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

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

AFS Transactions 395

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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- present, carbide can precipitate within that austenite because of
sing. Graphite nucleation through the addition of inoculants will the carbon solubility inflection in the solidus curves (Fig. 5). This
result in eutectic arrests over 21 OOF, but only very slow cooling phenomenon was shown to occur experimentally.13 Gray rim on
will raise the arrest to 2140F. Conversely, the addition of a few a white iron interior as in Figure 6 is the result of the metastable
PPM of Te and Bi can depress the arrest until it becomes the carbide eutectic solidification following an initial beginning in the
Fe-Fe3C arrest (Eq. 8) and eutectic solidification is completely stable system. This can occur at temperatures above the carbide
metastable. 7,15,16 However, very slow cooling cannot be employed eutectic temperature once austenite is present from the stable eutec-
to locate the carbide eutectic because the Fe-C-Si alloys will tic reaction.13 This transition from the stable eutectic to the metast-
graphitize unless they are very low in Si and hypoeutectic in com- able eutectic can occur at any temperature between the two eutectic
position. 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
The transition from the Fe-Gr to the Fe-Fe3 eutectic can occur or eutectic carbide structure requires undercooling without any
between the temperature of the former and the latter on Figure 5 graphite nucleation to near the temperature expressed by Equation
once austenite is present when the stable eutectic begins to solidify. 8 for the percent silicon in the alloy. However, the metastable
This is evident from the DTA data for the Fe-C system.4 and Table eutectic may also be undercooled below Equation 8 by metallurgical
7. This phenomenon is revealed in Figure 6, the cross-section of 7,16-18
processing. Equations 6 and 8 thus represent the stable and
a thermal analyses cup sample showing a stable eutectic gray iron metastable eutectic reaction temperatures under specified cooling
rim and a metastable white iron interior. The metastable eutectic conditions; namely very slow cooling for the former and the absence
can follow the stable eutectic reaction with only 5-1 OF further of prior Fe-Gr solidification in the latter. Otherwise both eutectic
undercooling once austenite is present. As soon as austenite is 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 system. However, even with the Te cup and the Te addition the
Fe-Fe3C eutectic with subsequent stable eutectic solidification can iron will not solidify entirely in the metastable system if the carbon
also occur. 8 and silicon percentages are too high, as will be shown.
The first example will follow the carbide eutectic behavior at
Solidification of Cast Irons
0.18% to 0.23% Si, 3.67 to 4.86% C, and % C + VA % Si carbon
The application of the Fe-C-Si solidification diagram for interpret- equivalent carbon equivalent 3.49 to 4.92. Table 2, series I, lists
ing the results of cooling curve measurements will now be illus- the compositions and liquidus and eutectic temperatures. The com-
trated. In the typical foundry cooling curve test, the molten iron bustion method was used to analyze for % C, the atomic absorption
is poured into a core sand cup containing a thermocouple connected method for Te, and the other elements were determined with the
to a recorder. The sample size is such that cooling and solidification spectrometer. The chemical compositions in Table 2 range from
from about 2372F (1200C) to 1922F (1000C) requires about 4-6 hypereutectic to hypoeutectic and cross both the graphite and car-
minutes. Typical cooling curves are shown in Figure 7. The liquidus bide eutectic valleys. Fracture and metallographic analysis shows
and eutectic arrests are then read from the cooling curve. In the that Te treatment caused carbide eutectic solidification at an average
illustrations to be cited, the molten iron was produced in an induc- temperature for 0.21% Si of 2095F. Undercooling of the carbide
tion furnace from a mixture of pig iron, steel, carbon, and ferrosili- eutectic can occur because no graphite is present. Location of the
con as needed. Melting and holding temperature was 2750-2800F. data points on the eutectic valley region of the diagram is shown
Samples were poured at intervals to gain composition ranges as in Figure 8. Figure 8 shows that carbide eutectic temperature (bulk
shown in Table 2. Sample cups may have interior surfaces coated arrest) is nearly constant over the % C studied at 0.18-0.23% Si.
with either an A1 2 0 3 or a tellurium powder wash. The latter is Further, kish graphite appears in the microstructure when the
used to cause the metal to freeze in the carbide eutectic mode. graphite liquidus or the extended austenite carbon equivalent
The cups then can be used to follow either the graphite or the liquidus is exceeded. This is expected from the diagram boundaries.
carbide eutectic systems. Tellurium in the amount of 0.005% to The carbon equivalent-liquidus temperature points in Figure 8 fall
0.02% can also be added to the iron to better follow the carbide somewhat above the liquidus temperature curve, Equation 1. This

