Graphite nucleation control in grey cast iron

M. Chisamera1, I. Riposan*1, S. Stan1, D. White2 and G. Grasmo2

A research programme has been undertaken to achieve a more detailed understanding of
graphite nucleation control in grey cast irons, at different sulphur (0?02–0?1%), residual aluminium
(0?001–0?010%) and zirconium (0?001–0?015%) levels in iron melts. It was found that three groups
of elements are important to sustain a three stage model for the nucleation of graphite in grey
irons:
(i) strong deoxidising elements (Al, Zr) to promote early formed very small microinclusions,
oxide based, which will act as nucleation sites for later formed complex (Mn,X)S compounds
(ii) Mn and S to sustain MnS type sulphide formation
(iii) inoculating elements (Ca, Sr, etc.) which act in the first stage or/and in the second one of
graphite formation, to improve the capability of (Mn,X)S compounds to nucleate graphite.
It was confirmed that 0?07%S level is beneficial for graphite nucleation in grey irons with a lower
incidence of carbides and undercooled graphite, compared to 0?023%S cast irons. Low residual
Al level (0?001–0?003%) results in higher chill and more undercooled graphite and lower eutectic
cell count, in inoculated irons. A 0?007–0?010%Al content in the melt is important to sustain type A
graphite nucleation and reduced chill. Not only inoculation but also the preconditioning (Al or/and
Zr) of the base iron has a strong beneficial effect on the solidification pattern of cast irons. Both Al
and Zr sustain the type A graphite formation with a lower degree of undercooling and free
carbides. These elements were associated in a complex alloy (FeSi based), very efficient in
preconditioning of grey irons for thin wall castings, at a low addition rate.
Keywords: Grey irons, Graphite nucleation mechanism, Preconditioning, Inoculation, S, Al, Zr role

Introduction equivalent or rapid solidification of thin section, appears

Hypoeutectic and near eutectic range (carbon equivalent
CE53?4–4?2%) characterises high performance grey cast
iron. Structural features for these irons are mainly as
short, stubby graphite flakes (ASTM type A), fine
pearlite matrix, limited free carbides content, less
shrinkage and free from dross and pinholes/blowholes.
The morphology of the eutectic graphite is primarily
determined by the level of undercooling before eutectic
nucleation.1,2 A lower degree of undercooling promotes
the eutectic solidification with randomly oriented,
uniformly distributed graphite flakes (ASTM type A).
At moderate undercooling, the resultant eutectic cell
with fine flake graphite at the centre, surrounded by
courses flake graphite appears as a rosette (ASTM type
B). Considerable undercooling results in a generally fine
spacing of graphite flakes, randomly oriented within
interdendritic regions (ASTM type D). An extreme form
of type D, which is promoted by very low carbon
1
POLITEHNICA University of Bucharest, 313 Spl. Independentei, RO-
060042 Bucharest, Romania
2
ELKEM Foundry Products Division, N-4675 Kristiansand, Norway
*Corresponding author, email riposan@foundry.pub.ro
as ASTM type E graphite.
The chemistry of the base iron and also of the
treatment alloys, such as preconditioners and inoculants
is very important to control the iron structure. This is
carried out by preventing undercooling very close to the
metastable eutectic temperature (D and E types graphite
formation) or below it, where carbidic (white) structures
are formed. This objective is sustained by the formation
of a large number of nuclei particles which can initiate
nucleation with a low degree of undercooling. The
nucleation potency of existing or newly formed solid
nucleation sites is usually increased by inoculating
elements, such as Ca, Sr, Ba, rare earth etc., but
depending on the base iron contribution, such as affected
by Mn, S, O, Al, N, etc.
Background
Recent research works have identified a three stage
nucleation process for generating graphite in grey cast
iron.3–8 By means of electron microscope investigations,
it has been revealed that a nucleus for a graphite flake
consists of a particle with a body of sulphide surround-
ing a nucleus core of complex oxide (Fig. 1): 1 – small
oxide based sites (usually less than 2?0 mm) are formed
in the melt; 2 – complex (Mn,X)S compounds (usually

ß 2008 W. S. Maney & Son Ltd.

Received 21 May 2008; accepted 11 July 2008
DOI 10.1179/136404608X361639 International Journal of Cast Metals Research 2008 VOL 21 NO 1–4 39
Chisamera et al. Graphite nucleation control in grey cast iron

nucleation in grey irons, at different sulphur contents in

base iron subjected to preconditioning with Al or/and Zr
and inoculation.

