J. Mater. Sci. Technol., 2012, 28(9), 853858.

Chemical Compositions, Microstructure and Mechanical

Properties of Roll Core used Ductile Iron
in Centrifugal Casting Composite Rolls
Yunlong Bai,Yikun Luan, Nannan Song, Xiuhong Kang , Dianzhong Li and Yiyi Li
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang
110016, China
[Manuscript received March 14, 2011, in revised form December 21, 2011]

The industrial manufacture processes of three kinds of roll core used ductile irons have been investigated
via systematical experiments. Effects of the ratio of C/Si, pig iron, nodularizer and alloying method on the
microstructure and mechanical properties of the heavy section ductile iron have been analyzed. It has been
found that when treated with RE-Mg plus Sb, high quality nodular castings can be produced even if much
anti spheroidizing alloy elements are included in the pig iron. The alloy element Sb played an important role
in the control of graphite morphology.
KEY WORDS: Centrifugal casting; Roll; Heavy section ductile iron; Micro-alloying with Sb

1. Introduction
Ductile iron, as the material for the roll neck and
roll core of centrifugal composite casting rolls, has
been widely used for a long time[1] . With the development of rolling technology, mechanical properties
of the ductile iron will face higher requirements. The
tensile strength of the roll cores should increase to
400 MPa[2] . In general, the diameter of roll necks is
400600 mm and that of roll cores is 5001000 mm,
which belongs to heavy-section ductile iron. The slow
solidification rate and long eutectic freezing time of
heavy section castings tend to cause graphite degeneration, the formation of chunky graphite, graphite
flotation and intercrystalline carbide, which leads to
the decrease in mechanical properties[35] .
During the process of heat treatment, high thermal stress and structural stress arise on the interface of composite rolls, which therefore puts forward
higher requirements for the properties of the ductile iron. In order to obtain fine metallurgical fusion
on the working layer materials and the ductile iron
Corresponding author. Ph.D.; Tel./Fax: +86 24 23971429;
E-mail address: xhkang@imr.ac.cn (X.H. Kang).

of the centrifugal composite roll, it is needed that

the pouring temperature for ductile iron of the roll
core is higher than that for heavy-section ductile iron,
which aggravates degradated spheroidization and inoculation fade.
The techniques adopted for heavy-section ductile
iron are as follows[611] : (1) choosing a proper carbon saturation and silicon-carbon ratio to optimize
chemical compositions; (2) sorting out charging materials and taking measures to reduce the content of
spheroidizing interference elements; (3) using nodulizers as well as spheroidizing methods with various element contents; (4) adding microelements to increase
graphite nucleation capacities or graphite nucleation
quantity and using long-acting inoculants or different
inoculation techniques to decrease inoculation fade;
(5) controlling the cooling rate of the castings; (6)
adopting alloying or heat treatment to refine matrix
structure and improve the properties. The integrated
application of the above techniques is the main technical scheme adopted in industrial production, with
the purpose to control the morphology and distribution of the graphite and obtain ideal microstructure
as well as mechanical properties.

854

Y.L. Bai et al.: J. Mater. Sci. Technol., 2012, 28(9), 853858.

Table 1 Chemical compositions of the ductile iron samples (wt%)

No.
I
II
III
No.
I
II
III

C
3.003.20
3.103.30
3.203.40
Ni
<0.50
0.500.60
<0.50

Si
2.602.80
2.402.50
2.102.30
Mo
<0.20
0.250.35
<0.10

Mn
<0.30
0.400.60
0.300.50
Cu

P
<0.06
<0.08
<0.08
Sb

S
<0.02
<0.02
<0.015
Re

0.400.50

<0.01
0.0150.020

0.010.03
0.010.03

Cr
<0.10
0.300.50
<0.10
Mg
0.050.08
0.030.06
0.020.05

Table 2 Experimental scheme of ductile irons

Scheme
A
B
C
D
E

Chemical composition
I
I
II
III
III

Pig iron
(a)
(b)
(a)
(b)
(b)

