The Fe-C-Si Solidification Table 1.

Fe-C Liquidus and Eutectic Points

Diagram for Cast Irons Temperature T Liquidus* Gr. Liquidus* 7 Liquidus** Equation 1

C F XC tC

R.W. Heine
University of Wisconsin-Madison, Madison, WI 1350 2462 2.47 - 2.49 2.25
1300 2372 3.02 4.63 3.06 2.76
ABSTRACT 1250 2282 3.50 - 3.55 3.28
1200 2192 3.93 4.37 4.01 3.79
An Fe-C-Si diagram for cast irons for both the stable Fe-graphite
and metastable Fe-iron carbide solidification processes and the
transition between the two is presented. Equations marking the Gr Eutectic* Gr Eutectic**
boundaries of proeutectic and eutectic solidification are provided 1154 2109 4.26 - - 4.26
for both metastable and stable systems. The diagrams for both
1150. 5 2102.7 4.39 4.39 4.3
systems are shown graphically.
Carbide Eutectic* Carbide Eutectic**
Correlation of solidification processes in cast irons with the 1148 2098 4.30 - - 4.33
diagram boundaries is demonstrated. Solidification of the metast- 1147 2096.2 - - 4.42 4.34
able eutectic at predicted carbide eutectic temperatures requires
that graphite nucleation and growth be avoided at higher temper-
*ASM Handbook, ref. 1
atures. Otherwise carbide eutectic can follow at the higher temper-
**B. Chicco and U. K. Thorpe, ref. 4.
atures. The diagram predicts that carbide nucleation can occur
at 5-IOF or more below the temperatures at which the stable
eutectic nucleates once austenite is present. This behavior de-
scribes the potential transition from the stable to the metastable
solidification process even in binary Fe-C alloys.
The diagram is presented as a solidification diagram and not
as a ternary phase diagram, since it is derived from cooling curve
data. It does not indicate the beginning and ending of solidification lent data in recent research reported by B. Chicco and W.R.
processes and involved multicomponent alloys. It is constructed Thorpe.4 Comparison of the data in Table 1 reveals a shift from
on rectangular coordinates. Nevertheless, the diagram is most 4.26% C at 1154C to 4.39% C at 1150.5C for the Fe-Gr eutectic
useful in cast iron metallurgy. and from 4.30% C at 1148C to 4.42% C at 1147C for the Fe-Fe3C
eutectic by the latter investigators. They identify the carbide eutec-
tic temperature as a second inflection about 3.5C (6.3F) after the
INTRODUCTION Fe-Gr eutectic temperature arrest has been reached in the DTA
The cast iron composition region of the Fe-C-Si phase diagram curve.
has been investigated by many researchers. Because the alloys
shift readily from the stable iron-graphite phase system to the Chicco and Thorpe also obtained a higher liquidus temperature
metastable carbide system (or to a mixture of the two) during curve using the DTA method. The handbook data1 was determined
solidification, the ternary alloy system, stable or metastable, has from diffusion couple equilibration or thermodynamic calculations.
not been quantitatively established. Attempts to apply the presently In both cases the austenite liquidus curves are higher than those
known Fe-C and Fe-C-Si' diagrams to the analysis of solidification of earlier investigators5,6 who used the cooling and heating curve
of cast irons are quite unsatisfactory. However, an Fe-C-Si solidifi- method on less pure alloys. Since Chicco and Thorpe and the
cation diagram based on cooling curve data closely correlated with handbook data disagree, it is evident the austenite liquidus and
the phase diagram for both stable and metastable systems can be eutectic points are still in dispute. Hence, entering the Fe-C-Si
constructed. The stable system was described in references 2 and ternary from an uncertain Fe-C binary austenite continues the di-
3. The metastable system and its relationship to the stable system lemma. The diagram here reported ignores this problem since it
will be presented in this paper. The transition between the two is developed from cooling curves and proceeds for engineering
systems will also be described. Application of this diagram to purposes.
solidification phenomenology in cast irons will also be considered.
Since the diagram is based on cooling curves of alloys of more
than three components, it is not a phase equilibrium diagram. Fe-C-Si SOLIDIFICATION DIAGRAM CONSTRUCTION
Further, its construction does not follow that of classical ternary
Applied to cast iron solidification, interest centers on the austenite
phase diagrams. Rectangular coordinates are used; all surfaces are
liquidus surface and the eutectic. This region has been presented
regarded as planes forming straight line intersections. Nevertheless,
for the stable system in earlier work (Fig. I). 2 - 3 Figure 1 shows
the diagram is most useful in cast iron metallurgy.
a projection onto the Fe-C binary plane of the austenite and graphite
liquidus surface at compositions of 1, 2, 3, and 4% Si and their
THE IRON-CARBON DIAGRAM
intersection in the stable Fe-Gr eutectic. The composition scale
The basis of the ternary system resides in the Fe-C binary alloy includes carbon and carbon equivalent, CE. Carbon equivalent,
system. Even here there is question as to its applicability to a CE = C + VA Si, is a very useful concept for cast iron metallurgy
solidification diagram. Reference is made to the data for the auste- in the Fe-C-Si alloys. The coefficient VA for silicon applies to the
nite liquidus, graphite liquidus, and eutectic point in Table 1 ex- liquidus only. Other coefficients are used for the graphite liquidus
tracted from reference 1, authored by J. Chipman, and the equiva- and eutectic. 2

