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Thermodynamic Properties of Iron-Base Alloys

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ASM Handbook, Volume 15: Casting
ASM Handbook Committee, p 41-55
DOI: 10.1361/asmhba0005190
Thermodynamic Properties of
Iron-Base Alloys
Doru M. Stefanescu, Ohio State University
Seymour Katz, S. Katz Associates
THE STRUCTURE AND PROPERTIES of
cast metals are sensitive to numerous impurities.
Because purification of melts generally adds con-
siderable cost to castings, the lowest cost and sur-
est defense against contamination is careful
selection of scrap. Purification is generally
reserved for elements that are so pervasive that
avoidance is impossible. This is exemplified by
sulfur and oxygen removal from cast iron and
steel, respectively, and removal of alkali and alka-
line earth elements from aluminum. Because of
their immediate importance, aspects of the physi-
cal chemistry of these processes are reviewed.
The structures and properties of steel and cast
iron also depend on the control of the solidifica-
tion structure in castings. To accomplish this, it
is necessary to understand and control the thermo-
dynamics of the liquid and solid phases and the
kinetics of solidification (nucleation and growth
of various phases). The information linked to the
practical interests that thermodynamics can pro-
vide when considering iron-base alloys encom-
passes a rather wide range. Only two issues are
addressed in sections on thermodynamics in this
article. The first is the calculation of solubility
lines, relevant to the construction of phase dia-
grams, and the second is the calculation of the
activity of various components, which allows for
the determination of probability of formation
and relative stability of various phases. Alloying
elements are then discussed in terms of their influ-
ence on the activity of carbon, which provides
information on the stability of the main carbon-
rich phases of iron-carbon alloys, that is, graphite
and cementite. Information on the iron-oxygen
system can be found in the article “Inclusion-
Forming Reactions” in this Volume.
Purification of Ferrous Melts
One of the most important processes involved
in cast iron and steel production is desulfurization.
For steels, desulfurization is necessary to reduce
Copyright © 2008 ASM International®
All rights reserved.
www.asminternational.org
the level of inclusions, leading to stronger and ratio (DR), that is, the ratio of sulfur concen-
more fatigue-resistant steels. For cast iron, desul- trations: desulfurizer to metal
furization is practiced in the manufacture of duc-
tile iron castings in order to develop spherical The three variables can be related as follows
graphite morphology. Ductile iron is used in through a mass balance on sulfur:
applications where high fracture toughness is
needed. Sulfur is removed from iron and steel ð%SÞi
ð%SÞf ¼ (Eq 3)
when the metals are liquid. Although a variety of 1 þ W ðDRÞ
reagents are employed to remove sulfur, namely,
calcium, magnesium, sodium, and rare earths, For liquid-desulfurizing slags that are not satu-
the most important is calcium. Common forms rated with respect to calcium sulfide (CaS),
of calcium include the metal; alloys such as cal- the maximum value of DR, that is, the equilib-
cium silicon (CaSi); the oxide, calcium oxide rium value, can be predicted from thermody-
(CaO); and the carbide, calcium carbide (CaC2). namic considerations:
Despite the use of various forms of calcium, the  
ð%SÞslag CS fS K14
governing chemical reaction in all cases appears ðDRÞmax ¼ ¼ (Eq 4)
to be the same (Ref 1, 2): ð%SÞT max K15 hO
CaO þ S ¼ CaS þ O (Eq 1) where CS is the slag sulfide capacity, defined as
(Ref 3):
The equilibrium constant for the reaction (Eq 1)  1=2
is: pO2
CS ¼ ð%SÞslag (Eq 5)
pS2
aCaS hO
K9 ¼ (Eq 2)
aCaO hS and K14 and K15 are the respective equilibrium
constants for the reactions:
For both cast iron and steel, target sulfur con-
centrations after desulfurization are in the range
of 0.006 to 0.010% S. In electric-melted cast 1
O2 ¼ O (Eq 6)
iron and steel, the sulfur levels before desulfur- 2
ization are 0.02 to 0.03% S, while input sulfur
levels to the cupola are generally much
higher—0.1 to 0.2% S.
1
Requirements for Desulfurization. For rea- S2 ¼ S (Eq 7)
2
sons related to reaction kinetics and thermody-
namics, the final sulfur (%S)f concentration and fS is the activity coefficient for 1 wt% S in
achieved in desulfurization processes depends the standard state.
on three factors: Equation 4 can be derived from Eq 2. Using
known input and desired output sulfur values, Eq
 Initial sulfur concentrations (%S)i 3 gives the required desulfurization ratios as
 Amount of desulfurizer used, usually expressed a function of weight fraction desulfurizer. These
as the weight fraction of desulfurizer to data are plotted in Fig. 1 for two cases. In the
metal, W electric-melting case, initial and final
 Extraction efficiency of the desulfurizer, sulfur concentrations were assumed to be 0.03
which is measured by the desulfurization and 0.008% S, respectively. In the cupola-melting
42 / Principles of Liquid Metal Processing

1
Table 1 Theoretical weight ratios: desulfurizer to iron to achieve 0.008% S in
various systems
Weight ratio, Wdesulfurizer/Wiron

Type of melt Slag composition T, K CS ( 104)(a) fS ho ( 104)(b) (DR)max(c) W

A. cast iron—cupola 44 CaO-15MgO-5Al2O3-36SiO2 1773 2.7 5 1.3 90 0.13

0.1 B. cast iron—cupola CaOsat-Al2O3 1773 59 5 5.0 417 0.027
(ladle desulfurized)
B C. cast iron—electric CaOsat-Al2O3 1773 59 5 5.0 417 0.0065
D. steel—electric CaOsat-Al2O3 1873 316 1 0.45 5280 0.00052
A
(a) CS is obtained from optical basicity correlations (Ref 3). fs is based on iron composition (Ref 4). (b) Case A: ho is governed by Si/SiO2 equilib-
0.01 rium based on respective concentration in iron and slag (Ref 5). Cases B and C: ho is governed by Si/SiO2 equilibrium with aSiO2 ¼ 1 due to ladle
exposure to air (Ref 6). Case D: ho is governed by Al/Al2O3 equilibrium with %Al = 0.05 (Ref 1), assumed no contact with air. (c) K14 and K15 data
from Ref 7

10-3
10 100 103 104 104
Desulfurization ratio (DR), (% S)slag/(%S)iron

Fig. 1 Weight fraction desulfurizer required to achieve

given desulfurization ratios. Plots for electric-
melted iron and steel (curve A) assume initial sulfur
concentrations [%(S)i = 0.03] different from those of
cupola-melted iron [(%S)i = 0.10] (curve B).

case, the equivalent concentrations were 0.10 and

0.008% S. The cupola line applies for both cupola
iron and ladle-desulfurized cupola iron.

