A Study of Corrosion Fatigue Crack Propagation of 403 Stainless Steel in Aqueous Environments

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8008753
ABREGO, LILLIAN
A STUDY OF CORROSION FATIGUE CRACK PROPAGATION OF 403 STAINLESS

STEEL IN AQUEOUS ENVIRONMENTS
The Ohio State University PH.D. 1979
University
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i n n f\j pn ^ mm A o a n o .lOinA d i n
A STUDY OF CORROSION FATIGUE CRACK
PROPAGATION OF 403 STAINLESS STEEL
IN AQUEOUS ENVIRONMENTS
DISSERTATION
Presented in Partial Fulfillment of the Requirements for

the Degree Doctor of Philosophy in the Graduate
School of The Ohio State University
By
Lillian Abrego, B.A., M.S.
*****
The Ohio State University

1979
Reading Committee :
Prof. James A. Begley Approved By
Prof. John P. Hirth

Prof. Digby D. Macdonald frtment of Metj r e a l
Engineering
DEDICATION
To my Mom and Dad
11
ACKNOWLEDGEMENTS
I would like to express my deep appreciation to my ad

viser, Dr. James A. Begley for his guidance and aid during
the course of this research work. I would also like to ac
knowledge the encouragement of Dr. Roger W. Staehle in the
pursuit of my studies.
In addition I wish to thank Ross E. Justus for his aid
in the machine shop and Don Muifield for his help in the elec
tronics problems; thanks are also due to Tonie Biggert, who
seemed to be able to handle any problem that arose. Appre
ciation is also extended to Bud Farrar for his help in metal-
lagraphy, scanning electron micrography, and for his help in

making the laboratory a pleasant place to work.
I would also like to mention my peers with whom I star
ted school and without whose camaraderie I could never have
finished. Foremost among them is Robert D. Mack whose en
couragement when things seemed blackest is deeply appreciated;
I would like to thank him for the discussions that helped in
writing this manuscript. Next, there is Jeff Colwell and
Bruce Miglin whose friendship and sense of humor helped in
surviving classes and long hours in the laboratory. And
iii
there is Cicily Horan, who was not a student, but proved to
be a good friend and one of the unforgettable people at Ohio
State.
Finally, acknowledgements are extended to a National
Steel Foundation Fellowship and to the Electric Power Re
search Institute for their support and interest in this
work.
IV
VITA
March 2, 1947 Born - El Paso, Texas

1970 ___ B.A., Our Lady of the Lake
College, San Antonio, Texas
1971-1975 ... Research Assistant,
Chromalloy American Corp.,
San Antonio, Texas
1976-1978 ___ Babcock and Wilcox Fellow,
The Ohio State University,
Columbus, Ohio
1978 ....... M.S., The Ohio State Uni
versity, Columbus, Ohio
Summer 1978 . Research Scientist, Lawrence
Livermore Laboratory,
Livermore, California
1978-1979 ___ National Steel Foundation

Fellow, The Ohio State
University, Columbus, Ohio
FIELDS OF STUDY
Major Field: Metallurgical Engineering

Studies in Corrosion. Professors Mars G. Fontana and
Roger W. Staehle
Studies in Fracture Mechanics. Professor James A.
Begley
Studies in Thermodynamics. Professors Robert A. Rapp,
George St. Pierre, and Rudolph Speiser
Studies in Physical Metallurgy. Professors John P.
Hirth, Gordon W. Powell, and Glyn Meyrick
Studies in Solid State Physics. Professor Rudolph
Speiser
V
TABLE OF CONTENTS
DEDICATION .........................................
ACKNOWLEDGEMENTS ................................... iii
VITA .............................................. V
LIST OF TABLES ..................................... x
LIST OF FIGURES..................................... xi
LIST OF PLATES...................................... xvi
1.0 INTRODUCTION................................... 1
2.0 LITERATURE SURVEY ............................. 3
2.1 Introduction ......................... 3
2.2 Metallurgical Aspects of 12%
Chromium Steels............................ 4
2.3 Fracture Mechanics Aspects of
Fatigue.................................... 9
2.3.1 Fracture MechanicsMethods............ 10
2.3.2 Fatigue Crack Growth................. 13
2.4 Environmental Aspects of

Fatigue ................................... 25
2.4.1 Introduction......................... 25
2.4.2 Stress Corrosion Cracking-Hydrogen
Embrittlement of Martensitic Stain
less Steels ......................... 26
2.4.3 General Corrosion and Pitting
Behavior............................. 29
2.4.4 Corrosion Fatigue...,................ 31
vi
2.4.5 Corrosion Fatigue Crack Growth
Mechanisms. .... ... 46
2.5 Summary
3.0 EXPERIMENTAL PROCEDURE........................... 50
3.1 Introduction................................ 50
3.2 Experimental Apparatus...................... 51
3.2.1 Material............................... 51
3.2.2 Specimen Geometry ..................... 51
3.2.3 Closed Loop Servo-Hydraulic
Fatigue Machine ...................... 55
3.2.4 ElectrochemicalEquipiment ............. 62

3.2.5 Electrolytes........................... 62
3.3 Experimental Techniques..................... 65
3.3.1 Specimen Preparation................... 65
3.3.2 Precracking Procedure.................. 65

3.3.3 Measurement Techniques................. 66
3.3.4 Fatigue Crack Growth Test
Procedure.............................. 71
3.3.5 Fatigue Crack Growth Data
Reduction.............................. 75
3.3.6 Fatigue Crack Threshold
Determinations ........................ 77
3.4 Fractography ............................... 78

4.0 EXPERIMENTAL RESULTS ............................ 80
4.1 Introduction................................ 80
4.2 Air ............ i.......................... 80
4.2.1 Fatigue Crack Growth Rates in Air...... 80
4.2.2 Fractographic Results.................. 84
vii
4 ,3 Water ................................. 92
4.3.1 Fatigue Crack Growth Rates in

Water............... 92
4.3.2 Fractographic Results................. 97
4.4 Sodium Chloride............................ Ill

Sodium Chloride....................... Ill
4.5 Sodium Sulfate.-............................ 130

Sodium Sulfate........................ 130
4.6 Sodium Phosphate and Sodium Silicate....... 135
Sodium Phosphate and Sodium
Silicate. .......................... 135
4.6.2 Fractographic Results ................ 135

4.7 Open Circuit Potentials.................... 140
5.0 DISCUSSION ..................................... 143
5.1 Introduction............................... 14 3
5.2 Effect of Environment...................... 14 3

5.2.1 Air................................... 143
5.2.2 Water................................. 143
5.2.3 Sodium Chloride and Sodium Sulfate 145
5.2.4 Effect of pH.......................... 149
5.2.5 Sodium Phosphate and Sodium
Silicate.............................. 155
5.3 Effect of Test Frequency................... 158
viii
5.4 Model for Dissolution Assisted
Crack Growth. ...... 161
5.4.1 Anodic DissolutionApproach .......... 161

5.4.2 HydrogenEmbrittlementApproach.......... 175
6.0 CONCLUSIONS....................................... 179

BIBLIOGRAPHY ............ 181
IX
LIST OF TABLES
1. Fatigue Crack Laws for Several Steels .,.,, 17

2. Threshlold Stress Intensiy Data for Some
Engineering Steels ....................... 24
3. Summary of Fatigue Crack Growth Laws for
the Various Environments Shown in Figure
18........................................ 40
4. Mill Chemistry of 403 Stainless Steel .... 52
5. Heat Treatment of 403 Stainless Steel..... 52
6. Mechanical Properties of 40 3 Stainless

Steel .................................... 52
7. Test Matrix .............................. 64
8. Power Law Expressions for Fatigue Crack
Growth Rates in Water .................... 96
Growth Rates in Sodium Chloride
Solutions ................................ 117
Growth Rates in Sodium Sulfate
Solutions ................................ 132
Growth Rates in Phosphate and
Silicate Solutions ....................... 137
12. Pitting- Potentials in Sodium Chloride and
Sodium Sulfate at lOOC ........ . 148
13. Calculation of i ........... 172

ave
14. Hydrogen Penetration Distances ......... 178
X
LIST OF FIGURES
1. The 0.1% carbon portion of the ironchromium-

carbon phase diagram ........................... 6
2. The effect of tempering temperature on the
mechanical properties of 403 stainless stee] 7
3. The effect of tempering temperature on
strenght and ductility ......................... 8
4. The effect ot tempering temperature on
fracture toughness ........ 8
5. Three basic modes of crack surface displace
ments and the equations that describe the
elastic stress field in the vicinity of
the crack tip in a body subjected to Mode I
deformations................................... 11
6. Schematic representation of fatigue
crack propagation in steel..................... 15
7. Summary of fatigue crack propagation rates for
martensitic steels in air...................... 18
8. Schematic of monotonie and cyclic plastic

zones......................................... 20
9. Schematic of "plastic blunting process"
of fatigue crack propagation................... 22
10. Effect of tempering temperature and stress

intensity of the velocity of SCC cracks........ 28
11. Effects of tempering temperature on tough
ness (Kjp) and crack velocity in water of
a 12% chromium steel......................... 28
12. Effect of heat treatment on the corrosion
rate of 410 stainless steel in a salt fog
environment.................................... 30
XI
13. Effect of heat treatment on corrosion rate
of 410 stainless steel in various acidic
environments .................. 30
14. Corrosion fatigue S-N curves of smooth
bar specimens exposed to various environ
ments ........................ .......... 32
15. Corrosion fatigue S-N curves of notched

bar specimens exposed to various environ
ments........................................... 32
16. Air and corrosion fatigue curves for a 13Cr-Fe
alloy (austenitized at 950C, tempered 680C)
in a 10% ammonia nitrate........................ 33
17. Schematic of types of corrosion fatigue
behavior........................................ 35
18. Summary of fatigue crack growth data for
AISI 403 ....................................... 38
19. Summary of fatigue crack growth data for
AISI 403 in variousmarineenvironments.......... 39
20. Effect of test frequency and stress inten
sity on the growth rate of corrosion fatigue
cracks in a 12% chromium steel exposed
to water....................................... 41
21. Growth rates of fatigue cracks in a 12%

chromium steel as a function of cyclic
frequency, environmnet, and heattreatment ...... 41
22. Effect of loading wave form on the fatigue

crack growth rate of 12Ni5Cr3Mo steel
below in 3% sodium chloride solution..... 44
23. Diagram of compact-tension samplegeometry....... 56
24. Typical closed loop system..................... 58
25. Diagram of load train.......................... 60
26. Diagram of corrosion cell with load train
and sample..................................... 61
27. Working diagram of Shaevitz LVDT................ 68
XX I
28. Schematic of sample showing the load line
and gage line conversion. 70
29. Sample calculation converting A.V to crack

length , 72
30. Example of fracture surface after fatigue
testing showing the area of the machine notch,
precrack zone, and the fatigue surface and final
failure where the sample was pulled apart....... 73
31. Schematic diagram for a vs N data reduction
by means of incremental polynomial method....... 76
32. Crack length vs cycles in air showing

agreement between LVDT measurements and
microscope .................................... 81
33. Fatigue crack propagation rate, da/dN,

vs stress intensity range, A K at 25C
showing agreement between optical and
compliance techniques........................... 82
34. Fatigue crack growth rate vs AK in air at
lOHz and 40Hz, 25 and lOOC..................... 83
35. Fatigue crack growth rate vs AK in water,
pH7, lOOC tested at various frequencies......... 93
pH7, lOOC, tested at various frequencies .
showing A region............................. 94
25 and lOOC, pH 7 and 10 cycled at lOHz......... 95
38. Fatigue crack growth rates vs AK in O.OIM
sodium chloride, pHlO, lOOC tested at
various frequencies............................. 112
39. Fatigue crack growth rates vs AK in O.OIM
various frequencies showing A region........ 113
40. Fatigue crack growth rates vs AK in IM
sodium chloride, cycled at lOHz at
various pH's.................. 114
41. Fatigue crack growth rates vs A K in
sodium chloride and water, 25C cycled at lOHz.... 116
xiii
42. Fatigue crack growth rates ys AK in 0,OIM
and IM sodium sulfate, lOOC tested at
10 and 40 Hz,...... 131
43. Fatigue crack growth rates vs AK in IM

sodium phosphate and IM sodium silicate.......... 136
44. Open circuit potentials vs solution pH
measured during fatigue crack propagation
tests........................................... 142
45. Summary of the effect of the different
environments studied on A .................. 146
46. Polarization curves of 403 stainless steel
in IM sodium chloride solutions at lOOC
and scan rate of lOOOmV/min..................... 150
in O.OIM sodium chloride at 10OC and
scan rate of 25 mV/min......................... 151
in IM sodium sulfate solutions at lOOC and
scan rate of lOOOmV/min........................ 152

in O.OIM sodium sulfate at lOOC and
scan rate of 25 mV/min. ....................... 153
in IM sodium phosphate and IM sodium
silicate at lOOC and scan rate of25 mV/min....... 156
51. Plot of environmental crack growth rate in
m/cycle as a function of test frequency for
three AK values in water,lOOC, pH7............... 160
52. Typical change in current density (i) and
strain (e) with time in a straining elec
trode experiment................................. 16 3
53. Plot of environmental crack growth rate in
m/sec vs test frequency in water, lOOC,
for three A K values.............................. 164
54. Plot of environmental crack growth rate vs
stress intensityrange, AK for the four
frequencies studied.............................. 16 5
XIV
55. Schematic showing process of film rupture
and crack extension due to dissolution as
in (A), two different test frequencies are
shown in (B) whre the frequency at the top
is faster than the one below..................... 167
56. Dissolution at the crack tip with more than
one film rupture event and non-idealized
crack extension.................................. 174
XV
LIST OF PLATES
I. Microstructure of as received 403 stainless

steel........................................ 53
II. Microstructure of quenched and tempered
403 stainless steel........................... 54
III. Compact-tension sample used in corrosion
fatigue crack propagation studies with
LVDT extension tubes in place with teflon
blocks........................................ 57
IV. Corrosion cell in place in MTS load frame
with LVDT, thermometer, and reference elec
trode in place....... 63
V. Compact-tension sample in MTS load frame
with LVDT attached and traveling microscope
in place...................................... 67
VI. Fracture surface of sample fatigued in air
at 25C, lOHz shown at three stress inten
sity ranges and three magnifications :
500X, lOOOX and 10 ,000X........................ 85
VII. Fracture surface of sample fatigued in air
at lOHz, 25C at 3 stress intensity
ranges and three magnifications: 50OX,
lOOOX, and 10,000X............................. 87
VIII. Fracture surface of smaple fatigued in air
at 40Hz, 25C at two stressintensity ranges
and three magnifications: 500X, lOOOX and
10,000X....................................... 90
IX. Fracture surface of sample fatigued in air
at 25C, 40Hz at stress intensity ranges
where ^K., was determined and shown at three
magnifications : 500X,lOOOX, and 10, OOOX........ 91
XVI
X. Fracture surface of sample fatigued in
water, pH.7 at lOOC, 40Hz, at two stress
intensity ranges at three magnifications
500X, 100X, and 5000X. . ......... ........ 98
XI. Fracture surface of smaple fatigued in
water, pH7, lOOC, 40Hz at two stress
intensity ranges where A K was deter
mined at three magnifications: 500X,
lOOX, and 10,OOOX.......................... 99
XII. Fracture surface of sample fatigued in

water, pH6.5, lOHz at three stress inten
sity ranges and three magnification:
lOOX, 500X, and lOOOX................. 100
XIII. Fracture surface of sample fatigued in
water, pH7, lOOC IHz at three stress
intensity ranges and three magnifications :
lOOX, 500X, and lOOOX ........................ 102
XIV. Fractures surface of sample fatigued in

water, pH7, lOOC, O.lHz at thress stress
intensity ranges and at three magnifi
cations : 500X, lOOOX, and lOOOOX............. 104
XV. Fracture surface of sample fatigued in
water, pH6.5, lOHz with striation
spacing of %0.3y at magnifications of
500X, IBOOX, and 10,OOOX.................... 107
XVI. Fracture surface of sample fatigued in
water, pH6.5, lOOC at lOHz at AK20
showing a grain with no evidence of
striation markings........................... 10 8
XVII. Fracture surface of sample fatigued in
water, pH7, 24C, lOHz at three stress
intensity ranges and three magnification :
lOOX, 500X, and lOOOX........................ 109
XVIII. Fracture surface of sample fatigued in
O.OIM sodium chloride, pHlO, lOOC, lOHz
at three stress intensity ranges and three
magnifications : lOOX, 500X, and lOOOX....... 118
XIX. Fracture surface of sample fatigued in
IM sodium chloride, pH2, lOOC, lOHz
at three stress intensity ranges and three
magnifications : lOOX, 500X, and lOOOX....... 120
xvii
XX, Fracture surface of sample fatigued in
IM codium chloride, pHlO, lOOC at lOHz
at three stress intensity range and
three magnifications: lOOX, 500X and 1000X....122
XXI. Fracture surface of sample fatigued in
O.OIM sodium chloride, pHlO, 24C, lOHz
at three stress intensity ranges and
three magnifications: lOOX, 500X and lOOOX.... 124
X X II. Fracture surface of sample fatigued in

IM sodium chloride, pHlO, 25C, lOHz at three
stress intensity ranges and three
magnifications: lOOX, 500X, and 100OX. ..... 126
XXIII. Fracture surface of sample used to determine
A K .. at low stress intensity ranges
photographed at three magnifications :
lOOX, 500X, and lOOOX...................... 128
XXIV. Fracture surface of sample fatigued in

O.OIM sodium chloride, lOOC 40Hz at low
stress intensity ranges used to deter
mine A photographed at three magni
fications: lOOX, 500X, and lOOOX...... . 129
XXV. Fracture surface of sample fatigued in
IM sodium sulfate, pH7, lOOC, lOHz at
three stress intensity ranges and at
three magnifications: lOOX, 500X and lOOOX.... 133
XXVI. Fracture surface of sample fatigued in
IM sodium phosphate, pHlO, lOOC, lOHz
at three stress intensity ranges and
three magnifications : 500X, lOOOX, and
lOOOOX...................................... 138
XXVII. Fracture surface of smaple fatigued in
IM sodium silicate, pHlO.5, lOOC, lOHz.
Deposit is evident on the fatigue fracture.. . 141
XVlll
1.0 INTRODUCTION
This research work has concerned itself with the cor
rosion fatigue crack growth properties of 403 stainless

steel. The material is a 12% chromium steel in the quenched
and tempered condition, whose primary application in indus
try is as steam turbine buckets. The environments of inte
rest have been those whcih are found in steam turbine ap
plications. The electric power generating industry is
concerned with the corrosion fatigue properties of this
material because of the rotating speeds and cyclic stres
sing that the buckets undergo.

