cubic. As a result low-temperature
The terra drawing for tempering originated from the old blacksmith's expression
"drawing the temper." Drawing in its correct sense means pulling a wire through a
die to reduce the cross section.
Fundamentals
of
Heat Treatment
of
Steel 275
tempering produces no appreciable change in hardness. Tempering at
400F. (200C.) or lower is, therefore, commonly used for quenched
high-carbon tool steels which must be very hard but should be free from
internal stresses.
When tempering medium and high carbon steels in this low tempera-
ture range of 180 to 480F., it has been established that some sort of transi-
tion carbide (not Fe
3
C) is precipitated. The composition of this carbide
seems to have the composition approaching Fe
2
C or Fe^C.,. As the tem-
pering temperature goes higher this first carbide is absorbed and re-
precipitated as cementitc (Fe
3
C)
.
When drastically quenched carbon steel is tempered at 500F.
(260C.) or higher, the particle size of the iron carbide increases. How
far this return to stability proceeds depends upon the tempering tem-
perature and to a lesser extent upon time. Most of the growth of carbide
particles at any definite temperature occurs in the first few minutes; the
reaction then slows down but continues for some time. In practical heat
treatment the time for tempering is rarely less than 30 min. for each inch
of cross section.
As the carbide particles grow larger, it follows that there will be fewer
of them to act as minute keys to prevent slip (see Fig. 13.4) . Hence, hard-
ness and strength decrease, and ductility, as measured by elongation and
reduction of area, increases. The higher the tempering temperature, the
larger the carbide particles and the more stable the resulting structure.
Finally, when the tempering temperature is within a few degrees of the
A, transformation temperature, the cementite has grown to particles so
Fie. 1S.8. Structure of high-carbon steel quenched in ice water and tempered (A)
at 575-F. (300C.) and (B) at 1100
o
F. (595C); etched
500x-
276
large that they are readily visible with the microscope at low magnifica-
tions, and the properties are practically the same as those of a steel of
corresponding carbon content cooled slowly through the A
x
temperature.
Structural changes in tempering can be followed by microscopic ex-
amination of polished and etched specimens but not so closely as by
dimensional changes and other methods. Martensite which has a struc-
ture similar to that shown in Fig. 13.6 is white after etching, that is,
etches slowly. Tempering at 575F. (300C.) produces, for the same
degree of etching, a dark, almost black, structure indicating precipitation
and considerable growth of the carbide particles. After tempering at
1100F. (595C.) , the particles have increased in size so that they are
visible in the microstrucfure. These two stages are shown in Fig. 13.8.
Tf quenched steel contains retained austenite and is not cold treated
to transform the retained austenite to martensite, tempering is somewhat
more complex. The martensite will go through the various stages of tem-
pering just described. However, the retained austenite will, at about
450F. to 500F., transform to a dark etching bainite, %vhich is quite hard,
and may result in a little increase in hardness.
QUESTIONS
1. What happens to the structure of a small piece of .8% carbon steel con-
taining a mixture of large and small grains when it is subjected to the
following treatments: (a) heated slowly to about 1400F., held 80 min.,
and cooled slowly to room temperature; (b) heated slowly to 2000F., held
30 min., and cooled slowly to room temperature; and (c) heated slowly to
2000F., held 2 hr., and cooled slowly to room temperature?
2. Define grain-growth tendency. Compare grain-sue control by submicro-
scopic particles and by controlling the heating above the critical. Why is the
former method preferable?
3. What ,is critical cooling rate? What is its effect on the austenite-pearlite
transformation and on the resulting structure of high-carbon steel? Is a
cooling rate of 600F. per sec. more or less than the critical cooling rate
for eutectoid steel.
4. When a high-carbon steel is cooled faster than at the critical rate, what
is the effect on the crystal structure, the appearance under the microscope,
and the properties? What is martensite, and why is it hard?
5. Why is high-carbon steel that is drastically quenched unstable? What unde-
sirable conditions may accompany this instability and how may they be
avoided?
6. Describe the changes in structure and properties that take place when
drastically quenched steel is reheated to (a) 350F.; (b) 600F.; and (c)
1200F.
7. What effects have the alloy elements on the temperature at which austenite
transforms to pearlite? How are these effects related to heat-treatment?
Fundamentals
of
Heat Treatment
of
Steel
277
8. Name the three principal variables affecting the hardness of quenched
steel. If other factors are constant, which will be the harder one as
quenched: (a) steel containing 0.30 or 0.60 per cent carbon? (b) steel con-
taining 0.60 or 0.80 per cent carbon?
9. Define hardenability.
What is its relation to grain size and to the alloying
elements present? Distinguish between shallow-hardening and deep-harden-
ing steels.
10. In what classes of steel is deep hardening important? Why?
11. Describe process annealing.
12. How does grain size effect hardenability?
15. What factors determine the grain size of steel after process annealing?
14. What is the relationship between grain size and toughness?
15. What are two standards for classifying grain size?
16. Describe the effects of hot working on grain size.
17. What factors determine the amount of retained austenite after quenching?
CHAPTER
The Operations
of
Heat Treatment
14
Omar C. Moore, M.S., Associate Professor of Chemical
Engineering, Alabama Polytechnic Institute, Auburn,
Alabama
Robert E. SHAFFER, M.S., Associate Professor of En-
gineering, University of Buffalo, Buffalo, New York
1 HE value of heat treatment to mankind, em-
phasized in previous chapters, has little relation to the proportion of the
world's steel tonnage that is treated. This tonnage amounts, in the
United States, to possibly two or three million tons annually, certainly
less than 5 per cent of the total amount of steel used. Heat treatment
is most valuable for tools and dies, which are in turn a very small propor-
tion of heat-treated steel.
Heat treatment is ordinarily an expensive operation, because costly
furnaces, quenching baths, apparatus for controlling the atmosphere in
the furnace, and temperature-recording and -controlling equipment are
necessary. Some treatments cost as much or more than the steel itself, but
this is no criterion of the value of the operation. Moreover, the cost of
steel and of treatment is usually a very small part of the cost of the
finished article and is even a smaller proportion of the value of the article
to industry. One example will indicate this. The steel in a die may cost
$2 and the heat treatment may increase this to $4. On this $4 die, the
machine work frequently costs $100, but the completed die will turn
out thousands of pieces of a finished product at a cost which is a very
small fraction per piece of the cost of a similar product turned out, one by
one, by hand.
Owing to the economic value of a properly heat-treated article and to
the customary expense of the machine work to prepare this article for
use, it is poor economy on the part of the engineer to take chances on
the quality of the steel or the heat treatment so that a few cents may be
278
The Operation
of
Heat Treatment 279
saved. It is, furthermore, poor practice for the engineer to design ex-
pensive tools, dies, or other parts without requesting the metallurgist to
advise whether the finished article will or will not survive the heat treat-
ment satisfactorily. Thousands of dollars are wasted every year because
tools and other articles, which cost much to machine, crack in quench-
ing. Such waste can usually be prevented by the intelligent selection of
the proper steel and by avoiding, in the design, sharp corners or reentrant
angles where stresses concentrate. This factor is discussed in some detail
later in this chapter.
The operations of heat treatment discussed in this chapter are those
used for carbon steels, most alloy steels, and some nonferrous alloys.
Modifications of these operationsused for a few high-alloy steels, for
certain other iron alloys, and for a number of nonferrous alloysare
described in the chapters where these materials are discussed or in the
chapter on precipitation hardening.
Color
Orange-
Salmon
Bright-
Red
Cherry
Medium\
Cherry
]
Dork l
Cherry
)
14.1. Heating Cycle
Uniform and consistent results from any cooling cycle can be obtained
if the proper care has been taken in the heating of the steel prior to the
method of cooling. The steel must be heated slowly to the proper tem-
perature range and held at this temperature long enough for homogeniza-
tion of the austenitic structure. The temperature used and time required
are functions of the chemistry of the
steel, section size and shape, prior grain
900
size, original condition of the steel, prior
850
heat treatments, or mechanical working.
boo The usual time requirement at heat for
750 homogenization of the austenite for a
TOO
forging or casting, is one hour per inch
650 of section thickness. This is not a firm
1.60 rule and is frequently neglected. How-
ever, adequate time at heat must be
provided for solution of carbides, and
also, if uniformity of product is to be
achieved upon cooling for the diffusion
of carbon and alloying elements from areas of high concentration into
the lean areas.
Modern heat treating equipment should provide some means of sur-
face protection for the steel during the heating cycle. The use of con-
trolled atmospheres in heat treating furnaces is becoming standard prac-
0.40 0.80 120
Percentage Carbon
FlC. 14,1. Temperature ranges
for the heal, treatment of carbon
steels. (Metah Handbook)
280
tice. If during heating the steel is exposed to combustion gases or air in
the furnace, it will oxidi/e, dccarburize, or both. An oxidized surface is
easily detected and can be removed by machining or grinding. Decarburi-
zation does not show and will result in low surface hardness and poor
mechanical properties if not removed.
Protective atmospheres are provided by several different methods and a
number of different gases are used, including hydrogen, nitrogen, carbon
dioxide, and sulfur dioxide.* With the proper selection and composition
control of the furnace atmosphere it is possible to produce heat treated
parts free of scale and decarburization.
14.2. Annealing
Process annealing is the recrystallization of a cold-worked steel, by heat-
ing below the A
t
transformation temperature, usually in the range be-
tween
800
to 1200F., the exact temperature being governed by the
amount of cold working, composition, grain size, and time held at heat.
Heating to the proper temperature affects complete recrystallization and
restores the original structure and properties. Too high a temperature or
too long time at heat may produce a coarsening of the grain size with a
subsequent loss of toughness, hardness, and strength.
For full annealing, the steel is heated slowly to from
50
to 100F.
above the A
3
transformation (Fig. 14.1) , held at this temperature until
uniformly heated, and then slow cooled to room temperature. The cool-
ing may be done in the furnace, or in an outside pit covering the steel with
asbestos, sand, lime or cinders. The rate of cooling is in the range of
5
to 20F. drop per minute.
The objects of annealing are to soften the steel for machining, to re-
fine the grain structure, to relieve stresses from cooling or machining,
and to increase ductility. In hypoeutectoid steels it produces the poorest
strength and wear resistance of any structure except spheroidizing. An-
nealing is commonly used for castings and forgings to reduce the coarse
grain structure prior to machining.
14.3. Normalizing
The steel is heated slowly at least 100F. above the A
s
or A
cm
transformation (Fig. 14.1) for the proper time, and then cooled in still
air. The cooling rate can be varied by changing volume of air or air
Discussion of controlled atmospheres and equipment is outside the scope of this

book. For a more complete description see: American Society for Metals, Metals Hand-
book. The Society Cleveland, 1948.
The Operation
of
Heat Treatment 281
temperature. The normal rate of cooling is the range of
120
to 200F.
per minute, depending on section size and air conditions.
Normalizing of low carbon content steels is usually done for stress relief,
grain size refinement, to improve toughness and to increase strength and
ductility.
Steels containing over 1%
carbon, slowly cooled from high tempera-
tures, may have the excess carbides forming in a network around the
grains of pearlite. This carbide network is stable and unaffected by re-
heating to the annealing and hardening temperatures (Fig. 14.1). This
carbide formation will increase machining costs and produces an un-
desirable condition in the heat treated part. By heating above the A
cm
temperature and normalizing, insufficient time is available for the excess
carbide to form a network around the grains or to form large plates in the
pearlitic structure.
Some finished parts, castings, forgings, and rolled shapes to be used after
a normalizing treatment should be given a temper to relieve cooling
stresses resulting from non-uniformity of cross section. This temper will
usually give a noticeable improvement in ductility with little or no change
in hardness or strength.
14.4. Spheroidizing
The spheroidized structure, ferrite and carbides, is usually produced
by prolonged heating, 3 to 8 hours at a temperature slightly above or
below the A! or A
3 2
,
transformation. The prolonged heating causes
the carbides to coalesce into spheres, completely destroying the pearlitic
formation and resulting in a matrix of ferrite with the carbon in the form
of spheroidal carbides. The time for spheroidizing is usually lessened by
a normalizing treatment prior to spheroidizing.
In medium and high carbon steels the spheroidized structure has the
lowest hardness, strength and wear resistance, but the best machineability,
toughness, and ductility.
Though the spheroidized structure is desirable for machining and form-
ing, it may cause some difficulty in heat treatment. The carbide material,
if in large spheres, may not go into solution when a simple heating and
quenching cycle is used, resulting in spotty and low hardness. It is desir-
able to give steels of this type a normalizing treatment prior to the
hardening cycle to help break up and to dissolve the excess carbide areas.
A similar structure of a ferritic matrix with spheres of undissolved
carbides will result if a martensitic structure is tempered at a high tem-
perature 12001250F. This method of producing the spheroidized struc-
ture is not recommended because of the problems involved in quenching
higher carbon steels.
282
14.5. Quenching for Hardening
For hardening, the sieel is slowly heated above the A.
t
transformation
range (Fig. 14.1). The hardening temperature range for carbon steels is
the same as the full annealing range. The steel is usually held at heat
long enough to insure uniform heat distribution in all sections. It is then
removed from the furnace and immediately quenched in the cooling
medium.
In carbon steels it is generally true that the faster the heat is extracted,
the harder, stronger, and more wear resistant the finished part will be.
High hardness is frequently accompanied by excessive brittleness. Water
quenched high-carbon steels will often crack or shatter if dropped, or if
allowed to stand overnight before tempering.
The common quenching media are air, oil, water, and brine solutions.
Selection of the proper quenching medium is based on the chemistry
of the steel, section size and shape, and the final mechanical and physical
properties
required. Air has the slowest cooling rate, and brine solutions
the fastest rate. The cooling rate of a quenching medium will vary with
the amount of agitation, temperature, and composition. Water at 65F. is
considered to have a cooling rate of one; brine solutions have as much
as twice the cooling rate of water; oils vary from
15% to 50% of the cool-
in rate of water.*
Hardening
of a steel is usually required because of the demand for the
maximum of one or more of the mechanical or physical properties that
the steel is capable of assuming. Sometimes because of size, shape, varia-
tion in cross section, or some production problem, a compromise must be
maele. If this must be done, a careful study of the different cooling media
should be made in order to select the one best suited to produce the best
compromise of mechanical and physical properties.
For lower carbon steels, water is usually used because of its low cost,
easiness of handling, and availability. In medium and high carbon
steels, oil is often used because it produces less warpagc, distortion, and
cracking than with a water quench. However, by using an oil quench
instead of water, maximum hardness, strength, and wear resistance may
not be obtained.
When the heated steel is quenched in a liquid, there are
two distinct
steps or stages of heat removal that are passed through before reaching
the temperature
of the quenching medium.
Step One: The vaporization
period. In this period of the cooling cycle
the
quenching medium will vaporize when it comes in contact with the
American Society for Metals Handbook. The Society, Cleveland, 1948.
pp.
616-619.
The Operation
of
Heat Treatment 283
steel. If the vapor is allowed to form a film around the part being
quenched, the cooling rate is slow because the vapor film insulates and
blocks off contact between the cooling liquid and the steel. By breaking
up the vapor film and allowing the liquid to vaporize and be carried away,
the fastest cooling rate is achieved. The breaking up of this vapor film is
accomplished by proper agitation or circulation of the quenching liquid
or by agitation of the parts being quenched, or both.
Step Two: The liquid period. After the quenched pari has lost suffi-
cient heat so that the liquid is no longer vaporized upon contact, the
removal of heat is now a simple problem of heat transfer and the rate of
heat loss is relatively fast as compared with the vapor cycle.
The difficult and critical period in quenching is the elimination of
the vapor film. Prolonging this step may result in unsatisfactory harden-
ing. The part may have areas which arc low in mechanical properties, or
the entire microstructure may be unsatisfactory and fail to produce the
required mechanical properties.
The internal stresses introduced by quenching are the result of
(1)
dimensional changes in cooling,
(2)
large temperature gradients between
surface and center, and
(3)
the change in volume accompanying the
change from gamma to alpha iron. If the steel is ductile, these changes
cause slight plastic flow of the grains which relieves the stress. In high-
carbon steels where no plastic deformation takes place these stresses may
build up to a high value.
Stress distribution in quenching is complex and difficult to analyze
accurately. In many instances, it is certain that the sum of the induced
stress and the working stress is near or above the tensile strength of the
steel. Thus, it was found* that in hollow cylinders the stress that was in-
troduced by quenching at the inner surface of the hole was about 150,000
lb. per sq. in. As the working stress on these cylinders was 100,000 lb. per
sq. in., the total stress was 250,000 lb. per sq. in. or close to the actual
tensile strength of the steel.
Internal stresses may affect the strength and ductility and frequently
cause warping and cracking. The magnitude of these stresses is de-
pendent on the size and shape of the piece, the kind of steel, the quench-
ing temperature, and the coolant. When the stress builds up to a value
higher than the tensile strength, the steel cracks. There are two types
of such defects:
(1)
local cracks, which are usually external and start
at sharp comers or deep tool marks, and
(2)
internal cracks, which
follow the major axis of the piece. Quenching in water is more likely to
O. V. Greene, Trans. Am Soc. Steel Treat., v. 18, 1930,

pp.
369-403.
284
cause cracking than quenching in oil or air. Coarse-grained steels crack
more readily than fine-grained material. Localized heating in grinding
frequently causes cracking, as does increasing the temperature from which
the steel is quenched.
The best procedures in avoiding quenching cracks are as follows:
(1)
use generous fillets where the contour changes and avoid tool marks
which may act as a notch;
(2)
avoid rapid heating, especially through
the transformation range, which may cause cracking because of the un-
even expansion;
(3)
temper immediately after quenching; and
(4)
quench in oil instead of water wherever possible.
14.6. Tempering
The previous discussions of the principles underlying quenching in-
cluded details of structural changes and related changes in properties.
Some of these changes in physical properties are often desirable, particu-
larly where hardness and wear-resistance are of importance. However, this
increase in hardness, strength and wear-resistance is at the expense of
ductility because, in most instances, the brittleness has also increased. The
extent of brittleness, coupled with hardness, etc., depends on the severity
of quench and the percentage of carbon in the steel. Tempering lowers
the hardness and strength and decreases wear-resistance; it also increases
ductility.
The purpose of tempering is not to decrease hardness but rather to
restore ductility and improve toughness. A way of doing this and at the
same time retaining the original hardness and strength would be desirable.
However, since tempering does decrease the hardness and strength, but
at the same time restores ductility, it would be well to consider what is
desirable in the way of strength. Generally a structural part is not sub-
jected to deformation until it breaks; it is the stress capacity without
permanent deformation which is important.
Tempering should be carried out at the highest temperature that will
insure retention of sufficient strength so that the part can withstand loads
comparable to its yield strength. The higher the temperature, the
tougher the product, but this will necessarily be at the expense of hard-
ness and strength.
For tempering, the hardened steel is reheated in a furnace, in heavy
oil, in molten salts, or in molten lead, and held long enough for the
heat to penetrate to the center. For most steels, the speed ol cooling after
tempering is of little consequence, provided the steel was not heated
to the transformation temperature. In practice, the cooling after tem-
pering is usually in the air.
The Operation
of
Heat Treatment 285
The metallographic structure of tempered steel will be further dis-
cussed in Section 14.7, where tempering is compared to other heat treat-
ment processes.
14.7. Isothermal Treatments
One result of the study of the subcritical transformation of austenite,
which also led to the S. curve, by Bain and his associates* was the dis-
covery of austempering, a process of interrupted quenching whereby
high-carbon and low-alloy steels of suitable composition and cross section
can be hardened without cooling to atmospheric temperature, thus elimi-
nating the possibility of introducing high quenching stresses with possible
distortion or cracking. The process cannot be used if a very hard mar-
tensitic structure, as obtained by water quenching high-carbon steels and
tempering at 200 to 300F. (100 to 150C), is desired; but it may be
used to obtain a structure corresponding to tempered martensite of any
required degree of fineness, such as is usually attained by cooling rapidly
to room temperature followed by reheating to 400F. (200C.) or above.
At any temperature below the
A\
transformation and above the tem-
peratureabout 400F. (200C.) where martensite is formed, the aus-
tenite transforms to pearlitej of definite structure at a definite rate. If,
therefore, small specimens of high-carbon steel are heated above the
transformation temperature and are quenched very rapidly into a bath
maintained at any intermediate temperature, for example, 500 to 800F.
(260 to 425C.) ,
and if the specimen is held in this bath for a definite
time, the transformation of the retained austenite and the resulting struc-
ture may be controlled closely. Steels so treated are more ductile than
similar steels cooled rapidly to room temperature and tempered at a
temperature that produces a corresponding structure. The hardness and
strength of the austempered steel are about the same as if the steel had
been quenched and tempered in the usual manner, but elongation, reduc-
tion of area, and impact resistance are usually higher. The explanation
advanced for the higher ductility in the austempered steel is its freedom
from submicroscopic cracks that are caused by drastic quenching (to
form martensite) and not subsequently healed by tempering.
A schematic representation of austempering is shown in Fig. 14.2.t
To
prevent any transformation of the unstable austenite to pearlite,. the
specimen must be small enough to cool past the nose of the S curve very
rapidly; for the steel whose diagram is given in Fig. 14.2, it must cool
E. C. Bain and E. S. Davenport, U.S. Patent 1.924,099, Aug. 29, 1933.
f
Based on diagram by F.
J.
McMulkin, Iron Age, v. 157, June 27, 1946, p. 58.
%
(or Bainite)
.
286
Engineering
Metallurgy
1400
I30C
Mostly \morfensife
I5min.30min. Ihr.
I I
Bhr. Icty .
1200
MOO
-11000
900,
800".
700
|
E
600
"
500
400
300
200
100
10,000 100.000 1000
Time, sec.
Fig. 14.2. Schematic T-T-T diagram for carbon steel showing critical-cooling-rate
curve, M
B
temperature, and temperatures for austempering and martcrnpering. (Mc-
Mulkin)
through the temperature range of 900 to 1000F. (480 to 540C.) in about
1 sec. The specimen is therefore quenched rapidly into a bath maintained
at the desired temperature-600F.
(315C.) in Fig. 14.2-and held in the
bath until the transformation to bainite (emulsified ferrite and cementite)
is complete, that is, for about 45 min. Structural changes are now com-
plete, and the specimen may be cooled, at any rate, to room temperature.
A process that carries the principles underlying the subcritical de-
composition of austenite farther than austempering is martempering,
which was developed a few years ago by Shepherd.* In this process the
*
B. F. Shepherd has described martempering in a number of papers. A lucid
description, which also includes an elementary discussion of the transformation of
austenite to martensite in quenching and isothermally, as mapped by the S curve, is
contained in two arUcles by Shepherd in Production Eng.,
July, 1945, p. 438, and Aug.,
1945,
p.
515.
The Operation
of
Heat Treatment 287
steel is quenched at its critical rate or fasterso that it will pass the nose
of the S curve without any transformation of the austeniteinto a bath
maintained at a temperature slightly above the M
s
point, in other words
just above the temperature where martensite starts to form. This tempera-
ture varies with carbon content and slightly with the amount of alloying
elements present, but for high-carbon and many alloy steels it is ap-
proximately 400F. (200C.) . The steel is held in this bath just long
enough for the temperature to become uniform throughout the cross
section, after which it is removed and cooled in air. A schematic repre-
sentation of martempering is shown in Fig. 14.2. The specimen is
quenched at the critical cooling rate or faster into a bath maintained at
about 450F. (230C.) and held in this bath for a sufficient time to be
heated through (about 1 min. for a small specimen of the steel shown
in Fig. 14.2) . It should be noted that the specimen should not be heated
so long that the line where bainite begins to form is crossed by the time
axis at this tempering.
Martcm|>ering is based on the principle that, if austenite is retained
by rapid cooling down to the temperature where martensite begins to
form, the austenite-martensite transformation will proceed, regardless of
the cooling rate from this temperature down to atmospheric temperature;
and that on cooling slowly, as in air, from about 400F. full hardness will
result without the concomitant high internal quenching stresses which
are characteristic of drastically quenched high-carbon or alloy steels. Ac-
cording to Shepherd, this treatment improves the mechanical properties,
especially ductility and toughness. The method can be used for heavy
sections and for pieces of irregular shape which often crack in the usual
hardening operation.
Martempering resembles austempering only in that the quenching is
interrupted at an intermediate temperature; but the steel is not held at
this temperature long enough for any appreciable amount of the austenite
to transform. In martempering, therefore, the austenite transforms to
hard martensite, while the steel is cooling slowly from this intermediate
temperature to atmospheric temperature; in austempering the steel is
held at the intermediate temperature long enough for the austenite to
transform to a ferrite-carbide aggregate of desired structure and prop-
erties.
Patenting is a very old process used to heat treat medium- and high-
carbon rods which are to be cold drawn into high-strength wire. The
rods or the wire (if patenting is used as an intermediate stage in drawing
coarse wire to finer sizes) are heated to a temperature considerably above
the A
3
transformation temperature, so that some grain growth takes place,
288
and cooled in air or quenched in a bath of molten lead maintained at
850 to 950F. (455 to 510C). The object of patenting is to produce a
fairly coarse austenitic grain that transforms in the air or at the lead-bath
temperature to large pearlite grains which are made up of fine ferrite
and cementite. Such a combination of controlled overheating and finely
dispersed carbide and ferrite in the pearlite is essential for the steel to
withstand the cold work to which the wire is subjected in drafting and
is also essential if satisfactory quality is to be secured.
Patented and cold-drawn wire for use in cables in suspension bridges
is fairly high in carbon and has a final strength of around 225,000
lb per sq. in. and an elongation of about 2 to 6 per cent in 10 in. Patented
and cold-drawn wire is the only suitable material found thus far for
suspension-bridge cables. A high-carbon wire, cold drawn and then
quenched and tempered so that it has the same mechanical properties,
is unsatisfactory. The reason for this is not clear, but the first attempt
to use heat-treated wire instead of patented and cold-drawn material
ended so disastrously that it is doubtful whether it will ever be tried
again." Patented and cold-drawn wire has been used for suspension-
bridge cables for many years, and failures are unknown. The most that
can be said is that apparently the equiaxed structure of the heat-treated
wire does not resist so well as the elongated "fibrous" structure of the
cold-drawn material the propagation of minute cracks on the surface,
formed when the wire is bent around the anchorage shoes.
Some emphasis should be given to the advantages of austempering and
martempering as compared to tempering a martensitic steel. A tougher,
more shock-resistant steel is obtained in austempering or martempering.
Tempering involves the decomposition of martensite to granular mix-
tures of cementite and ferrite in which the cementite particles tend to
be round rather than lamellar as in pearlite. Temperature and time,,
primarily temperature, are important factors, along with the amounts of
alloying elements in the case of alloy steel, in determining the size of
the separated carbide particles. At very low tempering temperatures the
resulting decomposition products are hardly discernible under the micro-
scope. Tempering at progressively higher temperatures results in micro-
structures that can be resolved under the microscope; the carbide par-
The wire used in the construction of the Mt. Hope Bridge, at Providence, and the
Ambassador Bridge, at Detroit, both ot which were suspension bridges, contained 0.80
per cent carbon and was oil quenched and tempered. Although the mechanical prop-
erties were satisfactory, the wires began to fail soon after the cables were spun; the
bridges had to be dismantled and rebuilt with the usual patented and cold-drawn
wires in the cables. See E. E. Thum, Metal Progress, v. 21, 1932, No. 6; v. 22, 1932,
No*. 1, 2, and 3.
The Operation
of
Heal Treatment 289
tides are progressively larger, and eacli micro-structure is softer and
tougher than the preceding one. The structure in which the divorced
cementite, embedded in the ferrite matrix, can be seen with moderate
magnification is termed spheroidite.
In the practice of austempering, the formation of martensite structure
is avoided by suddenly cooling the heated steel to a predetermined tem-
perature at which only bainite forms and by holding it there for sufficient
time to complete the transformation of austentite to bainite. Thus a
product having ductility (toughness) comparable to that of a tempered
steel is obtained in a single operation and without subjecting it to the
quenching necessary to produce martensite.
Martempering, which produces a hard martensitic structure, avoids
the high internal quenching stresses produced in a fully hardened steel
by drastic quenching.
Attention should be called to the commercial limitations of austem-
pering and martempering. In practice, small section sizes (plain steel)
up to
y
4
inch respond best to the above method because of the necessity
of suppressing the austenite-to-pearlite transformation. The maximum
size that can be effectively treated, though, is determined by the composi-
tion and characteristic S-curve of the alloy.
14.8. Case Hardening Processes
There are many important industrial products, such as gears, cam-
shafts, piston pins, and the like, which should have a hard, wear-resistant
surface and a tough core. Carburizing is the most widely used method
of securing such a combination of properties. In this process, unalloyed
low-carbon or low-carbon alloy steel is heated in contact with a carbon-
aceous material, from which the steel absorbs carbon. The depth of
absorption depends on temperature, time, the alloying element present
(if any) , and the carburizing compound. With a commercial compound,
a case
%
in. deep is obtained by heating for 8 hr. at 1700F. (925C).
Two general methods are in use: pack carburizing and gas carburizing.
In the former, the steel article, fully machined and finished except for a
small allowance for grinding, is packed, together with the compound, in
a heat-resistant alloy box. The carburi/ing compound is coke or charcoal
mixed with an "energizer," which is usually barium carbonate. At the
carburizing temperature, the barium carbonate dissociates into barium
oxide and carbon dioxide; the latter reacts with the carbon in the char-
coal to form carbon monoxide gas (CO
a
+ C = 2CX)) . This gas reacts
with the iron at the surface of the steel to form iron carbide. By diffusion,
the carbon then penetrates below the surface. In the other method, used
290
Engineering
Metallurgy
Fie. 14.3. Structure of slowly cooled carburized steel (A) at the surface and (B)
in the transition zone between surface and core. The structure of the low-carbon core
is shown at the bottom of B; etched.
100x-
chiefly for small articles, the steel is heated in a retort furnace into which
a gas composed of hydrocarbons or carbon monoxide is introduced. This
method is more rapid than pack carburizing, and the case depth can be
more closely controlled.
After carburizing for a sufficient time at the proper temperature (both
of which have been standardized) , the carbon at the surface varies from
about 0.8 to about 1.1 per cent. This grades off uniformly with in-
creasing distance from the surface, until at a depth of >/
4
or s/
A
in. the
structure is unaffected. Typical structures of slowly cooled carburized
steel, at the surface (A) and in the transition zone (B) , are shown in
Fig. 14.3.
Carburized steel is always heat treated to produce the required hard-
ness of the case and usually to improve the ductility of the core, which
may be too coarse-grained from the long heating at high temperature.*
After heat treatment, the case of carburized steel articles is martensitic in
structure and very hard, and the core has the ductility of low-carbon
Sec Metals Handbook,
1948, pp. 681-G85, for a detailed description. See also S.
Epstein, The Alloys
of
Iron and Carbon, Vol. I, Constitution, McGraw-Hill Book
Company, Inc., New York,
pp.
335-340, for a discussion of principles.
The Operation
of
Heat
Treatment
291
steels. Even greater toughness and shock resistance, combined with a hard
surface, can be secured by carburizing a low-carbon alloy steel,
especially
one containing 3 to 5 per cent nickel.
Austenite grain size is important in carburizing steels. After carburiz-
ing and heat treatment, a
coarse-grained material has a uniformly hard
surface, but the core may not have such high impact resistance as is
generally desired. Fine-grained steels, on the contrary, are prone to
carburize irregularly and develop soft spots on the surface after heat
treatment. These conditions can frequently be avoided by special quench-
ing techniques, most of which use a spray of water under pressure, or
by the use of alloy steel.
Nitriding, an established process for producing a hard surface on
steel, uses nitrogen as the hardening agent instead of carbon. It was in-
vented by Adolph Fry in Germany about thirty years ago and is now used
widely in applications where a superhard surface combined with consid-
erable corrosion resistance and resistance to softening at elevated tem-
peratures is desired. It is used by the automotive and aircraft industries
for valve seats and for guides, gears, and piston pins of
internal-com-
bustion engines and in a number of applications in steam plants and oil
refineries.
The process consists of heating the finish-machined article in a closed
container into which ammonia gas is forced under pressure. At a tempera-
ture of 850 to 1000F. (450 to 540G.) the ammonia is mostly dissociated
into nitrogen and hydrogen. The former combines with the iron and
other elements in the steel to form complex nitrides which diffuse into
the surface layers. This diffusion is slow; a case varying in depth from
0.0005 to 0.02 in. is obtained after 5 to 25 hr.
Unalloyed carbon steels cannot be nitrided successfully. Some alloying
element which forms a stable nitride must be present. The steels used
for nitriding, therefore, contain chromium,
aluminum, molybdenum, and
vanadium in various combinations. Aluminum and chromium are the
effective elements in producing high hardness, while molybdenum and
vanadium increase the toughness of the steel and also increase the depth
of penetration of the nitrogen. Nitriding steels are usually heat treated
before nitriding to obtain the desired mechanical properties, which are
not affected by the treatment with ammonia, provided that the steels were
tempered prior to nitriding at the same or higher temperatures than used
during the treatment with ammonia.
The outstanding advantage of nitriding is high surface hardness and
wear resistance. This surface hardness cannot be equaled by any other
method known to ferrous metallurgy. It averages a Vickers hardness
292
Engineering
Metallurgy
number
of 1200 as compared with 650 to 700 for quenched high-carbon
steel of maximum hardness.
Another
advantage is that no subsequent heat treatment is necessary,
as it is for carburized
steel. Nitriding is, however,
accompanied by an
increase
in the size of the section. This growth is dependent upon the
time and
temperature of the operation but is constant for a given
set of
conditions. It averages 0.001 to 0.002 in. for the usual temperatures and
for nitriding
periods of 15 to 20 hr. To allow for this growth, parts that
are to be nitrided
are machined so that they are undersize
by the amount
of the
expected growth. If it is desired to prevent the absorption of
nitrogen in certain areas, these are plated with nickel or coated with tin.
Nitriding is a relatively costly process. In the first place, special alloy
steels are necessary; in the second, nitriding equipment
is expensive. A
nitrided
camshaft, for example, costs from 5 to 15 times as much as a
comparable article which has been carburized and heat treated. Since the
cost depends largely upon the quantity treated, an appreciable reduction
in cost would result if the demand for nitrided steel would permit large-
scale production.
Cyaniding
is another method used to produce
case hardening. This
process uses molten sodium cyanide, sodium chloride, and sodium
carbonate
as the bath in which the steel is immersed. The case produced
is very thin, seldom over
0.002 of an inch, and the temperature required
is from 1300 to 1600F. (700 to 870C).
A modification
of the cyaniding process is to bubble ammonia gas
through
the molten
salt bath, thus liberating
nitrogen faster and in-
creasing
the nitrogen
content of the case. This modified process is termed
chapmanizing.
Carbonitriding
involves both carburizing and nitriding
in a single
operation
by heating
the steel
(1
200-1
600F) in a carburizing gas
(CH
4 ,
GjH
8
,
etc.) containing ammonia. This process has gained wide
acclaim and many steel parts are being case-hardened by this method
today. Lower temperature
processing results in a case similar to a
nitrided steel. Higher
temperatures produce a case like a carburized
steel.
Nitrided
cases are very stable; the hardness is unaffected
by long heat-
ing at temperatures
as high as 750 to 850F. (400 to 455C.) and is not
affected by heating for short periods at temperatures as high as 1000 to
1 100F.
(540 to 595
C
C.)
.
The surface is resistant
to such corrosive agents
as the atmosphere,
alkalies, crude oil, tap water, salt water except when
it is moving, ethyl gasoline, and many others. It is, however,
not resistant
to mineral acids. It has the highest wear resistance
of any ferrous material
The Operation
of
Heat Treatment
293
and is finding increasing use in applications where this property is of
prime importance.
14.9. Flame Hardening and Induction Hardening
There are a number of applications for steel articles that should be
hard only in a relatively small area on the surface. For such uses, it is
not economical to heat treat a section weighing 100 lb. or more by the
usual method of heating in a furnace followed by quenching and temper-
ing, or by carburizing to harden the whole surface. In some cases, heat
treating a complex section by the usual method causes too much
distortion. Also, it is not generally economical to operate a furnace for
the treatment of a single piece. For heat treatment under such conditions
as these, flame hardening and induction hardening have been developed
recently.
Flame hardening consists of heating above the A
a
transformation tem-
perature any desired external spot of the finished steel article, as for ex-
ample the teeth of a gear (Fig. 14.4),* with an oxyacetylene torch. This
is adjusted for flame composition so that the steel does not oxidize. The
distance of the torch from the work and the time of heating are also
controlled so that the steel does not become overheated to the point
where grain growth is serious. As soon as the surface area is at the proper
temperature, it is quenched and immediately tempered to relieve quench-
ing stresses.
Two general methods are used. In the first, the steel piece is fixed and
the torch moves across the area to be heated at a predetermined rate. This
must be controlled carefully as the temperature of the oxyacetylene flame
is approximately 6300F. (3500C.) , but the piece to be hardened
should not be heated higher than 1475 to 1550F. (800 to 850C.) . In
the second method, the torch is stationary, and the steel piece moves
slowly under the flame. The hot area is usually quenched in water, which
is conveniently conveyed through one tube of the torch and flows out of
an orifice under pressure just behind the flame.
In addition to economy under certain conditions, flame hardening has
other advantages. It does not scale or pit the surface; it has no effect on
the chemical composition; it hardens only at the surface and to a depth
of not more than
\/
4
in., and distortion is minimized. Its disadvantages are
that it is more costly than the usual methods if large numbers of identical
pieces are to be treated, and that high-carbon steels and very coarse
grained steels cannot be treated, as they arc likely to crack at the surface.
R. L. Rolf, Trans. Am. Soc. Metals, v. 27, 1939,

pp.
43-00.
294
Fie. 14.4. Flame hardening the teeth of a large gear. (Rolf)
Steels most suitable for flame hardening are carbon steels containing
0.35 to 0.60 per cent carbon and low-alloy steels containing 0.25 to 0.50
per cent carbon. Such articles as alloy-steel gears which have been heat
treated so that they have optimum strength and toughness can be ef-
fectively hardened on the surface of the teeth by this method.
Differential hardening by induction is a recently developed method for
securing high hardness on a relatively small bearing surface and is es-
pecially applicable to heavy-duty crankshafts* and to gear teeth, the ends
of shafts, pins, hubs, and similar sections that act as thrust bearings.
The surface to be hardened is enclosed in a perforated induction block
that surrounds the steel but does not touch it. A high-frequency current
of 2,000 to 200,000 cycles (from 25 to 50,000,000 may be used) is passed
through the block, inducing eddy currents which rapidly (in I to 5 sec.)
*
The method is described in detail by M. A. Tran and W. E. BcnninghofT in Trans.
Am. Soc. Metals, v. 25, 1937, p. 935. Sec also Induction Hardening, American Society
for Metals, Cleveland,
1946, 172
pp.
This is a series of lectures covering theory and
practice.
The Operation
of
Heat Treatment
295
Fie. 145. Cross section of a crankshaft showing hardened (while) bearing surfaces,
etched. (Tran and BenninghofJ)
heat the surface to be hardened to a temperature above the upper trans-
formation temperature. As soon as this occurs, water under pressure is
sprayed onto the hot surface through the holes in the induction block.
The heating and quenching cycle and other conditions are
controlled,
so that if steel of the proper composition and grain size is used, the bear-
ing surface will have a hardness of about 60 Rockwell C (600
Brinell)
to a depth of i/jj in. or more, and decarburization, grain growth, and dis-
tortion will be prevented.
One of the most difficult problems to solve in the manufacture of in-
ternal-combustion engine crankshafts is how to secure a combination of
high hardness and wear resistance on the bearing surfaces and ample
toughness and relatively easy machinability for the rest of the shaft. This
problem has been solved by induction hardening. The shaft can be heat
treated by quenching and tempering at a high temperature, or even by
normalizing, to obtain a structure of fine pearlite, which has satisfactory
toughness and ductility and can be machined fairly easily. Hardening by
induction heating produces a bearing surface with ample hardness and
wear resistance and leaves the fillets, where the stress concentrates,
ductile and relatively stress-free. An etched cross section of a heavy-duty
induction-hardened crankshaft is shown in Fig. 14.5. The hard bearing
surfaces are readily apparent. Heat treatment by induction heating has
expanded rapidly in the past few years; at present approximately one
third of all the quenched and tempered parts used in the United States
are hardened by this method.*
E. L. Cady, Materials and Methods, v. 24, Aug., 1946.

pp.
400-410. This is an
excellent summary with emphasis on the economic aspects.
296
QUESTIONS
1. Why is complete Austenization of hypoeutectoid steels essential for full
hardening? Why is only partial austenization sufficient for hypereutectoid
steel to be hardened?
2. What is process annealing? What is full annealing? Explain the difference
between these two annealing processes on the basis of prior processing,
temperature required, changes in micro constituents, cooling rates and
general usage.
3. What are the objects of normalizing low carbon steels? Of normalizing
high carbon spheroidized steels?
4. Compare air, oil, water, and brine as quenching media. What is the mass
effect in quenching?
What other conditions affect the selection of the
proper quenching medium?
5. What causes internal stresses in quenched steels? Why should these internal
stresses be relieved?
6. How is spheroidized
structure obtained? What are the reasons for spheroidiz-
ing? What problems arise in the heat treatment of a spheroidized structure
for full hardness?
7. What is the overall objective of tempering? Correlate the effects that
tempering has on the hardness, brittleness. strength, and toughness
properties.
8. List the metallographical structures produced in tempering a steel when
martensite decomposes
at progressively increased temperatures. Compare
the physical properties of these different
structures.
9. What is meant by austempering, and what are its advantages and limita-
tions?
10. Compare martempering with austempering.
11. Why is carburizing limited to low-carbon or low-carbon alloy steel, and how
is carburizing
accomplished?
12. Compare the processes: cyaniding, nitriding, and carbo-nitriding.
CHAPTER
Carbon Steel as an
Engineering Material
15
Arthur
C. Forsyth, Ph.D., Associate Professor of Metal-
lurgical Engineering, University of Illinois, Urbana,
Illinois
J.
Edward Krai.ss, M.S., Head, Department of Mechani-
cal Technology, New York City Community College,
Brooklyn, New York
Jf
OR a thousand years before 1850 man's en-
tire stock of ferrous metals consisted of cast iron, wrought iron laboriously
made in small quantities at high cost, and a few high-carbon steel tools
made even more laboriously and at still higher cost. These were valuable
materials and represented a long step forward from the metals of the
bronze age, but they were too costly or too low in quality to be used in
building railroads, bridges, buildings, and ships. Between 1850 and 1860
Henry Bessemer in England and William Kelly in the United States made
discoveries which led to the development of a process for making carbon
steel in quantities large enough and at a cost low enough to spark a cen-
tury of industrial progress.
A reasonably accurate understanding of this progress can be obtained
from the following production figures: 800,000 tons in 1870, 28 million
tons* in 1900, 119 million tonsf average world production between 1935
and 1939
(42
million tons in the U. S.)
,
and 253 million tonsj between
1951 and 1955 (103 million tons in the U. S.) . This shows an increase of
over 100% in the last twenty years. Before World War II approximately
95 per cent of the steel produced in the world was carbon steel. This per-
Estimate by Sir Robert Hadfield, The (London) Times Trade and Engineering
Supplement,
Jan. 28, 1953.
f
Steel, Jan. 4. 1943.
p. 357, Average Production of Steel (1935-1939) for Ingots and
Steel for Castings, 119,454,600 toss. Same period for the United States, 42.176,600 tons.
t
Steel, Vol. 140, No.
1, p. 172, Average World Production of Steel (1951-1955) for
Ingots and Steel for Castings, 253,032,163 tons. Same period for the United States,
103,065,068 tons.
297
centage has now dropped to about 90.8 per cent (in the United States)
,
but carbon steel is still the most important metallic material on a tonnage
basis.
About 1.3 per cent of the carbon steel produced annually is poured into
castings
-
)- which are used in the form the metal assumed in the mold with
no further mechanical treatment. The remaining 98.7 per cent is poured
into ingots that are hot worked by rolling, forging, or pressing into a
large variety of finished or semifinished products. Most finished wrought
sections receive no further treatment, but a few are subjected to some
form of heat treatment before use. Some semifinished wrought products
are processed further by additional hot working; the rest are fabricated
into the desired form by cold working. (See Section 1 1 .9.) Cold-worked
steels may or may not be heat treated before being used.
There are, therefore, four major classes of finished products of carbon
steel: castings, hot-worked products, cold-worked products, and heat-
treated products. It is impossible to decide which of these four classes
is the most important in present-day economic life, since each plays a
definite role for which there is no understudy. Without hot-rolled
I beams, there would be no skyscrapers; without heat-treated tools they
could not be built; without cold-drawn wire for elevator cables, they
could not be used; and without castings for steam and water lines,
they would not be habitable. It is the same in most other industries: each
class of carbon steel is indispensable, and the cost or tonnage is no
criterion of its value to man.
15.1. Carbon-Steel Castings as Engineering Materials
Unalloyed steel castings have many industrial uses. Despite the fact
that their mechanical properties are generally inferior to those of hot-
worked steel of the same composition, the proportion of castings to rolled
or forged material remains substantially unchanged year after year. The
reasons for this are twofold:
(1)
Sections that are so complex as to be dif-
ficult or even impossible to fabricate by rolling or forging can be pro-
duced readily at low cost by casting;
(2)
castings are cheaper than
forgings if a few pieces of a fairly intricate shape are desired. The eco-
nomical production of such articles by forging is possible only when a
Steel, Vol. 140, No. 1, p. 174, Average U. S. Alloy Steel Production, Total Ingots
and Castings, 9,488,097 tons (1951-1955).
+ Steel, Vol. 140, Xo. 1, p. 178, Average U. S. Production of Carbon Steel Castings,
(1951-1955) 1,216,948 tons.
Carbon Steel as an Engineering Material 299
Table 15.1. Chemical Composition and Minimum Mechanical Properties for Medium
Strength and High Strength Steel Castings
*
Chemical Composition
(per cent) Tensile Yield Elonga- Reduc-
(maximum)
t
Strength Point tion in tion in
Grade (lb. per
sq. in.)
(lb. per
sq. in.)
2 in.
(per cent)
Area
(per cent)
C Mn Si
Nl 0.25 0.75 0.80
N2 0.35 0.60 0.80
N 3 1.00
U. 60-30 0.25 0.75 0.80 60,000 30,000 22 30
60-30 0.30 0.60 0.80 60,000 30,000 24 35
65-30 65,000 30,000 20 30
65-35 0.30 0.70 0.80 65,000 35,000
J
24 35
70-36 0.35 0.70 0.80 70,000 36,000 22 30
80-40 80,000 40,000 18 30
80-50 80,000 50,000 22 35
90-60 90,000 60,000 20 40
105-85 105,000 85,000 17 35
120-95 120,000 95,000 14 30
150-125 150,000 125,000 9 22
175-145 175,000 145,000 6 12
A.S.T.M 1955 Standards, Part One, Ferrous Metals, 27-55, and A148-55, pp.
1026
1027 and 1035-1036.
f
Maximum sulphur 0.06 per cent; maximum phosphorus 0.05 per cent. For each
reduction of 0.01 per cent carbon below the maximum specified, an increase of 0.04 per
cent manganese above the maximum specified will be permitted to a maximum of 1.00
per cent.
X
When agreed upon by the manufacturer and the purchaser, and when full annealing
is required by the purchaser, the yield point value of the 65-35 class shall be 33,000 psi
instead of 35,000 psi.
large number of pieces of a simple shape are produced thus spreading
thinly the cost of the expensive forging dies.
Steel for castings may be melted by any of the processes enumerated
in Table 11.1. Most of it is made by the basic or acid open-hearth or the
acid electric process. The open-hearth process is used for melting steel
for large castings; the acid electric process, owing to its flexibility and
to the high temperatures obtainable, is favored for small castings, espe-
cially those of intricate shape. Steel castings are used for railroad equip-
ment, especially for underframes of cars, for agricultural and excavating
equipment, various parts of machines, electric equipment, and a large
variety of small parts and fittings.
There are several grades of steel castings for which specifications have
been issued by the American Railway Association, the United States
300
government, and a number of technical societies. Typical specifications
for chemical composition and minimum tensile properties are given in
Table 15.1.
For high-strength castings (above 80,000 lb per sq. in. tensile
strength), the chemical composition, with the exception of maximum
percentages of sulphur and phosphorus, is not specified; the foundryman
is permitted to adjust the percentages of carbon and manganese and to
use alloying elements, if necessary, which, when combined with a suit-
able heat treatment, will result in the desired properties. (See Table 15.2.)
15.2. Factors Affecting the Properties of Carbon-Steel Castings
Since the properties of carbon-steel castings are greatly improved by
heat treatment, many castings are now annealed, normalized and an-
nealed, or normalized and spheroidized. Quenching and tempering of
castings of such shape that distortion is not likely to be serious, are used
more and more frequently.
Table 15.2. Mechanical Properties of Steel Castings*
Steel castings are generally specified by mechanical properties, leaving to the producer
control of the chemistry within certain limits, t
Structural GradesCarbon Steel
Tensile Strength psi 60,000 70,000 85,000 100,000
Mechanical Properties
J
Mod of Blast in Tension, psi: 30.1 x
10
30.0 x 10
6
29.9 x
10"
29.7 xlO
6
Tensile Strength, 1000 psi: 60(a) 70(b) 85(c) 100(d)
Yield Point, 1000 psi: 30 38 50 70
Elong in 2 in., %:
32 28 24 20
Reduction of Area, %: 55 50 40 46
Hardness, Bhn: 120 140 175 200
Impact, Izod, Ft-Lb:
(70
F)
30 30 20 30
(-50
F) 8 10 10 15
Fatigue Str, (End Limit), 1000 Psi: 25 31 38 47
*
Selected data from "Materials Engineering File Facts." Materials and Methods vol. 38,
No. 4, 1953, pp. 153. Data sheets include current specifications, physical and mechanical
properties, thermal treatment etc. for carbon and alloy steel castings.
f
"Summary of Standard Specifications for Steel Castings" may be found in Materials
and Methods, Vol. 36, No. 1, 1952, pp.
121 and 123. Minimum mechanical properties and
maximum chemical compositions are listed.
X
Normally expected values in the production of steel castings for the tensile strength
values listed.
(a) Annealed, (b) Normalized, (c) Normalized and Tempered, (d) Quenched and
Tempered.
Carbon Steel as an Engineering Material
V
SxSJC
301
^
V
'&N*S?
Fie. 15.1. Photomicrographs of Typical Microstructures o Small Steel Castings con-

taining 054% C, 0.60% Mn., 0.84% Si., 0.032% P. and 0.036% S. Notice the change in
grain size due to the following heat treatments. A-as cast, B-normalized 1700F.
(926C). C-annealed 1700F. (926C), and D-quenched from 1700'F. (926C.) tempered
at 1200F. (651 C). Nital etch lOOx. Courtesy of
the Mining and Metallurgy Depart-
ment, University of Illinois.
Large castings cool so slowly in a sand mold that a very course angular
structure results. If the casting is not too large, simple annealing will
refine the grain and improve the properties (Fig. 15.1C) , but such
treatment does not effect complete homogenization in large castings.
These are subjected to high-temperature normalizing followed by a grain-
refining treatment. Quenching and tempering produce the finest structure
(Fig. 15. ID illustrates the structure for small castings) and the best com-
bination of properties.*
Grain size is directly related to the rate of cooling from the solidifica-
tion temperature to the A
3
transformation temperature. It follows, there-
Table 152 shows the normally expected values for mechanical properties in the
production of steel castings for the tensile strength values listed.
302
fore, that a small casting usually has smaller grain size and better proper-
ties than a large casting; moreover, if the casting is not heat treated, it is
also true that in large castings the properties are better near the surface
than at the center,
f
The factor of greatest importance to the properties of cast carbon steel
is carbon content. If other things are equal, increasing the carbon in-
creases the tensile and the yield strength and decreases elongation, re-
duction of area, and impact resistance. When the carbon is higher than
0.50 per cent, the casting is usually so brittle, even after heat treatment,
that it is used only for a few specific applicationsfor example, rolls and
dieswhere hardness and wear resistance are the most important prop-
erties.
In general, carbon-steel castings of satisfactory mechanical properties
can be made readily by regulating the carbon content and by using a
simple annealing or normalizing treatment. The minimum properties
given for medium strength castings are conservative and are easily attained
in commercial production (compare properties in Table 15.1 and 15.2)
.
Cast carbon steels containing 0.20 to 0.40 per cent carbon have an
endurance ratio between 0.40 and 0.50. In the cast condition the ratio
is usually between 0.40 and 0.43. Heat treatment (that is, annealing,
normalizing, or quenching and tempering) improves the ratio, but it is
usually somewhat lower than the endurance ratio of a comparable steel
that has been hot worked. Heat treatment also improves the yield ratio,
elongation, and reduction of area of cast carbon steel and increases the
resistance of the material to single-blow impact. The added cost of heat
treatment is usually justified if castings are to be subjected in service
to stresses of considerable magnitude (Table 15.2).
15.3. Hot-Worked Carbon Steels as Engineering Materials
Most hot-rolled or forged carbon steels contain between 0.05 and 0.30
per cent carbon and are used for sheet, plate, strip, tubes, pipe, various
structural sections, tinplate and other coated sheets, and a large number
of semifinished sections that are hot or cold worked into bars, wire, sheet,
and tubes. Also included in this class is the well-known "machine steel"
(containing about 0.20 per cent carbon and 0.40 per cent manganese)
,
which is used for a wide variety of low-stressed machined parts and is
the mainstay of every crossroads blacksmith shop in the world. Medium-
carbon steels containing between 0.30 and 0.70 per cent carbon are used
for railway materials, especially rails, for a large number of forgings, and
fOwing to the mass elfect and lo segregation, it is frequently a serious problem
to cast a test specimen that has properties truly representative
of
ihe casting.
for high-strength wire. The higher carbon grades, containing 0.70 to 1.30
per cent carbon, are used largely for tools and cutlery and to a lesser
extent for springs and wire. Low-carbon steels are rarely heat treated;
the medium-carbon grades may or may not be heat treated, depending
upon their use; the high-carbon steels are almost always used in the
hardened and tempered condition.
The properties of hot-worked carbon steel are affected by
(1)
the
composition,
(2)
the several variables present in hot working, and
(3)
the rate of cooling from the rolling temperature. Except for deep-drawing
sheet, this third factor is not important for low-carbon steels; in the case
of small sections of medium- and high-carbon steels, air cooling may
cause enough hardening to mask any effect of moderate changes in com-
position or of variations in the hot-working operation. The effect of
composition is discussed in the next section. Of the three variables in-
herent in hot workingdirection of work, amount of work, and finishing
temperaturethe first is the most important. In general, specimens cut
longitudinally and transversely to the direction of hot working have about
the same tensile strength and yield strength, but the elongation, reduc-
tion of area, and impact resistance of the transverse specimens are lower
than those of the longitudinal specimens. This difference in directional
properties is present even in clean steels, but it is accentuated by in-
clusions which are plastic at hot-working temperatures and which are
thus elongated into fibers by the mechanical work.
15.4. Effect of Composition on Static Properties of Hot-Worked
Carbon Steels
The effect of carbon on the tensile properties of hot-worked basic
open-hearth steels containing between 0.30 and 0.60 per cent manganese
and between 0.02 and 0.04 per cent phosphorus is shown in Fig. 15.2.*
The center line of the hatched area represents the properties to be ex-
pected most frequently. The top and bottom boundaries of the hatched
area give the limits of the properties to be expected at least 95 per cent
of the time in the testing of commercial rolled or forged basic open-hearth
steel of these carbon percentages. The data used for plotting Fig. 15.2
were obtained mostly by statistical analysis. It is safe, therefore, to con-
clude that of 1000 specimens of 0.20 percent carbon steel about 700 will
have a tensile strength of between (53,000 and 65,000 lb. per sq. in., and
The values in Fig. 15.2 are a summary of all the data given by
F, T. Sisco, in
The Alloys
of
Iron and Carbon, Vol. II, Properties, Chap. 4,