Desulfurization ratio, (%S)slag /(%S)iron

The relationships illustrated in Fig. 1 are use- 103
ful in defining systems that will provide the
Desulfurization ratio, aCaS/as

necessary desulfurization conditions. Four sys-

tems are compared in Table 1. These cover
cupola- and electric-melted cast iron and elec-
tric-melted steel. Also examined are two liquid 100
slag systems: a basic cupola slag (dicalcium sil-
icate saturated) and a CaO-saturated CaO-
Al2O3 slag.
Table 1 shows that:
 The best desulfurizing cupola slags have lower
sulfide capacity and desulfurization ratio than 100
slags used in ladle desulfurization; the conse-
quence is the need for much larger quantities
of slag*.
 Compared to steel, cast iron desulfurization
benefits from higher fS because of the pres- 10
ence of relatively high concentrations of car-
bon and silicon in cast iron.
 Ladle desulfurization systems that are
exposed to air suffer higher hO and, as
a result, poorer desulfurization than may
otherwise be anticipated.
10
For the cupola slag case in Table 1, the ther- 0.7 0.9 1.1 1.3 1.5 1.7 1.9 2.1 2.3
modynamically predicted value of (DR)max = 90 Slag basicity
is in good agreement with measured data
(Fig. 2). This indicates that the cupola desulfur- Fig. 2 Desulfurization ratio-basicity comparisons for cupola (closed circles) and laboratory data (open circles).
ization process operates close to equilibrium Equilibrium values are indicated by the angled line. The vertical line indicates the slag basicity above
which slags are saturated at 1500  C (2730  F), with respect to dicalcium silicate. This is the point at which the
levels. Further evidence for this is given Fig. 3, observed DR should equal (DR)max. Source: Ref 2
which plots desulfurization data for a cupola
operated with varying amounts of municipal fer-
rous refuse in the charge. The upper portion of The lower portion of Fig. 3 is a comparison of Mn þ O ¼ MnO (Eq 8)
Fig. 3 plots CS and oxygen activity. The latter is (DR), measured and calculated. The good agree-
expressed as the partial pressure of oxygen. ment found is evidence that near-equilibrium
conditions existed. Therefore, the overall cupola desulfurization
*The actual differences are less than those indicated. Cal- For the cases discussed previously, the oxy- reaction is:
cium sulfide has only limited solubility in CaO-Al2O3 slags.
As a result, a minimum W = 0.01 is needed to maintain the
gen activity in cupola iron has been found to
CaS-unsaturated condition. be governed by the reaction (Ref 5, 8): CaO þ S þ Mn ¼ CaS þ MnO (Eq 9)

0.01
Cs
(p o2)−1/2
Mn
Slag sulfide capacity
−3
10
10−4
10−5
100
50 Measured
Desulfurization ratio
Calculated
20
10
5
2
1
0 20 40
Municipal refuse in charge, %
Fig. 3 Slag sulfide capacities, oxygen activities, and
desulfurization ratios, measured
calculated, for a cupola operated with municipal ferrous
refuse as a charge material. Source: Ref 8
Considerably lower sulfur could be achieved
(Ref 2) if hO were governed by:
C þ O ¼ CO
However, equilibrium for this reaction has not
been observed.
This discussion has concerned CaS-unsatu-
rated slags. However, a desulfurizing slag, satu-
rated with CaS, can in many cases continue to
desulfurize as long CaO is present. In this case,
the ultimate sulfur levels are not as low as those
for CaS-unsaturated slags. Nevertheless, CaS-
saturated slags can produce sulfur levels that
are more than sufficient for cast iron and steel
applications. In fact, CaS-saturated conditions
are often employed in industrial applications
because much less desulfurizer is required.
In addition to the CaS-saturated liquid slags,
totally solid slags such as CaO and CaC2 are
in the same category, because CaS does not
form solid solutions with these materials. Also
in this category are desulfurizers containing
small amounts of liquid phase. These materials
possess the desirable properties of liquid and
solid slags. That is, they combine the fast reac-
tion rates of liquid slags with the large desulfur-
izing capacities (high CaO concentration) of
solid slags.
The final sulfur concentrations attainable
under CaS-saturated conditions can be obtained
from Eq 2 by setting aCaS = 1. For ladle desul-
furization, the most important industrial desul-
furizers are also CaO-saturated, that is, aCaO = 1.
108 (0.02)
Sulfur concentration in iron, wt %
0.01
107
(po2)−1/2
106
10−3
(6 ⫻ 10−4)
0 0.5
Silicon concentration in iron, wt %
Fig. 4 Equilibrium sulfur concentrations for CaO
desulfurization calculated with Eq 11 and 12,
assuming aCaO ¼ aCaS ¼ aSiO2 ¼ 1. Source: Ref 2
60 80 100
Applying the condition of double saturation to
Eq 2 yields:
hO
and
ð%SÞr ¼
K9 fS
In the ladle desulfurization of cast iron, hO is
governed by the reaction (Ref 2):
1 1
(Eq 10) Si þ O ¼ SiO2
2 2
where aSiO2 ¼ 1. This is attributed to the expo-
sure of the iron to air (Ref 2). Sulfur concentra-
tions obtained with Eq 11, assuming silicon-
silicon dioxide (Si-SiO2) equilibrium and
aSiO2 ¼ 1, are given in Fig. 4. In continuous
ladle-desulfurization processes, equilibrium sul-
fur levels are achieved when input sulfur levels
are low but are only approached when input
levels are high. This is illustrated in Fig. 5
with desulfurization data for CaC2 (Ref 2).
Other desulfurizers such as CaO-CaF2 behave
similarly.
High desulfurization rates are needed for
effective desulfurization in the short times
required. For CaO-base desulfurizers, the pres-
ence of relatively small amounts of liquid phase
(<25 vol%) significantly increases the rate of
desulfurization. This is illustrated in Fig. 6, in
which the rates of desulfurization by CaO with
varying amounts of calcium fluoride (CaF2) are
compared. The faster rates obtained with CaF2
additions were due to the formation of a CaO-
CaF2 liquid phase that provided a path for
CaS diffusion from the reaction interface into
the porous CaO particle. This prevented the
normal rapid development of an impervious
CaS coating on the CaO surface (Ref 10, 11).
A similar explanation, involving liquid-phase
formation, was used to account for the higher
Thermodynamic Properties of Iron-Base Alloys / 43
0.1
Inlet S 0.015 – 0.03%
Inlet S 0.06 – 0.08%
%C ⬚C
3.7 1550
4.0
3.7
1500
Measured sulfur concentration, wt %
4.0
3.7
1450
4.0
3.7 0.01
1400
4.0
1.0 1.5 2.0 2.5 3.0
1
10−3 1
(Eq 11)
(6 ⫻ 10−4)
0.0006 0.001 0.002 0.004
Theoretical sulfur concentration, wt%
Fig. 5 Comparisons of the sulfur concentrations in
(Eq 12) production-continuous desulfurization using
CaC2 with the sulfur concentrations from Eq 11 and 12.
Open circles indicate electric-melted iron. Closed
circles indicate cupola iron. Source: Ref 2
CaO desulfurization rates of steel when alumi-
num was concurrently added (Ref 12, 13).
Another rate-controlling variable in ladle
desulfurization is bath agitation. For gas-stirred
melts, the desulfurization rate constant k is
a function of gas flow rate Q, _ that is, k / Q_ n .
For well-dispersed solid-liquid mixtures, the
rate of diffusion-controlled interphase reaction
is a relatively weak function of Q,_ that is, n 
0.2 to 0.4 (Ref 14–16). For a poorly dispersed
system, such as a ladle of iron with a cover slag
of desulfurizer, agitation has a much greater
influence on the rate constant, with n typically
in the range of 1.0 to 2.5 (Ref 14–16). This is
due to the entrainment of increasing amounts
of top slag into the liquid metal with increasing
_ This effect is illustrated in Fig. 7, which
Q.
plots the apparent mass transfer coefficient for
desulfurization versus the gas flow rate.
Deoxidation. In the manufacture of steel,
FeO-saturated conditions (0.2%O) are
approached as a result of oxygen blowing to
remove carbon and silicon as the respective
oxides. To make a steel product, the oxygen
levels are subsequently lowered to 0.005 to
0.02% O by reactive alloy additions of
44 / Principles of Liquid Metal Processing