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 2600

2500

fa
o 2400 -
fa
fa
E- 2300-
fa
fa
a
fa
E- 2200 -

2100 -

2000
1.0 2.0 3.0 4.0 5.0
PERCENT CARBON OR CARBON EQUIVALENT
Fig. 1. Stable Fe-Gr eutectic region of the Fe-C-Si solidification diagram.2

Austenite Liquidus Surface
The austenite liquidus surface is described by:
TAL =2856.2 - 175.2 (%C +VA% Si), F
or = 1569 - 97.3 (%C + VA% Si), C (1)
where TAL is the temperature of the austenite liquidus. Equation
1 was determined by cooling curve measurements of alloys melted
at a temperature of 2650F (1454C) in a closed system under
deoxidized argon. 2,3.
The liquidus in the Fe-C system where Si = O is the curve
against which the carbon equivalent. Equation 1, is matched. The
carbon equivalent is defined as the equivalent percentage of carbon
which will cause as much change in the liquidus as a one percent
change in silicon. The coefficient VA means that a 1% Si increase
will lower the liquidus temperature as much as a 0.25% C increase.
Both %C and CE may therefore be plotted on the same scale and
projected onto the Fe-C binary plane as in Figure 1. Each 1 %
silicon line on Figure 1 is shifted 0.25% C from the Fe-C liquidus.
A shifting of the liquidus is a common experience with synthetic
Fe-C-Si cast irons and actual cast irons. For example, residual Mg
and rare earth elements, Ce, present in ductile iron cause the
liquidus to follow Equation 3 closely. Metallurgical variables in
the melting process, ladle treatments, residuals and other variables
can shift the liquidus as illustrated by Equations 1-3. However,
construction of the solidification diagram requires a reference au-
stenite liquidus which is chosen as Equation 1. This liquidus can
be duplicated in the foundry under specified conditions.16"18,21
The liquidus values from Chipman,1 and Chicco and Thorpe, 4
are compared with Equations 1-3 in Figure 2. As expected, they
do not agree. This is because Equations 1-3 were determined with
cooling curve experiments and less pure alloys. Nevertheless, Equ-
ation 1 is used as the reference liquidus because the cooling curve
technique is extensively used in foundry process controls. Equation
1 also agrees well with early investigators of the Fe-C system who
used cooling curves. 5,6

Equation 1 represents the liquidus only for one condition: melting Graphite Liquidus Surface
under deoxidized argon. When C 0 2 was admitted to the deoxidized
argon as an oxidizing agent the relationship changed to: 2-3 Equation 4 2 presents the graphite liquidus for Fe-C Si alloys:
TGL = 700.4 %C + '/3% Si) - 873.7, F
OTAL =2902 - 184 (%C + VA% Si), F
orTGL = 389.1 (%C - 503.2, C2 (4)
or = 1594.4 - 102.2 CE, C (2)
Note that CE = C + Vi Si in these equations. The constant '/?
A further change (to Equation 3 *3) was caused by melting the
indicates that increase of 1% Si will have the same effect as a
alloys to result in a residual % Al of over 0.01%:
decrease of 0.33% C on the graphite liquidus. The lines correspond-
HTAL =2804 - 165.7 (%C + VA% Si), F ing to 1, 2, 3, 4% Si are shown projected on the Fe-C binary in
or = 1540 - 92.06 CE, C (3) Figure 1.

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 Fe-CTal,F=2884.3-l82.lx%C,Ref.3
a Ref. I-Chipman
2400
o Ref.4-Chico and Thorpe
-L Ref. 6-Carpenter and Keeling
Ref.5-Ruer and Goerens
T Ref. 3
Equation 2
fa
m 2300 Equotion I
fa
fa Equation 3

3
fa
fa
fa 2200

2100 -

2.5 3.0 3.5 4.0 4.5

PERCENT CARBON
Fig. 2. Comparison of austenite liquidus temperauresfrom references I -6. References 2,3.5,6 utilized cooling curve measurements and impure alloys.
References 1 and 4 utilized diffusion couples, DTA, or thermodynamic calculations.