The buckets are attached to the turbine by a serrated
fir tree type design which introduces a notch in the base

of the turbine blade; this area then becomes a potential
source for crack growth. Consequently, a fracture mechanics

approach to corrosion fatigue in chloride, sulfate, phos
phate, and silicate solutions using compact-tension speci
mens was undertaken. The experiments were performed in

non-pressurized solutions at room temperature and lOOC.
This dissertation documents the experimental work
undertaken, the results, and the crack growth model used
to explain the fatigue crack growth observed. The
1
principle variables in this study have been the anions, the
solution pH, and the test frequency. Since the operating
turbine temperature is about lOOC, the majority of the tests

were conducted at that temperature although some room tem
perature work was conducted.

2.0 LITERATURE SURVEY
2.1 Introduction
Fatigue is defined as the tendency of a metal to fracture
under repeated cyclic stressing. Corrosion fatigue is
the reduction of fatigue resistance due to the presence of

a corrosive medium; it is defined in terms of the mechanical
properties of a material structure. There are three general
variables which are encompassed in this research work. These

are the metallurgical, mechanical, and environmental aspects
of corrosion fatigue.
This literature survey encompasses these three topics.
In the first part, the metallurgical development and use of
12% chromium steels is reviewed. In the second part the
fracture mechanics variables encorporated in fatigue studies
are reviewed; this section is focussed on the experimental
variables used in this research project. The final part

deals with the environmental effects on fatigue ; it reviews
the corrosion properties of martensitic stainless steels, the

corrosion fatigue testing variables considered in the process,
and the corrosion fatigue studies which have been performed
on 12% chromium steels.

2.2 Metallurgical Aspects of 12% Chromium Steels
The main reason for the existance of stainless steels is

resistance to corrosion. Chromium is the main alloying
element,and the steel should contain at least 11%. (1) The
12% chromium steels fall into a group o f stainless steels

which are hardenable because sufficient austenite is formed
at elevated temperatures to produce martensite upon cooling.

The original alloy in this group of steels was Type 420
developed in England for cutlery (2) with a carbon content
around 0.3%; its usefulness was limited to applications where
it could be used fully hardened. Lowering the carbon content
produced a grade which could be tempered to produce a wide
and useful range of hardnesses. Type 40 3 grew out of a need
for a special quality alloy capable of meeting the numerous
specifications required in the turbine industry. (3)
The trends in chromium alloying with reference to the

iron-chromium-carbon phase diagram (4) are that chromium:
(1) in solid solution tends to eliminate the a-, y trans

formation; (2) in solid solution, increases the time neces
sary for completion of any transformation; and (3) forms
carbides readily which are soluable in high temperature
austenite but almost insoluble in low temperature austenite
or ferrite.
Essentially carbon free alloys with 12% chromium are
soft and ductile, but when enough carbon is present to
produce austenite at elevated temperatures, the alloys may
be heat treated to useful hardness ranges.
A look at the 0.1% section of the ternary phase dia

gram (Figure 1) shows that the amount of austenite formed
depends on temperature and composition. Only steels fully

austenitic at solution temperature will harden fully on cool
ing. Any delta ferrite at solution temperature remains in
the structure and reduces the attainable strength. The up
per temperature for transforming all ferrite except delta
ferrite to austenite is 955C (1750F), and increasing this
temperature may lead to the formation of delta ferrite even

in steels wholly austenitic at lower solution temperatures
(5); the presence of this soft ductile phase lowers the at-
tainble strength of the alloy.

Secondary phases may form in these alloys; most of
these phases are undesireable. These are carbides, Laves
phase, chi, sigma, alpha prime, molybdides, columbides,

borides and silicides. Most of these have deleterious ef
fects on the mechanical properties.
Figures 2, 3, and 4 summarize the effect of heat treat
ment on the mechanical properties of martensitic stainless
steels.
isoor
0.10% c a r b o n
1600 - -
a+y+L
1200
ar-MjjCs
a+yM2jC
800
a+M,c
a+M,Cj
J rMjjC., j
600 ; -V 1
I X
/ r
400 L _
10 20 30 40 50 60
vVe^qni Her cent a qe i. r romiurn
Figure 1. The 0.1% portion of the iron-chromium-carbon

phase, diagram. (4)
G nnell H a rd n es s
200
2l 50 2 % Y i e ld S ir, 200
100
Typical Anol;SS
50
40
20
100
In ilo l Horder>inq I
80 l e O O F - 1 /2 Hr - Oil Q uench
. . . . . . . . Typ e 416 /
60
20
4 Hours A'r fool !~|/2 HQur_vQiL:

4C0 12 C O 1600 2000
R E HE AT iN G T E M P E R A TURE
t c
O
Figure 2. The effect of tempering temperature on the

mechanical properties of 403 stainless steel. (2)
2000
2 0 o |- 12% chrom ium steul.0 2 % C
0 . 5 h 1 0 6 0 C , a i r c ool f ul ,
180 - + t e m p e r e d . 10 ti 600
DOB specim ens / /
160 _ * Kp . c r a c k arrest /
.ri5 o o - Kp . c r a c k m itialion y / 500

f^140 'E
E
z oi
Bi20 400
1/1
c
100 o
300 ^
80-
)
5 60 200
500 1 2 % chioiiiiiini bt f f l , 0.2 % C 40

0, 5 h 1060"C .III cooled
to o
20
K, s e c
7icm Iumj Iu j
ulliniele leiibilc s t i e i u j l h _I_ I L

200 4 00
GOO
temp nruj lempci.iiui e.C
0 100 200 300 400 500 600 700
.inoe.iluiij teinpeiitluie ( " C 3
Figure 3. The effect of tempering tem Figure 4. The effect of tempering

perature on strength and temperature on fracture
ductility. (28) toughness. (28)
00
2.3 Fracture Mechanics Aspects of Fatigue
One of the more important applications of 403 stainless

steels is as steam turbine blades (where operating tempera
tures do not exceed 480C (900F)); this industrial application
is due to their excellent damping capacity along with the

room temperature yield and fatigue strengths which are needed
due to the length of these blades (36-60 in) and the high
operating speeds (1500 ft/sec). (5) Since these blades are

usually attached with fir-tree type serrated fastenings, the
blade material must be evaluated for failure possibilities

if a notch is present.
If one accepts the fact that real structures contain
discontinuities, then the progressive crack extension due to

the application of a load must be understood. It is in this
area that fracture mechanics has become the primary approach
to controlling fatigue failures.
It is not the intention of this survey to do a complete
analysis of linear elastic fracture mechanics since there
are several texts that do that very well (6, 7, 8), but
rather to introduce the parameters which are important in
the application of fracture mechanics to the field of fati
gue control. The review of fracture mechanics is conducted
by presenting work that has been done primarily on alloy

systems which are pertinent to this research work. This in
cludes areas such as subcritical crack growth and fatigue
crack propagation along with mechanisms which are used to
10
describe crack propagation.
2.3.1 Fracture Mechanics Methods
The recent development of fracture mechanics has shown
that there are three primary factors that control the sus
ceptibility of a structure to fracture (7); (1) material

toughness (Kjj^) , (2) crack size (a) , and (3) stress level
(a). Linear elastic fracture mechanics is based on an ana
lytical procedure that relates the above three factors, i.e.
it relates the stress-field magnitude and distribution in

the vicinity of a crack tip to the normal stress applied to
the structure, to the size , shape and orientation of the
crack or discontinuity to the material properties.
To establish methods of stress analysis for cracks in
elastic solids, it is convenient to define three types of
relative movements of two crack surfaces shown in Figure 5.
Mode I is the opening mode. Mode II is the sliding or shear
mode, and Mode III is the tearing mode. Each of these de
formation modes corresponds to a basic type of stress field
in the vicintiy of crack tips. In any problem, the defor
mation at the crack tip can be treated as one or a combina
tion of these local displacements.
This research work is confined to Mode I type deforma
tion, so further remarks are confined to that mode.

11
MO D E I
MODE n
mode ru
o*
M d f l N I T U D E OF S T R E S S
/ A L O N G X A X I S , CT,
NO M INA L CRA CK
STRESS IIP
COS-? ( I - S I N - S I N I
l/l
C O S (l + S I N SIN I
Figure 5. Three basic modes of crack surface displacements

and the equations that describe the elastic-plas
tic field in the vicinity of a crack tip in a
body subjected to Mode I deformation. (9)
12
The stress analysis method at the crack tip was deve

loped by Westergaard (10) and used by Irwin (11) to describe
the stress displacement fields at the crack tip as shown in
Figure 5. These equations represent the case of plane strain

and are exact in the limit as r approaches zero and are a
approximation in the region where r is small compared with
the x-y planar dimensions; they also show that the distribu
tions are invariant in components subjected to Mode I defor-
tion. Further, the magnitude of the elastic stress field
can be described by the single parameter, Kj, the stress in

tensity factor. Thus, the applied stress, crack shape, size,
orientation and structural configuration of a component sub
jected to this deformation affect the value of Kj, but do not
alter the stress field distribution.

Unstable fracture can then be defined in terms of the
stress intensity factor; it occurs when the stress intensity
at the crack tip reaches a critical value Kq . For Mode I
deformation and plane strain conditions (small plastic zone)

the critical stress intensity for fracture instability is
Kjc, which represents the inherent ability of a material to

withstand a given stress field intensity at a crack tip and
to resist progressive tensile crack extension. Dimensional
analysis shows that must be linearly related to the ap
plied nominal stress, a, and the square root of the crack
length, a, or the general form:

13
K = a/pY (1)
where Y is a parameter that depends on the specimen and crack

geometry. (The engineering units are MPaVn? or KSlVin^* )
Thus, the K jq of a material represents the terminal con
ditions in the life of a component; the total useful life is
determined by the time necessary to initiate a crack and to
propagate the crack from subcritical size to the critical
size. Crack initiation and propagation may be caused by
cyclic stresses in the absence of an aggressive environment,
by an aggressive environments under sustained load, or by any

combination of these conditions.
2.3.2 Fatigue Crack Growth

Conventional fatigue testing generates design fatigue
curves based on the prediction of cyclic life from data on

nominal stress vs elapsed cycles (S-N) curves to failure. When
using unnotched specimens, this type of data represents both
the number of cycles required to initiate a crack in a spe
cimen and the number of cycles required to propagate the crack
to failure. The number of cycles corresponding to the en
durance limit primarily represents initiation life. Conse
quently, S-N curves do not necessarily provide information
on safe-life predictions in structures having surface irregu
larities or crack-like discontinuities since their exis
tance may eliminate the crack initiation portion of the fati-
14
gue life of a component.
Crack propagation information, on the other hand, may

be obtained from a number of sample geometries. Starting
with a sharpened crack, cyclic loads are applied and the re
sulting change in crack length, a, monitored as a function

of the number of cycles, N. The fatigue crack growth rate
is determined from the a vs N curve. Paris and Erdogan (12)
postulated that the stress intensity factor, K, which is a
function of stress and crack length, was the overall control

ling factor in the fatigue propagation process, thus, fati
gue propagation rates are generally plotted against the stress
intensity range, AK (AK = K -K . ). Figure 6show that
max man ^
this plot for steels can be divided into three regions : Re
gion I exhibits a fatigue threshold cyclic stress intensity,
AK^^, below which cracks do not propagate; Region II repre
sents the fatigue crack propagation behavior represented by
da/daN = A( AK)^ (2)
where da/dN is the fatigue crack growth rate, AK is the stress

intensity range defined above, and A, n are constants; Region
III is where the rate of fatigue crack growth increases as
K increases to either K_^ or K^. In some cases K_^ is
max IC C IC
replaced by because may be affected by cyclic soften
ing or hardening during the fatigue process.

15
REGION I R E GI ON H REGION m
S TR ESS -1 N T E N S I T Y - F A C T O R RANGE,
A K j _ LOG S C A L E
Figure 6. A schematic representation of the fatigue crack

growth in steel.
16
Fatigue Crack Growth in Region II

In the early 60's, a number of investigators tried to
derive the power law expression which would explain crack
growth. A number of these expressions have been derived for
a number of materials. Crooker and Lange (13) have summar
ized much of this data. However, engineering estimates of
crack growth in steels can be divided into three groups
which reflect the microstructural difference. (7) Table 1

lists the fatigue crack growth rates in martensitic, ferrite-
pearlite and austenitic steels; these groups reflect varia

tions in mechanical properties which are also listed in the
table.
Fatigue crack growth data for various strength marten
sitic steels. Figure 7, show that the primary factor affect
ing the growth rate in Region II is the AK; mechanical and

metallurgical properties have negligible effect on the crack
growth. Clark (14) and Logsdon (15) have found slight vari-
tions in the growth law expression for 40 3 stainless steel
fatigue tested in air. Clark determined

da/dN = 0.16 X 10"^ , (3)
and Logsdon found

da/dN = 0.29 X lO"^ AK^*^. (4)
A change in the stress ratio, R (= o lUx.rJ./ a iTlaX) does not
influence significantly the crack growth rate in this region.
(16) In addition, Barsom (17) found that variation of the

TABLE 1
FATIGUE CRACK GROWTH LAWS FOR SEVERAL STEELS
Steel Rate Law Yield Strength Tensile Strength Strain Harden

Orp (KSI) ing Exponent
V S
Austenitic 3.0 X 10 30<o<i50 n > 0. 3
Ferrite- 3.6 X 10 30<a^80 50< o^llO 0.15^n^ 0.3

Pearlite
Martensitic 0.66 X 10 70 oz90 n"? 0.15
M
-J
18
H10 ' 0.27 X lO' (AK,)^
- - ^ ' 0 . 6 6 X lO' ( A K , ) ^ - ^
W H E R E A Kl IS IN ksi V in c i )
10
o - 12 N i STEEL
Q - 10 Ni S T E E L
1.0 ksi yinch ' 1.0998 MN/m^^^ - H T - 130 S T E E L
- H Y - 80 S T E E L
Iinch 25.4 mm
1.0 ' I 'I I 1 1 III I I L,l..l_i_l I l l I I ,1,1 I I IIII I 11 II

10 -' 10* 10* 10* 10*
C R A C K - G R O W T H RATE, d o / d N , inch pr c/cl
Figure 7. Summary of fatigue crack propagation rates

for martensitic steels. (7)
19
cyclic test frequency in a room temperature air environment,
caused very little, if no change in the fatigue crack growth
rates of the steels he investigated. He also studied the ef
fect of cyclic wave form (sinusoidal, triangular, square,
positive sawtooth ( ) , and negative sawtooth )) on a
12Ni-8Cr-3Mo maraging steel; no effect was found by the form
of the cyclic-stress fluctuation on the rates of fatigue
crack growth.
Bathias and Pelloux (18, 19) have found that in
martensitic steels tested under constant cyclic load, fatigue

striations are observed on the fracture surface and each
striation corresponds to one load cycle; it is a measure of
the crack advance or local rate of advance of the crack front.
They also confirmed the existance of a cyclic plastic zone

within the montonic plastic zone pictured in Figure 8 ; the
reversed plastic zone is one-fourth the size of the monotonie
zone.
Mechanisms for Fatigue Crack Growth in Region II
Most crack growth mechanisms in fatigue acknowledge
that it takes place in two stages. The first stage is actua-
ly crack initiation and is characterized by propagation of
the crack on a plane oriented at 45' to the stress axis and
by crystallographic fracture facets. In stage II the plane
of crack propagation is at 90' to the stress axis and the

fracture surface is covered by striations running parallel
to the crack front. Crack propagation rates in Stage II
20
MONOTONIC
PLASTIC
ZONE
REVERSED
FLOW
PLASTIC
ZONE
Figure 8. Schematic of monotonie and cyclic plastic zones

(2 0 )
21
growth can reach microns/cycle, while in Stage I, the order

is angstroms/cycle.
The mechanism of Stage II growth is known as the plastic

blunting process. (21) Figure 9 proposed by Laird shows that
as the tensile load of a cycle is applied as in 9a and 9b,

a small double notch is formed; when the specimen is defor
med to a maximum tensile stress, 9c, the stress concentra
tion is lessened and the crack tip broadens to a semi-circu

lar configuration. Upon compression. Figure 9d, the crack
faces are crushed together, and the new crack surface created
in tension is forced into the plane of the crack and partly
folded by buckling the very front of the crack tip into an
other notch as in Figure 9e.
Modifications have been made to this process (22), but
Beardmore and Feltner (23) have observed striations on low
carbon martensitic steels, indicating that Stage II cracks

grow by the blunting and sharpening process.
Fatigue Crack Propagtion in Region ^ (low A k )