A. anil Include not only
laboratory investigations and other data but also the data obtained in Germany by
statistical analysis of more than 100,000 individual tests.
0.1 0.2 0.3 0.4 0.5
Carbon, per cent
Fie. 15.2. Effect of carbon on tensile properties of hot-worked carbon steels.
about 970 will have a tensile strength (60,000 to 68,000 lb. per sq. in.)
which falls within the hatched area for steel of this carbon content. There
will, however, be about 30 specimens, or 3 per cent of the whole, with a
strength falling above or below the limits shown. These proportions
should hold for steel of any carbon content between 0.05 and 0.70 per
cent.
The elongation values used for Fig. 15.2, if not originally determined
on a 2-in. gage length, were converted to this gage. In connection with
the elongation it should be noted that the usual flat specimen for plate,
sheets, and similar products has a gage length of 8 in.; hence, values
given in Fig. 15.2 are some 20 to 30 per cent higher than would normally
be obtained on an 8-in. gage* The increase in Brinell hardness with in-
If standard flat specimens of basic steel of about 60,000 lb. per sq. in. tensile
strength and with gage lengths of 2, 4, and 8 in. are tested, the respective elongation
values will be approximately 45, 35, and 30 per cent, respectively.
creasing carbon approximately parallels the increase in tensile strength:
each 0.10 per cent carbon raises the hardness 20 numbers, from about
100 for 0.10 per cent carbon steel to 220 for 0.70 per cent carbon steel.
Although both manganese and phosphorus affect the tensile strength,
the influence of the former is unimportant in most carbon steels. For
example, if a basic open-hearth steel containing 0.20 per cent carbon
and 0.50 per cent manganese has a strength of 65,000 lb. per sq. in., in-
creasing the manganese to 0.80 will increase the strength only 3,000 to
4,000 lb. per sq. in. Phosphorus increases the tensile and the yield
strength about 1,000 lb. per sq. in. for each 0.01 per cent present. In
basic open-hearth steels, this element is commonly so low that it has
little effect; in acid steels, however, there is usually enough present so
that it exerts considerable strengthening action. Thus, acid steel is usually
stronger, with lower elongation and reduction of area, than basic steel
of the same carbon content.
15.5. Effect of Composition on Other Properties
Increasing the carbon of hot-rolled steel decreases the impact resist-
ance; low-carbon basic open-hearth steels have an Izod value of 50 to 60
ft.-lb.; for hot-rolled steels containing 0.50 to 0.80 per cent carbon, it is
usually less than 20 ft.-lb. Increasing the phosphorus decreases the im-
pact resistance; an acid Bessemer steel is not so tough as basic open-
hearth steel of otherwise identical composition. The brittleness induced
by phosphorus is discussed in

11.10. In connection with impact resist-
ance it should be emphasized that this property is greatly affected by
grain size, direction of hot working, amount and distribution of inclu-
sions, and other factors (aside from chemical composition) related to
the structure.*
These factors may have so much influence on the impact resistance that
the effect of variations in composition may be completely obscured.
The endurance limit of hot-worked carbon steels increases with the
tensile strength. Owing, however, to the fact that high-carbon steels
have less plasticity under load than low-carbon steels, and are more
likely to contain internal stresses, the endurance ratio is usually between
0.35 and 0.42, compared with 0.50 to 0.60 for wrought iron, ingot
iron, and steels containing less than 0.35 per cent carbon.
The modulus of elasticity of carbon steels is between 29 and 30 million
lb. per sq. in and is not greatly affected by composition and heat treat-
ment. Some of the other physical constants and most of the electric and
magnetic properties are affected, more or less, by changes in composition.
Also see: Temper Kmbrittlement in Plain Carbon Steels, by
J.
F. Libsch, A. E.
Powers and G. Bhat, Trans. A.S.M. Vol. 44, 1952,
pp.
1058.
306
Since these properties are not of great importance to most engineers,
discussion of them is omitted here.
15.6. Cold-Worked Carbon Steels as Engineering Materials
Cold working has two advantages. First, sections of certain sizes,
shapes, or surface finishes can be produced more readily and more eco-
nomically by this method than by any other. Some important industrial
products, in fact, cannot be produced at all except by cold working; it
would be economically impracticable to produce by any other method
wire small enough to be woven into screens or in quantities large enough
for modern telegraph and telephone systems. In addition, cold working
is the most effective and the cheapest method of securing a smooth sur-
face and accurate size. Second, certain combinations of properties char-
acteristic of cold-worked material cannot be secured by any other
process; for example a tensile strength of 300,000 to 400,000 lb. per sq.
in., combined with considerable ductility, can be attained readily.
The economic value of cold-worked carbon steel is attested by the
fact thai in an average year about 3 million tons of wire* 12 million tons
of sheet* and strip, and 1.8 million tons of bars* and other cold-worked
products are made in the United States. Sheet, strip, tubes, and bars are
cold worked primarily to obtain certain sizes, shapes, and surface finishes
economically. High strength is usually of secondary importance. Further-
more, most cold-rolled sheet and strip, and some cold-drawn wire, espe-
cially the low-carbon grades which are used for screens, fences, barbed
wire, nails, screws and nuts, telegraph and telephone lines, and for many
other common applications, are annealed before use. Because annealing
completely destroys the effect of cold work, the properties of such ma-
terial need not be considered further here.
Carbon steels that are cold worked to secure high strength as well as
to produce special shapes and sizes and are not subsequently annealed
comprise an important class of engineering materials. The properties of
these steels and how cold working affects them are, therefore, worthy
of considerable attention. This class of material includes some low-carbon
sheet, strip, and wire, but the most important is wire containing about
0.25 to 1.00 per cent carbon used for needles, surgical and dental instru-
ments, music (piano) wire, springs, rope and cable wire, and numerous
other purposes where high quality and reliability combined with high
tensile strength and considerable ductility are required.
Estimated from -Shipments of Steel Products". Steel Vol. 140, No. 1, 1957,
pp.
176.
10 20 JO 40 SO 60 70 SO SO 92
Reduction by cold working, percent
Fig. 15.3. Stress-strain curves of cold-worked low-carbon steel (Kenyan and Burns)
15.7. The Important Properties of Cold-Worked Steel
The static properties ordinarily determined on cold-worked steels are
tensile strength and elongation, usually with a gage length of 10 in. for
wire and of 2 or 8 in. for sheet and strip. Owing to the small cross section
of most cold-worked materials, reduction of area, which is a valuable
measure of ductility, cannot be determined accurately. Yield strength is
rarely determined on cold-worked wire and sheet or strip; but for cold-
rolled bars of large enough cross section so that accurate measurements
are possible, yield strength and reduction of area are frequently reported.
Cold working increases the yield strength; with reductions in cross sec-
tion of 30 to 70 per cent it is at least 90 per cent of the tensile strength,
and with higher reductions it may for practical purposes be the same as
the tensile strength.
As shown by Fig. 15.3,* the stress-strain curve of
severely cold-worked steel is curved from the origin; the elastic limit is,
therefore, very low and may be zero.
Several unstandardized tests are used to determine the ductility of
cold-worked wire and sheet. Some of these are crude, but in experienced
hands they give reliable indications of excessive brittleness or local ir-
regularities. The most common of these is the bend test in which a speci-
men of definite size, clamped in a vise and bent 180 deg. over a definite
radius, must not crack. In another test, a specimen is bent back and
R. L. Kenyan and R. S. Burns, Trans. Am. Soc. Metals, v. 21, 1933. p. 595.
308
forth 90 deg. over a mandrel until failure occurs. The number of 90-deg.
bends before failure is a measure of the ductility.
Another test of the ductility of wire is the twist. A specimen of suit-
able length is twisted in a machine, which has one revolving head, until
it fails by shear. The number of 360-deg. revolutions of the movable head
of the machine is the number of twists. Some metallurgists consider that
the twist is a good measure of ductility; others believe that its principal
value is to detect local irregularities or flaws in the wire.
10 20 30 40 50 60 70 80 90 100
Reduction ofarea in drafting,percent
Fie. 15.4. Effect of cold working on ihe tensile strength of carbon steel, (l.egge)
15.8. General Effects of Cold Working on Strength and Ductility
These particular properties are markedly affected by cold work and the
effect it produces on grain structures. Cold work rapidly increases the
tensile strength while decreasing the ductility. The latter is evident by
the decrease in elongation. The change in these properties is directly
10 20 30 40 50 60 70 80 90 100
Reduction ofarea in drafting.percent
WW. 15.5. Effect of cold working on the elongation of carbon steel. (Legge)
related to the amount of cold work. Figure 15.4*
gives an indication of
the effect of cold working on the tensile strength. The effect of cold work
is directly related to the carbon content of the steel. As the carbon content
increases, the tensile strength increases more rapidly and to a greater
degree for each increment
in the reduction in area.
The converse effect is evident when the elongation is considered. This
value reduces sharply with small amounts of cold work and does not vary
greatly with the carbon content (Figure 15.5). As the reduction in area*
is increased, the effect
on the elongation is very much smaller.
One should bear in mind that the figures referred to only approximate
the properties resulting from cold work. While the amount of cold work is
the prime varible having an effect on strength and ductility, it is not the
The term reduction of area is used in cold working to signify the amount that
the cross section has been reduced by the cold working operation. It should not be
confused with the same term used in tensile testing.
310
Engineering
Metallurgy
sole factor. Composition is important,
and the structure of the material
has an effect, particularly for medium and high carbon steels.
Another factor that causes variation in total effect is the cross-sectional
area. Table 15.3 indicates the variations that exist as a result of this
factor. Obviously a
1"
bar is less affected at the center than a wire would
be.
Table 15.3. Effect of Cold Rolling on the Tensile Properties of a Steel Containing
0.14 Per Cent Carbon.
Property
Annealed
Reduced 30
per cent by
cold rolling
Reduced 60
per cent by
cold rolling
58,800
34,040
27,500
41.7
65.8
80,600
75,300
98,100
t)e> inn
15 600
-ininn
22
58
10 5
43
Since the degree of cold work cannot be equal in all directions, the
grain shape is changed, mechanical twinning occurs, and preferred orien-
tation of the grains also results. While cold working generally has the
same effect on the properties of sheet and strip as it has on wire, mechani-
cal directionality shows up in sheet and is usually undesirable.
Condition
Tensile
strength,
lb. per
sq. in.
Hot-rolled strip
Cold rolled 50 per cent
Annealed
Yield
strength,
lb. per
sq. in.
40,000
96,000
33,000
Elongation
in 2 in.,
per cent
28
2
38
The effect on the properties varies with the carbon content. A reduc-
tion by cold rolling of 60 per cent has the following effect on strip:
Carbon,
per cent
0.10
0.20
0.30
0.50
Increase in tensile
strength, per cent
65
63
61
57
Decrease in
elongation, per cent
70
70
68
67
15.9. Variables Affecting the Properties of Cold-Worked Wire
There are many variables which affect the properties of cold-drawn
carbon steel wire. Only a few may be referred to at this point. Approxi-
mately 85 per cent of all wire used today is drawn from either acid Besse-
mer or basic open-hearth low-carbon steels. Hard-drawn Bessemer wire is
from 10 to 15 per cent stronger than the hard-drawn open-hearth wire.
The tensile strength of Bessemer varies from 90,000 to 150,000 lb. per
square in. while the open-hearth varies from 80,000 to 125,000 lb per
sq. in. for similar sizes. A slightly increased elongation and a greater
ability to withstand twist is characteristic of the basic open-hearth wire.
The effect of cold work on the grain structure is particularly notice-
able in wire. The fragmentation and distortion of the grains occurs
throughout the material since we are dealing with small cross sections.
The effect of galvanizing low-carbon cold-drawn wire is a reduction
in tensile strength, an increase in elongation, but this is complicated by
the induced brittleness as shown in a twist test. This brittleness is
probably caused by the formation of a brittle iron-zinc compound at
the interface between the steel and the zinc coating. Here failure starts
easily under the torsional stresses.
High-strength wire for cables, ropes, and springs and for music wire
is usually made from high-grade deoxidized medium and high-carbon
steel. The steel is rolled into rods which are patented. The best combina-
tion of strength and ductility results from drawing a lead-patented rod.
Air patenting is cheaper, but the properties of the wire are not as good.
Wire drawn from either lead- or air-patented rod is, however, much
superior to that drawn from a hot-rolled rod. Hard-drawn music and
cable wire drawn from lead-patented rod has a strength of 160,000 to
220,000 lb. per sq. in. in sizes of 0.2 to 0.3 in. and of 280,000 to
400,000 lb. per sq. in. in sizes smaller than 0.1 in. in diameter. Despite
the high strength and low elongation
(0.5 to 1.5 per cent in 10 in.), the
wire is very ductile and withstands many
90
bends and can be wrapped
around itself or rolled into long springs of small diameter without
cracking.
The wire used for the cables of large suspension bridges is an acid open-
hearth steel containing about 0.80 per cent carbon, 0.50 percent man-
ganese, and low sulfur and phorphorus. The wire is drawn from patented
rods, and the usual size is 6 gage (0.192 in. in diameter) . It has an average
tensile strength of 215,000 to 225,000 lb. per sq. in., a yield strength for a
permanent set of 0.75 in. in 10 in. of 160,000 to 175,000 lb. per sq. in., an
elongation of 3 to 7 percent in 10 in., and a reduction of area of 25 to 30
percent. Rope or cable formed from high-strength wire has, owing to its
312
Engineering
Metallurgy
construction, a breaking strength which is never more than 90 per cent,
and usually only
70 to 80 per cent, of the sum of the breaking strength
of the individual wires.
15.10. Effect of Cold Working on Dynamic Properties
As has been pointed out previously the transition temperature has an
effect on these
properties. Although cold working increases the endurance
limit by about the same percentage as it increases the tensile strength,
this means relatively
little because most cold-worked material has such a
small cross section that standard highly polished specimens usually can-
not be tested. For specimens of wire tested with the surface produced by
the die, the endurance ratio varies from about 0.50, for material con-
taining 0.05 per cent carbon, to 0.25 to 0.35, for high-carbon wire having a
tensile strength of 275,000 to 350,000 lb. per sq. in. The low value for
hard-drawn high-carbon wire is largely due to high internal stresses as
reheating the wire to effect a partial or complete recrystallization of the
grains raises the ratio.
Cold working also decreases the resistance of carbon steel to impact.
The magnitude of this decrease depends primarily upon the amount of
cold work and the carbon contenthigh-carbon steels are embrittled to a
greater degree than low-carbon materialsand upon other variables.
The actual Izod impact value may be as low as 5 to 10 ft. -lb. In general,
however, notched-bar impact resistance is not an important property of
cold-worked material.
15.11. Heat-Treated Carbon Steels as Engineering Materials
As we approach the problem of heat treatment, it would be well to
review a few definitions. The two treatments that we are particularly
concerned about are annealing and normalizing. Annealing is a process
involving heating and cooling, usually applied to induce softening.
Normalizing is a process in which steel is heated to a suitable temperature
above the transformation range and is cooled in still air at room
temperature.
With the exception of carburizing and annealing of cold-worked
material, low-carbon steels are seldom heat treated. Quenching generally
improves the properties but hardly enough to justify the cost. Medium-
carbon steels are frequently heat treated; the general improvement in
strength and ductility, in machinability, or in some other property due to
thermal treatment is usually well worth while. Since high-carbon steels
are used primarily for tools where high hardness is the chief requirement,
these materials are always quenched and tempered. Frequently they are
also annealed or normalized to improve machinability or the structural
condition prior to quenching.
The effect of heat treatment on the properties of cast steels having
been treated earlier in this chapter and the characteristics of treated high-
carbon steels being more easily presented in the chapter on tool steels, it
remains only necessary to briefly cover the properties of medium-carbon
steels after heat treatment.
Referrring to our definitions as a basis, it is easy to point out that
annealing is used primarily to improve the machinability of medium-
carbon steels. Comparing steel in the 0.30-0.60 per cent carbon range, we
find very small differences in the physical properties. The tensile and
yield strengths are 6,000 to 10,000 lb. per sq. in. lower while the elonga-
tion and reduction in area are a bit higher. While no effect is evident on
the endurance ratio, slight increases in impact strength are apparent.
Hot-rolled and normalized medium-carbon steels have practically
the same tensile properties. This can be attributed to the fact that most
carbon steels after hot working are air cooled from temperatures very
close to the normalizing temperatures. Since normalizing produces a
homogeneous structure, it can be justified, economically, for large cross
sections after forging or rolling. In addition to producing a finely divided
evenly distributed carbide, it eliminates directionality due to mechanical
fibering of inclusions such as oxide, slag, etc.
Owing to the residual stresses introduced by quenching, medium-carbon
steels are seldom used in the quenched and untempered condition. The
properties of such materials are therefore of little interest. If, however,
the internal stresses are relieved by tempering, quenched medium-carbon
steels become valuable structural materials.
If quenched steel is tempered at a temperature high enough so that
the particle size of the carbide changes, strength and hardness decreases
and ductility increases almost uniformly as the tempering temperature in-
creases. This is shown in Fig. 15.6, which gives the ranges of properties
(included within the hatched bands) that result 95 per cent of the time
from tempering water- and oil-quenched 0.40 to 0.50 per cent carbon steels
at increasing temperatures.
Charts showing the effect of tempering on the tensile properties of
quenched carbon and alloy steels of varying carbon content are widely
available in the literature and in a number of handbooks. It should be
emphasized, however, that these charts, while undoubtedly of value in
indicating the properties to be expected most of the time, should never be
used for specification purposes as individual specimens frequently vary
considerably from the average shown on the chart.
314
600
_l_
800
Tempering temperature, deg. F.
1000
1200 600 800
500 600 700 300 400 500
Tempering temperature, deg. C.
600 700
Fic. 15.6. Effect of tempering on the properties of 05 in. bars of water-and
oil-quenched 0.40 to 0.50 per cent carbon steel (S.A.E. 1045). (Sisco, The Alloys of
Iron and Carbon, Vol. II, Properties, McGraw-Hill Book Company, Inc., New York,
1937, p. 200.)
Carbon steels containing the usual amounts of manganese (0.30 to 0.90
per cent) are shallow hardening. The time available to quench a carbon
steel past the nose of the S-curve is usually less than a second, with the
result that even on severe quenching martensite forms only in very small
pieces or on the surface of larger sections. Consequently, the structure of
a carbon steel quenched in oil or even in water generally consists of a
little martensite mixed with a relatively large amount of a ferrite-
cementite transition structure. It will be shown in the chapters on harden-
ability that the mechanical properties of a quenched and tempered steel
are in general better if the structure before tempering was almost wholly
martensite rather than a mixture of martensite and one or more transition
constituents. The primary reason why low-alloy steels are favored for
quenched and tempered parts is that the alloying elements increase
hardenability and thus increase the likelihood that martensite will be
formed in large quantities when the steel is quenched in oil.
Carbon Steed as an Engineering Material 315
15.12. Effect of Section Size on the Properties of Heat-Treated
Medium-Carbon Steels
It is well known by metallurgists generally, but by surprisingly few
engineers, that the properties of steel determined on a small heat-treated
bar of steel may not be representative of the average properties on a
large bar similarly treated. The effect of mass on properties is important.
Since in many industrial applications large sections are used, it may be
more essential for the engineer to know the average properties or, in
some cases, the minimum properties than to know the properties at the
surface. It is not always practicable to test full-sized I beams or locomo-
tive axles; hence, data that indicate the effect of increasing size of section
are of considerable value.
A heavy section cannot be cooled as rapidly as a thin section; the in-
terior of a heavy section, cooling more slowly than the surface, transforms
not only at a later time but at a higher temperature and therefore to a
softer product than the surface. This results in differences in properties
between the exterior and the interior, possible distortion, residual stresses,
etc. If we were to heat and quench a series of bars of SAE 1045 steel of
different diameters from
\/
2
"
to
5", the smallest piece would cool most
rapidly and each succeeding piece more slowly
Size of Bar Surface Hardness
0.5"
59
1.0 58
2.0 41
3.0 35
4.0 30
5.0 24
A study of the surface microstructure reveals that for the hardest
material the microstructure is predominately martensitc, and as hard-
ness decreases, the amount of martensite decreases rapidly and pearlite in
varying degrees of coarseness appears. If the bars are cut and a hardness
survey taken of the cross section, it would show the variation in cooling
rate from outside edge to center by the variation in hardness. (Fig. 15.7).
In most large sections the cooling rate upon quenching decreases as
the distance from the surface increases and, if other variables do not
enter importantly, hardness and strength decrease and ductility increases
slightly. Data for medium-carbon steel are given in Fig. 15.7. The effect
of mass is more pronounced in water-quenched than in oil-quenched
material, and for the same quenching treatment the effect of mass is
less pronounced with high tempering temperatures than with lower
temperatures.
316
Diameter
Fie. 15.7. Hardness of series of SAE 1045 steel bars heated and quenched.
The endurance ratio of quenched and tempered carbon steels is 0.50
0.05 unless the quenching treatment has introduced stresses which
were not wholly relieved by tempering. When such stresses are present
the ratio may be as low as 0.30 or 0.40. Quenching and tempering usually
have a favorable effect on impact resistance, which, in general, is much
higher than that of a rolled steel of corresponding composition. Temper-
ing increases the impact resistance of a quenched steel: if the Izod value
of a water-quenched 0.30 per cent carbon steel is 10 ft.-lb., it will be 20
to 25 ft.-lb. after tempering at 700F. (400C.) and 45 to 65 ft-lb. after
tempering at 1100 to 1200F. (595 to 650C.) . The modulus of elasticity
is, of course, unaffected by thermal treatment.*
QUESTIONS
1. By what per cent has the steel production in the United States increased in
the last twenty years?
2. Why should the per cent production of carbon steel in the United States be
less now than it was before World War II?
*
Sec footnote,
p. 305.
3. Give two reasons why a large tonnage of steel is melted and poured into
castings every year. How is steel for castings usually melted? What is the
general relation between structure, heat treatment, and properties of cast
carbon steel? Does carbon steel have a low or high hardenability?
4. How does the per cent of carbon in steel castings affect the hardness of the
martensite produced when the castings are quenched?
5. What carbon content in steel castings would be most likely to cause cracking
during the quenching cycle? If cracking during quenching were a real possi-
bility, what heat-treating cycle could be used to prevent cracking?
6. How would the rate of cooling from die rolling temperature affect the
properties of hot worked carbon steel?
7. Name the three general classes of hot-worked carbon steel, and give the
principal industrial uses of each class. Which of these three classes leads in
tonnage?
8. List the principal variables that affect the properties of hot-rolled carbon
steel. What tensile properties would be expected 95 per cent of the time
from hot-rolled steel containing 0.15 per cent, 0.30 per cent carbon? How
do manganese and phosphorus affect the tensile strength of hot-rolled
carbon steel?
9. What is the effect of carbon on notched-bar impact resistance? on en-
durance limit? on modulus of elasticity?
50. Why are steels cold worked? What properties are ordinarily determined on
cold-drawn wire and on cold-rolled bars? What is the effect of cold working
on the yield point? How is the ductility of cold-worked wire usually deter-
mined?
11. What is the general efTect of cold working on tensile strength and elonga-
tion? If a hot-rolled rod containing 0.15% carbon has a tensile strength of
60,000 lb. per sq. in. and an elongation of 25% in 10 in., what strength
and elongation would be expected in drawing to wire with (a) a reduction
of 40%? (b) a reduction of 70%?
12. What percentage increase in tensile strength can normally be expected if
automobile fender steel is cold rolled 50%? What is the effect of this reduc-
tion on the elongation? Give typcial tensile properties (a) of small sizes of
music wire, and (b) of wire for suspension bridges.
13. What is the general effect of cold working on the impact resistance and on
the endurance limit of carbon steel?
14. What general classes of carbon steel arc heat-treated? What is the advantage
of either annealing, or normalizing, or quenching and tempering such
steels? What is the general effect of tempering on the tensile properties? For
a tempering temperature of about 1000F., what would be the expected
properties of a 1-in. round bar of 0.45% carbon steel (a) when quenched in
water? (b) when quenched in oil?
15. If a small specimen of hot-rolled carbon steel containing 0.45% carbon has
a tensile strength of 93,000 lb. per sq. in., a yield strength of 54,000 lb, per
sq. in. an elongation of 20% in 2 in., and a reduction of area of 85%. what
treatment can be used to increase these values to 103,000: 70,000; 25; and
60; respectively? With these latter tensile properties for a heat-treated small
section, what would be the corresponding properties at the center of a 4-in.
bar?
CHAPTER
Low -
A Hoy Steels as
Engineering Materials
16 Robert E. Bannon, S.M., Professor of Metallurgy,
Newark College of Engineering, Newark, New
Jersey
Sic>fUND Lever.v Smith, M.Met.E., Professor of Metal-
lurgy, College of Mines, University of Arizona, Tucson,
Arizona
Al.I.OY steels are about seventy years old. The
pioneer investigations of the effect of the various alloying elements on
carbon steel were made between 1875 and 1890 in England, Germany,
France, and, to a lesser extent, the United States. Owing to the high
price of alloying metals, the only use for these materials on a relatively
large scale was in armor plate. By 1910, alloying metals were much
cheaper, and from then on industrial applications multiplied rapidly,
especially between 1915 and 1918 when there was an abnormal demand
for high-quality alloy steel for war materials. This demand, together
with the approximately simultaneous development of the first "stainless"
steel, stimulated metallurgists all over the world to investigate the effect
on carbon steel of all possible combinations
of many alloying elements.
The result has been alloy steels by the hundredssteels containing one
alloying element in addition to carbon, and steels containing half a dozen.
Before World War II much of the research work on alloy steels was of
the hit-or-miss type or was carried out to develop a steel that would
duplicate the properties of a patented composition without actual in-
fringement. One result of this frenzied research between 1910 and 1950
was a phenomenal growth of metallurgical literature; another was the
development
of many unnecessary alloy steels which, with slightly dif-
ferent compositions, duplicate the characteristics of some of the older
and better-known steels. However, some remarkable developments have
resulted from this mass of hit-or-miss research, including several new
steels and special ferrous alloys with splendid properties and of much
value to industry. It has also shown to engineers that alloy steels make
318
Low-Alloy Steels as Engineering Materials 319
possible the design of certain structures that would be impossible with
unalloyed carbon steels and cast irons. Without alloy steels the modern
airplane, the streamlined railroad train, the modern automobile, and
many other important developments would never have been brought to
their present efficiency.
The most characteristic indication of the increasing value of alloy
steels to the engineering professions is that their production has increased
at a greater rate than total steel production. The output in 1910 was
600,000 tons, or 2 per cent of the total; in 1939 it was more than 3,000,000
tons, or about (i per cent of the total output of the steel industry. During
1944, when total steel production in the United States reached 89,642,000
net tons of ingots, alloy-steel ingot production was 10,630,000 net tons,
which is 12 per cent of the total. The demand for alloy steels in the
average prosperous postwar year, for example 1960, cannot be foreseen
now; probably it will average about 8 or 10 per cent of the total.
The amount of published data on alloy steels and cast irons is so large
that it is now impossible for a metallurgist to know everything that is
going on in this field; it is a hard job even to keep up with developments
in a single branch.* To summarize adequately, in a single book, the
present status of knowledge of alloy steels is a difficult task, and it is,
of course, quite impossible to give many details of their properties in
three short chapters. Consequently, the discussion in this and the next
two chapters is restricted to a brief description of the characteristics of
these materials and to a concise outline of the metallurgical fundamentals
in the relation of the common alloying elements to carbon steels.
16.1. Balanced Compositions in Low-Alloy Steels
A workable definition of alloy steels and a general classification of
these materials into low- and high-alloy steels, including common compo-
sitions for the low-alloy grades, are given in Chap. 11. Many low-alloy
steels, especially the S.A.E. grades, are purchased under specifications
that give desired ranges for the various alloying elements and for carbon
and manganese and usually maximum percentages for sulphur and phos-
phorus. Widely available in the literature and in handbooks are charts
of average, typical, or minimum mechanical properties of the various
steels after definite heat treatments. Such specifications and charts are
the result of long experience and arc of unquestioned value to engineers.
Alloys of Iron Research, founded in 1930 by The Engineering Foundation of New
York, is reviewing this literature and correlating and summarizing the most important
of the world's research on alloy steels and cast irons. Results are published in a series
of monographs.
320
In the past few years, however, there has been a trend toward making
use of steels of "balanced composition" or of definite hardenability rather
than attaching too much importance to rigidly specified compositions
and the necessity of accepting the data in mechanical-property charts.
Steels of "balanced composition" are those in which the percentages
of carbon and alloying elements, as well as the heat treatment (if any)
,
are varied to produce a desired combination of properties for a particular
application. Assume, for example, that for a structural application a steel
must have a minimum yield strength of 50,000 lb. per sq. in. as rolled,
must weld readily, and must not air harden after welding. A steel con-
taining 0.30 per cent carbon, 0.75 per cent of alloy metal A, and 0.5 per
cent of alloy metal B has the required strength and welds readily, but it
air hardens unless specially treated during or after welding. Because this
composition is not balanced for this particular application, the carbon
is reduced to 0.15 per cent, and the amounts of the alloying metals are
increased to 1.0 and 0.75 percent, respectively. The yield strength is
still well above the required minimum, the material still welds readily,
but owing to a better balance of the carbon and metals A and B the steel
does not harden in air after welding.
Producing steel with a definite hardenability is primarily a problem in
balancing the composition correctly. The effect of carbon and of the
various alloying metals on hardenability is known with considerable ac-
curacy (this is discussed in detail in the next two chapters) , with the
result that steels having a definite response to quenching can be readily
produced by balancing the amounts of carbon and of the one or more
alloying metals which are readily available.
The final criterion in the selection of an alloy steel for a specific appli-
cation is economy. Any alloy steel is more costly than plain steel of cor-
responding carbon content and should not be used for a structure or a
machine merely because it contains one or more special metals, or be-
cause the steelmaker says it is better than some other steel. Alloy steel
should be used only if considerable weight can be saved, or if the de-
sign can be materially simplified, and only if its total costmeaning the
cost of the steel, of its treatment (if any) , and of fabricationis less,
when spread over the expected life, than the total cost of any competing
material.
16.2. General Effects of the Alloying Elements on Carbon Steel
The general effects of the common alloying, elements on the structure
and, consequently, on the properties of carbon steel are discussed in
Chaps. 12 and 13. It is the purpose of the discussion in this and the next
two chapters to expand this and to show how these alloying elements
are used to produce steels which are more satisfactory for certain appli-
cations than the unalloyed carbon steels.
Hot-rolled carbon steel is low in cost and has excellent properties, and
with certain carbon percentages these properties can be still further
improved by heat treatment. Carbon steel also has several disadvantages
as an engineering material. An important disadvantage is the rapid de-
crease of ductility as the carbon (and the strength) increases. Another
is that, because it is shallow hardening, optimum combinations of prop-
erties in heat-treated material can usually be attained only in small sec-
tions. A third disadvantage is that carbon steels, whether hot rolled or
heat treated, suffer marked deterioration of properties when used at
temperatures considerably below or above normal. Alloying elements are
added to carbon steels to overcome, partly at least, these disadvantages.
The principal effect of the alloying elements in low-alloy steels is to
increase hardcnability by heat treatment. In addition, all the common
alloying elements dissolve in the ferrite and strengthen it to some extent.
Five of these elements also form carbides, but of these only molybdenum,
vanadium, and tungsten have a strong carbide-forming tendency. Chang-
ing the properties of carbon steel materially by the formation of such
carbides is important chiefly in the high-alloy and the tool steels, which
are discussed in later chapters.
The ferrite-hardening (and -strengthening) potency of the elements
forming solid solutions with iron varies (increasing from chromium to
2 4 6 e 10 12 It 16 IB 20 22
Alloying element in alpha iron, per cent
Fie. 16.1. Effect of the common alloying elements, when dissolved in iron, on its
hardness. (Bain)
322
phosphorus), as shown in Fig. 16.1.* None of these, with the possible
exception of phosphorus, is so potent as carbon. In fact, the strengthen-
ing effect is small, provided that the carbon content and the structure are
held constant. This is shown by the curves for the furnace-cooled speci-
mens plotted in Fig.
16.2.f
If, however, the structure is altered by chang-
ing the treatment, that is,
by taking advantage of the
effect of the element on har-
denability, small amounts
of an alloying clement may,
as shown in Fig. 16.2, have
a great effect. In fact. Fig.
16.2 shows that chromium
increases the hardenability
enough so that high tensile-
strength values result from
moderately slow (air)
cooling.
240
230
220
210
200
190
180
4no
I
160
150
140
8
.130
-n
1ri2o
"no
J
100
90
80
70
60
50
12 3 4 5 6 7
Chromium, percent
Fie. 165. Effect of carbon, chromium, and cool-
ing rate on the tensile strength of carbon steels.
(Wright and Mumtna)
ft */
o\
V
f
0/
y
c
1
i
f>
1 /
/
V
1
/
(
/
/
/
/
*
/
tiro10tr</
.
c
urn wee c
xjicg
__ __
0.30
~OJ0
%c
__

--
.
-
16.3. Effects of Phospho-
rus, Manganese,
and Silicon
Of the alloying elements
which dissolve in the fer-
rite, phosphorus, as just
noted, is the most potent in
its strengthening action
(Fig. 16.1) . The addition
of 0.01 per cent of phos-
phorus increases the tensile
and the yield strength ap-
proximately 1,000 lb. per
sq. in., that is, by about as
E. C. Bain, Functions
of
the Alloying Elements in Steel, American Society for
Metals, Cleveland, 1939, p. 66. Data reported by C. R. Austin (Trans. Am. Soc. Metals,
v. 31, 1943, p. 331) indicate that the strengthening effect of manganese and molybdenum
in small percentages is greater, and that of chromium is slightly less, than those
shown by Bain's data in Fig. 16.1. Neither Bain's nor Austin's data arc very precise,
because the iron used was not of high purity and the slope of the curves shown in
Fig. 16.1 may be altered by future work. The ferrite-strengthening cirect of the alloying
elements is, however, not of great importance.
t
Plotted from data by E. C. Wright and P. F. Mumma, Trans. Am. Inst. Mining
Met. Engrs., v. 105, 1933,
pp.
77-87.
Low-A Hoy Steels as Engineering Materials 323
much as these properties are increased by carbon. This strengthening is,
moreover, attained with less sacrifice of elongation and reduction of area
than in the case of carbon addition.f Another advantage is that phos-
phorus, either alone or more intensely if copper is present, increases the
resistance of the steel to atmospheric corrosion. Phosphorus is favored
as an alloying element chiefly in low-carbon steels that are used in the
rolled or normalized condition.
Manganese, added to steel in amounts in excess of that necessary to
combine with the sulphur and to deoxidize the metal0.1 to 0.25 per
cent for most steelspartly dissolves in the ferrite and partly replaces
iron in iron carbide (Fe
a
C) to form a carbide that may be represented by
(Fe,Mn)
3
C. If the manganese is below 2 per cent, the amount of this
carbide formed is small. Moreover, this substance is so much like iron
carbide that it has in itself no appreciable effect on structure and prop-
erties. The effect of manganese in solid solution is less than that of phos-
phorus; the amount by which 0.01 per cent manganese increases the
tensile strength varies with the carbon content from about 100 to 500 lb.
per sq. in.; it increases the yield strength somewhat more than this. A
yield strength of at least 50,000 lb. per sq. in., together with good duc-
tility, can be readily attained in hot-rolled structural shapes of 0.20 to
0.30 per cent carbon steel by adding 1.00 to 1.75 per cent manganese.
Manganese in amounts exceeding about 0.75 per cent has a strong
effect on the hardenability of carbon steel. In steels that are heat treated,
this effect is an advantage, since it permits the use of less drastic quench-
ing mediums, which means less distortion or cracking. In hot-rolled struc-
tural steel increased hardenability may be a disadvantage, unless the
carbon is very low, because air hardening may occur in cooling from the
rolling temperature with serious loss of ductility. In general, manganese
reduces the ductility of untreated carbon steel, but this is not serious if
the carbon is low.
Silicon in the amounts present in low-alloy steels dissolves in the ferrite.
Its effect on tensile strength is somewhat greater than that of manganese
(Fig. 16.1) ; it raises the yield strength and yield ratio and does not
appreciably reduce ductility. Its effect on hardenability is strong but not
so strong as that of manganese. It has no appreciable effect on corrosion
resistance when present in small amounts. In other than the low-alloy
structural steels discussed later in this chapter, silicon is used as an
alloying element in one important group of spring steels that contain
about
2 per cent silicon, 0.60 to 0.90 per cent manganese, and 0.50 to
f
Phosphorus is likely to make steel cold short, that is, brittle when cold, unless
the carbon percentage is low.
140
120
^
100
5?
=9 80
a
c
c
8
60
40
20
,Reducfion ofarea_
per cent
(A) Nickel
(with carbon 0.20%)
Tensile strength.,
I
|
Reduction ofarea.
percent
-
(B)Chromium
(withcarbon 0.20%)
70
601
50 -
40 c
30-
c
o
I 2 3 4 I 2 3
Alloying element, per cent
Fig. 16.S. Effect of (A) nickel and (B) chromium on the tensile properties of
rolled carbon steels. (Bain and Llewellyn)
0.65 per cent carbon (the S.A.E. 9200 series) and in certain steels for
electric apparatus.
16.4. Effects of Nickel and Chromium
Nickel dissolves in the ferrite of carbon steel and exerts a strengthen-
ing effect that is somewhat less than that due to phosphorus, silicon, or
manganese (Fig. 16.1) . The effect of nickel on the tensile properties of a
0.20 per cent carbon steel is plotted in Fig. 16.3A,* which shows that in
the hot-worked (unhardened) condition nickel has little effect on elon-
gation and reduction of area; it does, however, raise tensile and yield
strengths considerably. In the heat-treated condition, nickel steels are
characterized by high impact resistance, which remains high at low
temperatures.
Nickel does not form a carbide. It increases the hardenability of carbon
steels mildly, being less effective in producing deep hardening than
molybdenum, manganese, or chromium. It also increases the resistance
Figures 16.3A and B are based on data quoted by E. C. Bain and F. T. Llewellyn,
Trans. Am. Soc. Civil Engrs., v. 102, 1937, p.
1249.
of carbon steel to some forms of corrosion, especially in combination with
copper.
Chromium dissolves in the ferrite and also forms carbides if the carbon
is high. As indicated by Figs. 16.1 and 16.2 its ferrite-strengthening ef-
fect when in solid solution is weaker than that of any of the common
alloying elements, but it increases hardenability greatly, as shown by
the curves for the air-cooled specimens in Fig.
16.2.* The effect of
chromium on the tensile properties of small air-cooled (hot-rolled) sec-
tions of a 0.20 per cent carbon steel is plotted in Fig. 16.3B. In such
sections, the increase in tensile and yield strengths and the decrease in
elongation and reduction of area are much greater than the correspond-
ing effects of nickel. Although chromium is a toughening element and
increases the impact resistance of very low carbon steels, its primary
function is to increase hardenability, decrease the magnitude of the mass
effect, and, of course, increase corrosion resistance, especially if more than
3 per cent is present. Owing to its effect on hardenability, chromium
is a common addition to the S.A.E. nickel steels in the proportion of
about half as much chromium as nickel.
Chromium is used widely as an alloying element in high-carbon steels,
where it forms a carbide and also dissolves in the ferrite. When these
materials are quenched and tempered at a low temperature, they are very
hard and have good wear resistance. They contain about 1.0 per cent
carbon and 0.75 to 1.50 per cent chromium and are used for tools, dies,
and ball bearings.
16.5. Effects of the Other Common Alloying Elements
The other alloying elements used in low-alloy steels are copper, molyb-
denum, vanadium, and, to a very limited extent, tungsten. Copper, in the
small amounts added to carbon and low alloy steels dissolves in the fer-
rite, but its effect on tensile and impact properties is small. If more than
0.6 per cent is present, the steels, as noted in another chapter, may be
precipitation hardened. Copper is most useful as an alloying clement for
its effect on atmospheric corrosion. The addition of 0.10 to 0.40 per cent
reduces this variety of corrosion so much that a large proportion of low-
carbon sheets, especially when very thin, and many of the new high-
strength structural steels now contain copper.
*
If the carbon is low (below 0.08 or 0.09 per ceni), chromium up to approximately
3.0 per cent has only a small effect on the hardness and strength when steel is air
cooled. For example. Franks (R. Franks. Trans, Am. Soc. Metals, v. 35, 1945, p. 616)
reported an increase in tensile strength from 55,000 to 70,000 lb. per sq. in. in 0.08 per
cent carbon steel when chromium was increased from to 3 per cent. With 6 per cent
chromium, the strength was 197,000 lb. per sq. in.
326
Molybdenum, vanadium, and tungsten are strong carbide formers. In
the amounts present in low-alloy steels a portion of these three elements
dissolves in the ferrite and probably strengthens it moderately (Fig.
16.1). Vanadium is valuable chiefly for its effect on austenite grain size.
Steels containing 0.10 to 0.20 per cent are usually fine-grained and are
not so readily coarsened by overheating as some of the other low-alloy
steels. Molybdenum, vanadium, and tungsten all contribute to deep hard-
ening, and the first two are very effective in small amounts. Molybdenum
or vanadium is used in a number of low-alloy steels, especially the
S.A.E. grades, usually together with another alloying element, such as
chromium, nickel, or manganese. Owing to its strong effect on harden-
ability and to the fact that the world's largest deposit of molybdenum
ores is located in the United States, the use of molybdenum as an alloy-
ing element has increased greatly in the last few years. The most im-
portant function of tungsten and, to a lesser extent, of molybdenum is
to increase the hardness and stability of the structure of alloy steels, espe-
cially at elevated temperature. For this purpose, relatively large amounts
are required, usually in conjunction with chromium. This is discussed
in a later chapter.
16.6. Low-Alloy Structural Steels as Engineering Materials
As noted previously, there are two broad classes of low-alloy engineer-
ing steels: the structural steels and the S.A.E. steels. The structural steels
have a higher yield strength than carbon steels; they are usually of care-
fully balanced composition and are used for structural purposes without
heat treatment other than natural or controlled cooling after hot rolling.
The S.A.E. steels are, in general, much more costly than the low-alloy
structural steels and should be heat treated to obtain optimum properties.
In contrast to the structural steels, in which the function of the alloying
elements is primarily to strengthen the ferrite and to produce a fine
pearlite when the material is air cooled, in the S.A.E. steels the alloying
elements also affect the response of the steel to thermal treatment and,
in a few cases, harden it by forming carbides.
Low-alloy steels of high yield strength are forty years old. One of the
first contained about 0.25 per cent carbon and 1.50 per cent manganese
and was used between 1900 and 1915 to reduce dead loads in long-span
bridges and steamship construction in the United States and in England.
A little later, a deoxidized carbon steel (misnamed silicon steel) was
developed in the United States. This material contained 0.25 to 0.35 per
cent carbon, 0.70 to 1.00 per cent manganese, and 0.20 to 0.40 per cent
silicon. In the hot rolled condition the yield strength of these two steels
Low-Alloy Steels as
Engineering Materials 327
was 45,000 lb. per sq. in. or higher, and a considerable tonnage was used
for bridges between 1915 and 1928. A steel o similar yield strength,
containing 0.12 per cent carbon, 1 per cent silicon, and 0.70 per cent
manganese, was developed in Germany in 1925 but, owing to its variable
quality, it was not used long. This German steel is important because
it was the first attempt to produce a steel that had high yield strength
but was low enough in carbon to be welded readily without the trouble-
some brittleness in and around the weld that frequently results from
welding a steel containing more than 0.20 per cent carbon and 0.75 per
cent manganese.
About fifteen years ago, the depression stimulated steel manufacturers
to investigate the possibility of producing a low-cost, easily weldable,
tailormade steel that would have strength properties and resistance to
atmospheric corrosion much superior to those of ordinary structural steel.
The depression also focused the attention of engineers upon the desir-
ability of reducing cost in certain structures by the use of smaller sec-
tions of a steel of higher strength, and by welding instead of riveting.
The result was that the steelmakers produced the steels and the engineers
used them for railway rolling stock, streetcars, trucks, buses, cranes, steam
shovels, and similar structures. One of the essential factors in this ad-
vance was the realization that tensile strength is not always the best
criterion of the suitability of a steel for certain structural uses, that re-
sistance to buckling or crumpling, which is related to yield strength, is
essential, and that increased corrosion resistance is an economic necessity
in many engineering structures.
The low-alloy structural steels have, as rolled, approximately twice
the yield strength of low-carbon steel, combined with high ductility, easy
weldability, and a resistance to atmospheric corrosion which is much
higher than that of carbon steel. In tonnage lots, they cost 15 to 50 per
cent more than comparable sections of plain carbon steel. Owing pri-
marily to their high yield strength, it is possible to reduce the size of a
section 25 to 35 per cent and still design a structure that has ample stiff-
ness. Despite somewhat higher fabricating and machining costs, it is fre-
quently possible to save 10 to 15 per cent of the cost of a structure by
the use of the properly selected low-alloy steel.
16.7. Composition and Properties of the Low-Alloy Structural Steels
The first of the present crop of some thirty of these steels was made in
1929 and contained 0.30 per cent or less carbon, 1.05 to 1.40 per cent
manganese, 0.60 to 0.90 per cent silicon, and 0.30 to 0.60 per cent chro-
mium. Known under the trade name of Cromansil, this steel attracted
328
considerable attention, and a number of others followed it quickly under
such trade names as Cor-Ten, Man-Ten, Hi-Steel, Jal-Ten, Konik, Yoloy,
Otiscoloy, N-A-X, Tri-Ten, Carilloy T,, and others.
As a group, the low-alloy structural steels are characterized by low
carbon (to improve ductility and weldability, and to prevent air harden-
ing) and by the presence of at least two, and sometimes as many as six,
of the following alloying elements: manganese, silicon, nickel, copper,
chromium, molybdenum, phosphorus, boron, and vanadium. During
the war titanium was an important minor constituent in these steels. The
percentage of alloying elements is usually low. Manganese is 1.70 per
cent or less, with an average of about 1.25 per cent. Silicon is 1 per cent
or less, the usual amount being between 0.20 and 0.70 per cent. Nickel
varies from 0.3 to 2.0 per cent, and copper, owing to its favorable effect
on resistance to atmospheric corrosion, is usually at least 0.10 per cent
and may be as high as 1.50 per cent. Molybdenum, if present, is less
than 0.40 per cent, and chromium is less than 1 .5 per cent. Phosphorus,
if used as an alloying element, is between 0.05 and 0.20 per cent, vanadium
up to about 0.1, and boron around 0.003 per cent.
In all the low-alloy structural steels the composition is balanced to
ensure for hot-rolled sections a minimum yield strength of 50,000 lb. per
sq. in., a tensile strength of 70,000 to 105,000 lb. per sq. in., and an elon-
gation of 18 to 30 |>er cent in 8 in., depending upon composition. The
impact resistance of most of these steels is satisfactory; usually it is higher
than 25 ft. -lb. Claims have been made that the endurance ratio is higher
than for carbon steels, but not enough data have accumulated yet to
accept this as generally true. As a group, the steels have a resistance to
atmospheric corrosion considerably superior to that of carbon steels.
These steels are outstanding in the relation of properties to cost. There
are too many of them now; probably there will be some casualties in
the next few years, but it seems certain that some will survive and that
the survivors will be widely used as structural materials where a saving
in weight is important.
16.8. The S.A.E. Low-Alloy Steels
Of the alloying elements in low-alloy steels, nickel and chromium were
the first used commercially. Steels containing about 3 per cent nickel
were forged into armor plate between 1885 and 1890, causing a revolu-
tion in naval warfare. Chromium was used even earlier: steels containing
0.60 per cent were installed as main members of the Eads bridge over
the Mississippi River at St. Louis in 1874. Extensive use of the steels in-
cluded in the S.A.E. grades began about 1910. It has been claimed with
considerable justification that the availability of these steels at a fairly
reasonable cost was the chief factor in the development of the automo-
tive and aircraft industries, and that without them the weight per horse-
power of internal-combustion engines would be at least twice, and the
efficiency less than half, what it is today.
Nearly fifty years ago, the Society of Automotive Engineers proposed
specifications for the composition of a number of low-alloy steels that
were being used at that time by the automotive industry. These specifi-
cations were adopted in 1911, and since that time the compositions
recommended in the S.A.E. specifications have been used widely in all
branches of mechanical manufacturing in the United States and abroad.
Revision and extension of the specifications have kept pace with progress
in the automotive and steel industries, with the result that engineers
generally look upon the S.A.E. steels as the most satisfactory low-cost,
high-quality steels commercially available for the production of auto-
motive and aircraft equipment and machine tools, and they know that
these steels will give satisfactory service when properly treated. and used.
in 1941, the Society of Automotive Engineers in collaboration with the
American Iron and Steel Institute made major changes in the composi-
tion ranges of their standard steels. These changes consisted primarily
of adopting narrower ranges for chemical analysis as made on a specimen
representing a whole heat, plus an allowance for check analyses on indi-
vidual specimens from the same heat. At the same time the American
Iron and Steel Institute issued standard analysis specifications for low-
alloy steels, which are known as A.I.S.I, specifications and which, in
general, follow the same system of classification as is used by the S.A.E.
The S.A.E. specifications for low-alloy steels for 1956 cover 114 steels
divided into eight series. These are shown in Table 16.1.* The A.I.S.I,
specifications cover 170 steels divided into 13 classes, eight of which are
the same and have the same series numbers as the S.A.E. grades.
The system of classifying these low-alloy steels is evident from Table
16.1. Series 1300 comprises the medium-manganese steels; 2300 contains
3.50 per cent nickel; and 2500 contains 5.00 per cent nickel. The 3100
series contains nickel and chromium but the amounts are different in
In addition to specifications for low-alloy steels, both the Society of Automotive

Engineers and the American Iron and Steel Institute have standardized unalloyed
carbon steels. The S.A.E. specifications cover 22 carbon steels (series 10XX) ranging
from less than 0.10 to 1.05 per cent carbon, and 10 high-sulphur free-machining steels
(series 11XX) containing up to 0.15 per cent sulphur and as much as 1.65 per cent
manganese. These specifications are given in the S.A.E. Handbook, 1956 edition,
pp.
51-55, and in Steel Products Manual, Sec. 2. Carbon Steel, Semi-finished Products,
published by the American Iron and Steel Institute, New York, 3d rev.,
June, 1943.
330
the 3100, and 3300 series. The 4000 series is made up of plain molyb-
denum steels, the 4100 series of chromium-molybdenum, the 4600 and
4800 series are nickel-molybdenum, and the 4300 series which is popu-
lar in the aircraft industry contains nickel, chromium, and molybdenum.
The last two digits of an S.A.E. or an A.I.S.I, number indicate the middle
of the carbon range; thus, a 2330 steel contains 3.25 to 3.75 per cent
nickel and 0.28 to 0.33 per cent carbon. The larger number of A.I.S.I.
steels is due chiefly to more detailed specifications according to carbon
Table 16.1. Basic Numbering System and Composition Ranges for S.A.E. and
A.I.S.I. Low-Alloy Steels
*
Series
Composition range, per cent
S.A.E.
or A.I.S.I.
Manganese Nickel Chromium
Molyb-
denum Other
1300 1.60 to 1.90
2300
2500
3.25 to 3.75
4.75 to 5.25
3100
3300
1.10 to 1.40
3.25 to 3.75
0.55 to 0.75
1.40 to 1.75
4000
4100
4300
4600
4800
1.65 to 2.00
1.65 to 2.00
3.25 to 3.75
0.80 to 1.10
0.40 to 0.90
0.20 to 0.30
0.15 to 0.25
0.20 to 0.30
0.20 to 0.30
0.20 to 0.30
5100
5200
0.70 to 0.90
1.20 to 1.50
6100 0.80 to 1.10 0.15 min. V
8600
8700
0.40 to 0.70
0.40 to 0.70
0.40 to 0.60
0.40 to 0.60
0.15 to 0.25
0.20 to 0.30
9260
9300
9800
0.70 to 1.00
3.00 to 3.50
0.85 to 1.15
1.00 to 1.40
0.70 to 0.90
0.08 to 0.1
5
0.20 to 0.30
1.80 to 2.00
Si
t86BO0 0.40 to 0.70 0.40 to 0.60 0.15 to 0.25 Boron, .0015
to .0020
'S.A.E. Handbook, Society of Automotive Engineers, New York, 1956, pp.
50-55;
Steel Products Manual, Sec. 10, Alloy Steels, American Iron and Steel Institute, New York,
3d rev., June 1945, pp.
13-30.
t
xxBxx, B denotes Boron Steel.
percentage. For example, in the S.A.E. series 4100 there are 10 steels, cov-
ering a carbon range from 0.17 to 0.53 per cent; in the corresponding
A. I.S.I, series there are 18 steels to cover the same range of carbon.
In addition to carbon and alloying elements, these specifications give
ranges for manganese (regardless of whether it is an alloying element)
,
silicon, sulphur, and phosphorus. The A.I.S.I. specifications also carry
letters that identify the process by which the steel was made: A for the
basic open-hearth, D for the acid open-hearth, and E for the electric-
furnace process.
Some of the low-carbon S.A.E. alloy steels do not conform exactly to
the ranges shown in Table 16.1. For example, in the low-carbon 4100
steels, the chromium is lower (0.40 to 0.60 per cent) and the molyb-
denum is higher (0.20 to 0.30 per cent) than in the steels containing
more than 0.30 per cent carbon. The manganese in most standard S.A.E.
steels varies widely. The 2300 series is typical; manganese is 0.40 to 0.60
per cent in the low-carbon grades, and 0.60 to 0.80 or 0.70 to 0.90 per
cent in the higher carbon steels.
The standard S.A.E. and A.I.S.I. steels are only a small fraction of the
low-alloy steels used commercially. Some of these other steels vary
slightly, but many vary greatly, from the standard compositions given in
Table 16.1. A few of them, which are widely used and which vary
slightly, usually in only one element, are given S.A.E. numbers prefixed
by the letter X. An example is X3140, the nominal composition of which
is given in Table 16.2. In this steel the chromium is 0.70 to 0.90 instead
of 0.55 to 0.75 per cent.
16.9. The S.A.E. Low-Alloy Steels as Engineering Materials
Composition, series number, and recommended heat treatment for all
the S.A.E. steels are given in the S.A.E. Handbook and in many other
readily accessible sources and need not be considered here. These steels
are more expensive than the low-alloy structural steels, and, further-
more, they must be heat treated to be of the greatest value. They are
widely used in the construction of automobiles and aircraftespecially
enginesand for machine tools, particularly for highly stressed parts such
as crankshafts, camshafts, axle and other shafts, gears, bolts, studs, steer-
ing knuckles, spindels, collets, and valves.
A few of the S.A.E. low-alloy steels are used in the rolled and air
cooled conditions; there is one series, discontinued as standard by S.A.E.
a few years ago, which contained less than 2 per cent nickel, that was
widely used for engine bolts and boiler plate and, to a lesser extent, for
bridge and ship construction. The medium-manganese series 1300 is also
used occasionally as rolled and air cooled, and a few of the low-alloy
structural steels discussed in

