CHINA FOUNDRY Vol.8 No.

Influence of Si, Ce, Sb and Sn on

chunky graphite formation
*Hideo Nakae1, Masayuki Fukami2, Takayuki Kitazawa3 and Ying Zou4
(1. Lab. for Mater. Sci. and Tech., Waseda Univ., Tokyo,Japan; 2. JFE Steel Corp., Japan; 3. Nippon Steel Corp., Japan; 4. Appl.
Mech. and Eng., Waseda Univ., Tokyo,Japan)

Abstract: The thirteen mother alloys, C%+1/3Si% = 4.45%, differing in their Si, Ce, Sb and Sn contents, were
prepared. Seventy grams of these alloys was remelted in a high purity alumina crucible at 1,450ºC under an Ar
atmosphere, and then cooled at 30 K/min for obtaining their cooling curves. Their graphite morphologies were
observed using an optical microscope and an SEM. Their three-dimensional graphite shapes were observed by the
SEM using the samples whose matrices were etched off with an acid-aqua solution, to confirm the chunky graphite.
For discussing the influence of the Si and Ce contents on the chunky graphite formation, two experiments
were carried out. In the first one, the Si contents were changed from 0 to 4% in the 0.15%Ce alloys, and for the
second one, the 3.5%Si and 4%Si samples that differed in the Ce contents of 0.1 and 0.2% were used. In the third
experiment, the influence of Sb and Sn on the chunky graphite formation was investigated by using the 4%Si and
0.1%Ce samples. The results showed that with the increase of the Si content, the volume fraction of the chunky
graphite increases, while the volume fraction of the ledeburite decreases, and the chunky graphite volume fraction
in the 0.2%Ce samples is higher than that of the 0.1%Ce samples. The effect of the Sb and Sn additions on the
prevention of chunky graphite formation cannot be confirmed due to their high Si contents. Therefore, further studies
will be needed in this field.

Key words: chunky graphite; spheroidal graphite; graphite morphology; solidification of cast iron
CLC number: TG143.5 Document code: A Article ID: 1672-6421(2011)01-096-05

S pheroidal graphite (abbreviated SG) cast iron is widely

used in industry due to its excellent mechanical properties
and good castability. Nevertheless, it is well-known that the
graphite morphology changes from SG to chunky graphite
(abbreviated CHG) in heavy SG castings [1,2]. The motivation
of this study is to elucidate the CHG formation mechanism.
There are many reports that have described the alloying
elements, such as Si, Ni, Ce and Ca, as the CHG formation
elements and Sn, Sb and Te as the preventing elements[1-3].
The Si and Ni are graphitizing elements, the Ca and Ce are the
spheroidizing elements and the Sn, Sb and Te are the elements
that prevent spheroidizing. It is well known that the Sb and
Te can neutralize the influence of Ce on the CHG formation.
Tsumura [4] reported the influence of the Sb addition on the Ce-
treated SG iron. The influence of Ca was reported by Church [5].
*Hideo Nakae
Male, born in 1941, Dr. Eng., Professor. He was a senior researcher in
Mechanical Eng. Res. Lab. Hitachi Ltd. from 1971 to 1983, and Director of
KAGAMI Memorial Lab. for Materials Sci. and Tech., Waseda Univ. from
2003 to 2006. He has nearly 20 publications. His research interests mainly
focus on the interface between solid and liquid and cast iron. He received
six Best Paper Awards from Japan Foundry Eng., Soc. and Japan Institute
of Metals. He was Past President of Japan Foundry Engineering Society.
E-mail: h.nakae@waseda.jp
Received: 2010-07-06; Accepted: 2010-08-20
Nevertheless, nobody has yet explained the formation
mechanism of the CHG, therefore, we prepared Fe-C-Si-Ce
samples for discussing the CHG formation mechanism using
constant cooling rate experiments [3].
1 Experimental procedure
We prepared eight kinds of Fe-C-Si-Ce alloys with different
Si and Ce contents for discussing the influence of Si and Ce on
the CHG formation. Another five samples, using the 4 mass%
(abbreviated %) Si and 0.1%Ce alloys, the Sb-samples and Sn-
samples, were prepared in order to study the influence of Sb
and Sn on the CHG formation. To produce these samples, we
used electrolytic iron, high purity graphite (>99.99%), pure Si
(>99.999%), pure Ce (>99.9%), pure Sb (>99.9%) and pure Sn
(>99.9%). These alloys were melted using an Al2O3-lined 7 kg
high-frequency induction furnace under flowing Ar. The melts
were cast into ceramic molds that were 15 mm in diameter
and 300 mm in length. The chemical compositions of these
samples are shown in Table 1. Their sulfur contents were less
than 0.005%.
Seventy grams of these samples was remelted in a high
purity aluminum crucible under an Ar atmosphere at 1,450℃
using an electric furnace, as shown in Fig. 1, and the samples
were then cooled at the rate of 30 K/min at 1,200℃. The