1 interaction coefficient eM O is a large negative

number, and as a result, fO decreases signifi-
cantly even at relatively low concentrations of
M. To obtain exact values for [%O] or hO,
equations for K22 can be found in Ref 1 and 7.
0.5 0% CaF2 As indicated by Eq 14, the oxygen concentra-
tion can be reduced if a complex deoxidation prod-
uct is formed so that aMx Oy <1. Common
deoxidation systems of this type are Si-Mn,
2% Al-Si-Mn, or Al-CaO. An advantage, in addi-
tion to lower oxygen, is that less deoxidizer is
required in solution to achieve a given level of
0.2 oxygen. This is illustrated in Fig. 9, which plots
the oxygen activity of iron as a function of the
8%
concentration of CaO in the calcium aluminate
inclusion. Separate lines are given for alumi-
num concentrations ranging from 0.001 to
%S/ %So

0.05% Al. Also indicated is the oxygen activity

0.1
when pure aluminum oxide (Al2O3) is the reac-
tion product. The data in Fig. 9 show that an
oxygen activity of 4 ppm can be produced at
three aluminum levels—0.002, 0.005, or
5% CaF2
0.01%—depending on whether the respective
0.05 deoxidation product was CaO-saturated calcium
aluminate, CaAl2O4-saturated calcium alumi-
nate, or Al2O3.
20% The levels of total oxygen measured in steel
melts considerably exceed equilibrium levels
(Ref 7). Two possible explanations are the
10% kinetic limitations in the deoxidation reaction
0.02 and the ineffective separation of deoxidation
products from the melt. Consideration of the
first possibility suggests that the most important
kinetic limitation would be oxygen and/or
deoxidant solute diffusion to inclusions in the
0.01 melt (Ref 7). Considering the presence of 105
0 10 20 30 40 50 60 to 107 inclusion particles in a cubic centimeter
Time, min of melt, deoxidation to equilibrium levels of
10 to 20 ppm would require a few minutes.
Fig. 6 Desulfurization rates of carbon-saturated iron, containing 0.4% Si, with CaO and varying amounts of CaF2 at Appreciably longer times would be needed to
1450  C (2640  F). Source: Ref 9 reduce oxygen to less than 1 ppm, as with rare
earth additions. For most cases, oxide formation
appears faster than oxide particle separation
10 For single-element deoxidation, expressed by: from the bath. Thus, for applications that
depend on dissolved oxygen, such as desulfur-
xM þ yO ¼ Mx Oy
constant (k ), s -1 ⫻ 10-3

5 (Eq 13) ization or CO blowhole formation, equilibrium

Desulfurization rate

oxygen values can be assumed to exist after rel-

2
1 •
k a Q0.25
0.5
0.2
0.05 0.1 0.2
Gas flow rate (Q ) , m3 • kg-1 • s-1 ⫻ 10-6
Fig. 7 Dependence of CaO desulfurization rate
constant on the rate of gas flow through
a reactor. Source: Ref 16
electropositive elements. The low oxygen con-
centrations are necessary to maintain the num-
ber of oxide inclusions at a suitable low level,
to prevent the formation of CO blowholes, and
to ensure effective desulfurization.
the equilibrium oxygen concentration in the liq-
uid steel, obtained by rearranging the equilib-
rium constant expression, is:
•
k a Q 2.1  y1
a
Mx Oy
ð%OÞ ¼ x y (Eq 14)
K22 ð%MÞx fM fO
0.5 1 2 5 10 The calculated equilibrium values of oxygen solu-
bility in liquid iron at 1600  C (2910  F), based on
Eq 14, are given in Fig. 8 for several elements as
a function of the concentration of the element,
assuming aMx Oy ¼1 . As seen among the common
deoxidizers, aluminum produces the lowest
oxygen. Although not shown, rare earth metals
produce even lower oxygen (Ref 17). Figure
8 plots data for oxygen concentration and oxy-
gen activity. In all cases, oxygen activity
decreases with increasing levels of deoxidizer,
but the oxygen concentration can go through
a minimum. This occurs in cases where the
atively short reaction periods. For consider-
ations of the inclusion content of steel, the
kinetics of particle separation need to be
considered.
The limiting case of particle flotation at
velocities obtained from Stokes’ law calcula-
tions is shown in Fig. 10. Inclusion size versus
time of flotation is plotted. The particles pro-
duced during deoxidation are generally small
(<5 mm, or 200 min.); accordingly, separation
times are long. The times indicated in Fig. 10
are representative of conditions in a quiescent
bath. Times are considerably shorter for stirred
melts because articles grow by collision and coa-
lescence to sizes of 30 to 100 mm (Ref 7). The
efficiency of coalescence of particles is material
dependent. The energy of adhesion of particles
is determined by the wetting characteristics
of the particle, measured by wetting angle.
For example, the force of adhesion of Al2O3
 Thermodynamic Properties of Iron-Base Alloys / 45

1 20
0.002
% Al
Oxygen concentration
Oxygen activity ao ∫ wt% O for %X Æ 0 0.001
Iron oxide saturation 16

Oxygen activity of iron, ppm 0

V2O4
0.1 MnO
SiO2 Cr2O4
12
B2O3 CO 0.002
Oxygen is solution, wt %

Cr2O3
0.005

B2O3 V 2O 3 8
0.01
0.005
0.01

4 CaAl2O4 0.01
saturated CaO
Ti3O5 saturated
Ti2O3 0.05 0.05
10-3
0
30 40 50 60 70
Al2O3
CaO concentration, mass%

ZrO2 Ti2O3 Fig. 9 Concentration of oxygen and aluminum in

liquid steel in equilibrium with calcium
10-4 -3 aluminate at 1600  C (2910  F); arrows indicate oxygen
10 0.01 0.1 1 10 values when the reaction product is pure Al2O3. Source:
Deoxidizer in solution, wt % Ref 18

Fig. 8 Deoxidation equilibria in liquid iron alloys at 1600  C (2910  F). Source: Ref 17

107
5
Z, number of nuclei • cm−3
0.05%O removal, µm
Inclusion size for

106
10

15

20 105

A B C
30

40
0.1 1 10 100
Flotation time, min

Fig. 10 Calculated time of flotation of inclusions in

stagnant melts as a function of inclusion
size. Melt depth: A, 50 mm (2 in.); B, 500 mm (20 in.);
C, 2000 mm (80 in.). Source: Ref 7

particles with a wetting angle of 140 is twice that

for SiO2 with a wetting angle of 115 . On this
basis, Al2O3 inclusions are expected to cluster
more easily than SiO2 inclusions, a phenomenon
that has been observed in practice (Ref 7).

Thermodynamics of Ferrous Systems

Fig. 11 Phase diagram for the binary iron-carbon system. Source: Ref 19
For binary systems, only the iron-carbon and
iron-silicon systems are discussed in this arti- The Iron-Carbon System metastable (Fe-Fe3C) equilibria. The most
cle. Information on the iron-oxygen system is recent diagram is shown in Fig. 11. The solubil-
available in the article “Inclusion-Forming The phase diagram of the binary iron-carbon ity of carbon in iron is described in Eq 15–20,
Reactions” in this Volume. system includes the stable (iron-graphite) and Eq 21. (Ref 20, 21).
46 / Principles of Liquid Metal Processing