Nodulizer
M
M
R
R
R

Pig iron is the primary raw material for producing

ductile iron. Pig iron contains such interferential microelements as As, Sn, Sb, Pb, Bi, Ti and Te that all of
which have bad influences on spherification of ductile
iron. During the production process of heavy-section
ductile iron these interferential elements should be
eliminated as drastically as possible[12,13] . Due to the
resource scarcity in high-quality pig iron in China,
the provision of high-quality materials remains to be
a problem which impeding the development of domestic rolling industry. Therefore, techniques mentioned
above will increase production cost and the mismatch
of some techniques will not lead to desirable outcomes.
This study, by using average-quality pig iron and lowprice alloy, focuses on the control technique for the
prevention of degradated spheroidisation and inoculation fade to produce high-quality heavy-section ductile iron. The main aim of this study is to find a sound
process of producing heavy-section ductile iron used
for centrifugal casting rolls via the chemical compositions, microstructure and mechanical properties of
the ductile irons.
2. Experimental
2.1 Design of chemical composition
The chemical compositions of the ductile irons
used in this work are shown in Table 1. In order
to prevent graphite flotation, hypoeutectic components are chosen for the three chemical compositions,
and silicon-carbon ratio is controlled with the proximity in carbon equivalent values. High-silicon-and-lowcarbon principle is adopted in Ductile iron I. It has
the largest silicon-carbon ratio among the three kinds
of ductile iron. The content of the alloy elements is
controlled so that there is a certain amount of ferrite
in the matrix of the ductile iron which will increase
the plasticity and thus resist the transformation stress
as well as the thermal stress. Fe-Si-Mg and Ni-Mg alloys are used as nodulizers in order to obtain spherical
graphite with high roundness. The silicon-carbon ra-

Alloying

Ni, Cr, Mo
Cu, Mn, Sb
Cu, Mn, Sb

Subject
Roll neck
Simulated sample
Roll neck
Roll neck
Quenched sample

Size/mm
460 1850
460 1850
460 1850
460 1850
24

tio of Ductile iron II is between those of the other two

kinds of ductile iron. RE-Mg alloy is used for Ductile
iron II; Ni, Cr and Mo alloy is used for strengthening
the matrix so as to improve its strength and hardness. Meanwhile, in order to avoid large amount of
carbides, the amount of inoculated silicon has been
increased.
2.2 Experimental scheme
Under the real production conditions of the factory, the scheme shown in Table 2 is adopted. In the
experiment, two kinds of pig iron are used. Pig iron
(a) is of high-quality with a microelement average of
0.065%. While, pig iron (b) is of average-quality with
a microelement average of 0.186%. In Table 2, M
stands for Fe-Si-Mg+Ni-Mg nodulizer and R stands
for RE-Mg nodulizer. In experimental scheme E, as
to ductile iron III, before pouring, a small amount
of melted iron is dropped into the cold rinse bank to
obtain quenched samples, which are used to examine
the nuclei and growth of graphite in its early growth
period. The quenching samples contain 0.02% Sb as
the same weight added into the melted iron during
the later period of spheroidization. Spheroidization
treatment is adopted at about 15201530 C after the
desulfurization of the original melted iron. The period
from the beginning of speheroidization to pouring is
2022 min. Pouring temperature is 14101420 C and
stream inoculation technique is adopted during the
pouring process. Annealing treatment is adopted for
rolls and simulated specimens (scheme B in Tables 2
and 3). Annealing temperature is 650 C. Tensile, impact and metallographic specimens are obtained along
the circumference line with a diameter of 310 mm
and in the range of 180300 mm to the end along the
axial direction.
3. Results and Discussion
3.1 Microstructure
After being ground and polished, the samples were

Y.L. Bai et al.: J. Mater. Sci. Technol., 2012, 28(9), 853858.

855

Fig. 1 Microstructures of the inner core produced by ductile iron A

Fig. 2 Microstructures of the cast block produced by ductile iron B

Fig. 3 Microstructures of the cast block produced by ductile iron C

etched with 2% nitric acid alcohol solution. Microstructure analysis was carried out by optical
microscope.
Figs. 14 show the microstructure
of the roll neck and the simulated specimens, in
which Figs. 1(a)4(a) show general morphologies and
Figs. 1(b)4(b) the details of the carbide or graphite
in different ductile irons. From Figs. 1 and 2, it can
be seen that the quality of the pig iron affects the
morphology of graphite. The matrix of the ductile
iron made of high quality pig iron is composed of ferrite and pearlite, as shown in Fig. 1. Statistical tests
have been carried out on ten images for this sample.
The tested fraction of the cementite is less than 5%,

while the spherical graphite is mainly distributed on

the ferrite matrix. Most of the graphite is spherical,
together with some chunky graphite. The matrix of
the ductile iron made of average-quality pig iron is
mainly ferrite. The graphite is chunky. Hence, it is
difficult to get a good spheroidization result in Ductile iron I spheroidized by Ni-Mg when the pig iron
has a high content of intereferential elements.
Fig. 3 shows the microstructure of Ductile iron II
made of high-quality pig iron. The matrix of ductile iron II is pearlite. After statistical analysis, the
fraction of cementite is more than 10%, due to the addition of carbide forming elements Cr, Mo, etc.. RE