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2300 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
2200 ' a DO. with Gray Rim

fa

_ ^ v _ .
o

3
2100
fa

fa
EH

2000

Carbide
1900 -

1.0 2.0 3.0 4.0 5.0 6.0


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 Figure 10 reports a similar analysis for series El-8 of 0.98-1.05%
phenomenon which will be discussed later. 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
The next example will follow the carbide eutectic behavior in occurs at 2064F vs. 2073F and at 4.47 CE vs. 4.52 calculated,
alloys of 2.24-2.28% Si 2.69-4.08% C, and 3.25-4.65 carbon, respectively. In this case, there is no gray rim and the carbide
series H in Table 2. Because of the high percent silicon, tellurium eutectic measured is 9F below the calculated value.
was added to the iron to cause it to solidify carbidic. Figure 9 Data for series J in Table 2 are plotted in Figure 11. The carbide
shows the austenite liquidus temperature, TAL vs. CE first; point eutectic temperature varied from 2020 to 2028F and silicon
A for sample H5-1. The same liquidus is also plotted vs. the varied from 2.55-2.70%. Calculated carbide eutectic temperature
analyzed percentage carbon; point C, Figure 9. Then the % C is at that percent silicon is 2005 to 2010F. Gray rim has caused the
plotted on the projected 2.25% Si curve at the liquidus temperature; measured carbide eutectic to be significantly above the calculated
point B, Figure 9. Points B and C should superimpose if there is carbide eutectic.
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, In Figures 8-11, agreement of the austenite liquidus temperatures
H7-1, and H7-2 are seen to overlap closely as expected. Regarding with both the percent carbon and carbon equivalent values appears
sample H3-2, undercooling can occur readily since it is actually to be good. The 0.2% Si and 1.0% silicon alloys, series I and E,
a hypereutetic composition. Both the stable and metastable eutec- reveal carbide eutectic undercooling below the calculated temper-
tics are also shown in Figure 7. Without the Te cup, Hl-1 and ature. Control of the melting process can produce either the calcu-
H2-1 cast gray, while the carbide eutectic develops with the Te lated eutectic or undercooled eutectic as long as no graphite is
coated cup, HI-2 and H2-2. The average CET was measured as
present. 7.16-18 The 2.25% Si and 2.70% alloys, series H and J,
2036F at 4.68 CE compared with the values of 2028F and 4.72 had measured carbide eutectic temperatures somewhat above the
CE calculated from Equations 8 and 9. However, the presence of calculated values. They also had kish and/or gray rim structures.
gray rim is the reason the carbide eutectic temperature is above
This illustrates the principle that once the graphite eutectic austenite
the calculated value by 8F.
is present, the transition to the carbide eutectic can occur with a

