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Classification and Basic Metallurgy of Cast Iron

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DOI: 10.1361/asmhba0001001

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ASM Handbook, Volume 1: Properties and Selection: Irons, Steels, and High-Performance Alloys
ASM Handbook Committee, p 3-11
DOI: 10.1361/asmhba0001001
Classification and Basic Metallurgy
of Cast Iron
Doru M. Stefanescu, The University of Alabama
THE TERM CAST IRON, like the term
steel, identifies a large family of ferrous
alloys. Cast irons are multicomponent fer-
rous alloys, which solidify with a eutectic.
They contain major (iron, carbon, silicon),
minor (<0.1%), and often alloying (>0.1%)
elements. Cast iron has higher carbon and
silicon contents than steel. Because of the
higher carbon content, the structure of cast
iron, as opposed to that of steel, exhibits a
rich carbon phase. Depending primarily on
composition, cooling rate, and melt treat-
ment, cast iron can solidify according to the
thermodynamically metastable Fe-Fe3C
system or the stable Fe-Gr system. When
the metastable path is followed, the rich
carbon phase in the eutectic is the iron
carbide; when the stable solidification path
is followed, the rich carbon phase is graph-
ite. Referring only to the binary Fe-Fe3C or
Fe-Gr system, cast iron can be defined as an
iron-carbon alloy with more than 2% C. The
reader is cautioned that silicon and other
alloying elements may considerably change
the maximum solubility of carbon in austen-
ite (7). Therefore, in exceptional cases,
alloys with less than 2% C can solidify with
a eutectic structure and therefore still be-
long to the family of cast iron.
The formation of stable or metastable eu-
tectic is a function of many factors including
the nucleation potential of the liquid, chemi-
cal composition, and cooling rate. The first
two factors determine the graphitization po-
tential of the iron. A high graphitization po-
tential will result in irons with graphite as the
rich carbon phase, while a low graphitization
potential will result in irons with iron carbide.
A schematic of the structure of the common
types of commercial cast irons, as well as the
processing required to obtain them, is shown
in Fig. 1.
The two basic types of eutectics--the
stable austenite-graphite or the metastable
austenite-iron carbide (Fe3C)---have wide
differences in their mechanical properties,
such as strength, hardness, toughness, and
ductility. Therefore, the basic scope of the
metallurgical processing of cast iron is to
Copyright © 1990 ASM International®
All rights reserved.
www.asminternational.org
manipulate the type, amount, and morphol- terminology is the commercial one. A first
ogy of the eutectic in order to achieve the division can be made in two categories:
desired mechanical properties.
• C o m m o n c a s t irons: For general-purpose
applications, they are unalloyed or low
Classification alloy
• S p e c i a l c a s t irons: For special applica-
Historically, the first classification of cast
tions, generally high alloy
iron was based on its fracture. Two types of
iron were initially recognized: The correspondence between commercial
and microstructural classification, as well
• White iron: Exhibits a white, crystalline
as the final processing stage in obtaining
fracture surface because fracture occurs
common cast irons, is given in Table 1. A
along the iron carbide plates; it is the result
classification of cast irons by their commer-
of metastable solidification (Fe3C eutectic)
cial names and structure is also given in the
• Gray iron: Exhibits a gray fracture sur-
article "Classification of Ferrous Casting
face because fracture occurs along the
Alloys" in Volume 15 of the 9th Edition of
graphite plates (flakes); it is the result of
Metals Handbook.
stable solidification (Gr eutectic)
Special cast irons differ from the common
With the advent of metallography, and as cast irons mainly in the higher content of
the body of knowledge pertinent to cast iron alloying elements (>3%), which promote
increased, other classifications based on microstructures having special properties
microstructural features became possible: for elevated-temperature applications, cor-
rosion resistance, and wear resistance. A
• G r a p h i t e shape: Lamellar (flake) graphite
classification of the main types of special
(FG), spheroidal (nodular) graphite (SG),
cast irons is shown in Fig. 2.
compacted (vermicular) graphite (CG),
and temper graphite (TG); temper graph-
ite results from a solid-state reaction
(malleabilization) Principles of the Metallurgy
• Matrix: Ferritic, pearlitic, austenitic, of Cast Iron
martensitic, bainitic (austempered)
The goal of the metallurgist is to design a
This classification is seldom used by the process that will produce a structure that
floor foundryman. The most widely used will yield the expected mechanical proper-
Table 1 Classificationof cast iron by commercial designation,microstructure, and
fracture
Commercial designation Carbon-rich phase Matrix(a) Fracture Final structure after
Gray iron . . . . . . . . . . . . . . . . . . . . . . . Lamellar graphite P Gray Solidification
Ductile iron . . . . . . . . . . . . . . . . . . . . . Spheroidal graphite F, P, A Silver-gray Solidification or
heat treatment
Compacted graphite iron . . . . . . . . . Compacted vermicular F, P Gray Solidification
graphite
White iron . . . . . . . . . . . . . . . . . . . . . . Fe3C P, M White Solidification and
heat treatmenttb)
Mottled iron . . . . . . . . . . . . . . . . . . . . Lamellar Gr + F%C P Mottled Solidification
Malleable iron . . . . . . . . . . . . . . . . . . . Temper graphite F, P Silver-gray Heat treatment
Austempered ductile iron . . . . . . . . . Spheroidal graphite At Silver-gray Heat treatment
(a) F, ferrite; P, pearlite; A, austenite; M, martensite; At, austempered (bainite). (b) White irons are not usually heat treated, except for
stress relief and to continue austenite transformation.
4 / Cast Irons