In Figure 5 it is obvious that the simple power rela
tionship previously proposed is violated for low AK condi

tions (Region I); the crack growth rate diminshes rapidly .
to a low level. In this region it has been found that the
stress ratio, R = a . /a , strongly affects the crack
min max
growth rate. (6) When a limiting stress inensity factor
range (the threshold level, AK^^) is defined, it represents

a service operating limit below which fatigue damage is
22
(a)
\ \ \
(e)
(n \ ^
Figure 9. Schematic of plastic blunting and sharpening

process of fatigue crack propagation. (21)
23
highly unlikely. Table 2 lists the for some engineering

alloys; it is evident that the R ratio has a strong effect
on AK^^. Vosikovsky (24) has compiled data on the effect of

stress ratio on ferritic and martensitic steels to show the
effect of stress ratio on AK^^. Paris et al (25) and McEvily
and Gaallagher (26) also found that the R ratio was signifi
cant in affecting the AK^^ for material tested in air and
vacuum.
Laird (21) has pointed out that the difficulty in under
standing the mechanisms in the slow growth regime is the
general lack of features on the fractures surfaces; there is
a very small amount of plastic blunting at the tip so that
the sharpening process on compression is minimized, such that
resolvable striations will not be left on the fracture sur
face.
Benson and Edmonds (27) examined fracture surfaces of
quenched and tempered martensitic steels tested in the AK^^

region and found that the crack path was transgranular with
respect to prior austenite grains and bore no relationship
to the lath boundaries ; they determined a AK^^ value of
5.5 MPa/m for R=0.4. In addition, when comparing AK^^ to
the fatigue limit, they found that tempered martensite had a
low AK_^^ and a high fatigue limit indicating the conflicting
requirements for resistance to crack initiation and crack
growth in steels. The quenched and tempered structures

also showed evidence of intergranular cracking at the low AK's
24
TABLE 2
THRESHOLD DATA FOR SOIVLE ENGINEERING ALLOYS
M aterial R M Pa Vm k si\/ln 7
9310 Steel 0.25 - 6 .1 - 5 .5

0,9 - 3 .3 3
A533I3 Steel 0.1 8 7.3
0.3 5.7 5.2
0.5 4.8 4.4
0.7 3.1 2.8
0.8 3 2.75
A508 0.1 6.7 6.1
0.5 5.6 5.1
0.7 3.1 2.8
T-1 0.2 5.5 '5
0.4 4.4 -4
0.9 - 3 .3 -3
Ti-6 Al-4 V 0.15 6.6 6
0.33 4.4 -4
! 8 / 8 A u sten itic steel 0 (). 1 5.5
0.33 5.9 5.4
0.62 4.6 4.2
0.74 4.1 3.7
C o p p er 0 2.5 2.3
0.33 1.8 1.6
0.56 1.5 1.4
O.KO 1.3 1.2
6 0 ,'4 0 brass 0 3.5 3.2
0.33 3.1 2.8
0.51 2.6 2.4
0.72 2.6 2.4
N ickel 0 7 .9 7.2
0J3 6.5 5.9
0.57 5.2 4.7
0.71 3.6 3.3
(Ref. 6)
25
This section has presented the major points concerned

in applying fracture mechanics to the study of metal fatigue.
The principle parameters involved in fatigue testing and eva
luation which were used in this research project were reviewed.
The nest section covers the addition of an aqueous environ
ment to the effects of fatigue.
2.4 Environmental Aspects of Fatigue

2.4.1 Introduction
Corrosion fatigue is the nuclation and growth of sub

critical cracks due to the simultaneous action of aggressive
environments and cyclic stresses; the complexity of the pro
cess is due to the fact that it includes elements of fatigue,
stress corrosion cracking (SCC), hydrogen embrittlement (HE),
pitting, intergranular and general corrosion. (28) The fati
gue behavior of an environment-material system can be studied

by establishing the deviation of the corrosion fatigue be
havior for the system from the fatigue behavior of the

material in a benign environment.
This portion of the survey presents the literature per-.
taining to martensitic stainless steels in terms of SCC, HE,
pitting and corrosion fatigue; in the treatment of corrosion
fatigue, the variables of corrosion fatigue testing and the
mechanisms proposed for crack growth are presented.
26
2.4.2 Stress Corrosion Cracking-Hydrogen Embrittlement

Stress corrosion crack growth in a statically loaded
structure is caused by interactions of chemical and mecha
nical processes at the crack tip. The highest plane-strain

stress-intensity factor value at which subcritical crack
growth does not occur in a material statically loaded in an

aggressive environment is designated Because
for an environment-material system defines the plane-strain
K^value above which SCC growth can occur under static loads,
the corrosion fatigue behavior for the system could be al
tered when the maximum value o f A K ( = K - K . ) in a
max min
given load cycle exceeds .
McGuire, Troiano and Heheman (29) studied the suscepti
bility of 410 staninless steel to SCC in a 3% sodium chloride
solution doped with sodium sulfide as function of the material
strength level. They found that SCC occurred only when the
alloy was heat treated to a yield strength level of 120KSI
(827 MPa) at 25C and 175 KSI (1207 MPa) at lOOC. Hydrogen
permeation experiments as a function of applied potential
found three regions: (1) increasing permeation with increas
ing cathodic polarization; (2) a cathodic protection poten
tial range where no permeation occurred; and (3) and an anodic
region with localized corrosion and hydrogen permeation.
These experiments indicated that strength level has no ap
preciable influence on hydrogen permeation.

27
Hoke (30) reported that induction melting of 410 stain
less steel greatly improved the resistance to SCC in a simi

lar electrolyte as used by McGuire et al. In this case arsen
ic was used as a poison, but he did not report either the
heat treatment or strength levels of the steels he used.
Additional SCC work has been performed by McCord et al

(31) on 403 stainless steel with a yield strength of 85 KSI
(586 MPa)and a number of 12 % chromium steels with yield
strengths below 116 KSI (800 MPa). Using dead weight load
ing in 3.5% sodium chloride solutions at 150P (65C), they
found no failure occurred in the material after 4400 hrs
of loading.
A study of the effect of tempering temperature on the
SCC susceptibility of a 13% chromium martensitic steel in

3% sodium chloride at 25C by Hewitt and Hockenbull (32) in
dicated that in constant load testing, the material tempered
at 650C showed no evidence of cracking but only pitting and
general corrosion. Figure 10 and 11 are summaries of the ef
fect of tempering temperature on SCC; tempering at 550C and
above results in little. SCC effects.

By using the slow strain rate technique to determine the
suscepibility of martensitic stainless steels to SCC in 3%
sodium chloride solutions (cathodically polarized), Surey (33)
found that a tempering of 600C (R^ 23) resulted in the highest

% reduction in area while specimens with a lower tempering
treatment had a lower reduction in area; the tempering at
slit.-bb iiliib ily Ky mill
100__________ ^ _________ 3 0 0 400
10^
tem pering t e n i p e i a t m o C 12% c h r o m i u m s t e e l
o 2 5 C ,l5Cf
* 100 0 , 5 h 1 0 50 C . oir c o o l e d
-200
t e m p e r e d 10 h
10^ s t r e s s c o r r o s i o n c r o c k v e l o c i t y in
450 distilled HgO. 2 3 C , K = 4 5 MN m ^ ' 2 -180
A 475 I/I
\ -5
E 10^4
o o
2
d> o
>
200. 400
U
O
U
C -7
5
in 10
o
0
1
12% cliromium s t e e l . 0 . 2 % C
0,5li 1 0 6 0 C air c o o l e d
t lempered lOh ic?-
S()i,-cimen t y p e DCS
( i iv i ro n m e iiO d is tin e c l HÔ
ru-miieraluie; 2 3 C
-10
10 ,
10 1
80 100 120
m 2bo- 300 50 6ob^
20 40 60 tempering temperature (C )
stress i n l e r i s i l y (K , M N in
Figure 10. Effect o f tempering temperature Figure 11. Effect of tempering tem
and stress intensity on the perature on toughness (K^^) and
velocity of SCC cracks. (28) crack velocity in water of a
12% chromium steel.
NJ
00
29
60OC however, did not completely eliminate the susceptibility

to SCC during cathodic polarization. On the other hand,
polarizing the samples anodically while slowly straining, led

to a minimum in the % reduction in area on samples tempered
at 600C.
In summary, the SCC behavior of martensitic stainless

steels is strongly influenced by mecrostructural variations
resulting from the heat treatment.(34)
2.4.3 General Corrosion and Pitting Behavior

Corrosion rate work (35) investigating the effect of
chromium on the corrosion resistance of steels in water has
shown that martensitic stainless steels have higher corro
sion rates than ferritic and austenitic stainless steels; in
general the trend is that the higher the chromium content

the greater the corrosion resistance.
Examining the pitting potentials for a martensitic
stainless steel, Johnson (36) found that the material is

susceptible to pitting in solutions with chloride concentra
tions of 10-10,000 ppm; very little change of these potentials
was noted in the pH range 3-8 at room temperature.
Figures 12 and 13 show the effect of heat treatment on
pitting and the general corrosion rates for 410 stainless
steels; in each case, corrosion rates can be greatly influen
ced by the tempering temperature. (2, 37)

080
2 0 % 8 Il roq
.070 3 ' 4 Hr Periods
tn
5 060 t-
I \ 0 % HAc
Z Boi l i nq
1 - 5 0 Hr P e r i o d !
ifi
g ObO
30
iij
I
Type 410
n, i II Cr 12 5 0
w 04 0 W
H
4
:
z 2 5 % MNO
o
Ui 120 F
o 3 4 Hr P e r i o d s
(r
or
o
l i- u
020
a' s 200 600 1000 14 00 IHOO w
o
Quenched
HLMEAI IMG TEMPERATURE 'F 4
X

>
J
<3
Figure 12 Effect of heat treatment on As
Quenched
200 1000 1400 1800
corrosion rate of 410 stain PCHFATirJG t e mp e r a t u r e : *F

less steel in a salt fog
environment. (2)
Figure 13. Effect of heat treatment
on corrosion rate of 410 stain
less steel in various en
vironments. (2)
U)
o
31
In summary, the general corrosion resistance of themar-

tensitic stainless steels is superior to carbon steel.(38)
It is dependent on the heat treatment and the steels are sus
ceptible to pitting attack.
2.4.4 Corrosion Fatigue
Having reviewed the corrosion behavior of martensitic

stainless steels, it is possible to examine the corrosion
fatigue aspects; first the S-N type information available is
presented then it is followed by crack growth type discus
sions .
The effects of corrosion fatigue on stainless steels
were initially studied through the testing of smooth or
notched specimens under cyclic loads; the results were plots
of the applied cyclic stress amplitude, S , as a function of
the number of cycles to failure. Figures 14 and 15 show the
tremendous effect water and chlorides have on the fatigue
behavior of a 13 % chromium steel.

Additional work on the effect of an aqueous environment
on the fatigue limit is shown in Figure 16; Cowley et al (39)
demonstrated the electrochemical nature of the corrosion fati
gue process by increasing the corrosion fatigue life of a

13% chromium steel in a 10% ammonium nitrate solution by
anodic protection.
SCO
500
13 > C : sled (x 20 Cl 13 )
Goa 610 10 650 M N / m *

envilm iient
G u ,j - 760 - 830 M N /m *
notched rotating b e n d sp ecim en s

400 /y y ' aii,~50/ fh m ean load lero
400
frequency 50 Hi
tem perature 23*C
d istilM w ater
300
w|
200
e n v iro n m e n t ;
\'i a q u e o i i f -5 0 % rh
13 / Cl s ire l
NaCi solution
6"m - 6IU l o ( i M M N / m
100
Tu,, - 760 to 8 3 0 M N / n i * too d istilled w ater
i d l . i t m g {htikI s p e c i m e n
1% aqufroui
m ean fco NaCI so lu tio n
lie q u e jity 50 H i
tem p e iîtix e 23*C
10 *) io -4 - -4 -
N.inil>r of C ycles to failure , ^
10 10'
N umber of cycles to fa ilu re , N
Figure 14. Corrosion fatigue S-N curves Figure 15. Corrosion fatigue S-N
of smooth bar -speciments ex curves of notched bar speci
posed to various environ mens exposed to various en
ments . (28) vironments. (28)
U)
to
33
JjMBEr CYCLES :PsrfEss
Figure 16. S-N curves for a 13Cr-Fe alloy (austenitized at

950C, tempered at 680C) tested in air and in 10%
ammonia nitrate in various conditions. (42)
34
A review of the S-N type of fatigue data (39, 40, 41)

on 403 stainless steel has confirmed that whether the mate
rial is in a steam or chloride environment, there is a loss
in the total fatigue life o.f the material from that in air.
In addition, testing in chloride solutions produced pitting
and intergranular fracture (40); the loss in fatigue life of

the alloy was found to occur regardless or heat treatment.
In fatigue crack growth behavior, it is worthwhile to
establish base-line data in a benign environment, then deter

mine the environmental effect. Figure 6 showed the type of
crack growth behavior that might be expected in a steel; the
crack growth rate was plotted as a function of the stress in
tensity range, AK. It is also possible to plot crack growth
rate, da/dN, as a function of the maximum stress intensity,
K , and obtain a curve similar to Figure 6.

max
Figure 17 shows such a plot. The effect of the environ
ment in corrosion fatigue is to enhance da/dN below the

and to possibly lower the threshold stress intensity value.
Three types of corrosion fatigue are shown in Figure 17.

Type A behavior represents a corrosion fatigue effect due to
the synergistic action of the environment and the mechanical
fatigue process. Type B behavior is representative of cor
rosion fatigue dominated by the static loading effects of
see. When K <K no corrosion fatigue takes place,

max xoCu
but when K > a substantial increase in da/dN occurs
due to corrosion fatigue. This type of behavior is often

3,5
A g g re s sive
Type A
inert
Log X tnax
Aggresive
Type B
In ert
cn
'ÎSCC
L o g Kfnax
Aggressive-^
Type C
nert
Log
Figure 17. Schematic of types of corrosion fatigue behavior
(43)
36
found with high strength steels in hydrogen environments.

Most environment-material systems exhibit behavior similar
to Type C, which is a combintion of Types A and B . (43)
In corrosion fatigue, as in fatigue in a benign environ
ment, the crack growth rate is a function of the stress in

tensity range. This relation, however, is also affected by
the test frequency of the applied load, the shape of the
wave form, the maximum stress intensity, as well as AK.
Although in a benign environment, the measure of microscopic
material damage (da/dN) produced by fatigue loading is a

cycle dependent parameter, i.e. frequency independent, this
behavior is valid only if the material is not strain rate
sensitive or if the crack growth rate is not influenced by
environmental attack.(44)
The following paragraphs discuss experimental studies
which document the effect of fatigue testing variables on

the crack growth rates observed in aqueous environments.
The discussion centers on the fatigue behavior of steels
with little or no SCC component.
Effect of moisture on cyclic crack growth
Studies of fatigue crack growth (45, 46) have found that
materials which are resistant to sustained load cracking suf
fer an increased fatigue crack growth rate when exposed to

water vapor. Logsdon (15) found that distilled water at
520F (270C), 1200 psi, had a moderate effect on the crack
growth rate of 403 stainless steel.; his results are shown
37
in Figure 18 along with the heat treatments of the material

studied.
Clark (14) generated fatigue crack growth data for 40 3
stainless steel with a heat treatment similar to #933 in

Figure 18 in various marine turbine environments; he found
that room temperature distilled water, seawater, and sulfur
ons acid had little effect on the crack growth over that in
air. But in the same environment at 200F (9 3C),there was
an enhancement of the crack growth rate. Figure 19 shows a
summary of the effect of the various environments he studied;

Table 3 summarizes the power law relationship for the curves
in Figure 19.
Effect of cyclic frequency
The effect of test frequency on the crack growth rate
is best demonstrated by Figures 20 and 21. Figure 20 is |the
effect on the crack growth rate of an untempered 12% chromium

steel; the highest growth rates are at the slowest test fre
quency. This cyclic frequency dependence is typical of

materials susceptible to SCC. Figure 21 shows the growth
rate vs frequency at one value of AK; the large frequency
effect is minimized when the material is tempered at 7IOC,
where no SCC behavior is noted.

Ferritic steels also have cyclic frequency dependent
crack growth in water environments (47), while austenitic
stainless steels are not affected by a water environment.
(48)
38
-1 r-n r lOOO
U f ,.-.
.',/n';
M/.
& /, *
C
O l 'I 100
#
!:l
I

9. 637
]ikWirontr*ni
RooO! ffm p -i9 ir

------- 933 Ram temp A>r
/f 4i ------ 933 520 F, i2oopsi.
------- R oopi temp A if
le ' 10 F ftl)U fitf T w Hz.

