Materials Transactions, Vol. 51, No. 1 (2010) pp.

176 to 185
#2010 The Japan Institute of Metals

EXPRESS REGULAR ARTICLE

Eect of Silicon and Bismuth on Solidication Structure

of Thin Wall Spheroidal Graphite Cast Iron
Hiromitsu Takeda, Hiroyuki Yoneda and Kazunori Asano
Department of Mechanical Engineering, School of Science and Engineering, Kinki University, Higashiosaka 577-8502, Japan
Although the thinning of spheroidal graphite cast iron castings has been promoted to reduce the weight of the castings, the thinning tends to
cause chilling. Due to the chilling, the required mechanical properties can not be obtained. The addition of certain elements is a way to solve this
problem. In this study, the spheroidal graphite cast iron melt containing minor Bi, 3.3 to 3.7 mass%C and 2.0 to 3.2 mass%Si was poured into a
stepped plate mold to obtain the thin wall castings, and observation of their graphite and matrix microstructure, thermal analysis during the
solidication process of the melt in the mold and the qualitative analysis of elements inside the spheroidal graphite by FE-EPMA were carried
out.
It was found that an increase in the Si/C mass ratio in the spheroidal graphite cast iron was eective for decreasing the amount of cementite
(chill) in the matrix, and the chill was further inhibited by adding 0.01 mass% Bi even for the thin wall castings of 2 mm. Amounts up to
0.01 mass%Bi promoted renement of the graphite, increased the graphite nodule, and promoted ferritizing of the matrix. It was also found that a
high Si/C mass ratio in the spheroidal graphite cast iron promoted the eects of Bi. The temperature of the eutectic start and that of the eutectic
solidication end increased due to the 0.01 mass%Bi. The temperature of the eutectoid transformation start increased and the stability eutectoid
transformation of the thin wall castings was promoted by containing a minor amount of Bi. It was conrmed that substances including Bi and Mg
existed in the graphite containing Bi. These results lead to the conclusion that the Bi compound and the Mg compound acted as heterogeneous
nuclei of the graphite, and the nuclei promoted the crystallization of the graphite, and then the graphite nodule increased.
[doi:10.2320/matertrans.M2009255]
(Received July 23, 2009; Accepted October 22, 2009; Published December 9, 2009)
Keywords: spheroidal graphite cast iron, thin wall, bismuth, chill, graphite nodule, matrix microstructure

1.

Introduction

Cast iron has been produced in quantity as castings for

automobile parts and industrial machines, because it has an
excellent castability, good wear resistance and damping
capacity. In recent years, the reduction in weight and size of
the machine products has been promoted to reduce the energy
consumption, use of raw materials and emitting of greenhouse gas. This trend leads to the promotion of thinning of
the spheroidal graphite cast iron castings. However, the cast
iron melt in a thin wall is exposed to rapid cooling, and
cementite (chill) tends to increase in the matrix. The chilling
causes a decrease in the mechanical properties of the
castings. Generally, a ferrosilicon (Fe-Si) alloy containing a
small amount of elements, such as aluminum, calcium, and
barium, is added to the cast iron melt as a graphitizer to
prevent the chill. For the spheroidal graphite cast iron, it is
reported that the critical graphite nodule count for preventing
the chill exists for each cooling rate.1) This indicates that an
increase in the graphite nodules in the matrix is eective for
preventing the chilling. It is reported that the addition of a
small amount of bismuth (Bi) is eective for increasing the
graphite nodule count.25) Based on this nding, the inoculant
containing Bi6,7) or pure Bi8) is sometimes added to the
spheroidal graphite cast iron melt. However, Bi is classied
as a graphite spheroidization inhibition element because the
spheroidization is inhibited by including excessive Bi in the
cast iron. Some researchers have reported the critical content
of Bi to inhibit the graphite spheroidization. Morrogh9)
reported that the graphite spheroidization starts to interfere
when the Bi content exceeds 0.003 mass%, and the spheroidization is completely inhibited when the Bi content is
0.006 mass%. Donoho10) reported that the graphite spheroidization is inhibited by 0.005 mass%Bi or more in the melt,