Pearlite + Graphite
(~xFe + Fe3C)

Solid-state transformation Gray

7 + Graphite cast
iron
eutectoid interval) Slow X
/ G aoPnh
itmesh!Ple d ept: (cooling through Ferrite + Graphite
r ds
(~Fe)
High

~Medi Flake Compacted Spheroidal

Liquid Solidification um k
cast iron J ,.~ 7 + Fe3C + Graphite Mottled cast iron
(iron - carbon- Graphitization
alloy) potential

Solid-state transformation
~ , y + Fe3C r Pearlite + Fe3C White iron
(cooling through
eutectoid interval)
Reheat above
eutectoid interval

3' + Fe3C.-~,-7 + Graphite .I[ 7 + Fe3C

Hold above
Cool eutectoid
through interval
eutectoid
interval

Pearlite + Temper graphite Ferrite + Temper graphite

41.
Malleable iron

Fig. 1 Basic microstructures and processing for obtaining common commercial cast irons

ties. This requires knowledge of the struc-
ture-properties correlation for the particular
alloy under consideration as well as of the
factors affecting the structure. When dis-
cussing the metallurgy of cast iron, the main
factors of influence on the structure that
one needs to address are:
• Chemical composition
• Cooling rate
• Liquid treatment
• Heat treatment
In addition, the following aspects of com-
bined carbon in cast irons should also be
considered:
• In the original cooling or through subse-
quent heat treatment, a matrix can be
internally decarburized or carburized by
depositing graphite on existing sites or by
dissolving carbon from them
• Depending on the silicon content and the
cooling rate, the pearlite in iron can vary
in carbon content. This is a ternary sys-
tem, and the carbon content of pearlite
can be as low as 0.50% with 2.5% Si
• The conventionally measured hardness of
graphitic irons is influenced by the graph-
ite, especially in gray iron. Martensite
microhardness may be as high as 66
HRC, but measures as low as 54 HRC
conventionally in gray iron (58 HRC in
ductile)
• The critical temperature of iron is influ-
enced (raised) by silicon content, not
carbon content
The following sections in this article dis-
cuss some of the basic principles of cast
iron metallurgy. More detailed descriptions
of the metallurgy of cast irons are available
in separate articles in this Volume describ-
ing certain types of cast irons. The Section
" F e r r o u s Casting A l l o y s " in Volume 15 of
the 9th Edition of Metals Handbook also
contains more detailed descriptions on the
metallurgy of cast irons.
Gray Iron (Flake Graphite Iron)
The composition of gray iron must be
selected in such a way as to satisfy three
basic structural requirements:
• The required graphite shape and distribu-
tion
• The carbide-free (chill-free) structure
• The required matrix
For common cast iron, the main elements
of the chemical composition are carbon and
silicon. Figure 3 shows the range of carbon
and silicon for common cast irons as com-
pared with steel. It is apparent that irons
 Classification and Basic Metallurgy of Cast Iron / 5

I
Graphite free Graphite bearing
I , %C + 1/3%Si = Spheroi al irons

4.0 ~ ~ , ~ ,~.

I
Pearlitic Martensitic
I
High-chromium iron
I
Ferritic
I
Austenitic
I
Acicular
(11-28% Cr)

I
white iron white iron
(Ni-Hard)
High strength

I
i wear resistant
Wear Wear Wear, corrosion, m

resistant resistant and heat resistant u 2.o IIIIIIIIIIIIIIIIIIIIIIIIIIH--White

,rons
7~,~ t ~ M a l l e a b l e irons
18O/o Ni 18% Ni, 5o/0 Si
f Ni-resist Nicrosilal
ASTM A 532 %(2 + %6% Si = 2.0
Corrosion and Heat and 1.0
heat resistant corrosion resistant

0 ~ - - S t e e l s
ASTM A 439
0 1.0 2.0 3.0 4.0

I
5O/o Si iron (Silal), High (15%)silicon iron,
I ,ts";".
Silicon, %
3 Carbon and silicon composition ranges of
common cast irons and steel. Source: Ref 2
heat resistant corrosion resistant
ASTM A 518 or A 518 M (metric)

