Paper 05-203(05).

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AFS Transactions 2005 © American Foundry Society, Schaumburg, IL USA

Effect of Alloying Elements on the Eutectic Temperatures in Cast Iron

T. Kanno, T. Kikuchi, I. Kang

Kimura Chuzosho Co., Sunto-Gun, Shizuoka-Ken, Japan
H. Nakae
Waseda University, Shinjuku-Ku, Tokyo, Japan

Copyright 2005 American Foundry Society

ABSTRACT

Using a thermal analysis system consisting of three cups (First: Inoculated, Second: Base melt, Third: Te added), the effects
of alloying elements on graphite eutectic temperature and cementite eutectic temperature of cast iron and the difference
between them (DTE) were investigated.

The order of elements (graphitization elements) that expand DTE is as follows: Si > Al > C(CE < 3.5%)> Cu > P > Ni >
C(CE > 3.5%). The order of elements (chilling elements) that narrow DTE is as follows: B > S (> 0.45%) > V > Cr > S
(<0.45%) >Nb > Sn > W > Mn > Mo > Sb. DTE is related to the distribution coefficient of elements between cementite and
austenite. When S and Mn coexist, the eutectic temperature and graphite shape are determined by dissolved S and dissolved
Mn.

INTRODUCTION

In the phase diagram of Fe-C, there are two systems simultaneously as follows; one is stable system and the other is
meta-stable system. This is a unique phase diagram observed only in Fe-C phase diagram. The stable system means the
eutectic solidification of austenite and graphite. The meta-stable system means the eutectic solidification of austenite and
cementite.

The purpose and the principle of the present study will be explained from an equilibrium phase diagram of Fe-C binary
system. Figure 1 (a) indicates an equilibrium phase diagram of Fe-C binary system, and Figure 1 (b) shows the three cooling
curves obtained by this experiment, while Figure 1 (c) represents the micro structure of the respective cooling curves. As
gray cast iron is cooled from the liquid state, a primary crystal appears first. By measuring this primary crystal temperature, it
becomes possible to determine the carbon equivalent (CE value). Next, in the equilibrium phase diagram of Fe-C binary
system, two different eutectic temperatures appear, which are not found in the equilibrium phase diagram of other binary
alloys. Generally, the eutectic temperature (A) is called stable eutectic temperature, while the eutectic temperature (C) is

Figure 1. Relationship between Fe-C phase diagram, cooling curve and microstructure.
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called metastable eutectic temperature. The stable eutectic temperature (A) is a eutectic temperature of the melt where there
exists a sufficient quantity of graphite nucleus and that graphite is generated sufficiently. Conversely, the meta-stable eutectic
temperature (C) is a eutectic temperature of the melt where there is no graphite nucleus and that graphite is not generated
(state of complete chill). In the present study, (A) will be called graphite eutectic temperature (TEG), (C) will be named
cementite eutectic temperature (TEC), and the difference between the two eutectic temperatures will be referred to as DTE in
order to make it easy to understand.

Since the measurement of graphite eutectic temperature is possible in the presence of a sufficient quantity of graphite nucleus,
the graphite eutectic temperature can be measured by means of a cup in which an inoculant is added. For the measurement of
cementite eutectic temperature, a cup in which tellurium (Te) is added can be used, because absence of graphite generation is
the only condition for it. Moreover, a cup without any additive can be used, for measuring the basic eutectic temperature of
the molten metal. The present study aims at investigating the influences of alloying elements on the respective eutectic
temperatures, by using 3 different types of cup.

EXPERIMENTAL METHOD

Figure 2 indicates the 3-cup thermal analysis used for this experiment and the outline of the cooling curves obtained (Kanno,
1997). This measuring system consists of 3 vessels (cups) in which a thermocouple is installed respectively, a CPU for
fetching and processing the electromotive force of the thermocouples, and a TV monitor for displaying the processed data.
Each vessel (cup) consists of a shell mould with an inside diameter of 30 mm and a height of 50 mm, having a chromel-
alumel thermocouple with a diameter of 0.6 mm protected by a silica tube installed at the center. The molten metal mass in
the vessel was adjusted to 250±10 g.

Figure 2. This is the illustration of thermal analysis system:

(A) inoculated (3.0g); (B) base melt; (C) Te added (0.75g).