1 – oxide based nucleus/core; 2 – complex Mn sulphide
body/shell; 3 – graphite nucleation
1 Three stage model for graphite nucleation in grey iron
less than 5?0 mm) nucleate at these microinclusions;
3 – graphite nucleates on the sides of the (Mn,X)S
compounds with lower crystallographic misfit with
graphite. In inoculated irons the (Mn,X)S compound
is more complex at lower Mn/S ratio and has higher
compatibility for graphite nucleation, especially with
inoculating elements contribution.
The hypothesis is that the oxides form as stable
microinclusions in the iron melt first and act as an
effective nucleation site for complex manganese sul-
phides, similarly to steel melt solidification.9–14 The
number of solid microparticles per volume of iron melt
is extremely high,15 but the ability of these particles to
nucleate graphite is strongly improved by the precondi-
tioning or/and inoculation before solidification.16
It has been found that three groups of elements are
important to sustain graphite nucleation in industrial
grey cast irons:
(i) strong deoxidising elements, such as Al and Zr,
to promote early forming microinclusions
(ii) Mn and S to support MnS type sulphides
formation
(iii) inoculating elements which act in the first stage
and/or in the second stage of graphite formation,
to improve the effectiveness of (Mn,X)S com-
pounds to nucleate graphite.3–8,17–19
The current experimental investigation in this paper was
designed to evaluate the possibility to control graphite
Experimental
Uninoculated and inoculated grey irons were tested in
three experimental programmes, which mainly consid-
ered S, Al and Zr as important influencing factors on the
solidification pattern. To ensure a low level of trace
elements, relatively pure synthetic pig irons were initially
prepared in coreless induction furnace (acid lining,
1500 kg, 250 Hz) from selected steel scrap, graphite
recarburiser and low aluminium ferrosilicon.
The experimental heats (Table 1) were obtained by
remelting the base synthetic pig iron in a smaller
induction furnace (acid lining, 100 kg, 2400 Hz), with
different additions, such as selected steel scrap (up to
10%), sulphur (FeS), high purity ferrosilicon (74?6%Si,
0?006%Al), FeMn80 and FeP18. The iron melts were
heated to 1500–1520uC for 10 min and then were tapped
into the inoculation ladle. Different FeSi based alloys
were used as inoculants (Table 2).
The sulphur variation (from 0?023 to 0?072%S)
according to the first experimental programme was
recorded by FeS addition into the furnace after melting
and deslagging. Low aluminium, Ca–FeSi alloy was
used as inoculant (0?4 wt-% ladle addition). Round bars
at 10 and 30 mm in diameter and standard W2 wedge
test specimen (ASTM A 367) were used (furan resin
mould, 1340–1350uC pouring temperature).
In the second experimental programme aluminium was
considered as the possible influencing factor while it is
added as preconditioner and by inoculation. The base iron
was recorded at very low content of residual aluminium
(0?001–0?002%) and low level of carbon equivalent
(CE53?6%). Al metallic was added into the furnace
before tapping as preconditioner. Unpreconditioned and
Al preconditioned base irons were also ladle inoculated by
very low (0?01%Al) and high (1?97%Al) aluminium levels,
Ca–FeSi alloys, at 1?0 wt-% addition. As result, a large
range of residual aluminium was obtained (0?002–
0?010%Al). The bars of 15 mm in diameter and 4 C type
chill test sample (ASTM A 367) were cast in furan resin
moulds (1330–1350uC).

Table 1 Chemical composition of experimental irons

Irons chemical composition*, wt-% Carbon

Infl. equiv.
Programme factor Heat Precond. Inoc. C Si Mn P S Al Zr (CE), %

I S 1 – UI{ 3.22 1.73 0.74 0.12 0.023 0.001 – 3.76

– Ca–FeSi 3.25 1.99 0.75 0.12 0.024 0.001 – 3.87
2 – UI 3.27 1.75 0.78 0.13 0.072 0.003 – 3.84
– Ca–FeSi 3.31 1.95 0.77 0.13 0.071 0.003 – 3.94
II Al 3 – UI 3.21 1.08 0.45 0.15 0.091 0.002 – 3.58
– Ca–FeSi 3.05 1.81 0.44 0.15 0.094 0.002 – 3.64
4 Al UI 3.21 1.10 0.46 0.15 0.092 0.007 – 3.59
Ca–FeSi 3.04 1.85 0.44 0.15 0.093 0.007 – 3.64
Ca,Al–FeSi 3.01 1.79 0.45 0.15 0.10 0.10 – 3.59
III Zr 5 – UI 3.15 1.49 0.62 0.20 0.10 0.002 – 3.70
Zr UI 3.15 1.52 0.62 0.20 0.097 0.003 0.011 3.71
6 – Sr–FeSi 3.29 1.67 0.57 0.21 0.097 0.003 – 3.90
Zr Sr–FeSi 3.20 1.67 0.55 0.21 0.099 0.004 0.013 3.81
*Typical trace levels (max.): 0?06%Cu, 0?03%Ni, 0?05%Cr, 0?05%Mo, 0?003%V, 0?006%Sn, 0?005%Sb and 0?005%Ti.
{
UI5uninoculated.

