CHINA FOUNDRY

Vol.4 No.1

Eutectic solidification mode of

spheroidal graphite cast iron and
graphitization
*Hideo Nakae1, Sanghoon Jung1 , Takayuki Kitazawa2
(1. Department of Materials Science and Eng., Waseda Univ., Tokyo, Japan; 2. Graduate Student, Department of Materials Science and
Eng.,Waseda Univ., Tokyo, Japan)

Abstract: The shrinkage and chilling tendency of spheroidal graphite (abbreviated SG) cast iron is much greater
than that of the flake graphite cast iron in spite of its higher amount of C and Si contents. Why? The main reason
should be the difference in their graphitization during the eutectic solidification. In this paper, we discuss the
difference in the solidification mechanism of both cast irons for solving these problems using unidirectional
solidification and the cooling curves of the spheroidal graphite cast iron. The eutectic solidification rate of the SG
cast iron is controlled by the diffusion of carbon through the austenite shell, and the final thickness is 1.4 times the
radius of the SG, therefore, the reduction of the SG size, namely, the increase in the number, is the main solution
of these problems.

Keywords: spheroidal graphite cast iron; shrinkage; chilling tendency; eutectic solidification; graphitization
CLC number: TG143.5

Document Code: A

here are many papers which describe the shrinkage and

chilling tendency of SG cast iron [1, 2, 3], nevertheless, no
one has succeeded in explaining the mechanism without mold
wall expansion, i.e., swelling [1, 4]. It is well known that shrinkage
and chilling tendency of SG cast iron is much greater than that
of flake graphite (abbreviated FG) cast iron in spite of its larger
amount of C and Si contents. Why? The main reason should be
the difference in their graphitization during eutectic solidification.
Therefore, we discuss their eutectic solidification modes based
on the unidirectional solidification experiments and thermal
analysis of their solidification based on microstructure
observations.
If we can understand the reasons and develop a prevention
method, it will allow us to produce the sound SG iron castings.
We already discussed the SG formation mechanism using the
unidirectional solidification method for Fe-C, Ni-C and Ni-CMg alloys [5] and discussed the shrinkage formation mechanism
of SG iron castings [6]. SG is directly crystallized from its melt
and is covered with an austenite shell at the onset of the eutectic
solidification [7, 8]. Nevertheless, they did not discuss the increase
in the thickness of the austenite shell during the eutectic
solidification. We think that the thickening is the main factor for
the bottle neck of the graphitization, namely the diffusion of
carbon in the austenite shell.
*Hideo Nakae
Male, born in 1941, Prof. Research interest: solidification
processing etc.
E-mail: h.nakae@waseda.jp

Received date: 2006-10-26; Accepted date: 2006-12-20

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Article ID: 1672-6421(2007)01-034-04

1 Eutectic solidification rate of SG

cast iron
In order to discuss the influence of the solidification rate, R, on
the graphite morphology during the eutectic solidification, we
have to estimate the R of an equiaxed grain, namely, an eutectic
cell. In this research, we used the very slow unidirectional
solidification rate, R, such as from 0.5 mm/h to 2 mm/h for the
Fe-C alloy and from 2 mm/h to 150 mm/h for the Ni-C alloys. If
we consider the R of the plate castings with a 30 mm thickness,
the solidification time must be about 10 to 15 min. Therefore,
the macroscopic R is then 15 mm/15-10 min = 1.0-1.5 mm/min
= 60-90 mm/h. Nevertheless, this R must be the solidification
rate of the columnar ledeburite structure. If we consider the
microscopic solidification rate, R, which is the solidification rate
of each eutectic cell, and assume that the diameter of the eutectic
cell is about 2 mm, the cell is also solidified within 10 to 15 min,
therefore, the R value is 4-6 mm/h. On the other hand, the
diameter of a SG is usually less than 50 m in the SG cast iron.
If we consider the volume fraction ratio between graphite and
austenite, the thickness of the austenite shell is 1.4 times the SG
radius [9], therefore, the thickness is 70 m. The eutectic
solidification rate of the SG iron is then about 0.2 mm/h. This
means that the eutectic solidification rate of the SG iron is much
lower than that of the FG iron, nevertheless, the graphitization is
poorer than that of the FG iron.

2 Sample preparations
For the discussion of the formation mechanism of SG, the S/L
interfacial morphology of the Ni-C alloys was investigated using

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February 2007

the self-sealing unidirectional solidification (abbreviated UDS)

method as shown in Fig. 1. For the experiments, we prepared
Ni-C and Ni-C-Mg alloys. To produce the Ni-C alloys, we used
Ni pellets (Ni>99.97 mass% (abbreviated %)), high purity
graphite (C>99.99%) and Ni-Mg alloy (20%Mg). The chemical
composition of the Ni pellets is as follows: 0.00005%Co,
0.0001%Cu, 0.0015%Fe, 0.0003%S and <0.01%C. For the S
addition to the Ni-C alloy, we prepared the arc melted Ni-S parent
alloy using the Ni pellets and high purity S (S>99.99%).