Eutectic Region Austenite Solidus Surface

The intersection of the austenite and graphite surfaces forms the
stable eutectic valley shown in Figure 1. The stable Fe-Gr system
eutectic is defined by Equations 5~ and 6:
%C = 4.26-0.3167% Si (5)
Eutectic Temperature, TE= 2110 + 11.7 x % Si, F
orTE = 1155 +6.5 x % Si, C (6)
The metastable Fe-carbide eutectic is defined by Equations 7 and
8: 7,8
% C = (100-%S:/100) (7)
Carbide eutectic temperature, CET = 2102.8 - 36.34% Si, F
(8)
The location of the carbide eutectic occurs on the extended Fe-Gr
binary liquidus for reasons given elsewhere 2 7 , 8 The eutectic com-
bination of %C + '/4%Si = CE can also be plotted on the extended
Fe-C binary autenite liquidus line. The projection of both stable
and metastable eutectic compositions on the base plane of the
ternary system is shown in Figure 3 and in rectangular coordinates
in Figure 4.
The Fe-C-Si solidus surface in the stable system is given by Equ-
ation 9
TAS = 2783.1 - 320.2% CE,
TAS = 1528.4 - 177.9% CE, C (9)
where TAS is the temperature of the austenite solidus, and CE =
0.18% Si +%C.
The intersection of the solidus and eutectic planes is defined by
Equation 10:2
%C = 2.17% Si (10)
Solidus lines for the Fe-Gr and Fe Fe3C systems projected on
the base plane are shown in Figures 3 and 4.
The Carbide Phase
In the binary Fe-C system the carbide is assumed to be Fe 3 C. In
the ternary Fe-C-Si system an iron silico carbide has been identified
as Fe 10 Si 2 C 3 by Humphreys and Owen. 9 Other investigators have
referred to the same carbide as the "x-constituent",10 "Maries car-
bide"" , and the "Hurst and Riley carbide." 12 Assuming the carbide

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 Fe -Gr Eutectic
C Solubility in y

Gr Solubility in y

1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0
%Si
Fig. 3. Eutectic compositions and carbon solubility in austenite projected onto Fe-C-Si ternary base plane.

to be an iron silico carbide solid solution varying from Fe 10 Si 2 C 3 ,

it may be positioned on the basal plane as depicted in Figures 3
and 4. The metastable eutectic tie lines of liquid, carbide, and
austenite may then move down the carbide eutectic valley and
away from the Fe-C binary as shown in Figure 4. The Fe-Gr tie
lines of liquid, austenite, and graphite also move down the eutectic
valley but toward the Fe-C binary (Fig. 4).

The carbide phase can nucleate and grow at any termperature

after austenite has nucleated, even in hypereutectic compositions. I3
Even when graphite has nucleated first and is followed by austenite, Solubility
Griny
the carbide phase can nucleate and grow in the Fe-C-Si composi-
tions. I3 This is another manifestation of the same behavior observed
in binary Fe-C alloys, in which DTA measurements show that the
carbide eutectic is nucleated about 3.5C (6.3F) lower than the
graphite eutectic begins to solidify.4

Fe-Gr AND Fe-Fe3C SYSTEMS

I -
Figure 5 shows the stable and metastable Fe-C-Si systems superim-
posed on the Fe-C binary. The austenite liquidus, graphite liquidus,
graphite and carbide eutectic valleys and solvus, and extended
austenite carbon equivalent liquidus are all shown projected on the
PERCENT CARBON
Fe-C binary. The composition scale may be read either as percent
carbon or as carbon equivalent %C + VA Si on the austenite liquidus
line. This is a convenience that has significant application, as will Fig. 4. Eutectic compositions and carbon solubility in austenite plotted
be described. All lines on the projected diagram (Fig. 5) are located on rectangular C-Si coordinates.

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 2300

2200
, 5/o2o/o
fa
o \_-A_

\
H 2100 \ * \

fa
2%SiL + / \ \ \ / ^ y L+Cor
b d
ie /

7
-f-v-/
2000
4 % Si

1900 - Carbide

1.0 2.0 3.0 4.0 5.0 6.0

PERCENT CARBON OR CARBON EQUIVALENT
Fig. 5. Metastable region of the F-C-Si solidification diagram.

Fig. 6. Gray rim at the edge and eutectic gray cells in the interior of vertically sectioned eutectometer cup showing metastable eutectic interior, nital
etched. 3x. Shrinkage porosity is present in the white iron.

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 2400 using Equations 1-10. The carbide eutectic points are shown on
1316 the extended graphite liquidus; they have also been projected onto
the extended austenite liquidus. The usefulness of these points will
become evident when application of the diagram to cast iron sol-
2300 idification is considered. For the moment, it must be realized that
1260 the carbide eutectic points were determined in a unique way. 7,8,15
P'3-
MKH. Sufficient undercooling was caused to avoid the Fe-Gr reaction
w 2760F Supht. pl and obtain the metastable eutectic reaction.
2200 (I5I6C) MKE
1204 3.07 CE F Supht.
(I499C) Eutectic Undercooling
s
w
0.01 %Bi
1.35% Si 3.07 CE
1.35% Si Because the boundaries of the diagram have been determined with
cu cooling curves or calculated from cooling curve data, more or less
a 2100
g 1149 undercooling is inherent. This is especially true with near eutectic
compositions. The rising eutectic temperature with increasing sili-
con content in the stable system (Fig. 1 and Eq. 8) is not observed
2000 unless solidification occurs very slowly. When cooling through
1093 the eutectic takes about 60 minutes, the stable Fe-Gr eutectic arrest
follows the silicon relationship in Equation 8 as demonstrated
elsewhere.23 However, cooling through the Fe-Gr eutectic in 3 to
6 minutes results in an arrest near or just below the 2111 binary
1900
1038 Fe-Gr eutectic temperature. 2,8,14 For example, at 2.5% Si the cal-
4 3 2 culated Fe-Gr eutectic temperature is 2140F, but the observed
TIME, m i n u t e s arrest in the typical thermal analysis of a gray iron sample might
Fig. 7. Cooling curves for graphite and carbide eutectic solidification of
the same iron poured into an alumina-coated cup and a tellurium-coated
cup, respectively.