16.7 are essentially S.A.E. 1320 containing
a small amount of copper to increase resistance to atmospheric corrosion.
Most of the S.A.E. steels are used in applications, especially in moving
parts, where stresses are relatively high, and they must be quenched
(usually in oil) and tempered to secure the maximum combination of
strength and ductility. When properly heat treated, they combine high
ductility with high strength. Compared with carbon steels of the same
tensile strength and hardness, heat-treated low-alloy steels have 30 to 40
per cent higher yield strength, 10 to 20 per cent higher elongation, and
35 to 40 per cent higher reduction of area. The impact resistance of the
S.A.E. steels is frequently twice that of a carbon steel of the same tensile
strength.
The most important characteristic of the S.A.E. low-alloy steels as a
class is that they are deeper hardening than carbon steels; in other words,
the mass effect is smaller. It is easier to harden large sections of low-
alloy steels throughout than is the case with carbon steels. Moreover,
as the critical cooling rate is much lower, oil quenching can be used to
attain high strength and hardness with less possibility of distortion or
the introduction of high internal stresses.
Tempering temperature,deg. C.
700
1200 1400
900 1I0O 1300 800 1000
Tempenng temperature,deg. F.
Fig. 16.4. Elfect of tempering on the tensile properties of oil-quenched (A) nickel-
chromium (S.A.E. 3140) and (B) nickcl-chroniium-molybdenum (S.A.E. 4S40) steels.
{S.AM. Handbook, 1941)
16.10. The New Metallurgy of Low-Alloy Steels
For many years charts of average or minimum tensile properties and
hardness (occasionally impact resistance as well) of S.A.E. and other
low-alloy steels, as quenched and tempered at various temperatures, were
published in the S.A.E. Handbook and in other readily available sources.
The properties indicated by these charts were, moreover, commonly
used by engineers in the design of machines and other important equip-
ment. Figure 16.4 shows two such charts.
These charts of properties were considered invaluable because of the
commonly held assumption that each alloy steel had a set of mechanical
properties after heat treatment that was characteristic of, and due to, its
chemical composition, and that, in general, these properties could be
reproduced at will by subjecting any steel of the same specified composi-
tion range to the same thermal treatment. This assumption is statistically
valid, but the accompanying and widely held assumption that certain
low-alloy steels have inherently a better combination of strength and
ductility than others (Fig. 16.4) is not valid, at least insofar as the as-
sumption is based on charts of mechanical properties.
Table 16.2. Typical Tensile Properties of S.A.E. Low-Alloy Steels (0.35 to 0.45
Per Cent Carbon) Quenched in Oil and Tempered at 1000
F. (540 C.)
*
Elon- Reduc-
Nominal chemical Tensile Yield gation tion
Steel composition, per cent strength, strength, in of
No. lb. per lb. per 2 in., area,
sq. in. sq. in. per per
C Mn Ni Cr Mo cent cent
1340 0.40 1.75 141,000 120,000 18 52
2340 0.40 0.75 ! 3.50 137,000 120,000 21 60
3140 0.40 0.75 1.25 0.60 143,000 119,000 17 57
X3140 0.40 0.75 1.25 0.75 155,000 1 30,000 17 55
4140 0.40 0.75 1.00 0.20 170,000 147,000 16 56
4340 0.40 0.65 1.75 0.65 0.35 184,000 160,000 15 52
4640 0.40 0.65 1.80 0.25 151,000 131,000 19 56
*
Data obtained on standard test specimens machined from bars less than 1 .5 in.
in diameter.
Some typical tensile properties of S.A.E. low-alloy steels containing
0.35 to 0.45 per cent carbon as quenched in oil and tempered at 1000F.
(540C.) are given in Table 16.2. These properties were collected by
Hoyt* and are undoubtedly representative. For a definite heat treatment.
tensile and yield strengths vary as much as 40,000 lb. per sq. in., and the
variation in ductility as measured by elongation and reduction of area is
considerable. The existence of such lists of properties (and published
charts of properties) makes it understandable that engineers designing
a crankshaft for an internal-combustion engine, for instance, believed
that there is a marked inherent difference in the mechanical properties
of heat-treated low-alloy steels.
Two relatively recent events in ferrous metallurgy were mainly re-
sponsible for the development of what might be called a new philosophy
of low-alloy steels and for changing greatly our ideas about the relation
between composition and properties. They were also primarily respon-
sible for the disappearance of mechanical-property charts from the S.A.E.
Handbook (in 1942) and from many other publications and for the
almost overnight development during World War II of the National
Emergency steels, an accomplishment in which American metallurgists
can take much justifiable pride. These two events were the work of
Janitzky and Baeyertzf on the similarity in mechanical properties of heat-
treated low-alloy steels, and the practical application of the principles
underlying the relation of carbon, alloying metals, and hardenability.
The relation among carbon percentage, the amount of alloying ele-
ments present, hardenability and other variables, and the properties of
steel is discussed in detail in the next two chapters. In brief, this relation
is as follows: If M per cent of nickel and N per cent of chromium pro
duce a structure of 50 per cent martensite at the center of an oil-quenched
2-in. bar of steel containing 0.45 per cent carbon; and if X per cent of
manganese and Y per cent of molybdenum produce the same structure
in an oil-quenched bar of the same size and approximately the same
carbon content, the tensile properties of the two steels after tempering
to the same hardness will for all practical purposes be identical.
16.11. Similarity of Properties of Heat-Treated S.A.E. Low-Alloy
Steels
Some of the data obtained by Janitzky and Baeyertz are reproduced
in Figs. 16.5 and 16.6. These investigators quenched 1-in. round bars of
S. I.. Hoyt, Metals and Alloys Data Book, Reinhold Publishing Corporation, New
York, 1943, 334
pp.
+ E.
J.
Janitzky and M. Baeyertz, in Metals Handbook, American Society for Metals,
Cleveland, 1939,
pp.
515-518. The work of Janitzky and Baeyertz on the similarity
of properties of heat-treated low-alloy steels was antedated by several years by work
done but not published by the metallurgical laboratory of General Motors Corpora-
tion which resulted in the removal of the old-style property chart from General
Motors Standards several years previously. The first publication of a part of this
work was by A. L. Boegehold, Metal Progress, Feb., 1937, pp.
147-152.
260
240
|220
b
200
\ 180
1*160
1
1
140
I
120
100
o
y.
1
^
9
"7
Yields*-en -jtn-
,
A
G
7
t*~
7

Wc ter quenched
&

S. A. .1330
* 2330.
& 3130
v 4130
a
5130A
&9
613
80 120 160 200
Yield strength
,
thousand lb.pcrsq.in.
240 20 40 60
ofarea, per cent
Fig. 165. Tensile properties of water-quenched and tempered S.A.E. low-alloy
steels containing about 0.30 per cent carbon. (Janitzky and Baeyertz)
a number of S.A.E. alloy steels in water and oil and tempered them at
various temperatures in accord with recommendations given in the
S.A.E. Handbook. Yield strength, elongation, and reduction of area were
plotted against tensile strength with the result shown in Figs. 16.5 and
16.6. For tensile-strength values of less than 200,000 lb. per sq. in., there
is little difference in the steels. At high strength values considerable scatter
is evident; this is undoubtedly due to internal stresses caused by quench-
ing rather than to any inherent difference in the steels.
The data reported by Janiuky and Baeyertz in 1939 have been con-
firmed since by a number of other investigators. Patton,* for example,
plotted tensile properties and Izod impact resistance for 409 tests on 180
heats of 37 grades of carbon and low-alloy steels. The steels used were
mostly N.E. and S.A.E. grades, but a considerable number of others were
included; all of the steels, however, were of such a composition that it
was reasonably certain that the test specimen hardened completely in
quenching. For tensile-strength values of 100,000 to 200,000 lb. per sq.
W. G. Patton, Metal Progress, v. 43, 1943,

pp.
726-733.
336
280
260
j-240
_220
"2
200
l80
c
I
"160
a.
.s
140
120
~
'
1

-r
9
*H

r
A 1
j 09
n
Yiela'strength>. 6* *
A A A
PI _._L--_
(*
3
-a- //I
?/n
3
A
c
Oil quenched
* S.AE.234S
3115-
3240
.
a 4310-
4fi-
.
S/15

/
5
i L
,
r
^Reduction
ow
J
f-
-
Of area
->
.
1/
h
V
'
I 1 1
[a J
80 120 160 200 240
Yield
strength,
thousand lb. per sq.in.
20 40 60
ofarea, per cent
Fie. 16.6. Tensile properties of oil-quenched and tempered S.A.E.
low-alloy steels
containing about 0.40 to 0.45 per cent carbon. (Janitzky and Baeyertz)
in.,
yield-strength, elongation (in 2 in.), and reduction-of-area
values
fell close to a line
representing expected values in at least two-thirds of
the tests, and 90 per cent of the
values fell within a band that varied
not more than 5 per cent from the expected values.
Of the values that varied more than 5 per cent from the expected
values the variation was such that no single steel and no group of steels
could be considered superior to any other steel or group of steels. It was
also evident that steels heat treated to a tensile strength
above 200,000
lb. per sq. in. contained
internal stresses that were responsible for con-
siderable scatter in properties. Impact resistance was more erratic than
other property values, varying 20 per cent or more from the line of ex-
pected values.
The most recent correlation of
mechanical properties, for low-alloy
steels containing 0.30 to 0.50 per cent carbon, is shown in Fig.
16.7.*
Courtesy
American Society for Metals.
100 120 140 160 180 200
Tensile Strength, 1000 psi
FlC. 16.7. Normally expected mechanical properties (heavy line) and average varia-
tion (hatched band) of quenched and tempered low-alloy steels containing 0.30 to 0.50
per cent carbon (Metals Handbook, 1948, page 458).
16.12. The Engineering Properties of the S.A.E. Low-Alloy Steels
Some typical tensile properties of S.A.E. carbon and low-alloy steels,
including a few triple-alloy (N.E.) steels, collected from various sources
are given in Table 16.3. All the steels whose properties are given in this
tabulation were heat treated to a tensile strength of 150,000 lb. per sq. in.
(Brinell hardness number approximately 300) . The similiarity in proper-
ties of the low-alloy steels is evident; also evident is the inferior yield
strength and ductility of the carbon steels which are inherently shallow
hardening in the sizes treated, namely,
1-
to li^-in.
bars.
The effect of tempering on the tensile properties of 1-in. round bars
of S.A.E. low-alloy steels containing 0.30 to 0.35 and 0.40 to 0.45 per cent
carbon is shown by the charts of Fig. 16.8. These are the properties that
can be expected 90 per cent of the time if an S.A.E. low-alloy steel of a
size that will harden with a structure of approximately 50 per cent
martensite at the center when quenched in oil is tempered at the tem-
peratures shown.
Table 16.3. Typical Tensile Properties of S.A.E. and N.E. Carbon and Low-Alloy
Steels Heat Treated to a Tensile Strength of 150,000 lb. per sq. in.
*
Elon- Reduc-
Nominal chemica Tempering Yield gation tion
Steel composition, per cent temperature strength, in 2 of
No. lb. per
sq. in,
in.,
per
area.
per
C Mn N1 Cr Mo V F. c. cent cent
1045 0.45 0.75 600 315 114,000 10 35
1060 0.60 0.75 750 400 113,000 15 45
1080 0.80 0.40 950 510 111,000 16 47
1340 0.40 1.75 950 510 128,000 16 50
2340 0.40 0.75 3.50 950 510 132,000 20 59
3130 0.30 0.65 1.25 0.60 850 455 128,000 17 57
3140 0.40 0.75 1.25 0.60 950 510 127,000 17 56
X3140 0.40 0.75 1.25 0.75 1000 540 130,000 17 55
4065 0.65 0.80 0.20 1100 595 130,000 16 47
4130 0.30 0.65 0.65 0.20 1050 565 131,000 20 61
X4130 0.30 0.50 0.95 0.20 1050 565 130,000 20 57
4140 0.40 0.75 1.00 0.20 1100 595 131,000 18 60
4340 0.40 0.65 1.75 0.65 0.35 1200 650 130,000 19 57
4640 0.40 0.65 1.80 0.25 1000 540 131,000 19 56
5140 0.40 0.75 1.00 1000 540 130,000 18 55
6150 0.50 0.75 1.00 0.18 1200 650 135,000 18 54
8640 0.40 0.90 0.50 0.50 0.20 1050 565 133,000 17 53
8740 0.40 0.90 0.50 0.50 0.25 1100 595 130,000 18 56
8750 0.50 0.90 0.50 0.50 0.25 1200 650 129,000 18 54
8950 0.50 1.00 0.50 0.50 0.40 il200 650 133,000 18 57
9440 0.40 1.10 0.45 0.40 0.12 1050 565 130,000 18 57
*
All test data obtained on standard specimens machined from bars 0.75 to 1.5 in.
in diameter. All quenched in oil except 1045, which was quenched in water.
Tempering temperature .deg.C.
400 500 600 300 400
600 800 1000 1200 60O 800
Tempering temperature, deg.F.
1000
Fie. 16.8. Effect of tempering on the normally expected tensile properties of low-
alloy steels containing (A) 0.30 to 0.35 per cent carbon, and (B) 0.40 to 0.45 per cent
carbon.
160
ISO
140
E
130
It"
||II0
|
3100
J-6 90
if
TO
1.1 so
||40
ûj 30
*
zo
A. X3I40
'
Carbon 0.407.
, Manganese
015V
Nickel 1.25%
Chromium 0.157.-
e<fccf/on
ofarea
fjrnaation
in 2in.
B. 8b30"
Carbon
0.30,
Mawnese 0.807.
Nickel. 0.657.
-
Chromium 0.507.
Molybdenum
0.257."
Reduction
of
area
^pn0jonin2in.
"6
- c
si
I 2 3
Diameier of section, in.
I 2 3
Diameter of section.in.
Fig. 16.9. Effect of mass on the normally expected tensile properties of (A) a
through-hardening (X3140) steel, and (B) a semithrough-hardening (8630) steel,
quenched in oil and tempered at 1000F.
The mechanical properties of heavy sections o heat-treated low-alloy
steels depend on how deeply the material hardens in quenching and
upon several other variables such as grain size, quenching tenqjerature,
and quenching medium. The higher the carbon (up to about 0.60 per
cent) , the harder and stronger is the material at and near the surface;
and, in general, the higher the percentage of alloying metals promoting
hardenability, the harder and stronger is the steel both at the surface
and throughout the cross section.
The effect of section size on two low-alloy steels is shown in Fig. 16.9.*
The nickel-chromium steel X3140 could be classed as a through-harden-
ing material, and the triple alloy steel 8630 is undoubtedly semithrough-
hardening material. Both steels have a relatively high strength (after oil
quenching and tempering at 1000F.) in small sections; and in both
steels the strength decreases as the size of section increases, but the
tensile and yield strengths of 8630 decreases to a greater extent and more
rapidly with increasing section size than those of X3140.
The impact resistance of the low-alloy steels depends on a number of
variables including composition, grain size, thermal treatment, and
others. Patton, whose data were discussed in the previous section, plotted
the Izod impact values given for the 400 specimens and found that the
normal expected value decreased from 85 or 90 ft.-lb. for steels with
100,000 to 120,000 lb. per sq. in. to about 20 or 25 ft.-lb. for steels or
200,000 lb. per sq. in., leveling off at this value for higher tensile strengths.
Because impact resistance is very sensitive to slight variations in struc-
ture, Patton found much more scatter than in any of the other properties.
The endurance ratio of polished specimens of low-alloy steels is ap-
proximately the same as, or perhaps slightly lower than, for carbon
steels. Available data in the literature give ratios of 45 to 50 per cent
with the average a little below 50. Because of internal stresses, the en-
durance limits of heat-treated low-alloy steels with a tensile strength of
250,000 lb. per sq. in. or higher do not exceed approximately 100,000
lb. per sq. in.
QUESTIONS
1. Why should low-alloy steels be balanced?
2. Give as many advantages as you can as to why low-alloy steels arc becoming
so popular.
8. Explain the effects of adding small amounts of nickel to steels.
4. Explain the effects of adding small amounts of chromium to steels.
Data on X3140 from International Nickel Co., Handbook on Nickel Steels,
2,
1934; data on 8630 from Republic Steel Corp., Handbook on N. Steels, 1943.
5. Explain the effects of adding small amounts of molybdenum to steels.
6. Explain the effects of adding small amounts of vanadium to steels.
7. Explain the effects of adding small amounts of tungsten to steels.
8. Explain the effects of adding phosphorus to steels.
9. What arc the disadvantages of adding phosphorus to steels?
10. Name three alloying elements that arc carbide formers.
11. Why is the carbon content low for low-alloy steels?
12. What advantages do low-alloy steels have compared to plain carbon steels
when quenched?
IS. Name twenty specific uses for low-alloy steels.
14. Compare in chart form the physical properties of low-alloy steels containing
0.40 per cent to a plain carbon steel containing 0.4 per cent carbon.
15. Explain why silicon is not used to any great extent in low-alloy steels.
16. List various sources where physical properties of low-alloy steels may be
obtained.
17. What do the letters S.A.E. stand for?
18. What do the letters A.I.S.I. stand for?
CHAPTER
Hardenability
17
Walter M. Hirthe, M.S.M.E., Assistant Professor of
Mechanical Engineering, College of Engineering
Marquette University, Milwaukee, Wisconsin
Richard O. Powell, College of Engineering, Tulane
University, New Orleans, Louisiana
r
OR more than a thousand years, hardness
has been the most highly valued attribute of iron-carbon alloys; in fact,
the word "steel" has long been an accepted synonym for hardness, dura-
bility, and reliability. This is natural; to early social groups, with limited
knowledge of the properties of the metals then available, unhardenable
wrought iron was no better, and in many instances worse, than properly
made and fabricated bronze. When wrought iron was carburized and heat
treated, however, the resulting steel was far superior to anything pre-
viously available, not only for weapons, but also for plowshares and other
tools essential to an agricultural and pastoral society. It is not surprising,
therefore, that hardness became a supreme and lasting virtue in metals,
and the medieval metal worker who knew how to produce hardened steel
was for centuries considered something of a magician.
Today, as well as a thousand years ago, no one questions the im-
portance of hardness and its accompanying high strength; in fact, the
ease with which hardness and its related properties can be controlled by
thermal treatment makes steel man's most important metallic material.
Owing, however, to inherent limitations in our present methods of
thermal treatment, hardness may be only superficial. Metallurgists have
realized for many years that hardenability, which, briefly, is the depth to
which martensite will form in definite sections under definite cooling
conditions, is often as important as actual hardness, and there are many
applications for which steel should be practically as hard and strong at
or near the center as at the surface. Surface-hardened steels are valuable
for many engineering uses, but if weight is to be saved and high stresses
342
Hardenability 343
withstood, steels hardened throughout are necessary. In additionand
this is equally importanta steel hardened throughout by quenching has
properties, as tempered to a definite hardness, that are superior to the
properties of a steel tempered to the same hardness but not hardened
throughout.
17.1. Hardness and Hardenability in Carbon Steels
Among engineers who use heat-treated steel there is considerable con-
fusion concerning the difference between hardness and hardenability,
that is, between the maximum hardness that a steel attains in quenching
and the depth to which it hardens. There is no direct and close relation
between the two, despite the fact that hardness is used to measure
hardenability. An example or two should make this clear.
Suppose that two 1-in. bars of carbon steel containing, respectively,
0.30 and 0.70 per cent carbon are quenched from above the transforma-
tion temperature into ice water or iced brine. The surface hardness of
the first will be approximately 55 Rockwell C and that of the other one
about 65 Rockwell C. Both bars will harden to a depth of about
\/
A
in.
The hardness values of the two steels differ (at the surface), but the
hardenability is the same.
If small specimens of either carbon or low-alloy steels are cooled from
the proper
quenching temperature at the critical cooling rate or faster,
so that no transformation occurs before martensite begins to form, the
0.40 0.5O 0.60
Carbon, percent
0.70 0.80 0.90
Fjc. 17.1. Relation between carbon content and maximum martensitic hardness
(upper curve), and maximum hardness usually attained (hatched band). {Based on
data by Burns, Moore, and Archer, and by Boegehold)
344
maximum hardness attainable depends on the carbon content. This is
shown by Fig. 17.1.* It should be emphasized that the upper curve shows
the maximum hardness obtained when the specimen is entirely marten-
sitic in structure. In the commercial heat treatment of carbon and low-
alloy steels this is rarely realized, except with very small sections. Ordi-
narily the martensite is contaminated by varying small amounts of transi-
tion structures that reduce the hardness appreciably. In consequence,
many metallurgists put the highest practical hardness obtainable in the
commercial quenching of these steels at 5 to 10 Rockwell C numbers
below the maximum, as is shown by the hatched area in Fig. 17.1.
17.2. Hardness and Hardenability in Low-Alloy Steels
The difference between hardness and hardenability is also well illus-
trated by Fig. 17.2,* which shows hardness values over the entire cross
section of quenched bars of various diameters of S.A.E. 1045 (0.45 per
cent carbon) and S.A.E. 4140 (0.40 per cent carbon, 1.0 per cent
chromium, 0.20 per cent molybdenum) steels. If 1-in. bars of these two
steels are quenched in water from above the transformation temperature
(Fig. 17.2), their hardness at the surface is practically the same; at the
center, however, S.A.E. 4140 has a hardness of 59 Rockwell C, whereas
S.A.E. 1045 has a hardness of only 34 Rockwell C.
This illustration shows clearly that two steels of about the same carbon
content may have the same hardness at the surface but a different harden-
ability. They may also have a very different hardness at the surface and a
different hardenability, depending primarily upon the relation of the
cooling rate to the location of the nose of the S curve and, consequently,
upon whether the rate of cooling is sufficient to prevent much pearlite
from being formed during quenching.
17.3. Cooling Rate and Hardenability
In many ways steel is a very cooperative metal and responds readily
to the treatments man gives it, no matter how unreasonable or illogical
these may be. In other ways, however, it is as stubborn as the traditional
army mule, and, like it or not, we can do little about it. Heat extraction
is typical of this characteristic. We can put heat into a piece of steel by
The upper curve of Fig. 17.1 is based on data collected by
J.
I.. Burns, T. L.
Moore, and R. S. Archer, Trans. Am. Soc. Metals, v. 26, 1938, pp.
1-36. The hatched
band is based primarily on data given by A. L. Boegehold, S. A. E. Trans., v. 52,
1944,
pp.
472-485.
*
Based on diagrams published in U. S. S. Carillory Steels, Carnegie-Illinois Steel
Corporation. Pittsburgh., 1938, 214
pp.
Hardenability 345
1
S.A.E. 04! ,QUEN
i
i
:hed in
i
WAid
1 f
1 I
V /
\ /
\
\
- J
)
/
V
\
S
\ /
'
/
s
\
\
-::
;>
m
*--
H
"::z.
:
A
^
*
~*
--
--H
Diameter of bar.in. Diameter of bar, in.
Fig. 17.2. Hardness over entire cross section of bars of various diameters of
S.A.E. 1045 and S.A.E. 4140 steels quenched in water. (U. S. S. Carilloy Steels)
electrical or other methods at almost any rate we choose, but we cannot
extract the heat from the interior any faster than thermal conductivity
will permit. No matter how fast we chill the surface, the heat will flow
from the center to the surface of a large section at a slow rate, which is
largely unaffected by the composition of the material. This process is
complicated by the fact that during quenching the steel conforms ap-
proximately with Newton's law of coolingthat heat loss is proportional
to the temperature difference between the bar and the quenching medium
and also by the fact that, quenching mediums vary greatly in their
ability to extract heat from the surface of hot steel.
And it must be remembered that it is not always desirable to quench
steels drastically in water, as this treatment is likely to result in high
internal stresses which may cause severe warping, cracking, or some other
unhappy consequence.
346
17.4. Time Delay and Hardenability
The relatively slow heat transfer from the center to the surface of a
section 1 in. or larger severely limits our ability to cool steel rapidly
enough to secure deep hardening, if the critical cooling rate is high.
There is consequently
only one method of securing deep hardening:
reduce the critical cooling rate. In other words, what we do is to decrease
the tendency of austenite to transform to pearlite in the temperature
range of the nose of the S curve, or to bainite at lower temperatures;
this is another way of saying that we push the line of the S curve that
marks the beginning of austenite transformation below the critical tem-
perature to the right so that more time is available for the steel to cool
to 600F. (315C.) or below without such transformation.
Below the A
t
transformation temperature, austenite is, of course, un-
stable; and the more the temperature is lowered, the greater becomes
the instability. The tendency of unstable austenite to transform increases
with lowered temperatures; but this is counteracted to a degree by the
fact that as the steel gets colder it gets more rigid; that is, its ability to
transform decreases.
The forces involved
in the tendency of unstable austenite to transform
to pearlite, bainite, or martensite are complex, and at present they are
not well understood.
The net result, however, is that in all steels there
is a time interval, commonly known as time delay, which elapses before
the unstable austenite begins to decompose. This interval may be very
short or very long, depending upon a number of factorsin addition to
temperature, which is most importantthat include among others homo-
geneity of austenite, grain size, and chemical composition.
Small differences in time delay are important in hardenability; but
even so, all carbon steels and many low-alloy steels have a time delay at
the nose of the S curve that is rarely more than 3 to 5 sec. (for con-
tinuous cooling), which means that few of them harden to the center
except in very small sections. In other words, changes in the S curve
due to continuous cooling may be important in the heat treatment of a
razor blade or a small tool but not of a 2-in. shaft or a 55-mm. gun tube.
17.5. Variables Affecting Hardenability
There are a number of variables that affect time delay and thus affect
hardenability. Homogeneity of the austenite increases its sluggishness
and thus increases time delay. Heating long enough or at a high enough
temperature to ensure homogeneity is also likely to change the grain size,
and since grain size greatly affects hardenability it is difficult to untangle
the two variables. It is, however, a fact that, if one or more areas in the
Hardenability
347
austenite are high or low in carbon or in alloying elements, transforma-
tion during cooling will be accelerated. Premature transformation in a
segregated area has a "trigger action" that sets off transformation over
the whole section, thus decreasing time delay and hardenability.
Since homogeneity depends on diffusion and diffusion takes time, one
of the common but insufficiently recognized causes of a variation in
hardenability in steels of the same composition is insufficient time at the
quenching temperature for the austenite to become homogeneous. This
is also the reason why the hardenability of a steel as determined in the
laboratory, where the homogeneity factor is likely to be taken care of,
may differ from the hardenability of the same steel heat treated in large
lots in the plant.
Another and even more important factor is austenite grain size. Trans-
formation begins principally at the grain boundaries; hence, as the num-
ber of grains increases, the likelihood that transformation will start
quickly is increased. Small grain size thus decreases time delay and
lowers hardenability. On the other hand, increasing grain size decreases
the chances for transformation to begin quickly; it lengthens the total
time for the reaction to start and increases hardenability.
Much work has been done in this field, which can be summarized
briefly by stating that if other factors do not enter, increasing the grain
size from about 8 (A.S.T.M. rating) to 5 or 6 will double the time
available for the austenite to cool to a low temperature without trans-
forming to pearlite; and increasing the grain size to 2 or 3 will more
than double the time and it may even triple it.
Grain-size control during melting is relatively simple; it would, there-
fore, be easy to increase the hardenability of shallow-hardening grades
by using a steel that would be coarse grained just before quenching.
Unfortunately, however, the consequences might not be pleasant. Coarse-
grained steels frequently crack if cooling is drastic, and they are likely to
be sadly lacking in toughness (impact resistance) at room temperature
and below. In fact, this lack of toughness is usually so dangerous that
most steels that are to be used in highly stressed parts are deliberately
made fine grained, and deep hardening is secured by the use of alloying
elements.
By a proper balance of carbon content and the various alloying ele-
ments, the critical cooling rate can be lowered so much (that is, the
time delay is greatly increased) that the steel will harden deeply when
large sections are quenched in oil or even on cooling in air. This, and
the methods used for measuring hardenability, are the subjects covered
in the following sections.
348
Engineering
Metallurgy
17.6. Methods of Determining Hardenability
The first of several tests proposed to measure hardenability directly
is the penetration-fracture (P-F) test developed by Shepherd.* This in-
volves quenching short bars,
%
in. in diameter, in a brine solution after
homogenizing for 30 min. at 1450, 1500, 1550, and 1600F.
(790, 815,
845, and 870C). The bars are fractured and the fracture is compared
with a standard. One half is polished on the end and etched with acid to
determine the depth of hardening. The steel is rated according to the
numerical values of the fracture (grain size) and the penetration (hard-
enability). The test demands considerable skill and experience. It has
never been used widely except by companies making or using large
quantities of high-carbon tool steel. It is possible by this test to classify
tool steels as sensitive or insensitive to grain growth with increasing
quenching temperature and as deep or shallow hardening.
Unquestionably, the most reliable test for hardenability is made simply
by quenching bars of varying sizes from the proper temperature, cutting
the bars in half, and determining Rockwell C hardness from center to
surface. These values are then plotted as a U-shaped diagram similar
to that shown in Fig. 17.2. For a study of the hardenability complete
enough to rate a steel accurately it is necessary to prepare, quench under
controlled conditions, and measure the hardness of, the transverse sections
of five to eight or more bars varying in diameter from
i/,
to 4 in. or more,
which takes 15 to 20 hr. This is the only disadvantage of the test, but it
is a major one.
Twenty years ago, when hardenability was attracting wide attention,
one of the important problems in the field was to devise a simple, readily
reproducible, comparatively accurate test to determine the relative re-
sponse of the commonly used medium-carbon and low-alloy steels to
quenching.
It had been apparent for some time that, if the hardness values at the
center of quenched bars are plotted against the diameter, depth-harden-
ing curves result. Four such curves are shown in Fig. 17.3. The two
curves in Fig. 17.3A are plotted from the data given in Fig. 17.2, and the
difference between the shallow-hardening carbon steel (1045) and the
deep-hardening chromium-molybdenum steel is clear. The curves plotted
in Fig. 17.3B are from hardness data on two low-alloy steels which differ
slightly in response to quenching. The hardenability of these two steels
is practically the same for
\/
r
and s^-in. bars and for bars larger than H/
in., but it varies considerably with intermediate sizes.
B. F. Shepherd, Trans. Am. Soc. Metals, v. 22, 1934, pp.

979-1016.
Hardenability
349
3 4 5 'h V4 I
Diameter of bar. in.
Fig. 17.3. Depth-hardening curves for (A) water-quenched shallow-hardening (1045)
and deep-hardening (4140) steels and (B) two low-alloy steels differing in hardenability
in intermediate sizes.
It was, of course, immediately recognized that any test that could be
used to determine hardenability rapidly and cheaply must distinguish
not only between deep- and shallow-hardening steels where differences
are great (Fig. 17.3A) but also between the hardenability of two steels
whose depth-hardenability curves resemble those plotted in Fig. 17.3B.
Such a test was developed by Jominy
and his coworkers at the research
laboratory of General Motors Corporation and has now been standard-
ized and is used for specification and control purposes.*
17.7. The Jominy End-Quench Hardenability Test
The Jominy test consists of quenching the end of a 1-in. round bar
under controlled conditions and determining the hardness (Rockwell C)
at intervals along the bar, beginning with the quenched end. The fixture
and the test bar are shown in Fig. 1 7.4. The test bar is
rough-machined
and normalized by heating to
approximately 150F. (85C.) above the
A
3
transformation. After holding at this temperature for 30 min. the bar
is cooled in air and finish-machined to the dimensions shown in Fig. 14.6.
It is then heated in a nonscaling atmosphere to about 75F. (40C.)
above A
z
and held 20 min., after which it is rapidly withdrawn from
the furnace by the collar, placed in the fixture, and a column of cold
The method has been tentatively standardized by American Society for Testing
Materials (A. S. T. M. Standards, Part 1A, 1955, A255-48T,
pp.
636-642) and by Society
of Automotive Engineers (Handbook, 1953,
pp.
112-120).
350
45'-.
\Unimpe<kdwaterjti
-/*-
I
1
+
water passing through a i/-in. pipe
and under pressure sufficient to rise
2i/
in. above the opening is directed
against the red-hot end until the
specimen is cold.
Two flat surfaces 1 80 deg. apart and
0.015 in. deep are ground longi-
tudinally on the bar, and Rockwell C
hardness measurements are taken at
%6
-in. intervals, beginning at the
quenched end and extending for
about 2 in. The hardness values are
plotted against distance from the
quenched end, which results in curves
similar to those in Fig. 17.5.
Owing to the method of quenching
and to the laws of heat flow, the
Jominy bar when cold has a structure
and hardness that result from cooling
rates which vary from about 600F.
(335
8
C.) per sec. on the quenched face
and about 420F. (235C.) per sec. at
%e
in. from the quenched end to
less than 10F. (5C.) per sec. at the other end of the bar. These are
equivalent to the center cooling rate of a i/g-in round bar quenched in
agitated cold water as one extreme and a 4-in. round bar quenched in oil
as the other.
Some typical curves obtained by the
Jominy test arc reproduced in
Fig. 17.5.* In these the distance is shown as inches from the quenched
end; in many curves it is shown as the number of sixteenths of an inch.
The horizontal hardness value indicated by the short dashed lines is the
average maxima obtained by quenching unalloyed steels of the median
carbon content indicated.
r
l-in. round
specimen
Waterat 7tttS'
'i-in. inside diam
orifice
From quick-
opening valve
.._'
Fig. 17.4. The Jominy standard
end-quench hardcnability test.
17.8. Relation of the End-Quench Test to Actual Cooling Rates and
the Selection of Steel by Hardenability
Jominy and a number of others, including a Society of Automotive
Engineers' committee on hardenability tests/ have done much work in
W. K. Jominy, Metal Progress, v. 38. 940.
pp.
685-690.
fS. A. E. Handbook,
1953, "Recommended Practice for Determining Harden-
ability,"
pp.
112-120
Hardenability
Rate of cooling at I300R, F. per sec.
351
420190 100 75 55 45
'/4
3/
8
'/
2
5/
8
3/
4
Distance from water cooled end, in.
/
Fig. 175. Jominy end-quench curves for carbon and low-alloy sleels containing
0.40 per cent carbon. (Jominy)
recent years in correlating Jominy distance and hardness with cooling
rates. Such a correlation is shown in Fig. 17.6, in which is plotted the
cooling rate at center and surface and at various radii, bar size, and the
position on the Jominy bar. By using the values given in Fig. 17.6, we
can readily tell what the hardness should be at the center, at one-half
radius, at three-fourths radius, and at the surface of any steel whose end-
quench curve has been determined.
Suppose, for example, that we want to select a steel for a li^-in. round
shaft that should be quenched in oil and tempered at a fairly high tem-
perature and that should have a minimum Rockwell C hardness of about
35 at the center and 40 at the surface. Tempering at 1000F. (540C.)
causes an average reduction in hardness of 15 to 20 numbers at the
surface and 7 to 10 numbers at the center; so the hardness of the steel as
quenched in oil should be 55 to 60 Rockwell C at the surface and 42 to 45
Rockwell C at the center. According to Fig. 17.6, the center cooling rate
in oil for a li^j-in. round bar is 25F. per sec. and the corresponding
distance on the Jominy bar is
% 6
in.; the surface cooling rate is about
90F. per sec, and the Jominy distance is slightly more than
% 6
in.
It is evident from the curves shown in Fig. 17.5 that our requirements
can readily be met by S.A.E. X3140 but not by the other four 0.40 per
cent carbon steels whose curves arc reproduced in Fig. 17.5. There are,
of course, many other low-alloy steels that will serve equally well for this
application.
352
Goolinq rate.deg. F. per sec. at 1300'F.
4
lllll 1 8 ? ssssa ^350=93^3355*
i i i i i i
/
/
/
/
A
3
.c
i/r
/
/
/
/
/..,
f Ml î
/
/
42
12
s
\1
m
1
Water-quenched rounds
n
2 J 4 5 6 1 8 9 10 12 14 16 18 20 24 32 48
Distance from quenched end, sixteenths of on inch
FlG. 17.6. Correlation of surface, center, and intermediate cooling rates, bar sizes,
and distance from quenched end of Jominy bar, for oil and water quenching round
bars. (Boegehold)
17.9. Virtues and Shortcomings of the Jominy End-Quench Test
The Jominy test can be made relatively quickly and cheaply, and the
curves for a particular lot of steel obtained in one laboratory check
closely with results from other laboratories. This agreement is fortunate
because even before a tentative standard was worked out by the American
Society for Testing Materials in 1942, it was put to good use in the war-
time development of the low triple-alloy steels.
In brief, the method used when the common alloying elements became
short and had to be conserved, and when insufficient time was available
for extensive mechanical and service testing, was to make up experimental
heats of the new triple-alloy steels, adjusting the composition according
to the expected effects of carbon and the alloying elements, and to deter-
mine the end-quench hardness characteristics. If the end-quench curve of
Hardenability
353
the new steel coincided closely with that of one or more of the
standard
higher alloy steels, it was reasonably certain that the new steel could be
substituted for these standard steels with considerable
assurance that it
would have the mechanical properties desired after heat treating to obtain
a definite hardness at a definite distance on the Jominy bar.
The Jominy
test will tell with accuracy whether the nose of the S
curve has been missed in quenching and that there is no pearlite in the
microstructure of quenched bars of certain diameters. It will not tell,
however, whether the structure as quenched is contaminated by bainite.
There is little difference in the hardness of martensite and that of acicular
bainite which forms just above the M
R
temperature, but there is a marked
difference in the properties of tempered
martensite and those of tempered
bainite of about the same hardness. Consequently, because the end-
quench test does not make this distinction, there is no guarantee that
structure and properties will be exactly what is required.
There are other shortcomings of the end-quench test. These are not
inherent in the test itself; rather, they arc precautions that should be
observed in applying the results too widely. If a steel is segregated or
otherwise heterogeneous (and many large heals are), Jominy
curves of
a specimen cut from a segregated bar will be
different from the curves
of specimens cut from a bar that is not segregated, even though the two
bars were rolled from the same heat. Another shortcoming is that the
test tells only the
hardenability of a round bar. To determine harden-
ability of other shapes, and especially of odd-shaped sections, such as
a gear blank, a rather complicated procedure must be used.
17.10. Hardenability Bands
About ten years ago, the steel industry, represented by the American
Iron and Steel Institute, and the major consumers of heat-treatable
carbon and low-alloy steels,
represented by the Society of Automotive
Engineers, worked out hardenability bands for a few steels, to be used for
specification purposes. The composition limits of three of these steels,
designated by the letter H (Table 17.1),
are somewhat wider than
ordinarily permitted. Three such bands for the steels given in Table 17.1
are shown in Fig. 17.7. The steelmaker must produce a material whose
hardenability is within the specified limits, and he is, therefore, given
slightly more latitude in chemical composition so that he can make ad-
justments of the analysis while the steel is still in the furnace. Thus, if
the chromium is on the low side and cannot be increased readily, he
can keep manganese, or molybdenum, high to ensure that the harden-
ability will be within the required limits.
354
Table 17.1 Composition Limits (1955) for Three Low-Alloy Steels for Which
Hardcnabihty (H) Is and Is Not Specified
Steel
Chemical composition, per cent
No.
C Mn Si Ni
Cr Mo
4140
4140H
8640
8640H
8740
8740H
0.38-0.43
0.37-0.44
0.38-0.43
0.37-0.44
0.38-0.43
0.37-0.44
0.75-1.00
0.65-1.10
0.75-1.00
0.70-1.05
0.75-1.00
0.70-1.05
0.20-0.35
0.20-0.35
0.20-0.35
0.20-0.35
0.20-0.35
0.20-0.35
0.40-0.70
0.35-0.75
0.40-0.70
0.35-0.75
0.80-1.10
0.75-1.20
0.40-0.60
0.35-0.65
0.40-0.60
0.35-0.65
0.15-0.25
0.15-0.25
0.15-0.25
0.15-0.25
0.20-0.30
0.20-0.30
Incidentally all H steels are made by a practice
that ensures fine grain,
which means that the hardenability is obtained solely by adjusting the
chemical composition.
17.11. Relation of Hardenability to Engineering
Properties
If two steels are treated so that their structure is the same, their
important engineering
properties will be the same most of the time.
The work of a number
of investigators
has established this beyond ques-
tion, and it is universally
accepted as fundamental
in ferrous metallurgy.
For steels used in highly stressed engineering
structures and machines,
the primary
object of heat treatment is to produce optimum properties
by controlling the size, character, and distribution of the carbide, and
the chemical composition
is the principal variable by which this control
can be exercised.
Thus, the amount of carbon is controlled to ensure that the martensite
or other phase formed by thermal ueatment-and the structure resulting
from a change in these constituents by temperingwill have the required
hardness and strength; and one or several alloying elements
are added, if
necessary, to ensure that the desired structure and properties will be at-
tained at the depth beneath the surface that is required for a specific
application.
Optimum properties result from a structure that is mostly
martensitic
before tempering.
Theoretically two steels having the same structure should have the same prop-
erties all the time. This, however, is an ideal to he approached but hardly attained.
There are a number
of factors other than structure that may affect properties. The
principal one is internal stress, which may be produced by any of a number of
manufacturing operations. Another is gas, taken up by the metal during melting,
refining, or fabrication. These, and possibly others, are undoubtedly responsible for
the fact that the properties of steels having the same structure vary considerably
from the normal in about one case in ten.
Hardcnability 355
4 8 12 16 20 24 28 32
Distance from quenched end of specimen.sixteenths of an inch
Fig. 17.7. Hardenability bands for three 0.40 per cent carbon low-alloy steels.
(Society of Automotive Engineers and American Iron and Steel Institute)
In ordinary heat treatment it is therefore desirable to have martensite
before tempering and, if possible, to avoid cooling at a rate slightly
lower than the critical (commonly known as slack quenching), in which
case bainite or a mixture of martensite and bainite will be formed. In
all but the very shallow-hardening steels, it is relatively easy to obtain
martensite upon quenching sections less than about 1 in. in cross section;
but if optimum properties are required in heavy sections, a steel with
high hardenability should be used. Slack quenching results in a low
yield ratio (low yield strength as compared with tensile strength) and
frequently lower elongation, reduction of area, and impact resistance than
are desired.
In general, a deep-hardening steel in which martensite will form in
quantity even in large sections will, after tempering, have a yield ratio
of 92 to 88 per cent; a shallow-hardening steel in which the structure is
mostly bainite will, after tempering to the same hardness, have a ratio of
85 to 75 per cent or even lower, depending on how much bainite is
formed. The effects of slack quenching are especially apparent in the
notch toughness of low-alloy steel at or below room temperature. Fre-
quently the impact resistance of a steel containing pearlite or bainite as
quenched is only a fraction of the impact value of the same steel when
356
tempered to the same hardness but quenched to ensure a structure that
was almost entirely martensitic before tempering.
Tempering
naturally reduces hardness and strength, but for a given
degree of tempering the reduction is greater if the quenched structure
contains much bainite than if it is primarily martensite. As a result, the
center portion of heat-treated heavy sections may be too soft and weak.
17.12. Relation of Tempering to Hardenability
Fundamentally,
tempering accomplishes two objectives: First, it re-
lieves dangerous
internal stresses, which may cause brittleness or even
warping
or cracking; and second, it improves ductility and toughness
by causing transformation of any hard, brittle martensite present to a
more ductile aggregate of ferrite and cementite. Concomitantly with
the increase in ductility, hardness and strength are decreased.
Since quenched
steel is almost never used in engineering structures
and machines
without tempering, it may be justifiably asked why end-
quench data are obtained on a quenched specimen instead of on one that
is quenched and tempered. The answer is that, if the Jominy bar were
quenched and tempered, we would not get the information we want and,
further, that such information as we would get might be misleading.
The final structure and properties of a quenched and tempered carbon or
low-alloy steel depend to a large degree on the quenched structure, and
the end-quench test gives a fairly accurate picture of the hardness and its
accompanying
structure (and the corresponding cooling rates) for sections
of various sizes quenched in various mediums. For that reason it is the
as-quenched structure that is the essential variable in determining the
final properties of a heat-treated steel, and it is very important that we
know how this structure
may be controlled.
17.13. Fundamentals of Calculated Hardenability
In 1942 Grossmann, a pioneer for many years in exploring the funda-
mentals ol quenching and tempering, presented his classic paper on cal-
culated hardenability.*
The data reported in this paper showed that the
hardenability
of most carbon and low-allow steels could be predicted
within a limit of error of 15 to 20 per cent, provided the complete
chemical composition and grain size were known and thai the austenite
before quenching was homogeneous and free from undissolved carbides.
The work was based on the concept that "pure" steel has a fundamental
hardenability due to carbon alone, and that the final hardenability can
M. A. Grossmann, Trans. Am. Inst. Mining Met. Engrs., v. 150, 1942.
pp.
227-259.
Hardenability
357
"0
0.10 0.20 0.30 0.40 0.50 0.60 0.10 0.80 0.90 1.00
Carbon, per cent
Fie. 17.8. Relation among ideal diameter, D carbon content, and grain size.
(Grossmann)
be calculated by multiplying this basic hardenability by a factor for each
chemical element present. Grain size may be taken into account either
in the fundamental hardenability of "pure" steel or in the final product
of multiplication.
In working out his method Grossmann had to make another and, as
it turned out later, considerably more questionable assumption. This was
that the hardenability should be based on a bar of ideal diameter (Di),
defined as the diameter (in inches) of a bar that would show no un-
hardened core in an ideal quench, which was in turn defined as a quench
in which the outside of the bar is instantly cooled to a temperature of
the quenching medium. This, of course, is a condition that is never at-
tained in practice, but Grossmann believed that it could be used as a
reference point.
358
3.80
3.60
i /
/
8.80
8.40
8.00
7.60
7.20
*.
J
**"/
/
Cr
3.40
3.20
3.00
/ j
/
/
r
J
1
/
/
\i
/
J
2.80
g2-60
^
/
Mn
right,
scale
k S< /
/
a*
6 00
c
e*2.40
1.2.20
"I" 2.00
3
,
/
,' /
'
/
560
-
ji I /
S
/
520^
4
80
a
i
y
2 1.80
M
4
40
1.60
1.40
1.20
1.00
/e x tension
4
00
/of Mn curve
3.60
u
0.80 1.20 1.60 2.00
i i i
3.20
c. 0.!10
1."
1
l.i
mi- nt,
2.
pei
)0 2.40
cent
2.80 3.20 3.60
FlG. 17.9. Multiplying factors Cor the live common alloying elements. (Boyd and
Field)
Using the assumption of ideal diameter and ideal quench, Grossmann
determined experimentally the hardenability factors for all of the ele-
ments commonly found in steel either as residuals or purposely added.
By using these factors it is easy to calculate the ideal diameter (D,) of
a bar that will just harden in an ideal quench, and by applying the proper
correction it is easy to calculate the diameter
(/)) of a bar Uiat will just
harden in any of the commonly used quenching mediums.
Basic data for the hardenability in terms of D, of "pure" steel, as de-
pendent on carbon content and grain size, are given in Fig. 17.8. The
multiplying factors for a variety of chemical elements are given in Fig.
17.9.* The factors shown in Fig. 17.9 arc those determined by Gross-
mann, modified in some cases by later data.f Using the factors in Fig.
17.9, the ideal diameter D, can be readily calculated as indicated by the
data in Table 17.2.
It is important to remember that all elements present (except the
gases) should be determined and taken into account in making the cal-
culation. Thus, if only carbon, manganese, and silicon were considered
for steel 1040 in Table 17.2, the ideal diameter would be 0.81 in., instead
L. H. Boyd and
J.
Held. "Calculation of the Standard End-Quench Hardenability
Curve from Chemical Composition and Grain Size," Contributions to the Metallurgy
of
Steel, No. 12, American Iron and Steel Institute, New York, Feb., 1946, 25
pp.
|- See, for instance, Trans. Am. Inst. Mining Met. Engrs., v. 154, 1943, pp.
386-394: or
"Symposium on Calculated Hardenability," ibid., v. 158, 1944,
pp.
125-182; or "Sym-
posium on Hardenability," ibid., v. 167, 1946,
pp.
559-734.
Hardenability
359
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Bl
CM CM CM CM
- c
o
O o d d
<
1
P
c>
CM c> CM
CJ
fiS
o * to
o O d d
I*
a cc r- r~
c
T
t >.
o
to
1
CO
g
(0
o
o
2
o
2
U
o
a- O z
X
X
X
of 0.98 in., an error of 17 per cent, which would increase if the amounts
of residual nickel, chromium, and molybdenum were higher than shown
in the table. Sulphur and phosphorus need not be considered if these
impurities are low, and no factors are given for them in Fig. 17.9. The
factor for 0.02 per cent phosphorus is 1.05 and the factor for about 0.03
per cent sulphur is 0.97 (sulphur decreases hardenability); consequently,
in most high-grade carbon and low-alloy steels the effects of these two
elements cancel out.
17.14. The Accuracy of Calculated Hardenability
Continued work over the past ten years has demonstrated that attempts
to calculate hardenability by the use of multiplying factors represent an
oversimplification of the problem. We now know that additional vari-
ables are involved, variables that are difficult to determine. Nevertheless,
the calculation of hardenability has been used with considerable success
in practice where its limitations are understood.
Recent work indicates that there probably are two hardenabilities,
one affecting the transformation of austenite to i>earlite and the other
the transformation of austenite to bainite, but there are few data which
make it possible to differentiate the two. For example, it has been shown
that nickel has more effect on the austenite-bainite than on the austenite-
pearlite transformation, so that the curve for the multiplying factor for
nickel may have a different location from that shoivn in Fig. 17.9, depend-
ing on the structure that results from the transformation. This un-
doubtedly explains the discrepancies found by several investigators in
attempting to confirm Grossmann's multiplying factors for nickel and for
some of the other alloying elements.
The most important fact 'that was unrecognized by Grossmann and
some of the other early workers in the field of calculated hardenability
is the intensifying effect that one alloying element may have upon
another. For example, if manganese, chromium, or molybdenum is
present, the effect of nickel on hardenability is much greater than its effect
as a single alloying element. Similarly molybdenum is more effective in
increasing hardenability in a steel containing nickel than in one contain-
ing chromium as the second alloying element.
As a result of these recent discoveries it can be concluded that no line,
either curved or straight (see Fig. 17.9), can be drawn that will show
precisely the effect of an alloying clement on hardenability in all types of
low-alloy steels. The calculation of hardenability can be used most
successfully and reliably on alloy steels containing only one alloying
element.
Hardenability 361
Distance from quenched end, in.'
1
l'"ic. 17.10. Kffect of boron on the end-quench characteristics of some carbon and
low-alloy steels. (American Iron and Steel Institute)
17.15. The Effect of Boron on Hardenability
One of the most intriguing metallurgical discoveries of the past ten
years or so is that very small amounts of boron greatly increase harden-
ability in some carbon and low-alloy steels. The increase results from the
addition of Q.002 to 0.003 per cent, as ferroboron, or as a complex alloy
containing 0.5 to 10 per cent boron and iron, aluminum, silicon, titanium,
and other elements in various combinations, or even as boric acid or
borax. Some typical end-quench curves for untreated and boron-treated
steels are reproduced in Fig.
17.10.*
American Iron and Steel Institute. "Report on Special Alloy Addition Agents,"
Contributions to the Metallurgy of
Steel, No. 9, The Institute, New York, 1942, 30
pp.
362
The steel to which boron is added should be fine-grained and thor-
oughly deoxidized as boron is an efficient deoxidizer, and trouble is
occasionally encountered in assuring that the boron is uniformly dis-
tributed in the metal. Very small amounts of boron are difficult to deter-
mine by chemical analysis, and it is not certain what residual percentage
is the most effective, nor have we any definite knowledge of the mech-
anism by which this element affects hardenability. We do know, how-
ever, that an addition of less than 0.001 per cent is ineffective, and that
if more than 0.003 or 0.004 per cent is added there may be a decided
decrease in hardenability.
The only definite knowledge to date is that boron increases harden-
ability by increasing the time available for the steel to cool past the nose
of the S curveit pushes the nose to the rightbut even here its effect
may not be enough to increase the hardenability of shallow-hardening
steels materially as Fig. 17.10 shows. Why it should increase the harden-
ability of 4023 but not of 4042 (Fig. 17.10) is not easily explained.
Data on the effect of boron on mechanical properties are erratic and
no definite conclusions can be drawn yet. It has no perceptible effect on
the properties of the steel as rolled, normalized, or annealed, nor on the
maximum hardness after quenching. In heat-treated steels it frequently
is responsible for improved yield ratio and ductility, but whether this is
a direct effect or a by-product of its effect on hardenability is impossible
to judge at present.
QUESTIONS
1. Explain the difference between "hardenability" and "maximum hardness"
of a steel.
2. Why is the "maximum hardness" of a steel less than the hardness usually
obtained in commercial quenching for a given carbon content?
3. Compare the hardness at the center of a 5 in. round of S.A.E. 4140 with
the hardness at the center of a 1 in. round of S.A.E. 1045 when both are
quenched in water.
4. How does the "delay time" vary with temperature in the isothermal trans-
formation of austenite?
5. Define "critical cooling rate."
6. What is the effect of a variation of grain size on hardenability?
7. What is the effect of a variation
in the homogeniety of the austenite on
formation diagram and hardenability?
8. How does deoxidation practice influence hardenability?
9. What is the relationship between the "C-curves" of an isothermal trans-
formation diagram and hardenability?
10. Discuss several methods of determining hardenability.
Hardenability 363
11. What is the hardness at the % radius of a 2 in. round of S.A.E. 4640
quenched in oil?
12. If a steel specification is based on a hardness of 50 Re for an equivalent
Jominy distance of six-sixteenths, which of the steels in Fig. 17.6 would
be acceptable?
13. What are the advantages and disadvantages of the Jominy hardenability
test?
14. What are "hardenability bands" and "hardenability steels?"
15. What are the advantages and disadvantages of "slack quenching?"
16. Define "ideal critical diameter" and "ideal quench."
17. What is the effect of a proeutectoid phase on hardenability?
18. Calculate the ideal critical diameter for the following composition:
C = 0.40 Grain size No. 5
Mn = 0.60
Si = 0.30
19. Calculate the ideal critical diameter for the following steel:
C = 0.40 Grain size No. 8
Mn = 0.60 Cr = 0.50
Si = 0.30 Mo = 0.20
20. What is the effect of boron on hardenability?
CHAPTER
Special Purpose Steels
18
Frederick Leo Coonan, D.Sc, Professor and Chairman,
Department of Metallurgy and Chemistry, U. S. Naval
Postgraduate School, Monterey, California
Jules
Washington Lindau, III, M.E., Associate Professor
of Mechanical Engineering, University of South
Carolina, Columbia, South Carolina
oOME types of service in industry require
unusual properties in metals. Many of the alloys discussed in the previous
chapters are not entirely satisfactory for these specialized requirements;
many alloys that are satisfactory do not conveniently fall into the estab-
lished patterns developed in the earlier chapters. Included in this group
are alloys particularly suitable for
(1)
tools and dies,
(2)
corrosion and
heat resistance,
(3)
magnetic applications,
(4)
wear resistance,
(5)
low
temperature, and
(6)
ultra high-strength service.
The alloys in two of these categories will be treated in separate chapters.
Chapter 19 is concerned with tools and dies, and Chapter 21 with wear
resistance. Most of the discussion here will be concerned with steels
developed for resistance to corrosion and, to a lesser extent, with alloys
utilized in service involving magnetic effects.
18.1. Classes of Stainless Steels
The element chromium combines readily with oxygen forming an
oxide that is thin, tightly adherent, self-healing, and that protects the
metal itself from further attack. When dissolved in iron, it forms an alloy
that has similar stainless and oxidation-resisting properties.
The chromium bearing steels may be divided into three classes:
(1)
special purpose steels containing 3.5 to 10 per cent chromium with or
without 0.5 to 4 per cent silicon, nickel, molybdenum, or tungsten as addi-
tional alloying elements;
(2)
corrosion- and heat-resisting steels con-
taining more than 10.0 per cent chromium and not more than 2 per cent
364
Special Purpose Steels 365
of another alloying element; and
(3)
corrosion- and heat-resisting steels
containing more than 10 per cent chromium and more than 2 per cent of
one or more other alloying metals.
Chromium steels containing 3.5 to 10%
chromium have better cor-
rosion and heat resistance than the S.A.E. low-alloy steels containing
chromium (see Fig. 18.3) and have excellent properties at elevated tem-
peratures. Steel with about 0.10 per cent carbon, 4 to 6 per cent chro-
mium, 0.40 to 0.75 per cent silicon, and about 0.50 per cent molybdenum
is used widely in oil-refining equipment. Another steel in this class is
silchrome, a material commonly used for automobile- and
airplane-engine
valves and containing about 0.50 per cent carbon, 7 to 10 per cent
chromium, and 1.00 to 3.75 per cent silicon. Silchrome is resistant to
attack by the exhaust gases of
internal-combustion engines and has satis-
factory strength and hardness at a dull red heat. Moreover, it costs
considerably less than the highly alloyed valve materials containing
nickel, chromium, and silicon.
The most important high-alloy steels in which chromium is the only
alloying element in large amounts are those included in class 2. These
may be divided into four groups:
2/1. Low-carbon, high<hromium steelusually called stainless iron
containing 12 to 18 per cent chromium and less than about 0.14 per cent
carbon.
2B. Cutlery steels containing 12 to 16 per cent chromium and 0.20 to
0.60 per cent carbon.
2C. Tool and die steels containing 12 to 18 percent chromium and
0.70 to 2 per cent carbon.
2D. Heat-resisting steels containing 20 to 30 per cent chromium, with
less than 0.50 per cent carbon for hot-worked material, and with 0.50
to 2.5 per cent carbon for castings.
Small amountsgenerally less than 2 per centof nickel or other metals
are occasionally added to the plain chromium steels. With the exception,
however, of 0.15 to 0.50 per cent sulphur to improve machinability, the
addition of small percentages of a second alloying element is not common.
The principal corrosion- and heat-resisting steel of class 3 is the fa-
miliar low-carbon 18 per cent chromium, 8 per cent nickel alloy known
to metallurgists and engineers as
188. This is a very important high-
alloy engineering steel. Despite the cost, the amount of 188 used per
year has increased enormously. Most of the 188 steels contain no
other alloying element. A few that must have exceptional stability at
elevated temperatures contain larger percentages of chromium nickel,
366
2000
-hromium.ato
10 20
|
nic per cent
30 40
1 1
H
1800
-3200
1600
,w
elf
-2800
1400
-2400
UJ
<->l200
/*/p/ a
cr
T3
u" 1000
I
800
Q.
3a.
nmcfW
h20Q0-
Up to +
gcim T7
1-
3
-1600
1
^**
*.
3fc_
/
T]
V
E
600
'"Sw
^_
i
-1200
|
\
V 1
|
400 1
i|
-800
1
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200
y4// ha
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h>
-400
1
B
n
1
Alpha
+
"n
Sigma
, |
-0
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'
-200
1
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1
1
if
Zhr
2C
om um
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pet ce
*
-.f
) scI
Fro. 18.1. Iron-rich portion of the iron-
chromium phase diagram. (Kinzel and Crafts)
plus cobalt, tungsten, or molyb-
denum, and some contain ti-
tanium or columbium, added
to stabilize the carbon and pre-
vent intergranular corrosion.
This is discussed later.
In the past several years new
manganese bearing and disper-
sion hardening types of austeni-
tic steels have been developed.
These will also be discussed in
a later section of this chapter.
! 18.2. Constitution of High-
Chromium Steels
Chromium in amounts less
than 30 per cent dissolves com-
pletely in carbonless iron. It
has marked effects on the tem-
perature of the /f
3
transforma-
tion, where alpha changes to
gamma iron, or vice versa, and
on A
4
, where gamma changes
to the high-temperature modi-
fication of alpha (delta) iron,
or vice versa. These effects are
important in commercial high-
chromium steels and should re-
receive some attention.
A portion of the iron-chromium diagram for alloys containing less than
50 per cent chromium is shown in Fig. 18.1.+ From this diagram it is
evident that adding 8 per cent chromium to carbonless iron lowers the
A
t
point slightly and lowers the A
4
point nearly 275F. (15()C.) . Further
additions of chromium raise /J., and at the same time lower A
4
until, with
the addition of about 12 per cent chromium, these two points merge. The
result is what is known as the gamma loop and is a characteristic of
several binary alloy systems of which iron is one component.
The significance of the gamma loop is plain. If an alloy containing 10
per cent chromium and 90 per cent iron is heated slowly, no change in
+
A. B. Kinzel and Walter Crafts, The Alloys
of Iron and Chromium,
Vol. I, Low-
Chromium Alloys, McGraw-Hill Book Company, Inc., New York, 1937. p. 43.
structure occurs until a temperature of 1650F. (900C.) is reached.
Here the alpha solid solutions changes to gamma solid solution. If heating
is continued, the gamma remains unchanged until a temperature of
2350F. (1200C.) is reached, where it changes to alpha (delta) solid
solution. On slow cooling, the reverse changes take place. If, now, an
alloy containing 15 per cent chromium and 85 per cent iron is heated,
no change (except grain growth) takes place between room temperature
and the melting point, and, conversely, no structural change occurs in
cooling. Alloys containing more than 12 per cent (and less than 30 per
cent) chromium and very little or no carbon have no allotropic trans-
formations.
The concentration limits of the gamma loop are changed by carbon,
which moves the extreme limit of the loop to the right and at the same
time increases the width of the duplex alpha-plus-gamma field. Thus,
the loop, which with negligible carbon extends to 12 per cent chromium,
extends to about 18 per cent chromium with 0.40 per cent carbon. These
relationships are complicated further by the carbides which are formed
by chromium and which together with iron carbide (Fe
3
C) form
(Cr.Fc)
7
C
3
and (Cr.Fe)
4
C in the commercial high-chromium steels. The
iron-chromium carbides are partly soluble in the gamma solid solution
but not in the alpha solid solution and may be retained in supersaturated
solid solution by quenching, in a manner analogous to the retention of
iron carbide in the gamma iron of unalloyed high-carbon steel.
18.3. Relation of the Constitution of High-Chromium Steels to
Their Heat Treatment
From the foregoing discussion it is evident that we should know from
the composition whether high-chromium steels will or will not respond
to heat treatment. Thus, a steel containing 12 to 18 per cent chromium
and less than 0.13 per cent carbon (class 2A,