40 International Journal of Cast Metals Research 2008 VOL 21 NO 1–4


2 Influence of sulphur content and sample diameter on a
chill, b carbides, c undercooled graphite and d eutectic
cell count of uninoculated (UI) and inoculated (Ca)
irons (programme I)
Zr preconditioning was investigated in the third
experimental programme with 0?03 wt-%Zr addition as
FeSiZr alloy (43?5%Si, 30?8%Zr and 0?56%Al). It was
added in the melt stream during tapping (1450uC) into a
small ladle (3 kg melt, acid lined). The melt was
International Journal of Cast Metals Research
Chisamera et al. Graphite nucleation control in grey cast iron
3 Eutectic cell structure of inoculated irons, for a low
and b high sulphur level (30 mm dia. sample, 20 : 1,
stead reagent)
mechanically stirred on the ladle (steel rod). Low
aluminium, Sr–FeSi alloy was added on the melt surface
in the ladle (0?3 wt-%) at 1400–1420uC after deslagging
and was mechanically stirred for y1 min (steel rod).
Experimental unpreconditioned and Zr preconditioned
melt, as uninoculated and Sr inoculated iron, was
poured (1380–1400uC) into the test castings (furan no
bake bonded mould): wedge test specimen (20 mm in
width, 50 mm in height and 75 mm in length) and round
bar specimen (20 mm in diameter).
Chill sensitivity was evaluated as clear chill and total
chill of the wedge test samples. The measurement of chill
was recorded according to a controlled procedure, to
avoid hot shaking effect on the solid state transforma-
tion. Later the wedge was fractured and their fractures
were analysed. The portion nearest the apex entirely free
of any grey spots is designed as clear chill. If the wedge is
measured at the junction of the grey fracture with the
appearance of chilled iron, the measurement shell by
designed as total chill.
The effects of S, Al or Zr in uninoculated and
inoculated iron were also analysed by comparing the
microstructure (graphite morphology, free carbides
amount and eutectic cell count) of irons treated in
different conditions and solidified at different cooling
rates.
Results and discussion
In the first experimental programme (I) low sulphur
(0?023–0?024%) and high sulphur (0?071–0?072%) base
irons, at normal manganese (0?74–0?78%) and low
aluminium content (0?001–0?003%) were inoculated
with low aluminium (0?03%), Ca bearing FeSi alloy.
According to the first experimental programme data
(Figs. 2 and 3), the content of sulphur in the melt has an
important influence on the solidification pattern of cast
irons. For comparable carbon equivalent, manganese,
phosphorus and trace elements levels (Table 1), both
uninoculated and Ca inoculated irons are depending on
the sulphur content. Clear chill and total chill values,
which were applied to evaluate the chill results and to
compare the behaviour of cast irons are shown in
Fig. 2a. The favourable influence of inoculation was
observed in all cases. It can be also seen that sulphur
level appears to have a significant beneficial influence on
the chilling sensitivity of both uninoculated and
inoculated cast irons.
A number of particular trends in the structure
formation could also be identified. As can be seen in
Fig. 2, inoculation, cooling rate and sulphur level are
important influencing factors. The highest carbides and
undercooled graphite amount level was found for
2008 VOL 21 NO 1–4 41
Chisamera et al. Graphite nucleation control in grey cast iron