and Cole11) reported that the spheroidization is inhibited

by 0.006 mass%Bi or more. On the other hand, for the cast
iron containing titanium,12,13) it has been reported that the
graphite spheroidization is interfered by containing about
0.001 mass%Bi. These reports indicate that a small amount of
Bi inhibits the spheroidization and the critical Bi content
changes due to the content of the main element and the
existence of other elements. Silicon (Si), the main element of
cast iron, is a graphitizing element. Horie et al.1) reported that
the graphite nodule count in the spheroidal graphite cast iron
increases by increasing the Si content or carbon equivalent
(CE). However, there are few reports on the eect of the C
and Si contents for a constant CE of the graphite and matrix
structure of the thin wall spheroidal graphite cast iron
containing Bi. Moreover, there are no reports which examine
the eect of Bi on the solidication process of the thin wall
spheroidal graphite cast iron by a thermal analysis.
In this study, the spheroidal graphite cast iron melt with
various Bi, C and Si contents were poured into a stepped plate
mold to obtain the thin wall specimens, and the relationship
between the thickness of the specimens, the graphite
spheroidization rate, graphite nodule count, and area fraction
of ferrite and pearlite was examined, and then the eect of the
Si and Bi contents on the graphite and matrix structure was
examined (experiment A). Subsequently, the thermal analysis of the spheroidal graphite cast iron melt was carried out,
and the eect of Bi on the eutectic solidication and the
eutectoid transformation reaction was examined (experiment
B). Moreover, structure of the spheroidal graphite in the
specimens containing Bi was analyzed in order to examine
the Bi distribution. Based on these results, the eects of Si
and Bi on the microstructure of the thin wall spheroidal
graphite cast iron and the graphite renement mechanism by
Bi were examined.

Eect of Silicon and Bismuth on Solidication Structure of Thin Wall Spheroidal Graphite Cast Iron
Table 1
C

177

Chemical composition of raw materials (mass%).

Si

Mn

Cr

Cu

Zn

Pig iron

4.22

0.099

0.027

0.029

0.015

0.032

Electrolytic iron

0.02

<0:005

0.0001

<0:001

0.009

0.002

0.001

0.002

Fe-Si alloy

0.028

75.93

0.022

0.010

2.

-3 3.76 2.06 0.046 0.022 0.010 0.010 0.040 4.45

0.55
0.67
0.67

-3 3.62 2.38 0.045 0.021 0.011 0.010 0.042 4.41

0.66

3-1 3.54 2.81 0.042 0.023 0.008 0

0.038 4.48
-2 3.53 2.80 0.044 0.021 0.009 0.005 0.044 4.46

0.79
0.79

-3 3.52 2.78 0.047 0.022 0.010 0.010 0.041 4.45

0.79

4-1 3.31 3.21 0.050 0.020 0.010 0

0.048 4.38
-2 3.32 3.23 0.042 0.020 0.010 0.005 0.046 4.40

0.97
0.97

-3 3.33 3.22 0.045 0.020 0.010 0.010 0.045 4.40

0.97

5-1 3.44 2.10 0.040 0.021 0.009 0

0.037 4.14
2 3.45 2.20 0.043 0.022 0.011 0.010 0.041 4.18

0.61
0.64

0.045 4.45

0.92

2 3.41 3.21 0.047 0.022 0.010 0.010 0.042 4.48

0.94

Measuring point

150

Mg

2-1 3.63 2.45 0.041 0.022 0.010 0

0.043 4.45
-2 3.61 2.42 0.043 0.023 0.010 0.005 0.039 4.42

6-1 3.40 3.14 0.042 0.023 0.008 0



Bi

R
R thermocouple
thermocouple

50

50

50

50

0.56
0.53

Mn

10

1-1 3.75 2.10 0.041 0.022 0.012 0

0.037 4.45
-2 3.77 2.00 0.043 0.022 0.011 0.005 0.044 4.44

Si

250

Si/C

200

CE

No.

75 75

Table 2 Chemical composition, CE and Si/C mass ratio of cast iron

specimens (mass%).

200

CE=C+Si/3+P/3

Experimental Procedure

Raw materials with the chemical composition shown in

Table 1 were used to fabricate the cast iron specimens. They
were placed in a graphite crucible and melted in a small high
frequency induction furnace (10 kWh, 3 kHz) under an Ar gas
atmosphere, followed by graphite spheroidizing, inoculation
and Bi addition at 1773 K. The graphite spheroidizing,
inoculation and Bi addition were simultaneously carried
out by adding the spheroidizing agent (45.92 mass%Si, 4.93
mass%Mg, 2.37 mass%Ca, 0.66 mass%Al, 1.84 mass%RE),
inoculant (75.77 mass%Si, 1.28 mass%Ca, 2.16 mass%Al),
and pure Bi (99.9 mass%Bi), respectively. As a result of a
preliminary experiment, it was found that the yield of Bi in
the spheroidal graphite cast iron was 8% in this experiment
condition. The addition of the inoculant was 0.3 mass%.
Table 2 shows the chemical composition, CE and Si/C
mass ratio of the specimens. Specimens No. 1 to No. 4
were used in experiment A. In experiment A, the target
chemical composition of the specimens was as follows: 3.3,
3.4, 3.5 and 3.7 mass%C, 2.0, 2.4, 2.8, and 3.2 mass%Si. The
CE(=C+Si/3+P/3) was set to 4.4 (constant). The target
contents of Mn, P, S and Mg were 0.04, 0.02, 0.01
and 0.04 mass%, respectively. As a result of a preliminary
experiment, it was found that the graphite spheroidization
was insucient when the Bi content exceeded 0.01 mass%.
Therefore, the Bi content was set to 0.005 and 0.01 mass%.
The ratio of the Si content to C content (Si/C mass ratio) was
used as a parameter, showing an increase in the Si content for

