J. Mater. Sci. Technol., 2012, 28(9), 853–858.

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 of the centrifugal composite roll, it is needed that

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 devel-
opment 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
400–600 mm and that of roll cores is 500–1000 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 degen-
eration, the formation of chunky graphite, graphite
flotation and intercrystalline carbide, which leads to
the decrease in mechanical properties[3–5] .
During the process of heat treatment, high ther-
mal stress and structural stress arise on the inter-
face of composite rolls, which therefore puts forward
higher requirements for the properties of the duc-
tile 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).
the pouring temperature for ductile iron of the roll
core is higher than that for heavy-section ductile iron,
which aggravates degradated spheroidization and in-
oculation fade.
The techniques adopted for heavy-section ductile
iron are as follows[6–11] : (1) choosing a proper car-
bon saturation and silicon-carbon ratio to optimize
chemical compositions; (2) sorting out charging ma-
terials and taking measures to reduce the content of
spheroidizing interference elements; (3) using noduliz-
ers as well as spheroidizing methods with various el-
ement 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 tech-
nical scheme adopted in industrial production, with
the purpose to control the morphology and distribu-
tion 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), 853–858.

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

No. C Si Mn P S Cr
I 3.00–3.20 2.60–2.80 <0.30 <0.06 <0.02 <0.10
II 3.10–3.30 2.40–2.50 0.40–0.60 <0.08 <0.02 0.30–0.50
III 3.20–3.40 2.10–2.30 0.30–0.50 <0.08 <0.015 <0.10
No. Ni Mo Cu Sb Re Mg
I <0.50 <0.20 0.05–0.08
II 0.50–0.60 0.25–0.35 <0.01 0.01–0.03 0.03–0.06
III <0.50 <0.10 0.40–0.50 0.015–0.020 0.01–0.03 0.02–0.05

Table 2 Experimental scheme of ductile irons

Scheme Chemical composition Pig iron Nodulizer Alloying Subject Size/mm
A I (a) M Roll neck φ460 × 1850
B I (b) M Simulated sample φ460 × 1850
C II (a) R Ni, Cr, Mo Roll neck φ460 × 1850
D III (b) R Cu, Mn, Sb Roll neck φ460 × 1850
E III (b) R Cu, Mn, Sb Quenched sample φ2–φ4

Pig iron is the primary raw material for producing
ductile iron. Pig iron contains such interferential mi-
croelements 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 domes-
tic 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 low-
price alloy, focuses on the control technique for the
prevention of degradated spheroidisation and inocula-
tion fade to produce high-quality heavy-section duc-
tile 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 compo-
sitions, 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 compo-
nents are chosen for the three chemical compositions,
and silicon-carbon ratio is controlled with the proxim-
ity in carbon equivalent values. High-silicon-and-low-
carbon 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 al-
loys are used as nodulizers in order to obtain spherical
graphite with high roundness. The silicon-carbon ra-
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 hard-
ness. 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 fac-
tory, 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 1520–1530 ◦ C after the
desulfurization of the original melted iron. The period
from the beginning of speheroidization to pouring is
20–22 min. Pouring temperature is 1410–1420 ◦ 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, im-
pact and metallographic specimens are obtained along
the circumference line with a diameter of Φ310 mm
and in the range of 180–300 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), 853–858. 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. Mi-
crostructure analysis was carried out by optical
microscope. Figs. 1–4 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 fer-
rite 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 Duc-
tile 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 duc-
tile iron II is pearlite. After statistical analysis, the
fraction of cementite is more than 10%, due to the ad-
dition of carbide forming elements Cr, Mo, etc.. RE
856 Y.L. Bai et al.: J. Mater. Sci. Technol., 2012, 28(9), 853–858.

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

Table 3 Mechanical properties and nodulizing grade of ductile irons

Scheme Position Rm /(N/mm2 ) A/% Ak /(J/cm2 ) Hardness, HB
A Roll neck inlet 430–450 3.0–4.5 9–11 220–260
B Simulated sample inlet 390–420 2.5–3.5 8–10 200–230
C Roll neck inlet 520–550 1.5–2.5 4–6 240–280
D Roll neck inlet 580–620 2.5–3.5 7–9 240–270