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February 2011
Table 1: Chemical composition of samples (mass%)
Sample No. C Si Ce Sb Sn
0 Si 4.40 ＜0.005 0.16 - -
2 Si 3.79 2.00 0.16 - -
3 Si 3.50 3.00 0.17 - -
4 Si 3.18 3.98 0.17 - -
3.5Si-0.15Ce 3.49 3.58 0.12 - -
3.5Si-0.25Ce 3.48 3.58 0.21 - -
4Si-0.15Ce 3.31 4.08 0.13 - -
4Si-0.25Ce 3.37 4.10 0.24 - -
4Si-0.1Ce 3.49 3.93 0.09 - -
0.02Sb 3.23 4.11 0.08 0.02 -
0.14Sb 3.24 4.06 0.10 0.14 -
0.05Sn 3.25 4.19 0.11 - 0.05
0.10Sn 3.26 4.10 0.10 - 0.10
Fig. 1: Schematic of constant cooling rate experiment
SG: 5%, CHG: 0%, Led: 95% SG: 9%, CHG: 69%, Led: 22%
Fig. 2: Influence of Si on CHG graphite formation
Fig. 3: Three dimensional graphite shapes of 2% to 4%Si samples
The 69th WFC Paper
cooling curves were measured by a B-type thermocouple
located at the center of the sample in order to discuss the
solidification mechanism. All of the graphite morphologies
were observed using an optical microscope and a SEM. Their
three-dimensional graphite shapes were observed by the SEM
using the samples whose matrices were etched off with a
hydrochloric aqua solution.
The volume fractions of the CHG portion were measured
using thirty microstructure photos of fifty magnification. The
cooling curves were differentiated to determine the transition
points, namely the onset and end points of the SG and CHG
formations.
2 Results and discussion
2.1 Influence of Si on CHG formation
The influences of the Si contents on the graphite morphology,
observed by an optical microscope and their fractions in each
graphite portion, are shown in Fig. 2. In this figure, SG, CHG
and Led mean the volume fractions of SG portion, CHG
portion and ledeburite portion, respectively. There is no CHG
and 95% of the matrix is ledeburite in the 0 Si sample and
the volume fraction of CHG in the 4 Si sample is 92%. The
CHG fraction increases with the increasing of the Si contents
and that of the ledeburite decreases. Their three-dimensional
shapes of the CHG, observed by SEM are shown in Fig. 3. As
can be clearly seen, the graphites are highly continued each
other; therefore, we confirmed that they are CHG.
SG: 6%, CHG: 82%, Led: 12% SG: 8%, CHG: 92%, Led: 0%
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The cooling curves of these samples are shown in Fig. 4. The
cooling curves are slightly different from that of the sand mold
castings [6]. Namely, the eutectic solidification temperature of
the SG gradually decreases, but for the sand mold castings, it
stays constant as Sertuucha et al.[7] reported. Nevertheless, the
CHG solidification temperature stays nearly constant with a
significant recalescence, the same as the solidification of the
flake graphite. This means that the solidification rate of the
CHG iron is much higher than that of the SG iron due to the
difference in the solidification mode as shown in Fig. 5.
Fig. 4: Influences of Si contents on cooling curves
Fig. 5: Schematic solidification models of flake
graphite, CHG and SG irons
SG is directly crystallized from the melt and covered with
an austenite shell at the onset of the eutectic solidification [8] as
shown in Fig. 5 [8,9]. Moreover, the thickness of the austenite
shell for the SG increases with time up to 1.4 times of the
graphite radius, r , for the pure Fe-C alloy. On the other hand,
the thickness of the austenite layer at the tip of the CHG stays
nearly constant during the eutectic solidification. Therefore,
the solidification rate of SG is lower than that of the CHG due
to the difficulty in carbon diffusion.
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2.2 Interaction of Si and Ce on CHG formation
The interaction of Si and Ce for the 3.5%Si and 4%Si is shown
in Fig. 6. As can be clearly seen, the difference in the CHG
fraction is small; nevertheless, in the 0.25%Ce samples the
volume fraction is slightly greater than that of the 0.10%Ce
samples. Moreover, a very small amount of ledeburite
formation in the 4%Si-0.25%Ce sample is confirmed by the
optical microscope.
Led: 6%
Fig. 6: Influence of Si and Ce contents on graphite
morphology
If we look at the cooling curves of these samples, shown in
Figs. 7 and 8, the formation of ledeburite in the 4%Si-0.25%Ce
sample can be confirmed by the differentiated curve during the
final stage of the solidification. Moreover, the differentiated values
in the SG formation period are less than zero while that in the
CHG formation stage, the value is more than zero. This can be
explained by the solidification mode of CHG mentioned in Fig. 5.
We show the volume fractions of the SG and CHG,
measured by the optical microscope, and by the solidification
time, in these figures. They are very similar to each other. This
means that the solidification time agrees with the volume of
the solidification due to the constant cooling rate.
Fig. 7: Cooling curve and the differentiated
curve of 3.5Si-0.25Ce sample
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February 2011