18.1) will or will not
harden depending upon the relative amounts of chromium and carbon.
If the steel contains 0.12 per cent carbon and 13 per cent chromium,
some austenite is formed if the steel is heated to 180()F. (980C.) , and
this transforms to martensite upon quenching. If the steel contains 0.06
per cent carbon and 16 per cent chromium, no phase changes take place,
and the steel does not harden when quenched from 1800F. (980C).
Low-carbon high-chromium steels in which no phase changes take place
remain ferritic in structure at all temperatures. They are relatively soft
and ductile, and the only change caused by heating is grain growth
which reduces the ductility.
Fig. 18.2. Structure of (A) oil-quenched cutlery steel containing 0.30 per cent
carbon and 12.7 per cent chromium, and (B) oil-quenched high-carbon chromium
steel containing 0.70 per cent carbon and 17.5 per cent chromium; etched. 500
X-
(Kinzel and Forgeng)
Cutlery steels containing 12 to 16 per cent chromium and 0.20 to 0.60
per cent carbon (class 2B,

18.1) undergo a phase change: when they
are heated to about 1800F. (980C.) , the alpha solid solution changes
to gamma and the carbide goes into solution. These steels respond to
heat treatment very much like unalloyed high-carbon steels. In a steel
containing 12 per cent chromium the structure is entirely pearlitic with
only 0.3 per cent carbon when the steel is cooled slowly; it is, conse-
quently, martensitic when the steel is cooled rapidly (Fig. 18.2)
.*
These
cutlery steels differ from unalloyed steel containing 0.80 to 0.85 per cent
carbon chiefly in that the chromium lowers the critical cooling rate, that
is, they become as hard when quenched in oil, or even in air, as an un-
alloyed high-carbon steel when quenched in water.
Since steels containing 12 to 14 per cent chromium and 0.30 to 0.40
per cent carbon correspond to unalloyed "eutectoid" steels, it follows
that high-chromium steels containing about 1 per cent carbon (class 2C,
18.1) are hypereutectoid and, when quenched and tempered, have

numerous excess carbide particles in the microstructure (Fig. 18.2B)
,
which increase the wear resistance and make the steels useful for tools
and dies.
Courtesy of A. B. Kinzel and W. D. Forgeng.
Special
Purpose Steels
369
The heat-resisting steels containing 20 to 30 per cent chromium (class
2D,

18.1) may or may not respond to heat treatment, depending upon
the carbon content. The carbon range for this class is 0.5 per cent or less
for steels which are hot or cold worked, and from 0.5 to 2.5 per cent
for those which are used in the form of castings. At room temperature
the steels containing about 25 per cent chromium and less than 0.70 per
cent carbon are ferritic; their structure consists of alpha solid solution
and the carbide (Cr,Fe)
4
C, and no phase changes take place in heating.
These steels cannot be hardened; they can, of course, be annealed if
cold worked.
The higher carbon grades respond to quenching, but this treatment
is seldom used as no advantage results. High-carbon castings containing
20 to 30 per cent chromium are very hard as cast and must be annealed
if machining is necessary.
The price of ferrochromium (70 per cent chromium) used in the manu-
facture of high-chromium steel varies inversely with the carbon per-
centage. Ferrochromium containing less than 0.5 per cent carbon, which
must be used to produce high-chromium steels with low carbon per-
centages, is much more costly than ferrochromium containing 4 to 6
per
cent carbon. The economic factor is, therefore, important in selecting a
high-chromium steel for a certain application; the advantages
resulting
from the use of a steel containing less than 0.12 per cent carbon, instead
of one containing 0.40 per cent, must be balanced against the higher
cost of this material.
18.4. Mechanical Properties of High-Chromium Steels
As remarked in a previous chapter (16.4),
chromium has little
solid-solution effect, that is, when dissolved in alpha iron, it strengthens
the iron relatively little. This is shown by the data in Table 18.1 for
annealed steels. If the composition is such that the steel undergoes a
phase change, the principal effect of chromium is to increase the harden-
ability, thus producing marked changes in properties with relatively
slow cooling rates.
The tensile properties of high-chromium steels cooled in air or oil
depend obviously upon how much carbon is present and upon what
proportion of the carbides dissolves in the gamma solid solution at high
temperatures. Some typical values for tensile properties of low-carbon
12 to 15 per cent chromium steel and for cutlery steel are given in Table
18.2. The high-chromium steels are more resistant to tempering than
carbon and low-alloy steels. Increasing the tempering temperature has
little effect on the properties until a temperature of 950 to 1050F. (510
370
to 565C.) is reached when there is a sudden decrease in tensile strength,
yield strength, and hardness and a moderate increase in ductility.
The impact resistance of the quenched and tempered low-carbon and
medium-carbon (cutlery) steels is in general satisfactory, except when
the steels are tempered at, or cooled slowly through, the temperature
range 875 to 1000F. (470 to 540C.) . For reasons yet unknown this
treatment causes brittleness, which is manifested by very low notched-
bar impact resistance. The endurance limit of both the hardenable and
the unhardenable high-chromium steels is about one half of the tensile
strength or approximately the same as for carbon and low-alloy steels.
The modulus of elasticity, however, seems to be somewhat higher; most
available data indicate that it is between 31 and 32 million lb. per sq. in.
18.5. Corrosion and Oxidation Resistance of High-Chromium Steels
Although high-chromium steels are more resistant to certain kinds of
corrosion than any other ferrous material, they are not corrosion re-
sistant in the broadest sense of the term. Neither are they always stain-
less. In fact, to some forms of attack, they are no more resistant than the
unalloyed carbon steels.
Steels containing 10 per cent or more chromium are resistant to oxidiz-
ing mediums and to corrosion caused by fruit juices, food products, and
beverages. The low-carbon 12 to 18 per cent chromium steels are re-
sistant to a large number of organic acids and to all concentrations of
nitric acid, except 65 per cent boiling nitric acid. They are also resistant
to strong alkalies and to many salt solutions but are readily attacked by
chlorides and other halides. Sulphuric acid, except when concentrated
and cold or when containing nitric acid, and hydrochloric acid of all
concentrations attack these steels readily.
In general, corrosion resistance is a function of the amount of chro-
mium dissolved in the iron, but the relation is not direct. Corrosion re-
sistance is not important with low percentages of chromium; it becomes
more pronounced as the chromium increases from 4 to 10 per cent and
increases very rapidly with slightly more than 10 per cent. The corrosion
resistance is thought to be due to the formation of a thin, tight, adherent
film of chromium-iron oxide which, if broken, is self-healing unless the
corrosive agent (as, for example, hydrochloric acid or chlorides) dis-
solves the film as rapidly as it is formed. It is generally assumed that in
order to produce a self-healing film there should be at least one atom
of chromium to seven atoms of iron. Increasing the chromium from 10 to
30 per cent increases the corrosion resistance, but the increase is not
proportional to that of the chromium.
Table 18.1. Effect of Chromium on the Tensile Properties of Annealed Steels
Containing 0.10 Per Cent Carbon*
Chromium, Tensile strength, Yield strength, Elongation in Brinell
per cent lb. per sq. in. lb. per sq. in. 2 in., per cent hardness
50,000 38,000 44 90
5
65,000 26,000 38 135
12 72,000
35,000 36
140
15.5 75,500
42,500 33 148
17 80,000 47,000 30 155
27 84,500
55,000 26 160
Based on E. E. Thum, Metal Progress, v. 29, No. 6, 1936, pp.

49-57. 104.
TABU 18.2. Typical Tensile Properties of High-Chromium Steels*
Composition, Quenched and Tensile Yield Reduc-
per cent tempered at strength, strength, Elongation tion of
lb. per
sq. in.
lb. per
sq. in.
in 2 in., area,
C Cr F. C.
per cent per cent
400 205 146,000 135,000 15 38
600 315 145,000 134,000 15 40
0.09 12.2 800 425 143,000 134,000 16 46
1000 540 135,000 120,000 20 52
1200 650 95,000 79,000 29 60
400 205 170,000 160,000 8 18
600 315 168,000 160,000 10 20
0.09 800 425 166,000 160,000 15 45
1000 540 160,000 148,000 18 46
1200 650 90,000 83,000 21 50
600 315 240,000 208,000 3 5
800 425 245,000 210,000 5 20
0.30 13.0 1000 540 250,000 195,000 7 20
1200 650 160,000 138,000 12 38
1400 760 140,000 105,000 14
i
45
Based on data by 1).

J.
Giles, The Book of
Stainless Steels, American Society
for Metals, Cleveland, 1935, pp.
267-276; and O. K. Parmiter, Trans. Am. Soc. Steel
Treat., v. 6, 1924, pp.
315-340.
372
Carbides, if not in solution, have a deleterous effect on corrosion re-
sistance. For this reason, the cutlery steels should be heat treated if op-
timum corrosion and stain resistance is desired. The alloys containing
carbon in excess of that which dissolves in the gamma solid solution at
high temperatures are not so resistant to oxidizing mediums as the lower
carbon steels.
The high-chromium steels rust slowly when exposed to the atmosphere,
but the thin coating can readily be wiped off, leaving the surface under-
neath unaffected. Steels containing 12 to 14 per cent chromium and less
than 0.12 per cent carbon are, therefore, widely used for automobile and
building trim. In industrial at-
mospheres, especially those con-
taining sulphur, the high-chro-
mium steels may pit badly.
The resistance of the high-
chromium steels to oxidation at
elevated temperatures increases
with the chromium but, as
shown in Fig. 18.3, the increase is
not important until more than
10 per cent chromium is present.
With higher chromium percent-
ages the increase in oxidation re-
sistance is fairly uniform until
about 20 per cent chromium is
present, when the resistance is
very high. The data shown in
Fig. 18.3 were obtained* by heat-
ing 0.5-in. cubes with ground sur-
faces for 48 hr. at 1830F.
(100()C.) . With the exception
of a few iron-nickel-chromium
and iron-chromium-aluminum
alloys, steel containing 20 to 35 per cent chromium is the most resistant
of the ferrous alloys to high-temperature oxidation.
45
40
35
JO
25
8 20
usfe
~bon
./c

e/5
Chromiurr stee Is
|
V
'faint ess sree/s
\
\
Vj
Chrome ron
1
1
12 16 20 24
Chromium,percent
28 J2
Fie. 18.3. Effect of chromium on the re-
sistance of chromium steels to oxidation at
1830F. (lOOO-C). (MacQuigg)
18.6. The Constitution of 18-8
Nickel (as well as chromium) is soluble in both alpha and gamma
iron. When in solution it (1)
lowers the A
3
point, where alpha iron
C. E. MacQuigg. The Book oj Stainless Steels, American Society for Metals. Cleve-
land, 1935, pp.
351-368.
373
j-2800uJ
-2400
i
-2000
u
-1600"
-1200
J
-800
L
2800 v
-2400
g
-2000
5 10 150 5 10 150 5 10 15
N ickel .per cent
Fig. 18.4.
4 born)
Effect of chromium on phase changes in iron-nickel alloys. (Bain and
transforms to gamma on heating and where gamma transforms to alpha
on cooling, and
(2)
makes these allotropic changes, especially the one
on cooling, very sluggish. A small portion of the iron-nickel phase dia-
gram is shown in the upper left corner in Fig. 18.4.+ As noted on a pre-
vious page
(p. 366) , chromium restricts the
temperature-concentration
region where the gamma solid solution is stable, that is, it produces a
gamma loop; nickel, on the contrary, increases the limits of this area.
When chromium is added to the iron-nickel solid solution it dissolves.
The first effect is a lowering of the delta- (alpha-) gamma transforma-
tion temperature and a widening of the field where delta (alpha) is
stable. This is apparent from the sections of Fig. 18.4 showing phase
relations for alloys containing S and 6 per cent chromium. As the chro-
mium is increased, the area of the delta (alpha) region is increased
f
E. C. Bain and R. H. Aborn, in Metals Handbook, American Society for Metals,
Cleveland, 1939,
pp.
418-422.
374
further, and with 9 per cent or more the low-temperature area where
alpha is stable is also increased. Increasing the chromium thus moves
the boundaries of the gamma and the alpha-plus-gamma phase regions
to the right.
Consider now the small diagram at the lower left in Fig. 18.4 for 18
per cent chromium: if 3 per cent nickel is added and the alloy is heated,
no phase changes take place at any temperature. If, however, 8 per cent
nickel is present and the alloy is heated, a phase change occurs at about
660F. (350C.) , and some of the alpha solid solution changes to gamma
solid solution. If the alloy is heated still further, this allotropic change
continues until at 1200F. (650 C.) all the alpha has changed to gamma.
There is no further change if the heating is continued almost to the melt-
ing point. Now, if the alloy is cooled, the reverse changes should take
place, that is, gamma should start to transform to alpha at 1200F. and
should be completely transformed at 660F. Owing, however, to the
sluggishness of the reactions, only a small amount of alpha is actually
formed in slow cooling, and it is relatively easy to suppress by rapid
cooling the formation of any and thus to obtain at room temperature an
alloy that is entirely austenitic.
Austenitic steels are strong and ductile and are readily deformed cold
into a variety of useful products. For a combination of maximum re-
sistance to corrosion by certain mediums, austenitic structure at room
temperature, and other useful properties the most economical composition
is 18 per cent chromium and 8 per cent nickel, with carbon as low as
is commercially possible. With this composition it is advisable to guard
against the presence of any alpha by heating the material to 1830 to
2010F. (1000 to 1100C.) and quenching it in water or in an air blast.
Increasing the nickel to 10 per cent or more increases the stability of
the austenite but also increases the cost.
18.7. The Role of Carbon in 18-8
If 188 could be made free from carbon, many of the troubles
of the
manufacturers and users of this steel would be over. Unfortunately, how-
ever, this is difficult, and even if made by the best commercial prac-
tice, 188 contains 0.06 and frequently as much as 0.12 per cent of this
element.
Unfortunately also, only about 0.01 or 0.02 per cent carbon
is soluble in the iron-chromium-nickel austenite at room temperature.
This solubility increases with increasing temperature as shown in Fig.
Carnegie-Illinois Steel Corporation has produced 18-8 with carbon well under
0.06 per cent by feeding oxygen into the molten bath during refining. See Electric
Furnace Steel Proceedings, Am. Inst. Mining Met. Engrs., v. 3, 1945,
pp.
107, 108, 127.
IOUU
d?.
1
CL+Ls
--
--
--
~-
3*y
+l
^
,-
r^ ,_ -2400
--
__
--
~~
-r
____
--
-
-T ,'
y+L+carbide
-?fififl
I000
Y
CUUU
LL
i(a;/* A>
'
r
?
H600
*?
D
7
'
""!
""
*'-
CO
"!
-1200-^
D.
|
500
. a+vtcarbide
E
-800,"
r
i tearbi'a n
e
-400
i
q
i
i
1 i C i
:cr pon
2
pe- cent
0.3 0.4
Fig. 185. Effect of temperature on the solubility of carbon in iron-chromium-
nickel austenite. (Kinzel and Franks)
Fig. 18.6. Structure of (A) quenched 18-8 and (B) quenched and reheated 18-8
showing carbide precipitation at grain boundaries; etched. 250
X-
(Kinzel and Forgeng)
376
18.5,f
until at 1830F. (1000C.) 0.14 per cent, and at 2010F. (1 100C.)
0.22 per cent is soluble. One advantage of quenching 188 is that the
carbon is held in supersaturated solution at room temperature. This
carbon, however, will precipitate if conditions are favorable. Severe
cold working may cause some precipitation; in additionand this is most
importanton heating to a high temperature, as in welding or in service
in superheaters or other equipment operating at elevated temperatures,
some carbon precipitates from solution.
If this were the only thing that happened, it would not be serious.
However, when the carbon precipitates, it is apparently thrown out of
solution at the grain boundaries as a chromium carbide, thus impover-
ishing the austenite grains adjacent to the boundaries in chromium and
making them susceptible to corrosion. The usual structure of quenched
188 showing the polyhedral grains of austenite is pictured in Fig.
18.6A,* the carbides which have precipitated at the grain boundaries
are shown in Fig. 18.6B.
Carbide precipitation occurs frequently if 188 is heated in the range
570 to 1470F.
(300 to 800C.) , making the material very susceptible
to a form of attack known as intergranular corrosion or intergranular
disintegration. It is very hard to detect and was the cause of a number
of disastrous failures before a cure was found.
Carbide precipitation can be prevented by reducing the carbon to
0.02 per cent or less, which is not easily attained commercially, and it
can be reduced innocuous by adding titanium equivalent to 5 times the
carbon content, or columbium equivalent to 10 times the carbon content,
to the steel when it is made. Both of these elements combine with the
carbon to form a stable carbide and prevent the carbon from combining
with the chromium. When
188
is "stabilized" with titanium or colum-
bium it can be used at elevated temperatures or can be welded without
danger of premature failure.
18.8. Properties of 18-8
The austenitic chromium-nickel steels can readily be cold rolled into
sheet or strip or cold drawn into wire. They can also be riveted, soldered,
or welded. Welding is now commonly used for fabricating 188. Because
of its high electric resistivity and low thermal conductivity, spot welding
has been especially successful. This method of joining is used in the
f
A.. B. Kinzcl and R. Franks, The Alloys of Iron and Chromium, Vol. II, High-
Chromium Alloys, McGraw-Hill Book Company, Inc., New York, 1940, p. 275.
Courtesy of A. B. Kinzel and W. D. Forgeng.

377
construction of the stainless-steel streamlined trains which have attracted
much attention recently.
Austenitic chromium-nickel steel has, as quenched, a fairly high tensile
strength with high ductility and resistance to impact (Table 18.3). It
hardens rapidly by cold work (Table 18.3) . The increase in tensile and
in yield strength is greater and the decrease in ductility is considerably
less than that caused by comparable cold working of low-carbon steel.
Carbon increases the strength (Table 18.3) . The endurance ratio of
quenched 188 is 0.40 to 0.45, that is, somewhat lower than the usual ratio
for carbon and low-alloy steels. Peculiarly, the endurance limit is usually
higher than the proportional limit.
Table 18.3. Typical Mechanical Properties of Austenitic Chromium-Nickel Steel
Composition,
per cent
Tensile Yield Elonga- Reduc-
Condition of specimen strength,
lb. per
strength,
lb. per
tion in
2 in.,
tion of
area,
Izod
impact.
C Ct Ni sq. in. sq. in. per cent per cent ft-Ib.
0.16 18.0 8.0 Water-quenched bars 90,000 37,500 68 78 Ill
0.17 18.0 8.0 Watcr-qucnchcd bars 96,500 40,000 65 75 103
0.07 17.9 8.5 Cold-rolled bars, 15% 142,700 117,800 30 61 88
0.07 17.9 8.5 Cold-rolled bars, 40% 227,600 201,000 11 43 17
0.07 18.0 9.5 Cold-drawn wire, 60% 263,000 4
0.16 16.0 10.2 Cold-drawn wire, 85% 273,000 3
0.07 18.0 8.0 Water-quenched sheet 86,400 33,500 63
0.16 18.0 8.0 Watcr-qucnchcd sheet 93,300 46,600 57
0.06 18.0 14.0 Watcr-qucnchcd bars 80,000 63 75
0.14 18.0 14.0 Water-quenched bars 90,000 53 70
0.14 25.0 20.0 Watcr-qucnchcd bars 90,500 50,000 47 63 90
The coefficient of expansion of 18-8 is about 50 per cent higher than
that of carbon steels, and the thermal conductivity at normal temperatures
is about 0.04 cal. per sec. per sq. cm. as compared with 0.16 cal. per
sec. per sq. cm. for low-carbon steel. The stress-strain curve of 188 is
curved from the origin. This steel has, therefore, a low proportional
limit, no yield point, and no true modulus of elasticity. The secant
modulus varies from 26 to 28 million lb. per sq. in. The austenitic chro-
mium-nickel steels have exceptionally high resistance to creep. This is
discussed in a later chapter.
Nickel increases the resistance of low-carbon 18 per cent chromium
steels to corrosion by nonoxidi/.ing mediums, permitting these materials
to be used economically in environments where the high-chromium steels
containing no nickel would be attacked rapidly. These austenitic steels
378
are resistant to many organic acids, organic solvents, and oils which
attack the high-chromium steels. Their resistance to staining in the at-
mosphere is also higher than that of the plain chromium steels. Their
oxidation resistance is high, especially at 1650F. (900C.) , and if the
chromium and nickel are both increased, they may, if not highly stressed,
be used at temperatures
as high as 2010F. (1100C). The corrosion
and oxidation resistance and the strength and stability at high tempera-
ture can be increased by the addition of silicon, tungsten, molybdenum,
cobalt, or columbium.
18.9. Recent Developments in Stainless Steels
There are a number of elementsfor example, carbon, nitrogen, and
titaniumthat affect the phase boundaries of the 18 per cent chromium
section of the ternary iron-chromium-nickel diagram. As a result, the
188 alloy may have a duplex structure of ferrite and austenitc unless
precautions are taken to prevent it. It is also evident that lowering the
nickel slightly (see the 18 per cent chromium section in Fig. 18.4) will
make it impossible to produce a structure consisting entirely of austenite
even by quenching. In fact, the 188 composition is so critical that some
metallurgists believe that with very low carbon and 8 per cent or slightly
less nickel, an austenitic structure is possible chiefly because the small
percentage of nitrogen introduced during metling prevents normal phase
changes. In practice, an austenitic structure is assured by rapid cooling
(Sect. 18.6) and by keeping the nickel well over 8 per cent, especially if
the carbon is less than about 0.08 per cent.
The ferrite chromium-nickel steels, which are magnetic, are much
stronger and less ductile than the austenitic material. They have not
been used industrially, as their properties, including corrosion resistance,
are not enough better than those of low-carbon 16 to 18 per cent chro-
mium alloys
(
which are also ferritic) to justify the much higher cost.
One of the disadvantages of the austenitic chromium-nickel steels is
that high strength can be attained only by cold workingheat treatment
is used solely to ensure the proper structure. This limits the application
of such cold-worked material as sheet, tubes, strip, and wire products.
Some years ago, Smith, Wyche, and Gorr* discovered that by adding
0.50 to 1.00 per cent titanium, which is a ferrite former, to a steel contain-
ing about 0.07 per cent carbon, 17 per cent chromium, and 7 per cent
nickel a ferritic structure can be readily produced; this structure can
R. Smith, E. H. Wyche, and W. W. Gorr. Trans. Am. Inst. Mining Met. Encrs.,
v. 1G7, 1946,
pp.
313-345.
Special Purpose
Steels
379
be hardened by precipitation of a
carbide that is retained in super-
saturated solution in the ferrite matrix by a suitable heat treatment.
The heat treatment consists of heating the alloy to
temperatures be-
tween about 1400 and 2000F. (760 and 1095C.) to produce a homo-
geneous austenitic structure, followed by cooling to room temperature
(at any rate faster than slow furnace cooling) . The alloy is then reheated
to temperatures between 950 and 1050F. (510
and 565C.) to precipi-
tate the hardening constituent.
This steel, known as stainless W, has many desirable properties. Repre-
sentative mechanical
properties are given in Table 18.5. In addition to
the high tensile strength, it has a high yield strength and a definite
modulus of elasticity, which is about 28 million lb. per sq. in. The en-
durance limit on polished
specimens varies from 80,000 to 90,000 lb. per
sq. in., depending on the treatment; for specimens of sheet having a
normal rolled surface it is about 30 per cent of the tensile strength.
Stainless W has much lower ductility than the austenitic material,
which in view of its
strength and structure is not unexpected. The steel
is readily welded. Its corrosion resistance is apparently the same as that of
austenitic 188, and it is not subject to intergranular embrittlement.
This steel has been the forerunner of a group developed to meet a need
in industry for austenitic alloys that respond to a hardening heat treat-
ment. Approximate compositions of representative members are given in
the table below.
Table 18.4. Nominal Composition of Prccipitation-Hardenahle Grades
Designation C Cr Ni Other
Stainless W
17-4PH
0.07
0.04
17
16.5
7
4
0.70Ti, 0.20A1
4.0Cu, 0.35Cb + Ta
17-7PH
AM350
0.07
0.07
17
17
7
4
I.IOAI
2.75Mo
17-10P
17-14 Cu-Mo
HNM
0.12
0.12
0.30
17
16
19
10.25
14
9.5
0.25P
2.5Mo, 3Cu, 0.45Cb, 0.25Ti
3.5Mn, 0.30P
Data from Roach and Hall, Materials and Methods, April 1956, p.
144.
The steels, except Am350, noted in the table, contain elements forming
compounds that are soluble in austenite at elevated temperatures but
that may be retained in a supersaturated condition in the phase existing
Table 18.5. Typical Room-Temperature Mechanical Properties of Precipitation-
Hardcnable Grades
Ten Yld. Elong. Hard- Charpy Endur.
Str. Str. in ness,
Im- Limit
Designation Condition 1000 1000 2 in. Rock- pact 1000
psi psi
%
well C Ft-lb psi
Stainless W Annealed 135 95 7 25
_
Aged
'A
hr. at
950
F. 210 195 7 43

80
Aged
Vi
hr. at
1050
F. 190 170 8 39

17-4PH Annealed 150 110 12

Aged 1 hr. at 900
F. 195 180 13 43 19 90
17-7PH Annealed 130 40 30 R
b
85
^_ ^_
Treated at 1400
F. 145 100 9 31

Aged at
950
F. 215 200 8 45 6 78
AM350 Annealed 186 52 22 R
b
94 100

Subzero cooled 197 110 12 40

Tempered at 750 F. 199 159 11 41 51 80
17-10P Annealed 89 37.5 70
Rb82
120'
Aged 137 88 25 30
40'

17-14 Cu-Mo Annealed at 2250
F.
and aged 86 42 45 R
b
80 110'

HNM Annealed at 2000 F.
aged at 1200
F. 153 110 26.5 34 18

Data from Roach and Hall, Materials and Methods, April 1956, p. 145.
at room temperature. Subsequent heating to temperatures in the vicinity
of 1000F. will produce a finely dispersed precipitate that is accompanied
by an increase in hardness and strength.
The treatments producing this hardened condition have been described
for stainless W. Alloy 17-4 PH responds in a similar fashion. Mechanical
properties are given in the table. The alloy 17-7 PH on annealing remains
austenitic. It is however unstable and may be converted to martensite on
cold work or by cold treatment. Subsequent heating to about 1000F. will
produce a precipitate in a state of dispersion that will cause a marked
increase in hardness and strength.
The alloys with appreciably higher nickel, 17-10P, 17-14, HNM, will
remain austenitic on rapid cooling from about 1900F. and retain disper-
sion hardening compounds in solution, on aging at about 1300F. the
compounds precipitate. The presence of phosphorus will intensify the
hardening effect.
The continuing expanding use of nickel has led to a shortage of the
available supply of this metal. In an effort to alleviate to some extent this
381
situation, several low-nickel,
high-manganese austenitic stainless steels
have been developed as well as nickel-free, heat-resisting austenitic alloys.
Approximate compositions are given in the table below.
Table 18.6. Composition of New High Manganese Grades
Designation C Mn Cr
1
Ni N
A1S1' 201
A1S1' 202
CMN*
G-192
8
0.15 max.
0.15 max.
0.65
0.55/0.65
5.5/7.5
7.5/10.0
12
8.0/9.0
16.0/18.0
17.0/19.0
25
21.25/22.75
3.5/5.5 0.25 max.
4.0/6.0 0.25 max.
0.45
0.30/0.40
1
Designation of the American Iron & Steel Institute.
2
Crucible Steel Co. of America.
8
Allegheny Ludlum Steel Corp.
Data from Roach and Hall, Material/! arts Methods, April 1956, p.
138.
Table 18.7. Typical Tensile Properties of High-Manganese Grades
Designation Form Condition Test
Temp. F
Ten Str.
1000 psi
Yld. Str.
(0.2%)
1000 psi
Elong.
%
A1S1 201 Sheet
Sheet
Annealed
\i
Hard
Room
Room
115
150
55
105
55
25
A1S1 202 Sheet Annealed
Room 105 55 55
CMN Sheet Ann. & Aged 1200 76

10
G-192
Bar Hot worked Room 149 84 11
Data from Roach and Hall, Materials and Methods, April 1956, p. 139.
The mechanical properties of types 201 and 202 are essentially the same
as A1S1 301 (17
Cr-7Ni) and A1S1 302. Corrosion tests seem to indicate
that type 201 is comparable in corrosion resistance to 301, and type 202
resembles 304.
18.10. Superstainless Steels
During the early years of World War II, American metallurgists were
faced with an urgent and difficult problem in the metallurgy of
high-alloy steels: to develop a superstainless steel for use in turbosu-
382
perchargers and gas turbines (jet engines) . In addition to its great
importance for military aircraft and propelled missiles, solution of the
problem would probably have far-reaching peacetime ramifications, be-
cause it has been known for some time that a gas turbine has a high
over-all efficiency for power generation in marine and other forms of
transportation.
The problem was to develop an alloy that would have a relatively long
and useful life as highly stressed wheels, buckets, and other parts of
turbines, when operated at very high temperatures and when exposed
to highly corrosive hot gases. Two methods of attack were used: to pro-
duce a superstainless steel based on the 188 analysiswhich has excel-
lent elevated-temperature propertiesand to develop further existing
nickel-rich and cobalt-rich alloys of the Inconel, Stellite, and Hastelloy
types, which are extremely heat- and corrosion-resistant. Some of the
principal alloys developed and used during the war are given in Table
18.8.
Early in World War II, German engineers were ahead of ours in the
design of jet engines, but the lack of suitable alloying elements was re-
sponsible for an average life for these power units of much less than
100 hr. After designs were perfected in the United States, the following
typical requirements for alloys for superchargers were set up: they should
withstand a stress of at least 12,000 lb. per sq. in. at 1500F. (815C.)
for at least 1,000 hr. without failure and be resistant to exhaust gases
containing tetraethyl lead. For gas turbines, temperature and stress con-
ditions were somewhat less severe. It is to the credit of American metal-
lurgists that most of the alloys listed in Table 18.8 meet the requirements
satisfactorily.
For industrial gas turbines, economics will be more important than
it was for military aircraft during the war. Some of the elements used
in large quantities during the past three or four years in alloys for turbo-
superchargers and jet enginescobalt is an example-will be too scarce
or too costly to be used in turbines which must develop power eco-
nomically; further, the life of the alloys must be much longer, up to at
least 100,000 hr., for example, for a marine turbine. Turbine efficiency
increases rapidly with increasing temperalure so that postwar super-
stainless alloys must withstand very high temperatures for long periods
of time. None of the alloys available now will meet this requirement
unless stresses are much below those characteristic of superchargers and
jet engines. If high stresses must be withstood at very high temperatures
and for long periods of time, new alloys must be developed. Tt is to be
expected, therefore, that some of the alloys listed in Table 18.8 will
Table 18.8. Chemical Composition of Supcrstainless Steels and
Alloys for Turbosuperchargers and Gas Turbines
Heavy Nonferrous
Alloy
designation
Nominal composition, per cent
C Mn Si
'
Cr Ni j
Co Mo W Cb Ti
Supcrstainless
steels:
19-9 DL
19-9 W-Mo
S
495
0.30
0.10
0.45
0.45
0.40
1.00
0.60
1.00
1.00
0.60
0.55
0.50
0.50
0.60
0.60
19.00
19.00
14.00
9.00
9.00
20.00
20.00
44.00
20.00
20.00
1.25
0.40
4.00
4.00
4.00
6.25
0.60
3.00
1.35
1.25
1.26
4.00
4.00
4.00
2.25
4.00
1.35
0.40
0.40
4.00
4.00
4.00
4.00
0.60
1.25
1.00
0.30
0.35
S 590
20.00 20.00
20.00 20.00
25.00
20.00
25.00
27.00
4.50
12.00
20.00
24.50
37.00
20.00
1
6-25-6
f
0.08 1.50
0.30 0.60
0.80 16.50
1.00
1.00
1.00
13.00
15.00
15.00
18.50
19.00
20.00
13.00
18.00
25.00
0.40
0.35
0.35
0.10
0.15
0.04
0.03
0.10
1.00
1.25
4.00 0.50
0.75
1.00
0.50
0.70
0.50
0.50
0.50
0.50
0.65
2.00
3.25
3.00 2.00
3.00
N 155 MultimctJ..
2.25
Rcfractalloy
25-20-2 Si
3.00
3.00
Heavy nonfer-
rous alloys:
0.15
0.10
0.25
0.40
0.40
0.05
0.15
0.75
0.60
0.60
0.60
0.30
0.75
1.00
0.25
0.60
0.60
0.60
0.25
0.75
1.00
13.00
15.00
27.00
26.00
27.00
16.00
78.00
74.00
2.00
32.00
16.00
65.00
55.00
65.00
35.00
50.00
5.00
5.00
6.00
29.00
17.00 5.00
Inconcl, modified
.
Stellite 6059
Stellite 30-422
Hastelloy B
Hastelloy C
*
Contains only 4 per cent iron.
t
Contains 0.10 per cent nitrogen.
X
In development stage, contains 0.15 per cent nitrogen.
Contains 0.70 per cent aluminum.

disappear, except for military use, in the next few years, and that other
and more economical or better alloys for industrial gas turbines will take
their place.
The supcrstainless alloys are important almost wholly for their strength
and corrosion resistance at elevated temperatures, and further discussion
is, therefore, deferred to a later chapter. The following data give a gen-
eral idea of the overall improvement in these alloys during the last few
years: The stress which causes failure in 1,000 hr. at 1200F. (650C.)
is 1,000 lb. per sq. in. for 3 per cent nickel (S.A.E. 2340) steel; 4,000 lb.
l'i
12
ID
I
O
*I0
c
o
S
*-,
/
/
/
b
6
1
/
1
/
J
"o
4
o
2
\J
o
C
I 9 2() 30 4() 5 ) 60 70 80 90 100
Nickel, per cent
Fie. 18.7. Coefficient of expansion of iron-nickel alloys between and 200 F.
{Marsh)
for the silchrome used before the war; 19,000 lb. for 17W (Table 16.4)
used at the start of the war; 30,000 lb. for gamma Cb used in 1944; and
36,000 lb. for 16-256 used at the end of the war.
18.11. High-Nickel Steels and Special Iron-Nickel Alloys
Nickel dissolves in gamma and in alpha iron and has a strong effect
on the position of A
3
, not only lowering it to atmospheric temperature or
below but, in addition, slowing greatly the rate of the phase change and
producing some anomalies in properties which are of great value to in-
dustry. Alloys of iron with 20 to 30 per cent nickel may easily be made
nonmagentic (despite the fact that both iron and nickel are magnetic).
Alloys of iron with 30 to 60 per cent nickel have variable and controllable
expansion characteristics which were discovered late in the nineteenth
century in France. The fact that alloys of iron with 45 to 85 per cent
nickel can be treated to produce high magnetic permeability and low
hysteresis loss has led to wide use of some of them in telephone, tele-
graph, and radio equipment.
As shown in. Fig. 18.7,* the coefficient of expansion between and
200 F. ( 18 and 100
C
C.) decreases to nearly zero as nickel approaches
*
Based on data in
J.
S. Marsh, The Alloys
of
Iron and Nickel, Vol. I, Special-
Purpose Alloys, McGraw-Hill Book Company, Inc., New York, 1938, p. 160.
385
36 per cent. Increasing the nickel from 36 to 60 per cent makes it
possible
to have any desired coefficient of expansion between 1 and 12
X
10
"
6
-
As
the result, a number of alloys have been developed for use in measur-
ing tapes, watch parts, and parts of machines and instruments which
must remain constant in
dimension despite temperature changes.
The
use of invar struts in
aluminum-alloy pistons is well known. Some of the
commercial alloys with controlled expansion characteristics are given in
Table 18.9.
If chromium and tungsten are added to an alloy containing
about 32
per cent nickel, the affect of temperature (in the vicinity of room tem-
perature) on the modulus of elasticity is zero. This alloy is known as
elinvar and is used for hairsprings of watches and for springs of other
precision measuring instruments. The invars and other high-nickel alloys
have the additional advantage that they have excellent corrosion re-
sistance.
The alloys known as permalloy, hipernik, and perminvar are used in
applications where their high or constant permeability produces marked
economics or increased efficiencies in
communication. Because under
weak magnetizing forces permalloy has a permeability many times
greater than that of all other ferrous materials except iron of the highest
purity,
permalloy is a commercially feasible high-permeability material.
The development of this alloy has made modern long-distance telephony
possible, and its use in the loading of submarine cables has speeded up
the transmission of messages several hundred per cent. Hipernik has
initial and maximum permeabilities much greater than those of com-
mercial grades of high-purity iron and the advantage of relatively high
maximum induction, which makes it valuable for use in radio trans-
formers.
The efficiency of radio loud speakers and other apparatus requiring
powerful permanent magnets has been greatly increased by the recent
development of the
iron-nickel-aluminum-cobalt
permanent-magnet ma-
terials (see Table 18.9) . In addition to alnico, two Japanese alloys are
noteworthy: the M.K., containing 25 to 30 per cent nickel, 20 per cent
cobalt, and 12 per cent aluminum; and the K.S., containing 10 to 25 per
cent nickel, 15 to 36 per cent cobalt, and 8 to 25 per cent titanium.
18.12. Austenitic Manganese Steel
Of the large number of high-alloy steels that have not been discussed
in this chapter, austenitic manganese steel is of sufficient
industrial im-
portance to deserve mention. This steel was discovered a number of years
386
Table 18.9. Commercial High-Nickel Iron-Nickel Alloys
Composition,* per cent
Name
Characteristic properties
Ni Co Cr W Al Cu
36
Low expansions from to
200 F. (-18 to
100
C.)
Supcrinvar . . 31 5 Zero expansion near room
temperature
32 5 2 Low thcrmoclastic coeffi-
cient
42
For sealing in soft glass
Kovar 29 17
For sealing in hard glass
Platinilc .... 46
Expansion same as platinum
Permalloy . . . 78.5
High permeability at low
field strengths
Hipernik .... 50
High permeability at higher
field strengths
Perminvar . . 45 25
Constant permeability over
a range of flux densities
Alnico I . . . . 20 5 12 Permanent magnet of high
magnetic hardness
Alnico II . . . 17 12.5 10 6 Same as above
Alnico III... 25
12 Same as above
Alnico IV... 28 5 12 Same as above
*
Balance of composition is mostly iron.
ago by Hadfield in England during his pioneer researches on alloys of
iron with manganese, silicon, nickel, chromium, and other elements. The
annual tonnage of high-manganese steel used is small, but, as is the case
with many ferrous materials, production is no criterion of its usefulness
to industry. High-manganese steel contains 1.00 to 1.30 per cent carbon
and 11 to 14 per cent manganese and is made by the basic open-hearth,
Bessemer, or electric process. It may be poured into ingots and rolled into
a variety of sections, or it may be cast in sand molds. Owing to its work-
hardening capacity when cold, it cannot be machined readily; hence,
if shaping is necessary, it usually must be ground. Economically this is
a great disadvantage.
In amounts under 50 per cent, manganese dissolves in alpha and
gamma iron. Like nickel it lowers the
A
3
temperatures where alpha
transforms to gamma in heating and where the reverse change occurs in
cooling, and slows the transformation rate. As noted in a previous chap-
ter, manganese also forms a carbide, (Fe.Mn)
3
C, which is closely allied
to Fe
8
C in structure and properties. Alloys containing 1.00 to 1.30 per
387
cent carbon and 13 per cent
manganese, if cooled very slowly so that all
phase changes take place, contain at room
temperature alpha solid solu-
tion plus excess carbide. In the usual cooling after hot working, or in a
mold in the case of a casting, these phase changes, owing to the low
reaction rates, do not take place, and the structure consists of the gamma
solid solution plus, possibly, a little alpha, plus excess carbide as massive
particles or as a network around the grains. With this structure the steel
is hard and brittle. If, however, the steel is heated to 1830 to 2010F.
(1000 to 1100C), the carbide goes into solution in the gamma, and
if the steel is now quenched in water, a structure consisting wholly of
austenite with no free carbide is obtained. Unfortunately, tempering to
relieve quenching stresses is
impossible because reheating in the tem-
perature range 930 to 1290F. (500 to 700C.) or even lower may cause
precipitation of carbide or change of some gamma to alpha and thus
may cause brittlencss.
As water quenched, rolled austenitic manganese steel has the following
properties:
Tensile strength, lb. per sq. in
130,000 to 160,000
Proportional limit, lb. per sq. in
40,000 to 60,000
Elongation in 2 in., per cent
60 to 70
Reduction o area, per cent
40 to 60
Brinell hardness
180 to 220
As is characteristic of austenitic alloys, the high-manganese steels have
no well-defined yield point and are nonmagnetic.
High-manganese steel is important industrially chiefly because of its
high abrasion resistance. Although the Brinell hardness of the heat-
treated steel is low, cold working causes a rapid increase to as much as
550 Brinell. As abrasion consists largely of cold working the surface, this
capacity for work hardening has important ramifications. Thus, in steam-
shovel buckets, in crushers, grinders, and other machines, and in rails,
cross-overs, switches, frogs and such sections where pounding, pressure,
or abrasion by rock and sand or by other metals are encountered, high-
manganese steel outwears high-carbon steel by several hundred per cent.
QUESTIONS
1. Name the three classes of high-alloy steels containing chromium as the prin-
cipal alloying element. Give the approximate composition of six common
high-chromium steels, and name the class to which they belong.
2. What is the effect of up to about 15 per cent chromium on the transforma-
tion temperatures in high purity iron? Describe the phase changes that take
place if an alloy containing (a) 10 per cent chromium and 90 per cent iron,
388
Engineering
Metallurgy
and (b) 20 per cent chromium and 80 per cent iron, is heated slowly to
2,500F. (1,370C) and cooled again.
3. What is the effect of carbon on the phase changes that take place when
alloys of iron and chromium containing up to about 20 per cent chromium
are heated to a high temperature and cooled again? What effect has carbon
on the response of these alloys to heat treatment?
4. What structure would be expected if the following steels were quenched
in oil or water: (a) 0.35 per cent carbon and 14.50 per cent chromium?
(b) 0.75 per cent carbon and 16.75 per cent chromium?
(c) 0.07 per cent
carbon and 15.80 per cent chromium? How does the hardenability
of a steel
containing 0.35 per cent carbon and 14 per cent chromium compare with
the hardenability of an unalloyed high-carbon steel?
5. What is the relation between the tensile properties and the carbon content
of heat-treated 14 to 18 per cent chromium steels? Give two peculiarities
in tempering quenched cutlery steels and the effect of these on tensile
strength and impact resistance. What is the relation between the chromium
content and the corrosion (and oxidation) resistance of chromium steels?
What is the effect of carbides on corrosion resistance? To what corrosive
media are the 12 to 18 per cent chromium
steels especially resistant? Why?
6. What is the general effect of nickel on the alpha-gamma transformations
in iron-chromium alloys? What is the effect of adding 5, 8, or 10 per cent
nickel on phase changes in alloys containing 18 per cent chromium and
approximately 82 per cent iron when they are slowly heated and cooled
between room temperature and 2,400F. (1,315C)? Why are alloys con-
taining 18 per cent chromium. 8 per cent nickel, and low carbon usually
austenitic at room temperature?
7. What is intergranular corrosion in 18-8?
What causes it? What is the under-
lying mechanism of the phenomenon? How is it prevented?
8. What are the characteristic mechanical properties
of 18-8, and what effect
has heat-treatment
on these properties? How does the resistance of 18-8
to corrosion and oxidation compare with that of the high chromium steels?
What are fcrritic chromium-nickel steels and what is stainless W?
9. What are superstainless steels? What alloying elements in addition to
chromium and nickel are used in these materials? What are the general
characteristics
of superstainless steels, and what are they used for?
10. Outline the main points of difference between the well-established 18-8
grade of stainless steel and the new group of these materials.
CHAPTER
19
Tool Steels, Die
Steels,
and
Cemented
Hard
Carbides
JOSEPH
Gi.rland, Sc.D., Assistant Professor,
Division of
Engineering, Brown University,
Providence, Rhode
Island
Joseph
J.
Kaufman, Instructor, Metallurgy
Department,
Academy of Aeronautics, Flushing, New York
XHE steady, if slow, advance of civilization over
the past ten or twelve thousand years has been largely the result of prog-
ress in the design of tools and in the material from which they are
fashioned: from stone to copper, then to bronze, and then to iron,
and after a long period to
carburized iron
(steel)-which was the
most important step of alland finally to high-speed and other alloy-
steel tools and sintered hard carbides, which made possible great reduc-
tions in the cost of finished structures and machines.
All tools can be divided broadly into two general classes:
(1)
cutting
and shearing tools and
(2)
forming tools. Requirements differ and should
be considered before the proper steel is selected. Thus, for cutting and
shearing, high hardness, ability to
withstand wear, stability of structure
to withstand the heat generated by the friction of the cutting edge
against the work, and a substantial amount of toughness to prevent chip-
ping and breakage are important. For
shearing tools, a lack of deforma-
tion or warping in heat treatment is usually also important. Forming
tools consist chiefly of dies, which are used to transfer their impression
to either hot or cold solid metal, or to molten metal. In addition to pos-
sessing the qualities necessary in a cutting or shearing tool, forming
tools must be resistant to distortion in heat treatment and to cracking
caused by sudden changes in temperature during use.
The representative types of tool steels and their principal
characteristics
are given in Tables 19.1 and 19.2. The recently adopted AISI-SAE classi-
fication is used. As Table 19.2 indicates, tool steels vary widely in
characteristics.
389
The selection of the proper tool steel for a certain machining operation
is difficult and is a problem in the solution of which the advice of the
tool-steel metallurgist is very helpful.
An accurate evaluation of a steel that is to be used for a specific tool
in a specific machining operation is practically impossible, and as a re-
sult, large quantities of tool steel are, and always have been, purchased
by brand name.
The only reliable performance test of a tool steel is to use it in actual
production and to use enough similar tools of the same steel to make the
results convincing. Large users of tool steel frequently distribute their
yearly or half-yearly requirements among a number of tool-steel manu-
facturers and keep accurate records of the performance of each brand.
At the end of this production test the company whose brand makes the
best showing receives 50 per cent or more of the business for the next
period.
19.1. High-Carbon Tool Steels
The steels of class W, Table 19.1, are the cheapest and, despite high
distortion in hardening, low resistance to softening at elevated tempera-
ture, and shallow hardening, the most widely used of the tool steels.
There are four classes, graded according to carbon content as follows:
1. Carbon 0.60 to 0.75 per cent; used for machinery parts, hot-forging
dies, rivet sets, battering tools, large chisels, and set screws.
2. Carbon 0.75 to 0.90 per cent; used for forging dies, boilermakers'
tools, hammers, sledges, mining tools, and miscellaneous blacksmiths'
tools.
3. Carbon 0.90 to 1.10 per cent; used for drills, saws, cutters, taps,
small shear blades and dies, anvils, wood- and stone-working tools of
various kinds, punches, and axes.
4. Carbon 1.10 to 1.40 per cent; used for small drills, taps and lathe
tools, files, cutlery and small edge tools, jewelers' tools and dies, brass-
and copper-working tools, wire-drawing dies, and razors.
The hardness and toughness of the high-carbon tool steels vary with
carbon content; they also vary with heat treatment, that is, with temper-
ing temperature. Since high hardness and considerable toughness are
incompatible in an unalloyed high-carbon steel, it is necessary to sacrifice
part of one or the other depending upon the use for which the tool is
intended. Thus, for razors, which must be very hard and which are not
ordinarily subjected to shock, a 1.20 per cent carbon steel, treated to
give a hardness of 60 to 65 Rockwell C, is used; but for a hammer or a
chisel, which must withstand impact, a steel containing 0.70 to 0.90
Tool Steels, Die Steels, and Cemented Hard Carbides 391
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Tool
Steels, Die Steels, and Cemented Hard Carbides 393
Tempering
femperature.deg.C.
100 300 500
"As
200 400 600 800 1000 I20C
quenched Tempering temperature, deg.F.
Fic. 19.1. Effect of tempering on the hardness of water-quenched high-carbon steel.
(GUI)
per cent carbon, treated to about 55 Rockwell C and with more tough-
ness, will be chosen.
Wear resistance, which usually is not so high in carbon steels as in
some of the alloy steels, is secured by the use of a 1.20 to 1.40 per cent
carbon steel, heat treated so that there will be numerous
well-distributed
excess carbide particles in a martensitic matrix. Such a structure (Fig.
19.2) is important for cutting tools and wire-drawing dies. Under the
quenching conditions necessary to obtain high hardness,
high-carbon
steels warp considerably. In tools of simple section this may be mini-
mized by quenching in special fixtures; for dies and some tools which
must be finish-machined before heat
treatment and for which stability
of dimensions is necessary, special nondeforming alloy steels, which
harden in oil or air, are used.
394
Fig 19.2. Structure of water-quenched high-carbon tool steel: small carbide particles
in martensitic matrix, etched.
500X-
High-carbon steels, even though of practically the same composition,
may differ in their response to quenching (hardenability). If the steel
has an inherent tendency to become coarse-grained when heated con-
siderably above the transformation temperature, it hardens relatively
deeply and uniformly when quenched but is likely to crack. If it is fine-
grained after such treatment, it is shallow hardening and may have soft
spots on the surface, but it is not so likely to crack in quenching. Un-
alloyed high-carbon steels are all shallow hardening compared with tool
steels containing considerable molybdenum or chromium, but the harden-
ability can be controlled to some extent by controlling the grain-growth
tendency during manufacture. The difference in hardenability between
two lots of high-carbon steels of identical chemical composition is shown
in Fig. 19.3.* Bars
% in. in diameter were quenched in brine from the
temperatures noted and were not tempered. The fractures of the "fine-
grained" bars are shown at the top, and those of the "coarse-grained"
bars at the bottom. The coarser grain and the greater depth of hardening
for the latter are clearly evident.
Unalloyed high-carbon steels arc apt to be inherently erratic in their
response to heat treatment. Even steels of the same composition, made
by the same manufacturer, may differ in their tendency toward grain
growth and in depth of hardening. To render the response to quenching
more uniform, small percentages of chromium or vanadium are frequently
*
Shepherd P-F hardenability test specimens.
Tool Steels, Die Steels, and Cemented Hard Carbides
395
Fie. 19.3. Fracture of quenched and
untempered high-carbon tool steel. Top,
fine-grained, shallow hardening; bottom,
coarse-grained, fairly deep
hardening. (Gill)
added to steels of class W.
Vanadium inhibits grain growth and chro-
mium increases
hardenability; both have a favorable effect which prob-
ably compensates for the increased cost.
As a class, the high-carbon tool steels are
characterized by high hard-
ness at the surface and a relatively soft core in all but very
small sections.
Owing to this soft core, Gill* rates these steels as tough and resistant to
shock. They are, as previously mentioned,
subject to
considerable dis-
tortion in quenchingdue to the formation of martensite at the surface
and of bainite or pearlite in the center, and to the stresses caused by
differential cooling of surface and centerwhich means that they are not
suitable for tools of complex or irregular shape.
Small amounts of nickel, chromium,
molybdenum, or
tungsten are
added to some varieties to increase hardenability and to
permit quench-
ing in oil instead of water.
19.2. Low Alloy Tool Steels
Low alloy steels of class L, which include the well-known ball- and
roller-bearing material containing about 1 per cent carbon and 1.2 to 1.5
per cent chromium (S.A.E. 52100) , are used to some extent for dies, rivet
sets, small rolls, and for a few cutting and shock-resisting tools. They are
relatively cheap, at least as compared with some of the
highly alloyed
tool steels, and have exceptionally high strength combined with relatively
good toughness. They are also much deeper hardening than the high-
carbon steels. Whether the steels are water or oil hardening depends
chiefly on the manganese content, which in the oil-hardening grades is
0.50 to 0.60 per cent.
Tool Steels, American Society for Metals, Cleveland, 1944.