' 2.TW0 L S)pCIOlS
g
pREQ =10Ni
10 ZO ,' i -'lOO ,V'r> .500

S^'ViS M-kn&'+y /C feir 'Torvê. A K , Wji. in'^^
(637) Austenitized at 1750F(955C) for 20 hrs,

oil quench, tempered at 1140F (620C) for 32 hrs
(933) Austenitized at 1750F for 16 hrs, oil
quench, tempered at 1150F (627C) for 27 hrs.
(484) Austenitized at 1750F for 16 hrs, oil
quench, tempered at HOOF(590C) for 27 hrs.
Figure 18. Summary of fatigue crack growth data for AISI

403. (15)
39
SULFUROUS
ACID, pH 2
200"F
S t e a m ,212T
DISTILLED
WATER; 2 0 0 T
/
SULFUROUS ACID
pH 2; 75T
403 S.S.
30 HZ
R = O.I
rl
10
10 20 30 40 50 00 80 100
AK (KSl-#)
Figure 19. Summary of fatigue crack growth data for AISI

403 in various marine turbine environments. (14)
40
TABLE 3
FATIGUE CRACK GROWTH RELATIONSHIPS

FOR AISI 40 3 IN VARIOUS ENVIRONMENTS
Environment Power Relationship for

da/dN(in/cycle)
Air, 75F -9 2 4
Distilled Water, 75F 1.6 X 10 ^ AK *
Sea Water, 75F
Sulfuous Acid, pH2,
75F 3.4 X 10 ^ AK^'^
Distilled Water, 200F A 1

4 . jL X 10"^
Sea water, 200F
Steam, 212F 4.5 X 10"^
Sulfurons Acid, pH2, 1.0 X 10-10

200F
Ref. 14
cyclic stress uitedsily (iiirje , AK , ^kcj.iiuii
JO 20 40 130 110 100 1:0 140 VO 100 .in
10 Hz . H .O 12 % Chrom ium s t e e l , Q2 o C
II K )'H z. H .O
1 2.3 Hz, H .O
1cm thick DCB sp e c im e n
2.3 H z. v.iaium R - 0 , te s t te m p e ra tu re 23 C
heat tre a tm e n t environm ent

H jO ! vacuum
0,5 h 1060 C , air cool
s a m e plus 10 h r'XlC/inr
E
A K = 6 3 MN III
2
CJ)
12% (.hKnimiiii S teel, 0 2 % C
CIO fi Kj CZJ C, ;iir
u
lent lliick DCB spccinxiit
H '0 o,
li st titniper.iluie 23 C
to 20
cyclic stress .risily i.jmji: , A K , ^M tjiii

inter
e:yt.liL Inxju* ii'.y , | M/
Figure 20. Effect of frequency and Figure 21. Growth rates of fatigue
stress intensity of the growth cracks in 12% chromium steel as
rate of corrosion fatigue cracks a function of cyclic frequency,
in a 12% chromium steel exposed environment, and heat treatment. its.
t-"
to water. (28) (28)
42
Gallagher and Wei (44) studied the effect of frequency

on 12Ni maraging steel in salt water at stress intensities
below This study resulted in fatigue crack growth
rates which were higher at the slower frequencies and slower
at the higher frequencieds. This behavior is similar to that
of material which is susceptible to SCC, so that a mild fre
quency dependence is possible even if there is no SCC crack
growth component.
The magnitude of the effect of frequency on the fatigue
crack growth rate depends strongly on the environment-mate

rial system. Thus, each environment-material system must be
characterized separately. Part of the frequency effect may
be due to the amount of solution chemistry modification that
occurs in the crack tip region. Brown (49) proposed that

various forms of localized corrosion have the common feature
of local acidification by hydrolysis, but excluded corrosion
fatigue from this type of behavior due to the amount of
pumping of the electrolyte that can take place. The alter
nate opening and closing of the crack results in pumping
the electrolyte into and out of the crack on each load cycle
which promotes mixing. Barsom (50) has reported a corro-
sionf fatigue crack pH of approximately 3 for a 12NiSCr3Mo
steel cycled at 0.IHz in a near neutral 3% sodium chloride
solution. Additional factors which influence modification
of the crack electrolyte are wave form, stress ratio, and
test geometry.
43
Effect of stress wave form
The effect of different wave forms, mentioned previously,

was said to have no effect on the crack growth rate in air.
A different situation exists in corrosion fatigue; it is
illustrated in Figure 22 where the data show that in a sodium
chloride solution, the crack growth rates under sinusoidal

and triangular stress fluctuations are almost identical but
higher than air. However, the environmental effects are neg

ligible when the steel is subjected to a square wave fluc
tuation. The material in this situation was tested below
ÎSCC' that the sustained loading effect in the square

wave shows negligible effects; thus, the environmental
damage below occurs only during transient loading. (7)
Effect
------ of ---------
stress ratio, R ---
---- (= K^/K__)
mxn max
Although there was no effect of variations of R in
Region II crack growth in air, in corrosion fatigue it is a
major variable. Generally, it appears that high R ratios
enhance the corrosion component of crack growth, while low R

ratios reflect more of the intrinsic material response.
This response may be due to the amount of crack opening
and closing which occurs during each fatigue cycle. Bamford
and Moon (47) and Miglin (48) found that variations in the
R ratio affected the fatigue crack growth rates in ferritic
and austenitic steels.

44
0-'
12NiSCr-Vo
STEEL
w
<t
cr
?
o

X
CORuRAOTSAIOANT -6c-ATiGUE
GOm
m/ O SiN U SO iC A U LOA*
A T P ,ANGULAR LOAD
O SQUARE load
10 20 30 50 60
S T R E S S - I N T E N S I T Y - F A C T O R R A N G E . <1K j . < s . / nG
Figure 22. Effect of loading wave form on the fatigue crack

growth rate of 12Ni5Cr3Mo steel below in
3% sodium chloride solution. (7)
45
Effect of test temperature
Wei (51) found that the fatigue crack growth rates of a

high strength aluminum alloy in distilled water is affected
by the test temperature; he postulated a thermally activated
mechanism for crack growth. The test temperature of the solu
tion may also influence the chemistry of the solution at the

crack tip, the kinematic viscosity and/or diffusion (52),
all of which are factors that have to be taken into account
if the electrochemical process is diffusion controlled.

Corrosion fatigue crack growth at low AK values
Only limited corrosion fatigue crack growth data have
been obtained at low AK values. The data suggest that the
threshold stress intensity factor, AK^^, for steel is not
affected by an aqueous test environment. Unfortunately, to
establish AK^^^ within a reasonable test time, data are ob

tained at high frequencies where the environment has limited
effect on the fatigue crack growth rate.

Paris et al (25) found that the crack growth rates
were more sensitive to the stress ratio at the lowest growth
rates considered to establish AK^^ than they are at higher
growth rates as in Region II crack growth. They found that
in A533 and A508 steels crack growth rates in distilled water
were slower than in air in the vicinity of the AK^^. Simi
lar results have been documented for 5% nickel steels.(53)
46
Clark (14) found that the environment had little effect

on the very slow fatigue crack growth rate properties of
AISI 403, whereas, the R ratio had a significant effect on
the very slow crack growth properties, i.e. the higher the
R ratio, the lower the AK., . He established that the AK^,

th th
for 403 in air or water (75F and 200F) is 3.1 KSI in
(3.4 MPa m) at a stress ratio of 0.9.
2.4.5 Corrosion Fatigue Crack Growth Mechanisms

A discussion of corrosion fatigue crack propagation
mechanisms can generally be divided into two types ; one

type of crack growth is "true" corrosion fatigue due to the
presence of an environment when SCC is absent; the other type
is stress corrosion crack growth under cyclic loads. How
ever, since the material investigated in this project was
not susceptible to SCC (54) , the mechanisms for corrosion

fatigue crack growth discussed here are confined to those with
no SCC component.
Pyle et al (55) developed a working model for active
dissolution during corrosion fatigue. Their model accounted
for crack development as well as propagation. They recog
nized that when a metal is .exposed to an environment while
it is subjected to continuously applied cyclic stress, the
extent to which fatigue crack initiation and propagation are
influenced will depend on (1) the thermodynamic tendancy of
47
the metal to react, (2) the reaction kinectics, and (3) the
type of reaction and reaction products. In aqueous systems,
the reaction can involve metal dissolution. They acknowledge
the fact that the dissolution process in corrosion fatigue is
located at the slip steps produced at the surface of the metal
because of their enhanced reactivity. The dissolution can

only occur at the step faces exposed to the electrolyte, and
the amount of dissolution possible will depend on the rate

of dissolution and cycling speed. They beleived the process
occurs as follows:
Dynamic plastic deformation during the tensile half cycle
allows localized dissolution at step edges on the crack front.
Reapplication of the tensile stress results in either further
plastic deformation or mechanical propagation by brittle
fracture. As the crack grows, the importance of dissolution
compared to mechanical propagation changes and the environ
ment becomes less important as the crack lengthens. The cri
tical factor in the amount of dissolution that occurs is the
slip step spacing.

Devereaux et al (56) , while studying an aluminum alloy
resistant to SCC in the solution in which they were studying
corrosion fatigue, noted a similarity between SCC and corro
sion fatigue. And although the crack tip environment in
fatigue is of a transient nature, a process was envisioned

where anodic dissolution is enhanced by plastic deformation.
48
which also inhibits the formation of an oxide film; an alter

nate mechanism would be the successive formation and rupture
of an anodic film.
Pelloux (57) postulated that corrosion fatigue in alu

minum in saline solutions may be explained by a mechanism of
stress sorption cracking, i.e. weakening of metal bonds at
the crack tip through the adsorption of the environment or
its constituents.
Wei (51), on the other hand, while studying the en
hancement of the fatigue propagation rate of aluminum in
water, proposed a hydrogen embrittlement mechanism; the ac-
cleration of the crack growth is caused by an increase in the
crack tip stress intensity produced by a build-up of hydrogen
pressure in internal "voids" ahead of the crack tip. The
hydrogen results from the cathodic reduction reaction ac
companying the dissolution of aluminum.
2.5 Summary
The literature survey has reviewed the metallurgical
and mechanical properties of martensitic stainless steels.
It has presented a fracture mechanics approach to fatigue
and introduced the variables and mechanisms responsible for
fatigue in benign environments. These principles were ap

plied to the problem of corrosion fatigue. The effects of
various parameters on the corrosion fatigue behavior of mar
tensitic stainless steels were discussed, and finally some
49
models for corrosion fatigue crack growth were presented.

However, a definitive description of the corrosion fati
gue process is not at hand due to the metallurgical, electro
chemical and mechanical aspects of the process which must be

taken into account. Although fatigue crack growth laws
were presented and are usful from a structural design stand
point, they are of limited value because they do not account

for, or incorporate, the environmental effects.
The section on corrosion fatigue outlined the factors
which affect fatigue crack growth rates. Since these factors
must be systematically controlled in order to sort out their
effects, the experimental program of this research work held
some of these parameters constant; for example only one wave
form (sinusoidal), one stress ratio (R=0.5) , and one mate
rial heat treatment were employed. The variables were cyclic
test frequency, the aqueous environment, and the test tem
perature. The test matrix and experimental procedure are
presented in the following section.
3.0 EXPERIMENTAL PROCEDURE
3.1 Introduction
Since the purpose of this research project was to de

termine the effect that various environments have on the
fatigue crack growth of Type 403 stainless steel, there are
a large number of experimental variables which had to be
taken into account. These may be broadly classified as metal
lurgical, mechanical, and environmental. This part of
the dissertation describes the experimental details that
were employed to determine the effect that the environ
ment had on fatigue using a linear elastic fracture mech
anics approach to the problem. The first part of this
section gives the details of the apparatus and instrumenta
tion, as well as the material composition and material
properties; the second section gives the procedural de
tails .
50
51
3.2 Experimental Apparatus
3.2.1 Material
The alloy used in this project was supplied by Cru
cible, Inc. The mill chemistry is given in Table 4.

Enough material was obtained so that all the test sam
ples used in this experimental program came from the same

heat to avoid minor heat to heat composition variations.
The "as received" microstructure of the material is shown
in Plate I.
The heat treatment for the material was similar to that
used in the steam turbine industry and is detailed in
Table 5; also listed in Table 6 are the mechanical pro
perties for the material after heat treatment, Plate II

shows the resultant microstructure consisting of tempered
martensite with some delta ferrite,

3.2.2 Specimen Geometry
To establish the minimum fatigue life of a component,
it is reasonable to assume that the component contains the
largest discontuinity that cannot be detected by an inspec
tion method. Consequently, the most successful approach to
study fatigue crack propagation is based on fracture
mechanics concepts. This approach utilizes a notched,

fatigue cracked specimen with the same type of geometry
used for determinations.
The specimen used was a compact toughness specimen
52
TABLE 4
MILL CHEMISTRY OF 403 STAINLESS STEEL
C ^ P S ^ Cr Ito Fe
0.10 0.48 0.019 0.01 0.30 11.71 0.10 bal,
TABLE ^
HEAT TREATMENT OF 40 3 STAINLESS STEEL
Austenitized at 950C (1750F)

for 1 hr.
Air Cooled.
Tempered at 550C (1200F)
for 1 hr.
TABLE 6
MECHANICAL PROPERTIES OF 403 STAINLESS STEEL
Ultimate Tensile 0.2% Offset Yield Elongation Hard-
Strength Strength ness
MPa KSI MPa KSI R^
784 113.8 682.4 100.3 22.3 22
53
Plate I. Microstructure of "as received" 403 stainless

steel. (500X)
XU":,
54
Plate II, Microstruecture of quenched and tempered 403

stainless steel, (,5G0X)
-V' V '*
55
(,CTS) with. 0.5 in nominal thickness. It was designed with
the dimensions outlined in ASTM specification E399-72. The

sample diagram is shown in Figure 23, The specimens were
L-T specimens, i.e. the rolling direction was normal to the

crack plane and the width was in the direction of the crack
propagation. Plate III shows a typical CTS specimen.
The stress intensity factor as a function of the
change in applied load and crack length for fatigue is
where ;
K = stress intensity factor, MPaVnP CKSI in)
AK = K - K .
max min
A P = applied load, N (KIP)
B = specimen thickness, m (in)
W = specimen width, m (in)
Y = f(a/W)
= 29.6(a/W)^ - 185.5( a / W ) + 655.7(a/W)5/2 -
1017 (a/W) + 638.9 (a/W)9/2.
3.2.3 Closed Loop Servo-Hydraulic Fatigue Machine

All the experiments were performed on closed loop
servo-hydraulic fatigue machines; one was a lOOkip capacity
Materials Testing Systems unit and the other one was a
20kip capacity unit manufactured by Instron, Inc. Figure
24 shows a typical closed loop system in a pictorial
block diagram. The "closed loop" is a continuous path of
56
ALL DIMENSIONS IN INCHES
1----- 1-----r
I > I I
I I -
I I I
_i-- 1
I
I
-a _
0.80
c:.
40
2,00
2.50
Figure 23. Details of corapact-tension specimens (CTS)
used in this project.

57
Plate III. Compact-tension sample used in corrosion fatigue
crack propagation studies with LVDT extension tubes in place

with teflon blocks.
LoAiJ C * Il ( F u r c r ) ( i i i l p u l
. M, U "
:
* 4 0 ////</
VALVE
t..ir SEKVO DHIVEK OH
CtNTHt JLLEH Cur;n(OI.I.EH KYLI,AUl IL M T S
SlU'l'LY
r r'IU*L
II.V f utl lAit- I E rf or *-4 J Q
I LKObACK
%KimOH
II
ACV
nDtHAAT
UO
LI
RC
f "Wf Aimiied
LVDT
Cunnrciur
l.vnr ( St r Vr) O u l u . i l
v , i . r . u j 11
Figure 24, Block diagram of typical closed-loop hydraulic testing
system.
U1
CO
59
interacting elements. If this path is broken at any point

while hydraulic pressure is applied to the servovalve, closed
loop control is lost and the hydraulic actuator applies full
force.
Testing was conducted in the lowest range necessary in

each system to achieve the maximum loads required. All the
testing was performed in tension to tension cycling with a
sinusoidal wave form in the load control mode, i.e. the load
range was held constant as the crack grew.
The determinations were conducted at a test frequency
of 40 Hz, while the progation tests were run at 40, 10, 1,

and 0.1 Hz.
The sample was placed into the testing machine by means
of a load train, which is diagramed in Figure 25; the details
of the corrosion cell are shown in Figure 26 with the load
train running through it. The sample grips or clevises and
pins were machined from a Type 410 stainless steel (similar
in composition to Type 403). The pull rods were machined
from Inconel 600, but only a small portion of the lower pull
rod, which was convered with teflon tape, was exposed to the
solutions. Thus, galvanic coupling due to compositional dif
ferences were precluded.
The solution temperature was adjusted by means of heat
ing tape wrapped around a pre-formed steel sheet thatcould
be slipped on and off the teflon corrosion cell. The

60
LOAD CELL
PULLROD ADAPTER
PULLROD
LVDT HOLDER
THERMOMETER
HEATER TEFLON
CELL
SEALS
PULLROD
ADAPTER
RAM
Figure 25. Diagram of load train

61
LVDT
Fullrod
LVDT Holder
Teflon Corrosion
_^Cell
LVDT Tube
LVDT CTS 4lO Stainless

Mounting Steel Grips
Blocks
Teflon Seals
0-Ring Seal
Pullrod
Figure 26. Diagram of corrosion cell with, load train

and sample in place.
62
temperature was controlled by means of a variac controller.
Naturally, when room temperature air tests were run,

the teflon cell apparatus was not employed and the speci
men was open to the air. The whole apparatus is picture in
Plate IV,
3.2.4 Electrochemical Equipment
Monitoring the open circuit potential was accomplished
with a standard calomel electrode CSCE). This electrode
was in a staurated solution of potassium chloride located
outside the corrosion test cell; it was connected to the
test solution by means of a teflon tube with a nylon cord
running through, it. The chord was saturated with solution
to provide conductivity between the two solutions. The
specimen and reference electrode were connected to a Wenkin
potentiostat to monitor the open circuit potneial. A Leeds
and Northrup Speedomax recorder were used to record the
potneial for the duration of a test.