In the vessel (A), 3 g (equivalent to 1.2 mass% of molten metal: hereinafter abbreviated as %) of an inoculant (Fe-37.6%
Si-12.4% Ca-8.6% Ba) was introduced in advance. However, in the test of sulfur (S: elements are hereinafter given with
atomic symbols), Mn and RE, an inoculant of Fe-50.4% Si-0.18% Ca-0.87% Al was used, to reduce the influences of Ca and
Ba. The volume of the inoculant was adjusted to an amount enabling to sufficiently graphitize the molten metal and measure
the graphite eutectic temperature (TEG) (Kanno, 1998). Nothing was added to the vessel (B), so that it can measure the basic
cooling curves of the molten metal. To the vessel (C), 0.75g (equivalent to 0.3% of molten metal) of 99.99% metal Te was
introduced in advance in the vessel. The volume of Te was adjusted to an amount enabling to sufficiently chill the molten
metal and measure the cementite eutectic temperature (TEC) (Kanno, 1998).

The molten metal was held at approximately 1500°C (2732°F). The basic composition of the molten metal was 3.1% C, 1.7%
Si, 0.75% Mn, 0.07% P and 0.05% S and only the content of the element was adjusted. The molten metal was poured into the
3- cup and the influence of various kinds of alloying element on the variation of eutectic temperatures was investigated.

RESULTS AND DISCUSSION

INFLUENCES OF ALLOYING ELEMENTS ON THE EUTECTIC TEMPERATURES

Figure 3 indicates the influences of C and Si on graphite eutectic temperature and cementite eutectic temperature, while
Figure 4 shows the influences of S and Cr. In the case of 1.7% Si, C increases TEG and TEC until it goes up to a
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concentration of 2.9% (CE = 3.5), but keeps them constant thereafter. Si makes TEG go up and makes TEC drop. This result
agrees well with that obtained by Oldfield (Oldfield, 1962).

Figure 3. Effects of C and Si on eutectic temperatures. Figure 4. Effects of S and Cr on eutectic temperatures.

In the case of S, an inflection point appears at 0.2%, as shown with an arrow mark in Figure 4. Namely, while S makes TEG
and TEC go up in the low-content area lower than the inflection point, it reduces TEG and TEC at content beyond the
inflection point. As reasons for it, generation of Manganese Sulfide (MnS) and influence of S on the interfacial energy
between graphite and liquid phase (Nakae, 1994) are conceivable. Cr makes TEG drop and makes TEC go up. Cr is therefore
a chilling element. This result agrees well with the result obtained by Oldfield (Oldfield, 1962).

Figure 5 indicates the summary of influences of alloying elements other than C on DTE. Under the influence of 1.7% Si,
DTE at a concentration of 0% indicates 28°C (50°F) in any of the alloying elements. Furthermore, as for Si, evaluation was
made at a Si concentration of 1.7 to 2.7%, because 1.7% was taken for the base content. As a result, the order of elements
with a large effect of expanding DTE per 1% content, i.e. a strong tendency for graphitization, becomes as follows:
Si > Al > C (CE<3.5) > Cu > Co > P > Ni > C (CE≥ 3.5) Equation 1
Still more, the order of elements with a large effect of narrowing DTE per 1% concentration, i.e. a strong tendency for
chilling, becomes as follows:
B > S( ≥ 0.45%) > V > Cr > S( < 0.45%) > Nb > Sn > W > Mn > Mo > Sb Equation 2

Figure 5. Effects of alloying elements on DTE: DTE = TEG − TEC.

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Table 1 indicates the summary of influences of 1% of respective elements on TEG, TEC and DTE calculated from the test
results. It further indicates the influences of 1% respective elements of on carbon activity by Neumann (Neumann, 1960), and
that on distribution coefficient and DTE by thermodynamic calculation of Kagawa (Kagawa, 1986). Here, Px(A/L) indicates
a distribution coefficient of element X between austenite and molten iron, Px(C/L) indicates a distribution coefficient
between cementite and molten iron, and Px(C/A) indicates a distribution coefficient between cementite and austenite.

In the first place, B, S, Sn, W, Sb are the elements which increase the activity of C, and ought to become graphitizing
elements. However, those elements narrow DTE and are turned into chilling elements. Next, as shown in Figure 3, the
eutectic temperature does not change even with an increase of C, in the case where the C content is higher than 2.9% (CE >
3.5). Therefore, in this area, the eutectic temperature does not change even if the carbon activity changes under the influence
of the respective elements. From what has been stated above, there is no way to explain any variation of DTE with the
influence of alloying elements, at a carbon equivalent (CE) higher than 3.5% which is the range of composition of general
flake graphite cast iron. However, this does not apply in the low C area lower than 2.9% (CE < 3.5%).