Fig. 2 Classification of special high-alloy cast irons. Source: Ref 1

The range of composition for typical un-
alloyed common cast irons is given in Table
have carbon in excess of the maximum The manganese content varies as a func- 2. The typical composition range for low-
solubility of carbon in austenite, which is tion of the desired matrix. Typically, it can and high-grade unalloyed gray iron (flake
shown by the lower dashed line. A high be as low as 0.1% for ferritic irons and as graphite iron) cast in sand molds is given in
carbon content increases the amount of high as 1.2% for pearlitic irons, because Table 3.
graphite or Fe3C. High carbon and silicon manganese is a strong pearlite promoter. Both major and minor elements have a
contents increase the graphitization poten- From the minor elements, phosphorus direct influence on the morphology of flake
tial of the iron as well as its castability. and sulfur are the most common and are graphite. The typical graphite shapes for
The combined influence of carbon and always present in the composition. They flake graphite are shown in Fig. 5. Type A
silicon on the structure is usually taken into can be as high as 0.15% for low-quality iron graphite is found in inoculated irons cooled
account by the carbon equivalent (CE): and are considerably less for high-quality with moderate rates. In general, it is asso-
iron, such as ductile iron or compacted ciated with the best mechanical properties,
CE = % C + 0.3(% Si)
graphite iron. The effect of sulfur must be and cast irons with this type of graphite
+ 0.33(% P) - 0.027(% Mn) + 0.4(% S) (Eq 1) balanced by the effect of manganese. With- exhibit moderate undercooling during solid-
Additional information on carbon equiva- out manganese in the iron, undesired iron ification (Fig. 6). Type B graphite is found
lent is available in the article "Thermody- sulfide (FeS) will form at grain boundaries. in irons of near-eutectic composition, solid-
namic Properties of Iron-Base Alloys" in If the sulfur content is balanced by manga- ifying on a limited number of nuclei. Large
Volume 15 of the 9th Edition of Metals nese, manganese sulfide (MnS) will form, eutectic cell size and low undercoolings are
Handbook. Although increasing the carbon which is harmless because it is distributed common in cast irons exhibiting this type of
and silicon contents improves the graphiti- within the grains. The optimum ratio be- graphite. Type C graphite occurs in hyper-
zation potential and therefore decreases the tween manganese and sulfur for an FeS-free eutectic irons as a result of solidification
chilling tendency, the strength is adversely structure and maximum amount of ferrite is: with minimum undercooling. Type D graph-
affected (Fig. 4). This is due to ferrite pro- ite is found in hypoeutectic or eutectic irons
motion and the coarsening of pearlite. % M n = 1.7(% S) + 0 . 1 5 (Eq 2) solidified at rather high cooling rates, while
type E graphite is characteristic for strongly
Other minor elements, such as aluminum, hypoeutectic irons. Types D and E are both
400 antimony, arsenic, bismuth, lead, magne- associated with high undercoolings during
sium, cerium, and calcium, can significantly solidification. Not only graphite shape but
~. 350 Y/Ill/! I 50 alter both the graphite morphology and the also graphite size is important, because it is
~"//11111!111 microstructure of the matrix. directly related to strength (Fig. 7).
=j 300 I 111,,, =
== ' ""/, 40 ==
250 ,i,,.
"//,1111%~,, 30 a~
Table 2 Range of compositions for typical unalloyed common cast irons
-~
=~ 200 ?_ [ Composition, % I
"'6 # Type of iron C Si Mn P S
150
711 - 20
100 G r a y (FG) . . . . . . . . . . . . . . . . . . . . . . . . . 2.5-4.0 1.0-3.0 0.2-1.0 0.002-1.0 0.02-0.25
3.25 3.5 3.75 4.0 4.25 4.5 4.75 Compacted graphite (CG) . . . . . . . . . . . . 2.5-4.0 1.0-3.0 0.2-1.0 0.01-0.1 0.01-0.03
Ductile (SG) . . . . . . . . . . . . . . . . . . . . . . . 3.0--4.0 1.8-2.8 0.1-1.0 0.01-0.1 0.01-0.03
Carbon equivalent, % White . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.8-3.6 0.5-1.9 0.25-0.8 0.06-0.2 0.06-0.2
General influence of carbon equivalent on Malleable (TG) . . . . . . . . . . . . . . . . . . . . . 2.2-2.9 0.9-1.9 0.15-1.2 0.02-0.2 0.02-0.2
I:I,T 4
H~. the tensile strength of gray iron. Source: Ref Source: Ref 2
2
6 / Cast Irons
Table 3 Compositions of unalloyed gray irons
Carbon
A S T M 48 class equivalent
20B . . . . . . . . . . . . . . . . . . . . . . . .
55B . . . . . . . . . . . . . . . . . . . . . . . .
4.5
3.6
Alloying elements can be added in com-
mon cast iron to enhance some mechanical
properties. They influence both the graphi-
tization potential and the structure and
properties of the matrix. T h e main elements
are listed below in terms of their graphitiza-
tion potential:
High positive graphitization potential (decreasing
positive potential from top to bottom)
Carbon
Tin
Phosphorus
Silicon
Aluminum
Copper
Nickel
Neutral
Iron
High negative graphitization potential (increasing
negative potential from top to bottom)
Manganese
Chromium
Molybdenum
Vanadium
This classification is based on the thermo-
dynamic analysis of the influence of a third
element on carbon solubility in the Fe-C-X
system, where X is a third element (see the
section "Influence of a Third Element on
Carbon Solubility in the Fe-C-X System" in
the article "Thermodynamic Properties of
Iron-Base Alloys" in Volume 15 of the 9th
Edition of Metals Handbook). Although list-
ed as a graphitizer (which may be true ther-
modynamically), phosphorus also acts as a
matrix hardener. Above its solubility level
(probably about 0.08%), phosphorus forms a
very hard ternary eutectic. The above classi-
t
rE
I-
Type D,E
Time
Characteristic cooling curves associated with
Fig. 6 different flake graphite shapes. ;rE, equilibri-
um eutectic temperature
v • -.~,',,, h ' ] , , ~ A ~ J t ~- t . -.-~--~u
[ Composition, % I
C Si Mn P S
3.1-3.4
<-3.1
2.5-2.8
1.4-1.6
0.5-0.7
0.6--0.75
0.9
0.1
0.15
0.12
!( ." . - - , I ,~ (.,', ,s,~ t
"m
Uniform distribution, Rosette Superimposed flake
random orientation groupings sizes, random
fication should also include sulfur as a carbide orientation
former, although manganese and sulfur can
combine and neutralize each other. The re-
sultant manganese sulfide also acts as nuclei
for flake graphite. In industrial processes,
nucleation phenomena may sometimes over-
ride solubility considerations.
In general, alloying elements can be clas-
sified into three categories. Each is dis- Interdendritic segregation, Interdendritic segregation,
cussed below. random orientation preferred orientation
Silicon and aluminum increase the graph-
Typical flake graphite shapes specified in
itization potential for both the eutectic and F i g . 5 ASTM A 247. A, uniform distribution, random
eutectoid transformations and increase the orientation; B, rosette groupings; C, kish graphite
number of graphite particles. They form (superimposed flake sizes, random orientation); D,
solid solutions in the matrix. Because they interdendritic segregation with random orientation; E,
interdendriUc segregation with preferred orientation
increase the ferrite/pearlite ratio, they lower
strength and hardness.
Nickel, copper, and tin increase the graph-
itization potential during the eutectic transfor-
mation, but decrease it during the eutectoid where D is the bar diameter (in inches). Equa-
transformation, thus raising the pearlite/ tion 3 is valid for bar diameters of 20 to 50 mm
ferrite ratio. This second effect is due to the (0.8 to 2 in.) and compositions within the
retardation of carbon diffusion. These ele- following ranges:
ments form solid solution in the matrix. Be-
Element Composition, %
cause they increase the amount of pearlite,
they raise strength and hardness. Carbon ................................... 3.04-3.29
Chromium, molybdenum, tungsten, and Chromium ............................ 0.1--0.55
Molybdenum ......................... 0.03-0.78
vanadium decrease the graphitization poten- Silicon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.6-2.46
tial at both stages. Thus, they increase the Nickel ............................... 0.07-1.62
amount of carbides and peadite. They con- Sulfur ................................ 0.089-0.106
centrate in principal in the carbides, forming Manganese ........................... 0.39--0.98
Copper .............................. 0.07-0.85
(FeX),C-type carbides, but also alloy the ~xFe
solid solution. As long as carbide formation
does not occur, these elements increase The cooling rate, like the chemical com-
strength and hardness. Above a certain level, position, can significantly influence the as-
any of these elements will determine the cast structure and therefore the mechanical
solidification of a structure with both Gr and properties. The cooling rate of a casting is
Fe3C (mottled structure), which will have primarily a function of its section size. The
lower strength but higher hardness. dependence of structure and properties on
In alloyed gray iron, the typical ranges for section size is termed section sensitivity.
the elements discussed above are as follows: Increasing the cooling rate will:
Element Composition, %
Chromium ................................. 0.2-0.6
Molybdenum .......................... 0.2-1 Maximum flake length, in.
Vanadium ............................. 0.1-0.2
0.006 0.010 0.015 0.020 0.025 0.030 0.035
Nickel ................................ 0.6-1 415 k 60
Copper ................................ 0.5-1.5
Tin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.04-0.08
345 50 -~
~=
The influence of composition and cooling
T0tc
rate on tensile strength can be estimated
"~
using (Ref 3): "~
= 205 ~ ~ 30 "~
m
135 20
TS = 162.37 + 16.61/D - 21.78(% C) 0.125 0.25 0.375 0.50 0.635 0.75 0.90
- 61.29(% Si) - 10.59 (% Mn- 1.7% S)
> Maximum flake length, mm
+ 13.80(% Cr) + 2.05(% Ni) + 30.66(% Cu)
+ 39.75(% Mo) + 14.16 (% Si)2 Effect of maximum graphite flake length
Fig. 7 on the tensile strength of gray iron. Source:
- 26.25(% Cu) 2 - 23.83 (% Mo)2 (Eq 3) Ref 3