For the stable system, that is, with graphite as The general equation used to describe the with the following remarks (Ref 23): XSi 
the equilibrium high-carbon phase, Eq 15–17 activity of a component 2 in a component 1 0.2; component 1 is iron; component 2 is
are used. For the liquid: according to the Darken formalism (Ref 22) is: silicon:
g2  
wt%Cmax ¼ 1:3 þ 2:57  103 t (Eq 15) log ¼ a12 ðX22  2X2 Þ (Eq 22) 153
go2 aFe-Si ¼  þ 3:02 (Eq 26)
T

in the interval 1152 to 2000 C (2106 to 3632
 where g2 is the activity coefficient of compo-
F), with t being the temperature in degrees
Celsius. Using thermodynamic quantities, nent 2 = a2/X2 (a2 being the activity of component
Eq 15 can be written as: 2 and X2 the mole fraction of component 2); go2 is 6863
the activity coefficient of component 2 in the log goSi ¼ 0:914  (Eq 27)
T
12:728 range of infinitely dilute solutions, that is, when
log XCmax ¼ %component 2 ffi 0; it is only a function of tem- As shown in Fig. 13, calculations with Eq 26
T
þ 0:727 log T  3:049 (Eq 16) perature (g2 ! go2 as X2 ! 0); and a12 is the and 27 are in good agreement with experimen-
function of temperature, usually of the shape tal data (note that the equation in Fig. 13 results
where XCmax is the maximum solubility of A/T + B, where A and B are constants. from introducing Eq 26 and 27 into Eq 22 and
graphite in liquid iron in mole fraction, and For the activity of carbon in an iron melt, using a natural logarithm rather than a common
T is the temperature in degrees Kelvin. Eq 22 is valid for component 1 (iron) and com- logarithm).
Equation 16 is valid for the interval 1425 to ponent 2 (carbon) with (Ref 23):
2300 K. For the austenite:  
1270
aFe-C ¼  þ 1:74 (Eq 23) Ternary Iron-Base Alloys
wt%Cmax ¼  0:435 þ 0:355  103 t T
(Eq 17)
þ 1:61  106 t2 Using a Taylor series expansion for the excess
partial molar free energy, one researcher derived
For the ferrite: 1180 an expression for the activity coefficient of com-
log goC ¼  0:87 (Eq 24)
  T ponent 2 in a multicomponent solution, which
11; 460 for dilute solutions can be written as (Ref 24):
wt%Cmax ¼ 2:46  103 exp  (Eq 18)
T Using the natural logarithm (base e) instead of
the common logarithm (base 10), Eq 22 can g2
ln f2 ¼ ln X2 e22 þ X3 e23 þ X4 e24 ; . . . (Eq 28)
For the metastable system, that is, with Fe3C be written as follows for the iron-carbon go2
as the equilibrium high-carbon phase, Eq 19–21 systems:
apply. For the liquid: where g2 is the activity coefficient of component
2714 2 dissolved in the three-component system, go2 is
ln gC ¼ 2 the activity coefficient of component 2 in the
wt%Cmax ¼ 4:34 þ 0:1874ðt  1150Þ T 

(Eq 25) range of infinitely dilute solution, and e22, e23,
t (Eq 19) 2920
 200 ln þ þ 4:01 2XC  XC2 e24, . . . are coefficients defined as:
1150 T

For the austenite: Equation 25 is in good agreement with experi- limit@ ln f2

e22 ¼ X1 !1
mental data, as shown in Fig. 12. @X2
wt%Cmax ¼  0:628 þ 1:222  103 t e23
limit @ ln f2
¼ X1 !1 (Eq 29)
@X3
þ 1:045  106 t2 (Eq 20)
The Iron-Silicon System
For infinitely dilute solutions, that is, X2 ! 0,
For the ferrite: Equation 22 can be used to calculate the X3 ! 0:
  activity of silicon in the iron-silicon system, e23 ¼ e32
10; 908
wt%Cmax ¼ 1:8  103 exp  (Eq 21)
T

Equation 15–21 can be used to calculate the

maximum solubility of carbon in various phases
(liquid, austenite, ferrite) as a function of tem-
perature. For example, to calculate the carbon
content of the stable eutectic, Eq 15 is used
with t = 1152  C (2106  F) to obtain %Cmax =
4.26%. Prediction of phase stability relies
heavily on knowledge of the activity of various
elements. In the specific case of iron-carbon
alloys, an increase in the activity of carbon in
the liquid parallels a greater ability of carbon
to separate as graphite; that is, the activity of
carbon is a measure of an increased tendency
of the alloy to solidify as the stable system.
On the other hand, a decreased activity of car-
bon reflects the carbide-promoting behavior of
the system, that is, the metastable solidification
Fig. 12 Dependence of the activity coefficient of Fig. 13 Dependence of the activity coefficient of
carbon on the mole fraction of carbon in silicon on the mole fraction of silicon in
tendency. liquid iron at 1550  C (2820  F). Source: Ref 23 liquid iron at 1600  C (2910  F). Source: Ref 23
 Thermodynamic Properties of Iron-Base Alloys / 47

Simplification of the Darken formalism for infi-
nite dilutions gives the interrelationship
between e and a, as follows (Ref 22):
e22
¼ 2a12
2:303
e33
¼ 2a13
2:303
e23 e32
¼ ¼ a23  a12  a13 ðEq 30Þ
2:303 2:303
The solute concentration is often given in
weight percent. For a ternary system, Eq 28 is
written:
log fi ¼ eii ½%i þ eij ½%j (Eq 31)
where the interaction coefficient e is related
to E by:
eii ¼ 230ðMi =M1 Þeii þ ½ðM1  Mi Þ=M1 log
eij ¼ 230ðMj =M1 Þeij þ ½ðM1  Mj Þ=M1 ðEq 32Þ
Data on interaction coefficients in liquid iron
for carbon, hydrogen, nitrogen, oxygen, and
sulfur are given in Table 2. For metallurgical
reactions involving dilute solutions, it is often
necessary to change the standard state from
pure component to that of 1 wt% in solution.
The free energy change is given by:
0:5585goi
Gs ¼ RT ln (Eq 33)
Mi
Free energies of solution DGs of selected ele-
ments in liquid iron are given in Table 3.
Ternary Fe-C-X Systems
Detailed equilibrium diagrams of the Fe-C-B,
Fe-C-Cr, Fe-C-Cu, Fe-C-Mn, Fe-C-Mo, Fe-C-
N, Fe-C-Ni, Fe-C-Si, and Fe-C-W systems are
available in Ref 25. Only the Fe-C-Si, Fe-C-P,
and Fe-C-Mn systems are discussed in this
article.
The Fe-C-Si System. The addition of silicon
to a binary iron-carbon alloy decreases the sta-
bility of Fe3C, which is already metastable,
and increases the stability of ferrite (the a field
is enlarged, and the g field is constricted). The
equilibrium diagrams in Fig. 14 show that as
the silicon content in the Fe-C-Si system
increases, the carbon contents of the eutectic
and eutectoid decrease (%Cmax decreases),
while the eutectic and eutectoid temperatures
increase (Ref 26). The activity coefficient, g2,
of component 2, dissolved in a three-compo-
nent system as a function of the concentration
X2 and X3 of dissolved components 2 and 3, is
described by Eq 34 (Ref 22):
g2
¼  2a12 X2 þ ða23  a12  a13 ÞX3
go2
þ a12 X22 þ a13 X32
þ ða12 þ a13  a23 ÞX2 X3
where a12 and a13 are the modified interaction
parameters of the two-component systems, a23 is
the modified interaction parameter that describes
the activity of both dissolved components, and
go2 is the activity coefficient of component 2 in
the range of infinitely dilute solution.
Starting from Eq 34, the activity of carbon
and silicon in an Fe-C-Si melt can be calculated
as a function of temperature and concentration
with the following relationships (Ref 23):
log aC ¼ð1180=T Þ  0:87 þ ½ð2540=T Þ þ 3:48 XC
 ½ð1270=T Þ þ 1:74 XC2 þ log XC
þ ½ð1423=T Þ þ 4:75 XSi
 ½ð153=T Þ þ 3:02 XSi
2
 ½ð1423=T Þ þ 4:76 XC XSi
log aSi ¼  ð6863=T Þ þ 0:914 þ ½ð306=T Þ þ 6:04 XSi
 ½ð153=T Þ þ 3:02 XSi
2
þ log XSi
þ ½ð1423=T Þ þ 4:76 XC
 ½ð1270=T Þ þ 1:74 XC2
 ½ð1423=T Þ þ 4:76 XC XSi ðEq 36Þ
The Fe-C-P System. Because the partition
coefficient of phosphorus between solid and liq-
uid iron is low, phosphorus segregates into the liq-
uid during solidification, and the melt becomes
supersaturated in phosphorus, which results in
the formation of Fe3P. Therefore, the four possible
solid phases of the stable and metastable systems
are austenite (g), Fe3P, Fe3C, and graphite. The
calculated liquidus surfaces for the four phases
and the eutectic lines formed by their interactions
are shown in Fig. 15, which is a superimposition
of the g-Fe3P-Fe3C and the g-Fe3P-graphite (Gr)
diagrams. Two ternary eutectic points are shown
in Fig. 15. To the left is L ! g + Fe3P + Gr at
954  C (1749  F) and yC = 0.099, yP = 0.123. To
ðEq 34Þ the right is L ! g + Fe3P + Fe3C at 948  C
(1738  F) and yC = 0.106, yP = 0.123. Here, yP =
XP/(1  XC), and yC = XC/(1  XC), where XP is
the weight fraction of phosphorus and XC is the
weight fraction of carbon. In general, it is agreed
that phosphorus does not have a strong graphite-
or carbide-stabilizing influence.
The Fe-C-Mn System. The influence of
increasing manganese contents in the Fe-C-Mn
system over the equilibrium phase diagram is
shown in Fig. 16. It is evident that manganese:
 Decreases the eutectoid temperature
 Increases the eutectoid interval, that is, the
range of temperature and carbon contents
over which a, g, and carbide can coexist
 Decreases the carbon content in the eutec-
toid and in the eutectic
 Increases the eutectic temperature (by approx-
ðEq 35Þ imately 3  C, or 5  F, for each 1% Mn)