2300
Series 1 - 0 . 2 0 % Si
L+ 7 n %C White Fracture
o CE DO.
%C White Fracture
2200 with Kish
CE DO.
fa
o
fa
fa
> 2100 r Carbide A Q A _ ^
l%Si Eutectic
fa
fa L
fe%Si +X
fa
f
2000 3 % Si

% Si \

1900 \ Carbide

1.0 2.0 3.0 4.0 5.0

PERCENT CARBON OR CARBON EQUIVALENT

Fig. 8. Plot of series I data of Table 2 on the carbide eutectic valley region of the Fe-C-Si solidification diagram. Note alloys are completely carbidic
when the composition is hypoeutectic.

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 2300
/ Series H-2.25% Si
/Ao CEvsTALS Corbide Eutectic
/ DO; Groy Rim
/C^ %CvsSi
' B o %C vsTAL a Carbide Eutectic
2200 / DO. with Gray Rim
/ Gray, CE
fa
o

fa
2I00
I
fa
fa
a
w
E-

2000

1900

1.0 2.0 3.0 4.0 5.0 6.0

PERCENT CARBON OR CARBON EQUIVALENT
Fig. 9 Plot of series H data of Table 2 on the carbide eutectic valley region of Fe-C-Si solidification diagram. Note that the highest %C alloys. Hl-I and
H2-I, required both Te alloy addition and Te cup to produce a carbide eutectic temperature, but even so gray rim was present. Compare with no gray
rim in Figure 8.

be in the range of 2070-2110F, depending on metallurgical proces-
sing. Graphite nucleation through the addition of inoculants will
result in eutectic arrests over 21 OOF, but only very slow cooling
will raise the arrest to 2140F. Conversely, the addition of a few
PPM of Te and Bi can depress the arrest until it becomes the
Fe-Fe3C arrest (Eq. 8) and eutectic solidification is completely
metastable. 7,15,16 However, very slow cooling cannot be employed
to locate the carbide eutectic because the Fe-C-Si alloys will
graphitize unless they are very low in Si and hypoeutectic in com-
position.
The transition from the Fe-Gr to the Fe-Fe3 eutectic can occur
between the temperature of the former and the latter on Figure 5
once austenite is present when the stable eutectic begins to solidify.
This is evident from the DTA data for the Fe-C system.4 and Table
7. This phenomenon is revealed in Figure 6, the cross-section of
a thermal analyses cup sample showing a stable eutectic gray iron
rim and a metastable white iron interior. The metastable eutectic
can follow the stable eutectic reaction with only 5-1 OF further
undercooling once austenite is present. As soon as austenite is
present, carbide can precipitate within that austenite because of
the carbon solubility inflection in the solidus curves (Fig. 5). This
phenomenon was shown to occur experimentally.13 Gray rim on
a white iron interior as in Figure 6 is the result of the metastable
carbide eutectic solidification following an initial beginning in the
stable system. This can occur at temperatures above the carbide
eutectic temperature once austenite is present from the stable eutec-
tic reaction.13 This transition from the stable eutectic to the metast-
able eutectic can occur at any temperature between the two eutectic
temperature ranges, Equation 6 vs. Equation 8. The result is mixed
stable and metastable eutectic structures referred to as "mottled
iron and gray rim" (Fig. 6). To gain a completely white fracture
or eutectic carbide structure requires undercooling without any
graphite nucleation to near the temperature expressed by Equation
8 for the percent silicon in the alloy. However, the metastable
eutectic may also be undercooled below Equation 8 by metallurgical
7,16-18
processing. Equations 6 and 8 thus represent the stable and
metastable eutectic reaction temperatures under specified cooling
conditions; namely very slow cooling for the former and the absence
of prior Fe-Gr solidification in the latter. Otherwise both eutectic
reactions can occur at temperatures intermediate between the two.

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 2300
Series E - 1 . 0 % Si
L +X a %C White Fracture,
Carbide Eutectic
l%Si o CE DO.
2200

fa
o

|2 2100
3
fa
WVOfT
\V\WL -D-\V
fa
\ \ \ Vl%Si
L+
fa \\\/2%si r \ \
2000 \ V3%Si
"V
%Si
i'4
\

1900 -

1.0 2.0 3.0 4.0 5.0

PERCENT CARBON OR CARBON EQUIVALENT
Fig .10. Plot of series E data of Table 2 on the carbide eutectic valley region of the Fe-C-Si solidification diagram. Note all alloys are completely carbidic.