Section thickness, in.
liB-45B
0.5 1.0
400500
C 350 ~ 40B
300
=~ 2oO~o ~ ~
35B
100
5 10 15 20 25 30 35 40 45 50
Section thickness, mm
(al
Section thickness, in.
0.5 1.0
300 . , l, i l,i
m 250 Class
150 -
35B
---30---25-
I --
,005 10
i i
15 20 25 30 35 40 45 50
Section thickness, mm
(b)
Influence of section thickness of the casting
"=~" 8 on tensile strength (a) and hardness (b) for a
series of gray irons classified by their strength as-cast
in 30 mm (1.2 in.) diam bars. Source: Ref 2
• Refine both graphite size and matrix
structure; this will result in increased
strength and hardness
• Increase the chilling tendency; this may
result in higher hardness, but will de-
crease the strength
Consequently, composition must be tai-
lored in such a way as to provide the correct
graphitization potential for a given cooling
rate. For a given chemical composition and
as the section thickness increases, the
graphite becomes coarser, and the pearlite/
ferrite ratio decreases, which results in low-
er strength and hardness (Fig. 8). Higher
carbon equivalent has similar effects.
The liquid treatment of cast iron is of
paramount importance in the processing of
this alloy because it can dramatically
change the nucleation and growth condi-
tions during solidification. As a result,
graphite morphology, and therefore proper-
ties, can be significantly affected. In gray
iron practice, the liquid treatment used is
termed inoculation and consists of minute
additions of minor elements before pouring.
Typically, ferrosilicon with additions of alu-
minum and calcium, or proprietary alloys
are used as inoculants. The main effects of
inoculation are:
• An increased graphitization potential
because of decreased undercooling dur-
ing solidification; as a result of this, the
chilling tendency is diminished, and
Classification and Basic Metallurgy of Cast Iron / 7
1.5
I IASTM~ 70
50
~ #-
20
_~
"~
1.5
,
ASTM A-48
I
,
3.4 3.6 3.8 4.0 4.2 4.4
Carbon equivalent, %
Influence of inoculation on tensile strength as
" ' 5 " 9 a function of carbon equivalent for 30 mm (1.2
in.) diam bars. Source: Ref2
graphite shape changes from type D or E
to type A
• A finer structure, that is, higher number
of eutectic cells, with a subsequent in-
crease in strength
As shown in Fig. 9, inoculation improves
tensile strength. This influence is more pro-
nounced for low-CE cast irons.
Heat treatment can considerably alter the
matrix structure, although graphite shape
and size remain basically unaffected. A
rather low proportion of the total gray iron
produced is heat treated. Common heat
treatment may consist of stress relieving or
of annealing to decrease hardness.
Ductile Iron
(Spheroidal Graphite Iron)
Composition. The main effects of chemical
composition are similar to those described for
gray iron, with quantitative differences in the
extent of these effects and qualitative differ-
ences in the influence on graphite morpholo-
gy. The carbon equivalent has only a mild
influence on the properties and structure of
ductile iron, because it affects graphite shape
considerably less than in the case of gray iron.
Nevertheless, to prevent excessive shrink-
age, high chilling tendency, graphite flotation,
or a high impact transition temperature, opti-
mum amounts of carbon and silicon must be
selected. Figure 10 shows the basic guidelines
for the selection of appropriate compositions.
As mentioned previously, minor elements
can significantly alter the structure in terms
of graphite morphology, chilling tendency,
3.5
56 \ ~ -High impact transition temperature
30
52 "OX ~ iGraphite flotation
-zx- ":!!iEiEiE ~EE~EZh.. ~
=xcesslve .~ i!~ii~!~ii:~:i:~:~:i:~:~:!:~:i:~:
:::::::::::::::::::::7::::::::::::::::::::
44
shrinkage " ~iiiiiiiii;iiiiiiiiiiiiiiiiiii
!iii!iiiiiiiiii!iiiiiiiii!iiiiiiiiii~
2.0 X "
40
1.5 ,Tendency to form white iron
30 3.4 3.5 3.6 3.7 3.8 3.9
Total carbon, %
32 ''~r;"" 1 0 Typical range for carbon and silicon con-
I- tents in good-quality ductile iron. Source:
Ref 2
24 and matrix structure. Minor elements can
promote the spheroidization of graphite or
20 can have an adverse effect on graphite
shape. The minor elements that adversely
affect graphite shape are said to degenerate
graphite shape. A variety of graphite shapes
4.6 can occur, as illustrated in Fig. 11. Graphite
shape is the single most important factor
affecting the mechanical properties of cast
iron, as shown in Fig. 12.
The generic influence of various ele-
ments on graphite shape is given in Table
4. The elements in the first group--the
spheroidizing elements--can change
graphite shape from flake through com-
pacted to spheroidal. This is illustrated in
Fig. 13 for magnesium. The most widely
used element for the production of sphe-
roidal graphite is magnesium. The amount
of residual magnesium, Mgre~id, required
to produce spheroidal graphite is generally
0.03 to 0.05%. The precise level depends
on the cooling rate. A higher cooling rate
requires less magnesium. The amount of
magnesium to be added in the iron is a
function of the initial sulfur level, Sin, and
the recovery of magnesium, -q, in the par-
ticular process used:
0.75 Sin+ Mgresid
MgaddeO - (Eq 4)
A residual magnesium level that is too
low results in insufficient nodularity (that is,
a low ratio between the spheroidal graphite
and the total amount of graphite in the
structure). This in turn results in a deterio-
ration of the mechanical properties of the
iron, as illustrated in Fig. 14. If the magne-
sium content is too high, carbides are pro-
moted.
The presence of antispheroidizing (dele-
terious) minor elements may result in graph-
ite shape deterioration, up to complete
graphite degeneration. Therefore, upper
limits are set on the amount of deleterious
elements to be accepted in the composition
of cast iron. Typical limits are given below
(Ref 6):
8 / Cast Irons