with respect to undercooled graphite control. Sulphur

4 Influence of Al preconditioning on a chill, b under-
cooled graphite and c eutectic cell count of uninocu-
lated (UI) and inoculated (Ca) irons (programme II)
uninoculated irons and the highest cooling rate condi-
tions (10 mm diameter sample). No influence of sulphur
was found in these irons. Inoculated irons show low
carbides sensitivity. Carbides sensitivity is lower with
increasing sulphur content but depending on the cooling
rate and inoculation application. At higher sulphur
level, carbides were avoided in inoculated irons for both
cooling rate levels and were significant decreased in
uninoculated irons at the lower cooling rate (Fig. 2b).
Undercooled graphite was present for uninoculated
irons, higher cooling rate, and lower sulphur content
irons (Fig. 2c). Not only inoculation but also the
increasing of sulphur content led to beneficial effects
level was also shown to be a key factor influencing
eutectic cell count (Figs. 2d and 3).
Aluminium residual was also found as an important
factor and as a possibility to improve structure
characteristics (programme II, Fig. 4). Low carbon
(3?0–3?2%), silicon (1?1%) and aluminium (0?002%) base
irons at the higher sulphur level (0?09–0?10%) were
subjected to aluminium preconditioning, before a
relatively high addition rate of Ca bearing FeSi alloy
(1?0 wt-% inoculant). In the above conditions, unin-
oculated irons present a high chill tendency and carbides
and undercooled graphite formation sensitiveness.
Aluminium increasing up to 0?007% level had a limited
beneficial influence on uninoculated irons as the chill
tendency and undercooled graphite were slightly
reduced. Inoculation appears to have a strong beneficial
effect, in all cases, but depending on the residual
aluminium content. The increasing of aluminium con-
tent up to 0?007–0?010% range in inoculated irons
showed clear beneficial effects as chilling tendency and
undercooled graphite amount were decreased, while
eutectic cell count increased.
It was confirmed that at more than 0?005%Al residual
(up to 0?010–0?015%Al), structure characteristics of
inoculated irons are improved without the detrimental
effect on pinholes in grey irons.
Zr preconditioning of the base iron led to important
benefits on the solidification pattern of uninoculated and
inoculated irons, too (programme III, Fig. 5). At
relatively lower content of residual aluminium (0?002–
0?004%), a 0?011–0?013% level of residual zirconium as a
result of FeSiZr preconditioning led to a strong
graphitising effect in uninoculated irons. Chill tendency
was drastically improved for both clear chill and total
chill evaluations. Free carbides were visibly reduced
while undercooled graphite was reduced. Sr–FeSi
inoculation at 0?3 wt-% addition rate was very efficient
for the considered irons at higher sulphur content (0?09–
0?10%). But also in these favourable conditions, Zr
preconditioning before inoculation led to better results,
with respect to chill sensitivity, reduced undercooled
graphite and increased eutectic cell count. These benefits
of Zr preconditioning are favourable to lower eutectic
undercooling solidification, graphite nucleation site
morphology, size and count.17–19
Based on the conclusions from laboratory experi-
ments a complex Al and Zr bearing FeSi alloy
(4%Al–4%Zr–1%Ca–FeSi)17 was designed for iron
melt preconditioning, mainly for grey irons produc-
tion in difficult conditions (low sulphur or/and low
aluminium base iron, thin wall castings, long holding
time, etc.) when carbides or/and undercooled graphite
are usually problems.17–19 Figure 6 illustrates some
representative beneficial results for cooling curves

Table 2 Inoculation representative parameters

Inoc. Inoculants chemical composition, wt-%

Influencing Inoc. add., Inoc.
Programme factor system swt-% Tech. Si Ca Al Sr Fe

I S Ca–FeSi 0.4 In stream (tapping) 1480–1500uC 76.0 1.2 0.03 – Bal.

II Al Ca–FeSi 1.0 In ladle (tapping) 1450¡10uC 74.8 0.75 0.01 –
Bal.
Ca,Al–FeSi 73.9 0.86 1.97 –
III Zr Sr–FeSi 0.3 In ladle (tapping) 1400–1420uC 77 0.01 0.01 0.8 Bal.