The undercooling of the Fe-Gr eutectic to temperatures below the
Fe-Fe3C eutectic with subsequent stable eutectic solidification can
also occur. 8
Solidification of Cast Irons
The application of the Fe-C-Si solidification diagram for interpret-
ing the results of cooling curve measurements will now be illus-
trated. In the typical foundry cooling curve test, the molten iron
is poured into a core sand cup containing a thermocouple connected
to a recorder. The sample size is such that cooling and solidification
from about 2372F (1200C) to 1922F (1000C) requires about 4-6
minutes. Typical cooling curves are shown in Figure 7. The liquidus
and eutectic arrests are then read from the cooling curve. In the
illustrations to be cited, the molten iron was produced in an induc-
tion furnace from a mixture of pig iron, steel, carbon, and ferrosili-
con as needed. Melting and holding temperature was 2750-2800F.
Samples were poured at intervals to gain composition ranges as
shown in Table 2. Sample cups may have interior surfaces coated
with either an A1 2 0 3 or a tellurium powder wash. The latter is
used to cause the metal to freeze in the carbide eutectic mode.
The cups then can be used to follow either the graphite or the
carbide eutectic systems. Tellurium in the amount of 0.005% to
0.02% can also be added to the iron to better follow the carbide
system. However, even with the Te cup and the Te addition the
iron will not solidify entirely in the metastable system if the carbon
and silicon percentages are too high, as will be shown.
The first example will follow the carbide eutectic behavior at
0.18% to 0.23% Si, 3.67 to 4.86% C, and % C + VA % Si carbon
equivalent carbon equivalent 3.49 to 4.92. Table 2, series I, lists
the compositions and liquidus and eutectic temperatures. The com-
bustion method was used to analyze for % C, the atomic absorption
method for Te, and the other elements were determined with the
spectrometer. The chemical compositions in Table 2 range from
hypereutectic to hypoeutectic and cross both the graphite and car-
bide eutectic valleys. Fracture and metallographic analysis shows
that Te treatment caused carbide eutectic solidification at an average
temperature for 0.21% Si of 2095F. Undercooling of the carbide
eutectic can occur because no graphite is present. Location of the
data points on the eutectic valley region of the diagram is shown
in Figure 8. Figure 8 shows that carbide eutectic temperature (bulk
arrest) is nearly constant over the % C studied at 0.18-0.23% Si.
Further, kish graphite appears in the microstructure when the
graphite liquidus or the extended austenite carbon equivalent
liquidus is exceeded. This is expected from the diagram boundaries.
The carbon equivalent-liquidus temperature points in Figure 8 fall
somewhat above the liquidus temperature curve, Equation 1. This

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 2300
2200
fa
_ ^ v _ .
o
3
2100
fa
fa
EH
2000
1900 -
1.0 2.0 3.0 4.0
PERCENT CARBON OR CARBON EQUIVALENT
Fig. 11. Plot of series J data of Table 2 on the carbide eutectic valley region of the Fe-C-Si solidification diagram. Note all alloys have gray rim and/or
kish; compare with Figures 8-10.
is an effect of the superheating temperature of 2750-2800F, a
phenomenon which will be discussed later.
The next example will follow the carbide eutectic behavior in
alloys of 2.24-2.28% Si 2.69-4.08% C, and 3.25-4.65 carbon,
series H in Table 2. Because of the high percent silicon, tellurium
was added to the iron to cause it to solidify carbidic. Figure 9
shows the austenite liquidus temperature, TAL vs. CE first; point
A for sample H5-1. The same liquidus is also plotted vs. the
analyzed percentage carbon; point C, Figure 9. Then the % C is
plotted on the projected 2.25% Si curve at the liquidus temperature;
point B, Figure 9. Points B and C should superimpose if there is
exact agreement of %C, %Si, and austenite liquidus temperature.
The B and C points for samples H4-2, H5-1, H5-2, H6-1, H6-2,
H7-1, and H7-2 are seen to overlap closely as expected. Regarding
sample H3-2, undercooling can occur readily since it is actually
a hypereutetic composition. Both the stable and metastable eutec-
tics are also shown in Figure 7. Without the Te cup, Hl-1 and
H2-1 cast gray, while the carbide eutectic develops with the Te
coated cup, HI-2 and H2-2. The average CET was measured as
2036F at 4.68 CE compared with the values of 2028F and 4.72
CE calculated from Equations 8 and 9. However, the presence of
gray rim is the reason the carbide eutectic temperature is above
the calculated value by 8F.
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1 1 '
/ Series J-2.7% Si
/A oCEvsTAL 8 Carbide Eutectic
/ o DO; Groy, Kish
/C A % C vsSi
' B a%CvsTAL&Corbide Eutectic
' a DO. with Gray Rim
Carbide
5.0 6.0
Figure 10 reports a similar analysis for series El-8 of 0.98-1.05%
Si. Again in this series, the data points agree well with the 1% Si
austenite liquidus projected on the Fe-C plane. The carbide eutectic
occurs at 2064F vs. 2073F and at 4.47 CE vs. 4.52 calculated,
respectively. In this case, there is no gray rim and the carbide
eutectic measured is 9F below the calculated value.
Data for series J in Table 2 are plotted in Figure 11. The carbide
eutectic temperature varied from 2020 to 2028F and silicon
varied from 2.55-2.70%. Calculated carbide eutectic temperature
at that percent silicon is 2005 to 2010F. Gray rim has caused the
measured carbide eutectic to be significantly above the calculated
carbide eutectic.
In Figures 8-11, agreement of the austenite liquidus temperatures
with both the percent carbon and carbon equivalent values appears
to be good. The 0.2% Si and 1.0% silicon alloys, series I and E,
reveal carbide eutectic undercooling below the calculated temper-
ature. Control of the melting process can produce either the calcu-
lated eutectic or undercooled eutectic as long as no graphite is
present. 7.16-18 The 2.25% Si and 2.70% alloys, series H and J,
had measured carbide eutectic temperatures somewhat above the
calculated values. They also had kish and/or gray rim structures.
This illustrates the principle that once the graphite eutectic austenite
is present, the transition to the carbide eutectic can occur with a
399
 Table 2. Liquidus and Eutectic Temperatures and Structures

