Materials Transactions, Vol. 52, No. 12 (2011) pp.

2184 to 2188
#2011 Japan Foundry Engineering Society

Cooling Rate and Graphite Structure of Final Eutectic

Solidification Part in Cast Iron*
Hirokazu Kawashima1 , Katutoshi Sigeno1 , Masaki Kusubae1 and Kazuhiro Tachibana2
1
Matsubara Co. Ltd., Seki 501-3924, Japan
2
Graduate School of Science and Engineering, Yamagata University, Yonezawa 992-8510, Japan

A CE meter cup was modeled using a casting simulation software and cooling curves at different points of the casting model were
calculated. In setting temp-solid fraction parameters, an Fe-C-Si ternary equilibrium phase diagram was used with a substantive temperature
range in the equilibrium phases so that the -Fe+G+L phases can be considered. In studying the calculated cooling curve, a rapid temperature
drop was found in the cooling curve in the final solidification period. This rapid cooling occurred during eutectic solidification. The structure
formed by the rapid cooling was found as chill or D-type graphite because the liquid phase is cooled rapidly to below the eutectic temperature.
This rapid cooling may be one of the causes of D-type graphite near the final solidification part of thick iron castings.
[doi:10.2320/matertrans.F-M2011829]

(Received January 25, 2011; Accepted September 7, 2011; Published November 25, 2011)
Keywords: computer aided engineering (CAE), cast iron, eutectic reaction, inverse chill, simulation, solidification

1. Introduction cup for cooling curve measurement in order to understand

In iron castings, the chilled iron structure called the inverse
chill can be formed at deep inner regions of thick castings.
Although obvious inverse chills have rarely been seen in
modern castings because of the improvement of the inocu-
lation technology, the microstructures that seem to be formed
by rapid cooling are often observed at the final solidification
part of the casting, for example, the D-type graphite.
The various causes of the inverse chill have been suggested
as follows:1)
(1) Carbide stabilizing elements segregate at the center of
thick castings,
(2) The inoculation is insufficient,
(3) And/or the cooling rate is particularly fast at the center
of the casting.
However, these suggestions are not enough to explain
sufficiently the reasons why the inverse chill is formed only
at the thick parts of the casting.
It is widely known that the rapid temperature drop can
be found at the point just after the end of the eutectic
solidification when primary differentiation is conducted on
a cooling curve recorded by a CE meter. However the
reasonable cause of the rapid temperature drop has not been
reported.
On the other hand, the conventional cooling curve
measured with a CE cup does not show the real cooling
curve because the temperature is measured through an outer
silica tube (4 mm, 1 mm-thick) for a thermocouple. There-
fore, it is difficult to measure the temperature with the CE
cup during the eutectic solidification.
We have simulated the cooling curve in the CE cup by
numerical analysis software, in order to see whether or
not the rapid temperature drop can be found at the final
solidification part just like the way it appears on the
conventional cooling curves with the actual measurement.
Also, we have allocated certain points in the simulated CE
*This Paper was Originally Published in Japanese in J. JFS 83 (2011) 3–6.
the possibilities of the formations of the inverse chills and
D-type graphite.
2. Experimental Procedures
2.1 Actual measurement
The molten iron was poured from a cupola into the
forehearth, and held for ten minutes. Then, the molten iron
with 0.05% amount of carbon inoculation was transferred to a
ladle. After 30 s from the inoculating, the molten iron was
poured into a CE cup connected with the digital recorder,
and the cooling curves were recorded until the end of the
solidification. The CE cup for this experiment was not the
tellurium-added type which is commonly used for measure-
ment of the cementite eutectic temperature, but the type
without any additives in order to record a cooling curve of
the practical cast iron. The temperatures were recorded at
intervals of 1/2 s for 300 s just after the pouring in order to
obtain the cooling curve until the post-solidification period.
Figure 1 shows the shape of the CE cup and the measuring
points. Table 1 shows the chemical composition of the cast
iron. Figure 2 shows the result of the actual measurement
and the curve calculated by primary differentiation.
2.2 Setting latent heat emission pattern
In order to find the appropriate pattern of the latent heat
emission, the temperatures at the thermocouple in the silica
tube just like a real CE cup were calculated. The latent
heat emission patterns were determined by the relationship
between temperature and solid fraction by using simulation
software. The definition of the transformation temperatures
were based on the result of the actual measurement and the
parameters were set as follows:
(1) The liquidus temperature (TL ) was assumed to be
1468 K measured by the actual measurement.
(2) The eutectic solidification start temperature (TES ) was
assumed to be 1418 K measured as the recalescence
temperature.
 Cooling Rate and Graphite Structure of Final Eutectic Solidification Part in Cast Iron 2185

Table 2 Material properties.