3.2.5 Electrolytes
The electrolytes studied are listed in the test matrix
in Table 7. The solutions were made of reagent grade salts
and double distilled, demineralized water. The pH was ad
justed with sodium hydroxide or the acid of the pertinent

salt (. such, as hydrochloric, phosphoric or sulfuric acid.)
The solutions were not deaerated; the only oxygen control
exercised was by the boiling of a solution during a test.
63
Plate IV. Corrosion cell in place in MTS load frame with

LVDT/ thermometer, and reference electrode in
place.
64
TABLE 7
TEST MATRIX
Environment Tempera Concentra PH Freq.

ture tion
(C) CM) CHz)
Air 100 10
25 40 determ.
HgO 25 7, 10 10
100 10 10 -
tl
7 0.1 -
II II
1 -
II II
10 -
II II
40 determ.
NaCl 25 0.01, 1' 10 10
100 1.0 2,7,10 10 -
II
0.01 10 0.1 -
II II II
1
II II II
10 -
II II
2,10 40 determ.
Na^SO
6 4
100 0.01 10 10
II
11 II
40 determ.
II
1.0 2,7,10 10
Na PO, 100 1.0 10 10
3 4 il II II
40 determ.
Na^SiO^ 100 1.0 10.5 10 -
Constants : R = 0.5
Waveform: sinusoidal
65
3.3 Experimental Techniques
The crack growth mesurements utilized a number of ap

proaches, each of which is described in detail in this sec
tion. In addition, the computer programs used for data re
duction are described along with a sample calculation for
determining crack lengths from voltage readings.
3.3.1 Specimen Preparation
Surface finish was not a critical parameter for this
test program. Each sample was sanded to a 240 grit finish

to provide a uniform surface finish, however. All the sand
ing was done in a direction perpendicular to the direction
of crack propagation. Specimens which were tested in air
using optical crack length measurements were finished through
600 grit paper. Then the area through which the crack would
grow was polished with 0.0 3 y alumina using a small polish
ing wheel attached to a 3/8 in drill.
For precracking purposes all samples were polished in

this manner.
3.3.2 Precracking Procedure
All the samples were precracked in air to an average
0.0 60 in beyond the machine notch. This type of precrack
ing had a twofold purpose : the first was to generate a
crack in the specimen with a stress intensity history
which was known and which would not influence the mechani
cal crack growth during subsequent fatigue study; the second
66
purpose was to produce a sharp crack with a small plastic

zone sufficiently distant from the machined notch wo as to
be free from residual stresses.
Precracking was accomplished in the load control, ten

sion-tension sinusoidal mode with a stress ratio, R=0.1.
This crack extension was accomplished in a series of steps
starting at a high stress intensity, 27,5MPa m C25KSI in)
and decreasing to a^K value which would be the initial value

for subsequent corrosion fatigue testing, 16,5MPa m, (15KSI in).
All precracking was done at a frequency of 10 Hz.

3.3.3 Measurement Techniques
Crack lengths were measured in two ways. In air, when
there was no corrosion cell, the crack was measured optical

ly on the sample surface with a travelling microscope or via
a compliance technique using a linear variable differential
transformer (LVDT). A Gaertner 50X travelling microscope
was used for the optical measurements; the crack length

could be determined to +0.001 in. Plate V shows a sample
in the MTS load train with the LVDT attached and the travel
ling microscope in place.
The LVDT is an electromechanical transducer that
produces an electrical output proportional to the dis
placement of a separate movable core. When the core is in the
center position (Figure 27, core at 0), the output is zero ;

when the core is moved, a differential voltage is induced.
67
Plate V, Compact-tension sample in MTS load frame with

LVDT attached and traveling microscope in place.
68
V O .T A G E
OUT
W
r

150
(- 50
50 100 150
CORE POSITION n t HOWINAL RANGE)
VOLTAGE OUT
O P P O S I T E P H ASE
NOMINAL RA NGE'
'M.
COflC A T -10 0% G0^5 AT 0 CORE AT 100%
(NULL POSITION I
C O R E OiSP L A C E M E N T
Figure 27, Working diagram for Shaevitz LVDT,

69
which varies linearly with changes in the core position.
Figure 27 is a continuous plot of output voltages vs core

position as a straight line passing through the origin.
The LVDT was mounted to the sample with teflon blocks
and extension tubes as shown in Plate III. The LVDT body
was mounted to one side of the machined notch, -while the
core was attached to the other side. Thus, as the crack
grew, the specimen opened and the voltage difference, AV,
I
increased. The 440.22 A.C. conditioner on the MTS console
was used as the signal conditioner. For long range testing,

an Esterline-Angus recorder was used to record A V. Two
different LVDT's were used for this work; the A determina
tions required a more sensitive LVDT than that used for the
crack propagation studies.
Measurement of a crack length with an LVDT is based on
the principle that as the crack grows, the specimen com
pliance increases thereby increasing the displacement at

the gage line. Standard values of the compliance as a func
tion of crack length are available in the literature for com-
pact-tension specimens.(58) These values correspond to the
load line displacement. The compliance obtained from a
fatigue test correspond to the gage line displacements. The
standard load line values were converted to gage line values

by means of similar triangles, as shown in Figure 28.
By using the compliance technique, it was possible to
convert A V to crack length; a sample calculation is shown
70
L.L, G.L.
G = crock length g +x
X = d i s t a n c e f r o m L.L. t o G.L. b 0
b = (BEA8/AF)LL
y = (BEA8/AP)GL /B E A 8 \ _ 'q + x \ / B E A S \
V A.P . 0 M A P /ll
Figure 28. Schematic of sample showing the load line and

gage line conversion.
71
in Figure 29. Because of occasional variablility in data
collection, and as a correction for the shape of the crack
front, it was necessary to insure that the A.V measured at

the start and end of a fatigue test was exactly equal to the
initial and final crack lengths. Figure 30 shows a fractured

surface after testing was completed. The Gaertener 5GX tra
veling microscope was used to visually determine the average
initial and final crack lengths.
3.3.4 Crack Growth Rate Test Procedure
All the tests were conducted in a similar manner

whether in air or in solution. This section describes the
test assembly procedure, LVDT placement, and load monitoring.
Initially, the teflon blocks were tightly bolted to the
sample, and then the extender tubes were screwed into the
blocks; the sample was then placed in the clevises and at
tached to the corrosion cell. Then the circular heater was
placed around the cell, and the whole system with a teflon
lid added, was screwed into the MTS load frame.
The LVDT was then positioned in its aluminum housing
at the end of the extender tubes. The MTS oscilloscope
was used to monitor the LVDT signal and insure that it was
well within the linear range. Once the LVDT was mounted, a
check on the load-displacement response was run; no test was

run unless there was less than 0.15% hysteresis.
72
A. = A.V slope of calibration curve for LVDT
AV = 0.88 V (typical LVDT initial voltage reading)

slope = 0.00 522 in/V
A 5 = 0.00459 in.
A = BEA /A P (compliance)
B = 0.5 in (specimen thickness)

E = 3 X 10^ lbs/in^ (elastic modulus)
AP = 1300 lbs (test load range)

A = 53.00 = f(a/W)
Then referring to the conversion of compliance values
at the load line to compliance values at the gage line

or by means of the polynomial fitted by the computer,
a/W = 0.45 or a = 0.900 in.
Figure 29. Typical calculation for conversion of A V data

to crack length.
73
FATIGUE
FRACTURE
MACHINE
SURFACE
NOTCH
Figure 30. Example of a fracture surface after fatigue
resting showing area of machine norch, pre

crack zone on ia-igue surface an final fa:
where rhe sample was pulled aparr.

74
The heater on the cell was then plugged in and the spe
cimen was allowed to reach lOOC, the test temperature. Mean

while the test solution was brought to boiling on a lab
burner. Then the solution was added to the test cell, and
the whole system was allowed to reach the test temperature
[usually a 10 min wait). Meanwhile, the reference electrode
and a condenser were positioned.
Since the load control mode was used for testing, the
MTS Amplitude Measurement Module (Model 440.51) and oscil
loscope were employed. The load was monitored by setting the
variable limits on the peak detector and setting error
limits (0.2%) on the load, then by watching the oscilloscope,
the output signal was made to fall within these limits by ad
justing the set point of span of the load signal.
For the lOHz tests, the peak detector and oscilloscope
were employed to measure AV. For the IHz and O.lHz test,
an MTS 4 30 Digital Indicator with an Esterline-Angus re

corder connected to it were used to measure AV.
The test sample was kept entirely immersed in solution
for the duration of every test. For tests involving a loss
of solution due to the long test duration, an additional
solution reservoir was attached to the corrosion cell to in

sure that the solution level did not drop.
75
3.3.5 Fatigue Crack Growth Data Reduction
Fatigue crack growth results are generally presented as

log of the crack growth rate (da/dN) vs log of the stress
intensity range, A.K. From this plot a fatigue crack growth
law of the form:

da/dN = C(AK)" (6)
where C is a constant and n is the slope of the line in
the log-log plot and can be calculated.
Data is obtained in terms of crack length., a, measured
optically or with a transducer, and the number of cycles,N.
This leads to a plot of crack length a, vs the number of

cycles, N. From this, the derivative of a vs N at a num
ber or points must be obtained along with the corresponding
value of A K.
An incremental polynomial technique was used to convert
a vs N data to da/dN vs AK. This methodinvolves fitting a
second order polynomial to sets of successive a vs N data

points. Pitting functions are used which minimize the de
viation between the fitted and observed crack lengths. The
da/dN values are calculated from the derivative of the func
tion of a vs N.
Figure 31 shows schematically how the a vs N data is
converted to log da/dN vs log A K . Since the a vs N curve
is best described as parabolic, successive sets of seven data
points were fit to a second order polynomial of the form (59)
76
O'
N (N irTihc of I'ydPn) N ( Number of C / C l ' i
:o'\ '-T
N ( N ' u m b e r o f C / C P'.)
</
/ P i i ' / P r o c e s s i n g
C o n v e r t i n g n vs. N D o l e fo d a / d N vs. A K j D a t a
Increm ental P olyn om ial

7-f't Sub' jrCMi p r9
r.r-r.':rirj -- r-.o*
'|I5( S ub'-,-roup
./
I 11 l o b r'ornliriln
1-og A
Figure 31. Schematic diagram for a vs N data reduction
by means of incremental polynomial method.

77
a = bQ + bj_{ (N-C2 )/C2 > + b 2 f /C 2 , (7)

where b^, b^/ and b 2 are regression parameters determined by
a least squares criterion. and C 2 are scaling factors.
C62) Then the crack growth rates are determined from the
derivative of the above expression which is:
da/dN = bi/C2 + 2 h ^ { /< z\]. (8)
The conversion of A V data to crack length was accomp

lished by means of a computer program. (.48) The data for
each sample evaluated consisted of the number of points
considered, P , P j_, and the correction factor; then
the N vs A.V data was read into the computer. The output
consisted of crack length, a; number of cycles, N; crack
growth rate, da/dN; the stress intensity range, AK. This
program also punched out a card deck of log da/dN vs log
A K, which was used with another program to generate the best
fit straight line through the data points.

3.3.6 Fatigue Crack Threshold Determinations
The procedure for load monitoring, LVDT installation,
AV determinations, and test start-up were the same as in the
previous section. However, in this portion of the program,

the objective was to stop the crack growth by gradually de
creasing the stress intensity range, viz the applied loads ;

all these tests were run at 40Hz.
The air determinations were made by following the crack
with the travelling microscope and the LVDT; crack extension
of 0.005 in or less could not be detected with the LVDT

78
because of the scatter in the A.V readings created by cycling

the sample at 40Hz. Also, as the load was decreased, the
crack opening decreased, decreasing the A V and increasing
the sampling error. The travelling microscope could detect

crack growth to +0.001 in.
The procedure here was to start the crack growing at the

same value of AK at which the precracking had stopped, and
allow the crack to extend beyond the previously formed plas
tic zone (approximately 0.020 in). Then the stress inten
sity range was decreased by 10% and the crack growth monitored,
The crack growth rate and average A K were calculated and
plotted as the data were generated. This step-wise proce
dure was continued until no crack extension was detected for
1 X 10^ cycles. When this point was reached, the load was
then increased to the level before the crack stopped grow
ing to insure that it would indeed grow again. Thus, it
was possible to bracket the value of A
3.4 Fractography
After fatigue testing, the fracture surface of all the

specimens was coated with Krylon acrylic spray to avoid
further corrosion. Fractographic studies were conducted on
the fracture surface using a JEOL scanning electron micros
cope. Since it was not possible to mount the entire sample
into the microscope, the fracture surface was cut from the
sample. The acrylic spray was removed from the sample prior
79
to its insertion into the microscope. Acetone immersion
and ultrasonic cleaning were used for this purpose.

Fractographs were taken at low AK, medium' A K , and high
A K values where appropriate. At every A.K location, pic

tures were taken at three magnifications.
4.0 EXPERIMENTAL RESULTS
4.1 Introduction
This section presents the results of this research work.

It is divided into groups of data obtained in a particular
electrolyte, i.e. the data are presented as results obtained
in air, water, chlorides, etc. Fatigue crack growth data are
followed by the fractographic results obtained in the
scanning electron microscope. The open circuit potentials
measured during the fatigue tests are summarized in a figure
at the end of this section.
4.2.1 Fatigue Crack Growth Rates in Air
Figure 32 shows a plot of crack length vs the number

of cycles for a sample fatigued in air at room temperature
at IQHz; the figure shows the crack lengths obtained by the
optical and compliance methods. Close agreement between the
techniques is evident. Figure 33 is the plot of da/dN vs AK
for the data shown in Figure 32.

Figure 34 shows the results of tests in air at 10 and
40 Hz and at 25 and lOOC. There is little change in the
crack growth rates due to the change in test frequency or
temperature.
80
CX38
(}36 A ir, 2 5 C
1.4
Crack Length vs. Cycles
(134 R = 0 . 5 , 10 Hz
o 1.3
(132 (A
A
A
1.2
'A
(130 A
en
en
c
c O)
O) (128 l.l
-m: o
O
(_)
Compliance o
O (126 o
?* A Optical .0
2**
0.24
%A
0.9
(}22
(>20 J I L 0.8
0 20 40 60 80 100 120 140 160 180 200 220
Cycles N, (x 10 )
Figure 32, Crack length vs cycles in air showing agreement between compliance
00
measurement and microscope.
82
Type 4 0 3
Stainless Steel
10
o
>\
o
r7
10
Z
"O TJ
\ Optical
o O
O Compliance ~o
t-requency = lOHz
R =0.5
25C
rG
Air 10
r8
10
0 20 30 40 GO 8 0 1 0 0
AK, iVI P q y p n
Figure 33. Fatigue crack propagation rate, da/dN, vs stress

intensity range, AK, in air at 25C showing agree
ment between optical and compliance techniques.
83
AK (ksi/lF . )
10
4 0 3 Stainless Steel l^
c6
10 Air
R =Q5
s -5
10
<7
o 10 jO)

o
10 d
Z 9
a
D
"O o
O 10 Hz IOOC o
10 Hz 25C l^
9 V 40 Hz 25C
10
10
2 3 4 6 8 10 20 30 40
A K ( M P a / r n )
Figure 34. Fatigue crack growth rate vs i K in air at 10

and 40. Hz, 25 and 100 C.
84
The Paris power law for the linear portion of the crack
growth is
da/dN = 7.11 X 1011 Cm/cycle) (9)
= 2.80 X 10"9 (A K) Cin/cycle) , (10)
whichagrees with the crack growthrates reported by Barsom
(7) and listed in Table 2 for martensitic steels. These
results are also in agreement with those reported by Clark
(.14) and Logsdon (15) .

Figure 34 also shows the slow crack growth region of
da/dN where A w a s determined. That value is
5.2< A K < 5.7 MPaVnT
4 . 7 < AK <5.2 KSlVIn
for R=0.5.
4.2.2 Fractographic Results in Air

Plates VI and VII are collections of fractographs of
the samples fatigued in air at 25 and lOOC, respectively,

at 10 Hz. The rows of pictures represent three regions of
the fracture surface investigated: 2CA K, 25^ K, and 3CAK.
The three columns are three magnifications of the areas
investigated.
Both of these plates show striation steps which when
viewed at 10,000X are seen as the striations for crack growth

whose spacing corresponds with the crack growth rate for the
particular A K 's examined. These surfaces show no sign of in-
tergranular crack growth.

Plate VI. Fracture surface of sample fatigued in air at 25C
R=0.5, lOHz at three stress intensity ranges
(AK) at three magnifications, 500X, lOOOX, and
10,000X.
85
AIR 25 c M
PJ
ri-
10 AK
(D
<
H
20 K s
00
CTi
Plate VII. Fracture surface of sample fatigued in air at
lOOC, R=0.5, lOHz at three stress intensity
ranges and at three magnifications, 500X, lOOOX,
and 10,000X.
87
88
Plate VII.
.

13
i*J- -*3c. V Ei;i

89
plates y i l l and IX show th_e fracture surfaces of samples
cycled at 40 Hz; at A.K>15, there are signs of fatigue

striations corresponding to crack extension, but at A K= 5,
there are no clear striation markings. This result is pro

bably due to the very low crack growth obtained in this
region.
90
Plate VIII, fracture surface of sample fatigued in air at

25C, 40Hz at two stress intensity ranges and
at three magnifications, 50OK, lOOOK, and
5000X,
Alr ZS C 40Hz
20 AK
30AK

Plate IX. Fracture surface of sample fatigued in air at 25C, 40Hz at stress
intensity ranges where A K, was determined and shown at three mag
nifications, 500X, lOOOX, and 10,000X.
Air 25 C 40Hz
i t
5 K
V
% '
VO
I-"
92
4.3.1 Fatigue Crack Growth. Rates in Water
The results of fatigue crack growth in water are shown

in Figures 35 and 36. Figure 35 shows the effect that cyc
lic frequency has on the crack growth rate in water at 10OC;

the 40Hz data have growth rates lower than that at lOHz,
while at IHz and O.lHz, there is not much difference in the
growth rates observed, although there, is a frequency effect
at tke lower A'.K region. The air line is included to show
that at all frequencies, there is an increase in the crack
growth, rates above those in air.

Figure 36 shows the slow crack growth area where the
A.Kth was determined. In water, 10OC, R=0.5, 40Hz,

4.4< AK^^<5.2 M P a
4 , 0 < A K t h < 4 . 7 KSlVlr?.
Figure 37 shows the crack growth rates in water at 25
and 10OC with the ph of 7 and 10 fatigued at lOHz, It is

evident that the pH value has no effect on the crack growth,
but the solution temperature does. The crack growth rate at
25C is not as low as in air nor as high as in boiling water.
The power law expressions for fatigue crack growth in
water under the various conditions studied are listed in
Table 8.
A K ( ks i V i n . ) 93
r5 10 20 30 40 60 80
10
HgO
pH7
lOO^'C
40 Hz -4
10
V 1.0 Hz
O 0.1 Hz
E 10
Z
TD o
\
O o
TD AirJOH z TD
m
10
r7
10
10 30 40 60 8 0 100
A K (M Po ym )
Figure 35, Fatigue crack growth, rate vs A,K in water, pH7,
lOC tested at various frequencies.