Type of Liquidus Eutectic

Sample Sample %C %Si %Mn %Te CE F max F Structure*

11 Te 4.86 0.18 . 0.0100 4.92 na 2087 White, kish Graphite

12 Te 4.67 0.22 - 0.0120 4.73 na 2087 White, kish Graphite
13 Te 4.44 0.21 - 0.0090 4.49 na 2089 White, kish Graphite
14 Te 4.22 0.18 - 0.0150 4.27 2098 2088 White
15 Te 4.04 0.23 - 0.0150 4.10 2147 2090 White
16 Te 385 0.23 - 0.0200 3.91 2187 2087 White
17 Te 3.67 0.23 - 0.0250 3.73 2246 na White
18 Te 3.43 0.23 - 0.0150 3.49 2269 2086 White
Hl-1 Plain 4.08 2.28 0.79 0.0060 4.65 na 2095 Gray, kish Graphite
Hl-2 Te 4.08 2.28 0.79 0.0060 4.65 na 2040 White, Gray mixture
H2-1 Plain 3.89 2.27 0.79 0.0095 4.46 na 2077 Gray, kish Graphite
H2-2 Te 3.89 2.27 0.79 0.0095 4.46 na 2039 White, Gray Mixture
H3-2 Te 3.69 2.25 0.81 0.0110 4.35 2088 2039 White, 7 mm GR
H4-2 Te 3.49 2.27 0.74 0.0122 4.06 2139 2035 White, 4 mm GR
H5-1 Plain 3.18 2.25 0.80 0.0146 3.74 2193 na Gray, White Specks
H5-2 Te 3.18 2.25 0.80 0.0146 3.74 2201 2039 White, 3 mm GR
H6-1 Te 3.00 2.24 0.75 0.0160 3.56 2237 2032 White, 5 mm GR
H6-2 Te 3.00 2.24 0.75 0.0160 3.56 2247 2036 White, 2 mm GR
H7-1 Plain 2.69 2.24 0.70 0.0165 3.25 2298 na White, 5 mm GR
H7-2 Te 2.69 2.24 0.70 0.0165 3.25 2303 na White, 4 mm GR
El Te 4.30 0.85 0.57 0.0053 4.51 na 2061 White
E2 Te 4.06 1.03 0.58 0.0098 4.32 na 2067 White
E3 Te 3.85 1.03 0.54 0.0120 4.12 2109 2063 White
E4 Te 3.50 1.03 0.50 0.0145 3.76 2194 2063 White
E5 Te 3.26 1.02 0.51 0.0170 3.52 2247 2062 White
E7 Te 3.12 0.98 0.46 0.0170 3.37 2294 2063 White
E8 Te 2.80 1.05 0.46 0.0180 3.06 2328 2063 White
Jl Te 3.86 2.70 - 0.0090 4.54 nv 2028 White, 8 mm GR, Kish
J2 Te 3.84 2.70 - 0.0118 4.52 nv 2020 White, kish Graphite
J3 Te 3.77 2.73 - 0.0132 4.45 nv 2025 White, 7 mm GR
J4 Te 3.60 2.75 - 0.0140 4.29 2104 2027 White, 5 mm GR
J5 Te 3.40 2.60 - 0.0165 4.05 nv nv White, 3 mm GR
J6 Te 3.21 2.55 - 0.0185 3.85 2156 2020 White, 5 mm GR
J7 Te 3.06 2.70 - 0.0210 3.74 2193 2020 White, 4 mm GR
J8 Te 2.83 2.65 0.0235 3.49 2239 2023 White, 4 mm GR

GE = % C + 1/4 % Si

GR is Gray Rim in millimeters on a 40 mon D cross section

nv - Thermocouple failure
na - no arrest

few more degrees undercooling just as it occurs in binary Fe-C
alloys. 19 This can occur at temperatures above 2110F in
hypereutectic alloys as demonstrated by Olin. 13
The illustrations cited deal mainly with the carbide eutectic. The
validity of the Fe-Gr portion of the diagram has been amply re-
ported. 3,8,14 The few gray fracture cases listed in Table 2 simply
illustrate the need for a Te-coated sample cup and Te addition to
the melt when high silicon alloys are studied. Even so gray rim
appears in the microstructure when over about 1.60% Si is present.
Even in Fe-C alloys gray rim occurs when the Fe-Gr eutectic
begins to solidify at the surface to a depth of 1 to 5 mm. And then
the carbide eutectic begins to grow and completes the solidification
process in a 40-mm cross-section.19 The gray rim nucleates and
grows about 5-1 OF or more above the carbide eutectic and the
transition occurs after austenite is present and the temperature falls.
In high Si near-eutectic irons a completely white fracture and the
calculated carbide eutectic temperature can only be obtained if
graphite nucleation can be completely suppressed. This can be
accomplished by lowering the percent carbon. Once graphite eutec-
tic nucleation occurs, austenite is present and carbide nucleation
can occur after a few more degrees undercooling, even though the