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 re-
duced, 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,
Fig. 5 Fracture of ductile iron C
the fraction of the cementite is much smaller. In ex-
perimental scheme D, the graphite is fine and spheri-
cal, and it disperses homogeneously. The situation of The ductile iron in experimental scheme C has a low-
the graphite in experimental scheme D is better than est toughness because of the high content of cemen-
that in experimental scheme A, B and C in aspects tite. Although ductile iron D is made of average-
of size, quantity, morphology and distribution. RE- quality pig iron, small and spherical graphite distrib-
Mg nodulizer can efficiently remove the interferential utes on the fine pearlite matrix, and accordingly the
elements in average-quality pig iron. The addition of overall mechanical properties are very good.
pure Sb to the liquid metal at a proper time can make There is a relation between the mechanical prop-
good use of the advantage of Sb in promoting nucle- erties and the microstructure of ductile iron D. Fig. 5
ation of pearlite and improving the morphology of the shows the tensile fracture of ductile iron D under
graphite. SEM. Spherical graphite departs from the matrix at
3.2 Mechanical properties their boundaries, and the matrix has a characteristic
of cleavage fracture. He et al.[20,21] show that when
Mechanical properties have been tested with the ductile iron suffers from uniaxial tensile stress, micro-
samples cut off from the similar position of the roll cracks initiate at the interfaces between matrix and
and the simulated specimens. The results are shown graphite which are vertical to the tensile stress, and
in Table 3. It can be seen that as compared with duc- then extend along the interfaces. The interfaces pro-
tile irons in experimental scheme C and D, the tough- vide fracture resistance to the cracks, and therefore
ness of the ductile iron in experimental scheme A and the spherical graphite has a stronger ability of pas-
B is much better because of the ferrite matrix. How- sivating the cracks and providing fracture resistance
ever, the tensile strength and the hardness are lower. than the degenerated graphite. Fig. 6 shows the
 Y.L. Bai et al.: J. Mater. Sci. Technol., 2012, 28(9), 853–858. 857
the graphite is spherical with a diameter of 2.5 µm.
In general, the diameter of the spherical graphite nu-
clei is 0.5–2.0 µm[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 concen-
trates at the fringe of the spherical graphite. At the
fringe of the spherical graphite, the content of Mg and
Fig. 6 Interface between graphite and pearlite matrix in
S is much less than that at the center of the spheri-
ductile iron C
cal graphite. Therefore, Sb presents atom adsorption
interface structure between spherical graphite and characteristic at the surface of the spherical graphite.
pearlite matrix. The interlamellar spacing of the Table 4 Chemical composition of the center
pearlite is about 0.25–0.35 µm. Lamellar cementite and fringe of the graphite
nucleates and grows directly at the surface of the
spherical graphite. In this situation, the pro-eutectoid Center Fringe
Element
wt% at.% wt% at.%
phase of pearlite transformation is cementite, which
C 15.50 34.54 17.80 43.48
agrees well with Zhu et al.[22] .
O 3.32 5.55
3.3 Action mechanism of Sb Mg 22.75 25.04 13.71 16.54
Si 0.58 0.56 1.87 1.96
In order to study the action mechanism of Sb, drop
S 22.39 18.69 9.53 8.72
quenched specimens were prepared with the purpose Sb 1.00 0.24
of testing the distribution of Sb at the initial stage of Ca 1.80 1.20 0.73 0.53
graphite growth. The sample in Fig. 7 was prepared Ce 5.11 0.98 1.79 0.38
with chemical composition III made of average-quality Nd 0.76 0.14
pig iron. The diameter of the samples was about Φ2– Fe 27.78 13.31 53.58 28.15
Φ4 mm. After being ground, the samples were ob-
served under SEM. It can be seen that the profile of

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), 853–858.
Based on the Spiral Growth Model proposed by
Double and Hellawell[24] , spherical graphite is poly-
crystal made of many pyramid single crystals which
grow radially from graphite nuclei. The datum plane
of the graphite pyramid is vertical to the radial direc-
tion of the graphite sphere. The surface of the spheri-
cal 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 spread-
ing rapidly to the graphite which makes the diameter
of the spherical graphite small[25] but also make the
graphite pyramids grow homogeneously along each di-
rection resulting in fine graphite with higher spherical.
The concentration of Sb on the surface of the spheri-
cal 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 un-
spheroidizing effect because of its high activity[26] . Af-
ter inoculation and spheroidisation, nodularizer RE-
Mg has removed O, S and other anti spheroidizing el-
ements 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 op-
timize the morphology of the graphite, enhance the
spheroidizing effect and improve mechanical proper-
ties 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 me-
chanical 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 suit-
able 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 compre-
hensive mechanical properties can be produced by us-
ing 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 spheri-
cal 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.
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