Table1. Effect of Various Elements on Graphite and Cementite Eutectic Temperature and Distribution Coefficient

Next, the observation will be made on the relationship between distribution coefficient and TEG, TEC of alloying elements.
Figure 6 indicates the schematic illustration showing the relationship between DTE and distribution coefficient. Si, Al, Cu,
etc. having a Px(A/L) larger than 1 increase TEG because they are distributed mainly on the austenite side between austenite
and molten iron. Moreover, P, Mo, Cr, etc. decrease TEG because they are distributed mainly on the molten iron side
between austenite and molten iron. Namely, they increase TEG if the distribution coefficient between austenite and molten
iron is larger than 1, but decreases TEG if that is smaller than 1. The same is also true between cementite and molten iron.
DTE is essentially the difference between TEG and TEC. Consequently, in disregard of molten iron, the alloying elements
make DTE drop if they are distributed on the cementite side between cementite and austenite, while they make DTE go up if
they are distributed on the austenite side between cementite and austenite.

Based on the Table 1, the relationship between DTE obtained from this experiment and Px(C/A) calculated by Kagawa
(Kagawa, 1986) is shown in Figure 7. Px(C/A) means the distribution coefficient between cementite and austenite. There is a
good relationship between them. There is a small difference in some element. The reason is that the composition used for the
calculation is not the same as that of this experiment.
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From what has been described above, the variation of DTE is determined by the distribution coefficient of alloying elements
between cementite and austenite, and not by the influences of the alloying elements on carbon activity.

Figure 6. Relationship between eutectic temperature and distribution coefficient.

Figure 7. Relationship between DTE and Px(C/A).

INFLUENCES OF SULFUR (S) AND MANGANESE (MN) ON EUTECTIC TEMPERATURE

Figure 8 indicates the relationship between the amount of Mn and two eutectic temperatures (TEG and TEC) for various S in
molten metals. In a molten metal with 0.01% S, TEG and TEC drop as the amount of Mn is increased. In a molten metal with
0.05% S or more, both TEG and TEC increase up to the inflection point, but drop beyond the inflection point. The inflection
point of eutectic temperature varies depending on the amount of S in the base molten metal. As shown in Figure 5 and
Table 1, Mn and S are the elements which basically reduce TEG and TEC, and S is stronger than Mn in this specific function.
For those reasons, in a molten metal with a small amount of S, the eutectic temperature drops because only the amount of
dissolved Mn increases mainly with an addition of Mn. In a molten metal with a high proportion of S, inflection points in
convex shape are produced because the amount of dissolved S decreases as generating MnS. From that point of view, the
eutectic temperature is believed to be determined, in a sense, by the amount of dissolved Mn and the amount of dissolved S.
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Figure 9 shows the relationship between the amount of Mn and DTE(=TEG-TEC) in the various S melts which is shown in
Figure 8. In the case of 0.2%S, DTE is increased about 2°C up to the inflection point. This value of 2°C is equivalent to the
rise by the addition of 0.12%Si and means a high value for graphitization of cast iron.

Figure 8. Relationship between amount of Mn and two Figure 9. Relationship between the amount of
eutectic temperatures (TEG and TEC) for various S melt.s Mn and DTE in the various S melts.

Figure 10 shows the relationship between Mn and S in the inflection point of DTE obtained from Figure 9. The inflection
points satisfy a relation Mn%=1.7 x S% + 0.3 where DTE becomes the maximum value. This relation is in agreement with
the relation between Mn and S which was led from Nakae as the best quality of material (Nakae, 1977). It is proved by
stoichiometric calculation that eutectic temperature is determined by dissolved S and dissolved Mn as follows. By
investigating whether MnS is observed or not in the microstructure, Okada verified that MnS is not generated under the
condition of [(Dissolved S%) x (Dissolved Mn% ) < 0.01] (1996, Okada). From Okada’s result and the molecular weights
relationship between Mn and S, the next four expressions are formed.

Figure 10. Relationship between Mn and S in the inflection point of DTE.

