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Vol.8 No.1

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 1,450C 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

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 Cetreated 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.

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 Snsamples, 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

E-mail: h.nakae@waseda.jp

Received: 2010-07-06; Accepted: 2010-08-20 96

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Table 1: Chemical composition of samples (mass%)
Sample No. 0 Si 2 Si 3 Si 4 Si 3.5Si-0.15Ce 3.5Si-0.25Ce 4Si-0.15Ce 4Si-0.25Ce 4Si-0.1Ce 0.02Sb 0.14Sb 0.05Sn 0.10Sn C 4.40 3.79 3.50 3.18 3.49 3.48 3.31 3.37 3.49 3.23 3.24 3.25 3.26 Si 0.005 2.00 3.00 3.98 3.58 3.58 4.08 4.10 3.93 4.11 4.06 4.19 4.10 Ce 0.16 0.16 0.17 0.17 0.12 0.21 0.13 0.24 0.09 0.08 0.10 0.11 0.10 Sb 0.02 0.14 Sn 0.05 0.10

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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.

Fig. 1: Schematic of constant cooling rate experiment

SG: 5%, CHG: 0%, Led: 95%

SG: 9%, CHG: 69%, Led: 22%

SG: 6%, CHG: 82%, Led: 12%

SG: 8%, CHG: 92%, Led: 0%

Fig. 2: Influence of Si on CHG graphite formation

Fig. 3: Three dimensional graphite shapes of 2% to 4%Si samples

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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.

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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. 4: Influences of Si contents on cooling curves

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. 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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Fig. 7: Cooling curve and the differentiated curve of 3.5Si-0.25Ce sample

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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. 3.5C-4Si 0.02 Sb 0.14 Sb 0.05 Sn 0.10 Sn T (K) 7.6 16.1 12.0 13.9 13.2 CHG (%) 81 88 91 83 85

Fig. 8: Cooling curve and the differentiated 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 not only an increase in the CHG fraction, but a significant recalescence for the formation of CHG. The recalescence, T, 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 that the significant undercooling during the

(a)

(b)

Fig. 10: Cooling curves and CHG and SG fraction of 3.5C-4.0Si (a) and 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.

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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.

References
[1] Karsay S I. Ductile Iron Production. Quebec Iron and Titanium Corp. , 1966. [2] Basutkar P K and Loper C R. Predicting graphite nodularity in heavy section ductile iron by thermal analysis. AFS report of research project, 1971: 1-17. [3] Nakae H, Jung S and Shin H C. Formation mechanism of chunky graphite and its preventive measure. J. Mater. Sci. Tech., 2008, 24: 289-295. [4] Tsumura O, Ichinomiya Y, Narita H, Miyamoto T and Takenouchi T. Effects of rare earth elements and antimony on morphology of spheroidal graphite in heavy-walled ductile cast iron. Imono, 1995, 67(8): 540-545. [5] Church N L and Schelleg R D. Detrimental effect of calcium on graphite structure in heavy section ductile iron. Modern Casting, 1970, (1): 5-8. [6] Bckerud L, Nilsson K and Steen H. Study of nucleation and growth of graphite in magnesium-treated cast iron. The Metallurgy of Cast Iron, B. Lux, I. Minkoff, F. Mollars (eds.), St. Saphorin (Switzerland): Georgi Pub. Co., 1975: 625-637. [7] Sertucha J, et al. Thermal analysis of the formation of chunky graphite during solidification of heavy-section spheroidal graphite iron parts. ISIJ International 2009, 49: 220-228. [8] Nakae H and Yamauchi T. Effect of sulphur on growth morphology of unidirectional solidified Fe-C alloys. J. Inst. Metals, 1994, 58: 30-36. [9] Tatsuzawa Y, Jung S and Nakae H. Cooling curve and graphite morphology in Ni-C alloys. Intl. J. Cast Metals Research, 2008, 21: 17-22. [10] Nakae H, Kitazawa T and Fukami M. Influence of solidification rate on graphite morphological change in cast iron. In: Proceedings of the 3rd International Conference on Processing Materials for Properties, 2009: 1085-1090.

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 undercooling 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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