400 AFS Transactions

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 temperature is above the carbide eutectic temperature.I3 Self-anne-
aling or graphitization of such carbides can occur rapidly above
2000F so they are not ordinarily seen in the final microstructure
unless manganese or chromium are high.
Solidification Boundary Shifts
In Fe-C-Si alloys and cast irons the austenite and graphite
liquidus and eutectic temperatures and compositions can be shifted
from those shown projected on the Fe-C diagram (Fig. 1,5). Pro-
cessing operations and melt treatment with graphite inoculants and
carbide promoters can cause substantial phase boundary shifts.
The importance of these boundary shifts is that they lead to changes
in solidification phenomenology.
Melt Processing and the Austenite Liquidus
Superheating temperature, time at temperature, charge materials,
and oxidizing melting environment are examples of melting process
variables that cause phase boundary shifts. Superheating tempera-
tures above 2650F raises the austenite liquidus temperature above
the reference liquidus of Equation 1. Equation 2 is not a reference
or baseline equation, as it represents only a particular standardized
melting condition. Greater effects of raising the liquidus above
Equation 2 are observed when extended holding time at higher
temperature and oxidizing melting conditions are extant.7,16"18
Conversely, the same refence shows that superheating below
2650F, short time at temperature, and reducing conditions can
lower the austenite liquidus even below Equation 3. Other variables
can cause even greater lowering of the liquidus. 8,16 " 19,20 So again
Equation 3 does not represent a reference base. Each melting
process must be individually evaluated to determine how it affects
the liquidus-CE relationship using Equation 1 as the reference
base. The change from Equation I, expressed as liquidus temper-
ature difference at a given CE, or as a CE difference at temperature
is an excellent measure of the effect of the process on the quality
of the iron produced21 The charge material, furnace type and how
it is operated, slags and refractories, also influence the liuqidus
shift.
Certain melt addition agents also shift the liquidus. For example,
when magnesium and cerium are added to a low sulfur iron to
produce ductile iron, the liquidus equation is:
TAL = 2856.2 - 1 7 5 . 2 ( % C +0.25%Si-0.7%Mg-1.25%Ce)
(11)
The percentages of Mg and Ce are usually small, respectively less
than 0.05% and 0.015%, yet the effect on the liquidus is to raise
it significantly.
Tellurium and bismuth additions to the melt in the amount of
1 to 100 PPM or as a mold coating provide an extreme example
of effect on the austenite liquidus. The liquidus is extended into
the hypereutectic range from 21 IF at 4.26 CE following Equation
1 down to below the carbide eutectic temperature (Fig. 5). The
range of shift diminishes at the higher carbon or carbon equivalent
concentrations because the graphitizing effect becomes dominant.
Emphasis has been given to liquidus shift caused by metallurgical
variables. Liquidus shift is accompanied by changes in the solidifi-
cation mode and may lead to casting defects. For example, long
austenite dendrites, few in number across a casting section, result
when the liquidus is raised significantly above the reference curve,
Equation 1. Casting defects may then occur.16"18,21 Excessive de-
pression of the liquidus can also lead to defects.7,16"18 However,
the liquidus can be stabilized near Equation 1 by good metallurgical
practices. Optimum solidification results are then obtained.
AFS Transactions
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Melt Processing and Eutectic Shift
Austenite liquidus shift to higher temperatures usually moves
the Fe-Gr eutectic to higher carbon equivalent. For example, Mg
and Ce in ductile iron shifts the eutectic composition to higher CE
about 4.40-4.45 in the typical ductile iron. 22,23 These elements
also promote the carbide eutectic unless offset by Fe-Si inoculation
after the Mg addition. When the eutectic is shifted to higher CE
valves, undercooling of the Fe-Gr eutectic is likely to occur. This
can be offset by adding Fe-Si as an inoculant, which again shifts
the eutectic back toward lower CE. Melting processes that lower
the austenite liquidus usually raise the Fe-Gr arrest temperature
and shift the eutectic to lower CE.
Conditions that raise the eutectic arrest temperature usually shift
the Fe-Gr eutectic to lower CE while those that depress the arrest
temperature usually shift the eutectic to higher CE and ultimately
to the carbide eutectic CE (Eq. 8). Tellurium and Bi additions of
ppm illustrate this effect. The processing conditions that raise the
austenite liquidus, namely superheating, time at superheating tem-
perature, oxidizing conditions, etc., depress the arrest temperature.