350
Fig. 1

Conguration of CO2 mold equipped with thermocouples.

the same CE values. It is known that the Si/C mass ratio has
a correlation with the tensile strength and hardness.14,15)
Specimens No. 5 and No. 6 shown in Table 2 were used
for experiment B. In experiment B, the carbon content was
set to 3.4 mass% (constant), the Si content was set to 2.2 and
3.2 mass%; the CE was 4.1 (hypoeutectic composition) and
4.4 (hypereutectic composition).
Melt was poured into the CO2 mold shown in Fig. 1 at
1673 K to obtain the stepped specimens plates with 2, 3, 5 and
10 mm thicknesses (50 mm width
150 mm length). In
experiment B, R thermocouples were inserted in the center
of the cavity and the thermal analysis of the melt was carried
out. To obtain a high heat sensitivity, the tip of the
thermocouple was exposed.
The microstructure in the center part of the specimen
(in the vicinity of the tip of the thermocouple) was observed.
The graphite spheroidization ratio, the graphite particle
diameter, the graphite nodule count and area fractions of the
graphite, ferrite and pearlite were measured by an image
analyzer. To obtain the mean values of these parameters, 10
optical micrographs were used for the measurement. These
values of the specimens generating chill were excluded.
Graphite particles with a diameter less than 1 mm were also

178

H. Takeda, H. Yoneda and K. Asano

eutectic solidication of the melt and eutectoid transformation process by the addition of Bi were examined. The
measurement points in the thermal analysis are shown in
Fig. 2.

TP

3.

TEU
TES

TEE

TEM
ET

TEDS
TEDE

Fig. 2 Measurement point on cooling curve.
Temperature of primary

crystallization (TP) ` Temperature of eutectic start (TES) Temperature
of eutectic undercooling (TEU) Temperature of eutectic maximum
(TEM) End of eutectic solidication (TEE) Eutectic solidication
time (ET) Temperature of eutectoid start (TEDS) End of eutectoid
transformation (TEDE).

excluded because it is dicult to distinguish the graphite.

The distribution of elements in the spheroidal graphite in
the specimen containing Bi was examined by FE-EPMA.
In the thermal analysis of experiment B, the changes in the

Thickness
t/mm

Results and Discussion

3.1 Eect of Bi and Si on microstructure (experiment A)

3.1.1 Microstructure
Figure 3 shows the microstructure of the specimens
without Bi. The microstructure in the center part and the
surface part of each thickness of specimens were almost
the same. The Si/C mass ratio is also shown in the gure.
When the Si/C mass ratio was 0.56, the specimen with a
10 mm thickness had a bulls eye type structure without
chill (Fig. 3(d)). The chill was partially observed in the
specimen with a 5 mm thickness (Fig. 3(c)) and the matrix
of the specimen with a 2 mm thickness was completely
chill. A similar structure was observed when the Si/C mass
ratio was 0.67 (Fig. 3(e)(h)). When the Si/C mass ratio
was 0.79, the chill was not observed in the specimens
with the thicknesses of 3, 5 and 10 mm (Fig. 3(j)(l)),
although the chill was partially observed in the specimen
with a 2 mm thickness (Fig. 3(i)). When the Si/C mass
ratio was 0.97, the no chill was observed even in the
specimen with a 2 mm thickness (Fig. 3(m)) and every
specimen contained ne nodular graphite particles. The
ferrite in the matrix increased as the Si/C mass ratio

10

Specimen
No.1-1

(a)

(b)

(c)

(d)
Chill

3.75 mass%C
2.10 mass%Si
Si/C =0.56
No.2-1

(e)

(f)

(g)

(h)

(i)

(j)

(k)

(l)

(m)

(n)

(o)

(p)

3.63 mass%C
2.45 mass%Si
Si/C =0.67
No.3-1
3.54 mass%C
2.81 mass%Si
Si/C =0.79
No.4-1
3.31 mass%C
3.21 mass%Si
Si/C =0.97

Fig. 3

100 m
Microstructure of specimens without Bi (0 mass%Bi) and various C and Si contents at CE4.4 (Nital etched).