The carbon content of these steels depends on the service require-
ments; if toughness is important as in pneumatic hammer pistons or
chisels, it is 0.40 to 0.70 per cent; but if maximum hardness and wear
resistance are necessary as in files, drills, and cutlery, it is between 0.90
and 1.10 per cent. The amount of chromium in the steel depends pri-
marily on the depth of hardening required, which in turn depends on
the size of the tool that is to be treated. Increasing the chromium from
0.50 to 1.50 per cent more than doubles the time available for the steel
to cool past the pearlite nose of the S curve without transforming.
Also in this class are high-carbon variants of some of the S.A.E. en-
gineering steels.
Most of the medium-carbon S.A.E. nickel-chromium or chromium-
molybdenum steels are fairly deep hardening;* increasing the carbon
to 0.60 to 0.70 per cent and maintaining the chromium at well over 1.0
per cent and the molybdenum at 0.30 per cent or more increases the
quenched hardness and the depth of hardening; at the same time the
steel retains considerable toughness. These steels are, therefore, finding
relatively wide use in many machine parts and especially in die blocks
for hot forging. These steels are generally quenched in oil.
19.3. Medium Alloy Tool and Die Steels
Advantage is taken of the effect of manganese or chromium when
dissolved in alpha iron of decreasing the critical cooling rate and of in-
creasing deep hardening to produce a valuable and extensively used class
of oil-hardening "nondeforming" tool and die steels (class O) . These
steels are used when the design of the tool or die is such that distortion or
cracking is likely to occur in water quenching. In this group there are
steels containing 0.90 to 1.45 per cent carbon. If the manganese is
1.60 per cent, the steel usually contains no other alloying element
although the addition of 0.10 to 0.25 per cent vanadium to reduce grain
growth is optional. To increase wear resistance the manganese may be
lowered to 1.20 per cent, and about 0.5 per cent chromium plus 0.5 per
cent tungsten may be added; or the manganese may be reduced to 0.25
per cent, and 0.75 per cent chromium and 1.75 per cent tungsten may be
added. These modified steels are not so likely to crack in quenching as
the higher manganese steels, but, on the other hand, they do not become
so hard. The steels of class O are quenched in oil from 1400 to 1500F.
(765 to 815C.) and are tempered at 325 to 500F. (160 to 260C.)
.
They are used as stamping dies, thread-rolling dies, dies for molding
plastics, punches, broaches, blanking dies, and especially as master tools
and gages.
Kor example, the SAE 3100 series and 4100 series.

Tool Steels, Die Sleeb, and
Cemented Hard Carbides 397
Silicon-manganese steel (S.A.E. 9255 and 9260)
containing 0.50 to 0.60
per cent carbon, 1.80 to 2.20 per cent silicon, and 0.60 to 0.90 per cent
manganese is widely used for springs. Recently it has become popular as
a tool steel, especially for punches, chisels, and shear blades, owing to its
low cost and is fairly high wear resistance and toughness (class S-5)
.
Strictly speaking, silicon-manganese steel is a misnomer, as the amount
of manganese is not greater than that present in many of the S.A.E.
carbon and low-alloy steels. Distortion in quenching is high, but it is
somewhat less than for plain high-carbon steels, and wear resistance is
higher. The steel hardens more deeply than high-carbon steel and is
tougher. To increase deep hardening, 0.20 to 0.40 per cent chromium
or 0.40 to 0.60 per cent molybdenum is occasionally added. Steels of class
S are usually quenched in water (or oil, if enough chromium and
molybdenum are present) from 1575 to 1625F. (860 to 885C.) and are
tempered at 350 to 600F. (175 to 315C.)
.
The medium-chromium and low-tungsten tool and die steels are fairly
or very deep hardening and, generally, can be hardened with little
distortion. They have higher resistance to wear than unalloyed high-
carbon steels and they have satisfactory toughness.
Steels of class
S
of low carbon content and therefore of relatively
high toughness, are used for chisels, punches, shear blades, and battering
tools and occasionally for dies. These steels do not have high resistance
to tempering. According to Gill, chisels of this steel have three times the
life of unalloyed chisel steel.
The steels in class A contain 1.0 per cent carbon and 1.0 per cent
molybdenum. Chromium varies from 1 .0 to 5.0 per cent, and manganese
varies inversely with the chromium from 3.0 to about 0.50 per cent. These
steels are air hardening and are widely used for intricate dies that must
maintain their dimensions accurately after heat treatment. They are used
for- blanking and forming dies, rolls, punches, and drawing dies but not
for dies that operate at high temperatures.
19.4. High-Alloy Tool and Die Steels
Dies that are to be used in applications where they are heated to tem-
peratures 600F. (315C.)
or
above are usually rather highly alloyed,
(class H). Steels in these classes are characterized by high hardenability
(the pearlite nose of the S curve of some of these steels is far to the
right of the time axis), very low distortion in heat treatmentwhich is
natural in view of the fact that most of the steels can be hardened in air
high hardness at elevated temperatures, and fairly good toughness. Most
Fie. 19.4. Structure of high-chromium die steels (A) forged and annealed,
750X".
and (B) oil quenched and tempered at 400F. (200C),
500x:
etched. (Kinzel and
Forgeng)
will withstand temperatures of 1 100F. (595C.) or even slightly higher.
This is to be expected as some of them approach high-speed steel in
composition and in many characteristics.
The structure pf the high-chromium die steels (class D) as forged and
quenched and tempered is shown in Fig. 19.4. Although, after annealing,
the Brinell hardness of these steels is 200 to 230, they are difficult to
machine. Steels of this type harden deeply with little distortion and do
not soften appreciably when tempered below about 900F. (480C.)
.
Their wear resistance is high. Despite high cost and difficulty of ma-
chining, these steels are among the best as dies for forming and trimming,
blanking, thread rolling, and wire drawing, as shear blades, bushings,
and rolls, and as small machine parts where resistance to abrasive wear
is important. They are seldom used as cutting tools.
19.5. High Speed Steels
The majority of today's tool steel cutting tools are made of high speed
steel. The principal types are given in Table 19.3.
Table 19.3. Classification of High-Speed Steel by Chemical Composition
AISI-
SAE Type
Nominal chemical composition, per cent
Class
C Mn Si W Cr V Mo Co
T-1
18-4-1 0.70
0.85
0.80
1.00
0.75
0,80
0.80
0.80
0.85
0.85
0.85
0.85
1.30
0.85
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
18.0
18.0
14.0
18.0
18.0
14.0
20.0
1.5
2.0
2.0
6.0
5.5
6.0
4.0
4.0
4.0
4.0
4.0
4.0
4.5
4.0
4.0
4.0
4.0
4.0
4.0
4.0
1.0
2.0
2.0
3.0
1.0
2.0
1.5
1.0
2.0
1.3
2.0
2.0
4.0
2.0
8.0
8.0
8.0
8.0
5.0
4.5
5.0
T-2
18-4-2
T-7
T-3
14-4-2
T-4
T-8
T-6
M-1
M-10
M-30
M-34
M-2
18-4-1
Co
14-4-2
Co
20-4-2
Co
Molybdenum W
Molybdenum . .
Mo WCo
Mo W Co
Mo W
5.0
5,0
12.0
5.0
8.0
M-4
M-35
Mo WV
Mo WCo
5.0
The familiar 18-4-1 composition has long been the basic type. But since
World War II, molybdenum is replacing tungsten in these alloys. Today,
80%
of all shipments of high speed steel are of types M-1, M-2, and M-10;
whereas type T-1 represents only 10% of all high speed steel being used.
In general, cutting performance increases with tungsten or molyb-
denum. Vanadium is necessary for satisfactory performance and approxi-
mately 1 per cent or more is always present. Chromium is held constant
at about 4 per cent, with carbon varying from 0.50 per cent (if toughness
at the expense of some hardness is desired) to as much as 1.50 per cent.
Cobalt has been used in the regular grades of high-speed steel with con-
siderable success. It increases red hardness and the efficiency of the tool
where temperatures are high as during heavy roughing cuts.
High-speed steel is hard, strong, and brittle at room temperature and
retains its hardness and strength at temperatures up to 1100 to 1200F.
(595 to 650C.)
.
The cutting performance of high-speed steel, which is from three to
fifty times that of unalloyed high-carbon steel of the same hardness, is
largely dependent upon the heat treatment. The optimum quenching
temperature depends upon composition, and a variation of 50F.
(30C.) from the optimum will affect the performance of the tool.
Engineers owe a large debt to two Americans, F. W. Taylor and
Maunsel White, who, while working at Bethlehem Steel Company in
October, 1898, discovered the "weird and novel" heat treatment which
gives high tungsten-chromium steel its property of red hardness. Taylor
and White found that a steel containing 1.14 per cent carbon, 0.18 per
cent manganese, 7.72 per cent tungsten, and 1.83 per cent chromium
performed poorly in rapid machining when heat treated in the usual
way. After considerable investigation the present-day treatment was
developed. This consists of heating the tool slowly to 1500F. (815C.)
,
then rapidly to a temperature slightly below the melting temperature
with modern high-speed steels this is 2200 to 2350F. (1205 to 1285C.)
,
which would ruin carbon or low-alloy steeland cooling it rapidly in
oil, or, sometimes, in air. The tool is then tempered immediately by
reheating to 1000 to 1150F (540 to 620C.) . When heat treated in
this way, high-speed steel machines at high speeds and with such heavy
cuts that the point of the tool becomes red hot, without losing any
hardness.
Although considerable work has been done on the constitution of
iron-tungsten-carbon alloys, little is known about the effect of 4 per cent
chromium and 1 to 2 per cent vanadium on these alloys. Studies of
microstructure indicate that high-speed steel when annealed consists of
a relatively soft (probably ferritic) matrix and a large number of par-
ticles of a complex carbide. When the steel is heated to a high tempera-
ture, the matrix changes to austenite and some of the carbides go into
solution. To produce red hardness and satisfactory cutting performance,
the temperature to which the steel is heated must be as high as possible
without causing incipient melting. When the steel is quenched from
this temperature, a structure such as is shown in Fig. 19.5
A*
results. It
is thought that the polygonal grains of the matrix are composed of
austenite plus untempered martensite. Reheating to 1()50F. (565C.)
tempers the martensite slightly so that it etches rapidly (Fig. 19.5B), and
upon cooling from the tempering temperature the
retained austenite
transforms to more martensite. The secondary hardening that results
from tempering is shown in Fig. 19.8
The cause of red hardness, the most important property of high-speed
steel, has not yet been explained satisfactorily. It is usually considered
to be related to the high stability of the complex carbide particles and
to the fact that the most favorable size of the particles for stability of
structure is not altered by temperatures as high as 1100F. (595 C.)
.
J.
I.. Gregg, The Alloys of
iron and Tungsten, McGraw-Hill Book Company, Inc.,
New York, 1934, pp. 294, 295.
Tool
Steels, Die
Steels, and
Cemented Hard Carbides
401
&4&&L
*3
,CK-^^^
<8f>*
L
FIO. 19.5. Structure of
high-speed steel; (A)
quenched and (B)
quenched and
tempered;
etched.
750x-
(Gregg)
The most
recent development in
high-speed
steels is the
substitution
of molybdenum for most of the tungsten (see
Table 19.3)
.
This was
pioneered by Richie* at
Watertown
Arsenal and by Emmons.t
who
developed the steels
commercially.
Molybdenum
has three
advantages
in
high-speed steel: (1)
Since it is
twice as effective as tungsten in pro-
ducing red hardness, only 6 to 9
per cent is necessary, as Table
19.3
shows-
(2)
it is cheaper
pound for pound than
tungsten; and
(3)
it is
not a
strategic material, as ample supplies of domestic ores are
available.
Initial
difficulties in the heat treatment of
molybdenum
grades have been
solved, so that, at present, there is
little difference
between
molybdenum
and tungsten base alloys as to
fabrication and tool
performance. 1
he in-
creased
consumption of
molybdenum
high-speed steels is due
mainly to
their lower price.
Compared to carbon tool steels, the
high-speed steels are
more expen-
sive and arc not as tough.
However, properly used in the
right kind
of
equipment, the
high-speed steels will
out-perform tools made from any
other type of steel. It is the only type of steel
which will stand up
to the high temperatures
generated at the
cuttting edge by modern,
high-
speed,
production
machines.
S. B.
Richie, Army
Ordnance, V. 11, July,
1930.
fj.
V.
Emmons, Trans.
Am. Soc. Steel Treat., V. 21, 193S,
p.
193.
402
Temperinq
temperature , deq.C.
SOO 400 soo ' 60
Tempering temperature,
deq. F.
Fig. 19.6. Effect of. chromium on the resistance of 0.35 per cent carbon steel to
tempering. (Bain)
19.6. Function of Alloy Additions in Tool and Die Steels
The structure of tool steels consists essentially of a dispersion of hard
carbide particles in a matrix of steel. The purpose of small alloy addi-
tions is to improve the properties of the matrix by increasing the harden-
ability and refining the grain si/e. The most common alloy additions to
low alloy steels are chromium, vanadium and manganese. Chromium in-
creases the depth of hardening and adds some wear-resistance; vanadium
increases toughness and limits grain growth; manganese permits oil
hardening with much less distortion than water quench. To further re-
duce the likelihood of cracking during cooling, about 1%
molybdenum
makes a steel air hardened.
Larger amounts of alloy elements, together with increased carbon
contents, form hard alloy carbides which are responsible for the superior
hot hardness and wear-resistance of alloy tool steels. The amount and the
dispersion of the carbide particles determine the hardness; the greater
the relative volume of the hard phase, the harder and more brittle the
steel. The principal function of large alloy additions to tool steels is to
increase the amount of the carbide phase.
Tempering
temperature, deg. C.
403
O 400 600 600 1000 1200
Tempering temperature, deg. F.
Fig. 19.7. Effect of molybdenum on the resistance of 0.35 per cent carbon steel
to tempering. {Bain)
As is evident from Table 19.1, tungsten, molybdenum, and chromium
are the most important alloying elements in medium and high alloy tool
steels, and together with vanadium they are more imi>ortant in high-
speed steel than in the ordinary tool and die steels. All three are soluble
to a considerable amount in gamma and in alpha iron and, more import-
ant, all three form hard and stable carbides. All three, when dissolved
in gamma iron, slow the reaction rate for austenite to transform to pearl-
itechromium and molybdenum strongly and tungsten weakly.
The carbides formed by these three metals dissolve to some extent
(depending on the amount of carbon and the temperature) in austenite
and can be retained in supersaturated solution by quenching. This in-
creases hardness and wear resistance. In addition, the carbides in excess
of those dissolved, if favorably distributed, greatly increase the resistance
of the steel to abrasive wear.
In contrast to tungsten, which has a minor cflect on hardenability,
chromium and molybdenum have a powerful effect. This was discussed
in detail in earlier chapters. The most valuable property of tungsten,
molybdenum, and chromium when present in relatively large amounts
404
Engineering
Metallurgy
Tempering tempcroture.deg.
C.
100 200 300 400 500 600
'
i
'
I
'
i
J
r
1-
48l ~_
As J00
quenched
703
500 700 900
Tempering femperalure^d
UOO
Fic. 19.8. Effect of tempering on the hardness of high-speed. (Emmons)
in steel containing sufficient carbon is that they make the steel "red
hard"; that is, the steel retains its hardness at elevated temperatures,
in some cases so high that the steel becomes red in color.
Tungsten, molybdenum, and chromium also increase the resistance to
tempering. This is shown by Fig. 19.6*
for steel with 0.35 per cent carbon
and increasing chromium, by Fig. 19.7* for steel with 0.35 per cent
carbon and increasing molybdenum, and by Fig.
19.8f
for high-speed
steel containing 0.70 per cent carbon, 18 per cent tungsten, 4 per cent
chromium,
and 1 per cent vanadium. The increase in hardness of these
steels when tempered between 900 and 1100F.
(480 and 595C.) is
due primarily to the transformation to martensite of some austenite re-
tained by the quenching treatment.
19.7. Cast Alloys
Alloys rich in cobalt, chromium and tungsten were developed and
placed on the market in 1907 under the name of Stellite. They contain a
high proportion of a hard constituent (complex chromium-rich carbide)
within a cobalt rich matrix phase.
Cutting tools of this type usually contain from 45 to
55% cobalt,
25 to
35% chromium,
12 to 17% tungsten, 1 to
3% carbon. The proper-
ties cannot be varied
by heat treatment, but are controlled by the com-
position,
the softer alloys having a higher strength. The tool grades
range in hardness from 40 to 64 Rockwell C. Considerable hardness and
E. C. Bain, Functions
of
the Alloying Elements in Steel, American Society fo*
Metals. Cleveland, 1939.
t J.
V. Emmons, Trans. Am. Soc. Steel Treat., v. 19, 1932,
pp.
289-332.
405
Fie 19.9. Typical
structures of sintered hard carbides. (A)
Tungsten carbide with
4 per cent cobalt. (B) Tungsten, titanium, tantalum and columbium carbides with
about 8 per cent cobalt. Polished with diamond dust and etched with alkali ferricyanide.
1.500X-
(Courtesy Kennametal Inc.)
strength are maintained at high
temperatures, their "red
hardness"
making these alloys superior to high speed steels in resisting wear at ele-
vated temperatures. At the same time they are appreciably weaker and
somewhat more brittle.
The alloys are sold commercially under a variety of trade names.
They are used as cutting tools and wear resisting parts. Since they are
expensive and have relatively low strength they are usually cast into
small pieces of the desired size and shape which are used as inserts sup-
ported by a stronger backing material. Or, thin layers can be welded as
a hard surface coating over steel parts.
19.8. Cemented Carbide Tools
Cemented carbides, also called sintered carbides, are used mainly
for tools and dies. They are the hardest of all metallic tool materials,
consisting largely of finely divided carbide particles embedded in small
amounts of a soft ductile metal, usually cobalt (see Fig. 19.9)
.
The hard, abrasive carbides of tungsten, molybdenum, titanium, tanta-
lum, zirconium, and other metals have been known for nearly seventy-
five years, but their use for tools is much more recent. It began about
twenty-five years ago in Germany and about twenty years ago in the
United States.
All cemented carbide tools contain tungsten carbide (WC) as the es-
sential constituent. The tungsten carbide may be used alone for the
machining of cast iron, nonferrous metals and plastics. But steel-cutting
grades, in addition, must contain titanium carbide. The carbides of
titanium and tungsten form a solid solution which has the outstanding
characteristic of resisting the abrasion of the steel chip as it glides over
406
the tool. Smaller quantities
of tantalum, columbium
and vanadium car-
bides are also added to some grades.
Cemented carbide tools are made by the methods of powder metallurgy.
The finely ground carbide powder is mixed with cobalt, pressed into the
desired shape, and sintered at 2450F (1343C) or above. The sintering
temperature is above the liquidus of the alloy system and densification
occurs in the presence of a liquid phase. The resulting product is sub-
stantially free from porosity.
The properties of sintered carbides vary with composition, particularly
with the proportion
of cobalt. In general, hardness is increased but
toughness
or shock resistance is decreased by smaller binder contents.
Tungsten
and titanium carbides are among the hardest materials known;
although
less hard than diamond, their hardness is of the same order of
magnitude as that of aluminum oxide, boron carbide and silicon carbide.
Depending upon the amount of cobalt used (which varies from 3 to
about
20 per cent), the Rockwell A hardness (diamond indenter, 60 kg.
load) ranges from 88 to 93, corresponding approximately to
a Rockwell
C hardness of 72 to 76. A good portion of this hardness is retained at the
high temperatures encountered during metal cutting, permitting a
cutting speed three or four times greater than that of high speed steels.
The material has little ductility, strength is determined by a transverse
rupture test and varies from 150,000 to 400,000 lb. per sq. in. The
cemented carbides have very high compressive strengths (500,000 to
900,000 lb. per sq. in.) . They also have some of the highest elastic
moduli known (up to 90,000,000 lb. per sq. in.)
.
Cemented hard carbides are widely used for wire-drawing dies, ex-
truding dies, and numerous other dies for burnishing or spinning metal
sections, such as metal radio tubes, shell cases, projectile jackets, eyelets,
and many others, and also for gages, thread guides, valve parts for
erosive materials, and the like. The most extensive application of these
materials is in mass-production machining of cast iron, steel (with Brinell
hardness values as high as
500) , and most of the other metals, and also
of many difficultly machined nonmetallic materials including plastics,
rubber, resins, glass, asbestos, and others.
Cemented carbides arc costly and the tool generally consists of a carbide
tip or insert brazed to a steel holder or shank, but great economies
frequently result from the use of these tools. The greater machining
speeds and increased tool life permit production increases between 30
and several hundred per cent while saving approximately one third of the
production costs.
QUESTIONS
1. Name the two main classes of tool steels. What properties are important
in each class? Give eight essential characteristics that tool steel should have,
and rate these in the order of their importance.
2. How are tool steels usually purchased? Why is it difficult to devise a per-
formance test to evaluate tool steels? How important is die cost of the steel
from which a tool is made?
3. Give the characteristic properties of high-carbon tool steel. What is the
approximate carbon content of the four main classes of high-carbon tool
steels, and whv is the carbon percentage adjusted according to the use to
which the steel is to be put? What carbon percentage would you specify
for the following: razor blade, hammer, drill, anvil, rivet set, small shear
blade, ax, and file?
4. What are the outstanding characteristics of the steels of class L? How is the
hardenability of these steels increased? Compare these steels with the S.A.E.
low nickel-chromium and chromium-molybdenum steels.
5. What are the principal alloying elements in the oil-hardening, nondefonn-
ing tool steels of class 0? Why are these steels widely used? What are they
used for? Give the important properties of the silicon-manganese steels
when used as tools.
6. What are the general effect of (a) chromium, (b) molybdenum, and (c)
tungsten on hardenability, wear resistance, tempering, and hardness at high
temperature?
7. What is the chief advantage of the medium-chromium, low-tungsten tool
and die steels as compared with high-carbon tool steels, and how do the two
groups compare in wear resistance, red hardness, and toughness? What are
the outstanding characteristics of the high-alloy tool and die materials?
What are the main alloying elements used in these high-alloy steels?
8. What is the approximate composition of the principal types of high-speed
steel? How is high-speed steel heat treated? Why is cobalt added to some
high-speed steels? What are the advantages and disadvantages of molyb-
denum high-speed steel as compared with the usual 18-4-1 material?
9. What is the most valuable property of high-speed steel, and what is the
usual explanation for this property? What variables affect the cutting per-
formance of high-speed steel?
10. What hard carbides are used as tool and die materials? How does the hard-
ness of these carbides compare with that of quenched tool steel? Describe
the structure of these tools.
11. Compare and discuss the compositions, microstructures and properties of a
typical stainless steel and a typical tool steel. Relate the microstructures to
the desired properties. (Note particularly the difference in carbon contents.)
CHAPTER
20
Cast Iron
CHARLES Arthur Naglkr, Ph.D., Associate Professor, De-
partment of Chemical and Metallurgical Engineering,
Wayne State University Detroit, Michigan
Kenneth E. Rose, M.S., Professor of Metallurgical En-
gineering, University of Kansas, Lawrence, Kansas
v*AST irons are alloys of iron and carbon con-
taining more than 2 per cent carbon. Other elements, notably silicon,
are generally present also. Metallurgically, cast irons are characterized by
(1)
an eutectic reaction during freezing, and
(2)
more carbon than can
be dissolved in austenite at any temperature.
In steel, carbon is rarely present in any form other than combined as a
carbide. However, iron carbide, or cementite, is a metastable compound
which can be decomposed to iron and carbon (as graphite) . Because of
the embrittling effect of cementite, most of the carbon in commercially
useful cast iron is converted to graphite unless the hardness and wear
resistance of the cementite is of primary importance.
Factors tending to encourage the decomposition of cementite are:
1. High temperature.
2. Time (especially at elevated temperature)
.
3. Slow cooling rates during freezing (a corollary of 1 and
2)
.
4. High carbon content.
5. Presence of graphite.
6. Presence of graphitizing agents (including silicon)
.
Cast irons may be classified roughly according to the percentage of
carbon, but because of the various ways in which the carbon is associated
with the iron, it is usually more convenient to make the classification
according to the form of the carbon, rather than the amount. The
following outline suggests a procedure for such a classification.
A. Carbon combined with iron as cementite.
1. White cast iron (usually about
2%
carbon).
2. Chilled cast iron (usually
3%
or more carbon)
.
408
Cast Iron
409
Fie. 20.1A. Flake graph-
ite in gray cast iron.
Fig. 20.1B. Spheroidal Fig. 20.2. Temper car-
graphite in nodular, 01 hon (graphite) in mallc-
ductile cast iron. able cast iron.
2.
3.
1
B. Carbon both in combined and elemental (graphite) form.
1. Mottled cast irona. mixture of white cast iron with graphite,
generally undesirable.
Gray cast irongraphite as thin, interdendritic flakes which form
during freezing. Cementite is present in pearlite in the matrix.
Gray cast iron is sometimes described as "steel plus graphite."
(See Fig. 20.1 A.)
Nodular or ductile cast irongraphite as spherulites which form
during freezing of specially treated irons. Massive cementite as
well as pearlite may be present in the as-cast condition. (See Fig.
20. IB.)
Pig iron
a product of smelting in the iron blast furnace, used
primarily as a raw material. Large, smooth, star-like flakes of
primary graphite or "Kish" are embedded in a matrix which is
essentially gray cast iron.
C. Graphite formed by heat treatment, some cementite remaining.
1. Pearlitic malleable cast ironmade by annealing white cast iron
to decompose the excess cementite, leaving a matrix of pearlite.
D. All carbon present as graphite in a matrix of ferrite.
1. Ferritic gray irongenerally undesirable for strength and wear
resistance, but may be made by annealing ordinary gray iron to
achieve the maximum machinability.
Ferritic malleable cast ironmade by heat treatment of white
cast iron to decompose both the excess cementite and the
cementite that would otherwise be in pearlite. (See Fig. 20.2.)
Ductile cast ironmade by annealing nodular cast iron to attain
a high degree of ductility. The carbide in such iron is decom-
posed as in malleable cast iron.
2.
3.
410
Engineering
Metallurgy
20.1. White Cast Iron as an Engineering Material
Cast iron containing all or nearly all the carbon in the combined form
has a silvery-white fracture and is known as white cast iron. Very hard
and brittle and practically unmachinable, it is important chiefly
(1)
as
an intermediate product in the production of malleable iron castings and
(2)
when it is produced, by regulating the composition and by cooling
rapidly,
as a thin, hard layer on the surface of a softer iron casting. The
latter product is known as chilled iron and is used where high surface
hardness and wear resistance are important.
The microstructure of white cast iron can be predicted from the iron
iron-carbide phase diagram used for steel; that is, it consists of cementite
and pearlite.
20.2. Malleable Cast Iron as an Engineering Material
Malleable cast iron is a valuable engineering material and is widely
used for machinery, railroad equipment and automobiles, agricultural
machinery, pipe fittings, hardware, household appliances, and in many
other applications. Intricate castings are more readily melted and
poured with white cast iron than with carbon steel and, despite the cost
of malleablizing, are cheaper than carbon-steel castings. Malleable cast
iron compares favorably with gray cast iron in machinability and with
low-carbon steel in properties.
To produce malleable castings, cast iron solidfying with a white frac-
ture is poured into a sand mold; the hard, brittle casting is then annealed
(malleablized) to dissociate the cementite. Malleable cast iron contains
2.0 to 2.5 per cent carbon, practically all of which is graphite (usually
called temper carbon) , 0.7 to 1.2 per cent silicon, 0.40 to 0.60 per cent
manganese, less than 0.20 per cent sulfur, and less than 0.10 per cent
phosphorus.
During the first stage of malleablization, at
1600
to 1700F., cementite
which is not soluble in the austenite is converted to ragged loosely formed
nodules of "temper carbon." Second-stage malleablization takes place at
or slightly below the lower critical (A,) temperature after cooling from
the first stage treatment. This causes the remaining cementite, including
that which normally would be in pearlite, to gi aphitize. Second-stage mal-
leablization is complete when the structure consists entirely of temper
carbon in a matrix of ferrite.
20.3. Engineering Properties of Malleable Cast Iron
White cast iron for malleablizing is melted chiefly in an air furnace;
some, however, is melted in a cupola. The tensile strength and elongation
Cast Iron
411
(as measured on a test bar) of cupola malleable iron are lower than those
of air-furnace malleable, but the bursting strength of castings is usually
considerably higher. Cupola malleable, therefore, is widely used for pipe
fittings. Most malleable iron is purchased under specifications issued by
the railroads or by the valve- and pipe-fittings industry. Most of these
specifications give the following as minimum properties:
Kind of malleable iron
Tensile strength,
lb. per sq. in.
Yield strength,
lb. per sq. in.
Elongation in 2 in.,
per cent
50,000
40,000
32,000
30,000
10
5
Reduction of area is usually about 20 per cent and is seldom determined.
Malleable cast iron is unique among ferrous materials in that the elon-
gation increases as the tensile strength increases. This is shown by the
data for air-furnace malleable given in Table 20.1. Malleable cast iron,
with a notched-bar impact resistance of 7 to 9 ft-lb., as compared with
1 ft.-lb. or less for gray cast iron, is much tougher than gray cast iron.
The modulus of elasticity is 25,000,000 lb. per sq..in., that is, slightly
lower than that of carbon steel. Malleable cast iron has an endurance
ratio of about 0.5, that is, the same as carbon steel. It is considerably
more sensitive to notches than gray cast iron.
Table 20.1. Tensile Properties of Air-Furnace Malleable Cast Iron*
Tensile strength,
lb. per sq. in.
per cent
Tensile strength,
lb. per sq. in.
per cent
51,000
52,000
53,000
54,000
16.5
17.0
17.6
18.3
55,000
56,000
57,000
58,000
19.0
19.6
20.3
21.0
In malleable iron, as in carbon steel, the tensile strength decreases
with increasing size of section; a typical change is from 55,000 lb. per
Proc. Am. Soc. Testing Materials, v. 31. 1931, Part II. p. 317. For ranges of com-
position and properties of American malleable iron, see Cast Metals Handbook,
American Foundrymcn's Society, Chicago, 3d ed., 1944,
pp.
308-314.
412
sq. in. for sections 0.25 to 0.50 in. in thickness to 45,000 lb. per sq. in. for
sections of 1.25 to 1.50 in. The yield strength, however, is practically
unaffected by section size. In contrast to steel, in which elongation usually
increases with mass, the elongation of malleable iron decreases; at the
center of a 2- or 3-in. section, for example, the elongation may be only
about half what it is at the surface.
Malleable cast iron has poor wear resistance, but in machinability it
ranks about the same as gray cast iron. It is easier to plane, drill, or mill
than carbon or alloy steels, including those containing lead or high
sulphur.
Recently, for a few special applications, the graphitizing operation in
the production of malleable has been modified, or alloying elements
have been added and special treatments used so that the annealed
material contains some pearlite. The properties of pearlitic malleable
cast iron depend upon the amount and distribution of the iron carbide;
usually it is stronger and less ductile than fully graphitized material.
A unique and now well-known example of a specially treated pearlitic
alloy malleable cast iron is in the crankshafts of some automotive engines.
The alloy is melted and cast under conditions that produce white cast
iron. It is malleablized by a treatment that produces small graphite
nodules in a matrix consisting almost entirely of pearlite. This treatment
is followed by a complex normalizing and annealing treatment. The
composition is approximately as follows: 1.5 per cent carbon, 0.7 per cent
manganese, 0.9 per cent silicon, 1.75 per cent copper, and 0.5 per cent
chromium.
20.4. Gray Cast Iron as an Engineering Material
Cast iron in which most of the iron carbide has dissociated into iron
and graphite is usually soft and readily machinable. It has a gray, almost
black, fracture and is thus known as gray iron. More than 90 per cent of
all the iron castings produced are of gray iron.
Gray cast iron is a low-cost material which is easily melted and cast,
and is economically machined. These are the primary reasons for its wide
use. Of the hundreds of engineering applications for gray cast iron, some
of the most important ones, together with the usual compositions, are
given in Table 20.2.*
The properties of gray cast iron that determine its suitability for
engineering uses are the result of controlling four variables:
(1)
chemi-
Trans. Am. t'oundrymen's Assoc, v. 39, 1932. pp.

56-64. For a complete list of
specific applications ot plain and alloy cast irons, see Cast Metals Handbook, Ameri-
can Foundrymen's Society, Chicago, 3d ed., 1944,
pp.
335-594.
Cast Iron 413
Table 20.2. Recommended Analyses of Plain Cast Irons for Common Engineering
Applications
Composition, per cent Typical charge,
per cent
Use
Cast-
Total Si Mn P S Pig iron Steel
C
scrap scrap
3.25 2.25 0.65 0.15 0.10 40 40 20 Automobile cylinders
3.35 2.25 0.65 0.15 0.10 40 40 20
Automobile pistons
3.40 2.60 0.65 0.30 0.10 50 45 5 Automobilccastings, general
3.50 2.90 0.65 0.50 0.06 60 40 Automobile piston rings
individually cast
3.40 2.10 0.60 0.50 0.10 35 55 10 Agricultural implements
medium sections
3.50 2.20 0.55 0.70 0.10 40 60 Agricultural implements
light sections
3.25 2.25 0.50 0.50 0.09 50 50 Machinerysections not
over 1 in.
3.25 1.75 0.50 0.50 0.10 50 40 10 Machinery1.5-in sections
3.23 1.25 0.50 0.50 0.10 50 25 25 Machinery2-in. sections
3.25 1.25 0.65 0.20 0.10 50 25 25 Pressure castingsair cylin-
ders
3.40 1.75 0.80 0.35 0.09 55 20 25 Gas-engine cylinderslight
3.40 1.50 0.80 0.35 0.09 55 20 25 Gas-engine cylindersme-
dium
3.40 1.25 0.80 0.35 0.09 55 20 25 Gas-engine cylinders
3.30 2.00 0.50 0.60 0.10 50 40 10 heavy Valves and fittings

3.50 1.15 0.80 0.10 0.07 70 30 Firepots and ketUes
3.50 1.00 0.90 0.20 0.07 90 10 Ingot molds
3.60 1.00 0.75 0.20 0.07 60 40 Pots for caustic soda
3.60 1.75 0.50 0.80 0.08 70 25 5 Light and medium sand-
cast water pipe
3.40 1.40 0.50 0.80 0.08 60 25 15 Heavy sand-cast water pipe
3.40 1.40 0.50 0.80 0.08 70 30 Soil pipe
3.35 0.65 0.60 0.35 0.12 12.5 80 7.5 Car wheels (0.90 per cent
combined C)
3.60 1.25 0.55 0.40 0.10 45 40 15 Chilled plow iron
3.75 0.85 0.50 1 0.40 0.10 45 40 15 Plow moldboards
cal composition,
(2)
rate of cooling from the solidification temperature,
(3)
special methods of melting, including superheating and ladle addi-
tions, and
(4)
heat treatment.
In addition to low cost and easy machinability, gray cast iron has a
number of propertiesnotably notch insensitivity, high damping capacity,
and high compressive strengthwhich make it especially valuable in
some applications. In tensile strength, ductility, and toughness, however,
it is much inferior to steel. In addition, the absence of a well-defined
yield point and modulus of elasticity makes it unsuitable for many engi-
neering structures. Despite its disadvantages, however, the production
of gray-iron castings is around 5 or 6 million tons a year in the United
States.
20.5. Structure of Gray Cast Iron
Considering gray cast iron as a carbon steel containing graphite, the
three primary metallographic constituents present at normal temperatures
are alpha iron (ferrite) , iron carbide (cementite) , and free carbon
(graphite). The cementite is usually associated with ferrite as pearlite
the same constituent found in carbon steeland the graphite is distri-
buted through the ground mass as irregularly shaped plates or flakes of
varying sizes. However, very rapid cooling from the melt may suppress
the formation of graphite and produce chilled iron, a type of white iron.
Very slow cooling increases the proportion of ferrite to pearlite. The
ferrite of gray cast iron, unlike the ferrite of low-carbon steel which is
relatively pure, contains all the silicon and a little of the phosphorus
in solid solution.
Of the elements in gray cast iron, carbon has the strongest effect on
structure and properties. This effect depends on the amount of total
carbon as well as on the relative amounts of combined carbon and of
graphite present. This in turn depends upon the silicon which decreases
the stability of the iron carbide, thus promoting graphitization. Next
in importance is phosphorus, which combines with the iron to form
iron phosphide (Fe
3
P) . A small amount of this compound dissolves
in the ferrite, the rest forms a eutectic (FeFe
s
P) with iron. When the
phosphorus is 0.1 per cent or above, the eutectic (known as steadite) is
visible as a distinct constituent in the microstructure (Fig. 20.3.) The
eutectic melts at a temperature of 1750 to 1800F. (955 to
980
C.)
,
much below the melting point of gray cast iron. If about 0.5 per cent
phosphorus or more is present, there is enough eutectic to make the iron
more fluid. High-phosphorus iron is, therefore, used for ornamental
castings and other thin, intricate sections. Owing to the hardness of the
phosphide eutectic, cast irons containing considerable phosphorus may
be harder to machine than low-phosphorus material. In the amounts
usual for American gray cast irons (Table 20.2)
phosphorus has little
effect on the strength, but it may increase the brittleness. For cylinders
and various kinds of pressure castings 0.5 per cent is, therefore, usually
the maximum permitted (Table 20.2) . The effect of phosphorus on
graphitization is negligible.
Cast Iron
415
Fie. 20.3. Phosphide cutcctic in gTay cast iron. (A)
100x;
(B) l.OOOx- The cutectic
is the irregular-shaped light-colored constituent shown in A. At high magnification its
duplex character is apparent. (Kunkele, Giesserci, v. IS, 19)1, p. 73)
Commercial gray cast iron always contains enough manganese to in-
sure that the sulphur is present as manganese sulphide. Owing to the
notch insensitivity of gray cast iron, more sulphur is tolerated than in
steel because manganese sulphide inclusions are not so likely to be loci
of weakness where failure will start under repeated stress. Manganese in
excess of the amount necessary to combine with the sulphur forms iron-
manganese carbide. This compound is more stable than iron carbide;
hence, manganese inhibits graphitization. In the amount usually present
(less than 1 per cent) the stabilizing effect of manganese is much less
important than the strong graphitizing effect of silicon.
20.6. Relation between Properties and Structure of Gray Cast Iron
There is a close relation between properties and structure of gray
cast iron. The properties are primarily dependent upon the character-
istics of the "steel" matrix and upon the amount and distribution of the
graphite. These in turn are dependent upon the variables already men-
tioned, namely, chemical composition, rate of cooling from the solidifi-
cation temperature, special methods of melting, and heat treatment.
The amount of iron carbide to be decomposed into iron and graphite
or to be left undecomposed depends (if the effect of cooling rate is ig-
nored) upon the amounts of total carbon and silicon. For small speci-
mens cast in sand molds the relation between total carbon, silicon, and
structure is shown in Fig. 20.4.*
?.b J.O i.l> 4.0 4.5
Silicon, per cent
5.0 5.5 6.5 7.
Fic. 20.4. The Maurer cast-iron diagram.
A
modification of the Maurer diagram by Coylet is shown in Fig. 20.5
in which approximate tensile strengths are plotted against composition.
This diagram shows that for small specimens cooled in sand molds the
highest strengths are attained if the total carbon is 2.00 to 3.25 per cent
and if the silicon is 1 .00 to 2.25 per cent.
20.7. Effect of Cooling Rate
The relation among properties, structure, and composition is affected
greatly by varying die rate of cooling from the
solidification temperature
to the gamma-alpha transformation temperature. As the mass is increased,
the cooling rate is decreased, and the dissociation of the iron carbide is
increased. Thus if a 1-in, sand-cast bar has a matrix corresponding to a
E. Maurer, Kruppsche Monatshelte, v. 5, 1924,

pp.
115-122.
+ F. B. Coyle, Trans. Am. Soc. Steel Treat., v. 12, 1927,
pp.
146-465.
Cast Iron
417
Z.50 3.00
Silicon. per cent
3.50 4.0C
"..50
Fie. 20.5. Cast-iron diagram showing cltect of carbon and silicon on tensile strength.
(Coyle)
0.50 per cent carbon steel, the same iron if cast as a 6-in. bar in sand will
ordinarily have a matrix that corresponds to a 0.10 per cent carbon steel.
On the other hand an iron of such composition that, when poured into
a sand mold it will have a matrix of pearlite, will, if poured into a cast-
iron mold, form white iron on the surface next to the cold mold but will
be pearlitic in the interior of the casting.
Thus, the lines of the Maurer diagram (Fig. 20.4) are moved to the
right if the cooling rate is increased, and to the left if the cooling rate is
decreased. The approximate relation among structure, cooling rate, and
properties is shown in Fig. 20.6.*
It is evident from the foregoing that the relation among the composi-
tion, cooling rate, structure, and properties of gray cast iron is not simple.
Another important factor, which adds to the complexity, is the size and
form of the graphite flakes.
20.8. Effect of Graphite Size on Structure and Properties
The strength of slowly cooled carbon-steel castings increases as the
carbon (cementitc) increases. The strength of slowly cooled gray cast
iron would also increase as the cementite increases if no graphite were
present. Graphite destroys the continuity of the grains of the "steel"
matrix and makes it weak and brittle. As the si/.e of the graphite particles
increases and as they become more flaky and platelike, the iron becomes
progressively weaker and more brittle.
*
Cast Metals Handbook. Am. Foundrymen's Soc, Third Edition, 1944, p.
360.
418
Engineering
Metallurgy
350
Strength increases
300
w
250
W
V
zoo
co
150
100
sc
S t r u c t u r
e
Hard andbrittle
*\hite iron. Cemenlite andai/stenife
Mottlediron. Cementite,grapliile
r
andpearlitc
|
Greatest strength. Hard to machine
Best nigh-test irons - Close gray iron. Graphite,
andpeartite
/air strength. Easymachining
yf,
,. .
,
4
ndZrf,wl
-^-p^Med^mgroy.ron.eraph,^
peartite ana fernte
and fair finish
.Lowstrength.
Opengrain.
Machines soft
Open gray iron. Graphiteand ferrite
"-
FJO. 20.6. Relation of hardness and strength o gray cast iron to structure and
section size. (American Foundrymen's Society)
High-strength cast iron must have a "steel" matrix containing consider-
able pearlite, and the graphite flakes should be small; there must, how-
ever, be 2.0 to 2.5 per cent graphite present if easy machinability is
required. The control of the graphite size is accomplished by five meth-
ods. The first consists of melting an iron of such composition that it
would normally solidfy with a white fracture and then treating it by
adding a special graphitizer, such as powdered silicon or calcium silicide,
just before the castings are poured. The second consists of melting an
iron that would normally solidify with a white fracture and mixing with
this a definite amount of a soft gray iron melted in another cupola. The
third method consists of melting gray cast iron and superheating it con-
siderably
above the usual casting temperature. This decreases the size
of the graphite flakes and increases the amount of pearlite in the casting.
The fourth, used considerably in Europe, consists of pouring a low-silicon
iron into a preheated mold. The fifth method consists of adding alloying
elements. To produce high-strength iron by any of these methods the
several variables, including the percentages of carbon and silicon, must
be controlled carefully.
20.9. Evaluation of Gray Cast Iron for Engineering Applications
The suitability of gray cast iron for engineering structures and ma-
chines is judged chiefly by tensile, transverse, and compressive strengths.
Cast Iron
419
Hardness, endurance limit, wear
resistance, and
other
properties may
be valuable criteria of its value for specific
applications. Most
metal-
lurgists experienced with cast iron consider the transverse test as the
best single source of
information on the quality of cast iron.
The transverse test is made by applying a load at the center of a cast
(unmachined) round bar, supported at each end, until fracture occurs.
The size of the bar depends upon the size of the casting and has been
standardized* at 0.875, 1.20, or 2 in. in diameter with a span of 12, 18,
or 24 in. between
supports. The load
necessary to fracture the bar and
the amount of deflection at the center at the moment of fracture are
noted. In the United States
transverse strength is reported as the load
in pounds; in Europe the load is converted by the formula
Pic
MR
=-u
to a value called modulus of
rupture. In this formula P is the
breaking
load, I the distance between supports, c the distance from the neutral
axis of the bar to the extreme fiber, and / the moment of inertia.
The relation of modulus of rupture to tensile strength varies with the
quality of the iron from 2.5 times the tensile strength for
low-strength
irons to approximately the same as the tensile strength for
high-strength
irons. Transverse strength or modulus of rupture is of value in design if
cast iron is used as a beam and especially in pipe subjected to heavy
earth loads.
Gray cast irons are graded by (minimum) tensile strength (in thou-
sands of pounds per square inch) into seven classes: 20, 25, 35, 40,
50, and 60. As discussed before, since the
stress-strain curves of gray
cast iron are curved from the origin, this material has no
proportional
limit nor modulus of elasticity. The secant modulus,
representing a
point on the stress-strain curve of 25 per cent of the tensile strength,
varies between 12 and 20 million lb. per sq. in.
In many engineering applications, for example machine beds,
columns,
pipes used as structural members, and various other supports, cast iron
is used for its strength in compression. This is determined by subjecting,
sand-cast bars 0.75 to 0.80 in. in
diameter and 1 to 3 in. long to a com-
pressive load until failure occurs. The stress-strain curve in
compression
is also curved from the origin.
Compressive strength is higher than tensile
strength; it varies from about 4 times the tensile strength for low-strength
irons to about 3 times the tensile strength for strong irons.
The other properties of gray cast iron can be
summarized in a series
of short sentences. Endurance limits are given in Table 20.2. The en-
A. S. T. M.
Standards, Pari 1, 1955, A48-40, pp.
1848-1854.
420
durance ratio, determined
on highly polished specimens, is more erratic
than for steel. Values between 0.30 and 0.60 have been reported. A very
important characteristic
of gray cast iron is the almost negligible effect
of surface on the endurance limit; the same notch which reduces the
endurance limit of steel as much as 75 per cent reduces the endurance
of soft cast iron less than 15 per cent. The impact resistance of cast iron
is low and is usually unimportant. Notched-bar tests are meaningless,
and drop tests are frequently
erratic. The damping capacity of gray cast
iron is higher than for any other ferrous material. Gray cast iron is readily
machinable unless the surface is chilled; conversely, if the surface is
chilled,
cast iron is very wear-resistant and is machined with great dif-
ficulty. It is relatively easy to produce gray-iron castings having a surface
layer in which the carbon is entirely combined as cementite. Chilled
gray cast iron is, therefore, widely used for large gears, for a variety of
rolls, for wheels of railway cars, and for many other articles where high
surface hardness and wear resistance are necessary. Machining the sur-
face, if necessary, is, however, a slow and costly operation.
20.10. Nodular or Ductile Cast Iron as an Engineering Material
The size, shape, and distribution of graphite in cast iron has a pro-
nounced effect upon strength and ductility. This may be illustrated by
comparing these properties in malleable cast iron with the same properties
in gray cast iron. The higher ductility in malleable cast iron is related to
the rounded, compact form of the graphite (temper carbon) , which causes
less disruption of the matrix than do the long slender flakes of graphite
in gray cast iron. Until recently, the rounded graphite form could be
achieved only by heat treatment of solid metal, but spherulitic or nodular
graphite can now be made to form during the freezing interval by means
of special treatments and additions developed and patented in the United
States and in several other countries. High strength and elongation of as
much as 20 to 25 percent are reported in cast iron made by these processes.
The total carbon in nodular cast iron is about the same as in gray iron.
Magnesium
or cerium are most widely used to promote the formation of
nodular graphite. Only a few hundrcths of a percent of these elements is
needed, but the addition must be made shortly before the metal is cast,
and the melt must be very low in sulphur.
Metallurgists do not clearly understand the mechanism of graphitiza-
tion in nodular cast iron. The high shrinkage in nodular iron castings
suggests that little, if any, formation of graphite occurs during freezing.
Furthermore, massive cementite is not uncommon in the as-cast metal,
and for maximum ductility this must be eliminated by a separate anneal-
ing heat treatment.
Cast
Iron
421
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422
Engineering Properties. Specifications
of the ASTM (A 399-55) recog-
nize two commercial grades designated as 80-60-03 and 60-45-10.
The first
of these is in the as cast condition; the second is an annealed grade. In
each, the first two sets of numbers indicate minimum tensile and yield
strengths in 1000 psi, and the third set indicates minimum
percentage
elongation.
Nodular iron is more readily machinable than gray irons of similar
hardness. It is somewhat stiffer than gray cast iron, having a modulus of
elasticity of 21 to 25 million psi. The damping capacity is between that
of gray iron and cast steel. Nodular iron has somewhat better resistance
to oxidation, but the resistance to atmospheric corrosion is about the
same as for gray iron.*
20.11. Melting and Casting of Irons
Different methods of melting are used in order to control the chemistry
and microstructure of cast iron.
The greatest tonnage of iron is melted in a cupola furnace, Fig. 20.7, a
cylindrical type of furnace mounted vertically on legs and lined with
refractory brick. Depending on the type of foundry operated, the furnaces
can be lined with either basic or acid brick. The lining of the cupola
with basic brick is a relatively new innovation. Cupolas are charged
some distance above the floor of the furnace, and depending on the
capacity, the charging door is located 15 to 30 feet above the tuyeres.
On the lower portion of the furnace is a group of tuyeres attached to
a wind box that supplies the necessary oxygen for combustion. The area
below the tuyeres makes up the molten metal reservoir, which is periodic-
ally tapped. Above the metal tap hole and usually on the opposite side
is the slap tap hole. Materials charged to the cupola are pig iron, scrap
iron or steel, coke, and flux. The materials are weighed accurately and
charged in alternate layers. The function of the cupola furnace is to melt
the various components of the charge, and the molten mass of metal
becomes carburized
by being in contact with the hot coke. The carbon
solubility in the iron will depend on the temperature of operation of the
cupola furnace. The carbon solubility will reach an equilibrium value
after a given length of time. Cupola furnaces are not operated under
equilibrium conditions. However, the time that the molten metal is
allowed
to remain in contact with the coke is carefully controlled. When
the metal is tapped from the cupola furnace, the air is shut off, and
A. S. M. Metals Handbook. Supplement-Metal ProgressVol. 66, No. 1-A, July 15,