A P4 Thermal Specific Latent
Density
P9 Material conductivity heat heat
P3 (g/cm3 )
P10 (cal/cmSdeg) (cal/gdeg) (cal/g)
P1
Casting FC250 6.4 0.05 0.17 50
P8 CE-cup Shell mold 1.7 0.0015 0.2 —
P7
P6 Quartz glass Silica grass 2.21 0.0032 0.17 —
P5

Table 3 Temp-solid fraction parameters.

TL TES TEE
A
Sect. A−A (a) TE ¼ 1 K
Temp, K 1486 1418 1417
Solid fraction 0.00 0.33 1.00
Fig. 1 Shape of CE-cup.
Temp, K 1486 1418 1408
(b) TE ¼ 10 K
Solid fraction 0.00 0.33 1.00
Table 1 Chemical composition of cast iron (mass%). Temp, K 1486 1418 1403
(c) TE ¼ 15 K
C Si Mn P S Solid fraction 0.00 0.33 1.00

3.32 2.05 0.739 0.051 0.087

iron, the CE cup and the silica tube used for this experiment.
1573
(1300) 1.0 Table 3 shows the parameters for the relationship between
Measurement
Differentiation temperature and solid fraction. The results of the calculation
1473
are shown in Fig. 3 (a), (b) and (c).
(1200) 0.0

2.3 Cooling curves at each measuring point

Cooling rate,K/s
Temp,K(°C)

1373 As shown in Fig. 1, nine measuring points were set in the

(1100) −1.0
following order:
(1) On the top of the silica tube (Point 1),
1273 (2) At the final solidification part, which is 4 mm above
(1000) −2.0
Point 1 (Point 3),
(3) On the same level of Point 3, at seven points from
1173
(900) −3.0 Point 3 to the casting surface with 2 mm intervals
0 50 100 150 200 250 300 (Point 4–10).
Time,s
The cooling curves at each point were calculated individu-
Fig. 2 Cooling curve and differentiation curve for measured. ally. Figure 4 shows the cooling curves at each point.

2.4 Observation of the microstructures

As to the eutectic solidification end temperature (TEE ), three The graphite structure and the matrix structure of the cast
different parameters were set to vary the eutectic temperature irons were observed in order to estimate the solidification
range (TE ) as follows: process and the cooling rate.
(a) Based on the Fe-C binary equilibrium phase diagram,
TEE was assumed to be 1417 K because the eutectic 3. Results
temperature is constant. Therefore, the minimum
temperature difference was defined by subtracting TEE 3.1 Actual measurement
from TES , i.e., TE : TES  TEE ¼ 1 K, As shown in Fig. 2, the rapid temperature drop was
(b) Based on the Fe-C-Si ternary equilibrium phase measured in the final period of the eutectic solidification, as
diagram,2) TEE was assumed to be 1408 K because well as the common case of cast iron cooling. The range of
Silicon content is taken into account on the eutectic the rapid temperature drop was from about 1393 K (1120 C)
temperature range, i.e., TE : TES  TEE ¼ 10 K, to about 1360 K (1087 C). The cooling rate during the rapid
(c) Based on the multiple equilibrium phase diagram, TEE temperature drop was about 3 K/s.
was assumed to be 1403 K because contents of
phosphorus, manganese, sulfur, etc. are also taken into 3.2 Comparison of latent heat emission patterns
account on the eutectic temperature range, i.e., TE : Comparisons between the cooling curves calculated by the
TES  TEE ¼ 15 K. three different parameters and the measured cooling curve
ADSTEFAN Ver.11, a casting simulation software, was used are shown in Fig. 3. The cooling curves of TE ¼ 10 K
for the calculation of molten metal flow and the temperature (Fig. 3(b)) and TE ¼ 15 K (Fig. 3(c)) obviously agreed
during solidification. Table 2 shows the properties of the cast with the measured cooling curve rather than the cooling
2186 H. Kawashima, K. Sigeno, M. Kusubae and K. Tachibana

Simulation
1533 Measurement
Differentiation(Simulation)
(1260) 1.0
Differentiation(Measurement)

1493
(1220) 0.0

Cooling rate,K/s
Temp, K(°C)

1453
(1180) −1.0

1413
(1140) −2.0

1373
(1100) −3.0
0 40 80 120 160 0 40 80 120 160 0 40 80 120 160
Time,s Time,s Time,s

(a) ΔTE= 1K (b) ΔTE = 10K (c) ΔTE = 15K

Fig. 3 Cooling curves and the first differentiation curves for measured and calculated values.