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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 begins to solidify at the surface to a depth of 1 to 5 mm. And then
alloys. 19 This can occur at temperatures above 2110F in the carbide eutectic begins to grow and completes the solidification
hypereutectic alloys as demonstrated by Olin. 13 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
The illustrations cited deal mainly with the carbide eutectic. The transition occurs after austenite is present and the temperature falls.
validity of the Fe-Gr portion of the diagram has been amply re- In high Si near-eutectic irons a completely white fracture and the
ported. 3,8,14 The few gray fracture cases listed in Table 2 simply calculated carbide eutectic temperature can only be obtained if
illustrate the need for a Te-coated sample cup and Te addition to graphite nucleation can be completely suppressed. This can be
the melt when high silicon alloys are studied. Even so gray rim accomplished by lowering the percent carbon. Once graphite eutec-
appears in the microstructure when over about 1.60% Si is present. tic nucleation occurs, austenite is present and carbide nucleation
Even in Fe-C alloys gray rim occurs when the Fe-Gr eutectic 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- Melt Processing and Eutectic Shift
aling or graphitization of such carbides can occur rapidly above Austenite liquidus shift to higher temperatures usually moves
2000F so they are not ordinarily seen in the final microstructure the Fe-Gr eutectic to higher carbon equivalent. For example, Mg
unless manganese or chromium are high. and Ce in ductile iron shifts the eutectic composition to higher CE
Solidification Boundary Shifts 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
In Fe-C-Si alloys and cast irons the austenite and graphite after the Mg addition. When the eutectic is shifted to higher CE
liquidus and eutectic temperatures and compositions can be shifted valves, undercooling of the Fe-Gr eutectic is likely to occur. This
from those shown projected on the Fe-C diagram (Fig. 1,5). Pro- can be offset by adding Fe-Si as an inoculant, which again shifts
cessing operations and melt treatment with graphite inoculants and the eutectic back toward lower CE. Melting processes that lower
carbide promoters can cause substantial phase boundary shifts. the austenite liquidus usually raise the Fe-Gr arrest temperature
The importance of these boundary shifts is that they lead to changes and shift the eutectic to lower CE.
in solidification phenomenology.
Conditions that raise the eutectic arrest temperature usually shift
Melt Processing and the Austenite Liquidus the Fe-Gr eutectic to lower CE while those that depress the arrest
temperature usually shift the eutectic to higher CE and ultimately
Superheating temperature, time at temperature, charge materials,
to the carbide eutectic CE (Eq. 8). Tellurium and Bi additions of
and oxidizing melting environment are examples of melting process
ppm illustrate this effect. The processing conditions that raise the
variables that cause phase boundary shifts. Superheating tempera-
austenite liquidus, namely superheating, time at superheating tem-
tures above 2650F raises the austenite liquidus temperature above
perature, oxidizing conditions, etc., depress the arrest temperature.
the reference liquidus of Equation 1. Equation 2 is not a reference
For example, raising the superheating temperature from 2500F to
or baseline equation, as it represents only a particular standardized
2850F will cause a maleable base white iron composition of 1.25%
melting condition. Greater effects of raising the liquidus above
Si and 2.50% C to shift from stable Fe-Gr eutectic solidification
Equation 2 are observed when extended holding time at higher
to metastable Fe-Fe3C eutectic solidification. Rapid cooling also
temperature and oxidizing melting conditions are extant.7,16"18
depresses the eutectic arrest temperature while slow cooling raises
Conversely, the same refence shows that superheating below
it to the Fe-Gr eutectic. Thus it is seen that metallurgical processing
2650F, short time at temperature, and reducing conditions can
of cast irons determines the extent of departure from the Fe-C-Si
lower the austenite liquidus even below Equation 3. Other variables
solidification diagram of Figures 1 and 5. The diagram is the
can cause even greater lowering of the liquidus. 8,16 " 19,20 So again
reference base to which the departure from solidification anticipated
Equation 3 does not represent a reference base. Each melting
from composition and caused by processing may be measured or
process must be individually evaluated to determine how it affects
predicted. Elements other than silicon can also shift the boundaries;
the liquidus-CE relationship using Equation 1 as the reference
phosphorus, for example, is expressed in the CE relationship as
base. The change from Equation I, expressed as liquidus temper-
CE = %C + VA% Si + Vi %P. Manganese has a negative coefficient.
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 SUMMARY
of the iron produced21 The charge material, furnace type and how
A solidification diagram for Fe-C-Si alloys of cast iron composition
it is operated, slags and refractories, also influence the liuqidus
has been proposed. Based on cooling curve measurements, it en-
shift.
compasses both stable and metastable solidification systems. Com-
Certain melt addition agents also shift the liquidus. For example, position boundaries are expressed by Equations 1-11. These boun-
when magnesium and cerium are added to a low sulfur iron to daries are depicted in Figures 1 and 5 by projections on the Fe-C
produce ductile iron, the liquidus equation is: binary. The Fe-Gr eutectic temperatures are observed to be in-
creased by silicon percentage, but only when very slow cooling
TAL = 2856.2 - 1 7 5 . 2 ( % C +0.25%Si-0.7%Mg-1.25%Ce) occurs. Complete solidification of the metastable eutectic requries
(11) sufficient undercooling to prevent graphite nucleation.
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
REFERENCES
it significantly. 1. ASM Handbook, vol 9. 1973. p. 275-278.
2. R.W. Heine, "The Carbon Equivalent Fe-C-Si Diagram and its Appli-
Tellurium and bismuth additions to the melt in the amount of
cation to Cast Irons," AFS Cast Metals Research Journal, Jun 1971,
1 to 100 PPM or as a mold coating provide an extreme example
p. 49.
of effect on the austenite liquidus. The liquidus is extended into
3. R.W. Heine, "The Fe-C Transformation Diagram Related to the Sol-
the hypereutectic range from 21 IF at 4.26 CE following Equation
1 down to below the carbide eutectic temperature (Fig. 5). The idification of Cast Irons," AFS Transactions, 1970, vol 78, p. 187.
range of shift diminishes at the higher carbon or carbon equivalent 4. B. Chicco and W.R. Thorpe, "Experimental Determinatin of the Au-
concentrations because the graphitizing effect becomes dominant. stenite and Liquid Phase Boundaries of the Fe-C System," AIME
Metallurgical Transactions A, vol. 13A, Jul 1982, p. 1293.
Emphasis has been given to liquidus shift caused by metallurgical 5. R. Ruer and F. Goerens, "Uber die Schmelz-Und Kristal-
variables. Liquidus shift is accompanied by changes in the solidifi- lisationsvorgnge bei den Eisen-Kohlenstoffslegierungen"; Ferrum v.
cation mode and may lead to casting defects. For example, long 14, p. 161 (1916, 1917).
6. H.C.H. Carpenter and B.F. Keeling, "The Range of Solidification
austenite dendrites, few in number across a casting section, result
and the Critical Ranges of Fe-C Alloys,"y/S/, v. 65, p. 224-261,1904.
when the liquidus is raised significantly above the reference curve,
7. R.W. Heine, "Liquidus and Eutectic Temperature Solidification of
Equation 1. Casting defects may then occur.16"18,21 Excessive de- White Cast Irons," AFS Transactions, vol 85, p. 537-544, 1977.
pression of the liquidus can also lead to defects.7,16"18 However, 8. R.W. Heine, "Carbon, Silicon, Carbon Equivalent, Solidification and
the liquidus can be stabilized near Equation 1 by good metallurgical Thermal Analysis Relationships in Gray and Ductile Cast Iron," AFS
practices. Optimum solidification results are then obtained. Transactions 1983, vol 81, p. 462.