Element Composition, %
Aluminum .................................... 0.1
Arsenic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.02
Bismuth ................................ 0.002
Cadmium ............................... 0.01
Lead ................................... 0.002
Antimony ............................... 0.002
Selenium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.03
Tellurium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.02
Titanium ................................ 0.1
Zirconium ............................... 0.1

These values can be influenced by the

I II III
combination of various elements and by the
presence of rare earths in the composition.
Furthermore, some of these elements can
be deliberately added during liquid pro-
cessing in order to increase nodule count.
Alloying elements have in principle the
same influence on structure and properties
as for gray iron. Because a better graphite
morphology allows more efficient use of the
mechanical properties of the matrix, alloy-
ing is more common in ductile iron than in
gray iron.
Cooling Rate. When changing the cooling
rate, effects similar to those discussed for
gray iron also occur in ductile iron, but the IV V VI
section sensitivity of ductile iron is lower.
This is because spheroidal graphite is less
affected by cooling rate than flake graphite.
The liquid treatment of ductile iron is
more complex than that of gray iron. The
two stages for the liquid treatment of ductile
iron are:
• Modification, which consists of magne-
sium or magnesium alloy treatment of the
melt, with the purpose of changing graph-
ite shape from flake to spheroidal
• Inoculation (normally, postinoculation,
that is, after the magnesium treatment) to
increase the nodule count. Increasing the VII
nodule count is an important goal, be- Typical graphite shapes after ASTM A 247. I, spheroidal graphite; II, imperfect spheroidal graphite; III,
cause a higher nodule count is associated " 5 " 1 1 temper graphite; IV, compacted graphite; V, crab graphite; VI, expJoded graphite; VII, flake graphite
with less chilling tendency (Fig. 15) and a
higher as-cast ferrite/pearlite ratio
Heat treatment is extensively used in the
• Hardening to produce tempering structures 420 ~ 61
processing of ductile iron because better
• Austempering to produce a ferritic bainite
advantage can be taken of the matrix struc-
ture than for gray iron. The heat treatments The advantage of austempering is that it 360 ~ Spheroidal 52
usually applied are as follows: results in ductile irons with twice the tensile
strength for the same toughness. A compar- 300 / L 43.5
• Stress relieving
• Annealing to produce a ferritic matrix ison between some mechanical properties Compacted
of austempered ductile iron and standard
• Normalizing to produce a pearlitic matrix 240 35 =
ductile iron is shown in Fig. 16.