94
A K ( ksi / I n . )
<5
10
r4
4 0 3 Stainless Steel 10
10
-6 HgO, pH 7
IOOC, R =0.5
10^
_0J - 7 _0J
CJ 10 o
o o
. C
10^
TD
Air
8 TD
\ 0
O o
TD O
10^
Hz
10
40 Hz
rS
10
2 3 4 6 8 10 20 30 40
A K ( M Pa / m )
Figure 36. Fatigue crack growth rates vs A.K in water, pH7,
lOOC tested at various frequencies showing the

AK^^ region.
A K (ksi VTn. ) 95
20 30 40 60 80
r5
10
0) O
o
>. O
o
c7
E
pH 7, 25C
a o
"O pH10,25C XJ
pH7, IOOC
4 0 3 S.S. pHIO, IOOC
l OHz r6
10
R = 0.5
rS
20 30 40 60 80 100
A K (M Pa T m )
Figure 37. Fatigue crack growth rate vs AK in water,
25 and lOOC, pH 7 and 10 tested at lOHz.

96
TABLE _8
POWER LAW COEFFICIENTS FOR FATIGUE CRACK
GROWTH RATES IN WATER

da/dN = C (4 K)."
pH Temperature Frequency C n
_____________________ U W __ (ZP/ g y le)____ ______
7 100 40 2.8 X 10-9 1.46

7, 10 100 10 2.3 X 10-9 1.75
7 100 1. 0.1 9.0 X 10"-^^ 3.44

7, 10 25 10 1.9 X 109 1.45
97
4,3,2 Fractographl.c Results in Water
Plate X shows the fracture surface of a sample fatigued

in water, pH7, 3.00C at 40Hz. AtA,K20, there is evidence
of both, transgranular and inter granular fracture; atAKSO,
the intergranular features are no longer evident, and the
fracture mode is primarily transgranular with secondary
cracking or branching evident.
Plate XI is the fracture surface at the low A K (AK5)

value where the A was determined. The surface retained
its mixed mode character, but it seems that intergranular
type fracture predominates.
Plate XII shows the fracture surface of a sample fati
gued at iOHz, 3.00.C, pH6.5. At A K20 and 25, the features
appear intergranular with the grain boundary areas outlined;

at A K30, the surface becomes more transgranular with secon
dary cracking appearing.

Plates XIII and XIV are the surfaces of samples fatigued
at 1 and 0.1 Hz, respectively. At these slower frequencies,
there are less intergranular features at A K20 and 25 than on
the sample cycled at lOHz; in fact, there are areas with
striation spacings on the samples fatigued at the slower
frequencies. These areas of transgranular fracture are

where the crack growth rate is slower than it is in samples
cycled at lOHz. At A K30, secondary cracking is evident,
which may account for the faster growth rate at A K30,

Plate X Fracture surface of sample fatigued in water, pH7, lOOC, at 40 Hz
showing two stress intensity range areas at three magnifications
500X, lOOOX, and 5000X.
HgO pH7 100 C 40Hz
30AK
20 AK
kO
00
Plate XI. Fracture surface of sample fatigued in water, pH7, lOOC at 40Hz
showing two stress intensity range areas where A was
determined at three magnifications: 500X, lOOOX, and 10,000X.
HjO- pH7- 100 C - 40 Hz
15AK
5 AK
UD
VO
Plate XII. Fracture surface of sample fatigued in water,
pH6.5, lOOC at lOHz at three stress intensity
ranges and shown at three magnifications:
lOOX, 500X, and lOOOX.
100
101
Plate XII,
Plate XIII. Fracture surface of sample fatigued in water,
pH7, lOOC at iHz at three stress intensity
ranges and three magnifications: lOOX, 500X,
lOOOX.
102
103
Plate XIII.
> ia < 10 II 0 r o ff I o u
Plate XIV. Fracture surface of sample fatigued in water,
pH7, lOOC at 0.1 Hz at three stress intensity
ranges and shown at three magnifications ;
500X, lOOOX, and 10,000X.
104
HgO -pH?-100 C- OJlHz P
rt-
30AK CD
tx
H
4" /
20AK
O
Ui
106
0.1 Hz than at A.K30, lOHz.
Plates XV and XVI show some high magnification photo

micrographs of transgranular and intergranular fracture
areas. Plate XV shows a mixed mode with a grain boundary

delineated and a grain with striation spacings of
which correspond to the observed crack growth rate atAK20.
Plate XVI is a grain which does not have any evidence of
striations on its surface. These two plates show that is
is possible to use the high magnification capability of
SEM to differentiate intergranular type of crack paths from
transgranular growth where striation spacings are left on
the fracture surface.
Plate XVII is a fractograph of a sample fatigued in
room temperature water; it too shows the mixed mode fracture
at lowA K's with more secondary cracking appearing at the
higher A.K.
Plate XV. Fracture surface of sample fatigued in water, pH6.5 at lOHz
with striation spacing of ^0.3p at magnifications: 500X,
1800X, and 10,000X.
HgO pH6.5 100 C lOHz
20K
o
Plate XVI Fracture surface of sample fatigued in water, Ph6.5, lOOC at lOHz
shown at A K20 showing a grain face with no evidence of striation
spacings.
20^K
o
00
Plate XVII. Fracture surface of sample fatigued in water,
pH7, 24C at lOHz at three stress intensity
ranges and three magnifications: lOOX, 500X,
and lOOOX.
109
110
Plate XVII.
is
m
I ll
4.4.1 Fatigue Crack Growth Rates in Sodium Chloride

In these solutions, tests were run at two concentra
tions of chloride, IM and O.OIM at pH 2, 7 and 10.
Figure 38 shows the effect of test frequency on the

fatigue crack growth rates in O.OIM sodium chloride, pHlO,
lOOC. These results are similar to the growth rates ob
tained in water. The sample cycled at 40Hz had a crack
growth rate faster than in air but slower than at lOHz.

The frequency effect was similar to the water results in
that test frequencies slower than lOHz did not produce an
increase in the crack growth rate.
Figure 39 is slow crack growth region where A was
determined. In sodium chloride, lOOC, pHlO, R=0.5, 40Hz
4.4< AK-h <5.2 MPa VT?,

4.0< A 4.7 KSlA/Trr.
An identical value for A K,, was obtained in O.OIM sodium
th
chloride, pH2. Thus, solution pH had little influence on
iKth-
Figure 40 shows the fatigue crack growth rates in IM
sodium chloride at lOHz, pH 2, 7, and 10 at lOOC. The crack
growth rate was almost identical to the growth rate obtained
in water, which also conincided with the growth rates obtained
in O.OIM sodium chloride, pHlO, lOOC. Consequently, the ef

fect of the chloride anion concentration and solution pH was
no worse than that produced by boiling water.
A K (ksi Vln.) 112
r5 10 20 30 40 60 80
10
I I
403 s.s.
0.01 M NaCI
pH 10
IOOC
HgO, lOHz, IOOC
10
cP
rP
_0)
jCD o
>>
o o
>>
o
10
Z
TD o
\
O XJ
TD
0.1 Hz
V 1.0 Hz
r5
O lOHz 0
4 0 Hz
-7
0
10 20 30 40 60 8 0 100
A K (M PavTfT)
Figure 38. Fatigue crack growth rates vs A,K in O.OIM

various frequencies.
113
A K ( ksi y in. )
<-5 1 2 3 4 6 8 10 20 30 40
10 El 1 1 1 ' 1 ' 1'1 1 1 1 '
-6
10 0.01 M NaCI
- pH 10
- IOOC 10^
R = 0.5 e OJ
^ 'O' o
>>>
O o
-
, * y I0 ~
^--Air
10^ # /
a - o
a a
-
/ -7
10
- / y 0.1 Hz
T / 1 Hz
10 /
-
/ 0
10 Hz
40 Hz
10
-
10
10 ! 1 ' 1 1 1 11 1 1 1 1
2 3 4 6 8 10 20 30 40
A K ( M Pa /n T )
Figure 39. Fatigue crack growth, rates vs AK in O.OIM

sodium chloride, pHlO, lOOC tested at various
frequencies and showing theAK^^ region.
A K ( ks i vTn.) 114
20 30 40 60 80
rS
10
o
CJ
r7
E
o
o
TD
M NaCI ID
pH 10
pH 7
4 0 3 S.S. pH 2
r6
10 Hz 10
R = 0.5
lOO^'C
v-8
20 30 40 60 8 0 100
A K ( M P g v7n )
Figure 40 Fatigue crack growth rates vs A K in IM sodium

chloride, IGOC cycled at lOHz at various pH's,
115
Figure 41 shows the data of chloride solutions and

water at room temperatxire, lOHz. The crack growth rate is
faster than in air, but less than in the boiling solutions.
And once again, the effect of chloride was no worse than that
produced by water.
Table 9 lists the power law coefficients for the tests
conducted in chloride solutions under various conditions.
4.4.2 Fracto'graphic Results in Sodium Chloride

Plate XVIII is the fracture surface of a sample cycled
at lOHz, lOOC in O.OIM sodium chloride, pHlO; Plates XIX and
XX are of samples cycled at lOHz, lOOC, in IM sodium chloride
pH2 and 10, respectively. All three samples, have similar
fracture features, which are like the surfaces produced

in water, lOOC, lOHz.
Plates XXI and XXII show the samples fatigued at room
temperature in O.OIM and IM sodium chloride, pHlO, respec
tively. There is less intergranular fracture in both these

samples than on the samples fatigued at lOOC; this ap
pearance is also similar to the room temperature water re
sults .
Plates XXIII and XXIV show the fracture surface of sam
ples used to determine the A values at pH 2 and 10 res
pectively. The features of mixed mode cracking are appa
rent in both plates, which are similar to the water results.
116
A K ( ksi m )
20 30 40 60 80
tor 6 10
10
0)
O o
O O '
-7
0
Z Z
TD TD
\
O HgO, pH 7 O
TD TD
o H2 O, pH 10
a I MNaCI , pHI O
4 0 3 S.S. 0 0.01 NaCI, pH 10
R =0 .5 r6
10
10 Hz
25C
s-8
10
10 20 30 40 60 8 0 100
A K (M PaTm)
Figure 41. Fatigue crack growth rate vs A K in sodium

chloride and water, 25C cycled at lOHz.
117
TABLE 9
GROWTH RATES m SODIUM CHLORIDE

SOLUTIONS
da/dN = C ^ K)^
Concen pH Temper Frequency C n
tration ature
on. CC) (.Hz) .Cm/cycle)
0.01 10 100 40 3.2 X 10-9 1.46

10 1.9 X 10-9 1.76
1 9.5 X lO"^^ 3.45
0.1 9.5 X 10-12 3.46
25 10 7.4 X 10"1 1.71
1.0 2,7, 100 10 1.9 X 109 1.76
10
10 25 10 7.4 X 10-10 1.71
Plate XVIII. Fracture surface of a sample cycled in O.OIM
sodium chloride, pHlO, lOOC at lOHz at three
stress intensity ranges at three magnification;
118
119
Plate XVIII.
M
Plate XIX. Fracture surface of sample cycled in IM sodium
chloride, pH2, lOOC at lOHz at three stress in
tensity ranges shown at three magnifications:
120
hj
IM NaCI* pH 2- 100 C 0
rt-
3 0 AK
(D
X
H
25K
1mm
Plate XX. Fracture surface of a sample fatigued in IM sod
ium chloride, pHlO, lOOC at lOHz at three stress
intensity ranges and at three magnifications:
122
IM NaCl'pHlO-lOO'C PJ
ft
30&K (D
20 AK
to
to
Plate XXI. Fracture surface of a sample fatigued in O.OIM
sodium chloride, pHlO, 24C at lOHz at three
stress intensity ranges and shown at three
magnifications: lOOX, 500X, and lOOOX.
124
d
O.OIM NaCI pHlO* 24 C (
rt
fD
20AK
to
Ln
Plate XXII. Fracture surface of sample fatigued in IM
sodium chloride, pHlO, 25C at lOHz at three
stress intensity ranges and shown at three
magnifications: lOOX, 50X, and lOOOX.
126
127
Plate XXII.
Plate XXIII Fracture surface of a sample used to determine A K., at low stress
intensity ranges, photographed at three magnifications: lOOX,
500X, and lOOOX.
O.OIM NaCI'pH2-100'C-40Hz
15AK
i-j
lO
00
Plate XXIV. Fracture usrface of a sample fatigued in O.OIM sodium chloride,
pHlO, lOOC at 40Hz at low stress intensity ranges used to de
termine A K . p h o t o g r a p h e d at three magnifications: lOOX,
500X, and lOOOX.
0.01M NaCl 'pHlO 100 C 40Hz
i
%
m m
I-*
to
VO
130
There was no evidence of pitting on these samples des

pite the fact that 403 stainless steel is susceptible to
pitting. (.2)
4.5.1 Fatigue Crack Growth Results in Sodium Sulfate

Figure 42 plots the fatigue crack growth rates in O.OIM
and IM sodium sulfate, lOOC at 10 and 40Hz. The results
coincide with the chloride and water results at these fre

quencies; the growth rate is unaffected by a change in pH
or anion concentration! This figure also shows the low
crack growth rate area where A was determined.

In sodium sulfate, lOOC, R=0.5, pHlO, 40Hz,
4 .4< A <5.2 MPaVnT,
4. 0< AKth <4. 7 KSlVlP,

which is the same value obtained in water.
Table 10 lists the power law coefficients for crack
growth rates in sulfate solutions at lOOC.
4.5.2 Fractoqraphic Results in Sodium Sulfate

Plate XXV shows the photomicrographs of a sample fati
gued in IM sodium sulfate, lOOC, pKlO, at lOHz. Only one
fracture surface is shown here because of the similarities

between these surfaces and those in chloride and water. This
sample shows evidence of intergranular cracking at the lower
A.Ks and secondary cracking at the higher AK's.
131
A K (ksi /IrT )
5 2 3 4 6 8 10 20 30 40
4 0 3 Stainless Steel I"

rS NOgSO^
10
IOOC, R = 0.5
10 '
_0J
o r7
o 10
Air 10
O
o
TD 10 o
"O
0.01 M, pHIOjOHz
-7
0.01 M, pH IO,40Hz - 10
9
IM.pHlO.IOHz
10 0 I M, pH 7, 10 Hz
10
-to
!0
20 30 40
A K ( M Pa / r n )
Figure 42. Fatigue crack growth rates v s A K in O.OIM and

IM sodium sulfate, lOOC tested at 10 and 40Hz.
132
TABLE 10
GROWTH RATES IN SODIUM SULFATE

SOLUTIONS
da/dN = C KK)"
Concen pH Temper- Frequency C n
traton atre
(^) (C) (Hz) (m/cycle)
1.0 10 100 10 2. 3 X 10"9 1.75

7
0.01 10 100 10 2.0 X 10"9 1.75
Plate XXV. Fracture surface of sample fatigued in IM sodium
sulfate, pH7, lOOC at lOHz at three stress in
tensity ranges and at three magnifications:
133
134
Plate XXV.
m i
i
135
The results of fatigue'crack growth, tests in sulfate

solutions at lOOC is that the anion concentration and solu
tion pH produce behavior that is no worse than that produced
by water at that temperature.
4.6.1 Fatigue Crack Growth Rates in Sodium Phosphate and

Sodium Silicate
Figure 43 shows the fatigue crack growth results in
IM sodium phophate and IM sodium silicate, lOOC at lOHz. In
these solutions, the material had growth rates similar to
those obtained in air. This figure also shows the low
crack growth area used to obtain the A in sodium phos
phate, which was
5, 2< A K .<5.7 M P a W
4 . 7 < & K t h < 5 . 2 KSI^flr?.
These values were identical to the A values obtained in
air.
Table 11 lists the power law coefficients obtained for
these solutions.
4.6.2 Fractoqraphic Results in Sodium Phosphate and Sodium
Silicate
Plate XXVI shows the fracture surface of a sample fati
gued in sodium phosphate, pHlO, lOOC at lOHz. The surface

shows no evidence of intergranular cracking or dissolution.
It is. possible to measure striation spacings of vO.ly at
A K25 which corresponds to the crack growth rate at that A K
136
A K ( k s i /TrT)
20 30 40
I G O T , R =0.5
c5
10
-7
o
o
-6 -
10
<8
Air
"O o
a
10
<-9 I M Na^PCîpHIO, 10 Hz
V I M NOjPO^, pH IO,40Hz
IM No^SiO^.pHIO, lOHz
I
rlO
20 30 40
AK ( M Pa /rrT )
Figure 43, Fatigue crack growth rate vs AK in IM sodium

phosphate and IM sodium silicate at lOOC.
137
TABLE 11
POWER LAW COEFFICIENTS' FOR FATIGUE CRACK
GROWTH RATES IN SODIUM PHOPHATE
SODIUM SILICATE SOLUTIONS
da/dN = C(A.K)^
Solu- pH Temper- Frequency C n

tion ature
(.C) CHz) (m/cycle)
Na^PCi 10 100 10 1.3 X 10~^^ 2.73
3 4
IM
Na,SiO, 10.5 100 10 2,5 X lO"^^ 2.55

4 4
IM
Plate XXVI. Fracture surface of sample fatigued in IM
sodium phophate, pHlO, lOOC at lOHz at three
stress intensity ranges and at three magnifica
tions: 500X, lOOOX, and 5000X.
138
139
Plate XXVI,
140
value. This surface resembles that produced by fatigue in

air (Plates- VI and VIIi .
No fractographic studies were conducted on samples
fatigued in sodium silicate solutions because of the

precipitate which deposited on the sample. Plate XXVII shows
a sample fatigued in the silicate solution with the de
posit on it. It was not possible to remove the precipi
tate without affecting the substrate.
4.7 Open Circuit Potentials
Figure 44 shows the open circuit potentials vs pH of