856

Y.L. Bai et al.: J. Mater. Sci. Technol., 2012, 28(9), 853858.

Fig. 4 Microstructures of the inner core produced by ductile iron D

Table 3 Mechanical properties and nodulizing grade of ductile irons
Scheme
A
B
C
D

Position
Roll neck inlet
Simulated sample inlet
Roll neck inlet
Roll neck inlet

Rm /(N/mm2 )
430450
390420
520550
580620

in the nodulizer can eliminate the bad effect of the

interferential elements[14,15] and reduce the content
of Si and Mg, which is helpful to avoid graphite
degeneration[16,17] . Hence, ductile iron II contains
mostly spherical graphite.
Fig. 4 shows the microstructure of ductile iron III
made of average-quality pig iron. In term of chemical
composition, the content of Si and Mg is further reduced, and the content of Mn is controlled to prevent
segregation. Alloying elements Cu and Mn are added
in order that the matrix is mainly pearlite[18,19] . With
the ferrite being prevented from precipitating along
the boundaries of austenite and graphite, there will
be a high content of C in the pearlite matrix. Hence,
the fraction of the cementite is much smaller. In experimental scheme D, the graphite is fine and spherical, and it disperses homogeneously. The situation of
the graphite in experimental scheme D is better than
that in experimental scheme A, B and C in aspects
of size, quantity, morphology and distribution. REMg nodulizer can efficiently remove the interferential
elements in average-quality pig iron. The addition of
pure Sb to the liquid metal at a proper time can make
good use of the advantage of Sb in promoting nucleation of pearlite and improving the morphology of the
graphite.
3.2 Mechanical properties
Mechanical properties have been tested with the
samples cut off from the similar position of the roll
and the simulated specimens. The results are shown
in Table 3. It can be seen that as compared with ductile irons in experimental scheme C and D, the toughness of the ductile iron in experimental scheme A and
B is much better because of the ferrite matrix. However, the tensile strength and the hardness are lower.

A/%
3.04.5
2.53.5
1.52.5
2.53.5

Ak /(J/cm2 )
911
810
46
79

Hardness, HB
220260
200230
240280
240270

Fig. 5 Fracture of ductile iron C

The ductile iron in experimental scheme C has a lowest toughness because of the high content of cementite. Although ductile iron D is made of averagequality pig iron, small and spherical graphite distributes on the fine pearlite matrix, and accordingly the
overall mechanical properties are very good.
There is a relation between the mechanical properties and the microstructure of ductile iron D. Fig. 5
shows the tensile fracture of ductile iron D under
SEM. Spherical graphite departs from the matrix at
their boundaries, and the matrix has a characteristic
of cleavage fracture. He et al.[20,21] show that when
ductile iron suffers from uniaxial tensile stress, microcracks initiate at the interfaces between matrix and
graphite which are vertical to the tensile stress, and
then extend along the interfaces. The interfaces provide fracture resistance to the cracks, and therefore
the spherical graphite has a stronger ability of passivating the cracks and providing fracture resistance
than the degenerated graphite. Fig. 6 shows the

857

Y.L. Bai et al.: J. Mater. Sci. Technol., 2012, 28(9), 853858.

Fig. 6 Interface between graphite and pearlite matrix in

ductile iron C

interface structure between spherical graphite and

pearlite matrix. The interlamellar spacing of the
pearlite is about 0.250.35 m. Lamellar cementite
nucleates and grows directly at the surface of the
spherical graphite. In this situation, the pro-eutectoid
phase of pearlite transformation is cementite, which
agrees well with Zhu et al.[22] .
3.3 Action mechanism of Sb
In order to study the action mechanism of Sb, drop
quenched specimens were prepared with the purpose
of testing the distribution of Sb at the initial stage of
graphite growth. The sample in Fig. 7 was prepared
with chemical composition III made of average-quality
pig iron. The diameter of the samples was about 2
4 mm. After being ground, the samples were observed under SEM. It can be seen that the profile of

the graphite is spherical with a diameter of 2.5 m.