Eect of Silicon and Bismuth on Solidication Structure of Thin Wall Spheroidal Graphite Cast Iron

Thickness
t/mm

179

10

Specimen
No.1-3

(a)

(b)

(c)

(d)

(e)

(f)

(g)

(h)

(i)

(j)

(k)

(l)

(m)

(n)

(o)

(p)

3.76 mass%C
2.06 mass%Si
Si/C =0.55
No.2-3
3.62 mass%C
2.38 mass%Si
Si/C =0.66
No.3-3
3.52 mass%C
2.78 mass%Si
Si/C =0.79
No.4-3
3.33 mass%C
3.22 mass%Si
Si/C =0.97

100 m

Fig. 4 Microstructure of specimens with 0.01 mass%Bi and various C and Si contents at CE4.4 (Nital etched).

increased. These results indicated that the chilling does not

occur and an increase in the ferrite structure in the matrix
is pronounced in the thin wall cast iron castings when the
Si/C mass ratio is high (high Si content). The specimens
containing 0.005 mass%Bi have almost the same microstructure as the specimens without Bi.
Figure 4 shows the microstructure of the specimens
containing 0.01 mass% Bi. When the Si/C mass ratios were
0.55 and 0.66, no chill was observed in the specimens with
the thicknesses of 3, 5 and 10 mm (Fig. 4(b)(d), (f)(h)).
When the Si/C mass ratio was high (0.79 and 0.97), no chill
was observed even in the specimen with a 2 mm thickness
(Fig. 4(i), (m)).
These results show that an increase in the Si content is
eective for decreasing the chill in the thin wall spheroidal
graphite cast iron, and the chilling is further inhibited by a
0.01 mass%Bi content.
3.1.2 Relation among Bi content, Si/C mass ratio,
thickness and microstructure
For all the specimens, the graphite spheroidization ratio
was 80% or more. When the Si/C mass ratio was 0.5, a
0.01 mass%Bi content slightly reduced the spheroidization
ratio in the specimens.
Figure 5 shows the relation between the Bi content, Si/C
mass ratio, thickness, and the graphite particle diameter
of the specimens. It can be seen that the graphite particle
diameter decreased as the specimen thickness decreased.
This is due to the fact that the cooling rate of the melt
increased as the thickness decreased. For the same Si/C mass

ratio, the graphite particle diameter tends to decrease as the

Bi content increases. This tendency is pronounced when the
Si/C mass ratio is small.
Figure 6 shows the relation between the Bi content, Si/C
mass ratio, thickness, and the graphite nodule count of the
specimens. The graphite nodule count increased by thinning
of the specimen. This is due to the high cooling rate of the
melt by the thinning as well as the graphite particle diameter.
The tendency that the graphite nodule count increased along
with the Bi content was observed for every thickness. This
tendency was also reported by Horie et al.2,3) and Sato et al.4)
The graphite nodule count increased as the Si/C mass ratio
increased. Generally, the addition of Si decreases the graphite
particle diameter and increases the nodule count.7,8) Also for
the thin wall spheroidal graphite cast iron castings used in
this study, an increase in the Si/C mass ratio increased the
graphite nodule count.
Figure 7 shows the eect of the Bi content and Si/C mass
ratio on the matrix structure. The graphite area fraction was
constant (approximately 10%) regardless of the Bi content or
Si/C mass ratio. The area fraction of ferrite increased and the
area fraction of pearlite decreased as the Si/C mass ratio
increased. For example, when the Si/C mass ratio was 0.97
and the thickness of the specimen was 10 mm, the area
fraction of ferrite increased about 20% and that of pearlite
decreased about 20% by a 0.01 mass%Bi content. When the
thickness of the specimen was 3 mm, the area fraction of
ferrite increased about 10% and the that of pearlite decreased
about 10% by a 0.01 mass%Bi content.

H. Takeda, H. Yoneda and K. Asano

Graphite particle diameter, d/ m

180

25

Graphite nodule count, NG /mm 2

Fig. 6

15
10

0.67
0.79
0.97

0.53

0.55

0.67
0.79
0.97

0.66
0.79
0.97

5
6 8 10
4
Thickness, t /mm

8 10
6
4
Thickness, t /mm

8 10
6
4
Thickness, t /mm

12

Relationship between the graphite particle diameter and the thickness of the specimens containing various amounts of Bi, C and Si.