Table 2 Interaction coefficients in ternary iron-base alloys for carbon, hydrogen, nitrogen,
oxygen, and sulfur at 1600  C (2910  F)
Element j eCj eHj eNj eOj eSj
Table 3 Free energies of solution in liquid
Aluminum 0.043 0.013 0.028 3.9 0.035 iron at 1 wt%
Boron 0.24 0.05 0.094 2.6 0.13
Mi, liquid iron at 1600  C (2910  F)
Carbon 0.14 0.06 0.13 0.13 0.11
Cobalt 0.008 0.002 0.011 0.008 0.003 Element i goi D Gs (cal
g
atom1)
Chromium 0.024 0.002 0.047 0.04 0.011
Aluminum (l) 0.029 15,100  6.67T
Copper 0.016 <0.001 0.009 0.013 0.008
Carbon (g) 0.57 5400  10.10T
Manganese 0.012 0.001 0.02 0.021 0.026
Cobalt (l) 1.07 240  9.26T
Molybdenum 0.008 0.002 0.011 0.004 0.003
Chromium (s) 1.14 4600  11.20T
Nitrogen 0.11 ... 0 0.057 0.01
Copper (l) 8.6 8000  9.41T
Niobium 0.06 0.002 0.06 0.14 0.013
½ H2(g) ... 8720 + 7.28T
Nickel 0.012 0 0.01 0.006 0
Manganese (l) 1.3 976  9.12T
Oxygen 0.34 0.19 0.05 0.20 0.27
½N2 (g) ... 860 + 5.71T
Phosphorus 0.051 0.011 0.045 0.07 0.29
Nickel (l) 0.66 5000  7.42T
Sulfur 0.046 0.008 0.007 0.133 0.028
½O2 (g) ... 28,000  0.69T
Silicon 0.08 0.027 0.047 0.131 0.063
½P2(g) ... 29,200  4.60T
Tin 0.041 0.005 0.007 0.011 0.004
½ S2(g) ... 32,280 + 5.60T
Titanium ... 0.019 0.53 0.31 0.072
Silicon (l) 0.0013 31,430  4.12T
Vanadium 0.077 0.007 0.093 0.14 0.016
Titanium (s) 0.038 7440  10.75T
Tungsten 0.006 0.005 0.002 0.009 0.01
Vanadium (s) 0.1 4950  10.90T
Zirconium ... ... 0.63 (3.0) 0.052
Tungsten (s) 1.2 7500  15.20T
Source: Ref 4, 7 Zirconium (s) 0.043 8300  11.95T
48 / Principles of Liquid Metal Processing
Fig. 14 Influence of silicon content on the solubility lines and equilibrium temperatures of the iron-carbon system. (a) to (c) Source: Ref 26, (d) to (g) Source: Ref 25
The carbide M3C, which is (FeMn)3C, is stable
over a wide range of manganese and iron con-
tents, extending at 1000  C (1832  F) from
Mn3C to nearly pure Fe3C. At high manganese
contents (for example, above 40% Mn), other
manganese carbides such as M5C2, M7C3,
M23C6, and M4C1+x(e) can form (Ref 25).
Influence of a Third Element on the Equi-
librium Temperatures. Various elements, dis-
solving in liquid and solid iron phases, change
the equilibrium temperatures on the iron-carbon
diagram, as indicated in Table 4. This results in
increased or decreased a and g fields.
Of particular interest for the case of cast iron is
the influence of third elements on the stable-
metastable eutectic interval (Tst  Tmet). In gen-
eral, elements that increase the Tst  Tmet interval
promote graphite formation, while those that
decrease the interval promote carbide formation.
Based on their specific influence on the Tst  Tmet
interval, third elements can be classified into the
following four groups (Fig. 17):
 Strong graphitizers that increase Tst and
decrease Tmet, such as silicon, aluminum,
nickel, and copper (Fig. 17a)
 Weak graphitizers that decrease both Tst and
Tmet but increase the Tst  Tmet interval
overall, such as phosphorus and arsenic
(Fig. 17b)
 Strong carbide stabilizers that decrease Tst
but increase Tmet, such as chromium, vana-
dium, and manganese (Fig. 17c)
 Weak carbide stabilizers that decrease both
Tst and Tmet, such as molybdenum and tung-
sten (Fig. 17d)
Real values for the Tmet
st
¼ Tst  Tmet interval
for a number of elements can be calculated with