Table 4 Influence of minor elements on

graphite shape
Compacted Graphite Irons
'~ 180 / / ~Flake_ 26 --'~°
Compacted graphite irons have a graphite
'~ 120 / 17.5

Element category
Spheroidizer . . . . . . . . . . . .
Neutral . . . . . . . . . . . . . . . .
oo/////
Element shape intermediate between spheroidal and
Magnesium, calcium, rare flake. Typically, compacted graphite looks
earths (cerium, lanthanum, like type IV graphite (Fig. 1 I). Consequent-
etc.), yttrium ly, most of the properties of CG irons lie in

Antispheroidizer
Iron, carbon, alloying
elements
between those of gray and ductile iron.
The chemical composition effects are sim-
oV
0 0.1 0.2 0.3 0.4 0.5
o
(degenerate shape) . . . . Aluminum, arsenic, bismuth, ilar to those described for ductile iron. Strain, %
tellurium, titanium, lead,
sulfur, antimony
Carbon equivalent influences strength less I:|a Influence of graphite morphology on the
obviously than for the case of gray iron, but ='~5" 1 2 stress-strain curve of several cast irons
 Classification and Basic Metallurgy of Cast Iron / 9

100 E 100 700 50

E
t~
E ~ 80
E No ule c ii~i~ii!.

~
o ~

60 ~ ++iiii+
+++++++++i+++i++
.............
V E
o~ 6O
,o ++D + +

; +0 j~
~;
"Z Flake - - C o m p a Spheroidal

g 20
%+ 400 20 2

I---
0.01 0.02 0.03 0.04 0.05 0.06 0+07 300 10
20 Residual magnesium, % Chill width
(a) 200 0
0.4 0.6 0.8 1.0 1.2 1.4
o 75% FeSi added as postinoculant
0 0.01 0.02 0.03 0.04 600 8
Residual magnesium, % Influence of the amount of 75% ferrosilicon
500 --Tensile s t r e n , , ~ " 7~ ' .~ 'j ~ "- 6 E:+r,$. 15 added as a postinoculant on the nodule
I:;,1, Influence of residual magnesium on graph- count and chill depth of 3 mm (0.12 in.) plates.
"'~5° 13 ite shape
m 400 / ~ Source: Ref 7
:~ "Elongation
300 .- 4
more than for ductile iron, as shown in Fig. t~
decomposition of Fe3C and the formation of
3 '~~
17. The graphite shape is controlled, as in the (n 200 temper graphite. The basic solid state reac-
case of ductile iron, through the content of 100 ~ rength tion is:
minor elements. When the goal is to produce -1
compacted graphite, it is easier from the Fe3C -~ 7 + Gr (Eq 5)
0 0
standpoint of controlling the structure to com- 0 20 40 60 80 100 The final structure consists of graphite and
bine spheroidizing (magnesium, calcium, and/ Nodularity, % pearlite, pearlite and ferrite, or ferrite. The
or rare earths) and antispheroidizing (titanium structure of the matrix is a function of the
and/or aluminum) elements. Additional infor- (b)
cooling rate after annealing. Most of the
mation is available in the article "Compacted Influence of residual magnesium (a) and malleable iron is produced by this technique
Graphite Irons" in Volume 15 of the 9th " ' ~ " 14 nodularity (b) on some mechanical proper- and is called blackheart malleable iron.
Edition of Metals Handbook. ties of ductile iron. Sources: Ref 4, 5
Some malleable iron is produced in Europe
The cooling rate affects properties less for by decarburization of the white as-cast iron,
gray iron but more for ductile iron (Fig. 18). and it is called whiteheart malleable iron.
In other words, CG iron is less section Heat treatment is not common for CG The composition of malleable irons must
sensitive than gray iron. However, high irons. be selected in such a way as to produce a
cooling rates are to be avoided because of white as-cast structure and to allow for fast
the high propensity of CG iron for chilling annealing times. Some typical compositions
Malleable Irons
and high nodule count in thin sections. are given in Table 2. Although higher car-
Liquid treatment can have two stages, as Malleable cast irons differ from the types bon and silicon reduce the heat treatment
for ductile iron. Modification can be of irons previously discussed in that they time, they must be limited to ensure a
achieved with magnesium, Mg + Ti, Ce + have an initial as-cast white structure, that graphite-free structure upon solidification.
Ca, and so on. Inoculation must be kept at a is, a structure consisting of iron carbides in Both tensile strength and elongation de-
low level to avoid excessive nodularity. a pearlitic matrix. This white structure is crease with higher carbon equivalent. Nev-
then heat treated (annealing at 800 to 970 ertheless, it is not enough to control the
°C, or 1470 to 1780 °F), which results in the carbon equivalent. The annealing time de-
1600
!! .0 pends on the number of graphite nuclei
available for graphitization, which in turn
1400 ;:!i~ ....~
i
+t.r
e ped
200
600 , i = i
Spheroidal graphite (SN~G 500/7)
I 87