800

(a) 0mass% Bi

600

(b) 0.005mass%Bi

Si/C

(c) 0.01mass% Bi

Si/C

Si/C

0.56

0.53

0.55

0.67
0.79

0.67

0.66

0.79

0.79

0.97

0.97

0.97

400

200

4
8 10
6
Thickness, t/mm

4
8 10
6
Thickness, t/mm

4
8 10
6
Thickness, t/mm

12

Relationship between the graphite nodule count and the thickness of the specimens containing various amounts of Bi, C and Si.

(a) t =3mm

0mass%Bi

(b) t =3mm
0.01mass%Bi

60
Area fraction (%)

Si/C

Si/C
Si/C

100
80

(c)
( 0.01mass%Bi

20

0
Fig. 5

(b) 0.005mass%Bi

(a) 0mass%Bi

40

Graphite

20

Ferrite

3.2

Perlite

0
(c) t =10mm 0mass%Bi
80

(d) t =10mm
0.01mass%Bi

60
40
20
0
0.5 0.6 0.7 0.8 0.9
Si/C

Therefore, the cooling curves of the thin wall spheroidal

graphite cast irons with the hypoeutectic and hypereutectic
compositions with dierent Si contents were subsequently
analyzed and the eect of Bi on the microstructure was
investigated.

1.0 0.5 0.6 0.7 0.8 0.9 1.0

Si/C

Fig. 7 Eect of Bi content and Si/C mass ratio on area fraction of graphite,
ferrite and pearlite (thickness (t); 3 and 10 mm).

These results show that the containing up to 0.01 mass%Bi

promoted the renement of the graphite, increased the
graphite nodule, and promoted the ferritizing of the matrix
of the spheroidal graphite cast iron. It was also found that the
increase in the Si content promoted the eects of Bi even
though the specimen is thin; i.e., the cooling rate is high.

Thermal analysis of thin wall spheroidal graphite

cast iron with Bi (experiment B)
3.2.1 Microstructure
Figure 8 shows the microstructure of the specimens with
the thickness of 10 mm in No. 5 and No. 6. Table 3 shows
the graphite spheroidization rate, the graphite particle
diameter, the graphite nodule count and the area faction of
the matrix structure of the specimens. Specimen No. 5 with 2
and 3 mm thickness contained the chill in the matrix. The
graphite spheroidizing ratio of the specimens without chill
was 80% or more, regardless of the Bi content. The mean
diameter of the graphite decreased and graphite nodule count
increased as the thickness decreased and the Bi content
increased, as well as the specimens from experiment A. The
area fraction of ferrite increased and that of pearlite
decreased somewhat as the Bi content increased.
3.2.2 Eect of Bi on eutectic solidication
Figure 9 shows the cooling curves of specimens No. 5
and No. 6. Although the primary crystallization start point
can be seen in No. 5, it can not be seen in No. 6. This is
due to the fact that specimen No. 5 has a hypoeutectic

Eect of Silicon and Bismuth on Solidication Structure of Thin Wall Spheroidal Graphite Cast Iron

(a) No.5-1 Bi 0mass%

(c) No.6-1 Bi 0mass%

(b) No.5-2 Bi 0.01mass%

(d) No.6-2 Bi 0.01mass%

181

100 m

No.6 (CE 4.4)

No.5 (CE 4.1)

Fig. 8 Microstructure of specimens No. 5 and No. 6 (thickness (t) = 10 mm) (Nital etched).

Table 3 The graphite spheroidization rate, the graphite particle diameter, the graphite nodule count and the area fraction of the matrix
structure of the specimens No. 5 and No. 6.
No. 5 (CE 4.1)
Specimen

No. 6 (CE 4.4)

No. 5-1

No. 5-2

No. 6-1

No. 6-2

0 mass%Bi

0.01 mass%Bi

0 mass%Bi

0.01 mass%Bi

Thickness mm

10

10

10

10

Graphite spheroidization rate

%

82.3

81.5

80.2

80.1

81.4

82.8

82.4

81.8

80.3

82.3

81.1

80.4

Average graphite particle diameter

mm

15.2

18.4

13.8

16.7

10.0

12.1

13.6

16.5

9.2

10.4

12.1

13.8

Graphite nodule count

mm2

344

187

426

227

1025

883

482

298

1179

1028

639

346

Graphite

10.6

11.6

11.6

10.4

12.2

12.3

11.1

11.4

12.4

11.5

10.7

10.2

Pearlite

57.8

54.1

53.9

52.9

19.5

10.3

11.2

10.6

18.9

10.9

9.4

8.9

Ferrite

31.6

34.3

34.5

36.7

68.3

77.4

77.7

78.0

68.7

77.6

79.9

80.9

Area fraction %

Temperature, Tem /K

1600
1500
1400
1300

TP
eutectic
TES
TEM
TEE

TES

(a) No.5
(CE 4.1, Si/C 0.6)

eutectic

(b) No.6
(CE 4.4, Si/C 0.9)