2.3 Influence of Sb and Sn on CHG formation

The microstructures of these five samples, the Sb-samples
and the 3.5C-4Si samples, are shown in Fig. 9. The Sb and
Sn are well known elements that prevent the CHG formation;
nevertheless, we cannot confirm the effect based on the
figure and Table 2. The three dimensional shape of the CHG
observed by the SEM shows that these elements affect the
graphite size by making it much finer.

Table 2: Influence of Sb and Sn addition on

CHG formation
Sample No. ΔT (K) CHG (%)
3.5C-4Si 7.6 81
0.02 Sb 16.1 88
0.14 Sb 12.0 91
0.05 Sn 13.9 83
Fig. 8: Cooling curve and the differentiated
0.10 Sn 13.2 85
curve of 4.0Si-0.25Ce sample

Fig. 9: Influence of Sb and Sn on graphite morphology for 4%Si alloys

If we look at the cooling curves of these

samples in Fig. 10, their addition produces (a) (b)
not only an increase in the CHG fraction, but
a significant recalescence for the formation of
CHG.
The recalescence, ΔT, was measured from the
onset of the CHG formation and their maximum
eutectic temperature for the morphological
transition from SG to CHG. The easiness of
solidification is the main reason for the CHG
formation. Nevertheless, the solidification mode
transfers directly from SG to ledeburite only in
the case of the pure Fe-C alloy or low silicon
alloys, as shown in Fig. 2, due to the difficulty
of graphitization. All of these results show Fig. 10: Cooling curves and CHG and SG fraction of 3.5C-4.0Si (a) and
that the significant undercooling during the 0.05Sn (b) samples

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SG formation, due to the increase in the difficulty of carbon
diffusion, produces the CHG.
We then propose the morphological transition model in Fig.
11 [10] based on the difference in the solidification mode of SG
and CHG, shown in Fig. 5. Nevertheless, these solidification
rates are only reference values.
Fig. 11: Graphite morphological transition
mechanism of SG to CHG and ledeburite
3 Conclusions
We discussed the influence of alloying elements on the
chunky graphite formation in view of the solidification mode
of the spheroidal graphite cast iron and that of the chunky
graphite cast iron. In this study, a number of experiments
were conducted for clarifying the chunky graphite formation
mechanism. We can finally conclude that the significant under-
cooling during the spheroidal graphite eutectic solidification
The paper was presented at the 69th World Foundry Congress, Hangzhou China 2010, republished in China Foundry with the
authors' kind permission.
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produces the morphological transition from SG to CHG
and ledeburite due to the increase in the difficulty of carbon
diffusion. This is the main reason for the CHG formation.
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