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[ Dissolved ⋅ S%] × [ Dissolved ⋅ Mn %] = 0.01 Equation 3

[ Mn % ⋅ in ⋅ MnS] = 1.71 × [S% ⋅ in ⋅ MnS] Equation 4
[ All ⋅ S%] = [ Dissolved ⋅ S%] + [S% ⋅ in ⋅ MnS] Equation 5
[ All ⋅ Mn %] = [ Dissolved ⋅ Mn %] + [ Mn % ⋅ in ⋅ MnS] Equation 6

From these equations, the following equation is formed and the dissolved S quantity can be calculated.
[ Dissolved ⋅ S%]2 − ([ All ⋅ S%] − [ All ⋅ Mn %] / 1.71) × [ Dissolved ⋅ S%] − 0.01 / 1.71 = 0 Equation 7

When the relation Mn%=1.7 x S% + 0.3 is substituted to the equation 7, the term of all S is eliminated and dissolved S
becomes fixed in 0.029%. In addition, it leads that the dissolved Mn becomes fixed in 0.34%. Nakae reported that the relative
hardness becomes the lowest when the relation [Mn%=1.7 x S% + 0.3] is fulfilled (Nakae, 1977). That is, the quality of cast
iron becomes best at one fixed value; dissolved S of 0.029% and dissolved Mn of 0.34%. MnS does not influence directly on
the eutectic temperature because of the two facts as follows. The first fact is that the temperature of inflection point does not
change with the amount of MnS. The second is that MnS is not insoluble in the melt.

Figure 11 shows the relationship between the amount of Mn and the eutectic temperature when 2 types of inoculants are used.
One contains much Ca and Ba (Fe-37.6% Si-12.4% Ca-8.6% Ba) and the other contains very few Ca and Ba (Fe-50.4%
Si-0.18% Ca-0.87% Al).

Figure 11. Relationship between the amount of Mn and the eutectic temperature (2 types of inoculants).

To the extreme point, the eutectic temperature of the melt using the inoculant containing much Ca and Ba is higher than that
of the melt using the inoculant containing very few Ca and Ba. After passing the extreme point, there is no difference in
eutectic temperatures. Since Ca and Ba have a strong affinity with S, they generate sulfides and decreases dissolved S. By
this function, the eutectic temperature becomes high at low content of Mn when the inoculant containing much Ca and Ba is
used. In addition, DTE at 0.3%Mn is 27°C with using the former inoculant and 23°C with using the latter inoculant (very few
Ca and Ba). It means that the value of DTE differs depending upon the type of inoculant.
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From the above results, it is found that the inoculant containing sulfide forming elements not only works as nucleus of the
graphite but also expands DTE. It is considered that Ca, Ba and CaS, BaS do not influence on the eutectic temperature
directly from the two reasons as follows. The first is the fact that Ca, Ba and CaS, BaS are insolvable in molten iron. The
second is the fact that the rising ratio of eutectic temperature corresponds to the decreasing ratio of the dissolved S.

Figure 12 indicates the relationship between Mn content and graphite structure with 0.3%S. S* means the dissolved sulfur
calculated with the equation 7. In a molten metal with a large amount of dissolved S (a), the growth of eutectic cells is
restricted, and there exists a lot of steadite (f) among the eutectic cells in spite of a comparatively small amount of P (0.07%).
Moreover, micrographic shrinkage cavities are observed among the eutectic cells. The graphite shape is slender, short and
curved. For those reasons, it can be said that a high concentration of dissolved S restricts the growth of eutectic cells and
graphite.

Figure 12 Relationship between Mn content and graphite structure with 0.3%S.

At the near inflection point where the DTE is maximized, the graphite structure (c) is slightly curved, but this graphite is
sufficiently grown. In a molten metal in which the amount of Mn is further increased and the amount of dissolved S decreases,
the graphite has many branches and remains linear and slender. Though no details are discussed here, the shape of graphite
changes from flaky to spherical, as the amount of dissolved S becomes extremely small (Kanno, 2001).