1200 i 180 500 ;+~ii;~;i~;~;i+~iP~;i;i+i;~;i;i~i;!i~;~i~;~!~i~i~;i~i~;i!i!i+:~k:~i;ii;i;~i~i~i~n.5

;Ii;~;~i~++ Section thickness, in.
160 0.6 0.8 1.2 1.6 2.4 4 6 8 12
600 I I I I I I 87
= 1000
400, O O .... "~, 58 ,..Compacted graphite cast iron
== \ +++++++++~
+++~+ .... ,o.. 2.b. ~. 500
m ~++++++++++++++++i 120 +++++i+i+i+~i+i+
_= 600 ~ \ .£ 300 - " Compacted g r a p h i t e 43.5 _~ .rE 400
"~ ~ Quenched and
m ~ ~ tempered 100 i~
300 43.5 ~
~- 600 ~ 80 ~- 200 ~ 29
--~ 200 ~'+:~"~:~:~:+ii:~i:~. ii+i:i:++ 29 .i
100
Flake graphite £
400 ~ ~ - 60
~00 I t I 145 + ~ - ~i+!+i!++i+i~++i+i+++ii+i+++i++i++i++i++
ASTM grades ~ 40 3.9 4.0 4.1 4.3 4.3 4.4 4.5 4.6
14.5 "-
200 I I Carbon equivalent, % 0 L o
0 5 10 15 20 15 20 30 40 60 100 150 200 300
Elongation, % Effect of carbon equivalent on the tensile Section thickness, mm
F i g . 1 7 strength of flake, compacted, and spheroi-
Properties of some standard and austere- dal graphite irons cast in 30 mm (1.2 in.) diam bars. Influence of section thickness on the ten-
"5" 1 6 pered ductile irons. Source: Ref 8 E:-r,~. 18 sile strength of CG irons. Source: Ref 10
Source: Ref 9
10 / Cast Irons

250 08 ~ /~o~ 50{

A
i
CE = constant
E
E 200
40c \
~2 o., - - F e S
[Mn]
+
0
IMnFelS~g" F
= I "~ 41k
~ X.~.~

-'G 150
~ 0.3
30C ~,,
"--L
~00 c~ (Mn 200
0.2

~
E
so 101 /
(11 B
I--
~ v
0 0 O
0.5 1.0 1.5 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 b 2 4 6 8 10 12
C/Si ratio Manganese, % Mn/S ratio

Influence of C/Si ratio on the number of "=151:"~"2 0

Influence of the MnlS ratio on the shape of Influence of the Mn/S ratio on the number
H ~ . 1 9 temper graphite clusters at constant carbon
r.'~
temper graphite. Bracketed elements are r-'_rlg. 2 1 of temper graphite clusters after annealing.
equivalent. Source: Ref 10 dissolved in the matrix. A, low-temperature holding for 12 h at 350 °C (660 °F);
B, no low-temperature holding

depends on, among other factors, the C/Si
ratio. As shown in Fig. 19, a lower C/Si
ratio (that is, a higher silicon content for a
constant carbon equivalent) results in a
higher temper graphite count. This in turn
translates into shorter annealing times.
Manganese content and the Mn/S ratio
must be closely controlled. In general, a
lower manganese content is used when fer-
ritic rather than pearlitic structures are de-
sired. The correct Mn/S ratio can be calcu-
lated with Eq 2. Equation 2 is plotted in Fig.
20. Under the line described by Eq 2, all
sulfur is stoichiometrically tied to manga-
nese as MnS. The excess manganese is
dissolved in the ferrite. In the range delim-
ited by the lines given by Eq 2 and the line
Mn/S = I, a mixed sulfide, (Mn,Fe)S, is
formed. F o r Mn/S ratios smaller than 1,
pure FeS is also formed. It is assumed that
the degree of compacting of temper graphite
depends on the type of sulfides occurring in
the iron (Ref I I). When FeS is predominant,
very compacted, nodular temper graphite
forms, but some undissolved Fe3C may
persist in the structure, resulting in lower
elongations. When MnS is predominant,
although the graphite is less compacted,
elongation is higher because of the com-
pletely Fe3C-free structure.
The Mn/S ratio also influences the num-
ber of temper graphite particles. From this
standpoint, the optimum Mn/S ratio is about
2 to 4 (Fig. 21).
The l i q u i d t r e a t m e n t of malleable iron
increases the number of nuclei available for
the solid-state graphitization reaction. This
can be achieved in two different ways, as
follows:
• By adding elements that increase under-
cooling during solidification. Typical ele-
ments in this category are magnesium,
cerium, bismuth, and tellurium. Higher
undercooling results in finer structure,
which in turn means more 3,-Fe3C inter-
face. Because graphite nucleates at the
-,/-Fe3C interface, this means more nucle-
ation sites for graphite. Higher under-
cooling during solidification also prevents
the formation of unwanted eutectic
graphite
• By adding nitrite-forming elements to the
melt. Typical elements in this category
are aluminum, boron, titanium, and zir-
conium
Bar diameter, in.
0.32 0.48 0.64 0.80
400
380iiiiiiiiiiiiiiiiiiii,i!ii
i 86
360
.E
The h e a t t r e a t m e n t of malleable iron de-
termines the final structure of this iron. It
has two basic stages. In the first stage, the
iron carbide is decomposed in austenite and
graphite (Eq 5). In the second stage, the
austenite is transformed into pearlite, fer-
rite, or a mixture of the two. Although there
are some compositional differences be-
tween ferritic and pearlitic irons, the main
difference is in the heat treatment cycle.
When ferritic structures are to be produced,
cooling rates in the range of 3 to 10 °C/h (5
to 18 °F/h) are required through the eutectoid
transformation in the second stage. This is
necessary to allow for a complete austenite-
to-ferrite reaction. A typical annealing cycle
for ferritic malleable iron is shown in Fig.
23. When pearlitic irons are to be produced,
different schemes can be used, as shown in
Fig. 24. The goal of the treatment is to
Bar diameter, in.
0.96 1.12 0.32 0.48 0.64 0.80 0.96 1.12
58 16
1,
..,=" o~ ................