In general, the diameter of the spherical graphite nuclei is 0.52.0 m[23] . Hence, the spherical graphite in
the present sample is at the initial stage of its growth.
During melting and nodulizing process, Sb in pig iron
forms Ce2 Sb, CeSb2 , Mg3 Sb2 , SbO2 , etc. It is also
proved that there are oxides or sulfides of nodulizing
elements at the center of the spherical graphite. Based
on the results of Fig. 7 and Table 4, it can be seen that
the profile cut through the graphite nucleus, and there
is no Sb at the center of the spherical graphite when
the addition amount of Sb is 0.02%, but Sb concentrates at the fringe of the spherical graphite. At the
fringe of the spherical graphite, the content of Mg and
S is much less than that at the center of the spherical graphite. Therefore, Sb presents atom adsorption
characteristic at the surface of the spherical graphite.
Table 4 Chemical composition of the center
and fringe of the graphite
Element
C
O
Mg
Si
S
Sb
Ca
Ce
Nd
Fe

Center
wt%
at.%
15.50 34.54
3.32
5.55
22.75 25.04
0.58
0.56
22.39 18.69
1.80
5.11
0.76
27.78

1.20
0.98
0.14
13.31

Fringe
wt%
at.%
17.80 43.48
13.71
1.87
9.53
1.00
0.73
1.79

16.54
1.96
8.72
0.24
0.53
0.38

53.58

28.15

Fig. 7 SEM photographs of the spherical graphite in Scheme E, (a) graphite centre, (b) EDS analysis at the
center, (c) graphite fringe, (d) EDS analysis at the fringe

858

Y.L. Bai et al.: J. Mater. Sci. Technol., 2012, 28(9), 853858.

Based on the Spiral Growth Model proposed by

Double and Hellawell[24] , spherical graphite is polycrystal made of many pyramid single crystals which
grow radially from graphite nuclei. The datum plane
of the graphite pyramid is vertical to the radial direction of the graphite sphere. The surface of the spherical graphite is enclosed by the datum planes of all the
pyramids around. Results from SEM show that Sb
stays on the datum planes of the pyramids, i.e. the
outer surface of the spherical graphite. During the
growth of the spherical graphite, Sb absorbing on the
surface of the spherical graphite forms a film. The film
made up of Sb can not only prevent C from spreading rapidly to the graphite which makes the diameter
of the spherical graphite small[25] but also make the
graphite pyramids grow homogeneously along each direction resulting in fine graphite with higher spherical.
The concentration of Sb on the surface of the spherical graphite decreases suddenly when the diameter of
the spherical graphite reaches a certain size. Thus, it
is difficult to determine the content of Sb with SEM.
Based on the above analysis, it can be seen that
Sb in ductile iron has two different effects. Sb in the
origin liquid metal together with Mg and Ce can form
a compound, which interferes the nodulizing process.
Compared with other elements, Sb has a higher unspheroidizing effect because of its high activity[26] . After inoculation and spheroidisation, nodularizer REMg has removed O, S and other anti spheroidizing elements effectively. The content of remaining RE and
Mg is at a reasonable level, and spherical graphite
begins to nucleate and grow. If Sb is added at this
time, it will display its advantage with the adsorption
mechanism. After spheroidisation, Sb added to the
liquid metal can also react with remaining RE, which
will thus abate the remaining RE0 s degenerating effect
on the spherical graphite in the heavy section ductile
iron. Hence, only adding Sb at a right time, can optimize the morphology of the graphite, enhance the
spheroidizing effect and improve mechanical properties of ductile iron.
4. Conclusions
(1) Ductile iron with sound spherical graphite and
ferrite matrix can be obtained by using high-quality
pig iron and Fe-Si-Mg+Ni-Mg nodulizer, but the mechanical properties are low. If the ductile iron is made
of average-quality pig iron, the degeneration of the
graphite is out of control. This process is not suitable for domestic production of centrifugal composite
casting rolls because of its high cost.
(2) If the ductile iron is made of high-quality pig
iron, nodulized by RE-Mg, and alloyed with Cr and
Mo, the mechanical properties can be strengthened.
But the toughness will decrease because of the high
content of cementite.
(3) Heavy section ductile iron with good comprehensive mechanical properties can be produced by using average-quality pig iron as row materials, RE-Mg
as nodulizer and being alloyed with Cu-Mn-Sb.