the data given in Table 4, which also includes
data on the influence of some elements on the
eutectoid temperature and on the maximum sol-
ubility of carbon in austenite. Two examples of
the use of data in Table 4 are provided as
follows.
Example 1: Calculation of the value of the
Tst  Tmet eutectic interval for a cast iron
Fig. 15 Calculated liquidus surfaces in the Fe-C-P phase diagram. Source: Ref 27
Fig. 16 Vertical sections through the Fe-C-Mn ternary phase diagram at (a) 4.92, (b) 12.8, and (c) 19.7 wt% Mn
Thermodynamic Properties of Iron-Base Alloys / 49
having 2% Si, 0.5% Mn, and 1% Cu by weight:
Tst ¼ 1154  C þ 4% Si  2% Mn
þ 5% Cu ¼ 1166  C
Tmet ¼ 1148  C  15% Si þ 3% Mn
 2:3% Cu ¼ 117:2 C
TFe- C  1154  1148 ¼ 6 C
TFe-C-Mn-Cu ¼ 1166  1117:2 ¼ 48:8 C
Example 2: Calculation of the temperatures
of the point of maximum carbon solubility in
austenite, TE and TE0 , for the aforementioned
iron:
TE ¼ 1154 C  10%Si þ 3:2% Mn
 2%Cu ¼ 1133:5 C
TE0 ¼ 1148 C þ 2:5% Si  2% Mn
þ 5:2%Cu ¼ 1157:2 C
Some typical experimental results for silicon,
chromium, and vanadium are shown in Fig. 18.
These results are in agreement with theoretical
predictions.
Partition of a Third Element Between
Various Phases in the Fe-C-X System. It has
been established from the thermodynamic stability
of phases involved in the eutectic solidification of
Fe-C-X alloy that the differences in the equilibrium
partition coefficients DP (= PM  PS, where PM
and PS are the partition coefficients of element X
between liquid and eutectic metastable or stable
solid), the partition of element X between austenite
g=L
and liquid, PX , and the partition of element X
Fe C=g
between cementite and austenite, PX 3 , are
related to one another and have similar effects
on graphitization during eutectic solidification
(Ref 28). Calculated and experimental data for
partition coefficients of various elements in
phases of iron-carbon alloys are given in Table 5.
Figure 19 illustrates the correlation between
the graphitizing influence of a third element
(expressed by the normalized addition of each ele-
ment required to increase or decrease the chill
depth by a given amount) and the DP value. It is
quite obvious that a definite correlation exists,
although silicon, aluminum, and titanium deviate
from the line. These three elements have a strong
affinity for nitrogen; this may explain their
higher-than-expected graphitizing influence.
Indeed, it is accepted that the nitrides may act as
50 / Principles of Liquid Metal Processing

nuclei for the stable eutectic, promoting gray solid-
ification. This is why experiments show that tita-
nium, for example, can act either as a carbide or
graphite promoter, depending on the nitrogen
content.
Influence of a Third Element on Carbon
Solubility in the Fe-C-X System. The influ-
XX ðEq 38aÞ
ence of a third element on the solubility of car-
bon can be expressed by (Ref 20):
%X ðEq 39Þ
XCX ¼ XCXmax  XCmax ðmole fractionÞ
%X
%C ¼ X
%Cmax
X
 %Cmax
 %Cmax ðwt%Þ
where XCX and D%CX represent the increase
or decrease of carbon solubility in mole fraction
or weight percent, respectively; XCmax and %
Cmax represent the saturation concentration in
the iron-carbon system calculated from Eq 15
or 16; and XCXmax and %CX max are the saturation
concentration in the Fe-C-X system.
The changes in carbon solubility resulting
from additions of third elements, X, are shown
in Fig. 20. These data are valid in the range from
1200 to 1700  C (2190 to 3090  F), with the
exception of silicon and sulfur at high
concentrations. In the region of low concentra-
tion of the third element (%X = 0 to 5%), the
change in the solubility of carbon can be repre-
sented by the temperature-independent linear
equation:
XCX ¼ m
or
0
ðEq 37aÞ %C ¼ m
X
ðEq 38bÞ
0
where m and m are solubility factors. In Eq 38a
and 38b, m and m0 as well as XCX and D% CX
are positive for an increase in the solubility of
ðEq 37bÞ
carbon and negative in the other case. It is also
generally accepted that carbide-promoting
elements increase the solubility of carbon
(activity coefficient of carbon in solution is
decreased), while graphite-promoting elements
decrease it (activity coefficient of carbon in solu-
tion is increased). Therefore, third elements that
have a negative solubility factor promote graph-
itization, while elements that have a positive sol-
ubility factor promote carbide formation. The
value of the solubility factor is proportional to
their effect. It must be noted, however, that the
accuracy of the prediction of the behavior of ele-
ments based on solubility factor is questioned in
Ref 28 for elements that have a strong influence
on the austenite liquidus.
As indicated in Table 6, experimental values
are close to the theoretical values for many ele-
ments. Equations similar to Eq 38a and 38b can
be used to calculate the change in the maximum
solubility of carbon in austenite upon the addi-
tion of a third element:
%CEX ¼ m0 g
Data for m0 g are also given in Table 6.
Multicomponent Iron-Carbon
Systems
Carbon Solubility in Multicomponent
Systems. Assuming that the values in Table 6
for m and m0 , which were determined for the
ternary Fe-C-X system, can be extended to mul-
ticomponent systems (in this case, the effect of
alloying elements on the solubility of carbon
can be considered to be additive, as shown in
Eq 41, at least in the region of low concentra-
tions), the saturation concentration of carbon
in multicomponent systems can be calculated
as (Ref 20):
%CSi;Mn;P;S;...
max ¼ %Cmax þ %CSi;Mn;P;S;... ðEq 40Þ

which is Eq 37b rewritten for multicomponent

Table 4 Influence of a third element on the temperature change of critical points on the systems. In turn:
iron-carbon diagram
+, increase; , decrease.
%CSi;Mn;P;S;...
max ¼ %CSi þ %CMn þ %CP
Maximum solubility of carbon in
austenite,  C/wt%X 
Eutectoid, C/wt%X 
Eutectic, C/wt%X 
Eutectic, C/at. %X(a) þ %CS þ . . . ðEq 41Þ
0 0 0 0
Element Metastable (E) Stable (E ) Metastable (S) Stable (S ) Metastable C Stable C Metastable C Stable C

Silicon 10 to 15 +2.5 +8 0–30 10 to 20 +4 3.25 10.91 Then, using Eq 15 and data from Table 6, Eq
Copper 2 +5.2 ... 10 2.3 +5 3.32 8.41 40 becomes:
Aluminum 14 +8 +10 +10 15 +8 7.74 0.91
Nickel 4.8 +4 20 30 6 +4 1.33 6.50 %CSi;Mn;P;S;... ¼ 1:3 þ 2:57  103 t  0:31% Si
Cobalt ... ... ... ... ... ... 2.23 1.48 max
Chromium +7.3  +15 +8 +7  4.97 10.23 þ 0:027% Mn  0:33% P
Manganese +3.2 2 9.5 3.5 +3 2 2.33 7.15  0:4% S  . . . ðEq 42Þ
Molybdenum   + +   8.90 12.36
Tungsten   + +   12.13 15.55
Boron ... ... ... ... ... ... 15.47 18.53 Saturation Degree and Carbon Equivalent.
Nickel ... ... ... ... ... ... 19.67 16.87 The iron-carbon diagram with letter notations
Titanium ... ... ... ... ... ... 16.91 18.91
Vanadium +6–8 ... +15 + 6–8  ... ...
for critical points (Fig. 21) is used in this sec-
Phosphorus 180 180 + +6 37 30 16.05 16.98 tion. It is well known that mechanical proper-
Sulfur ... ... ... ... ... ... .. . . 18.53 ties of cast iron strongly depend on the
(a )Calculated results. Source: Ref 21, 28 amount and shape of graphite. In turn, for
hypoeutectic gray irons, the amount of graphite
depends on the amount of eutectic.
The amount of eutectic can be calculated
with the lever rule. For hypoeutectic irons,
one can write:

Amount of eutectic
Sr ¼
Amount of eutectic þ amount of austenite
%Canal  %C0E
¼
%Canal  %C0E þ %C0C  %Canal
%Canal  %C0E
¼ ðEq 43Þ
%C0C  %C0E

Fig. 17 Classification of the influence of a third element in the Fe-C-X system on the graphite- or carbide-promoting where Sr is the rectified saturation degree, %
tendency in cast iron, based on their influence on the eutectic stable and metastable temperatures. (a) Strong Canal is the analyzed carbon content of cast iron,
graphitizers. (b) Weak graphitizers. (c) Strong carbide stabilizers. (d) Weak carbide stabilizers and %C0 C and %C0 E represent the carbon content
 Thermodynamic Properties of Iron-Base Alloys / 51