403 stainless steel in the solutions studied. The poten
tials were measured during the length of a fatigue test, but
little change was noted in the measured value during a test,
consequently, the values plotted on this figure are average
values.
There was no trend in the potential from one anion to an
other. But the potentials did become more active as the solu
tion pH became more acidic as noted in the chloride solu
tions .
The hydrogen stability lines are also plotted on this
figure. These lines correspond to the reaction
Hg
^2 = 2H+ 4- 2e (11)
at 25 and lOOC.
141
Piste. XXVTI, Fracture surface of a sample fatigued in IM

silicate, pHlQ.5, 100.C at lOHz. Deposit
is evident on the fatigue fracture surface.
%
142
O P E N C IR C U IT P O T E N T I A L S vs p H
-100
100
-200
-300
-100
O.OIM NoCi in
IM NcCl o
> -400 rn
-200
- -500
-300 No^SiO
<O.OIM N o^SO^--600
-400
-700
-500
0 2 4 6 8 10 12
pH .
Figure 44. Open circuit potentials vs solution pH measured

during fatigue crack propagation tests.
5.0 DISCUSSION
5.1 Introduction
This section is organized by effects produced on the
crack propagation by the variation in electrolytes, the
solution pH, and test frequency. A model is presented
for crack growth with the aim of explaining the crack
growth, behavior documented.
5.2 Effect of Environment

5.2.1 Air
In this research program, air was used as a reference
environment despite the fact that Speidel (28) and Barsom
(.7) have noted corrosion fatigue effects in materials tested
in air and compared to behavior in vacuum. The results from
this work, however, have agreed favorably with those docu
mented in the literature, indicating that air can indeed
be a reference environment for 40 3 stainless steel. The
fractographic studies of air environment samples indicate
that the crack propagation is by the alternate blunting and

sharpening process.
5.2.2 Water
The experimental results have shown that water is suf
ficient to produce an effect on the crack growth rate in all
143
144
th.e experimental conditions studied. This result is some

what at variance with the published results of Logsdon (14)
and Clark (.15); they found that at room temperature, a
distilled water environment had no effect on the fatigue

crack, growth rates. The conflict between these results is
probably due to the difference in test parameters, such, as

the R ratio and test frequencies, as well as material heat
treatment. There was agreement, however, in the boiling
water effect, which, increased the crack propagation rates
in all cases.
The appearance of the fracture surfaces of samples cyc
led in water indicate that there is more occurring in the
water environment than just the mechanical damage of cyclic
stressing. There is some evidence of striations in both the
25 and lOOC water samples, but the appearance of intergranu-
lar features indicate that either dissolution or some other
effect is aiding the crack growth. Since this material has
been heat treated at a temperature where it is immune to

stress corrosion cracking (Figure 10), the idea of imposing
a stress corrosion component on the corrosion fatigue ef
fect cannot be used to explain the enhanced crackgrowth
rate over that in air.
The presence of a water environment became less of a
factor at the low stress intensity range as the point
was reached. Clark (15) observed a similar result when he

145
determined A.K., for 403 stainless steel in a water environ-

tn.
ment. Paris et al (.25) found that the environmental effect
decreased at the low stress intensity ranges when they in-

vetigated the corrosion fatigue crack propagation behavior
of A533 steel in water.
The problem in determining is that the frequencies
used to determine the in a reasonable length of time

are too rapid to allow the solution to have much of an ef
fect. In addition, as the A i s approached, the amount
of crack opening is decreased which decreases the accessi
bility of solution to the crack tip area. The combination

of these processes lessens the importance of the solution
on the A value. In this research project, A is only
14% less than it is air. An examination of the fractographs

in theAK^b area in water, however, does show that the solu
tion played a part in the crack growth process. Plate XI
shows the intergranular character of the fracture surface
at A K5. But the dissolution component was insufficient
to accelerate the crack growth at these slow intensity
levels. Figure 45 is a summary of the A measured as a
function of environment.
5.2.3 Sodium Chloride and Sodium Sulfate
The results have shown that the addition of either of

these anions in either low (O.OIM) or high (.IM) concentration
does not produce a fatigue crack growth rate either slower

vs ENVIRONMENTS
0.01 a DIM
lOO'C AlaCI A/%?Oi,
plllO plllO
lOO'C m e iOOX
Figure 45. Summary of the effect of the differnt environments studied and
their effect on A Kth-
147
or faster than water alone. These anions do produce a shift
in the open circuit potential (Figure 441 which is pH de

pendent, but this shift is not significant in terms of fati
gue crack growth, rate.
Both, of these salts have similar properties, which may
account for their similar effect on 403 stainless steel.

Both of these salts dissociate easily in aqueous solutions
and both are pitting agents. Type 403 stainless steel is
known to be susceptible to pitting attack, (.2) The aqueous
solutions of these salts are unbuffered so that although the

pH of the bulk solution remained unchanged during a test,
there are areas where localized acidification may occur.(49,
61) There is some doubt, however, if the acidification did
occur, it it could remain localized due to the pumping ac
tion occurring as the sample is cycled.
Galvele (61) has found that the exposure of bare metal
in the presence of a chloride solution (through straining

electrode experiments) does not necessarily lead to local
ized corrosion unless the metal electrode potential is equal
to or higher than the pitting potential. Shalaby (62)
measured the pitting potentials of 403 stainless steel in
sodium chloride and sodium sulfate solutions; these are
listed in Table 12. Comparing these to the measured open
circuit potentials plotted in Figure 44, indicates that

the test sample was below the pitting potential in most
cases; of course, the situation at the crack tip may be
148
TABLE 12
PITTING POTENTIALS QF
403 STAINLESS STEEL AT lOOC
Salt Concentration pH Pitting Potential

(M) SHE (jriV) SCE(mV)
NaCl 0.01 2 + 15 -225
1.0 2 -120 -360

0.01 7 - 35 -275
1.0 7 -170 -410
0.01 10 315 + 75
1.0 10 -190 -430
Na^SO, 0.01 2 - -
1.0 2 965 725

0.01 7 - -
1.0 7 -
0.01 10 - -
1.0 10 - -
Ref. 62
149
slightly different since the potential measurement did
not take place there, but certainly, the absence of pits

in the fractographs of the samples from the chloride and
sulfate solutions indicates that the potential at the crack
tip was below the pitting potential. Therefore, there was
no acceleration in dissolution due to the presence of the
anion in that area.
A comparison of the fracture surface from the samples
fatigued in chloride or sulfate with those fatigued in

water indicate no differences among the three; the inter-
granular cracking in the salt solutions occurs at the same
stress intensity values as it occurs in water.
5.2.4 Effect of pH
A look at the fatigue crack growth rates in water,
chloride and sulfate solutions (Figures 37, 40 and 42, res

pectively) shows that pH has no effect on the crack growth
rate. This result is quite unexpected in that a change in
solution pH produces a marked change in the polarization
behavior of 403.
Shalaby (62) measured the polarization curves for 403

stainless steel in IM and O.OIM sodium chloride (Figures 46
and 47 respectively) and in IM and O.OIM sodium sulfate
(Figures 48 and 49, respectively) at lOOC. He found that
in O.OIM sodium chloride (pH 7 and 10) and the sulfate
solution of pH 7 and 10, 403 had a passive region; the open
circuit potentials during a fatigue test in O.OIM sodium
1,000 0 SCECmV) I Qoo 2,000
2 -
10 150
10
pH 2
pH 7
pH 10
rv
E
u
0
< 10
E
cn
c
(U
Q
c
CD
s_
10
D
u
/.^ A/
1,000 mV/min.
2
10
3
10
- 1,000 ,000 2,000
P o t e n t i a l , mV.
Figure 46. Polarization curves of 403 stainless steel in

IM sodium chloride solutions at lOOC and scan
rate of 1000 mV/rain.
2 - 1,000 0 1,000 2,000 151
0
I
10
E
o 0
< 10 p H 2
E p H 7
p H 10
<n
c
CD
Q
c
CD
\_
3
O
AISI 403
0.0!M N a d
100 C
25 mV/min.
3
10
- 1,000 ,000
P o t e n t i a l , mV^
Figure 47 Polarization curves of 403 stainless steel in

O.OIM sodium chloride at lOOC and scan rate
of 25 mV/min.
SCE (mV) , o o Q
- 1,000

u
<
E
p H 2
p H 7
c p H 10
CJ
V
25 m V/min.
,000 ,000 2,000

P o t e n t i a l , mV^
Figura 48. Polarization curves of 403 stainless steel in IM

sodium sulfate solutions at lOOC and scan rate
of 1000 mV/min.
SCE (jnV)
- 1,000 000 2,000 153
10
2
10
/,0 0 0 mV/min.

u
<r 10

(/)
c
a>
Q
c
a; 0,0
V-
\_
3
O
0
p H 2
p H 7
2
0
,000 0 ,000 2,000
P o r e n f i a i , mV^
Figure 49. Polarization curves in O.OIM sodium sulfate at

10C and scan rate of 25 mV/min.
154
chloride, IM and 0..1M sodium sulfate, pH 7 and 10
were at potentials which were in the passive region in their
respective polarization curves. In IM sodium chloride, how

ever, there was no passive region at any pH (Figure 46).
An increase in the crack growth rate would have been expec
ted in this solution,
Duquette and Uhlig (.63, 64) found that the corrosion
rate of iron in dearated, neutral water and 3% sodium
chloride is approximately the same, i.e. 0,1 mg/dm /day;

they also found that changing the solution pH from 2 to 10
did not markedly affect the fatigue endurance limit measured
in reversed bending type testing. They theorized that the
corrosion rate had to reach a critical value before an ef

fect on the fatigue endurance limit was detected. It may
be that there is not a significant difference in the cor
rosion rates in the solutions considered here to produce an

affect on the corrosion fatigue crack propagation rate.
As a result, it is not possibe to use the polarization

behavior to predict what will happen in terms of fatigue
crack growth effects. This inconsistency in solution be
havior may be due to the fact that conditions at the crack
tip are very different from the bulk solution; concentra-
gradients or potential variations may arise at various
portions of the crack front which may then affect the total
crack growth rate observed. An added variable is the
155
reactivity difference between, strained and unstrained metal,

which may cause slight variations in the polarization res
ponse of the metal.
5.2.5 Sodium Phosphate and Sodium Silicate
The results of fatigue crack growth in the phosphate

and silicate solutions (Figure 42) show that these anions
do not increase the growth rate over that in air. These
solutions are inhibitors which induce the formation of a
passive film. (65) The polarization behavior of 403, shown
in Figure 50, indicates that the stainless steel passivates
easily in these solutions.
The properties of these salts in solution are similar
in that both produce a basic solution when dissolved in

water by the anion extracting a proton from the water
giving a weak acid and hydroxl ion. Also, these salts are
polyprotic; their anions undergo a series of stepwise reac
tions with water, depending on the values of the ionization

constants and on the concentration of the salt. The solu
tion can vary from the pH where the salt anion concentration
is a maximum to the pH of pure water. The intermediate
anions of these polyprotic salts can act as either acids
or bases and will have buffer properties.
Consequently, both of these salts act as inhibitors..by
preventing the dissolution of iron in water. Corrosion in
sodium phosphate is reduced by the formation of a film on

156
SCE (mV)
4 0 3 S. S.
lO O T
25 fnV/min
pH 10
E
<
>
CO
Z
LU
Q
k-
Z
lU
C
cr
3
O
-lOCD 0 m <LCOO
POTENTIAL (SHE, mV)
Figure 50. Polarization curves of 403 stainless steel in

IM sodium phosphate and IM sodium silicate at
10OC and scan rate ot 25 mV/min.
157
cathodic areas increasing the cathodic polarization and

favoring the process of repassivation, C66) Sodium silicate
acts much the same way; it forms a silicate layer on the
metal surface which is self-healing when damaged. (.67)
Figure 50 shows the polarization behavior of 403 stain
less steel in IM sodium phosphate and IM sodium silicate.
A comparison of these curves, with the polarization curves
of sodium chloride and sodium sulfate shows that the main

difference among them lies in the height of the active peak
and in the low passive current density obtained in the sili
cate solution. There is, however, no large difference be
tween the passive current densities observed in the chloride
and phophate solutions. The difference observed in the cor
rosion fatigue behavior does, however, reflect the inhibitive

properties of the silicate and phosphate solution. This
effect is noted in the A value also. Figure 45 shows the
threshold value is restored to the value observed in air.
The fracture surface in Plate XXIV of a sample fatigued
in phophate resembles that of air (Plates VI and VII) com
plete with striation markings to sufficiently preclude any
material dissolution. Therefore, polarization curves cannot
be used as a critereon to predict corrosion fatigue crack
growth; and the presence of either silicate or phophate
removed the detrimental environmental aspect of corrosion
fatigue in an aqueous environment.

158
5. 3 Effect of Test Frequency

In air, tests conducted at 10 and 40 Hz produced the
same crack growth, rates (Figure 34) indicating that the
material is not strain rate sensitive. But in water and
O.OIM sodium chloride, there was a frequency effect; this

effect was nearly identical in both solutions. Figures 36
and 39 plot the crack growth rates as function of stress
intensity for water and O.OIM sodium chloride, respectively,
at frequencies of 0.1 to 40 Hz. The data suggest that
even A may be frequency dependent,
Becuase hostile environment effects decrease with in

creased cyclic-load frequency, the corrosion fatigue at A
at high cyclic-load frequencies would have a value close to
air. Barsom (7) has noted that A in a corrosion fatigue
environment is frequency dependent in that A increases as

the test frequency decreases. Although the experiments pre
sented here did not determine A at frequencies of 1 or
0.1 Hz, there is an indication that A K.;.^ would be frequency
dependent in agreement with Barsom.
This result can be considered in terms of what occurs
at the crack tip as the crack advances at low stress inten
sity values. There is still a blunting and sharpening pro
cess operating, but the process may be somewhat altered if

it is assumed that an oxide film is present. The specifics
of an oxide film formation is taken up in the model proposed
159
for crack advancement in an environment.

A further examination of Figure 36 indicates that the
effect of frequency saturates at 10 Hz as far as increasing
the crack, growth rates as the frequency decreases. Figure
51 plots the crack growth rate per cycle in an environment
with the crack growth rate per cycle in air subtracted out
as a function of test frequency. This difference in growth
is plotted at three stress intensity range values. At
AKo,25 MPa m, there is no frequency effect for frequencies
less than 40Hz. ButAK<25 an increase in frequency results
in higher crack growth rates; whereas atAK>25, an increase
in frequency results in a decrease in the crack growth rate.
The fractography of the samples also appears to be A K

dependent in that at low AK's there is evidence of intergra-
nular fracture, while at AK>25 all the surfaces show evidence
of secondary, transgranular cracking. The appearance of
the intergranular facets is evidence of a corrosion or dis
solution component for crack growth since the difference in
composition between the grain boundary area and the grain
itself, plus the mechanical interfacial differences would
make the grain boundary a preferrential dissolution site
and crack path.
If corrosion rates are used to account for the amount
of crack extension noted in Figure 51 on a per cycle basis,
then the corrosion rate if iron in water or sodium chloride
W ater, 100C
R = 0 ,5
oi
AK 25
ra
AK 20 >-6
~D
o --
~o
OJ 10 40
FREQUENCY (HZ)
Figure 51. Plot of environmental crack growth rate in m/cycle as a func
tion of test frequency for three AK values in water, 10C, pH7. (Ti
O
161
2
which, is ,1 ma/dm /day may be converted to a penetration
rate of 1.45 X 10*^^ cm/sec. Converting this to penetra
tion depth per cycle amounts to 1.45 X 10 cm/cycle at 10
Hz , or 1.45 X 10'^^ and 1.45 X 10~^ cm/cycle at 1 and 0.1 Hz ,
respectively. These penetration rates cannot account for
the environmentally enhanced crack growth rates.