(4) The experimental results indicate that with the

addition of Sb to the liquid metal at a proper time, Sb
will be adsorbed on the datum plane of the graphite
pyramid to form a film at the surface of the spherical graphite. The film influences the nucleation and
growth of the spherical graphite, which can result in
fine graphite with higher spherical as compared with
that in the ductile iron nodulized by Ni-Mg.
REFERENCES
[1 ] T.Z. Wen and Y.Z. Guo: Introduction to Technical
Characterisitics of Metallurgical Rolls, Hebei Science
and Technology Press, Shijiazhuang, 1995, 85. (in Chinese)
[2 ] Y.L. Bai: Special Casting & Nonferrous Alloys, 2001,
(1), 26. (in Chinese)
[3 ] A.L. Javaid and C.R. Loper: Trans. AFS, 1996, 103,
135.
[4 ] M.D. Chaudhari, R.W. Heine and C.R. Loper: Trans.
AFS, 1974, 82, 431.
[5 ] S.I. Karsay and E. Compomanes: Modern Casting,
1970, 58, 85.
[6 ] G.S. Cho, K.H. Choe, K.W. Lee and A. Ikenaga: J.
Mater. Sci. Technol., 2007, 23, 97.
[7 ] G. Toktas, A. Toktas, M. Tayanc and G. Toktas:
Mater. Des., 2008, 29, 1600.
[8 ] E.J. Guo, L.P. Wang and X.L. Yao: J. Chin. Rare
Earth Soc., 2003, 21(1), 44. (in Chinese)
[9 ] D.H. Wu, B.C. Liu, T.S. Bai, J. Liang and H.Y. Guan:
J. Tsinghua Univ., 1984, 24(3), 75. (in Chinese)
[10] P. Larranaga, I. Asenjo, J. Sertucha, R. Suarez, I. Ferrer and J. Lacaze. Metall. Mater. Trans. A, 2009, 40,
654.
[11] T.S. Bai, D.H. Wu, B.Y. Shi, J.S. Liao, R.L. Gao, S.X.
Zhang, R. Li and Y.P. Wu: Modern Cast Iron, 1983,
(1), 7. (in Chinese)
[12] H.R. Geng, Y.F. Ye, J.J. Ma and H.Y. Zou: J. Iron
Steel Res., 1996, 8(4), 37. (in Chinese)
[13] H. Yang, J.Y. Zhang, X.F. Bian and G.X. Sun: J. Iron
Steel Res., 1999, 11(6), 53. (in Chinese)
[14] H.W. Hoover: Trans. AFS, 1986, 94, 601.
[15] C.R. Loper: Proc. 4th Int. Symp. on Physical Metallurgy of Cast Iron, Tokyo, Japan, 1989.
[16] J.Y. Zhou and S. Engler: Casting, 1997, 11, 10.
[17] American Foundrymen0 s Society: Ductile Iron Handbook, Des Plaines, IL, 1992.
[18] E.N. Pan, M.S. Lou and C.R. Loper: Trans. AFS,
1987, 95, 819.
[19] J. Lacaze, A. Boudot and V. Gerval: Metall. Mater.
Trans. A, 1997, 28, 2015.
[20] Z.R. He, S. Ji and G.X. Lin: Acta Metall. Sin., 1993,
29(4), 153. (in Chinese)
[21] Z.R. He, G.X. Lin and S. Ji: Mater. Sci. Eng. A,
1997, 234, 161.
[22] X.Y. Zhu, Y.H. Liu and Y.B. Zhang: Trans. Mater.
Heat Treatment, 2007, 28, 85.
[23] D.M. Stefanescu: ASM Handbook, Casting, ASM International, Metals Park, OH, 1988.
[24] D.D. Double and A. Hellawell: Growth Structure of
Various Forms of Graphite in the Metallurgy of Cast
Iron, Georgi Publication, St. Saphorin, 1975, 509.
[25] Z.H. Li and Y.X. Li: Mater. Sci. Forum, 2005, 475
479, 2769.
[26] S.Y. Research Institute of Foundry: Ductile Iron,
China Machine Press, Beijing, 1982, 42. (in Chinese)