AFS Transactions 401

AFS Library Copy: Page 11 of 12 Pages, Provided to User for Internal Use and Not Public Redistribution or Resale.
Copyright 2006 American Foundry Society.
9. J.G. Humphreys and W.S. Owen; J1S1 vol 198, p. 38-45, 1961. 18. C. Leon, U. Ekpoom, and R.W. Heine, "Relationship of Casting
10. W.S. Owen and B.G. Street; 7/5/, vol 172, p. 15-18, 1972. Deffects to Solidification of Malleable Base Iron," AFS Transactions,
I I P . Maries; y/S/, vol 158, p. 433-436, 1948. vol 89, 1981, p. 323-344
12. J.E. Hurst and R. Riley; JIS1 vol 149, p. 213, 219, 1944. 19. J.E. Barton and R.W. Heine, "Gray Rim (Inverse Chill) and Mottle
13. K.R. Olen and R.W. Heine, "A Revision of Fe-C-Si System," AFS of Malleable Base White Iron," AFS Transactions, vol 85, 1977, p.
Transactions, vol 76, 1968. p. 369-384. 371-378.
14. L.E. Menawati, R.W. Heine, and C R . Loper, Jr., "Relationship of 20. P. Siegman, MS Thesis, 1984, UW-Madison Library.
Gray Iron Macro- and Microstructure to Cooling Curves," AFS Trans- 21. A. Alagarsamy, F.W. Jacobs, G.R. Strong, R.W. Heine, "Car-
actions, vol 78, 1970, 363-373. bonEquivalent vs. Austenite Liquidus: What is the Correct Relation-
15. A. Moore, "Carbon Equivalent of White Cast Iron," AFS Cast Metals ship for Cast Irons," AFS Transactions, vol 92, 1984, p. 871-880.
Research Journal vol 8, No. I, p. 15, Mar 1972 22. R.W. Heine, C R . Loper, Jr., and M. Chaudhari, "Characterization
16. U. Ekpoom and R.W. Heine, "Thermal Analysis by Differential Heat and Interpretation of Ductile Iron Cooling Curves," AFS Transactions,
Analysis (DHA) of Cast Iron," AFS Transactions, vol 89, 1981, p. vol 79, 1971, p. 399-410
27-38. 23. P.K. Basutkar, R.W. Heine, and C R . Loper, Jr., "Effect of Mg and
17. U. Ekpoom and R.W. Heine, "Metallurgical Processing Variables Ce Additions on the Fe-C-Si Diagram." AFS Transactions, vol 83,
Affecting the Solidification of Malleable Base White Cast Iron," AFS 1973, p. 336-340.
Transactions, vol 89 1981, p. 1-14. 24. R.W. Heine and C R . Loper, Jr., "Our Dendrites and Eutectic Cells
in Gray Iron," AFS Transactions, vol 77, 1969, p. 185.

DISCUSSIONS
Question: What is the influence of Si content on the carbide morphology W. Ind., Grovetown, GA)
and properties of the carbide which are produced? (G. Calboreanu, G & Answer: This aspect of the microstructure was not studied.

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