For example, raising the superheating temperature from 2500F to
2850F will cause a maleable base white iron composition of 1.25%
Si and 2.50% C to shift from stable Fe-Gr eutectic solidification
to metastable Fe-Fe3C eutectic solidification. Rapid cooling also
depresses the eutectic arrest temperature while slow cooling raises
it to the Fe-Gr eutectic. Thus it is seen that metallurgical processing
of cast irons determines the extent of departure from the Fe-C-Si
solidification diagram of Figures 1 and 5. The diagram is the
reference base to which the departure from solidification anticipated
from composition and caused by processing may be measured or
predicted. Elements other than silicon can also shift the boundaries;
phosphorus, for example, is expressed in the CE relationship as
CE = %C + VA% Si + Vi %P. Manganese has a negative coefficient.
SUMMARY
A solidification diagram for Fe-C-Si alloys of cast iron composition
has been proposed. Based on cooling curve measurements, it en-
compasses both stable and metastable solidification systems. Com-
position boundaries are expressed by Equations 1-11. These boun-
daries are depicted in Figures 1 and 5 by projections on the Fe-C
binary. The Fe-Gr eutectic temperatures are observed to be in-
creased by silicon percentage, but only when very slow cooling
occurs. Complete solidification of the metastable eutectic requries
sufficient undercooling to prevent graphite nucleation.
REFERENCES
1. ASM Handbook, vol 9. 1973. p. 275-278.
2. R.W. Heine, "The Carbon Equivalent Fe-C-Si Diagram and its Appli-
cation to Cast Irons," AFS Cast Metals Research Journal, Jun 1971,
p. 49.
3. R.W. Heine, "The Fe-C Transformation Diagram Related to the Sol-
idification of Cast Irons," AFS Transactions, 1970, vol 78, p. 187.
4. B. Chicco and W.R. Thorpe, "Experimental Determinatin of the Au-
stenite and Liquid Phase Boundaries of the Fe-C System," AIME
Metallurgical Transactions A, vol. 13A, Jul 1982, p. 1293.
5. R. Ruer and F. Goerens, "Uber die Schmelz-Und Kristal-
lisationsvorgnge bei den Eisen-Kohlenstoffslegierungen"; Ferrum v.
14, p. 161 (1916, 1917).
6. H.C.H. Carpenter and B.F. Keeling, "The Range of Solidification
and the Critical Ranges of Fe-C Alloys,"y/S/, v. 65, p. 224-261,1904.
7. R.W. Heine, "Liquidus and Eutectic Temperature Solidification of
White Cast Irons," AFS Transactions, vol 85, p. 537-544, 1977.
8. R.W. Heine, "Carbon, Silicon, Carbon Equivalent, Solidification and
Thermal Analysis Relationships in Gray and Ductile Cast Iron," AFS
Transactions 1983, vol 81, p. 462.
401
 9. J.G. Humphreys and W.S. Owen; J1S1 vol 198, p. 38-45, 1961.
10. W.S. Owen and B.G. Street; 7/5/, vol 172, p. 15-18, 1972.
I I P . Maries; y/S/, vol 158, p. 433-436, 1948.
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13. K.R. Olen and R.W. Heine, "A Revision of Fe-C-Si System," AFS
Transactions, vol 76, 1968. p. 369-384.
14. L.E. Menawati, R.W. Heine, and C R . Loper, Jr., "Relationship of
Gray Iron Macro- and Microstructure to Cooling Curves," AFS Trans-
actions, vol 78, 1970, 363-373.
15. A. Moore, "Carbon Equivalent of White Cast Iron," AFS Cast Metals
Research Journal vol 8, No. I, p. 15, Mar 1972
16. U. Ekpoom and R.W. Heine, "Thermal Analysis by Differential Heat
Analysis (DHA) of Cast Iron," AFS Transactions, vol 89, 1981, p.
27-38.
17. U. Ekpoom and R.W. Heine, "Metallurgical Processing Variables
Affecting the Solidification of Malleable Base White Cast Iron," AFS
Transactions, vol 89 1981, p. 1-14.
DISCUSSIONS
Question: What is the influence of Si content on the carbide morphology
and properties of the carbide which are produced? (G. Calboreanu, G &
402
AFS Library Copy: Page 12 of 12 Pages, Provided to User for Internal Use and Not Public Redistribution or Resale.
Copyright 2006 American Foundry Society.
18. C. Leon, U. Ekpoom, and R.W. Heine, "Relationship of Casting
Deffects to Solidification of Malleable Base Iron," AFS Transactions,
vol 89, 1981, p. 323-344
19. J.E. Barton and R.W. Heine, "Gray Rim (Inverse Chill) and Mottle
of Malleable Base White Iron," AFS Transactions, vol 85, 1977, p.
371-378.
20. P. Siegman, MS Thesis, 1984, UW-Madison Library.
21. A. Alagarsamy, F.W. Jacobs, G.R. Strong, R.W. Heine, "Car-
bonEquivalent vs. Austenite Liquidus: What is the Correct Relation-
ship for Cast Irons," AFS Transactions, vol 92, 1984, p. 871-880.
22. R.W. Heine, C R . Loper, Jr., and M. Chaudhari, "Characterization
and Interpretation of Ductile Iron Cooling Curves," AFS Transactions,
vol 79, 1971, p. 399-410
23. P.K. Basutkar, R.W. Heine, and C R . Loper, Jr., "Effect of Mg and
Ce Additions on the Fe-C-Si Diagram." AFS Transactions, vol 83,
1973, p. 336-340.
24. R.W. Heine and C R . Loper, Jr., "Our Dendrites and Eutectic Cells
in Gray Iron," AFS Transactions, vol 77, 1969, p. 185.
W. Ind., Grovetown, GA)
Answer: This aspect of the microstructure was not studied.
AFS Transactions