A different situation exists, if penetration rates are
calculated from current measurements taken from a strained
electrode. This data is rather limited, but it is available
for iron in borate buffer pH9 at 25C. The reactivity of
strained metal emerging as slip steps is quite different from
that of an immersed unstrained metal. C55) Staehle et al (68)
measured a current density of 1.0 A/cm^ for strained iron

which can be converted to penetration rate by using Faraday's
Law:
iA
Penetration Rate (cm/sec) = = T (.12)
Jbnp
with i = 1,0 A/cm^

A = 55.8 gm/mole
p = 8.0 gm/cm^
F = 96,500 coul/equiv
n = 2 equiv/mole
for iron dissolving as Fe^^. This results in 3.6 X 10 ^
cm/sec penetration. At lOHz, the rate would be 3.6 X 10 ^

cm/cycle and at .1 and 0.1 Hz, it is 3.6 X 10 ^ cm/cycle and
3.6 X 10"4 cm/cycle, respectively. Using this approach.
161
however, there is a higher penetration rate at the slower

frequencies than at the higher frequencies, which is intui
tively reasonable since the solution has a longer length of
time to act on the crack tip at the slower frequencies. But
the penetration rate alone does not take into account an
oxide forming on the crack tip as the crack advances. In
order to account for this action, a model for crack propaga
tion is proposed.
5.4 Model for Dissoltuion Assisted Crack Growth
5.4.1 Anodic Dissoltuion Approach

A model for crack growth must take into account what
occurs from the mechanical aspects of fatigue crack growth,
then what effects the presence of an aqueous environment
may add to the crack growth process. The process of film
formation on an electrode may occur through the metal dis
solution and oxidation. The reactions for stainless steel
involve iron and chromium:
Fe = Fe++ + 2e, (13)

3Fe++ + 4 H 2 O = FeÔj + 8 H+ +2e, (14)
Cr = Cr3+ + 3e, (15)
2Cr3+ + 3H 0 = CrgOg + 6 H+. (16)
The mechanical model applied to crack growth by Laird
(21) and operative in 403 as evidenced by the striations in
air is that the crack opens and blunts upon the application
of the tensile load and sharpens upon the compressive part
of the fatigue cycle. In the presence of an aqueous

162
environment, the exposure of clean metal at the tensile
part of the stroke results in metal dissolution due to film

rupture. For 403 stainless steel passivation may occur easily
due to the chromium, but the formation of the protective
oxide is not an instantaneous reaction, especially on a
strained material. (.6 8 ) So there is momentary dissolution of
the newly exposed metal, then upon the compressive portion
of the stroke, there is the mechanical sharpening, probably

along areas whcih had been preferentially dissolved during
the tensile portion of the stroke. Since grain boundaries

are usually areas of film discontinuities, they may be the
areas of preferential dissolution.
To account for the frequency effect, one must appeal to
the kinectics of passivation. Strained electrode studies
have shown the high current spikes that occur upon straining.
Figure 52 shows such a curve. A peak current density occurs
and then falls off to ^-0.1 A/cm^ after 0.011. sec.
To know how- much crack growth is occurring due to the
action of the environment on a time basis rather than on a
per cycle basis, the data plotted in Figure 51 is replotted
in Figure 53 as crack growth per sec vs frequency. At all
stress intensities, then, the crack growth rate is propor

tional to frequency. It further appears that the growth
rate begins to saturate at lOHz and would level off at fre
quencies exceeding 40 Hz. Figure 54 plots the crack growth
Q5
Fe/BORATE SOLUTION pH9 25G
cl 641 mV
0.4
<
rs
CD
V
Z
^ 02
cr
ID CO

0 to 20 30
TIME (msec)
Figure 52, Typical change in current density (i) and strain (e) with time
in a straining electrode experiment. (.6 8 )
w
164
-4
10
u
to
A K 34 0 >
r>
r5
10
/ A K 2 5
A K 20
*D
6
10
40
FREQUENCY CHZ)
Figure 53. Plot of environmental crack growth rate in m/sec

vs test frequency in water, lOOC for three'A K
values,
165
W ater, io o c , r =o .5
: 4 0 HZ
10 HZ r4
10
I
<0
o
,-S
N 10
IHZ
.-6
!0
20
AK
Figure 54. Plot of envrionmental crack growth rate vs AK

for the four frequencies studied.
166
rate due to an environmental effect vs the stress intensity
range. It is apparent from both Figures 53 and 54 that the

environmental effects are greatest at the highest frequencies
and that the effect is strongly A.K dependent at the slower
frequencies. It reaches an almost AK independent point at

40Hz. It appears that if the trend were continued, a fre
quency would be reached when the environmental effect of
crack growth would be stress inentsity independent.
The environmental crack growth plotted in Figure 53
can be expressed as
i a f
where i is the current density which can be calculated from

the crack growth using Faraday's Law and f is the test fre
quency. From a conceptual standpoint, it is possible to
visualize a process where there is a film covered crack tip,
then as the film is broken, there is a high dissolution rate
which drops off as in Figure 52, until the next film rupture
event; if these events are close together, the crack tip

spends more time at high current densities than it does at
lower ones. If the time between events is increased then
the crack tip area would still undergo the high current
spikes, but it would have more time for repassivation, film
repair, and thickening. The situation which is envisioned
in this process is illustrated in Figure 55.
CA) (B)
TIME
i
j
\__
TIME
Figure 55, Schematic showing process of film rupture and crack extension due
to dissolution as in (A); two different test frequencies are shown
in (B) where the frequency at the top is faster than the one be
low.
H
-J
168
Diegle and Vermilyea (69) have measured the strains
needed to fracture iron oxide films formed in caustic solu

tions and found that at 85C the fracture strain of rela
tively thin FeÔ^ C<100) is <3 X 10~^. Consequently, very
small strains are needed to rupture the films that may form
at the crack tip. One problem in using this type of measure
ment, however, is that the strains needed to rupture a film
that is forming as in Figure 52 are different from the strain
needed to fracture films that have already formed and are sub
sequently ruptured, as in the Diegle and Vermilyea work. It

can be noted in Figure 52 that the maximum current density
occurs while the electrode is straining and does not start
to decrease until the straining stops. But despite this ad
ded complication, the Diegle-Vermilyea measurement does pro

vide some measure of the strain needed for oxide rupture.
An understanding of the realtion between the dissolution
rate and frequency can be gained by considering the situation

drawn in Figure 55, where the current spikes that occur due
to film rupture events are idealized. Then the average cur
rent density measured as crack growth rate is
âve ^ m a x ' ^ " ^

where i^^^ is the current density from the crack growth rate,
n is the number of Îm rupture events, t^ is the time spent
at high cur re- density and f is the cycle frequency. Then
if is average strain rate, the total strain can be

169
expressed as
^tot = /f
' = nCtj^ + tth.
-cil. + t rup') C18)
where n, f, and are as previously defined, is the

time spent in film thichening (Figure 55), and t^^^ is the
time it takes to rupture the film. Then if eûp ^^rup'
n = 1___________ (19)
+ ttj, + (erup/^> ^
and substituting intoEquation17 gives
i = _____^max_____ _______ (2 0 )
but if a f, then t = af, (2 1 )
lave = ^ ^ (2 2 )
{ (t^f + t^^ f ) + ( )}
where is the strain needed to rupture the oxide.

But if (t^f + t^^^f) >> (E^_^p/a ) , which might occur at
high strain rates where the cycling is so fast that the
crack tip area is always at high current densities, then
igvp = ^max^D ^ , (23)

+ t^jjf)
j-ave ^max (24)

<d + t^^)
and the situation is frequency independent. The maximum

170
dissolution would be diffusion limited. If on the other
hand, the situation was one where + t_^^f) ,
i t f
= max D , (25)
is^^p/u)
and the average curremt density is frequency dependent, which

is the situation observed in the crack growth rate vs fre
quency dependence in Figure 53.
To test the validity of this model, it is necessary to
solve for and compare it to the current density cal
culated from the data; this involves knowing ilUo-X , tU , t+Uil
.y^,
and But there is not enough information to determine
all these parameters; however, if tp and i^^^ are estimated,
then t^j^ and e^-yp can be calculated and substituted into
Equation 22 such that i^_^^ may be calculated.
For this approximation it is possible to express Equa

tion 25 as
âve
where k may be found from Figure 53 and,
2. 4- 2
k = max D = 1.38 A-sec/cm
^rup
for &K 25 and a'^'l. As a first approximation, let t^vio^ sec
Ca lower limit value from straining electrode experiments)
and i v 30 A/cm^, then = 0.022.

max
171
From Equation 24, it is possible to solve for the ratio

of thickening to dissolving times,
^th = ^max - 1,
where i is the maximum current density at 40 Hz; Table 13
lists the environmental crack growth rates atA.K25 and their

equivalent values in terms of current density, i, which were
calculated from Faraday's Law CEquation 12),
Solving for t^^ and keeping i ^ ^ = 30 A/cm^, and
2
i = 24,1 A/cm gives t_^^ = 0.245 t^, Now, it is possible
to solve for i^^g in Equation 22 using the above values;
these current densities are listed in Table 13. Additional
calculations are tabulated for different values of imax and
t^; the parameters used to solve for i^^g in Equation 22
are listed in the lower portion of the table.
There is a fair degree of agreement between the calcul
ated and the experimental values, although the values for
Srup too high at the lower current values. At imax

2 3
ISO A/cm , and t^ = 10 sec, then = 0.11, which is
a reasonable strain value. The results from this analysis
indicate that straining electrode studies to date do not

strain fast enough. The electrodes need to by strained in
times of 'v-lO"^ sec to measure the current transient. The
difficluty in applying these calculations is the inability

to independently calculate values for the parameters in
TABLE 13
CALCULATION OF i
------------ ave
Frequency da/dt i i i
âve ave âve ave âve âve
(112) (m/sec) (A/cm^) (A/cm^) (A/cm^) (A/cm^) (A/cm^) (A/cm^) (A/cm^)
40 8.7 X 10^ 24.1 16.9 16.7 16.6 16.8 16.7 16.8
10 5.0 X 10"^ 13.8 9.1 8.7 8.5 8.8 8.7 8.8
1 5.0 X 10^ 1.38 1.36 1.29 1.26 1.30 1.29 1.30
0.1 5.0 X 10"^ 0.138 0.14 0.14 0.13 0.13 0.14 0.14
tg (sec) 10"^ lO"^ io ^ io"2 10"^ io ^
30 30 40 40 150 150
0.02 0.22 0.03 0.29 0.11 1.08

Eaup
(sec) 2.4 X 10'^ 2.4 X 10 ^ 6.6 X 10^ 6.6 X 10 ^ 5.22 X 10"^ 5.22 X 10~^
tth
NJ
173
Equation 22. However, Equation 22 does qualitatively des

cribe the environmentally enhanced crack growth.
The fractography is in keeping with this development.
An intergranular component may be expected since a grain
boundary area would be expected to be apreferential site for
film rupture, but striations would also be expected because
of the mechanical aspects of the growth process.
Evidence is support of this model has been published

by Ford and Silverman (.70) ; they found that the fatigue
crack propagation rate of 304 stainless in water at 97C has
the same crack growth vs frequency dependence as predicted
here.
This model, of course, has its limitations since it

necessarily simplifies the events occurring at the crack
tip. It was assumed that the film ruptureevents are con

fined to the crack tip region. This may not be the case.
The process may be more complicated as shown in Figure 56.
An additional problem with this approach is that the
crack growth process is relatively insensitive to a change
in the bulk solution pH. A filmed electrode approach may
be used in neutral to alkaline solutions where stability
diagrams (.72) indicate that iron and chromium oxides are
stable, but at acid pH's both the stability diagrams and
the polarization behavior indicate that there is no pas
sive region or stable oxide. A more complicated situation
174
SLIP-DISSOLUTION
N
W
Figure 56. Dissolution at the crack tip with more than

one film rupture event and non-idealized crack
extension.
175
may exist at the crack tip due to localized potential dif-

ferences. But the behavior documented in water and sodium
chloride is consistent with a dissolution process.
An additional limitation is that it is assumed that
the strain needed to rupture the film is reached as an
abrupt step function of the thickness. In reality, the
strain needed to fracture a film may change gradually as the

film thickens. Such a situation makes the events occurring
at the crack tip more complex and may lead to more than
one film rupture event per cycle, especially if the film
is not a uniform thichness.
5.4.2 Hydrogen Embrittlement Approach
One of the principles of the corrosion process is that
an oxidation reaction, such as iron dissolution, is accom
panied by a reduction reaction; both reactions must occur

simultaneously and at the same rate on the metal surface.
Hydrogen evolution is a common reduction reaction in acid or
deareated media:
2H'*' 4- 2e = H^.
But in order for this reaction to occur, the hydrogen

evolution reaction must be thermodynamically favored. The
measurement of the open circuit potential in the bulk solu
tion indicated that the samples were not at such a potential.
But, the conditions at the crack tip may be different; the
176
conditions may favor hydrogen evolution, A possible mech

anism of hydrogen embrittlement involves the reduction of
hydrogen ions to adsorbed hydrogen atoms at the crack tip,
adsorption of the atoms and diffusion of hydrogen atoms to

a position immediately below the crack tip surface. Once
a critical hydrogen content is reached, the crack may grow
to the depth where the hydrogen is effective and the cycle
may start again. This mechanism assumes, as in the pre
vious dissolution process, that the reaction rate at the
crack tip is localized there.
As a first approximation, it is possible to calculated
the diffusion distance for hydrogen during one fatigue

cycle at the frequencies considered. This calculation uses
-7 9
D = 10 cm /sec (.73) for hydrogen in iron at 90C. Table
14 lists the hydrogen penetration distances. It is evident
that the penetration distance decreases as the frequency in

creases. It appears that the damaged area would be less at
40Hz than at 1 Hz, and the crack growth rate would be
greater at the slower frequencies. This type of damage
would then be reflected in the crack growth rate. But
Figure 53 shows that the environmental crack growth com
ponent increases as the frequency increases; this behavior
in not consistent with the trend in Table 14.
Thus, the frequency dependence is not consistent with

a hydrogen diffusion mechanism. But it is possible that
177
since the film rupture model postulates a higher number of
film rupture events, and therfore, higher dissolution at

the faster frequencies, then hydrogen entry may be the
rate controlling process.
There is evidence in the literature that dynamic
hydrogen charging coupled with simultaneous deformation
degrades the mechanical properties of steels (71) enhan
cing crack propagation. The degree of degradation, however,
is dependent on the hydrogen fugacity and strain rate.
With the results presented here it is not possible to deter
mine how susceptible the material is to hydrogen embrit
tlement. Additional controlled potential experiments are
needed to establish what kind of fatigue behavior occurs
in the presence of hydrogen charging.
178
TABLE 14
HYDROGEN PENETRATION DISTANCES
X = Vo? (.74)
D = 10"^ cm^/sec [73)
Frequency Period x
(.cycles/sec) (sec) (.y)
0,1 10 10.0
1 1 3,16
10. 0.1 1,0
40 0.025 0,5
6.0 CONCLUSIONS
CD The crack growth rate in air is unaffected by cyc
lic frequency and temperature (.25 and lOOC) ; the crack
extension is by alternate blunting and sharpening process.
The A K.(.^ is 5.2 <AK.j.j^<5.7 MPa m, at R=0.5.

(2) The crack growth rates in water are higher than
in air at both room temperaure and lOOC; they are insen

sitive to a pH change from 7 to 10. TheAK^j^ at lOOC,
40H , R=0.5 is 4.4< AK^^<5.2 MPa m. The crack growth rate
was affected by a change in test frequency.
(.3) The crack growth rates in sodium chloride are
approximately the same as in water regardless of chloride

concentration (O.OIM and IM) and solution pH (2, 7, and 10);
the A in O.OIM sodium chloride, pH2 and 10, 40Hz, lOOC,
R=0.5 is the same as water. The frequency dependence in
O.OIM sodium chloride, pHlO, is similar to water.
(4) The crack growth rates in sodium sulfate are ap

proximately the same as in water regardless of sulfate con
centration (0.01 and l.OM) and pH (7 and 10); the A in
O.OIM sodium sulfate, pHlO, lOOC, 40Hz is the same as water.
(5) The crack growth rates in sodium phosphate are
approximately the same as in air; the A in IM sodium
phosphate, pHlO, lOOC, 40Hz is the same as air.
179
180
C6) The crack growth rates in sodium silicate are

approximately the same as in air,
O) The fractographic studies showed that in the
sodium chloride, sodium sulfate, and water solutions, there
was an intergranular cracking component along with a trans-
granular component and striation markings at low stress in

tensity ranges. No intergranular cracking was found in the
samples fractured in the sodium phosphate solutions.
C81 It was not possible to correlated the polarization
behavior of 403 stainless steel in the electrolytes studied
with the corrosion fatigue crack growth rates observed;
polarization behavior is insufficient to predict corrosion
fatigue effects.
(.9) The environmental component of crack growth on
a time basis was found to be proportional to the test fre

quency; a dissolution model was developed in light of these
results using a passivation kinectics approach.
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1

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INFORMATION TO USERS

The following explanation of techniques is provided to help you understand

2. When an image on the film is obliterated with a round black mark it is an

4. For any illustrations that cannot be reproduced satisfactorily by

A STUDY OF CORROSION FATIGUE CRACK PROPAGATION OF 403 STAINLESS

The Ohio State University PH.D. 1979

7, Tightly bound copy with p rin t lo st in spine

Presented in Partial Fulfillment of the Requirements for

The Ohio State University

Prof. John P. Hirth

To my Mom and Dad

I would like to express my deep appreciation to my ad

lagraphy, scanning electron micrography, and for his help in

search Institute for their support and interest in this

March 2, 1947 Born - El Paso, Texas

1978-1979 ___ National Steel Foundation

Major Field: Metallurgical Engineering

LIST OF TABLES ..................................... x

2.4 Environmental Aspects of

3.2.4 ElectrochemicalEquipiment ............. 62

3.3.2 Precracking Procedure.................. 65

3.4 Fractography ............................... 78

4.3.1 Fatigue Crack Growth Rates in

4.4 Sodium Chloride............................ Ill

4.4.2 Fractographic Results................. 115

4.5 Sodium Sulfate.-............................ 130

4.5.1 Fatigue Crack Growth Rates in

4.6.2 Fractographic Results ................ 135

5.2 Effect of Environment...................... 14 3

5.3 Effect of Test Frequency................... 158

5.4.1 Anodic DissolutionApproach .......... 161

6.0 CONCLUSIONS....................................... 179

1. Fatigue Crack Laws for Several Steels .,.,, 17

6. Mechanical Properties of 40 3 Stainless

13. Calculation of i ........... 172

1. The 0.1% carbon portion of the ironchromium-

8. Schematic of monotonie and cyclic plastic

10. Effect of tempering temperature and stress

15. Corrosion fatigue S-N curves of notched

21. Growth rates of fatigue cracks in a 12%

22. Effect of loading wave form on the fatigue

29. Sample calculation converting A.V to crack

32. Crack length vs cycles in air showing

33. Fatigue crack propagation rate, da/dN,

43. Fatigue crack growth rates vs AK in IM

49. Polarization curves of 403 stainless steel

I. Microstructure of as received 403 stainless

XII. Fracture surface of sample fatigued in

XIV. Fractures surface of sample fatigued in

X X II. Fracture surface of sample fatigued in

XXIV. Fracture surface of sample fatigued in

rosion fatigue crack growth properties of 403 stainless

sing that the buckets undergo.

fir tree type design which introduces a notch in the base

source for crack growth. Consequently, a fracture mechanics

mens was undertaken. The experiments were performed in

turbine temperature is about lOOC, the majority of the tests

perature work was conducted.

the reduction of fatigue resistance due to the presence of

variables which are encompassed in this research work. These

variables used in this research project. The final part

the corrosion properties of martensitic stainless steels, the

and the corrosion fatigue studies which have been performed

on 12% chromium steels.