TEM

Bi 0mass%
Bi 0.01mass%

TEE

Bi 0mass%
Bi 0.01mass%

TEU

TEU

1200

TEDS

TEDS
TEDE

1100

TEDE

1000
eutectoid

eutectoid

900
800
0

100

200

300 400
Time, T/s

Fig. 9

500

600

100

200

300 400
Time, T/s

Cooling curves of specimens No. 5 and No. 6 (thickness (t) = 10 mm).

500

600

182

H. Takeda, H. Yoneda and K. Asano

Temperature, Tem /K

1440

(a) No.5 (CE 4.1,Si/C 0.6)

(b)

No.6 (CE 4.4,Si/C 0.9)

1420
1400
1380
1360
Bi,mass%

1340
1320

TES

TEE

Bi,mass%

0.01

0.01

10
20
30
Cooling rate, K/s

40 0

TES

TEE

10
20
30
Cooling rate, K/s

40

Fig. 10 Eect of Bi content and cooling rate on temperature of eutectic start (TES) and end of eutectic solidication (TEE).

Table 4 The average cooling rate (K/s) to temperature of the eutectic start
vs. specimen thickness.
Specimen

No. 5
No. 6

Bi content
mass%

Thickness
2 mm

3 mm

5 mm

10 mm

35.2

10.7

5.0

2.0

0.01

37.8

15.9

5.1

2.1

37.5

17.9

9.6

4.7

0.01

40.0

18.8

11.7

5.7

composition which generates the solidication latent heat

by crystallization of the primary crystal austenite whereas
specimen No. 6 has a hypereutectic composition in which
the graphite crystallizes as the primary crystal. A steep
increase in the temperature from the temperature of the
eutectic undercooling (TEU) was observed by adding Bi.
This indicates that many or much amount of graphite
particles are simultaneously crystallized out, followed by
the rapid solidication of the melt. In addition, the temperature of the eutectic start (TES) and temperature of
the eutectoid start (TEDS) were high for the specimen
containing Bi.
Table 4 shows the average cooling rate from TP to TES for
each thickness of specimens No. 5 and No. 6. It can be seen
that the cooling rate was increased by containing Bi for every
specimen. This is probably due to the fact that the vapor
pressure of Bi is high16) and the yield of Bi in the melt is
thought to be bad. It is thought that the evaporation of a
quantity of Bi deprives the heat of the melt.
Moreover, the cooling rate of the specimen No. 6 was
faster than that of the specimen No. 5. This reason is thought
as follows: In the hypoeutectic composition (specimen No. 5),
the reduction in melt temperature was thought to be suppressed due to the solidication latent heat generated by the
primary austenite crystallization. On the other hand, in the
hypereutectic composition (specimen No. 6), it is thought
that the reduction in melt temperature is not suppressed
because little heat is generated when the primary graphite
crystallizes out.
Figure 10 shows the eect of the Bi content and cooling
rate on the temperature of the eutectic start (TES) and end

of the eutectic solidication (TEE). For every cooling rate,

the TES of specimen No. 6 is higher than that of specimen
No. 5. This is due to the fact that the CE of specimen No. 6 is
higher than that of specimen No. 5. Regardless of the cooling
rate of the specimens, the TES and TEE of the specimens
containing 0.01 mass%Bi were higher than those of the
specimens without Bi.
Figure 11 shows the eect of the Bi content and eutectic
solidication time (ET) for specimens No. 5 and No. 6.
Although the change in the ET by containing Bi was not seen
for specimen No. 5 (hypoeutectic composition), the ET was
decreased in specimen No. 6 (hypereutectic composition)
by containing Bi. As previously described, the graphite
nodule count of specimen No. 6-2 containing 0.01 mass%Bi
was more than that of specimen No. 6-1 without Bi. Ohi
et al.17) have researched the inuence of graphite nodule
count on the eutectic solidication of hypereutectic spheroidal graphite cast iron and reported that the eutectic
solidication time (ET) shortened as the graphite nodule
count increased. From this result, it is thought that ET is
shortened because an increase in the graphite nodule count
reduced the time required for graphite growth. Furthermore,
it is thought that an increase in the cooling rate of hypereutectic spheroidal graphite cast iron melt by Bi addition
shorten ET.
3.2.3 Eect of Bi on eutectoid transformation
Figure 12 shows the eect of the Bi content, thickness of
the specimen on the temperature of the eutectoid start
(TEDS) and end of the eutectoid transformation (TEDE)
for the specimens without chill. For specimen No. 5, the
TEDS increased, while the TEDE did not change by adding
Bi (Fig. 12(a)). For specimen No. 6 with the hypereutectic
composition containing 0.01 mass%Bi, the TEDS increased
and the TEDE decreased (Fig. 12(b)). As previously
described, the graphite nodule count increased and the
ferritizing was promoted by the Bi. The increase in the
graphite nodule count leads to a decrease in the distance
among the graphite nodules in the matrix. This promotes
the diusion of C in the matrix into the previously
crystallized graphite during the cooling after the eutectic
solidication. This probably leads to the phenomenon that
the eutectoid transformation reaction starts at a compara-