The 70g Fe-C-Ce sample was melted using an aluminum

crucible in an argon atmosphere, as shown in Fig. 2. The argon
was flowed at the rate of 500 mL/min during the melting, and
the sample was cooled at the rate of 0.6 K/s at 1 200. The
cooling curves were measured with a B-type thermocouple
located at the center of the sample for the discussion of the
solidification mode. The graphite morphology of the samples
was observed by an optical microscope and an SEM.

Fig. 1 Schematics of self-sealing unidirectional

solidification method

Fig. 2 Schematics of atmosphere controlled

furnace for thermal analysis

Ni-C alloys were produced using an Al2O3-lined 2 kg vacuum

induction furnace. The samples were cast into graphite molds
that were 6 mm in diameter and 200 mm in length. The chemical
compositions are shown in Table 1 for the Ni-C alloys.
Table 1 Chemical composition of Ni-C alloys.
C

Ni-C

2.22

<0.005

0.004

Ni-C-Mg

2.22

<0.005

0.004

0.44

Mg

Fe-C-Ce and Fe-C-S samples were prepared from high purity

electrolytic iron, high purity graphite and pure Ce and FeS. The
mother alloy was melted in a alumina lined 6 kg high frequency
induction furnace and cast into ceramic molds that were 20 mm
in diameter and 200 mm in length. The Ce and S contents were
respectively 0.2%Ce and 0.012%S.

3 Experimental procedure
The self-sealing UDS method [10, 11] was conducted by moving a
stage equipped with an electric furnace and the sample was fixed
for preventing vibration, as already shown in Fig. 1. The samples
were melted in high purity Al2O3 (99.9%) tubes. The melts, in
both the upper part and the lower part, were separated by a high
purity Al2O3 partition plate. We adopted this method to prevent
the Mg and Ce from oxidizing and evaporating during the
experiments. The moving speed of the furnace, namely R, was
set in the range from 2 mm/h to 150 mm/h for the Ni-C alloys
and from 0.5 mm/h to 12 mm/h for the Fe-C-0.2%Ce and Fe-C0.012%S alloys. The temperature gradient, G, at the S/L interface
was 3.0 K/mm for the Ni-C samples and that of the Fe-C alloys
was 5.0 K/mm. During the experiments, the samples were
quenched in chilled water in order to observe the graphite
structure and the morphology of the solid and liquid interface.

4 Experimental results
4.1 UDS experiments
The S/L interfacial morphologies in the UDS experiments of the
Ni-C and Ni-C-Mg alloys are shown in Figs. 3 and 4. The
formation of SG in the liquid phase is confirmed in all of these
samples. One of the reasons must be as follows, that there is no
nickel carbide in the Ni-C phase diagram, namely, the quenched
liquid has to solidify to graphite. The graphite is directly
crystallized from the melt and grows into SG [12]. On the contrary,
the existence of SG in the solid phase can be confirmed only in
the Ni-C-Mg alloy solidified at 150 mm/h as shown in Fig. 4. As
can be clearly seen, the solidification mode of this sample
becomes discontinuous in spite of the UDS experiments. This
means that the SG crystallizes directly from the melt and is
enclosed by an austenite shell during the eutectic growth [7,8],
then, the SG is entrapped with the continuously growing FG
phase as shown in the Fig. 4.
NI-C

Fig. 3 Microstructure of UDS sample

for Ni-C alloy (150 mm/h)

The critical transition rate from FG to SG is 150 mm/h for the

Ni-C-Mg alloy and the critical solidification rate for the Ni-C
alloy is 600 mm/h as Lux reported [7]. We then cannot confirm
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CHINA FOUNDRY

Vol.4 No.1

is the main reason why the degree of shrinkage and chilling

tendencies of the SG is greater than that of the FG. Moreover, if
we think about the eutectic solidification mechanism of SG cast
iron, the mode can be schematically shown as in Fig. 7. This
model shows that the thickness of the austenite shell increases
with time, therefore, the easiness of graphitization decreases with
time due to the fact that the diffusion rate of carbon is suppressed
by the increase in the thickness.