1954.
Cast Iron
423
FlG. 20.7. Section through a cupola furnace. (Whiting Corp.)
the tap hole is opened to allow the molten metal to flow from the
reservoir in the bottom of the cylindrical shaft furnace. After the tap is
completed, the tap hole is plugged and the air is again turned on and
melting continues until the next tap.
Raw materials that are charged into the cupola furnace ultimately
determine the chemistry of the melt that will be cast. The size of scrap
and pig charged depends on the size of the cupola furnace. Coke,
which is the fuel, is carefully selected on the basis of size, heating value,
chemistry, porosity, and strength, and must necessarily be low in sulfur
and phosphorus content. The molten iron in the cupola furnace has
a high affinity for sulfur and phosphorus, and invariably the sulfur
424
and phosphorus that are charged with the raw materials will be totally
accounted for in the molten iron. The slag produced in a silica brick-
lined cupola will not effect the removal of sulfur or phosphorus. In the
case of the basic lined cupola, the product will show a considerable
decrease in sulfur content due to the molten iron being in contact with
the basic slag. By far the best method of producing a low sulfur and
phosphorus iron is to minimize initially the charging of the two elements
into the cupola. The melting rate in the cupola furnace is controlled
by the amount of air that is admitted through the wind box into the
tuyeres. The air causes the combustion of the coke which in turn sup-
plies the heat for fusion. In controlling closely the operation of the
cupola with respect to air, it is not uncommon to find that the air is con-
ditioned to a constant humidity. Research work on the effect of moisture
on quality of iron has indicated the need for the control of moisture
to insure constant quality of iron. A study on the effect of moisture in
the air feed of a cupola furnace has indicated a definite relationship be-
tween hard spots in cast iron and a critical amount of moisture in the air.
The cupola furnace is considered to be an intermittent type of furnace.
On the basis of 24 hours of foundry operation, the cupola may be con-
sidered to operate 18 hours, and the remaining time allotted to repair of
the lining and to general maintenance on the furnace.
The melting of malleable iron is usually carried out in a reverberatory
or air furnace, Fig. 20.8. A relatively small tonnage is melted in electric
furnaces. The fuel used in the reverberatory furnace is usually powdered
coal or fuel oil. The raw materials added to the air furnace are scrap iron,
pig iron, and flux. Iron of various analyses are selected so that when
fusion and oxidation are completed the resulting melt is close to the
desired analysis. Some adjustments are made in final analysis by addition
of ferro alloys containing desired elements. It is well to mention that the
carbon content of the metal melted in the air furnace is considerably
lower than that produced in the cupola furnace and necessarily has a
higher melting and casting temperature. The feature that differentiates
the product of the cupola furnace from that of the air furnace is that the
fracture of the latter is white and that of the former is gray. The gray
fracture is caused by free carbon being in the form of graphite, and the
white fracture is caused by carbon being in solution. The molten iron is
cast into suitable molds for ultimate solidification into the desired shape
of ultization.
Prior to the casting of the metal from the melting furnace, various tests
are carried out on the molten metal to determine its suitability and
quality for casting. A chill test is carried out on gray cast iron to de-
425
Flo. 20.8. Section through a
reverberator^ or air furnace. [Whiting Corp.)
termine if the metal when cast will be free from a white cast-iron outer
layer. The test block is fractured and the depth of white layer measured.
A fluidity test is carried out to determine the flow characteristics of the
metal under certain standardized conditions. The test is carried out in a
spiral fluidity mold, the flow of the metal in filling the spiral being a
measure of the viscosity and tendency to produce useful casting. To
determine the quality of the iron after casting, physical tests such as
tensile strength, transverse breaking strength, and hardness tests are
carried out. The alloys are studied to determine the chemical analysis
with specific interest in such elements as carbon, silicon, manganese,
phosphorus, sulfur and others that may be present. Tests on iron that
are cast from the air or reverbratory furnace are as follows: study of
fracture to determine how much white cast iron is formed; chemical
analysis to determine the presence of such elements such as carbon,
silicon, manganese, sulphur, phosphorus, and others. In the case of white
cast iron the chemical analysis will predetermine whether the alloy will
satisfactorily be annealed to malleable iron. On a tonnage basis the
largest amount of iron cast as white cast iron is ultimately annealed into
malleable iron.
20.12. Ternary System of Iron, Carbon, and Silicon
Cast irons can be considered on a simplified basis as alloys of iron,
carbon, and silicon. In reality, the alloys contain, in addition to the
alloying elements mentioned, small amounts of phosphorus, sulfur,
manganese, and other elements. In order that we be able to interpret the
various changes that take place in the cooling of a cast iron from its
liquidus temperature to room temperature, it is imperative that we be-
come familiar with the ternary system of iron, carbon, and silicon.
The ternary system allows the plotting of die composition on the basal
temperature plane in three dimensions of carbon, silicon, and iron; the
vertical axis is temperature. Drawn in Fig. 20.9 is a corner of the
ternary system iron-carbon-silicon. The familiar iron-graphite constitu-
426
Fie. 20.9. Iron-rich corner of the ternary system of iron, carbon, and silicon.
tion system is recognized; the other section is for the iron-rich corner of
the iron-silicon system. The iron-silicon system contains a gamma loop,
which terminates at the transformation temperature from alpha to
gamma, and gamma to delta iron. A section taken through the system
at constant amounts of silicon illustrates the effect of silicon on the
temperature and composition of the eutectic and eutectoid of the system.
In Fig. 20.10 is illustrated sections taken through the system at constant
silicon content of per cent, 2 per cent, 3.8 per cent and (i.5 per cent.
It is readily noted in Fig. 20.10 that the transformation which takes
place at the solidus temperature line for the 2 per cent carbon alloy in
the iron-carbon system is simply a transformation of austenite-plus-
liquid to austenite-plus-cementite. In the case of the 2 per cent silicon
section of the iron, carbon, and silicon system, the transformation at 2
per cent carbon involves a three-phase region changing from liquid-plus-
austenite to austenite-plus-graphite. A region of austenite, cementite,
Cast Iron
427
1600
a-
i 1200
o
1000
800 v
600
#
7'
[
L
OX Si
7*0
\
L
J>
^
-^
/IsCa
r-
-/
V>
.^ r+Ca
a
+ ca
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Carbon, percent
600
0.5 1.0 1.5 2.0 2.5 3.0 35 4.0 45 5.0
Carbon, per cent
600
05 1.0 15 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Carbon, per cent
1400
o
.I200
-
a-
a 1000
\ 800
600
zl
6.5% Si
^p
"-^/
*Ca
a\ ^Sfcs^p
^
*tc*L 3
'
t
\-
71
J
L-a?
-a
>Ca
-
a*La
0.6 1,0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Carbon, per cent
Fig. 20.10. Sections through the iron, carbon, and silicon system at per cent silicon,
2 per cent silicon, 3.8 per cent silicon, and 6.5 per cent silicon. {Alloys of
Iron and
Silicon, Greiner, Marsh, and Stoughton, New York: McGraw-Hill Book Co., 1935.
428
3% Total Carbon. 2% Si
Liquid
A*L
A*C
-A,Pt C
A+C+G
A+G
AiP,C*G A
r P-,G
A.t>+$+F
P*C
(Whili
Iron)
P*C*G
(Mottled
Iron)
P*G P.G*
C
F.G
Foil
Cooling
Moderately
Foil
Cooling
Moderate
Cooling
Moderate',
Siow
Cooing
S'o*
Co:'-ng
c
L.Liquid
A, Austenite
P, Pearlite
C.Cementite
G
G, Graphite
F. Ferrite
K
Fie. 20.11. Transformation occurring during the solidification and the cooling of
cast iron. (Lorig)
and graphite is passed through prior to the formation of the solid phase.
This region is used in explanation of the formation of graphite from the
melt on solidification. The explanation of the freezing of iron, carbon,
and silicon alloys is complicated by the presence of two systemsthe
stable system of iron and graphite and the metastable system of iron and
cementite. In both systems prior to reaching the liquids temperature, the
carbon is in solution in the iron. Considerable changes occur during the
solidification of alloys according to the stable and metastable system. Al-
loys that freeze according to the stable system will give structures that con-
tain graphite plus transformation products of austenite upon cooling.
In the case of the metastable system, the products of transformation on
cooling contain iron carbide (cementite) plus transformation products of
the austenite. Hence, it is evident that an alloy has different microcon-
stituents formed, depending on the rate of cooling from above the
liquidus to room temperature. Fig. 20.11 above illustrates the rela-
tionship of cooling to microstructure for a 3 percent carbon, 2 percent
silicon cast iron. It is noted that on fast cooling the microstructure is
basically pearlite and cementite, and on slow cooling the microstructure
is ferrite and graphite. At an intermediate cooling rate, it is possible to
form a structure of cementite, pearlite, and graphite which is referred to
as mottled iron. In Fig. 20.11 notice that the rate of cooling determines
whether the stable or metastable constitution system is applicable in
considering the process of freezing. When alloys of iron, carbon, and
Cast Iron
429
Fig. 20.12. Types of graphite flakes in gray cast iron. (Tentative
recommended
practice for evaluating the microslructure of graphite in gray iron, ASTM designation
A247-41T).
silicon solidify
according to the stable system, the carbon is present in the
uncombined form of graphite.
Depending on the conditions of cooling,
nucleation, and other factors, the
graphite will assume a variety of sizes
and shapes. The flake-type chart for graphite is reproduced in Fig. 20.12.
Depending on the mode of
formation, any one of five different types of
graphite patterns can be formed, namely, uniform distribution random
orientation, rosette grouping random orientation,
superimposed flake
size random orientation,
interdenderitic segregation random orientation,
and interdendritic segregation preferred
orientation. The size of graphite
flakes is usually rated on the basis of length measured at 100
magnifica-
tions. All types of graphite flake patterns may be present in a section of
gray iron cast, with the exception of the superimposed flake size, which is
found typically in hypereutectic irons. It is generally agreed that the
flake type of graphite forms directly from the melt on
cooling below the
region of austenite plus liquid or austenite plus carbide of the stable sys-
tem of iron and carbon. The formation of graphite from the melt is
explained on the basis of the binary system of iron and carbon for
simplification purposes only. In explanation of the formation of the
interdendritic graphite pattern, which contains fine graphite, it is as-
sumed that the eutectic transformation takes place at a lower tempera-
ture than that of the large graphite flakes. This tends to
indicate that
the fine graphite structure is formed during the undercooling of the melt
(and the absence of residual nuclei in the melt to initiate the formation
of the graphite) . It can be generally concluded that all forms of graphite
found in cast irons form directly from the melt on solidification. The
innoculation of cast irons is practiced in many foundries to
control the
size of graphite flake formed in the cooling of various section sizes. The
amount of innoculant added will control the size and distribution of the
graphite flakes. Any one of a number of innoculants can be used, such
as ferrosilicon, calcium silicide,
combinations of titanium, aluminum
430
and silicon, mill scale, and others. In specially controlled heats of cast
iron it is possible by innoculation to alter the shape of the graphite. The
graphite formed on cooling after innoculation assumes the shape of
spheres. The chemical composition of the cast iron must be carefully
controlled with respect to sulfur, which must be present in an amount
less than 0.02 per cent. The spheriodizing additive may be cerium or
magnesium in alloyed forms. The addition of the innoculants results in
exothermic reactions, and care must be taken in making the alloy addi-
tion. The mechanism of the formation of the nodular graphite particle
on the cooling of the cast iron takes place in the following manner. The
addition of the cerium or magnesium to the cast iron, low in sulphur,
causes the graphite to crystallize in the form of nodules.
The constitution diagram of iron, carbon, and 2 per cent silicon can
be used to explain the formation of temper graphite during the long-
time annealing of white cast iron to form malleable cast iron. The
formation of temper carbon takes place in two stages during the mal-
leablizing of white cast iron. The first stage is carried out at a relatively
high temperature of 1600
to 1700F. by slowly heating to this tempera-
ture and holding until the cementite has decomposed into gamma iron
and temper carbon. The gamma iron dissolves in the austenite and the
carbon will be uncombined. The amount of carbon that remains in solu-
tion can be determined from the solubility of carbon in iron as deter-
mined in the constitution
system of iron, carbon, and
2 per cent silicon.
Prior to the second stage of malleablization the alloy is slowly cooled
from 1600 -
1700F. to
1200 -
1300F. and held at this temperature
until the austenite that had transformed on cooling into pearlite decom-
poses into ferrite and temper carbon. The amount of carbon that the
austenite will yield can be determined again from the carbon solubility
line. At approximately 1200F. the solubility of carbon in iron is less
than 0.10 per cent. The alpha iron formed dissolves in the ferrite, and the
uncombined carbon deposits on the temper carbon that was initially
rejected during first stage of malleablization.
20.13. Heat Treatment of Cast Iron
There are a number of methods whereby the heat treatment of cast
iron can be carried out. Briefly we can summarize the various type of heat
treatment under the headings of stress relief and growth, annealing and
normalizing, hardening and tempering, isothermal heat treatment, flame
hardening and induction hardening.
Stress Relief and Growth. Cast irons unless given a stabilizing heat
treatment are susceptible to growth on remaining at room temperature
Cast Iron
431
for extended lengths of time. It is common practice when time permits
to store gray cast-iron parts for a length of time of six months or more
to allow the natural growth to occur on aging at room temperature.
Growth in cast irons can be
accelerated by heat treatment, but the
heat-treating temperature is kept at a minimum to lessen graphitization
of the ccmentite phase. Cementite is unstable in the presence of silicon
and when held at slightly elevated temperatures, tends to break down into
graphite and ferrite. The breakdown results in a decrease in mechanical
properties of the iron. The room temperature aging of the gray cast iron
is most desirable in that no conditions are offered for the graphitizing
action. The temperature range used for the aging to promote growth is
between 700
and 1300F. It is well to mention that all gray cast irons do
not show growth on aging, and this problem has been investigated by
metallurgists for a number of years. There has evolved no acceptable
answer as to why some compositions of irons show the growth
phenomena and others do not. Suggestions have been made as to mechan-
ism of growth, and they embody some of the following concepts: due to
graphitization of some of the cementite, a volume expansion takes place;
penetration of oxygen at the grain boundaries and internal oxidation
occurs with an increase in volume; thermal gradients and volume changes
during heating and cooling. Depending on the type of heat treatment
cycle given the gray cast iron for dimensional stabilization, any or all of
the mentioned factors may apply. Oxidation is a growth factor from room
temperature up to about 800F. Cementite break-down is a factor in
temperature ranges from 800
to 1300F. Thermal gradients and volume
changes occur over all of the heat-treating ranges.
Annealing and Normalizing. The heat treatments of annealing and
normalizing are usually applied to gray cast irons for the purpose of
increasing machinability. The cooling rate from above the critical
temperature will affect the coarseness or fineness of the pearliteferrite
cementite aggregate associated with the graphite. As the coarseness of
the pearlite of the gray cast iron increases, the hardness of the material
decreases. It is possible to over-anneal a gray cast iron. During machining
of such material, tearing takes place, resulting in a poor surface finish.
During the annealing or normalizing cycles, graphitization may take
place with a lowering of the combined carbon content of the cast iron,
resulting in a decrease in strength. In determining the temperature above
which the cast irons must be heated to promote austenization, the usual
iron, iron-carbide diagram cannot be used. The proper section through
the ternary diagram of iron, carbon, and silicon should be consulted.
432
Hardening and Tempering.
The gray cast iron, the pearlitic malleable
irons, and the pearlitic nodular cast irons respond to heat treatment much
in the same manner as do plain carbon steels. The ability to respond
to heat treatment stems from the presence of carbon in the combined
state. The carbon present in the combined state causes the formation of
austenite when the ferrite-carbide aggregate is heated above the upper
critical temperature. Some graphitization may take place during the
heating to the austenitizing temperature. The cast iron is held at the
proper austenizing temperature until the desired degree of solubility of
carbon has taken place, and the alloy is then quenched. The usual
precautions taken in the heat treatment of cast iron are the same as
those for steels. To cause the formation of a completely martensitic
matrix from the austenite, it is necessary that the section be quenched
at, or faster than, the critical cooling rate. If the cooling is some-
what slower than the critical cooling rate, some of the soft pearlitic
constituents
are formed and associated with the martensite. When con-
ditions of service require properties other than high hardness, the irons
are given a tempering treatment. It is quite common to give the heat
treated cast iron, to be used in the martensitic condition, a stress-relief
heat treatment to minimize cracking during grinding and to minimize
the brittleness of the martensite. The tempering curves of hardness versus
time are similar to that obtained for steels. The hardness of the
martensite decreases as the tempering temperature is increased. The
resulting microstructure formed by the tempering of the martensite is
similar to those produced in hardening and tempering of steels. In study-
ing the hardenability response of cast iron, the Jominy hardcnability
type of bar can be used, the hardness being determined along the edge
of the bar in a manner similar to that for low alloy steels and plain
carbon steels. As one may anticipate, the hardness of the fully heat-
treated cast iron quenched at or faster than the critical rate is some-
what less than a steel of the same combined carbon content, due to the
presence of graphite. The presence of graphite in the martensite matrix
decreases the hardness considerably. The use of a light-load hardness
tester will verify the fact that the hardness of the martensite between
the graphite flakes is as great as the martensite in a lull heat-treated
steel. The presence of graphite in the matrix of the cast iron during
heat treatment to full hardness acts as a cushion and tends to minimize
the formation of quench cracks that many occur during the considerable
volume changes that accompany the transformation of austenite to
martensite.
Cast Iron
433
7.--"
noo
^
T 00M1
IIIT
it no
tiktiuti
in
If
\ ^ZUC
1
1
JOOH
MM
LTNI
Ui
s.ai
oo
J
^s.
I
*
too
^-
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1
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5
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I 000
p
ioo
N
N f,
V
if
iac
400
"s
V
*N
N
rl,n,
IOO
too
GRAY CAST IRON

C
- 3. 14
Mn
- 0. 81
P
- 0.219
S
- 0. 064
Si
-
2. 15
Fig. 20.13. Time. Temperature. Transformation (TTT) diagram for a cast iron.
(Nagler and Dondelt).
Isothermal Heat Treatment. The various types of cast irons such as
gray cast iron, pearlitic
malleable iron, and nodular cast irons can be heat
treated by any of the known isothermal transformation methods. The
TTT curve for cast irons does not differ greatly from that of low alloy,
high alloy, or plain carbon steels. Fig. 20.13 is a typical TTT diagram
for a cast iron. The combined carbon in the cast iron is an influencing
factor in determing the position of the upper nose of the TTT diagram.
As the carbon content increases, the upper nose of the TTT diagram is
shifted to the right. The maximum shift to the right is produced by a
eutectoid composition of combined carbon. Amounts of carbon above
or below the euctectoid
composition tend to shift the nose of the TTT
curve to the left. The cementite or the ferrite, whatever the excess pro-
eutectoid constituent may be, nucleates the transformation of austenite
to pearlite at the position of the upper nose of the curve. The products
of transformation produced
isothermally are identical to those produced
434
in steels. Starting at a temperature just below the lower critical tempera-
ture (Aij), coarse pearlite is formed; fine pearlite is formed at the upper
nose of the TTT curve; below the upper nose the upper bainite is
formed; at the lower range the lower bainites are formed; at the M,
temperature
manensite is formed from the austenite on cooling to room
temperature. The isothermal method of heat treating cast irons produces
increased
toughness of the matrix of cast irons.
Flame Hardening and Induction Hardening. The gray cast iron, pearl-
itic malleable cast irons, and the nodular cast irons respond to induction
and flame hardening. The principle of this process of hardening is to
heat rapidly above the upper critical temperature the surface of the parts
to the desired depth and immediately quench. The heated portion of the
iron is changed to an austenitic condition initially, and when quenched,
the austenite is converted
to a martensite. Depending on the thickness
of the section size, there may be no alteration in the properties of the
core. The intent of this form of heat treatment is to produce a marked
increase in hardness on the surface of the part with retention of un-
altered core properties. The hardened portion of the cast irons illustrates
the presence of a martensite matrix with graphite. This heat treatment
produces a hard-wearing
case on the tough shock-damping core of the
cast iron, and the depth of hardening can be controlled very closely.
20.14. Normal and Alloy Elements in Cast Iron
The normal elements in cast iron include such elements as carbon, sili-
con, manganese, phosphorus, and sulfur. The commonly used alloying
elements include copper, chromium, molybdenum, vanadium, and nickel.
Carbon. Carbon in cast iron is present in the uncombined and com-
bined forms. In the uncombined form the carbon can assume the shape
of flakes or nodules. In the combined form the carbon can be present as
a simple iron carbide (cementite) , binary carbide, and other complex
alloy iron carbide forms- The presence of the carbon in the uncombined
state is controlled by such factors as chemical analysis of the iron and the
cooling rate from the casting temperature. In the malleablizing of white
cast iron, an additional type of carbon is formed called tempered carbon.
Silicon. Silicon is generally considered as a graphitizing element. The
amount of silicon present in a cast iron determines whether the carbon
is present in the combined or uncombined state for a given cooling con-
dition. The graphitizing effect of the silicon can be somewhat offset
by the addition of carbide forming elements. Silicon dissolves in the fer-
rite and acts to toughen the iron.
Cast Iron
435
Manganese. Manganese combines with the
sulfur and forms manganese
sulfide, which is insoluble in iron and forms non-metallic
inclusions. Some
of the manganese may form manganese silicate, also present in the iron
as a
nonmetallic inclusion. The manganese remaining is dissolved in the
ferrite and acts as a ferrite toughener.
Phosphorus. Phosphorus is present in cast iron in the form of steadite,
a ternary eutectic of iron, carbon, and phosphorus. Steadite is a low melt-
ing constituent contributing to the fluidity of cast iron. The steadite
melts at about 1750F. The presence of phosphorus adds to the brittle-
ness of cast iron and tends to lower the impact strength of it.
Sulfur. Sulfur is present in cast iron in the combined form of man-
ganese sulphide or iron sulphide. Iron sulphide,
when form usually
occurs in the grain boundaries and reduces the impact toughness of the
iron.
Chromium. Chromium has a two-fold effect on cast iron: it dissolves in
the ferrite and is a carbide former. The chromium that dissolves in the
ferrite acts as a toughener. Chromium that is present in an amount over
that necessary to saturate the ferrite occurs in the pearlite as a massive
iron-chromium carbide.
Chromium has a tendency to produce a uni-
form fine-fracture grain size. As the per cent of chromium added to the
cast iron is increased, there is a tendency for the carbon to remain
in a combined form, and the fracture will be white. Chromium in the
amounts of from 0.15 to 2.00 per cent may be added to cast iron and still
provide gray fractures if suitable graphitizing elements are present.
Additions of chromium to the cast iron will increase tensile strength,
hardness, wear resistance and depth of chill, and corrosion and oxidiza-
tion resistance. Chromium will delay the isothermal transformation of
cast iron during heat treatment.
Molybdenum. Molybdenum dissolves in the ferrite and, to a limited
degree, is a carbide former. Molybdenum does not act as a graphitizing
agent. The addition of molybdenum to cast iron increases tensile
strength, hardness, transverse strength, and resistance to deflection on
transverse loading. The addition of molybdenum to cast iron when cast
into large section sizes tends to promote uniform structures. This results
in an iron of uniform strength, hardness, and density
throughout the
large section size. Molybdenum additions to cast iron promote
machin-
ability resulting from structural uniformity and a minimum occurrence
of large carbides. Molybdenum has little or no effect on retarding
isothermal transformation over the range of baintic transformation prod-
ucts. The isothermal transformation to pearlite products is retarded by
the addition of molybdenum.
436
Copper. Copper dissolves to a limited degree in the ferrite and acts
as a toughener, and is a mild promoter of the formation of graphite.
Copper tends to increase strength, hardness, wear resistance, and corro-
sion resistance. The addition of copper to cast iron reduces the tendency
to form a chill layer, hence increases machinability. Copper is not used
as an individual additive element but is usually added with such elements
as chromium, molybdenum, nickel, and vanadium.
Nickel. Nickel dissolves in ferrite and is a graphitizer. Nickel addi-
tions reduce depth of chill and tend to refine the grain size. Nickel is
effective in retarding the transformation of austenite over the whole
range of transformation.
If the graphitizing effect of nickel is disregarded,
nickel is considered to increase the strength, hardness, resistance to de-
flection, toughness, corrosion resistance, and machinability. In addition
to using the nickel in gray cast iron, it is utilized in martensitic cast iron
containing comparatively
large percentages of nickel and chromium. The
alloy has superior wear and corrosion resistance. A grade of cast iron
termed austenitic is cast with the addition of nickel and chromium for
service conditions requiring lo wexpansion and stainless qualities.
Vanadium. Vanadium when added to cast iron performs the role of a
strong carbide former. Vanadium retards graphitization and stabilizes
cementite and has a high affinity for carbon and combines to form
vanadium carbides. The addition of vanadium to cast iron tends to pro-
duce small uniformly distributed graphite flakes and decreases fracture
grain size and increases the tensile strength, transverse strength, hardness,
and machinability. Vanadium is alloyed in cast iron with elements such
as nickel, copper, chromium, and molybdenum. Vanadium, when added
to cast iron, acts as an effective deoxidizing agent in the removal of dis-
solved oxygen from the iron. Little to no effect can be found on the
isothermal transformation of cast irons because at ausieniting tempera-
tures the vanadium carbide is quite stable.
QUESTIONS
1. What is the general appearance of the fracture of gray, mottled, and white
cast iron? What is responsible for the different fractures of these three
classes of cast iron? What is their relative industrial importance?
2. What is the relation of gray cast iron to steel? In what respects are the
properties of gray cast iron inferior to those of steel? Give die variables that
affect the properties of gray cast iron. What characteristics make gray cast
iron a valuable engineering material?
3. How is a gray cast iron melted, and what raw materials are used? How is
the desired composition attained? How much carbon, silicon, and phos-
phorus are usually present?
Cast Iron
437
4. Name the primary metallographic
constituents in gray cast iron? Describe
the role played by carbon and silicon in iniluencing the structure as seen
with the microscope. What is steadite? Describe its appearance.
5. What is the
general relation between carbon and silicon, and the
structure
and appearance of the fracture? If a small
specimen of cast iron, poured
in a sand mold, contains 3.5 per cent carbon, what is the structure of the
matrix if the silicon is (a) 1.0 per cent? (b) 1.5 per cent? (c) 2.25 per cent?
For small castings, what
percentages of total carbon and silicon would you
specify to obtain a tensile strength of (a) 33,000 lb. per sq. in.?
(6)
38,000
lb. per sq. in.?
6. What is the effect of cooling rate on the structure of gray cast iron? If
the matrix of a small sand-cast bar has a structure corresponding to a steel
containing 0.60 per cent carbon, what would the matrix correspond to if
the casting was a block 6 to 8 in. square? What is the general effect of the
size of the graphite flakes on the properties? How is control of graphite-
flake size accomplished? Why is cast iron frequently annealed?
7. What tests are commonly used to evaluate gray cast iron for engineering
applications? Which is the best of these tests, and how is it made? How are
results reported? What is the approximate secant modulus of gray cast iron,
and how is it determined? What is the average compressive strength?
8. What properties would you consider to be
representative of (a) a high-
test gray cast iron? (b) a low-strength iron? (c) an average American gray
cast iron? How do the endurance limits, impact resistance, and damping
capacity of gray cast iron compare with those of carbon steel?
9. Why are alloying
elements added to gray cast iron, and when is die addi-
tional cost of these elements justified? What are the general effects of
(a) nickel? (b) chromium? (c) molybdenum?
10. How is malleable cast iron produced? What is it used for? Give the approxi-
mate tensile strength and elongation of American malleable cast iron. What
is the relation between the two? Compare endurance ratio, impact re-
sistance, and
machinability of malleable cast iron with those of gray cast
iron.
11. What are the significant differences between pig iron and gray cast iron?
In what way are they similar? In what respect does mottled iron resemble
un-annealed, nodular iron?
12. How does the development, or formation, of graphite in gray cast iron
differ from that in malleable cast iron? Give at least one reason for using
a lower carbon content in malleable iron than in gray iron.
13. In Table 20.2, study the percentages of carbon and silicon recommended
for various types of castings and satisfy yourself why these analyses arc good
for the particular application.
14. Why is closer control of chemical composition necessary in producing high
strength gray iron?
15. Draw a section through a cupola and label the operating parts.
16. List the
requirements of coke that would be suitable for use in a cupola.
17. Why are large amounts of sulfur and phosphorus undesirable in cast iron?
18.
Differentiate between a graphitizing element and a carbide-forming element.
19. What roles are performed by
alloying elements when added to cast irons?
20. What different types of graphite patterns are formed in gray cast iron.
CHAPTER
21
Mach inability,
We ar Resistance
,
and Deep - D rawing
Properties
Irvinc
J.
Lkvinson, M.S., Professor
of Mechanical En-
gineering, Lawrence
Institute of Technology, Detroit,
Michigan
oINCE complex metallurgical, mechanical, and
environmental factors are involved, a precise evaluation of machinability,
wear resistance, and deep-drawing is extremely difficult. This problem of
evaluation has been attacked from many fronts, but to date only gener-
alities have been formulated
no hard and fast rules exist.
21.1. Variables Affecting
Machinability
To remove metal by machining, the tool must first penetrate the
surface. The ease with which this occurs is a function of the static- and
dynamic hardness of the cutter and the metal to be machined, the rate of
penetration, the depth of penetration, the frictional and shear forces
involved, and the relative rigidity of the system.
Once the tool has penetrated the surface the chip formed should
readily break. While spectacular, the long coiled chip is not the desired
one. Breaking the chip mechanically involves a loss of power and thus
is not the most desirable answer. The ideal method of breaking the chip
is to provide a built-in breaker in the form of a weak and brittle con-
stituent. It is wrong to assume that because a metal is soft it is easy to
machine. Toughness is usually a corollary of softness, and, as a con-
sequence, the chips formed separate only with difficulty. In steel, a
completely spheroidized structure is considered the easiest to machine,
although the presence of some small pearlite islands does promote chip
breakage.
21.2. Evaluation of Metallic Materials for Machinability
Experience has shown that a correlation exists between the basic
physical properties of the metals and their machinability. Figure
21.1,
438
80
70
60
50
.40
c
'E30
.20
E
10
20
>
O
>
o-50
c
4<
15
30
zo
10
Machinability,
Wear
Resistance
Tensile
strength,
thousand lb.persg.in.
) 20 40 60 80 100 120 140
439
_l
r
1
\
i
i_
,
\
,
Feed S
*lmm.
_ perrevolution
Depth t=2mm.
o
V/oy.
truck
asts
t/eeb
irali
feels
feels
~X^
hfc^
'-'ft;
V
Heeds -Imm.
.
per revolution
Depth
t-4mm.
*s.
10 60 90 100
, |0
20 30 40 50 60
Tensile strength, kg.
per sq.mm.
Fig. 21.1. Relation of cutting speed for a tool life of 1 hr. to tensile strength for
cuts of 0.08 and
0.16 in. (A.
Wallichs and H.
Dabringhaus, Maschmenbau, v. 9,
1910, p. 251)
for example, shows that
machinability decreases with increasing
tensile
strength. This
property, together with hardness, is probably a good
criterion of
machinability. It is also true that, under controlled condi-
tions, there is very little
difference in the machinability of cast and hot-
rolled steels, of carbon and
low-alloy steels, or of acid and basic steels,
provided tensile
strength and hardness are the same.
Cast steels and
nonferrous alloys may be more difficult to machine
than
wrought material of the same
composition and structure if the
skin of the casting has cooled rapidly enough to harden it, or if the sand
has not been removed thoroughly from the surface.
Many efforts have been made to devise a
laboratory test to indicate
accurately
relative machinability in service. Recent attempts have been
concerned with the work-hardening capacity of the material cut, ihe
object being to use the maximum hardness so induced as a measure of
machinability.
21.3. Free Machining Steels
Despite the impossibility of evaluating machinability accurately, ex-
perience has shown that the machinability of some materials can be im-
proved by certain treatments and, further, that there are alloys of certain
compositions which can be machined more easily at high speed than
other alloys of the same general type. Such materials are, therefore, used
widely in automatic machines for mass production of machined parts.
The machinability of those low-carbon steels which arc too soft and
tough to machine easily is improved by heat treatment and, especially
by cold working. Quenching a low-carbon steel to increase the Brinell
hardness number from 90 or 100 to 170 to 210 improves its machinability
(provided, of course, that no martensite is formed by quenching) . Cold
working is even more effective in increasing the hardness and at the
same time decreasing the toughness; hence, most low-carbon steels that
must be machined economically are cold drawn or cold rolled. This
operation also has the advantage of producing a smooth surface.
The best and cheapest method of improving the machinability of low-
carbon steels is to add sulfur, or lead, or both. However, owing to the
Table 21.1. Relative Machinability Rating of Cold-Worked Free-Cutting Steels
Composition, per cent Machinabil-
S.A.E.
ity rating,
No.
per cent
C Mn S P
X1112 0.08 to 0.16 0.60 to 0.90 0.20 to 0.30 0.09 to 0.13 140
1112L* 0.08 to 0.16 0.60 to 0.90 0.10 to 0.20 0.09 to 0.13 140
1112 0.08 to 0.16 0.60 to 0.90 0.10 to 0.20 0.09 to 0.13 100
X1314 0.10 to 0.20 1.00 to 1.30 0.075 to 0.150 0.045 max. 90
XI 31
5
0.10 to 0.20 1.30 to 1.60 0.075 to 0.150 0.045 max. 87
1115 0.10 to 0.20 0.75 to 1.00 0.075 to 0.150 0.045 max. 81
1120 0.15 to 0.25 0.60 to 0.90 0.075 to 0.150 0.045 max. 78
XI330 0.25 to 0.35 1.35 to 1.65 0.075 to 0.150 0.045 max. 76
X1335 0.30 to 0.40 1.35 to 1.65 0.075 to 0.150 0.045 max. 72
XI340 0.35 to 0.45 1.35 to 1.65 0.075 to 0.150 0.045 max. 70
1020 0.15 to 0.25 0.30 to 0.60 0.055 max. 0.045 max. 63
1040 0.35 to 0.45 0.60 to 0.90 0.055 max. 0.045 max. 60
1010 0.05 to 0.15 0.30 to 0.60 0.055 max. 0.045 max. 53
*
Contains 0.20 to 0.25 per cent lead.
Machinability, Wear Resistance
441
high sulfur (plus high phosphorus for some of the steels), these "free-
machining" or "free-cutting" steels have much lower impact resistance
than low-sulfur steels of the same carbon content and should be em-
ployed, therefore, only where low impact resistance is not a handicap.
Leaded steel is a development of the past few years. The addition of
lead improves the machinability of low- as well as of high-sulphur steel.
Leaded steel is also more resistant to impact than high-sulphur material.
A somewhat similar effect is obtained in stainless steel with the
addition
of Selenium. The relative machinability of the free-machining steels com-
pared with three low-sulphur steels is given in Table
21.1.*
Iron carbide particles, if favorably located and of favorable shape, act
as chip breakers; thus, unalloyed carbon steels containing 0.20 to 0.40
per cent carbon, when properly annealed, machine much more easily
than those containing carbon below 0.15 per cent (Table 21.1). The
best chip breaker is manganese sulphide (MnS) . In high-sulphur steel, in-
clusions of MnS, when well distributed as small particles, break up the
chips very effectively and, as Table 21.1 shows, greatly improve ma-
chinability. Despite their low impact resistance large tonnages of high-
sulphur steels are used.
21,4. Relative Machinability of Steel and Nonferrous Alloys
An approximate evaluation of the relative machinability of some com-
mon ferrous and nonferrous materials can be made by averaging the data
re|>orted by Bostont for drilling, milling, and planning tests. They were
reported as the horsepower required to remove one cubic inch of metal
per minute. The order is as follows:
Horsepower per cu. in.
Material per min.
Magnesium alloys 0.30
Bearing bronze
0.35
Aluminum alloy,
8% Cu
0.35
Free-cutting brass
0.38
Manganese bronze 0.60
Hard cast iron 0.60
Malleable iron 0.75
Yellow brass, unleaded 0.85
Free-cutting, steel, cold drawn 0.90
Forged carbon steel, 020% C 1.12
Nickel steel, 0.40% C
1 .20
Annealed copper 1 .35
Tool steel, high carbon 1 .60
Low-carbon, high-chromium steel 1 .70
Monel metal
1.70
Adapted from a tabulation by H. W. Graham, Metal Progress, July, 1939, p. 53.

tO. W. Boston, Proc. Am. Soc. Testing Materials, v. 31, 1931, part II,
pp.
388-421.
442
This is not an infallible evaluation, and the order might be changed for
some of the alloys if the conditions of the tests were changed slightly.
It does, however, show that it requires much more power to machine the
free-cutting steels than is needed for some of the magnesium and alumi-
num alloys, some of the free-cutting brasses and bronzes, or cast or
malleable iron.
Soft gray cast iron, containing no hard excess carbide or phosphide
particles, and malleable iron are the most readily machinable of all fer-
rous materials, usually ranking higher than high-sulphur steel. The ease
with which these materials are cut is due primarily to the softness of the
ferrite plus the numerous small particles of graphite which act as chip
breakers and as a lubricant.
In general, copper- and aluminum-base alloys are easy to machine.
There is, however, enough difficulty with these alloys so that special
compositions are used for material that is cut in automatic machines.
Free-cutting brass and bronze contain 1 to 4 per cent lead; their ma-
chinability is 70 to 100 as compared to 20 to 30 for the same alloys con-
taining no lead.
21.5. Types of Wear
The importance of wear resistance needs no amplification. Wear oc-
curs in machines when shafts rotate; when pistons and valves operate;
when a gear meshes and drives another; when steel or cast-iron wheels
start, run, or stop on rails; when brakes are set; when excavating, con-
veying, crushing, or mixing machines handle sand, clay, rock, coal, or
minerals; when agricultural implements arc used; and in a multitude of
other engineering applications. Some of the most destructive wear of
metals is caused by rapidly moving soft materials; for example, the wear-
ing of hardened steel parts by cotton or silk thread in textile machinery
and the wear of turbine blades by high-velocity gases.
The wear of metals may be divided broadly into metal-to-metal wear
and abrasive wear. Another division is possible: into wear under rolling
friction or under sliding friction and, further, according to whether
lubrication can or cannot be used. The latter is, of course, most important
in the metal-to-metal contact of machine parts. Lubrication may be
omitted from detailed consideration because, although it greatly influ-
ences the rate of wear, it probably has little or no effect on the type of
wear. Wear resistance is an important property of metals used in ma-
chines even if lubrication is of the best, because perfect lubrication is
more of an ideal than a reality. Moreover, even if lubrication is so
thorough that it prevents a metal-to-metal wear, it frequently happens
Machinabiiity, Wear Resistance
443
that extraneous grit in the lubricant causes severe abraisive wear. Another
important factor entering into the wear of machines is corrosion of the
wearing surfaces caused by condensed moisture or acids in gases and
lubricants.
Wear involving a single type is rare; in most machinery, both abrasive
and metal-to-metal wear occur. This is the case in such parts as shafts
revolving in bearings, where abrasive wear occurs until the shaft and
bearing are "run in" and worn to a mirror finish, after which metal-to-
metal wear predominates. Since in such service wear can rarely be
avoided completely, even with the best lubrication, it is common to use
a hard metal and a relatively soft one together, the softer material being
used (as in a bearing) for the part which is most economical to replace.
In some kinds of excavating and material-handling equipment, abrasive
wear is the principal type involved.
21.6. Variables Affecting Wear Resistance
Like machinabiiity, wear resistance depends upon two factors, the
metallurgical and the mechanical. The latter has been discussed briefly
in the previous paragraphs and may, consequently, be dismissed with
the statement that wear of metal depends as much, or even more, on
the conditions of service as upon the metal used.
From the metallurgical standpoint, wear resistance is inversely pro-
portional to machinabiiity and, in general, directly proportional to hard-
ness. Hardness, however, is not the only metallurgical factor of im-
portance. Wear by abrasion, like machinabiiity, involves tearing off small
particles of the metal. Consequently, strength and toughness are im-
portant factors in resisting wear,
The wear resistance of the various carbon and alloy steels receives
attention elsewhere; it can be dismissed here with a brief mention of
the general types of ferrous material used for wear resistance. The first
and most common, especially for metal-to-metal wear, is a cast iron or
a steel with a surface of high hardness. Usually, in an application require-
ing high surface hardness, considerable toughness, especially of the core,
is also required. This combination of properties is attained by quenching
and tempering an alloy steel or by case carburizing or nitriding a carbon
or alloy steel and heat treating to produce high surface hardness com-
bined with considerable ductility in the core.
For abrasion resistance, two kinds of materials are used:
(1)
an aus-
tenitic steel, which is relatively soft but which, under the severe cold
working of the abrasion, transforms to martensitic; and
(2)
a carbon or
alloy steel, on which a hard surface layer of some special alloy is de-
posited by electric arc or other method.
80 130
70 120
.*60
3
110
c r.
?S0
a
:;.:
B
a
S*
=3
90
|30
!
60
*20
O
70
tt
io
at
50
50
0.16
0.15
g.gO.14
l| an
%.% 0.12
|1
a"
a
1
0.10
f-8* 0.09
S"
0.08
0.07
0.06
0.2.
{
|
.
c ocw/C"
-
r
'/,-
'
<
/
f x _
U-^x-f