Eutectic solidification time, ET /s

Eect of Silicon and Bismuth on Solidication Structure of Thin Wall Spheroidal Graphite Cast Iron

120 (a) No.5 (CE 4.1, Si/C 0.6)

100

183

(b)No.6 (CE 4.4, Si/C 0.9)

0 mass%Bi

0 mass%Bi

0.01 mass%Bi

0.01 mass%Bi

80
60
40
20
0
0

4
6
8 10
Thickness, t/mm

12 0

4
6
8 10
Thickness, t/mm

12

Temperature, Tem /K

Fig. 11 Eect of Bi content and thickness of specimen on eutectic solidication time.

1200
(a) No.5 (CE 4.1, Si/C 0.6)
1150
1100
1050
1000
950
900

Bi,mass% TEDS

850
800
0

(b)No.6 (CE 4.4, Si/C 0.9)

TEDE

Bi,mass%

0 Bi

0 Bi

0.01Bi

0.01Bi

10

Thickness, t/mm

12 0

TEDS

TEDE

10 12

Thickness, t/mm

Fig. 12 Eect of Bi content and thickness of specimen on the temperature of eutectoid start (TEDS) and end of eutectoid transformation
(TEDE).

tively high temperature and the ferritizing of the matrix is

promoted.
These results show that containing 0.01 mass%Bi increases the temperature of the eutectoid start and promotes
a steady eutectoid transformation of the thin wall spheroidal
graphite cast iron.
3.3 EPMA analysis of spheroidal graphite
Since the renement of the graphite nodule and the
increase in the graphite nodule count was recognized by
adding Bi, the inside of the spheroidal graphite in the cast
iron containing Bi was analyzed by FE-EPMA in order to
examine the eect of Bi on the graphite renement.
Figure 13 shows the SEI and the X-ray images of C and
Bi in the spheroidal graphite of a specimen containing
0.01 mass%Bi (specimen No. 5-2). It can be seen that Bi
exists in the vicinity of the center of the graphite.
Figure 14 shows the magnied observations of where
Bi was detected. It indicates that the center of the graphite

consists of the Bi oxide and the Bi sulde, because Bi, O

and S were detected from almost the same area. Moreover,
it is thought that a compound of Mg and Si exists
because Mg and Si were also detected from the same
area. Ce and La were also distributed in almost the same
position as S, although their detection brightness is low.
Ce and La are probably from RE in the spheroidization
agent. Igarashi et al.18) reported that MgS and MgO are
included in the vicinity of the center of the spheroidal
graphite in the spheroidal graphite cast iron without Bi.
This report supports the fact that MgS and MgO also exist
in the center of the graphite specimen without Bi in this
study.
Subsequently, the formation of compounds in the graphite
at the spheroidization temperature (1773 K) in the present
study was examined from the viewpoint of the standard
free energy of formation. The standard free energies of
formations of the oxide, sulde and silicide of Bi and Mg
are as follows:19)

184

H. Takeda, H. Yoneda and K. Asano

SEI

Bi

Fig. 13 Secondary electron image and X-ray images of C and Bi in the spheroidal graphite in the specimen containing Bi. (specimen
No. 5-2)

SEI

Bi

Mg

Si

La

Ce

Fig. 14 Secondary electron image and X-ray images of Bi, S, Mg, Si, O, La and Ce in a compound in the center of the spheroidal graphite
shown in Fig. 13.