Ni-C-Mg

100 m

Fig. 4 Microstructure of UDS sample

for Ni-C-Mg alloy (150 mm/h)

the existence of SG in the solid phase for the Ni-C alloy at the
rate shown in Fig. 3. Since it is believed that the critical rate,
150 mm/h, is amongst other factors, such as the roughening effect
of magnesium on the solid/liquid interfacial morphology, which
affects the continuity of the solid phase. The degree of continuity
needs to be quantified, such as the problem of the nucleation of
the graphite in the liquid.
On the contrary, based on the results of the Fe-C-Ce and Fe-C0.012%S alloys in Fig. 5, we cannot confirm any SG formation in
the solid phase due to the continuous growth mode, nor in the liquid
phase as the quenched liquid solidifies to ledeburite in the alloy.
Fe-C-Ce

Fe-C-0.012S

Fig. 7 Schematic representation of eutectic

solidification mode in SG cast iron

4.2 Cooling curve of SG and FG

We think that the difference in the diffusion of carbon should
affect their solidification process, therefore, the cooling curves
of the eutectic solidification of the Fe-C-Ce alloy were
measured using the atmosphere controlled furnace as shown in
Fig. 2. The cooling curve of the base metal, using a shell mold
with a 30 mm diameter, is shown in Fig. 8. The eutectic
temperature is almost constant at 1 140 and there is only a
slight recalescence due to the high solidification rate of ledeburite.
We confirmed that the microstructure is totally ledeburite.

200 m

Fig. 5 Microstructure of UDS sample for Fe-C-Ce and

Fe-C-0.012S alloy (12 mm/h)

The eutectic solidification modes of the SG and FG irons are

schematically shown in Fig. 6 based on these observations. This
means that the SGs are directly crystallized from the liquid and
covered with austenite at the onset of the eutectic solidification;
therefore, the eutectic growth rate of SG is then controlled by
the diffusion of carbon through the austenite shell. Nevertheless,
the tip of FG protrudes into the liquid [5, 9] and this mode is
identical during the eutectic solidification. This means that the
growth of FG is controlled by the diffusion of carbon in the liquid
and the solid. Therefore, the graphitization rate of carbon, the
growth rate, controlled by the diffusion of carbon, is more difficult
in the SG cast iron than that of the FG cast iron. This difference

Fig. 6 Schematic representation of eutectic

solidification modes in FG and SG cast iron

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Fig. 8 Cooling curve of Fe-C-Ce mother alloy

solidified in a shell mold

The cooling curves of the two re-melted Fe-C-Ce samples are

shown in Fig. 9. There are two solidification modes, namely the
stable system (graphitization) and the quasi-stable system
(ledebrurite). The onset of stable solidification is shown by arrow-1
at 1 135 and that of the quasi-stable solidification is shown by
arrow-2 at 1 115, and the sample temperature rises suddenly
(recalescence) to 1 130 and this temperature remains nearly
constant. The microstructure of these samples, melted in the argon
atmosphere and air, are shown in Fig. 10. There are small numbers
of graphite nodules in both samples, nevertheless, there are many
austenite dendrites and one SG surrounded by the austenite shell
for the sample melted in the air. The existence of many spheroidal
graphite nodules, surrounded by the austenite-shell, can be
confirmed in the sample melted in the argon atmosphere. This
means that the sample melted in air, was oxidized during the
melting and shifted to the hypo eutectic composition.

Research & Development

February 2007

Fig. 9 Cooling curves of Fe-C-Ce alloy solidified

at 0.6 K/s

Air

Ar-3%H2

iron has been discussed, along with a comparison of flake graphite

cast iron, based on the difference in the graphitization during
their eutectic solidifications. The difference in the graphitization,
namely the easiness of the graphitization during the eutectic
solidification, was discussed. The graphitization rate of the
spheroidal graphite cast iron is controlled by the diffusion of
carbon through the austenite shell onto the graphite surface.
Nevertheless, that of the flake graphite cast iron is controlled by
the diffusion not only through the austenite, but also the liquid.
This difference produces the great shrinkage and chilling
tendency of the spheroidal graphite cast iron.
The maximum austenite shell thickness of the spheroidal
graphite is 1.4 times the radius of the graphite, therefore, with a
reduction of the radius, the number of spheroidal graphite nodules
increases, which produces the good graphitization of the
spheroidal graphite cast iron.

References
[1]

200 m

Fig. 10 Influence of atmosphere on the microstructure

of the Fe-C-Ce alloy

Therefore, all of the SGs, crystallized in the liquid, grew during

the eutectic solidification by the diffusion of carbon through the
austenite shell. Nevertheless, the degree of graphitization
becomes difficult with an increase in the austenite shell thickness
during the eutectic solidification and finally the solidification
mode should be changed from stable to the quasi-stable system
due to the large undercooling as shown in Figs. 9 and 10. This
undercooling, caused by the increase in the austenite shell
thickness during the eutectic solidification, produces the great
shrinkage and chilling tendency of the SG cast iron. Therefore,
if we can reduce the thickness, these tendencies can be solved.
The final thickness of the austenite shell at the end of the eutectic
solidification becomes 1.4 times the radius of the SG [9].
Therefore, the reduction of the radius reduces the thickness of
the austenite shell, then the shrinkage and chilling tendency of
the SG cast iron can be reduced by an inoculation technique to
increase the number of SG nodules.

[2]

[3]

[4]
[5]
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[8]
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[10]

[11]

[12]

5 Conclusions
The shrinkage and chilling tendency of spheroidal graphite cast

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