Fig. 18 Influence of (a) chromium, (b) silicon, and (c)

Table 5 Equilibrium partition coefficients of a third element X in the Fe-C-X system

g=L Fe C=L
PX (a) PX 3 (a)
Element X calc exp calc exp PS PM DP = PM  PS

Silicon 1.71 1.72 0 0.05 1.55 0.78 0.77

Copper 1.57 1.62 0.12 0.08 1.43 0.78 0.65
Aluminum ... 1.15 ... 0.03 1.05 0.55 0.50
Nickel 1.46 1.61 0.43 0.32 1.33 0.90 0.43
Cobalt 1.18 1.13 0.59 0.60 1.07 0.85 0.21
Chromium 0.53 0.55 1.96 1.95 0.48 1.32 0.84
Manganese 0.70 0.75 1.03 1.21 0.64 0.90 0.26
Molybdenum 0.41 0.38 0.60 0.84 0.37 0.52 0.15
Tungsten 0.23 0.42 0.42 0.88 0.21 0.33 0.12
Boron 0.06 ... 0.22 ... 0.06 0.15 0.09
Nitrogen 2.04 2.04 2.12 ... 1.86 2.09 0.23
Titanium 0.04 ... 0.09 0.27 0.04 0.07 0.03
Phosphorus 0.15 ... 0.08 0.09 0.14 0.11 0.03
Sulfur 0.06 ... ... ... 0.06 ... ...
(a) calc, calculated; exp, experimental. Source: Ref 28

temperature of the multicomponent system. correlations. The so-called structural diagrams

Fig. 19 Correlation between the partition coefficient,
DP, and the graphitizing influence of a third
element in the Fe-C-X system. Source: Ref 28
of the eutectic and of the austenite, respectively,
at the eutectic temperature in the multicompo-
nent system (Fig. 21). Assuming the solubility
factors can be extrapolated to the hypoeutectic
region, %C0 C can be calculated with Eq. 42. A
similar approach can be used to calculate %C0 E
using data in Table 6 for m0 g:
%C0E ¼ 2:11  0:11% Si  0:35%P
þ 0:006% Mn  0:08% S ðEq 44Þ
In foundry practice, the following simplified
form of Eq 43 is used:
%Canal
SC ¼
%C0C
%Canal
¼ ðEq 45Þ
4:26  0:31% Si  0:33% P þ . . .
For more accuracy, %Cmax as a function of
temperature rather than %Cmax = 4.26 can be
used, where the temperature is the eutectic
Further simplification gives:
%Canal
SC ¼
4:25  0:3ðSi þ PÞ
where SC < 1 for hypoeutectic irons, SC = 1 for
eutectic irons, and SC > 1 for hypereutectic
irons.
Saturation degree is used in most of the
European literature. In the Anglo-Saxon litera-
ture and foundry practice, carbon equivalent
rather than saturation degree is used. Carbon
equivalent (CE) can be calculated as:
CE ¼ %Canal  %CSi  %CMn  %CP
 %CS  . . . ¼ %Canal þ 0:31%Si
þ 0:33% P  0:027% Mn þ 0:4% S
A eutectic iron has CE = 4.26%. It must be
noted that although Sr gives directly the amount
of eutectic in the structure (for example, Sr = 0.9
means 90% eutectic), SC and CE, although easier
to calculate, do not allow for exact estimation of
the amount of eutectic.
Structural Diagrams
For the practicing metallurgist involved in cast
iron production, one of the main applications of
the thermodynamics of the iron-carbon system
is the calculation of structure-composition
are used for this purpose.
The first and simplest structural diagram is
the Maurer diagram (Fig. 22a), in which the
ðEq 46Þ
as-cast structure is considered to be solely the
product of the carbon and silicon contents of
cast iron. Because it was recognized long ago
that solidification rate, as well as chemical
composition, plays a significant role in the for-
mation of the as-cast structure of casting, espe-
cially for cast iron, Laplanche (Ref 29) further
developed the Maurer diagram to include the
influence of cooling rate through the section
size (or bar diameter) of the casting (Fig.
22b). The k lines on the diagram are lines of
same structure (same degree of graphitization)
at a given cooling rate. The value k is an empir-
ical function of composition, as follows:
ðEq 47Þ
 
5
k ¼ 4=3 Si 1  ðEq 48Þ
3C þ Si
The correlation between k and cooling rate is
given in Table 7. Thus, if one wants to produce
a pearlitic iron in casting with equivalent sec-
tion sizes of 10 to 30 mm (0.4 to 1.2 in.) bar
diameters, Table 7 would suggest a k of 0.85
to 2.35. For example, k = 1.8 is then chosen.
A saturation degree, SC, is also selected
depending on the required mechanical proper-
ties (for example, SC = 0.8), and the intersection
of the k = 1.8 with SC = 0.8 will then give the
carbon and silicon required for the iron.
52 / Principles of Liquid Metal Processing

A further contribution to structural diagrams
was made by Patterson and Doepp (Ref 30).
This diagram (Fig. 23) encompasses not only
structure, composition, and cooling rate but also
a broad range of mechanical properties. Part of
this diagram is based on Laplanche’s k lines.
As an example of the way this diagram is
used, assume it is desired to pour a 50 mm (2
in.) diameter cast iron bar (or equivalent section
size) with a pearlitic-ferritic structure. A heavy
horizontal line is drawn from the y-axis at the
50 mm (2 in.) diameter bar location to the mid-
dle of zone IIb. This corresponds to a determina-
tion of k = 2.2. This k line can be followed to
the lower diagram until it intersects a prese-
lected saturation degree—in this case, SC =
0.6. The composition is now read as C = 2.6%
and Si = 3%, together with the equilibrium
! tem-
perature for the ðSiO2 Þ þ 2½C ½Si þ fCOg
reaction, which is 1460  C (2660  F). An addi-
tional explanation of the significance of this
reaction can be found in the article “Solidifica-
tion of Eutectic Alloys: Cast Iron” in this Vol-
ume. It must be pointed out that foundry
variables such as superheating and holding dur-
ing melting, charge composition (raw mate-
rials), and inoculation can cause significant
deviation from these calculations.
ACKNOWLEDGMENTS
Reviewed and adapted from Seymour Katz,
Composition Control, Casting, Vol 15, Metals
Handbook, 9th Edition, ASM International,
1988, p71–82; and D.M. Stefanescu, Thermo-
dynamic Properties of Iron-Base Alloys, Cast-
ing, Vol 15, Metals Handbook, 9th Edition,
ASM International, 1988, p 61–70
REFERENCES
1. R.J. Fruehan, Ladle Metallurgy: Principles
and Practices, Iron and Steel Society of
AIME, 1985, p 7–8
2. S. Katz and C.F. Landefeld, Cupola Desul-
furization, Cupola Handbook, American
Foundrymen’s Society, 1984, p 351–363
3. I.D. Sommerville, The Capacities and
Refining Capabilities of Metallurgical
Slags, Foundry Processes: Their Chemistry
and Physics, S. Katz and C.F. Landefeld,
Ed., Plenum Press, 1988, p 101–133
4. G.K. Sigworth and J.F. Elliott, The Ther-
modynamics of Liquid Dilute Iron Alloys,
Met. Sci., Vol 8, 1974, p 298–310
5. S. Katz and H.C. Rezeau, The Cupola
Desulfurization Process, Trans. AFS, Vol
87, 1979, p 367–376
6. S. Katz, D.E. McInnis, D.L. Brink, and
G.A. Wilkinson, The Determination of
Aluminum in Malleable Iron from
Measured Oxygen, Trans. AFS, Vol 88,
1980, p 835–844
7. E.T. Turkdogan, Physical Chemistry of
High Temperature Technology, Academic
Press, 1980
8. S. Katz and V.R. Spironello, Effect of
Charged Aluminum on Iron Temperature,
Silicon Recovery and Desulfurization in
an Iron-Producing Cupola, Trans. AFS,
Vol 92, 1984, p 161–172
9. C.F. Landefeld and S. Katz, Kinetics of
Iron Desulfurization by CaO-CaF2, Pro-
ceedings of the Fifth International Iron
and Steel Congress, Vol 6, Iron and Steel
Society of AIME, 1986, p 429–439
10. S. Katz and C.F. Landefeld, Plant Studies of
Continuous Desulfurization with CaO-
CaF2-C, Trans. AFS, Vol 93, 1985, p 215–228
11. S. Katz and B.L. Tiwari, A Critical Over-
view of Liquid Metal Processing in the
Foundry, Foundry Processes: Their Chem-
istry and Physics, S. Katz and C.F. Lande-
feld, Ed., Plenum Press, 1988, p 1–52
12. J. Niederinghaus and R.J. Fruehan, Desul-
furization Mechanisms for CaO-Al and
CaO-CaS in Carbon Saturated Iron, Metall.
Trans. B, to be published
13. E.T. Turkdogan, Physiochemical Phenom-
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in Melting, Refining and Casting of Foundry
Irons, Foundry Processes: Their Chemistry
and Physics, S. Katz and C.F. Landefeld,
Ed., Plenum Press, 1988, p 53–100
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S. Katz and C.F. Landefeld, Ed., Plenum
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Table 6 Solubility factors of various third elements for carbon-saturated Fe-C-X melts
Third element X DXX
C ¼ m
XX (a) D %CX = m0
%X D%CX 0
C ¼ mg %X
0
Atomic No. Symbol m exp m calc Validity m exp m calc Validity m0 g Validity