Alloying elements can be used in some Q 340 ....%iiiiiiiiil 49 ,= .I lO

grades of pearlitic malleable irons. The
manganese content can be increased to o~
-- 0

1.2%, or copper, nickel, and/or molybde- ~- 320 .... 46 m 8 ....... ' " ............

num can be added. Chromium must be t-

avoided because it produces stable car-

bides, which are difficult to decompose 300 43 6

during annealing.
Cooling Rate. Like all other irons, mallea-
280 40 4
ble irons are sensitive to cooling rate. Nev- 8 12 16 20 24 28 8 12 16 20 24 28
ertheless, because the final structure is the Bar diameter, mm Bar diameter, mm
result of a solid-state reaction, they are the
least section sensitive irons. Typical corre- (a) (b)
lations between tensile strength, elongation, 17[a 2 2 Influence of bar diameter on the tensile strength (a) and elongation (b) of blackheart malleable iron.
and section thickness are shown in Fig. 22. "b ° Source: Ref 13
 Classification and Basic Metallurgy of Cast Iron / 11

1250 940 °C with stable carbides (ll to 28% Cr), or a

/ 7 5 0 °C
stable austenitic structure with either sphe-
-<--First > < Second -->- roidal or flake graphite (18% Ni, 5% Si). For
stage stage corrosion resistance, irons with high chro-
960 1760 mium (up to 28%), nickel (up to 18%), and
o o silicon (up to 15%) are used.
940 °C
REFERENCES
~- 720 1330 ~-
705°C I I. R. Elliott, Cast Iron Technology, But-
I--- I-- terworths, 1988
530 °C
500 930 2. C.F. Walton and T.J. Opar, Ed., Iron
34
Castings Handbook, Iron Castings So-

/
940 °C ciety, 1981
250
~. 770 °C 3. C.E. Bates, AFS Trans., Vol 94, 1986,
0 12 24 36 48 60 p 889
Time, h 4. R. Barton, B.C.I.R.A.J., No. 5, 1961, p
Heat treatment cycle for ferritic blackheart < 25 15 668
"'~" 23 malleable iron. Source: Ref 1 5. R.W. Lindsay and A. Shames, AFS
>' V~/~' v
Trans., Vol 60, 1952, p 650

/
>lr<:
940 °C 6. H. Morrogh, AFS Trans., Vol 60, 1952,
achieve a eutectoid transformation accord- ~ 800 *C
p 439
ing to the austenite-to-pearlite reaction. In 7. D.M. Stefanescu, AFS Int. Cast Met.
some limited cases, quenching-tempering J., June 1981, p 23
24 35
treatments are used for malleable irons. 8. J.F. Janowak and R.B. Gundlach, AFS
Trans., Vol 91, 1983, p 377
Special Cast Irons 9. G.F. Sergeant and E.R. Evans, Br.
Special cast irons, as previously dis- Time, h Foundryman, May 1978, p 115
cussed, are alloy irons that take advantage I::;,r, 24 Heat treatment cycles for pearlitic black- 10. D.M. Stefanescu, Metalurgia, No. 7,
of the radical changes in structure produced H~. heart malleable irons 1967, p 368
by rather large amounts of alloying ele- II. K. Roesch, StahlEisen, No. 24, 1957, p
ments. Abrasion resistance can be im- 1747
proved by increasing hardness, which in (CrFe)7C 3 carbides, which are harder than 12. R.P. Todorov, in Proceedings of the
turn can be achieved by either increasing the iron carbides. Additions of 4 to 16% Mn 32nd International Foundry Congress
the amount of carbides and their hardness will result in a structure consisting of (Warsaw, Poland), International Com-
or by producing a martensitic structure. The (FeMn)3C, martensite, and work-harden- mittee of Foundry Technical Associa-
least expensive material is white iron with a able austenite. tions
pearlitic matrix. Additions of 3 to 5% Ni and Heat resistance depends on the stability 13. K.M. Ankab, O.E. Shulte, and P.N.
1.5 to 2.5% Cr result in irons with (FeCr)3C of the microstructure. Irons used for these Bidulia, Isvestia Vishih Utchebnik
carbides and an as-cast martensitic matrix. applications may have a ferritic structure Zavedenia-Tchornaia, Metallurghia,
Additions of 11 to 35% Cr produce with graphite (5% Si), a ferritic structure No. 5, 1966, p 168

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