2/3Bi2 O3 109:1 kJ/molO2

2/3Bi2 S3 42:9 kJ/molS2

MgO 733:7 kJ/molO2

2
3

MgS 395:2 kJ/molS2

Mg2 Si 8552:5 kJ/molSi

These values show that these Bi compounds and Mg

compounds are easily formed, and coexist in the melt after
the spheroidization. This fact and the results from the FEEPMA lead to the conclusion that Bi2 O3 and Bi2 S3 were
formed from Bi, O and S, and Mg2 Si was formed from Mg
and Si. Moreover, the reason why these compounds coexist
was considered. As expressed by eq. (6), the Bi sulde is
oxidized to form the Bi oxide.
2Bi2 S3 9O2 ! 2Bi2 O3 6SO2

When Mg in the spheroidizing agent diuses into the melt

during the spheroidizing treatment, Mg reduces the Bi oxide
to form MgO. However, under rapid solidication, the Mg
not used for the reduction combines with Si in the melt and
forms the Mg-Si compound in the vicinity of the Bi oxide and
Bi sulde. This leads to the coexistence of Bi2 O3 , Bi2 S3 and
Mg2 Si.
These results lead to the conclusion that the Bi compound
was rst formed, then the Mg compound was formed around

the Bi compound to form a nucleus, and then the graphite

crystallized out from the nucleus. The formation of such
many heterogeneous nucleation sites in the melt would lead
to the distribution of many ne graphite particles.
4.

Conclusions

The eect of Si and Bi on the microstructure of thin wall

spheroidal graphite cast iron has been investigated by
examining the microstructure and cooling curves of the
spheroidal graphite cast irons specimens with 2 to 10 mm
thicknesses. The results obtained are as follows:
(1) For the C and Si contents in the present study, an
increase in the Si/C mass ratio was eective for decreasing
the chill in the thin wall spheroidal graphite cast iron, and the
chilling was inhibited by containing 0.01 mass% Bi even
though the thickness of the specimen was 2 mm.
(2) Amounts up to 0.01 mass%Bi promoted renement in
the graphite, increased the graphite nodule, and promoted the
ferritizing of the matrix of the spheroidal graphite cast iron.
It was also found that the high Si content promoted these
eects of Bi even though the specimen is thin.
(3) The temperatures of the eutectic start and the eutectic
solidication end increased by 0.01 mass%Bi. Especially,
at the hypereutectic composition, the eutectic solidication
time was shortened by containing Bi. The temperature of the

Eect of Silicon and Bismuth on Solidication Structure of Thin Wall Spheroidal Graphite Cast Iron

eutectoid transformation start increased and the stable

eutectoid transformation was promoted by the Bi.
(4) The substance including the Bi and Mg compounds
existed in the vicinity of the center of the spheroidal graphite
in the cast iron containing Bi. This result indicates that these
compounds act as a nucleus of the graphite. It is thought
that this promotes the graphitzation to increase the graphite
nodule count.
REFERENCES
1) H. Horie, T. Miyate, M. Saito and T. Kowata: IMONO 56 (1984) 491
496.
2) H. Horie and T. Kowata: IMONO 60 (1988) 173178.
3) T. Kowata, H. Horie, M. Nakamura, S. Hiratsuka and A. Chida:
IMONO 65 (1993) 209214.
4) K. Sato, Z. Murakami and A. Chida: J. JFS 76 (1997) 124134.

185

5) J. H. Choi, J. K. Oh, C. O. Choi, J. K. Kim and P. K. Rohatgi: Trans.

AFS 112 (2004) 831840.
6) C. Labrecquem and M. Gagne: Trans. AFS 108 (2000) 3138.
7) K. Nakamoto, T. Kodera, T. Suzuki, Y. Mitiura and H. Horie: Reports
of the J. JFS Meeting 76 (1997) p. 119.
8) Y. Awaji and T. Takahashi: J. JFS 102 (2007) 3948.
9) H. Morrogh: Trans. AFS 60 (1952) 2033.
10) C. K. Donoho: Modern Castings 46 (1964) 608610.
11) G. S. Cole: Trans. AFS 80 (1972) 335348.
12) J. Verelst and A. DeSy: Giesserei 43 (1956) 305315.
13) I. Aoki and T. Tottori: Iron and Steel 43 (1957) 11911194.
14) W. Hiller and R. Walking: Foundry 90 (1962) 5457.
15) N. Nishi, T. Kobayasi and S. Taga: IMONO 48 (1976) 132138.
16) Chemical dictionary 7: Ed. by Chemical dictionary edit committee,
(Kyouritsu, Tokyo, 1997) p. 385.
17) T. Ohi and M. Fujioka: IMONO 54 (1982) 2126.
18) Y. Igarashi and T. Okada: J. JFS 70 (1998) 329335.
19) Iron and Steel handbook 1: Ed. by Japan Iron and Steel Inst. (Maruzen,
Tokyo, 1981) pp. 1416.