1493 Solid fraction

(1220)
1473 0 0.2 0.4 0.6 0.8 1.0
P3 (1200)
1473 P4
(1200) P5 TL
P6
1453 P7
(1180) P8
P9 1453
Temp,K(°C)

1433
P10 (1180)
(1160)
P3
P7
P3 Solidus ratio
1413
(1140)
Primary- γ
Temp,K(°C)

1433
1393 (1160)
(1120) P10

1373
(1100)
0 20 40 60 80 100 120 140 160 180 T ES
Time,s 1413 A type graphite
(1140)
D type graphite
Fig. 4 Calculated cooling curves of each point (P3P10). T EE

1393
curve of TE ¼ 1 K (Fig. 3(a)), especially on the final (1120)
20 40 60 80 100 120 140 160 180
solidification period. Therefore, it is clear that there is a Time,s
temperature range of the eutectic solidification. When
comparing the temperature ranges of TE ¼ 10 K and Fig. 5 The cooling curve of final solidification part and solid fraction.
TE ¼ 15 K, the temperature ranges are almost the same.
Considering all the information, we decided to use the
cooling curve of TE ¼ 10 K for further analysis. 3.3 Analyzing cooling curves for measuring points
The rapid temperature drop after the eutectic solidification Figure 4 shows that the most outer point (Point 10) took a
was well simulated by the numerical analysis for this steady cooling rate in the eutectic solidification period while
experiment although the recalescence at the graphite eutectic the temperatures at the more inner points were kept for the
period was not simulated. The rapid temperature drop can longer time at 1418 K (1145 C) before the rapid temperature
be commonly observed on the cooling curves with small drop. In the final solidification period in the simulated
undercooling by excessive inoculation or with solidification cooling curve, the rapid temperature drop of about 30 K
into white iron. Therefore, we have concluded that the occurred as well as the measured cooling curve.
calculation of the rapid temperature drop would not be Figure 5 shows the cooling curve and the solid fraction
affected by the nonexistence of the undercooling phenom- curve for the final solidification part (Point 3) during the
enon. solidification period. As shown in Fig. 5, it is clear that the
 Cooling Rate and Graphite Structure of Final Eutectic Solidification Part in Cast Iron
Point 3
Fig. 6 Graphite shape on Point 3, 7 and 10.
Fig. 7 Graphite shape of Point 3.
rapid temperature drop in the final solidification period
occurred even at the time when liquid phase remained inside
the castings.
3.4 Structure analysis
Figure 6 shows the graphite structures on the final solid-
ification part (Point 3), the most outer point (Point 10) and
the point in the middle of them (Point 7). On Point 3,
moderately-cooled structure (i.e., A-type graphite) and
rapidly-cooled structure (i.e., D-type graphite) appeared
together in mottled structure. Figure 7 shows the image of
-Fe+G+L.
the mottled structure by a low magnification. While Point 3
had some D-type graphite, Point 7 only had the A-type
graphite. Even on the most outer point (Point 10), its main
structure was the A-type graphite with the B-type graphite
rather than the D-type graphite. The matrix structure of the
D-type graphite area on the final solidification part was
pearlite structure as shown in Fig. 8.
2187
200 μ m/div
Point 7 Point 10
Fig. 8 D-type graphite matrix structure.
4. Analysis
The rapid temperature drops detected both on the
measured and the simulated cooling curves for Point 1 were
identified as the temperature drop during the eutectic
solidification in the final solidification period. By calculating
the cooling curves of the cast iron based on the temperature
range of 10 K in the eutectic solidification, it has become
clear that the temperature drop actually started not after but
during the solidification when the molten iron partially
remained in the phase of
As the result of the graphite structure observations at the
final solidification part, the mottled structure coexists with
the A-type and the D-type graphite. It is considered that the
mottled structure is an evidence to from the chilled structure
by the rapid temperature drop in the liquid/solid phase. The
cooling rate can be assumed to be faster than the general
cooling rate for thin castings due to the evidence that the
2188 H. Kawashima, K. Sigeno, M. Kusubae and K. Tachibana
matrix structure around the D-type graphite had pearlite
structure without the transformation to be ferrite.
5. Conclusions
According to the cooling rate of both the measured cooling
curve and the simulated cooling curve of cast iron, and
microstructure observations, the following conclusions have
been obtained:
(1) In analyzing the solidification process of cast iron, it is
recommended to use the model that has a certain temperature
range (approx. of 10 K) in the eutectic solidification in
accordance with the Fe-C-Si ternary equilibrium phase
diagram.
(2) The above-mentioned model enables us to confirm that
the rapid temperature drop on the actual measurement occurs
during the eutectic solidification.
(3) The matrix structure around the D-type graphite in the
final solidification part shows pearlite structure. This fact
supports the above-mentioned rapid cooling theory.
REFERENCES
1) Japan Foundry Engineering Society: Casting Defects and Their
Remedies, (Japan Foundry Engineering Society, Tokyo, 2007) p. 171.
2) American Society for Metals: Metals Handbook —Properties and
Selection: Iron and Steels—, 9th Ed. Vol. 1, (American Society of
Metals, Metals Park, 1978) p. 4.