>
/
X"*
_x--""
,
1 '
s
y*
ps-
]
Bscale
-i
yj
4
f^
Jr
r~
C
k^
o o Hardened
*
Normalized
D Annealed
d
\.
\
jS
X
k ^n
)
1
\
>
x
^.
S.,
^r~
.-
\
H
(,_
\,
X ""
*x.
\
>
V
o
-o
-'
^
0.4 0.6 0.8 1.0 1.2 1.4
Carbon, per cent
Fig. 21.2. Effect of carbon content and heat-treatment on metal-to-metal wear
of carbon steels. (Rosenberg)
21.7. Evaluation of Steel for Wear Resistance
The evaluation of the wear resistance of steels is one of the most diffi-
cult problems a metallurgist is called upon to solve. Simulating actual
service conditions by a laboratory testthe most important phase of this
problemcan be accomplished only rarely and then only if wear in
service occurs rapidly and if it is possible to design a machine which
duplicates service conditions exactly. Wear is usually a slow process.
Shidle* notes that, when a 5-ton truck has finally worn out, it has lost
only 5 lb. of metal. The useful life of the average automobile engine is
probably 100,000 miles; hence the difficulty of devising a test which will
simulate such service conditions accurately.
Several types of laboratory machines have been developed that deter-
mine the wear resistance of a material fairly rapidly and under relatively
closely controlled conditions. For determining metal-to-metal wear, the
N. G. Shidle, Automotive Ind., v. 66, Mar. 19, 1932, p. 449.
445
most common is the Amsler machine, which tests a specimen under pure
sliding or pure rolling friction, or a combination of the two. Pressures
can be varied at will, and wear can be determined at any temperature,
with or without lubrication. Some data on metal-to-metal wear at room
temperature of carbon steels, together with Rockwell hardness, are shown
in Fig. 21.2.*
For the determination of abrasive wear, two machines are commonly
employed: the Brinell and the Spindel (used widely in Germany) ,
which
use sand or emery as the abrasive. Much care is necessary in the selection
of the abrasives as these may not be uniform. The order of merit of a
series of steels and alloys with one abrasive may change completely if
another abrasive or a different lot of the same abrasive is used. It has
been said with considerable justification that machines for determining
resistance to abrasive wear are a better test of the abrasive than of the
metal.
The important fact to be recognized is that any wear-testing machine
determines the relative resistance of a series of metals or alloys under a
few carefully regulated conditions, but that the results obtained, while
valuable for comparing the materials, cannot be translated quantitatively
into probable life in service unless the test used duplicates in all respects,
including time, the conditions of service.
21.8. Importance of Deep-Drawing Properties
Practically all steels and most of the nonferrous alloys can be de-
formed cold, but how much deformation they will withstand without
failure, or without annealing to restore ductility, varies greatly, depend-
ing upon composition, structure, and other factors. In general, the higher
the ductility as shown by the tensile test, and the lower the hardness, the
more a material can be deformed without fracture. Thus, low-carbon
wire can be drawn through a die to a smaller size than high-carbon wire
without intermediate annealing to restore the original ductility and soft-
ness.
As cold forming by pressing or stamping is cheap and readily adapted
to large-scale production, this method is used widely, especially by those
industries producing automobile fenders and bodies and a variety of
small stamped utensils for domestic and other uses. With the exception
of aluminum and stainless steels, practically all deep-drawn products
are coatedgalvanized, tinned, painted, enameled, lacquered, or plated.
High tensile strength is usually not important; consequently, the ma-
S.
J.
Rosenberg, Iron Age, v. 128, 1931, pp.
1366, 1367.
terials most widely used are those with the least tendency to harden
when cold worked. The principal ferrous materials are, therefore, ingot
iron, unalloyed basic open-hearth steels containing 0.04 to 0.10 per cent
carbon, and the soft stainless steels, all in the form of thin-annealed or
annealed and slightly cold-worked sheets.
As the manufacture of deep-drawn products, such as of fenders and
bodies by the automotive industry, is a continuous low-cost operation,
it is common practice for fabricators of the grade of sheet to arrange
their various operations so that the material is worked until it strain
hardens almost to the breaking point before annealing is necessary. Steel
with a ductility just slightly below the standard will, therefore, show
excessive breakage.
Consumers' requirements have become more severe year by year. It is
only necessary to compare the automobile fender of
the last five years
with those of fifteen years ago to prove how the steel industry has kept
up with this demand by raising the quality of its deep-drawing stock.
There is still much room for improvement, both on the part of the steel
maker and on the part of the consumer of deep-drawing sheets. What is
needed most urgently is a test giving a reliable indication of drawability
and, even more importantly, a standardization of consumers' require-
ments.
21.9. Evaluation of Steel for Deep Drawing
Drawability is a weighted average of a large number of components,
including, among others, yield point and yield ratio in tension, hardness,
elongation, reduction of area, and possibly impact. Drawing different
shapes involves a different relation of the components; hence, even if all
the components were known and could be weighted correctly, it would
be necessary to change the weighting for different drawing operations.
The difficulty of weighing even the known components accurately is
increased by the virtual impossibility of determining accurately reduction
of areaprobably the most important componenton thin test speci-
mens Some users of deep-drawing stock have arrived at certain combina-
tions of tensile strength, elongation, and hardness for different thicknesses
of sheet to indicate satisfactory drawing properties, but such correlation
is worthless to others who draw their product under slightly different
conditions.
To overcome these difficulties, and in the hope that a single test could
be devised to measure drawability, much time and effort have been
devoted to the cupping test. Several varieties have been developed, chief
of which arc the Erichsen, used in Europe, and the Olsen, used in
447
';</
Fie. 21.8. Structure and Erichsen cupping tests o[ (A) fine-grained and (B)
coarse-grained low-carbon sheet steel. (F. Kbrber, Stahl u. Eisen, v. 47, 1927, p.
1158)
the United States.* Essentially, the test
consists of supporting a speci-
men of the sheet between two dies, while a ball or a plunger is brought
down against the specimen forcing it into the shape of a cup. The flow
of the metal can be followed in a mirror, and the first fracture can be
observed. The depth of the cup, or the pressure necessary to cause
failure, is measured. The test gives some information on how the ma-
terial deforms but not enough invariably to predict how it will deform
in service. Metallurgical opinion on the value of cupping tests is divided;
some metallurgists consider them not only unreliable, but actually mis-
leading.
Because the structure and the hardness of steel are important factors
in deep drawing, great care is exercised in the melting, rolling, annealing,
and finishing of the sheet so that the grain size will be controlled ac-
Cupping tests and their significance are discussed by S. Epstein and F. T. Sisco.
in The Alloys of Iron and Carbon, Vol. I, pp.
272-278, and Vol. II,
pp.
646-650 re-
spectively.
Strain-
Fic. 21.4. Stress-strain curves of low-carbon deep-drawing steel showing upper yield
point A, lower yield point B, and yield-point elongation E. Slight cold rolling reduces
the amount of yield-point elongation (second curve from right), and further cold
working eliminates it entirely (right).
curately and the hardness will be within certain limits. A fine-grained
steel can be deformed to a greater extent and has a much better surface
after deforming than coarse-grained material. This is shown in Fig. 21.3.
The surface of the fine-grained steel is smooth after cupping; the coarse-
grained material, on the contrary, has a crinkled "orange peel" surface.
21.10. Yield-Point Elongation, Stretcher Strains, and Deep-Drawing
Properties
Most annealed low-carbon steel used for deep drawing (0.04 to 0.10 per
cent carbon) has two yield points, an upper and a lower one. The upper
yield point (A in Fig. 21.4.) is the stress at which yield begins, and its
location is dependent to a considerable extent upon testing conditions.
The lower yield point (B in Fig. 2 1
.4)
represents the lowest stress to which
the applied load sinks during stretching; this value is probably more
characteristic of the material than the upper point.
The distance that the material stretches while passing through the yield
point is known as the yield-point elongation (E in Fig. 21.4) , and this
value is an important one in determining whether the sheet will have
satisfactory deep-drawing properties.
When annealed low-carbon sheet is deep drawn, strain linesknown
as stretcher strainsfrequently appear on the surface (Fig. 21.5). This
defect is analogous to the orange-peel surface caused by large grains
(Fig. 21.3). These same stretcher strains appear on the surface of a
tensile-test specimen which has a double yield point and considerable
yield-point elongation, and the severity of the defect apparently is related
directly to the amount that the specimen stretches between the upper
449
Fie. 21.5. Stretcher strains in cold-drawn low-carbon sheet.
(J.
Winlock and G. L.
Keltey, Trans. Am. Soc. Steel Treat., v. 18, 1930, p. 241)
and lower yield points. By subjecting deep-drawing sheet to a slight
amount (0.5 to 2 per cent) of cold rolling on a "temper mill," the yield-
point elongation is eliminated and stretcher straining is prevented. The
stress-strain curve for a steel in this structural condition is shown at the
right in Fig. 21.4.
There is still much to be learned about deep-drawing steels and their
behavior under extreme cold deformation. In general, microscopic ex-
amination, Rockwell B hardness, yield ratio, and yield-point elongation,
plus some form of cupping test, give about as much information on draw-
ability as can be secured at present.
21.11. Deep-Drawing Properties of INonferrous Alloys
In general, the working of metals and alloys of suitable properties by
deep drawing is an economical operation, and a considerable tonnage
of nonfcrrous materials is fabricated into finished and semifinished arti-
cles by this process. Second only to deep-drawing low-carbon steel in
tonnage is alpha brass, containing more than 62 per cent copper and
less than about 38 per cent /inc. The variables affecting the deep-draw-
ing properties of alpha brass are very important and have, as a result,
been subjected to more study than similar properties for any other deep-
drawing material with the possible exception of steel for automotive
fender and body stock.
The principal variables that affect the cold-working characteristics of
alpha brass are composition, hardness, and grain size. Ductility is lowered
by small amounts of tin, lead, and iron, and the presence of much beta
constituent should be avoided. Beta is a hard constituent that is likely
to occur if the copper is less than 62 or 63 per cent and may be present
even if the copper is 65 or 66 per cent. Considerable brass of this com-
position is deep drawn. To be readily subjected to a large amount of cold
deformation, the grain size should be small; the optimum size depends on
the nature of the drawing operation and to some extent on the degree of
smoothness desired on the surface. An average grain size of from 0.035
to 0.10 mm. is about right. Brass strain hardens readily and must be an-
nealed at intervals if the cold working is severe. The annealing tempera-
ture varies from 900 to 1100F. (480 to 590C.) and care is exercised to
prevent grain growth during annealing.
Deep-drawn brass will occasionally have an orange-peel surface, similar
to that found in deep-drawn steel (Fig. 21.3), caused usually by large
grain size. The principal defect to which deep-drawn alpha brass is
subject is season cracking, a variety of stress-corrosion cracking that is
encountered in a large number of nonferrous alloys and in some steels,
especially the stainless grades. Season cracking is due to a combination
of high internal stress and some forms of corrosion and has been espe-
cially troublesome in deep-drawn cartridge cases. It can be prevented by
annealing to relieve residual stresses.
Most of the other soft metals, especially aluminum, copper, lead, tin,
nickel, and zinc, and some of their alloys are deep drawn commercially
into a variety of useful shapes. In most cases, special techniques and
equipmentfor example, impact extrusion for collapsible tubes used
widely for drugs, cosmetics, and toilet articlesmust be used, and for
each metal there are special problems to be solved, many of which are
metallurgical. For example, one of the principal problems in deep draw-
ing aluminum is to prevent the abnormal grain growth which is likely to
occur in annealing, and which may cause a rough surface and premature
breakage of the deep-drawn part. In deep drawing high-purity copper,
abnormal grain growth is also a problem.
QUESTIONS
1. Calculate the theoretical horsepower required to machine a hollow monel
metal shaft having an outside diameter of 3.250 inches, an inside diameter
of 1.625 inches, and a length of 36.00 inches, from a blank 36>/j inches
long, having a outside diameter of 3% inches.
2. Design a dynamometer to determine the power required to turn a given
material in a lathe. Make use of the spring characteristic s of the tool holder,
and show how the power could be calculated on the basis of the data
obtained.
Machinability, Wear
Resistance
451
3. Compare the variables affecting machineability with those affecting wear re-
sistance. What conclusions can you draw?
4.
Discuss the effect of wear on fatigue life.
5. Differentiate between erosion, galling, and corrosion as a mode of wear.
List some examples of cadi.
6. Discuss the difference between rolling friction and sliding
friction as a
mode of wear.
7. Discuss the possibility of using radioactive materials to study the rate of
wear.
8. List the
environmental factors that effect wear resistance. Why are these
as important as the physical properties of the material itself?
9. Describe the cupping test and discuss its
limitations.
10. What is meant by "double-yield point" and how does it effect the deep-
drawability?
11. What benefits are obtained in having a homogeneous structure in a material
which is to undergo deep drawing?
12. Discuss the effects of lattice configuration on deep drawing properties.
CHAPTER
Corrosion
and Oxidation
22
Mars
G. Fontana, Ph.D., Professor and Chairman, De-
partment of Metallurgical Engineering, The Ohio
State University, Columbus, Ohio
Richard Edward Grace, Ph.D., Associate Professor of
Metallurgical Engineering, Purdue University, Lafay-
ette, Indiana
L4ORROSION causes destruction or deteriora-
tion of metals and alloys because of electrochemical or chemical reaction
with the environment. Corrosion can be considered as metallurgy in
reverse. For example, iron and steel are made from iron-oxide ores, and
they revert to oxides when rusting occurs.
The annual cost of corrosion in the United States is estimated at 6
billion. Practically all environmentswater, soils, acids, alkalies, gases,
oils, etc.are corrosive to some degree. Corrosion of fuel systems in
automobiles alone costs $100 million per year. One plant spends $2
million annually for painting to prevent external rusting of steel equip-
ment. Some of the results of corrosion are poor appearance, high opera-
tion and maintenance costs, plant shutdowns, contamination of products,
loss of valuable products, and safety hazards.
Corrosion can be classified in two general ways, namely
(1)
wet and
dry or
(2)
direct combination and electrochemical. Wet corrosion occurs
when liquids are present, usually electrolytes. Dry corrosion occurs in.
vapors and gases: a liquid phase is not present. Dry corrosion is usually
associated with high temperatures.
Direct combination usually involves reaction between a metal and
nonmetallic elements or compounds such as steam, oxygen, sulfur dioxide,
and chlorine at high temperatures similar to dry corrosion. This sub-
ject is discussed later under high-temperature oxidation.
22.1. Electrochemical Corrosion
The electrochemical theory of corrosion is the accepted theory. There
are two basic requirements:
(1)
anodes and cathodes must be present to
452
Corrosion and
Oxidation
453
form a cell, and
(2)
direct current must flow. The anodes and cathodes
may be very close together (local cells) or they may be far apart, for
example, two sections of pipe. The current may be
self-induced or it may
be impressed on the system from an outside source.
The anode, or anodic area, is where corrosion occurs and where
current
leaves the metal. The cathode, or cathodic area, does not corrode; cur-
rent enters the metal here. Anodes or cathodes can form on a
single
piece of metal because of local differences in the metal or in the environ-
ment. The metal at the anode dissolves, loses electrons, is oxidized, and
becomes an ion. This situation is shown
schematically in Fig. 22.1. The
Fie. 22.1. Formation of Ferrous Ions in the Corrosion of Iron.
electrons (e) are left on the metal and travel through it to the cathode.
Current flows in the opposite direction. Immersion or contact with an
electrolyte is required to complete the circuit or to carry current from
the anode to the cathode.
Corrosion in pure water (or acids) occurs as follows:
Fe
2e
=
Fe++ (Anode reaction)
2H+ + 2e
= H
2
(Reduction at cathode)
The overall reaction is:
Fe + 2H+ = Fe+++ H
2
.
The quantity of current which passes through this cell is directly pro-
portional to the amount of metal that corrodes. For example, one ampere
per year is equal to about 20 lbs. of steel. Anything that changes these
reactions or the cell circuit could reduce or increase corrosion. If the
454
hydrogen bubbles collect on the cathode and thus form an insulating
blanket, current flow is reduced and corrosion is practically stopped.
This is called polarization and, in this case, cathodic polarization
because it occurs on the cathode.
Most waters contain dissolved oxygen which combines with the hydro-
gen as shown in Fig. 22.2. This is cathodic depolarization and corrosion
proceeds. This is the basis for one of the earliest forms of corrosion con-
trol, namely deaeration of boiler water.
Steel
Wafer
+
2
-<-2H
2
Fig 22.2. Corrosion of Steel by Ordinary Water Containing Oxygen. Depolarization.
In neutral or alkaline waters the anode reaction is the same, but the
cathode reaction is:
H
2
+
i/
2 2
+ 2e = 2 OH-.
The overall reaction is
Fe + H
2
+
i/
?
2
=
Fe
(OH)
2
.
Fig 22.3 is a basic diagram which summarizes the requirements for
corrosion of metals by electrolytes.
Differences in the metal surface, or lack of homogeneity, may be due to
impurities, grain boundaries, orientation of grains, differences in composi-
tion of the microstructure, differences in stress, scratches, nicks, and holes.
It might be said that nature abhors a vacuumcorrosion abhors homo-
geneity.
22.2. EMF Series and Passivity
Different metals have different tendencies to corrode or vary in re-
activity. The familiar Electromotive Force Series, shown in Table 22.1,
Corrosion and Oxidation
455
lists elements in order of decreasing corrosion activity.
Hydrogen is
listed and shown as zero because a hydrogen electrode is used as the
reference electrode or half cell to measure the electrode potentials of the
other elements. The more negative the potential of an element is, the
greater the tendency to corrode.
Table 22.1
Electromotive Force Series Galvanic SeriesSea Water
Cation Volts
Magnesium and magnesium alloys*
Zinc
Na+
-2.71* 2S Al (Comm. pure)
Mg+
+
-2.40 Cadmium
A1 + ++
-1.70 24 ST Al (4.5% Cu, 1.5% Mg, 0.6% Mn)
Be + +
-1.69 ( Steel or iron
[Cast iron
U + + ++
-1.40
Mn ++
-1.10 13% Cr iron (active)
Zn++
-0.76 Ni-Resist (High Ni cast iron)
Cr
+ +
-0.56 (l8-8 (active)
U8-8-M0 (active)
Cr+ ++
-0.50
Fe
+ +
-0.44 Lead-tin solders
Cd++
-0.40 Lead
Co
+ +
-0.28 Tin
[Nickel (active)
llnconcl(active) (80% Ni, 13% Cr, 7% Fe)
Ni + +
-0.23
Sn
+ +
-0.14
Pb+
+
-0.12 fHastelloy B (60% Ni, 30% Mo, 6% Fe, 1% Mn)
Ichlorimct 2 (66% Ni, 32% Mo, 1% Fe)
H+ 0.00
Sb+
++
+0.10 Brasses (Cu-Zn)
Bi
+ ++
+0.23 Copper
Cu++
+0.34 Bronzes (Cu-Sn)
Cu +
+0.47 Cupro-nickcU (60-90% Cu, 40-10%Ni)
Ag+ +0.80 Moncl
(707c
Ni, 30% Cu)
Pb+
++ +
+0.80 Silver solder
Pt
+ +++
+0.86 (Nickel (passive)
l,Inconel (passive)
Au+++ +1.36
Au
+ +1.50t
rChromium steel (passive) (11 to 30% Cr)
18-8 (passive)
18-8-Mo (passive)
fHastelloy C (62% Ni, 17% Cr, 15% Mo)
ichlorimct 3 (62%
Ni, 18% Cr, 18% Mo)
Silver
Titanium
Graphite
Gold
Platinum
t
*
Anodic end
t
Cathodic end
456
According to the EMF
Series, the addition of chromium to iron should
increase corrosion; yet this mixture results in stainless steels. Aluminum
is active hut it is widely used for corrosion resistance. This effective
increase in nobility or corrosion resistance is due to passivity, which can
be simply defined as "a condition that causes the metal not to corrode
when it should." Passivity is generally due to surface films which act as
barriers between the metal and its environment. These films could be
absorbed gases or adherent corrosion products. A series for commercial
metals and alloys in a given environment could show different posi-
tions than indicated by the EMF Series. Table 22.1 gives the order for
the Galvanic Series (sea water) . Chromium, aluminum, and silicon
as elements or as alloy additions to steel are the three most important
from the passivity standpoint.
WET CORROSION
The Eight Forms of Corrosion
Corrosion may be classified into the eight forms in which it manifests
itself. The basis for this classification is the appearance of the corroded
metal. Some of these forms are unique, but all are interrelated. This
classification is arbitrary, but it covers practically all corrosion failures and
problems. The eight forms are (1)
uniform corrosion,
(2)
galvanic or
two-metal corrosion,
(3)
concentration cell corrosion,
(4)
pitting,
(5)
intergranular corrosion,
(6)
stress corrosion,
(7)
dezincification, and
(8)
erosion-corrosion.
22.3. Uniform Corrosion
Uniform corrosion or overall general attack occurs when anodic and
cathodic areas keep shifting, and corrosion takes place more or less uni-
formly over the entire exposed surface. The metal becomes thinner and
eventually fails. This form of corrosion accounts for most of the destruc-
tion of metals on a tonnage basis. From the technical standpoint, how-
ever, uniform attack causes the least concern largely because service
life can often be quite accurately estimated on the basis of relatively
simple corrosion tests. It is the localized form of corrosion that often
results in an unexpected failure.
22.4. Galvanic or Two-Metal Corrosion
When two dissimilar metals are in contact, or otherwise connected
electrically, and exposed to a corrosive electrolyte, coirosion of the less
resistant metal is increased and corrosion of the more corrosion-resistant
metal is decreased. All of the former usually becomes the anode, and
the latter the cathode. Current flows here similar to the situation shown
Corrosion and
Oxidatio7i
457
Environment
Current
leaves
./y
Current
enters
Fie. 22.3. Basic Diagram Showing Requirements for the Corrosion of Metals by
Electrolytes.
in Fig. 22.3. The driving force for the current is the potential generated
by the electrodes. This, of course, is the principle of the so-called dry
battery.
Table 22.1 shows a practical galvanic series for metals and alloys ex-
posed to actual sea water. The farther apart two metals are in this
series the greater the potential when they are coupled. The material
higher in the series becomes anodic to one below it. Magnesium and
copper would form a bad galvanic couple as far as corrosion is concerned.
In many cases, the accelerated attack occurs on the anodic metal near the
junction with the cathode. The effect spreads farther in a linear direction
as the conductivity of the environment increases.
An important effect that is often overlooked, and rapid failures result,
is the area effect, or the ratio of cathodic area to anodic area. A large
cathode and small anode accelerate further the attack on the anode.
For example, a metal by itself in a given environment may corrode at
X mils per year; the rate may be lOx when coupled to a more noble metal;
but it may be 1000X when the area ratio is large. Fig. 22.4 illustrates this
effect. Note that the steel rivets (small anodic area) are completely
corroded; whereas, the other specimen with a large anodic area still
represents a strong joint.
An excellent practical example of rapid failure because of an unfavor-
able area ratio concerns large tanks handling a solution mildly corrosive
;
*V
'
*&*:
-&&-
COPPER RIVETS
IN STEEL PLATE
LARGE ANODE
SMALL CATHODE
STEEL RIVETS
IN COPPER PLATE
LARGE CATHODE
SMALL ANODE
Fie. 22.4. Effect of Area Relationship on Corrosion of Rivets in Sea Water (15
Months). [Courtesy The International Nickel Co.)
to steel. The bottoms were made of 18-8 stainless steel, and they were
welded to ordinary carbon steel sides. The steel was covered with a
baked coating. Small defects in the coating exposed tiny anodic areas
which were in electrical contact through the welds with the larger
bottom area of stainless steel. The steel in the sidewalls near the welds
failed by perforation in several weeks.
22.5. Concentration Cell Corrosion
Anodes and cathodes can form because of differences in the environ-
ment. For example, a potential difference can be measured between two
identical copper electrodes immersed in different concentrations of hydro-
chloric acid. The cells formed because of differences in the environment
are called concentration cells. This form of corrosion is also designated
crevice corrosion, gasket corrosion, and deposit corrosion, and is usually
associated with stagnant conditions.
Corrosion and
Oxidation
459
Low Metal Ion
Concentration
High Metal Ion Concentration
Metal Ion
Concentration Cell Riveted Lap
Joint
High Oxygen Concentration
Low Oxygen Concentration
Oxygen Concentration Cell
Fig. 22.5. Typical Examples of Concentration Cell Corrosion. (Courtesy The Inter-
national Nickel Co.)
The most common forms of
concentration cells are oxygen cells
and ion cells as shown in Fig. 22.5. Fig. 22.6 shows attack on the face of
the flange of a pipe because of concentration cell corrosion. The inside
surface of the pipe is in good condition.
22.6. Pitting
Pitting corrosion is readily recognized because of pits or holes. This
is one of the most vicious forms of corrosion and one of the hardest to
predict. The anodic area remains stationary and corrosion progresses in-
wardly on one spot. Pitting can be considered as the intermediate situa-
tion between no corrosion (complete passivity) and uniform corrosion
(entirely active) in that the surface breaks down and corrodes only in
relatively small areas.
Fig. 22.6. Gasket Corrosion Caused by Concentration Cells.
Pitting often starts because of concentration cell effects such as under
a permeable deposit. The environment under the deposit becomes ex-
hausted of oxygen, or increases in ion concentration; whereas, the sur-
rounding metal away from the deposit is exposed to essentially a constant
concentration of oxygen or ions. The rate of penetration often acceler-
ates because the pit acts as a crevice and thereby increases the concentra-
tion cell effect. An unfavorable ratio of cathode to anode also exists.
This is one reason why the stainless steels often show severe pitting in
some environments with most of the surface showing no attack.
22.7. Intergranular Corrosion
Intergranular corrosion consists of selective or localized attack at the
grain boundaries of a metal or alloy. In some cases, complete disintegra-
tion of the metal results even though a relatively small portion of the
total weight is dissolved. The austenitic stainless steels, such as 18-8, are
particularly susceptible when they are not properly heat treated. If this
steel is heated in the range of about
950
to 1400F. for an
appreciable
time, it
becomes sensitized or susceptible to intergranular attack in
461
environments where high chromium content is needed for corrosion re-
sistance. The commonly accepted explanation for this
phenomenon is
that chromium carbides (Cr
23
C)
precipitate in grain boundaries. This
removes chromium from solid solution and lowers or depletes the chro-
mium in areas adjacent to the grain boundaries. This lowers the cor-
rosion resistance of these areas, and corrosion proceeds aided by galvanic
corrosion and a large cathode area represented by the grains, which are
cathodic. Fig. 22.7 shows intergranular attack, or weld decay as it is
often called.
Fife 22.7. Intergranular Corrosion of Welded 18-8 Stainless Steel.
The plate to the left of the weld in Fig. 22.7 contains about 0.60%
titanium. These steels are stabilized with niobium
(columbium),
titanium, and tantalum, which are strong carbide formers and thus
preferentially tie up the carbon so that chromium carbides cannot form.
The relatively new, very low carbon steels (0.03%
max.) can stand much
more abuse from this standpoint. Another procedure to minimize inter-
granular corrosion is to finally heat the part or equipment to about
1950F. at which point the chromium carbides dissolve, and then rapidly
cool by quenching through the sensitizing temperature zone.
Sometimes the stabilizing element fails to do its duty, as shown by
Fig. 22.8. In this case, intergranular corrosion occurs in a narrow zone
in the parent metal immediately adjacent to the weld or melted metal.
I"ic. 22.8. Knife-Line Attack of Stabilized 18-8 Stainless Steel.
The attacked zone is usually a few grains wide and hence has been
christened knife line attack. The mechanism is briefly as follows. The
metal next to the weld is heated to a very high temperature, and when
rapidly cooled, the niobium stays in solution because niobium carbide
does not have time to form. If this material is then heated in the sensitiz-
ing zone, chromium carbides form as if no stabilizing element were
present. Experiments have shown the niobium carbides dissolve at
temperatures over 2250F. One recommended cure for this situation is to
heat the material to around 1950F, where chromium carbides dissolve
and niobium carbides form.
Other alloys are also sometimes attacked intergranularly, as shown in
Figure 22.9, which is typical of attack on nickel and high-nickel alloys
when exposed to sulfur-bearing atmospheres at high temperatures.
22.8. Stress Corrosion
Stress corrosion could be defined in a general way as the acceleration
of corrosion by stress. In some cases, more or less over-all corrosion is
increased because of stresses in the metal. Stress corrosion is more gener-
ally interpreted as the type of attack that causes cracking, and it is this
form of failure that is under discussion here.
In most cases, the magnitude of the stresses required to cause stress
corrosion is high. These stresses could be due to applied loads or to
residual stresses, although failures because of the former are relatively rare
because most structures are over-designed. The most common of the
residual stresses that cause stress corrosion are those resulting from cold
working or cold forming and also the "locked-in" stresses resulting from
Corrosion and Oxidalion
463
Fig. 22.9. Intcrgranular Corrosion of Nickel at High Temperatures. Top SOX.
Bottom 500X.
welding. In a few cases, plant failures have occurred because of severe
thermal gradients in the metal, which cause high stresses. Tensile
stresses are required for cracking.
Stress corrosion usually occurs when over-all or uniform corrosion is
low and often negligible. It is somewhat similar to pitting in this respect
in that most of the metal is passive but active sites develop. The presence
of stress often accelerates this localized attack. A crack is initiated and
propagates to failure. Two of the earliest and classic examples of stress
corrosion arc the "season cracking" of brass cartridge cases and the
"caustic embrittlement" of riveted steel locomotive steam boilers. Am-
munition became worthless during the wet seasons. Boilers exploded be-
cause of cracks starting near the rivets or stressed areas.
Statements have been made to the effect that all metals and alloys
could be made to crack under selected conditions of stress and corrosion.
Fortunately stress corrosion happens much less frequently than other
forms of corrosion but cracking failures are often serious and unexpected.
Table 22.2 lists a number of metals and alloys and the environments in
which stress corrosion may occur. This does not mean that failure would
always develop in these combinations, but one should be aware of the
possibilities. For example, nickel is widely used in caustic services, and
cracking is difficult to develop unless severely cold-worked metal is used.
On the other hand, brass cracks readily in ammonia, and "as welded"
464
2 50
.200
>
g
150
100
10 20 30 40 50
%
CONCENTRATION
Fig. 22.10. Effect! of Temperatures and Concentration on Cracking of As-Welded
Steel Equipment in Sodium Hydroxide
Based
on Service Experience.
steel will fail quite readily in strong sodium hydroxide at elevated tem-
peratures. Fig. 22.10 shows the relation between temperatures and con-
centration of caustic on the cracking of as-welded steel. These data are
based on actual service performance.*
A number of theories have been proposed for the mechanisms of stress
corrosion. The Electrochemical Theory calls for susceptibility to selective
corrosion along more or less continuous paths and a high stress tending to
pull the metal apart along these paths. These continuous paths could be
along grain boundaries where a precipitated anodic phase, or an anodic
depleted zone resulting from precipitation, may exist. Trenching or
pitting results causing stress raisers or notches where cracks begin to
form and then propagate because of corrosion and stress at the point of
the crack. Differences in potential between the grain boundary area and
the grains have been observed. This theory explains the intergranular
cracking observed in some systems.
The Mechanical Theory states briefly that localized corrosion forms
the notch or stress raiser, but the propagation of the crack is then due to
mechanical effects, and corrosion docs not play a continuous role.
According to the Strain Accelerated Decomposition Theory an anodic
phase is formed because of the presence of stress. In other words a site
that is not susceptible to attack becomes susceptible because of a phase
decomposition or formation caused by stress.
'Corrosion, 7, 295-302 (1951), H. Vv". Schmidt, P.
J.
Gegner, G. Heincman.
465
Tabu: 222.
Environments That May Cause Stress Corrosion of Metals and Alloy's
Material
Aluminum alloys
Copper alloys
Cold alloys
Inconel
Lead
Magnesium alloys
Monel
Nickel
Ordinary steels
Stainless steels
Titanium
Environment
NaCl-HjOj
solutions
NaCl solutions
Sea water
Air, water vapor
Ammonia vapors and solutions
Amines
Water, water vapor
FeCh
solutions
Acetic acidsalt solutions
Caustic soda solutions
Lead acetate solutions
NaCl-KsCrO-i solutions
Rural and
coastal atmospheres
Distilled water
Fused caustic soda
Hydrofluoric acid
Hydrofluosilicic acid
Fused caustic soda
NaOH solutions
NaOH-NaaSiO*
solutions
Calcium,
ammonium, and sodium nitrate solutions
Mixed acids
(HsSOi-HNOs)
HCN
solutions
Acidic HiS
solutions
Sea water
Molten Na-PI alloys
Acid chloride
solutions such as MgClz and BaCh
NaCl-H202
solutions
Sea water
HjS
NaOH-H2S solutions
Red fuming nitric acid
The Anodic Shift
Theory explains the propagation
of the crack by
stating that when a certain stress
concentration is brought about by cor-
rosive attack (pitting or trenching) , some plastic deformation takes place
and the electrode
potential of the metal is shifted in an anodic direction
at the crack base
because of the latent energy
produced by the deforma-
tion. The anodic area produced in this manner is
attacked, and the crack
again produces stress concentration
sufficient for
plastic behavior. This
process can be visualized as a
continuous shifting in potential and simul-
taneous metal removal.
The Film Theory is another form of the electrochemical theory of
stress corrosion but suggests a different driving force than composition
differences. Stress
corrosion is
started by the usual
electrochemical
466
attack, and stress concentration at the base of the incipient crack is
sufficient to tear or break any protective film that may be present. The
crack is propagated by the simultaneous corrosion of the exposed metal
and tearing of any film that may form. The fact that potential differences
do exist between filmed and film-free metal surfaces has been confirmed
many times. In one case, the potential at the base of notches in alloys
subject to tensile stretching was found to be as much as 0.7 volt anodic
to the remainder of the specimen. Attack in these bare areas becomes
permanently faster than on the filmed surface, and preferential corrosion
occurs.
One of the mysteries of stress corrosion concerns an explanation of why,
in some cases, intergranular cracking occurs while in others the cracks
are transgranular
or across the grains.
The work of Priest, Beck, and Fontana* shows that corrosion and stress
must be present simultaneously for cracking to occur. Motion pictures of
crack propagation at actual speed show that cracking stops when cathodic
protection is applied, and propagation resumes when it is removed. This
indicates that the mechanical theory is not correct.
Failure is called corrosion fatigue when cyclic stresses are involved.
22.9. Dezinci fixation
As this term implies, the phenomenon of dezincification was first ob-
served on brasses. The zinc is selectively leached out of the alloy leaving
a brittle, weak, porous mass consisting predominantly of copper plus
copper oxides. The obvious mechanism is solution or corrosion of the
brass; then the zinc stays in solution, and the copper plates back on.
Dezincification can be readily observed because the attacked areas show
the color of copper as compared to the yellow brass. Brasses with 15 per
cent or less zinc are practically immune, and additions of tin, arsenic,
phosphorous, and antimony increase the resistance of brasses to dezincifi-
cation.
De/incification can occur uniformly, as shown in Fig. 22.11, or as the
plug type, or attack in spots. Fig. 22.12 shows a section through a de-
zincified plug and also the porous nature of a dezincified area.
The selective removal of one of the constituents of any alloy falls into
the category described here. The so-called graphitization
of cast iron is
a misnomer. What actually occurs is the removal or corrosion of iron
leaving the graphite network. Selective removal of cobalt in high-cobalt
alloys, and silicon in copper-silicon alloys have been observed.
Trans. ASM.
47, 473-492 (1955).
467
A
:-.'..
..
Fie. 22.12. Section Through Dezincified Plug.
Fie. 22.11. Uniform
Dezincification of Brass.
5000
45 50 55
DEGREES
CENTIGRADE
Fie. 22.13. Inhibiting Effect of Copper Ion in a Sulfuric Acid Slurry on Erosion-
Corrosion of I8-8SM0 Stainless Steel.
468
22.10. Erosion-Corrosion
Many metals and alloys depend upon surface films or corrosion
products for corrosion resistance. If these surface layers are removed
by mechanical wear effects, active and rapid corrosion occurs. Erosion-
corrosion is often encountered under conditions of high velocity, tur-
bulence, impingement,
and solids in suspension. Valves, pumps, elbows,
centrifugals,
agitators, and heat exchange tubes often fail because of
erosion-corrosion.
Fig. 22.13 shows the effect of high velocity on corrosion of I8-8SM0
stainless
steel by a sulfuric acid slurry. The x on the abscissa shows no
attack under static conditions. The curve marked "no copper" shows the
rapid increase in corrosion with temperature under high velocity con-
ditions. The addition of cupric sulfate reduced attack under these
conditions. Fig. 22.14 shows the typical wavy appearance due to erosion-
corrosion.
Fig. 22.14. Erosion-Corrosion of a Pump Impeller.
Cavitation may be considered as one form of erosion-corrosion. Rough-
ened surfaces or deep craters are often found on the trailing faces of ship
propellers and pump impellers. This is cavitation and is largely due to
the mechanical effect or pounding caused by the formation and collapse
of air or vapor bubbles in the liquid on the metal surface.
Fretting corrosion is the attack that occurs at contact areas between
metals under load and subject to vibration and actual slip at these sur-
faces. It is sometimes called chafing corrosion, friction oxidation, and
false Brinelling. The latter because the attacked areas often look like
mechanical indentations. The corrosion product on steel is usually a
Corrosion and
Oxidation
469
ferric oxide debris. Two
proposed mechanisms
involve tearing away of
metal particles because of seizing or galling and then oxidation of these
particles, or oxidation first and then wearing away of the oxides. Fretting
could be considered as one type of
erosion-corrosion.
22.11. Methods for Combating
Corrosion
Many corrosion problems can be solved by more than one
method
or means. Sometimes a combination is used. In any case, the most
economical solution to the problem is usually adopted. Methods for
combating corrosion are
arbitrarily classified into eight general categories
that cover essentially all corrosion problems.
Alloying, or better corrosion resistance, involves using materials with
better resistance to corrosion. If steel
corrodes, copper,
stainless steel,
or high-silicon iron may do the job. Proper heat treatment for optimum
corrosion resistance is also in this
classification.
Cathodic protection involves making the structure to be protected
the
cathode of a cell. This can be done by two general methods namely,
use of sacrificial anodes or impressed
currents. The most widely known
sacrificial anode system is galvanized steel where the zinc coating is the
anode and corrodes preferentially, thereby protecting the steel. Zinc and
magnesium anodes are also widely used. The important point is to have
direct current entering the entire surface of the structure to be
protected.
Impressed currents involve passing a direct current from an
external
source through an anode, through the corrosive environment, and then
to the structure. In this case, a very corrosion-resistant or
"permanent"
anode is needed. Carbon and 14.5% silicon iron (Duriron) are used for
impressed current anodes. Underground pipe lines, water tanks,
sea-going
vessels and piers are examples of structures using cathodic protection.
Metallic and inorganic coatings are typified by nickel, chromium, and
tin
electroplates, and glass and enamels. The principle here is to
install
a barrier to separate the metal from the
environment.
Organic coatings involve paint-type
materials, which act as a
barrier.
Proper metal surface preparation, such as sandblasting, is the most im-
portant factor, followed by a proper primer for good adhesion and com-
patability with over-coats, and then by good top coats themselves. The
use of an expensive paint does not
guarantee that good protection will
obtain.
Metal purification is not often utilized, but it does solve some
problems.
High-purity aluminum, which is
available at reasonable cost, is a good
example.
Contamination and catalytic effects are sometimes involved.
^.-4.3-rs--?
Fig. 22.15. Pump Casing Lined with F.puxy Resin. (Courtesy, The Duriron Co., Inc.)
Alteration
of
the environment often concerns addition or removal of
an ingredient in the environment. Deaeration is an example of the
former and inhibitors of the latter. An inhibitor is anything added to an
environment to decrease corrosion. In many cases, reduction of temp-
erature or concentration, without substantially affecting the process, solves
a corrosion problem or permits the use of less expensive materials such
as steel.
Corrosion and
Oxidation
471
Nonmetallic materials involve integral or monolithic
construction or
thick coverings such as sheet linings. These materials can be classed into
five general types: (a) carbon and graphite; (b) ceramics, such as stone-
ware, porcelain, fused silica, glass, brick, mortars, and cement; (c) plastics,
such as phenolics, vinyls, polyethylenes,
acrylics, epoxies, styrenes, nylon,
silicones, and fluorinatcd polymers (d)
natural and synthetic rubbers;
and (e) wood. Fig. 22.15 shows a
cast iron pump casing lined with a
plastic.
Design involves the shape of a structure. Equipment life can be pro-
longed or corrosion costs reduced through the use of bottom outlets de-
signed to drain completely, readily replaceable or interchangeable parts,
standard lengths of tubing, increased thickness in more vulnerable areas,
designing to prevent crevices or stagnant areas, and the use of
butt-welded
instead of riveted joints.
22.12. Corrosion Testing
Corrosion testing is conducted to evaluate or select a metal or alloy for
a specific environment or definite application, to evaluate a
given material
to determine environments where it is suitable or attacked, for controlling
corrosion resistance of a material or corrosiveness of an environment, or
for corrosion research purposes. These tests include laboratory, pilot
plant, large scale plant, or field tests.
The most important point in corrosion testing is to duplicate as closely
as possible the actual conditions to be encountered. Factors such as
temperature, concentration, velocity, aeration, time, galvanic effects, stress,
and intermittent or continuous operation must be considered. Chemical
and
metallurgical history of the specimens must be known and the
speciments identified. A clean metal surface is preferred.
Most corrosion tests involve determination of loss in weight of the
specimen and conversion to a rate of linear penetration for prediction
of life expectancy. An expression for corrosion rates that is widely used
by engineers is "mils per year," and its formula is as follows:
534 W
mils per year
=
DAT
W
= Weight loss in milligrams
D
= Density in grams per cubic centimeter
A
= Area in square inches
T
=
Time in hours.
472
22.13. Liquid-Metal Corrosion*
The use of atomic energy for commercial power has increased interest
in liquid metals such as sodium, lead, and lithium, as heat-transfer media.
In addition to the usual forms of corrosion, another important factor
enters the picture. This is mass transfer or the solution of the equipment
in a hot zone and deposition of this metal or alloy in a colder area. This
is due to marked change in solubility of one metal in another with change
in temperature. In addition, a more careful selection of materials of
construction must be made because equipment is not as readily accessible
for repair as in more conventional systems.
HIGH-TEMPERATURE
OXIDATION
22.14. High-Temperature Oxidation
High-temperature oxidation of metals and alloys, commonly called dry
corrosion, can be described as the chemical reaction of a metal or alloy
with oxygen, sulfur, nitrogen or any halogen. Generally, however, the
agents involved are solid alloys and oxygen gas. The resulting oxide is
generally less dense than the metal from which it was formed, and it has
poor light reflectivity, electrical conductivity, and mechanical strength.
While the term oxidation
can apply to many different kinds of reactions,
the common chemical change is the valence increase of the metal involved
to a higher positive value. In the subsequent paragraphs, the effects of
oxygen pressure, temperature, and substrate material are discussed to
point out the salient features of all oxidation
processes. Reference to
different metals and alloys will be made, but much practical information
can be gained from the metallurgical literature.
Little is known about the nuclcation of oxide phases on metal surfaces.
On the other hand, the growth of oxides has been studied extensively;
various theories and experimental techniques have progressed well enough
so that theoretical predictions can often be checked quite accurately.
Unlike simple diffusion studies in solid solutions, oxidation measurements
call for boundary conditions fulfilled at interphase interfaces. The gas-
solid oxide interface is the external boundary while the solid-oxide,
solid-
metal interface is the usual internal boundary. In rate studies of oxide
growth
it is usually desirable to know the oxygen pressure in the gas
phase and the oxygen solubility in the metal phase. These quantities fix
the concentration gradient
of cations and anions in the oxide phase, but
Certain of the material presented in Sections 21.1 to 21.13 of this chapter appeared
in a monthly column on Corrosion by M. G. Fontana for Industrial and Engineering
Chemistry, who gave permission
to reproduce it in this textbook.
Corrosion and
Oxidation
473
they do not give
information
about the
growth mechanism.
Oxygen pres-
sure is known to
influence the rate of oxide growth, but the effect is
rather small. Increased
temperature
generally increases the oxidation
rate; however, the criterion of
oxidation rate may yield
ambiguous re-
sults. For example, if the criterion for
oxidation were simply
grams of
oxide gained per unit area and unit time on a metal
substrate and the
oxide had a very high vapor pressure,
temperature increases
could result
in vaporization or loss
of oxide, yet
oxidation would
proceed rapidly.
An example of this behavior is the Mo,
Mo()
3
,
O, system at
temperatures
above 600C.
Internal oxidation occurs in
many copper and
silver-base
alloys and in
certain steels. This kind of
oxidation is
characterized by the
formation of small particles of oxides of the alloying
elements below the
external scale.
Since scaling or oxidation is primarily a deleterious effect,
engineers
are concerned with design problems in which the part to be
used may be
subject to hot gases. Size and shape retention may be
important
design
requirements, but frequently the electrical and optical
properties of the
oxide phase are
considered. In
electrical contacts, for example in relays,
the choice of an
oxidation-resistant
alloy is imperative,
because the
formation of a poorly conducting oxide scale can prevent electrical con-
tact from being made. The choice of
stainless steels and
aluminum
alloys
for kitchen utensils which should have eye
appeal is evident when it is
known that the oxides of these alloys are nearly transparent
and do
not materially affect the light reflectivity of
surfaces at low
temperatures.
Lastly, it is obvious that through oxidation the reduction in area of any
structural member designed to carry a given load may make the part unfit
for service. This effect on strength can be
magnified when parts are used
in fatigue-loaded
operations where the oxide is
continually cracked off and
fresh oxide forms at the expense of base metal.
22.15. Formation of Oxides
The most
common method for obtaining
quantitative
oxidation data
on metals and alloys is by measuring the weight gain per unit time and
unit area. In
vapor-deposition processes such as the
condensation reaction
at the cool end of a zinc retort, the
species which exists in the gas phase is
frequently the same species that exists on the substrate and the reaction
progresses because the substrate material is cold.
Similarly, in metal
cladding by vapor-phase
deposition, the
vapor may be a
different atomic:
species than the
substrate, but
intermetallic compound
formation is not
important in determining the rate of the condensation
reaction. The
driving force for these reactions is a
supersaturation brought about by a
474
temperature distribution. Furthermore, the nucleation of new grains in
these deposition processes occurs in the same way that nucleus formation
proceeds in the water-to-ice transformation, the growth of rock candy,
the freezing of metals, and the electrodeposition of metals.
The problem of nucleation of an oxide on a metal substrate is com-
plicated by the fact that the gas species chemically reacts with the sub-
strate form a structure of the type M
x
O
v
. The following single steps may
occur to a greater or lesser extent in the formation of any oxide. As is
evident from the listing, most of the steps are likely to affect the nucleation
rate and the growth rate of an oxide grain. The rate of any oxidation
reaction is governed by the single slowest step of the type listed below:
1. Surface adsorption of an O
t
molecule on metal.
2. Dissociation of
2
to O atoms.
3. Ionization of O to
0=.
4. Ionization of M to M+
x
and electrons.
5. Surface migration of O, 0, M or M+
x
.
6. Diffusion of O in the metal phase until the solubility limit is reached.
7. Nucleation of the oxide phase.
Once an initial oxide layer has been formed, several other possible
steps may occur. There are:
1. Diffusion of
2
gas within cracks in oxide film.
2. Surface adsorption of an
2
molecule on metal oxide.
3. Dissociation of
2
to O atoms.
4. Diffusion of 0=
through oxide layer.
5. Ionization of M to M+
x
and electrons at the metal-metal oxide
surface.
6. Diffusion of M+
x
through oxide layer.
Fig. 22.16 shows a sequence of microscopic steps that may be operative
when a bare metal surface is oxidized. Since the view has been taken
that the rate of oxidation is governed by the single slowest step, any
experimental work necessitates the reduction of a system of many factors
to a system in which a single variable can be studied to yield meaningful
results.
22.16. Dependence of Oxide Growth on Gas Pressure
The effect of pressure on oxidation rate has been successfully investi-
gated for very few metals. Among these are iron, copper, zinc, zirconium,
titanium, vanadium, and cobalt, reacting with oxygen. At various pres-
sures the dependence of a reaction rate of a solid with oxygen is intimately
related to the mechanism of the reaction. The conditions for growth are
related to the nonstoichiometry of the oxide phases developed, and the
Corrosion and
Oxidation
475
/ J~
LINES Of
Fic. 22.16. Gulbransen's
postulation of oxidation
mechanism,
a-adsorbed oxygen
film, b-fine mosaic structure of crystals,
c-nucleation of large crystals,
d-uniform
oxide layer appears. Taken from E. Gulbransen, W. R. McMillian and K. F. Andrew,
Trans. A. I. M. E. 200, 1027 (1954).
mechanism for growth is assumed to be diffusion
controlled within the
oxide phase. Two metals which have been studied
extensively are copper
and zinc. The following
paragraphs present the
information which
predicts and supports the pressure dependence of the
observed oxidation
rate.
1. The electrical
conductivity of Cm
2
was observed to increase with
oxygen pressure
according to the relation.^
Vs
a
= constant P
Q
J.
Gunderman, K. Hauffe. and C. Wagner, Zeit. phys. Chem., B37 (1937).
148.
Since the three variables that make up
electrical
conductivity are
concentration,
valence, and mobility of the
conducting species, varying
oxygen
pressure must change one or more of the variables to account for
the pressure
dependence. If the structure of the oxide is viewed as cation
deficient, the following model could
represent the structure of Cu
2
0.
Cu"
Cu*
O
Cu->
Cu^
o-
Cu<
0=
Cu*
Of
o-
Then, one oxygen
molecule may form two molecules of Cu
t
O by the
following relationship.
Ot +
4-
-*
4Cu
+
D + 4*"D +
2 c"*
Applying the law of mass action and realizing that the concentrations of
Cu+ vacancies and Cu++ions are identical, one finds
C
8
defects
=
constant
If the oxidation rate of copper is determined by the concentration of
defects operative in the oxide phase near the gas-oxide interface, then
oxidation rate a
C defects cc PjJ
Oj
Wagner and Grunewald* report that the oxidation rate of copper at
1000C. is a linear function of the seventh root of the oxygen pressure.
This agreement supports the theory reasonably well because such measure-
ments are difficult to make when the pressure dependence is so small.
Oxides which behave similarly are FeO, NiO, CoO, and AgÔ.
2. On the other hand, a class of oxides exists in which the electrical
conductivity decreases with increasing oxygen pressure. A typical ex-
ample of this type of oxide is ZnO. The following structure shows a
typical cation excess oxide.
Zn*
+
0- &++ 0-
Z"*+
0-
0-
Z"
++
o-
Z
n
*+
o- fir*
dB>
Zn
+
*
0-
Z
n
**
0-
Z
n+* 0-
CD
0-
Zn
++
0-
Z"
+
*
0-
Z"*
+
If the number of interstitial ion and electron defects were decreased by
an increased oxygen pressure according to the reaction,
i/aO,
+
<^f)
+ 2
(P)
->
ZnO
Electrical conductivity
or
Oxidation rate a
C defects a
ô
Vt
C. Wagner, and K. Grunewald, Zeit. phys. Chem., B40 (1938), 455.
Corrosion and
Oxidation
477
FIG. 22.17. The
oxidation-time relationships. Taken from O.
Kubachewski and B.
Hopkins. Oxidation
of
Metals and Alloys.
Butterworth's Scientific
Publications, London
(1953).
Various measurements have shown that
electrical conductivity varies
with the negative fifth root of the oxygen pressure, and the
agreement
with theory is
relatively good. Other oxides which possess cation excess
structures are BeO, Fe
t
O
s
,
MoO
s
and SnO
t
.
22.17. Dependence of Oxide Growth Upon Time
Various weight change versus time
relationships exist for oxidation
rates. Fig. 22.17 shows a composite graph of the
oxidation-time relation-
ships. The two most important of these empirical relations are the linear
and parabolic equations.
The linear relationship is the
simplest equation that has been found
to express experimental data. The
equation Am
= kt
relates the change in mass per unit area with time; k, is called the linear
rate constant. No other constant is necessary in this linear equation
because at t= o, [\m
=
o. Another form of this relationship is
Ax
=
k,*
where Ax is the change in thickness of the oxide layer. These
relations
have been found to apply when the molar volume of the oxide phase is
less than the molar volume of the parent metal which reacted. Physically,
these oxides cannot cover the entire metal surface; fresh metal surface is
continually exposed and the oxidation rate is quite constant. Common
metals which conform to this type of oxidation are lithium, sodium
and magnesium.
Pilling and Bedworth expressed their criterion of linear vs parabolic
oxidation rate by the following relation:
Mi
>.
Dm
<h
where M = molecular weight of oxide phase,
D =
density of oxide phase,
m
=
atomic weight of metal phase,
d = density of metal phase.
When the above ratio is less than unity, the linear rate law is obeyed;
but when the ratio is greater than unity, the parabolic rate law is called
for.
That is to say, if the molar volume of the oxide is greater than the
metal which reacted (but not too great to crack off under stress during
growth), a protective film would be expected. A simple statement of this
situation would be that the increase in film thickness would be inversely
proportional to the actual film thickness at any time. For example, if the
following equation were integrated
d(Ax)
= k
p 1_
dt Ax
to
Ax*
=
2k
p
t
we have a statement of the parabolic expression for rate of oxidation.
This "law" was enuciated by Pilling and Bedworth and frequently bears
their name. A similar expression for the change of mass of an oxide film
can be written by substituting
Am for Ax and changing the units k
p
accordingly. Fig. 22.18 shows typical oxidation data which follows the
parabolic equations. Protective films are found on many metals and alloys
and are highly desirable. Examples of these are aluminum, chromium,
copper, beryllium, titanium, and iron.
Lastly, some oxidation rates have been observed that are faster than the
parabolic rate at first but tend to protect the parent metal very well.
Examples of these rates are the cubic and logarithmic expressions which
follow:
(Ax)
3
=
k
c
t (cubic)
and
Ax =
A'log t
-+- b (logarithmic)
479
16-
* 6
00'
10 12
Fig. 22.18. Oxidation of oxygen-saturated titanium. Taken from M. Simnad, Aija
Spilners and 0. Katz, Trans. A. I. M. E. 203, 645 (1955).
These expressions are commonly used to represent data on very thin
oxide film formation at relatively low temperatures. At intermediate
temperatures most metals tend to behave parabolically, and at high
temperatures the linear rate is often observed. Engineering choices of
metals for a particular operation often necessitate the gathering of data
on oxidation resistance in the temperature interval desired and under
the exact service conditions of gas composition, moisture, pressure, and
surface preparation.
22.18. Dependence of Oxide Growth Upon Temperature
The temperature dependence of oxidation rate is generally the same
form as that for diffusion and ionic
conductivity. The following ex-
ponential relation applies for a single oxide in a given temperature in-
terval.
k
=
l-^r'l
In this expression, k is the experimental rate constant (linear, parabolic,
cubic, etc.) and C is a constant having the same units as k. A term called
/
480
Engineering
Metallurgy
the experimental activation
energy is given by
A,
while
R is the gas
constant
(1.986 calories/mole
degree) and T is the temperature
in
absolute units (Kelvin)
. Information about the mechanism
of oxidation
and electrical conductivity
can often be gained by comparing the experi-
mental activation
energy for diffusion
of a known species with
the activa-
tion energies
for oxidation
or electrical conduction.
If the values for
A are identical, one may generally assume that a diffusing species
accounts for a given
oxidation rate or an experimental
specific con-
ductivity.
Many accurate data are needed in this particular method of de-
ducing the mechanism of metallurgical reactions.
On the other hand, some metals and alloys tend to oxidize very rapidly
upon reaching
certain temperatures.
It has been observed that the
temperature
at which "catastrophic"
oxidation occurs frequently coin-
cides with the formation of liquid oxide phase, generally a binary or
ternary
eutectic. Severe attack of this type may actually result in a
weight loss
of the oxidized
specimen, because the oxide may volatilize
appreciably.
22.19.
Oxidation Prevention
Gold and platinum are the only metals which will not form
oxides in
air at room
temperature. Silver, palladium and rhodium oxides thermally
decompose
to the metals and oxygen gas at 190, 800 and" 1
100C, respec-
tively. In some instances it is possible to use one of the noble metals at a
temperature where its oxide simply cannot form. However,
high costs
prohibit such applications.
Cladding base metals with precious metals
has been attempted, but oxygen diffusion through the precious metal
coating is fast enough at elevated temperatures to oxidize the base metal
internally.
This kind of oxidation results in an oxide layer formed be-
tween the base and the precious metal.
One way to retard elevated-temperature
oxidation of carbon steels and
low-alloy
steels is to heat them in a neutral or reducing gas. Such pre-
cautions,
although expensive, are used in annealing low-carbon
sheet
and wire to prevent discoloration
or the formation of an oxide coating of
appreciable
thickness. If it is necessary to prevent
oxidation of medium-
and high-carbon steels by heating in a neutral or reducing
atmosphere
as is sometimes the case in heating treating toolsprecautions
must be
taken to prevent
decarburization of the surface layers. Removal
of carbon
from the surface with the production
of a soft outer layer is sometimes
more of an evil than scale formation.
The common method of protection of a metal or alloy is by the for-
mation
of a protective oxide film which inhibits further oxidation.
In
Corrosion and
Oxidation
481
designing a part for a
particular operation it may be
possible to
select
a
particular material that will
protect itself after a thin
film of oxide has
formed. The classic example of this is the Delhi pillar of India. This
mass of wrought iron, some 24 ft. high and
weighing about 6.5 tons, was
made by hand welding small blooms. It was erected about A.D. 300.
Owing to a "tight"
oxide coating and a pure, dry
atmosphere, it had
resisted corrosion
remarkably well for about 1600 years, but when
Had-
field brought a piece of the pillar to
England and
moistened the surface,
it rusted badly overnight.
Oxides formed on pure metals are
relatively simple in structure and
composition when compared with the
oxides formed on alloys which have
many
elements in solid
solution or have
several phases in their micro-
structure. When several oxide phases form, as on iron, the oxide
closest
to the metal, has the
highest per cent of the metal while the oxide
which
forms at the
external surface has the lowest per cent of metal. Thus,
when iron oxidizes at elevated
temperatures, an innermost layer of FeO,
and
intermediate layer of Fe
3 4
, and an outermost layer of Fe
2 3
appear.
When
alloying elements are present,
their oxides may
appear
separately
or as special oxides of the type AB,0,
where A and B denote metals and
x,
y
and z are small whole numbers.
Oxidation resistance of a pure metal
can be increased or
decreased by the
addition of
alloying elements.
Additions of chromium,
nickel, aluminum, and silicon to iron and steel
serve to increase the
oxidation resistance, because the oxides protect the
base metal. In these cases the oxidation rate tends to be parabolic.
Boron,
molybdenum, and vanadium markely decrease oxidation
resistance
of steels because the
resulting oxides are
nonprotective. In dilute
copper
alloys beryllium, aluminum,
magnesium, and
silicon increase resistance to
oxidation while titanium, cobalt, nickel, and manganese seem to have
little effect.
High chromium, usually together
with high nickel or high cobalt, is
necessary for resistance to oxidation at elevated
temperatures.
Typical
costly alloys include low-carbon 18 per cent chromium, 8
per cent
nickel
steel; 10 to 35 per cent chromium steel; 35 per cent nickel, 15
per cent
chromium steel; an 80 per cent nickel, 20 per cent chromium alloy; a 62
per cent nickel, 15 per cent chromium, 23 per cent iron alloy; the
nickel-molybdenum alloys of the Hastelloy type; the
cobalt-chromium
alloys of the Stellite type, and a number of others. All have long life at
temperatures of 1300 to 1800F. (700
to 980C.) or even higher and
are used in oil refineries, power plants, furnaces, and chemical plants.
A
typical oxidation study yielded the results shown in Fig. 22.19. Type
410and 430 stainless steels, having 11 per cent and 16 per cent Cr, were
482
Engineering
Metallurgy
too
TME M HOURS
Fig. 22.19. Oxidation of types 410 and 430 stainless (electropolishcd) at 1600"F in
moist and dry air. Taken from D. Caplan and M. Cohen, Trans. A. I. M. E. 194 1057
(1952).
oxidized at 1600F. in wet and dry air. The wet air caused rapid attack
on both steels in comparison with the dry air, and in both cases the oxide
formed on the 16 per cent Cr steel was more protective than that on the
1
1 per cent Cr steel.
One general feature in tailor-making an oxidation-resistant alloy is to
add an alloying element which has a very high affinity for oxygen and
whose oxide has very low electrical conductivity.
Such oxides either have
few ions free or able to migrate or have structures which hinder diffusion.
In either case, the oxides formed tend to be protective.
Another way of protecting
a base metal is by cladding it with another
metal which oxidizes very slowly. Cladding techniques include:
1. Metal spraying.
2. Hot dipping.
3. Roll cladding.
4. Casting.
5. Electroplating.
6. Cementation.
Corrosion and
Oxidation
483
While all of these methods are not generally suitable for the application
of a single metal on a base metal substrate, frequently two or more are
used with success. The use of nickel clad steel results in almost mirror-
like surface finishes after a year or longer of operation near room tem-
perature. Studies on the oxidation of
nickel-clad steel showed that the
oxide formed was invisible to the naked eye.
Chromium plating is as
effective as nickel, which is generally used as an undercoat for chromium
plated objects.
Aluminum-coated irons have been shown to be 30
times more resistant to oxidation than noncoated irons, and aluminum is
one of the most
versatile metals to clad with. Every clading technique is
used to a greater or lesser extent with aluminum-clad
products. Copper,
zinc, lead, brass, bronze, palladium, and rhodium are all used extensively
for
cladding to
hinder surface reactions.
QUESTIONS
1. Why do metals
corrode in electrolytes?
2. What is meant by anodic polarization?
3. Describe an example where two of the eight methods of combating
corrosion
arc used simultaneously.
4. A common piece of equipment used for heating water in a plant consists
of a shell-and-tube exchanger with water inside the tubes and steam in the
shell.
In many cases copper tubes with thick cast iron tube sheets are used.
Why?
5. Describe in detail procedures and
equipment needed to prevent inter-
granular corrosion of a large tank (for a railroad tank car) fabricated by
welding 18% Cr-8% Ni stainless steel (not stabilized).
6. Describe a test you would devise to
determine whether or not a
given
material would be
susceptible to stress-corrosion
(cracking) in a given en-
vironment.
7. Sketch a heat exchange system using liquid sodium
indicating a difficulty
that may arise because of "mass transfer."
8. Why are the stainless steels often used for applications involving heat and
oxidation resistance?
9. Based on the electrochemical theory of corrosion, why docs "graphitiation"
of grey cast iron occur?
10. Describe the mechanism of
knife-line" attack of the stabilized stainless
steels.
11. Describe a defect lattice which is a (a) cation deficient structure, (b) cation
excess structure.
12. The following data arc given for several metals and their oxides. Do
these
metals oxidize linearly or parabolically?
484
(A) Metal
Atomic Weight Density, g/rm
3
, 25C
Al
26.97 2.70
Be
9.02 4. SO
Cu
63.57
8.92
Pl>
207.21
11.34
Mg
24.32 1.75
Na
22.99
0.97
Zn
65.38
7.H
(B) Metal Oxide Molecular
Weight
Density, g/cmS,
25C
A1
L
,0
3
101.94
3.7
BeO
25.02
3.0
CiigO
143.14
6.0
CuO
79.57
6.4
PbO
223.21
9.5
MgO
40.32
3.7
Na,0
61.99
2.3
ZnO
81.38
5.5
13. Calculate the mobility
of electrons in a mole of pure solid copper at 25C,
if the specific conductivity
a
= cze^, where
a
= 10
ohm-' cm-*, c =
concentration
of carriers, z = valence of carriers, e = electronic charge and
/i = electron mobility.
14. Test the following
data for "fit" to the parabolic, linear, or cubic rate
laws for the oxidation of metal A.
Oxide Thickness,
A time, minutes
500
10
1000
40
2000
160
15. If the experimental
activation energy for oxidation of Zn to ZnO is 28.5
Kcal/mole and the frequency factor, C, is 2.8 x
10-
cmVsec, what is the
value of the oxidation rate constant at 400C?
16. Describe in your own words
the Pilling and Bedworth rule of oxidation.
17. Are metal oxides better or poorer electrical conductors than metals? Explain
your reasoning.
18. What is catastrophic oxidation?
19. If a first order interference color of yellow is seen on a slightly oxidized
tool steel, estimate the oxide thickness. Assume a representative blue
radiation of 4700 A, and that first order extinction
of blue occurs when
A"
= -.
.
when
A
is the wave length being destroyed and
v
is the index
of refraction of the oxide film
(^
~
3).
CHAPTER
Effect of
Temperature
on
MechanicalProperties of
Metals
23
James R.
Macdonai.d, Ph.D., Chairman,
Department of
Mechanical Engineering, School of Engineering, The
University of Mississippi,
University, Mississippi
George V. Smith, Ph.D., Assistant Director for Metal-
lurgical Engineering,
School of Chemical and Metal-
lurgical Engineering, College of
Engineering, Cornell
University, Ithaca, New York
FOR
centuries man's only interest in the reac-
tions of metals to stresses at elevated temperatures was related to the
reactions of the metals to stresses used to form them into usable shapes.
He learned that at elevated
temperatures metals could be subjected to
repeated instantaneous stresses of forging, rolling, or drawing without
fracturing easily.
Interest in metals for extended service at elevated
temperatures had its
beginning in 1924. Prior to that time most studies were confined to short-
time
high-temperature tests, for at that time there was no need to study
the effects of long-time stress at high
temperatures. But with the increased
temperatures and pressures being employed in the steam-power
generating
industry, problems that were not
understood began to develop. Equip-
ment
operating at high temperatures and
presumably designed conserva-
tively with an ample factor of safety
warped and even failed; the carbon
and low-alloy steels being used, instead of exhibiting only elastic deforma-
tion as well-behaved steels should, deformed plastically under surprisingly
low loads.
At normal temperatures, most
high-melting point metals and alloys
deform elastically under working loads. There is no appreciable
plastic
deformation
(permanent set) so long as the applied load does not
exceed
the elastic limit. Furthermore, most metals and alloys when subjected at
normal temperature to stresses above the elastic limitas in cold working
strain
harden; in other words,
permanent deformation
distorts the
grains and increases strength and
hardness. This also holds true at ele-
vated temperatures so long as the temperature is below that at which
rapid recrystallization takes place.
485
486
As is evident from this introduction, the problem facing the metallurgist
and engineer was a phenomenon involving small amounts of plastic de-
formation over long periods of time at elevated temperatures. This
phenomenon is called creep. Entering importantly into the problem of
creep is strain hardening, which is opposed to the softening that occurs
during
recovery and recrystallization. Recovery and recrystallization de-
pend upon time, temperature, prior plastic strain and the previous struc-
tural condition of the material. For steel, the recrystallization tempera-
ture ranges from about 700F. to the lower critical temperature.
23.1, The Importance of Creep
Dickinson
demonstrated in 1922 that steel deformed slowly at a red
heat under stresses which were much lower than the values used in what
was then considered
good design. The connection between this slow
deformation at high temperature and the failure of certain power-
generating equipment was established, and the importance of creep was
recognized. As a result, the American Society of Mechanical Engineers
and the American Society for Testing Materials set up a joint committee
in 1924 to study the phenomenon, to devise a method for determining
slow deformation, and to accumulate useful data on slow deformation of
industrially important metallic materials. This work has spread from
metals to ceramics and has develoj>ed considerable interest in a new
series of materials which are produced from mixtures of metals and
ceramics known as cermets.
Laboratories are continuing to study creep, and although many data
have been accumulated, much more needs to be done.
23.2. The Engineering Significance of Creep
In the selection of a steel or other alloy for high-temperature use the
mechanical properties of the material as determined at room temperature
are of little importance. The requirements for metallic material which
is to be used in various kinds of equipment operating at high tem[>eratures
vary widely, but in general the following are important:
(1)
The metal
should be resistant to oxidation or other attack by the hot gases (including
air) which are present;
(2)
it should have a stable structure which will
remain relatively unchanged under the stress and temperature conditions
imposed;
(3)
it should withstand the stress imposed with a negligible or
at least with a harmless amount of distortion for the useful life of the
equipment; and
(4)
it should withstand momentary overloads at the usual
operating temperature, or short periods of fluctuating temperature at
Effect of
Temperature 487
normal loads. There are few metallic materials which meet all these
requirements. It is, therefore, not easy for the metallurgist to supply
the engineer with materials suitable for equipment operating at high
temperatures and fairly high loads. This difficulty is not lessened by
the fact that engineers are usually uncertain about the exact loads and
the exact temperatures in the equipment they design and use.
The steam-power generating industry is an excellent example of the
trend to higher temperatures during the past years. In 1905, the initial
temperature of commercially used steam turbines was only 500F. In
a two-year period from 1906 to 1908 it was raised 100F. and it remained
at 600F. for nine years. In the next three years (1917 to 1920) it was
raised another 100F., but it was not until 1926 that the temperature
attained 750F. Making use of the accumulated high-temperature data
manufacturers increased the steam temperature to 950
by 1938. During
World War II there was no change because of the scarcity of critical
materials, but shortly thereafter the temperature was increased to 1 100F.
Certain units in the petroleum industry have always been operated
at metal temperatures in excess of those employed by the steampower
industry. The ability to do this is based on shorter expected metal life,
shorter operating cycles, and more frequent inspection, with opportunities
of replacement prior to fracture of the parts operating at the higher
temperatures. In fact, prior to 1930, operation of the thermal cracking
units was generally of the intermittent-coking type, so that the cycles were
very short, often only 40 to 50 hours. Today the length of the operating
cycle is often measured in months, or years, rather than in hours. Develop-
ments in high-temperature alloys have contributed to this ability to use
longer operating-time periods, which in turn have greatly increased pro-
duction because of less down-time of the units.
General conclusions with respect to temperature trends within the
chemical industry cannot be drawn because of the wide variety of
products manufactured by the different companies, and often within
the same organization. The requirements of this industry do extend from
moderate temperatures and extremely high pressures to very high metal
temperatures
(1800 to 2000F. (980 to 1095C.)) with low pressures.
During World War II there was an ever-increasing demand for stronger
and stronger alloys that could be used at higher and higher temperatures.
The exhaust turbosupercharger for aircraft engines involved rotor tem-
pertures up to 1350F. (730C.) and blade temperatures to 1500F.
(815C.) or even higher. The requirements for engines in present-day jet
planes are somewhat lower. The expected life in these applications is
488
currently relatively short, a fact which helps to simplify the metallurgical
asjjects of the problem. The temperatures in gas turbines for central sta-
tion power generation are somewhat lower and the expected life very
much longer.
Another application, just beginning to acquire importance, that
may require alloys that can be employed at very high temperatures is the
commercial use of nuclear energy for generating power.
c
/\
,s
z
ELEVAT
EMPERJ
ED
D
r TURE
<
J_
/
/
/
Uip
TE
^Xi
(
1
A
0-B ELASTIC DEFORMATION AT ROOM EM 'ERATURE '
A-C PLASTIC DEFORMATION. OR CREEP
A-0+ CREEP CURVE
A-D FIRST-STAGE CREEP F FRACTURE
- D-E SECOND-STAG-E CREEP
E-F THIRD-STAGE CREEP
i i i i . i i 1 1 1 1 1 1
u
TIME OF STRESS APPLICATION
Fic. 23.1. Diagrammatic sketch of elastic versus plastic properties.
23.3. The Creep to Rupture Curve
From Fig. 23.1 the complete creep curve under constant temperature
and constant load is seen to consist of three stages. The portion of the
curve AD, known as the first stage, represents a condition of continually
decreasing creep rate; section DE, the second stage, is one of substantially
constant creep rate; and EF, called the third stage, is one of continually
increasing creep rate and ends in fracture (rupture) . The total deforma-
tion to fracture in this case would be represented by OA, the elastic de-
formation, plus AC, the plastic deformation.
When tests are made at other loads (holding temperature constant)
or at other temperatures (holding load constant) , a family of curves, de-
picted schematically in Fig. 23.2, is obtained.
At relatively high temperature and load, the period of first-stage pri-
mary creep may be virtually absent; whereas, at relatively low tempera-
ture and load, creep may cease, for practical purposes.
The characteristic form of the creep curve (Fig. 23.1) led early inves-
tigators to suggest an interplay between the forces of strain hardening
Effect of
Temperature
489
Increasing temperature (constant load)
Increasing load (constant temperature)
Time
Fic. 235. Schematic illustration of creep at low and high temperatures and loads.
and strain softening, the latter arising from crystal recovery or in oc-
casional instances from recrystallization. According to this view, harden-
ing predominates during first stage or primary creep, and the creep rate
diminishes with time; whereas, during second stage creep, the forces of
hardening and softening balance one another, and the rate of creep is
essentially constant.
This conception of the creep curve is, in principle, still currently ac-
cepted, with refinements, however, as regards the
nature of the plastic
flow processes and crystal recovery.
The tertiary period of accelerating creep (third stage) is clearly as-
sociated with impending fracture. The mode of fracture at elevated tem-
peratures may be either transgranular, i.e., through the grains, or inter-
granular, i.e., between the grains. Transgranular fracture, which is the
predominant mode of fracture of metals at ordinary temperatures, is less
likely to occur, the higher the test temperature and the slower the rate
of deformation (or the longer the time for rupture) . The intergranular
mode of fracture is characterized by equiaxed rather than elongated
grains, by intensive intergranular voiding, by a minimization of local
"necking" deformation, and often by relatively low over-all strain at frac-
ture. Hence, little or no advance warning of impending fracture is
afforded.
23.4. Determination of Creep
The knowledge of what a metal might do over a short period of time
cannot be projected to cover a long period of time. Much effort was
wasted in the early work on determining the reactions of alloys to stresses
at elevated temperatures for longer periods by attempts to find a rapid
method. It took considerable time and effort to discover there was no
easy short cut. However, determination of short-time, high-tempcrature
Kir.. 23.3. Modern creep-testing equipment.
The
electric furnaces for heating the
specimens arc shown at the left (white): the lever system for loading the specimens
is above the furnaces. (Batlelle Memorial Institute)
tensile strength, which is a simpler test than the creep test, and of the
time to rupture in relatively short times, as determined in creep to rup-
ture tests at high stresses are usually undertaken, for the data are useful
in deciding whether an alloy is suitable for parts, as in rockets, that
would be subjected to high temperatures for short periods, or for parts
that would be under maximum stress or maximum temperature only dur-
ing the event of failure of other parts. Such data also point out which
alloys justify further investigation where the maintaining of stresses for
longer periods at elevated temperatures is required.
The American Society for Testing Materials has adopted recommended
practices for conducting creep tests, E22-41, and time for rupture tests,
E85-50T. These standards place restrictions on temperature distribution
and variation, on the sensitivity of the extensometer system, and on the
accuracy of the loading mechanism. Specimens are usually maintained un-
der constant load for at least 1000 hours, and the amount of creep is deter-
mined periodically during the test.
The difference in deformation between any two points divided by
the difference in time of the two points represents the creep rate at the
Effect of
Temperature
491
average of the periods of time. The stress that will result in an average
creep rate equal to an assigned creep rate is known as the creep strength
for the alloy at the specified temperature. The stress causing rupture at a
given temperature in a specific time is known as the rupture strength.
The equipment necessary consists of an electric furnace capable of
close temperature control and a suitable device for holding the specimen
in exact alignment in the furnace. The load is applied by dead weights
through a system of levers. A battery of modern creep-testing furnaces
and their auxiliary equipment is shown in Fig. 23.3. Test specimens
are usually 0.505 in. in diameter (cross section 0.2 sq. in.) and have a
gage length of at least 2 in.
From the data accumlated in a series of creep and rupture tests at
different stresses and temperatures, the information necessary for selec-
tion of working stresses is obtained. Fig. 23.4 shows the temperature
variation of the stresses necessary for 1 per cent creep at several time inter-
vals in comparison with the temperature variation of the yield and tensile
strengths determined in short-time tensile tests.
23.5. Effect of Variables on Creep
Creep is one of the most structure-sensitive properties of metals and
is, therefore, greatly influenced by
many factors that have little or no in-
fluence on the other characteristics. For example, a series of steels having
practically the same tensile properties and hardness at room tempera-
ture may shoiv wide differences in their creep
resistance at higher
temperatures.
Owing to the complexity of the subject, information is
not avail-
able concerning all the possible variables and it is probable that, as
yet, not all of these are known. Certain information is available regarding
many of them and among those to be considered are chemical composition,
heat treatment, grain size, method of manufacture, previous deformation,
and structural instability.
Chemical composition. In general, creep and rupture strengths of
metals increase with increase of the melting point. Thus, lead creeps
significantly at room temperature, iron at perhaps 800F., and molyb-
denum at perhaps 1500F. In any base, alloying additions are effective in
further strengthening a metal. The specific effect of an alloying addition
depends on whether it enters into solid solution or results in the appear-
ance of an additional phase. In general, greater strengthening can be
effected by dispersed secondary phases than by formation of a solid
solution.
Temperature, deg. C.
POO 800 900 1000 1100
Temperature, deg. F.
isoo
Fig. 23.1. Effect of temperature on short-time tensile properties and on creep
stress of cast carbon steel. (Kanter)
Low alloy steels, when appropriately heat treated, are in general most
effectively strengthened by alloying additions of so-called strong carbide-
forming elements, like molybdenum, vanadium, and tungsten, the first
two of which are extensively used for this purpose. Chromium is widely
employed to improve scaling resistance, but it is deleterious to creep
strength beyond about 1.5 per cent. Molybdenum is also an effective
strengthener of the austenitic chromium-nickel stainless steels. The ultra-
high strength alloys currently in use for high-temperature applications
often comprise a solid-solution base composition, containing, for example,
cobalt, nickel, chromium, and perhaps iron, with a dispersal phase or
phases resulting from alloying additions of such elements as columbium,
vanadium, molybdenum, and tungsten.
Heat Treatment and Microstructure. The effects of alloying additions
cannot be considered without reference to heat treatment, whereby con-
trol is exercised over the grain size and the nature and dispersion of the
precipitate phases. At the more elevated temperatures, creep and rupture
strengths are greater, the coarser the structural grain size. However, there
is some evidence that an optimum grain size exists for each temperature
and strain rate or rupture time, and it seems unwise to generalize too
broadly. Similarly, fine dispersions generally appear stronger at relatively
low temperature, and coarser dispersions stronger at higher teni]>eratures,
but exceptions exist.
Effect of
Temperature
493
70 000
60 000
10'
10"
Stress Cycles
-
Fig. 23.5. Effect of temperature on fatigue of 12 Cr steel. (Welch and Wilson)
Other Variables. The methods employed in manufacturing a metal
may exercise indirect but important effects. Included in this category are
melting process, deoxidation practice, casting temperatures, etc.,
varia-
tions of which result in variations of chemical composition and micro-
structure. For example, a higher casting temperature is conducive to
coarser grain size.
Strain hardening by prior cold working or by warm working may be
useful for increasing creep and rupture strengths for service temperatures
below the temperature range of recrystalli/ation.
The microstructure of metals and alloys used at elevated temperatures
often changes during service with consequent effect on properties and be-
havior (see Section 23.7) .
23.6. Fatigue and Combined Fatigue and Creep
In general, as temperature increases, fatigue strength progressively
decreases. At the same time, the slope of the curve of stress vs. number of
cycles becomes steeper, and, even for metals like steel, the curve does not
exhibit a horizontal portion corresponding to the "endurance limit," Fig.
23.5. Moreover, all environments, including air, become corrosive for
the usual structural metals and lower the fatigue strength accordingly.
An exception may occur to the general rule of decrease in fatigue
strength with increasing temperature when the temperature range is one
in which metallurgical changes occur that strengthen the metal. Such
may be the case for certain steels which undergo strain-aging at tempera-
494
Sites* to Mean Stress
5 10 15 20 25
Mean Stress. 1000 psi
Fie. 23.6. Stress combinations Tor 0.2% and .5% creep and for rupture of 24S-T4
aluminum at 500F.; cycle stress applied at 3600 times per minute. (ASM Metals Hand-
bonk, 1955 Supplement,
p. 184.)
tures up to 600-700F., so that the fatigue strength of such steels in this
temperature range is not much different than at room temperature.
At temperatures sufficiently high that creep occurs under static loads,
superimposed
cyclic stressing results in complex behavior involving
both creep and fatigue phenomena. Whereas there is an apparent
absence of plastic deformation in fatigue fractures at ordinary tempera-
tures, fracture at elevated temperatures under cyclic stress may show
both creep deformation and the conchoidal markings that characterize
fatigue.
Behavior under combined fatigue and creep conditions cannot be
predicted other than approximately from separately obtained creep and
fatigue data. Moreover, since creep and fatigue properties vary differently
with temperature, behavior under combined conditions cannot be
predicted for other temperatures from data obtained at one temperature.
Hence, it is necessary to conduct tests involving combined fatigue and
creep). Owing to the elevated temperatures of testing, certain variables
become more important than in fatigue at low temperatures. These in-
clude the effect of corrosive agents in the environment, the changes in
microstructure that may occur {see Sect. 23.8) , and since creep is time-
dependent, the frequency of cycling.
Typical results of combined fatigue-creep tests, are illustrated in Fig.
23.6 for the aluminum alloy 24S-T4 tested at 500F. The ordinate scale
Effect of
Temperature
495
charts the alternating stress in completely reversed loading, that is for
zero mean stress, whereas the abscissae axis corresponds to static loading,
that is, for zero alternating stress. Within the quadrant, there are both
a steady stress and a superimposed cycling or fatigue stress. At relatively
low mean stress, fatigue conditions
predominate and fatigue failure will
tend to determine working stress, whereas at low alternating stress, be-
havior corresponds more to creep conditions, and working stress will be
prescribed by excessive creep or creep-rupture. Fig. 28.6 indicates by the
perpendicular approach of the data curves to the axes that the super-
imposition of a small alternating stress on a given mean stress or of a
small steady stress on an alternating stress does not appreciably lower
the stress that can be supported.
23.7. Structural Changes During Creep
Most metals and alloys undergo changes in microstructure during heat-
ing at elevated temperatures. The changes cause changes in
properties,
9
AS POLLED
^
'
"
\