From what has been described above, the change of graphite shape can be explained with the influence of dissolved S. In the
molten metal with a large amount of dissolved S, the growth of eutectic cells is restricted and the growth of graphite is also
prevented, because of the S concentration in the solid-liquid interface (Merchant, 1962) (Lux, 1967). Furthermore, the
graphite is curved with the functioning of dissolved S. In a molten metal with a proper amount of dissolved S, S adheres to
the prism face of graphite to help the growth of graphite, and restricts branching (Nakae, 1994) (Nakae, 1991). As the amount
of dissolved S decreases, the branching of graphite becomes more conspicuous because austenite growth is priority over
graphite growth, and the graphite becomes linear because the graphite bending function of S weakens. As the amount of
dissolved S further decreases, the solidification form changes and the graphite takes a spherical shape.
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CONCLUSIONS

A research was made on the relationship between eutectic temperature and composition, by the method of 3-cup thermal
analysis. The results obtained through the researches are the following:

(1) The difference between graphite eutectic temperature and cementite eutectic temperature (DTE) is determined by the
distribution coefficient of elements between cementite and austenite.
(2) At a carbon equivalent (CE) beyond 3.5, the eutectic temperature does not change depending on the amount of C.
Therefore, there is no change in eutectic temperature in this area, even if the carbon activity changes under the influences of
various elements.
(3) The influences of various elements on DTE are given in the following order:

(a) Elements expanding DTE (graphitizing elements):

Si > Al > C(CE< 3.5) > Cu > Co > P > Ni > C(CE≥ 3.5)

(b) Elements narrowing DTE (chilling elements):

B > S( ≥ 0.45%) > V > Cr > S( < 0.45%) > Nb > Sn > W > Mn > Mo > Sb

(4) In the case where S and Mn coexist, the eutectic temperature is determined by the amount of dissolved S and the amount
of dissolved Mn.
(5) The graphite is curved as the amount of dissolved S is increased, and becomes linear as the amount of dissolved S
decreases.
(6) In the molten metal with a small amount of dissolved S, the graphite has many branches and remains linear. The shape
of graphite changes from flaky to spherical, when the amount of dissolved S becomes extremely small.

REFERENCES

Kanno, T., You, Y., Hiraoka, H., Morinaka, M., Nakae, H., “Effect of Alloying Elements on Graphite and
Cementite Eutectic Temperature of Cast Iron,” Proceedings of AFC-5, pp 137-(1997).
Kanno, T., You, Y., Morinaka, M., Nakae, H., “Effect of Alloying Elements of Graphite and Cementite Eutectic
Temperature of Cast Iron,” J. Japan Foundry Engineering Society, vol.70, pp 465-470(1998).
Kanno, T., Kang, I., Mizuki, T., Nakae, H., “Effect of S, Mn and RE on Eutectic Temperature of Cast Iron,” J. Japan
Foundry Engineering Society, vol.73, pp441-446(2001).
Kagawa, A., Okamoto, T., “Theoretical Evaluation of the Ability of Alloying Elements for Graphitization during
Eutectic Solidification of Cast Iron,” J. Japan Foundry Engineering Society, vol.57, pp113- 119(1985).
Lux, B., Kurz, W., The Solidification of Metals, Proc. Conf., The Iron and Steel Institute, pp193 (1967).
Merchant, H. D., Trans. AFS, vol.70, pp973 (1962).
Nakae, H., Kondoh, H., “Effect of Sulfur on the Solid-Liquid Interface Morphology of Unidirectionally Solidified Fe-C
Alloys,” J. Japan Inst. Metals, vol.55, pp437-443 (1991).
Nakae, H., Yamauchi, T., “Effect of Sulfur on Growth Morphology of Unidirectionally Solidified Fe-C Alloys,”
J. Japan Inst. Metals, vol.58, pp 30-36 (1994).
Nakae, H., Kiyosuke, H., Okada, S., “Influence of Phosphorus and Sulfur Contents on the Properties of Hypereutectic
Cast Iron,” J. Japan Foundry Engineering Society, vol.49, pp216-221 (1977).
Neumann, F., Schenck, H., Patterson, W., “Einfluß der Eisenbegleiter auf Kohlenstofflöslichkeit, Kohlenstoffaktivität
und Sättigungsgrad im Gußeisen,” Giesserei, vol.47, pp25-32 (1960).
Okada, A., Miyake, H., Chutetuno Sirarezaru Sekai, Kansai Univ. Publishing Department, pp160 (1996).
Oldfield, W., “Chilling Mechanism of Chromium in Cast Iron,” BCIRA J., vol.9, pp506-518(1961).
Oldfield, W., “The Chill-reducing Mechanism of Silicon in Cast Iron,” BCIRA J., vol.10, pp 17-27 (1962).