5 B 0.575 0.51 <0.04 0.539 0.462 <1.0 ... ...

6 C 0.67 0.68 ... 0.610 0.622 ... ... ...
13 Al 0.52 0.51 <0.05 0.220 0.215 <2.0 +0.04 <2
14 Si 0.71 0.68 <0.007 0.310 0.294 <5.5 0.11 <6
15 P 0.81 0.85 <0.048 0.331 0.349 <3.0 0.35 <0.4
16 S 1.00 1.02 <0.004 0.405 0.414 <0.4 0.08 <5
22 Ti +0.508 +0.44 <0.013 +0.159 +0.138 <1.6 2.08 <0.8
23 V +0.359 +0.33 <0.1 +0.105 +0.097 <11.0 +0.18 <1
24 Cr +0.215 +0.22 <0.13 +0.064 +0.062 <10.0 0.07 <20
25 Mn +0.105 +0.11 <0.30 +0.028 +0.029 <25.0 +0.006 <60
26 Fe 0.0 0.0 ... 0.0 0.0 ... ... ...
27 Co 0.10 0.11 <0.20 0.027 0.029 <40.0 0.017 <20
28 Ni 0.20 0.22 <0.10 0.051 0.055 <8.0 0.07 <6
29 Cu 0.313 0.33 <0.02 0.076 0.080 <3.8 +0.014 <5
32 Ge 0.677 0.66 <0.1 0.144 0.141 <14.0 ... ...
33 As 0.734 0.77 <0.07 0.151 0.159 <10.0 ... ...
41 Nb +0.51 +0.33 <0.045 +0.058 +0.030 <9.0 ... ...
42 Mo +0.24 +0.22 <0.14 +0.014 +0.012 <2.0 0.3 <4
44 Ru 0.0 0.0 <0.008 0.020 0.023 <1.5 ... ...
50 Sn 0.70 0.66 <0.02 0.110 0.104 <4.5 ... ...
51 Sb 0.79 0.77 <0.05 0.119 0.117 <15.0 ... ...
52 Te 0.85 0.88 <0.005 0.122 0.126 <1.5 ... ...
73 Ta +0.49 +0.33 <0.03 +0.004 0.009 <11.0 ... ...
74 W +0.256 +0.22 <0.05 0.015 0.01 <18.0 0.12 <12
76 Os 0.0 0.0 <0.013 0.035 0.035 <4.0 ... ...
78 Pt 0.224 0.22 <0.015 0.052 0.052 <6.0 ... ...
79 Au 0.333 0.33 <0.024 0.060 0.060 <10.0 ... ...
Fig. 20 Influence of third elements, X, on the 92 U +0.53 +0.55 <0.01 0.006 0.005 <5.0 ... ...
solubility of carbon in molten iron. (a) In (a) exp, experimental; calc, calculated. Source: Ref 20
mole fraction. (b) In weight percent. Source: Ref 20

16. J. Ishida, K. Yamaguchi, S. Sugiura, N.
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52, 1981, p 2–8
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18. E.T. Turkdogan, Slags and Fluxes for Fer-
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19. T.B. Massalski et al., Ed., Binary Alloy
Phase Diagrams, Vol 1, American Society
for Metals, 1986
20. F. Neumann, The Influence of Additional
Elements on the Physico-Chemical Behav-
ior of Carbon in Carbon Saturated Molten
Iron, Recent Research on Cast Iron, H.D.
Merchant, Ed., Gordon and Breach, 1968,
p 659
Fig. 21 The iron-carbon diagram with letter notations. S.S., soild solution
Thermodynamic Properties of Iron-Base Alloys / 53
21. N.G. Girsovitch, Ed., Spravotchnik po
tchugunomu litja (Cast Iron Handbook),
Mashinostrojenie, 1978
22. L.S. Darken, The Thermodynamics of
Ternary Metallic Solutions, Trans. TMS,
Vol 239, 1967, p 80, 90
23. F. Neumann and E. Dötsch, Thermodynam-
ics of Fe-C-Si Melts with Particular Empha-
sis on the Oxidation Behavior of Carbon
and Silicon, The Metallurgy of Cast Iron, B.
Lux et al., Ed., Georgi Publishing, 1975, p 31
24. C. Wagner, Thermodynamics of Alloys,
Addison-Wesley, 1952
25. Metallography, Structures and Phase Dia-
grams, Vol 8, Metals Handbook, 8th ed.,
American Society for Metals, 1973,
p 400–416
26. E. Piwowarsky, Hochwertiger Gusseisen,
2nd ed., Springer-Verlag, 1958
27. M. Hillert and P.O. Söderholm, White and
Gray Solidification of the Fe-C-P Eutectic,
The Metallurgy of Cast Iron, B. Lux
et al., Ed., Georgi Publishing, 1975, p 197
28. A. Kagawa and T. Okamoto, Partition of
Alloying Elements on Eutectic Solidifica-
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of Cast Iron, H. Fredriksson and M. Hillert,
Ed., North-Holland, 1985, p 201
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54 / Principles of Liquid Metal Processing

Fig. 22 Structural diagrams for cast iron. (a) Maurer diagram. (b) Laplanche diagram. See also Fig. 23. Source: Ref 29

Table 7 k lines for various structural ranges

Bar diameter
mm in. k for mottled structure k for pearlitic structure k for pearlitic-ferritic structure

30 1.2 0.65–0.85 0.85–2.05 2.05–3.10

20 0.8 0.75–1.10 1.10–2.25 2.25–3.40
10 0.4 1.05–1.50 1.50–2.35 2.235–3.50
 Thermodynamic Properties of Iron-Base Alloys / 55

Fig. 23 Patterson and Doepp structural diagram for cast iron. See the corresponding text for details. Source: Ref 30

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