'
-
v

v
*

AFTER
JQOOOHR. SERVICE
C-A40 STEEL IOOOX
Fig. 23.7. Carbide spheroidizalion in steel containing 05% molybdenum, (U.S. Steel
Corp. Research Laboratory.)
ORIGINAL HOOF
'
m?m
XIOOO
L

ORIGINAL HOOF
m
jgOOF I500F
'
i
'
i: 1 ty\
I300F I500F
Fig. 23.8. Microstrucniral changes in Cr-Ni-Mo austenitic siainless steel during 3000
hours creep tcsi. (U. S. Steel Corp.)
and hence, the material has different properties at different times after
being put in service. The rate at which the changes develop is principally
dependent upon the temperature and the time, but may also be influenced
by the imposed stress and the resulting strain. Large stresses and plastic
strains may greatly accelerate microstructural changes, whereas small
stresses and strains may not cause detectable differences from unstressed
material.
The kinds of readily observable changes in microstructurc which may
occur are varied, and include carbide spheroidization or graphiti/ation in
steels, recrystallization, grain growth and transformation or precipitation
processes of various kinds. Other changes such as strain-aging, temper
embrittlement of steels, 885F. embrittlement of high-chromium ferritic
steels are not readily, if at all, detectable in the microstructure.
In ferritic steels, carbide spherodization during service is widespread
as the temperature exceeds perhaps
900
F. A well-advanced example is
shown in Fig. 23.7 representing the microstructures of
i/ per cent
molybdenum0.15 per cent carbon steel before and after 30,000 hours
of service at about 1 100F. in a petroleum refinery. Clearly the properties
of the steel before and after service would be different. In some steels
the carbide phase may break down to elemental carbon (graphite) and
iron.
Microstructural changes during creep test of an austenitic Cr-Ni-Mo
stainless steel are shown in Fig. 23.8. In this material carbide and chi
phases, not differentiated in the illustration, precipitate. In other
Effect of
Temperature
497
Fie. 23.9. Thermal conductivity of various metalstemperature dependence. (Hay-
thorne)
. .000012
i
1 .00000;
0O0OOT
.000004
.000005
COEFFICIENTS OF
THERMAL EXPANSION
COEFFICIENTS ARE MEAN
VALUES FROM 70T TO
INOICATEO TEMPERATURE
JOO 400 800 MO O0 BOO 1400
TEwpepaTum - -f
Fie. 23.10. Coefficients of thermal expansion-temperature dependence. (Michel)
austenitic stainless steels, or in high chromium ferritic steels, sigma phase
may precipitate.
The microstructural changes that occur during exposure at elevated
temperatures generally, but not necessarily, cause a deterioration in
strength as measured at elevated temperatures. Often the most profound
effects are observed in loss of toughness at room or lower temperature,
and as a result the material may fail during shut-down periods rather
than at elevated temperatures. In a particularly severe instance the
notched-bar impact energy absorption of austenitic stainless steel exposed
at 1500F. (Fig.
23.8) , was lowered to 10-15 foot lbs.
23.8. Variation of Other Properties with Temperature
A number of properties of metals other than strength may be of interest
in the design and operation of equipment for service at elevated tempera-
tures. Among such properties are thermal conductivity, thermal ex-
pansivity, clastic modulus and thermal shock or thermal fatigue.
AUSTENITIC STEELS
leCi-BNI 13041
l8Cr-8Ni-Mo<3l6>
iec-aNi.Ti (321)
I8C'-8N1-CM347]
25Cr-l2NI 13091
25O-20NU3I0)
FERRITIC STEELS
0.10 CARBON
1, 00 CARBON
0.SM0
0.8C'-0.3MO
ICr-0.5Me
2Cr-0.M0
2 25Cr-IMo
3CY-0.5Mo-l.5S
3Cf-0.5Mp-l.5Si
5Cr-0.5Mo-Cb
5C'-0.SMO-TI
9Cr -IMo
l2Cf (410)
ITCr (430)
AOSTEMTiC
STEELS"
600 800 1000 1200
TEMPERATURE -
F
Fig. 23.11. Young's modulus E of various materialstemperature dependence.
(Michel)
Although thermal conductivity and expansivity vary with variation in
chemical composition, they are relatively unaffected by other metallurgical
variables such as heat treatment and microstructure. The variation with
temperature of thermal conductivity of a representative group of metals
and alloys is shown in Fig. 23.9. Fig. 23.10 shows a corresponding chart
for thermal expansivity. Of particular interest from the practical point
of view is the disparity between the expansion coefficients of carbon steel
and austenitic stainless steel, which leads to "thermal" stresses when the
materials are joined and heated, as they sometimes are. The austenitic
steels also have significantly poorer thermal conductivity at relatively low
Effect of
Temperature
499
temperature; at relatively high temperatures different steels
possess ap-
proximately the same conductivity.
The elastic moduli at elevated temperatures are sometimes needed for
computing elastic strains. These constants may change gradually with
composition, but are relatively insensitive to metallurgical structure.
With increasing temperature, both the tensile modulus (Young's) and
shear modulus decrease. The temperature variation of Young's modulus
for a
representative group of metals is shown in Fig. 23.11. The rate of
decrease is
approximately linear up to a certain temperature level which
depends upon the material, beyond which a more rapid decrease occurs.
Poisson's ratio does not change significantly with temperature.
Thermal shock and thermal fatigue represent a common mode of failure
in applications involving relatively rapid changes in temperature.
Thermal shock and thermal fatigue may be differentiated depending
on whether failure occurs after relatively few or many cycles, respectively,
of heating and cooling. There are no standardized tests by which to
measure these properties, and resort is had to special tests which attempt
to simulate actual service conditions. The stresses giving rise to
thermal
shock or fatigue are influenced by such properties as thermal expansivity,
thermal conductivity, strength and toughness and by the rate of change
of temperature and the geometrical shape of the part.
23.9. Design for Elevated Temperature Service
Although a number of properties will be of interest in the design of
equipment for successful operation at elevated temperatures, the govern-
ing criteria, at least where corrosive conditions are not severe, will
generally be the strength. Owing to creep
phenomena, however, strength
at elevated temperatures is not a simple property. From the very fact
that creep is occurring, the design engineer recognizes that in time, equip-
ment will either distort beyond a tolerable limit or will fracture or both.
It is necessary therefore to choose working stresses such that neither of
these events occurs. The amount of deformation that may be tolerated
depends on the specific application; in a steam turbine it may be only a
fraction of one per cent in 100,000 hours, whereas in steam piping, several
per cent deformation in the same interval may be tolerated. In all appli-
cations, of course, the working stress must not be large enough to cause
fracture.
In all equipment designed to operate under creep conditions it is
necessary to design for a specific life, not for unlimited life. The basic
information relating to the amount of deformation as a function of lime
comes from creep tests, which must be made under dynamic conditions if
l*S 2 * 2*6 Z * 6
K>
00 iooo oooo
Tim9.hr
Fic. 23.12. Design data for alloy containing 20 Cr-20 Ni-20 Co-3 Mo-2W-l
Cb-Bal.
le,
1200F. (ASM Handbook, 1955 Supplement)
service involves superimposed cyclic stresses. The basic data for design
against fracture comes from creep to rupture tests, from which it is pos-
sible to chart time for rupture as a function of stress. Although there is
a general relation between the stress for a specific amount of creep in a
certain time and the stress for rupture in a specific time, it is not always
possible to insure against fracture by insuring against excessive deforma-
tion, because the amount of deformation at fracture at elevated tempera-
tures may be less than that which the designer may be willing to accept in
a specific application. Moreover, design of equipment for long-life service
necessarily involves extrapolations, with attendant uncertainties as to
when creep will enter the third or accelerating-rate state.
A useful form in which to summarize creep and rupture data for the
design engineer is in the form of "design charts," an example of which is
given in Fig. 23.12. Such charts show the variation with stress of the time
for several specific amounts of creep, the time for transition to accelerat-
ing-rate creep and the time for fracture, and from them it should be
possible to select the working stress for specific applications.
For certain general classes of construction, permissable working stresses
may be set by Code bodies, an important one of which is the Boiler and
Pressure Vessel Code Committee of the American Society for Mechanical
Engineers.
23.10. Variation in Mechanical Properties at Reduced Temperatures
In addition to knowing the properties of metallic materials at elevated
temperatures, the metallurgist and engineer should know something of the
Effect of
Temperature
501
behavior o metals and alloys at reduced
temperatures. In
northern
latitudes, the metals used for rails and
railroad
equipment,
automobiles
and other machines are subject at times to
temperatures as low as 50
to
60F
below zero. During World War II a number of merchant ships
split into two sections while subject to low sea or air
temperatures.
Aircraft or guided
missies operating at high altitudes also
encounter low
temperatures, and
low temperatures are of
increasing
importance also
in the
chemical process
industry.
In a number of fields,
therefore, it is
necessary to know the
properties
of metals at reduced
temperatures. The testing of metals at these
tempera-
tures involves
experimental
difficulties, but equipment and
techniques
have been developed for
obtaining reliable test data, using
refrigerants
such as ice, dry ice (solid carbon dioxide) , liquid
nitrogen,
liquid air or
liquid helium.
Tensile test properties of a number of metals
and alloys at room temp-
erature and at -300F are given on page 504. These
data show that
tensile and yield strengths
increase as the
temperature
decreases. The
effect of
temperature on ductility,
however,
depends upon the nature
of the metal. For some, ductility
decreases, for
others it
increases. The
decrease in ductility of the carbon and
nickel steels and the 16%
Cr iron
are noteworthy and a
manifestation of a
general
characteristic
of ferritic
steels to undergo, with
decreasing
temperature, a
transition in the
character of the fracture from one that is relatively
ductile to one that is
relatively brittle.
The
temperature range over which the ductile to
brittle
transition
occurs for a
specific ferritic steel depends upon the state of stress and
the speed of testing. The
greater the
normal stress (acting
across a refer-
ence plane) relative to the shear stress (acting in the reference
plane)
,
the
higher the temperature at which the
transition
occurs.
Consequently,
in
notched bar specimens
which, compared to the tension test,
have a high
ratio of normal to shear stress,
increasing with the
sharpness of the
notch,
low ductility will be
experienced at
appreciably
higher
temperature
than
in the tension test and, in fact,
transition from
ductile to
brittle behavior
may occur at room or higher
temperature.
With increased
speed of test-
ing,
the transition from ductile to
brittle
behavior occurs at higher tem-
perature.
In line with the effects of stress state and speed of testing,
"impact-
testing of specimens
having
"keyhole" or "vee"
notches
has come into
widespread use for
evaluating the
"toughness" of metals.
Fig. 23.13
shows the variation
with temperature
of
notched-bar
impact energy to
fracture for a
number of ferritic steels and for an
austenitic
chromium-
502
nickel steel which does not exhibit a transition from ductile to brittle
fracture.
23.11. Effects of Metallurgical Variables
The transition from ductile to brittle fracture depends upon a number
of metallurgical
variables. The effects of these variables moreover may
not be revealed by the simple tension test unless made at extremely
low temperatures. It is possible therefore to have two heats of steel which
are nominally identical as judged by chemical analysis or by tensile
properties, in tests at room temperature, but one of which is tough in
notch-bar impact test at room temperature, the other brittle. It is also
possible to have two heats which exhibit similar notched-bar toughness at
room temperature, one of which undergoes transition to brittle behavior
at 50F, the other at

50F. It should be clear therefore that this charac-
70
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Temperature, deg.C.
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Temperature, deg.F.
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Fir. 23.13. Effect of low temperatures on the impact resistance of (A) water-quenched
low-carbon 8 per cent chromium, 8 per cent nickel steel; (B) annealed low-carbon 3.5
per cent nickel; (C) annealed low-carbon 13 per cent chromium steel; (D) normalized
0.35 per cent carbon, 1.5 per cent nickel, 0.0 per cent chromium steel; (K) annealed
0.35 per cent carbon steel; and (!') normalized 0.35 per cent carbon steel. Specimens
for steels B and E had keyhole notch; others had V notch. (The International Nickel
Company)
Effect of
Temperature
503
teristic of metals and the effects of
metallurgical variables thereon can be
properly studied only if tests are made over a range of
temperatures.
The specific
metallurgical variables that affect the
ductile to brittle
transition in ferritic steels include
chemical composition,
deoxidation
practice, finishing temperature of hot working, heat
treatment and the
resulting grain size and
microstructurc, degree of cold work, and strain-
aging or teni|>er
embrittlement, if any. Other factors
being the same,
transition temperature of steels
increases with carbon
content and de-
creases with manganese up to one per cent or more. Nickel is
generally
credited with being beneficial to
low-temperature
toughness of
low-carbon
steel; commercial steels are available
containing
3.5%
(Fig. 23.13), 5%
and 9% of
nickel with transition
temperatures
progressively lower the
greater the
nickel.
The transition temperature of
deoxidized ("killed")
steels is lower
than for
undeoxidized (rimmed or capped). Aluminum is the most
effective of the
elements usually used for
deoxidation, but silicon is
beneficial. The
lower the finishing
temperature of hot working,
the lower
the transition
temperature, and
normalizing after hot
working is bene-
ficial.
Transition
temperature decreases with decrease in grain size. Cold
work is detrimental in itself and may also induce strain-aging
which may
raise the
transition temperature
substantially. Of the
various micro-
structures
which may be imparted to ferritic steel, that of tempered
martensite
exhibits optimum
toughness, provided the
tempering treat-
ment is such as to avoid temper
embrittlement,
which has a
deleterious
effect on
toughness.
Since alloying
elements play a
prominent role in
determining to what extent the fully
martensitic structure can be ob-
'tained, they thus may exercise an indirect effect on toughness.
Transition from ductile to brittle fracture with lowered
temperature is
by no means a
characteristic solely of ferritic steels.
Although the an-
nealed,
wrought austenitic steels exhibit
toughness at -300F sub-
stantially
equivalent to that at room
temperature, as do a
number of other
metals having
the face-centered-cubic
crystal structure, it is now recog-
nized that most and perhaps all
metals not having this
crystal structure,
including zinc,
titanium,
molybdenum, and
tungsten do exhibit
transition
behavior.
23.12.
Design for
Low-Temperature
Service
The problem of design for
service at
reduced
temperatures, except for
applications in which corrosive
conditions are severe, is
essentially one
of
insuring
against brittle fracture.
This is not to say
that other prop-
erties, such as thermal
expansivity, are not of interest, and in some cases
controlling
factors.
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Effect of
Temperature
505
Since metals are stronger at reduced
temperatures than at room tem-
perature, working stresses based on room
temperature test data are
readily supported at low
temperatures, if the material
possesses adequate
toughness to preclude brittle behavior in the presence of
stress concen-
trations and fast speeds of loading.
Bi iuie
behavior in metals depends on the presence of tensile stresses,
and if these are
negligible, the designer need not be
concerned with the
problem of toughness. If, however, the
tensile stresses are
significant,
and the material of
construction is one that undergoes
transition from
ductile to
brittle behavior, the equipment should be
designed so that its
transition
temperature under service loads is below the lowest
service
temperature.
This is more easily specified
than effected
since the transi-
tion behavior is not a
simple property of a metal, and the range of
temperature over which it occurs
depends upon the
geometry and size of
the test specimen and speed of loading.
Consequently, data obtained on
small, laboratory test specimens are
of questionable
application to engi-
neering structures and the problem of design against brittle
fracture has
not been satisfactorily
resolved insofar as choosing the most
economical
material for a specific
application. If cost is not an important
considera-
tion,
brittle fracture can be easily guarded against by selecting high-nickel,
ferritic steel or
chromium-nickel
austenitic steel in the
ferrous group, or
one of the face-centered
cubic non-ferrous
metals, assuming
adequate
strength.
QUESTIONS
1.
What is creep, and why is it important to engineers? What are the principal
requirements for a metallic material to be used
satisfactorily in
equipment
exposed to high
temperatures?
2. How is creep
determined? What are the most important variables in creep
testing? How much time is necessary for a creep test?
3. How is the creep stress, which produces no more than the maximum
allow-
able distortion of the material over the expected life,
determined? How
accurate is such a
procedure? What is the
relation of creep to other mechani-
cal properties?
4. Describe what happens during the three stages of creep. What is the effect
of
strain hardening and recrystallization on
-
second-stage creep?
5. What is the effect on creep of (a) grain size? (b)
deoxidation? (c)
precipita-
tion hardening? (d)
condition of the iron carbide?
6. What is the relative creep strength (at constant temperature) of carbon,
plain molybdenum,
chromium-molybdenum,
plain high-chromium, and aus-
tenitic
chromium-nickel steels? How does the creep
strength of these steels
compare with the creep strength of the
supcrstainless steeb?
7.
Compare the suitability of carbon steel, brass, admiralty
metal, bronze, Monel
metal, duralumin, and the magnesium-base alloys for use at temperatures o
500 to 800F. (260 to 425C), Compare the creep strength of nickel and
Monel with Inconel and with the Hastclloy- and Stellite-type alloys.
8. What is the general effect of elevated temperature on the tensile strength,
yield strength, elongation, reduction of area, and endurance limit of metallic
materials? If a steel has a tensile strength of 120,000 lb. per sq. in. at room
temperature, what will be the approximate strength at I200F. (G50C.)?
at I100F. (760C.)?
9. What are stress-rupture tests? What is the significance of these tests? How
does the rupture strength at I200F. (fi50C.) of austenitic chromium-nickel
steel compare with that of superstainless steel and of the cobalt-rich non-
ferrous alloys?
10. Why is it important to know the effect of low temperatures on the properties
of metallic materials? What is the usual effect of these temperatures on
tensile and impact properties? What is primarily responsible for low-tem-
perature brittleness in carbon steels, and what alloys reduce this brittleness?
Index
Acid
process, 216, 217, 225
Activation energy for oxidation, 480, 484
Afterblow, 219
Ag-Cu system, 106
Age hardening, 51, 52, 111
Aging, 107
Air cooling, 254
Air furnace, 424
Allotropic transformation, 29, 51-52
Alloy steels,
classification, 241
composition, 242
high-quality
production of, 226-227
low-alloy composition, 319-326
low-alloy production, 319
low-alloy S. A. E.,
328-332
low-alloy similarity of properties, 332-339
low-alloy structural, 326-328
precipitation hardening, 126-127
Alloys, controlled expansion, 385-386
Alloys, for high temperatures, 198-202
Alloying effects, 47-51
Alloying elements, effect on carbon steel.
320-322
Alnico, 201
Annealing, alter cold work,
42-44
Alpha
Stabilizers, 256
Aluminum.
chemical properties. 134
deoxidation agent, 135
economics. 130
history, 129
manufacture, 132
nitriding agent, 135
ores, 131
outstanding properties, 131
physical properties, 133
purification, 133
thermite welding, 135
vs. steel, 130, 132
Aluminum alloys, 1 17-123,
alloying elements, 135
annealing, 1-18
brazing, 152
casting, 140
cold and hot working, 147
cold working vs. heat treatment, 147
composition, 138, 142
corrosion resistance, 150
free-machining, 136
function of alloy, 143-147
joining, 152
number code, 136, 137
precipitation heat treatment, 149
protection against corrosion, 155
riveting, 155
sand, mold and die
castings, 141
solution heat treatment, 149
tensile properties, 138
welding, 153
wrought, 136
American Iron and Steel Institute steel
specifications,
329-331
Amslcr test, 445
Annealing of cast iron, 431
Anodes and anodic areas, 453
Anode
reactions, 453-454
Anodization, 151
Area effect. 457
A.S.M.E.
boiler and pressure vessel code
committee, 500
A.S.T.M. standards, 299, 300,
carbon steel castings, 299, 300
Atomic imperfections, 14, 15
Atomic structure, 5
Aiistempering,
commercial
limitations, 289
critical cooling rate curve. 286
defined. 285
hardness and strength of austempercd
steel, 285
process. 285
to obtain greater ductility, 285
Austenite, defined, 246
Austenitic manganese steel, 385
Austcnilic stainless steel. 256
Austenitic steel, 374,
expansion of, 377
mechanical properties. 377
sensitization, 376
507
508 Index
Babbit. 192
Bainitc, 253. 289,
hardcnability, 257
Bars, carbon steel cold worked, 306
Basic process, 216, 219
Bayer process, 131
Bearing metals, 191
composition, 193
mechanical properties, 192, 194
Beginning of transformation, 252
Bend tests, low alloy steels, 77
Beryllium,
copper, 117, 124, 125, 127
manufacture. 157
toxicity, 159
use, 159
Bessemer process, 217
Binary equilibrium diagrams, 102
Binary system, 101
Blast furnace,
chemistry, 214
description, 212
efficiency, 214
products of, 213
Blow holes, in steel, 237-238
Boron, effect
on hardenabilily, 361
Brasses, 160, 168, 178, 179,
additions to. 178-180
cartridge, 170, 178
high, 168, 178
leaded, 178-179
low, 170
Muni/, metal, 169, 178
naval, 180
phase diagram. 165
red. 170, 178
special 180-181
yellow, 169, 178
Brinel] hardness, 70,
conversion tables 75, 76
Brittle fracture, 32, 82
Building-up principle, 9
Calculated hardenabilily, 356,
accuracy, 360
table, S59
Campbell process, 230
Carbide formers, 257
Carbide, precipitation, 37(5, 461
Carbide stabilizing, 257
Carbide tools, 405, 406
Carbon,
amount and importance in steel, 210-211
Carlion (Cont.)
in cast iron, 408. 109
solubility in iron, 216
Carbon monoxide, in steel, 237-238
Carbon steel,
castings, 298, 302
composition, 233-242
effect of alloying elements, 318-326
clfect of carbon, 247-250
elFect of chromium and nickel, 323
elfect of copper, 325
effect of molybdenum. 325
effect of manganese and silicon, 322
elfect of phosphorous, 322
effect of section si/c on, 315
effect of tempering, 338
cutectoid, 247
heat treated, 312
hypercutectoid, 247
hypocutcctoid, 247
silicon in, 239
tensile properties, 322, 324
tonnage production, 297, 306
Carbontriding, 292
Carburizing, defined, 289
Cast iron,
definition. -108
effect of section size, 415-417
machinabiliiy, 409, 412, 418, 420
relation of properties to cooling rate,
416-417
Cast tool alloy, 404, 405
Casting process, 25-28
Catastrophic oxidation, 480
Cathodes and cathodic areas, 453
Calhodic protection, 409
Cathode reactions, 453, 454
Cavitation, 468
Cemented carbide tools, 405, 406
Ccmentitc, defined, 245
Ccmcntitc. stability in cast iron, 408
Cermets. 198
Chapmani/ing, 292
Charging. 222
Charpy test, 83
Chemical interaction in metal solutions, 18
Chilled iron, 408, 410, 420
Chromium,
elfccl on tensile properties, 371
ferritcs, 369
in stainless steels, 364
in tool steels, 395, 398, 403
Chromium steel,
low-chromium, effect of chromium,
323, 325
Index
509
Chromium steel (Cont.)
engineering importance, 326-329
tensile properties, 371
heat treatment, 367
mechanical
properties, 369
resistance to oxidation and
corrosion,
370-372
Cladding
techniques, 482
Cobalt. 190-191,
alloys of. 201
uses', 201, 201
Coefficient of mass diffnsivity, 99
Coherent
precipitate, 21
Cold treatment, 274
Cold-worked carbon steel, 306
Cold-worked wire, 311
Cold-worked bars, sheet. 306
Cold working. 28,
40-42, 259,
306,
effects on strength and
ductility, 308
effect on
dynamic properties, 312
purpose, 232
Columnar grains, 27
Combating
corrosion, 469
Completion of transformation, 252
Composition, effect of, 303-305
Compression tests, 77
Concentration cell corrosion, 458
Continuous cooling, 254
Cooling curve, 98
Cooling rate, 344. 350
Cupola- furnace, 422
Copper, 162-164, 178-9,
arsenical, 178
lake, 163
leaded, 178
OFHC, 163
phosphorized, 178
production, 162
properties and uses, 164
silver-bearing, 178
tellurium, 178
Copper alloys.
165-189,
constitution, 165-178 to 181
nomenclature, 167
precipitation hardening, 117, 124-125
127
constitution. 165, 178-182
phase diagram, 165
Corrosion,
cost, 452
definition. 452
dry, 452
electrochemical,
452
fatigue, 92
rate, 471
Corrosion (Cont.)
testing, 471
wet, 452, 456
Covalent Bond, 10
Creep,
curve,
488-490
definition, 486
determination of, 489
effect of
chemical composition, 491
effect of Cr, Mo, 492
effect of micro-structure, 492
effect of variables, 491
importance of, 486
intergranular, 489
rale, 490
significance of, 486
stages, 488
strength, 491-493
transgranular, 489
Critical cooling rate, 255
Crucible
process, 230
Crystal systems, 11
Crystallographic fibering, 38, 39
Cubic system, 12
Cu-Al system, 108
Cu-Mo,
'379-380
Cu-N'i system, 102
Cupola, use, 215
Cupping test, 447
Curie temperature, 59
Cutlery steel. 365, 368
Cyaniding, 292
Cvclic stresses, at elevated
temperatures,
494
Damping capacity, 94,
of cast iron, 420. 122
DeBtoglie'a
equation, 6
Decarburi/ation, 91
Deep drawing.
evaluation of steel for, 446
properties of nonferrous alloys, 449
Defect lattice, 475
Defects in crystals, 14,
atomic
imperfections, 14, 15
importance of defects, 15
line imperfections, 14
surface
imperfections, 14
Deformation, 32
elastic, 488
of polycrystallinc
metal, 37-42
plastic, 488
Degrees of freedom. 100,
Dendrites, 26
510
Index
Design. 471
chan, 500
for elevated temperatures service,
499-500
for low temperature service, 504-505
Dczincification, 406
Die steels, 396, 397
Differential hardening, 294
Diffusion. 99
Dislocations 14, 15, 23
Dispersion hardening. 111
Domain, 58
Double yield point, 448
Ductile cast iron, 409, 420, 421
Duplex process, 229
Duplex Talbot process, 230
Dynamic Properties, 81
Effect,
carbon
in cast iron, 434
Chromium in cast iron, 435
composition,
302, 303
copper in cast iron, 436
gTain size, 301
molybdenum in cast iron, 435
nickel in cast iron, 430
phosphorus in cast iron, 435
silicon in cast iron, 434
sulphur in cast iron, 435
vanadium in cast iron, 436
Elastic limit 63, 64, 485
Elastic Modulus, 498, 499
Electrical conductivity of oxides, 475
Electrical resistivity, 58
Electromotive force series, 454, 455
Electric furnace, 226-227
Electron cloud diagrams, 6
Electron compounds, 21
Elongation 67, 68,
method of measuring, 67
yield-point elongation, 63
Energy level diagrams,
7
End-quench test, 349, 350, 352
Endurance limit, 87
Endurance strength, 88
Engineering, relation to metallurgy, 3, 4
Epoxy resin, 470
Equi-axed grains, 27
Equilibrium, 97
Erichscn test, 446
Erosion-corrosion, 468
Eutetic, 105
Eutcctoid, iron-carbon, defined, 247
Fatigue, 493,
combined with creep, 493-495
failure, 86
Eerrite,
defined, 246
strengthen, 256
Kick's law, 99
Flame hardening, 293,
of cast iron, 434
Fleming, Sir Ambrose, 3
Free-machining steels, 440
Fretting, 91
Fretting corrosion, 468
Ftigacity, 98
Full annealing of steels. 280
Furnace cooling, 254
Galvanic corrosion, 456
Galvanic series, 455
Gamma loop, 256, 366
Gamma rays, source materials, 204
Gamma stabilizers, 256
Gas carburizing, 289
Gibbs,
J.
Willard, 100
Gold, 190-191, 202
Grain boundaries, 17
Grain growth. 44,
and hot working,
267
control of, 265
in steel, above critical temperature, 264
soaking time and grain growth, 264
tendency for, 265
Grain refining, 257
Grain size, 15,
and properties, 29-31
control, 24-29
In relation to hardenability, 270
in relation to toughness and macliin-
ability, 266
measurement of, 266
process annealing and grain size, 264
Grains in metals, 15
Graphite,
comparison of forms in cast irons,
408-409
control in gray cast iron, 418
in malleable cast iron, 410
in gray cast iron, 412, 417
in ductile or nodular cast iron, 420
Graphite flake size, 429
Graphite precipitation, 257
Graphitizing agents in cast iron, 408
Gray cast iron, 409, 412-420,
properties, 412-415, 417-421
structure, 409, 414, 415. 418
Index
511
Grossman, 356
Hadfielcl steel, 256
Hall process, 132
Hansgirg process, 156
Hardenabilily,
and alloying elements, 269
and cooling rate, 344
and engineering
properties, 354
and tempering, 356
and time delay, 346
bands, 353
calculated, 356
determining, 348
effect of
boron on, 361
factors
affecting, 346
in carbon steels, 343
in low-alloy steels, 320. 344
in relation to grain size, 269
in relation to quenching medium, 270
Hardness,
conversion scales, 75, 76
conversion to tensile strength, 75
definition, 69
determination, 69-77
nonferrous alloys, 76
numbers. 75
tests compared, 72
tool steels, 392, 399
Hardening of cast iron, 432
Hardening
spheroidized steel, 281
Hastelloy, 199-200
Heat treatment, 300-302
Heat treating carburized steel, 289
Heisenberg's uncertainly principle, 6
Hexagonal system, 12
High manganese steel, 381
High nickel steels, 384
High speed steels,
classification, 399
composition, 399
heat treatment, 400
structure, 400
Homogcnizalion of
auslcnite, 279
Hoopes process, 133
Hot metal mixer, 222
Hot rolled, 303
Hot worked carbon steels, 302, 303
Hot working, 28, 38-40,
purpose, 231
Ideal diameter, 357
Ideal quench, 357
Impact specimens, 83
Impact strength. 81,
low-alloy steels, 328. 336,
340
Inconel,
199-200
Indices of direction, 13
Induction hardening, 293
of cast iron, 434
Ingot iron, definition, 211
Inhibitors, 470
Inoculants in cast iron, 429
Inoculation agents, 28
Insulators, II
Interference colors, 484
Intergranular
corrosion, 151, 376, 460
Intermediate phases in alloy systems, 20,
electron compounds, 21
intermediate solid solutions, 20
interstitial compounds, 21
laves phase, 21
normal intermetallic
compounds, 21
sigma phases, 21
Intermediate solid solution, 20
Intermetallic compound, 107
Internal stresses, 283
Interstitial compound, 21
Interstitial solid solution, 20, 101
Interstitial solutes, 20
Ionic bond, 10
Iron,
allotropy, 244-45
alpha, 244
cooling curve, 244, 245
Iron-carbon alloys,
critical temperature, 247
phase changes, slowly cooled alloys,
247-250
phase diagram,
245-247
Iron-chromium phase diagram, 366
Iron-nickel alloys, 384
Ironal, 201
Irreversibility. 99
Isothermal heat treatment of cast iron,
433
Isothermal transformation, 251
lzod test, 83
Jominy test, 349
Killed steel, 237-238
Knife-line attack, 462
l.aves phases, 21
Lead, 190-191,
alloys of. 193-195
in type metals, 194
uses, 197
Lever principle, 104
Lime boil, 223
512
Index
Line imperfections, 14
Liquid metal corrosion, 472
Liquid solutions, 19
Liquids, 102
Low alloy steels, 257,
A.I.S.I. steels, 329-331
chromium as an alloying element, 324,
325
copper in, 325
engineering importance, 318-340
general effects of alloying elements
320-322
manganese and molybdenum in, 322,
326
nickel and silicon in, 323, 324
prosphorus as an alloying clement, 322
properties, heat treated, 332, 340
S.A.E. steels, 328-332
structural, composition and properties,
326-328
tungsten and vanadium in, 325, 326
Low carbon steel, 125-126,
strain aging, 126
Low Temperature, 84
Machinability,
evaluation
of metallic materials for,
138, 441
ratings for free-cutting steels, 440
relation of cutting speed to tensile
strength, 438
variables affecting, 438
Malleable cast iron, 409-412, 421
Magnesium,
manufacture, 156
properties, 155
vs. aluminum, 156
Magnesium alloys,
casting, 158
corrosion resistance, 158
heat treatment, 157
precipitation hardening, 121-124
Magnetic properties, ferromagnetic ma-
terials, 58, 59
Mallcablizing cycle, 430
Malleablizing white cast iron, 410
Manufacture of iron, 212-214
Manufacture of steel,
Campbell process, 230
crucible process, 231
duplex process, 229
duplex Talbot process, 230
electric- furnace process, 226-227
Monell process, 230
super-refining process, 230
Manufacture of steel (Cont.)
Talbot process, 230
triplex process,
230
Martcmpering
compared to austempering,
287,
commercial limitations, 289
described. 286
underlying principle, 287
Martens.
2
Marlensite. 255
Mass transfer, 99
Mechanical fibering,
39
Mechanical properties,
299-300
in cast irons, 41
1, 421
Mechanical working, 28-29,
and engineering
properties 32-47
Melting the charge, 223
Metal purification,
469
Metallic bond, 1
1
Metallurgy,
as a science,
2
as an art, 1
importance
to engineers,
3, 4
Metals,
static properties, significance, 57-79
effect of micro-structure,
59
Metals in atomic reactors,
control
materials, 20-1
fuel elements,
203
gamma-ray
source, 204
structural materials, 203
Mg-Ca system, 107
Mg-I.i system, 109
Miller indices, 13
Miscibility of metals, 18
Modulus of elasticity, 63-65
Modulus of rigidity,
64
Modulus of rupture, in cast iron, 419
Molybdenum in tool and die steels, 396,
399, 403
Molybdenum in steel, effect on properties,
325, 326
Moncl, 199-200,
K-Monel, 125
Metal, 102
Process. 230
S-Monel, 125
Mottled cast iron, 409
Newton's law of cooling, 345
Nickel, 190-191, 199,
alloys of, 199-200
in cermets, 198
Index
513
Nickel in steel,
effect on properties, 323,
324
Nimonic, 199
Nitriding,
advantages, 291
defined, 291
limited to alloy steels, 291
process, 291
Ni-Vee Bronze, 127
Nodular cast iron, 409, 420, 421
Nodular graphite
formation, 430
Nodular pearlite, 253
Normalizing of steels, 280, 281
Nose of the curve, 254
Notch
sensitivity in cast iron, 413-420
Nondcforming tool and die steel, 396
Normal intermetallic compounds, 21
Normalizing of cast iron, 431
Notched-bar impact, 502
Notched-bar test, 85
Notch
brittlencss, 81
Notch constraint, 85
Notch sensitivity, 89
Objectives of annealing, 280
Olsen test, 446
Open-hearth processes, 220
Orange peel, 30
Ore boil, 223
Overaging, 52,
116-117,
precipitation hardening, 116
Oxidation,
high-temperature, 472
internal, 473
of copper, 475
of stainless steel, 482
of titanium, 479
of zinc, 476
prevention, 480
rate,
linear. 477
parabolic, 478, 484
cubic, 478
logarithmic, 478
resistant alloys, 481
Oxide formation, 473
Oxygen pressure, 475
Pack carburizing, 289
Passivity, 454, 455
Patenting, defined, 287,
use of
patented wire, 288
Paul! exclusion
principle, 7
Pearlite, 253,
defined. 247
hardcnability, 257
malleable cast iron, 412
Perfect crystal, 23
Pcritectic reaction, 108
Pitting. 459
Pewter, 191
Phase, 97
Phase diagrams in metal
systems, 19
Phase rule, 100
Phosphorus,
in gray cast iron, 413-415
in steel elfect on properties, 322
Physical testing, 59
Pidgeon process, 156
Pig iron,
classed, 409
composition, 211
Pilling and Bedworth rule, 478, 484
Planck's constant, 6
Plastic
constraint, 85
Plastic design, background for, 63
Platinum,
190-191, 202,
metals, 203
Polarization, 454
Polycrystalline metals, 16
Polyphase
structures, 49-51
Powder metallurgy, 29
Precious metals, 190, 202
Precipitates, 21,
coherent, 21
non-coherent, 21
Precipitation hardening, 52, 53, 107,
alloy requirements. 111
alloy steel, 126-127
aluminum alloys, 117-123
carbon steel, 125-126
copper base alloys, 117, 124, 125, 127
definition, 111
delayed precipitation, 113
dislocations, 115-120
elfect of temperature, 117
effect of time, 117
Guinier- Preston zones. 115
lattice conformity, 112
magnesium base alloys. 120-124
overaging, 116
process for, 1 12
theory of, 114
time and temperature effects, 114,
119-120
Prior history elfect in metals, 15
Process annealing of steels, 280
Proeulecloid cementite, 254
514 Index
Procutectoid fcrritc, 254
Properties of a spheroidized steel, 281
Properties of solid solutions, 20
Proportional limit, 63, 64
Protective atmospheres, 280
Protective oxidation, 478
Pumps, 470
Purpose of hardening, 282
Quality factors, 23, 24
Quantum numbers. 6
Quench cracks, 284
Quenching,
mechanism of, 270
media, 282
stages, 282, 283
Rate of growth, 27-28
Rate of nucleation, 27-28
Radiation damage, 53-54
Recovery, 42
Recrystallization, 28, 43, 45-46
Reduced temperatures, 500-505
Residual stresses, 93
Retained austenite, 274
Reverberatory furnace, 424
Rockwell hardness, described, 70, 71,
relation to other hardness values, 75
Rotating-beam test, 87
Rupture strength, 491
S.A.E. steels,
low-alloy, 328-332
properties, 333-340
specifications for, 329, 331
Scaling, 473
Sensitization of stainless steel, 460
Service factors, 54
Shear modulus, 64
Shear tests, 77
Shot pecning, 92
Sigma phase, 21
Silchrome, 365
Silicon in steel,
effect on properties, 239, 323
Silver, 190-191, 202
Size factor, in forming metal solutions.
18
Slip. 33-36
S-N diagram, 88
Solid solutions, 20,
alloys, 102
effects, 47-49
Solidus, 102
Solute atoms, 18,
clfcct of solute atoms on properties, 20
formation of intermediate phases, 20
interstitial solid solutions, 20
substitutional solid solutions, 20
Solution heat treatment, 111, 112,
alloy requirements, 112
elfect of quenching, 113
elfect of temperature, 113
Solutions in metal systems, 18,
factors controlling extent of solubility,
18
liquid solutions, 19
solid solutions, 20
Sonic testing, 78, 79
Sorby, 2
Space group, 12
Space lattice, 12
Specific gravity, of the heavy metals, 191
Spheroidite, 289
Sphcroidization. 495
Spheroidizing steels, 281
Stabilizing, 123-124
Stainless iron, 365
Stainless steels, classes of, 364
Stainless W. 379-380
Static mechanical properties, 60
Steel,
hardening of, early study. 2
mechanical treatment, 231-232
precipitation hardening
alloy steels, 126-127
low carbon steels, 125-126
stainless steel, 127
properties, charts, value, 333-334
strain aging, 126
world production, 208
Steel making processes, classification, 208
Stellite, 404, 405
Strain aging, 126
Strain hardening, 35-36, 493
Strain rate, 82
Strain softening. 489
Strengthening nonferrous metals,
precipitation hardening. 111
Stress concentration, 89,
locating and magnitude, 60
Stress corrosion, 462, 464, 465
Stress raisers, 60
Stress relief in cast iron, 430
Stress-strain curves. 307
Stress-strain curves, cast iron, 65,
low carbon, cold-worked steel, 62
common metals, 64
Index
515
Stretcher strains, 30, 448
Structural changes, 495-498
Structure of carburized steel, 290
Structure of steel,
effect of cold working, 259
Subatmospheric cooling, 258
Substitutional solid solutions, 101
Substitutional solutes, 20
Sulphur in cast iron, 413-415, 420
Super refining process, 230
Super saturated solid solution, 101
Super stainless steels, 382-383
Surface finish, 89, 91
Surface imperfections, 14
Surface protection during heating, 279,
280
Surface-rolling, 92
System, 97
Talbot process, 230
Temper embrittlement, 305
Temper graphite, 430
Temperature, effects of,
485-506
Tempered martensile, 285
Tempering,
and hardenability, 356
change in toughness, 275
effect on physical properties of steel, 284
method, 284
of cast iron, 132
purpose of, 284
retained austenite and quenching, 274
Tensile strength, metals 61-69,
standard specimens, 67, 68
standardization, 61
Ternary-system iron, carbon, silicon, 425,
427
Terne plate, 191, 196
Thermal conductivity, 497, 498
Thermal expansivity, 497, 498
Thermal fatigue, 499
Thermal shock, 499
Thermodynamics, second law of, 98
Thermostatics, 97
Time delay, 346
Tin, 190, 191,
alloys of, 192-193
in type metals, 194-195
plating, 197
Tin bronze, 125
Titanium carbide, 405,
manufacture, 159
properties, 159
use. 159, 160
Tool material,
cast alloys, 404, 405
Cemented carbides, 405
tool steels, 389-404
Tool steels,
characteristics, 389, 391, 392
chromium in, 395, 398, 403
classification, 391
composition, 391
high alloy. 397
high carbon, 390
high speed, 398-401
low alloy, 395
manganese in, 396
medium alloy, 396
molybdenum in, 396, 399, 403
properties, 392
silicon in, 397
structure, 394, 398, 401
tempering, 393, 402, 403
tungsten in. 399, 403
vanadium in, 399
Torsion tests, 77
Toughness, 502
Transformation on cooling of cast iron,
428
Transition elements, 9
Transition temperature, 83, 502
Transverse test, cast iron, 77
Triaxial stress, 85
Triple point, 101
Triplex process, 230
'ITT curve. 252
Tungsten carbide, 405, 406
Tungsten, in tool and die steels, 399, 403
Twinning, 36-37
Two-metal corrosion, 456
Type metals, 191-194
Types of graphite flakes, 429
Understressing, 93
Uniform corrosion, 456
Unit cell, 12
Uses of carbon steels. 302
Vanadium,
In steel, 325
in tool steel, 399
Van dcr Waals' bond, 10
Vicalloy, 201
Wave mechanics, 6
Wear resistance,
elfect of carbon content and heat treat-
ment, 444
516 Index
Wear resistance (Conl.)
evaluation of, 444
variables affecting, 443
Wear-types, 442
White cast iron, 408, 410
White metals, 190-191
Wire, carbon steel cold rolled, 30G
Working stresses, 499
Wrought iron, 2 1
1
Wrought iron, manufacture, 227, 229
Yield point, 06, 67
Yield strength, 66
Zinc, 191, 197
crystal structure, 198
die castings, 197
fabricating methods, 198
mechanical properties, 198
plating, 197
uses, 198

Engineering Metallurgy

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Engineering Metallurgy

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PITMAN METALLURGY

1 on the chlorine atom.

Fie. 2.11. The size factor in the formation of solutions in metals.

peritectic with a minimum

The metallurgical engineer, of course, is expected to be familiar with all.

Solution Heat Treatment

By permission from Structure 8c Properties of Alloys, Brick & Phillips, McGraw-

Busk and Miranda Trans. AIME. IG6. 346. 1946.

T6 Solution heat treated and then artificially

T7 Solution heat treated, then stabilized.

T8 Solution heat treated, cold worked and then artificially aged.

9.2 that, if the aluminum is higher than this, the structure

0.30 per cent carbon is equivalent to 4.5 per rent Fe

E. S. Davenport and E. C. Bain, Trans. Amer. Inst. Min.

The structure of severely cold-worked steel is unstable in that the fragmented

A complete and wholly satisfactory explanation of the hardness of martensite will

Discussion of controlled atmospheres and equipment is outside the scope of this

O. V. Greene, Trans. Am Soc. Steel Treat., v. 18, 1930,

R. L. Rolf, Trans. Am. Soc. Metals, v. 27, 1939,

E. L. Cady, Materials and Methods, v. 24, Aug., 1946.

Fie. 15.1. Photomicrographs of Typical Microstructures o Small Steel Castings con-

In addition to specifications for low-alloy steels, both the Society of Automotive

W. G. Patton, Metal Progress, v. 43, 1943,

Data on X3140 from International Nickel Co., Handbook on Nickel Steels,

B. F. Shepherd, Trans. Am. Soc. Metals, v. 22, 1934, pp.

18.1) are hypereutectoid and, when quenched and tempered, have

Based on E. E. Thum, Metal Progress, v. 29, No. 6, 1936, pp.

Based on data by 1).

Courtesy of A. B. Kinzel and W. D. Forgeng.

Contains 0.70 per cent aluminum.

Tool Steels, American Society for Metals, Cleveland, 1944.

Kor example, the SAE 3100 series and 4100 series.

Trans. Am. t'oundrymen's Assoc, v. 39, 1932. pp.

3.30 2.00 0.50 0.60 0.10 50 40 10 heavy Valves and fittings

E. Maurer, Kruppsche Monatshelte, v. 5, 1924,

A. S. M. Metals Handbook. Supplement-Metal ProgressVol. 66, No. 1-A, July 15,

GRAY CAST IRON

Adapted from a tabulation by H. W. Graham, Metal Progress, July, 1939, p. 53.

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