42 International Journal of Cast Metals Research 2008 VOL 21 NO 1–4


5 Influence of Zr preconditioning on a chill, b undercooled
graphite, c carbides and eutectic cell count of uninocu-
lated (UI) and inoculated (Sr) irons (programme III)
analysis of 0?10 xwt-%Al,Zr–FeSi alloy addition before
0?30 wt-%Ca,Zr,Al–FeSi inoculation. This foundry
(automotive component producer) used electrically
melted base iron and experienced carbides occurrence
in sections up to 5 mm as a major problem.
Representative temperatures of cooling curves, such as
the lower (TEU) and higher (TER) eutectic temperatures
and the temperature of the end of solidification (TES)
increased, as the result of preconditioning (Fig. 6a). As a
result, the most important parameters of solidification
had a beneficial evolution, compared to the equilibrium
temperatures in the stable/graphitic (Tst) and metastable/
white (Tmst) systems (Fig. 6b). Al,Zr–FeSi precondition-
ing led to the decreasing of conventional undercooling at
the beginning of eutectic solidification DTm (Tst2TEU)
and at the end of solidification DT3 (TES2Tmst). The
increasing of the levels of parameters DT1 (TEU2Tmst)
and DT2 (TER2Tmst) shows the decreasing of the
sensitivity to undercooled graphite formation. The lower
recalescence level (DTr5TER2TEU) is also a beneficial
effect of preconditioning of these hypoeutectic grey cast
irons. Recalescence is a function of the amount of
austenite and graphite that are precipitated during the
first part of eutectic freezing. With high recalescence
values there might be a risk of microshrinkage and
porosity, especially in soft moulds.
International Journal of Cast Metals Research
Chisamera et al. Graphite nucleation control in grey cast iron
6 a representative temperatures and b parameters of
cooling curves of unpreconditioned and 0?1 wt-%Al,Zr–
FeSi preconditioned and 0?3 wt-%Ca, Zr,Al–FeSi inocu-
lated hypoeutectic grey iron in foundry conditions
As a result, the quality of automotive castings was
improved: carbides and undercooled graphite eliminated
from 3 mm sections, type A graphite promoted, heat
treatment eliminated, tensile strength increased (from
250 to 283 N mm22).
Conclusions
The graphite formation capacity in hypoeutectic grey cast
irons (3?6–3?9%CE), with low (0?023%) and high (0?07%)
sulphur contents, uninoculated and ladle inoculated (Ca–
FeSi, Sr–FeSi or Ca,Zr,Al–FeSi alloys), as received or
with Al or/and Zr preconditioning before inoculation has
been examined. Clear and total chill was determined in
wedge specimens, as well as structures (graphite mor-
phology, carbides amount and eutectic cell count) in
round bars over a range of diameter size (10–30 mm).
Based on this work the following main conclusions can be
drawn.
1. It was confirmed the importance of strong deoxidis-
ing elements (Al, Zr), sulphur and inoculating elements
(Ca, Sr) to sustain a three stage model for the nucleation
of graphite in grey irons at lower eutectic undercooling:
complex (Mn,X)S compounds, nucleated on the oxide
based sites act as major nucleants for flake graphite.
2. The level of 0?07%S is beneficial for graphite
nucleation in inoculated grey irons with a lower inciden-
ce of carbides and undercooled graphite, compared to
0?023%S cast irons.
3. Not only inoculation but also the preconditioning
(Al or/and Zr) of the base iron before inoculation has a
strong beneficial effect on the solidification pattern and
the graphite nucleation control in grey irons respectively.
4. The range of 0?007–0?010%Al is favourable for
lower chill tendency and undercooled graphite occurrence,
2008 VOL 21 NO 1–4 43
Chisamera et al. Graphite nucleation control in grey cast iron
at higher eutectic cell count of inoculated irons compared
to 0?001–0?005%Al residual irons.
5. As both Al and Zr sustain the type A graphite
formation at lower eutectic undercooling and free
carbides avoidance, these elements were associated in a
complex alloy (Al,Zr,Ca–FeSi) found to be very efficient
in preconditioning of grey irons for thin wall castings in
foundry conditions, at a low addition rate (0?10 wt-%).
Acknowledgement
Laboratory research was conducted by POLITEHNICA
University of Bucharest, Romania, with the collabora-
tion end founds provided by ELKEM AS Foundry
Products Division, Norway.
References
1. C. R. Loper, Jr and R. B. Gundlach: Proc. AFS Int. Inoculation
Conf., Chicago, IL, USA, April 1998, AFS, Paper 01.
2. C. R. Loper, Jr: AFS Trans., 1999, 107, 523–528.
3. M. Chisamera, I. Riposan, S. Stan and T. Skaland: Proc. 64th
World Foundry Cong., Paris, France, September 2000, WFO,
Paper RO-62.
4. I. Riposan, M. Chisamera, S. Stan, T. Skaland and M. I. Onsoien:
AFS Trans., 2001, 109, 1151–1162.
5. I. Riposan, M. Chisamera, S. Stan and T. Skaland: Int. J. Cast
Met. Res., 2003, 16, 105–111.
6. M. Chisamera, I. Riposan, S. Stan and T. Skaland: AFS Trans.,
2004, 112, 867–877.
44 International Journal of Cast Metals Research 2008 VOL 21
7. I. Riposan, M. Chisamera, S. Stan and T. Skaland: Proc. 66th
World Foundry Cong., Istanbul, Turkey, September 2004, WFO,
775–790.
8. I. Riposan, M. Chisamera, S. Stan and T. Skaland: Proc. AFS Cast
Iron Inoculation Conf., Schaumburg, IL, USA, September 2005,
AFS, 31–41.
9. M. Wakoh, T. Sawai and S. Mizoguchi: ISI J. Int., 1996, 36, 1014–
1021.
10. N. Sano: Proc. 2nd Canada–Japan Symp. on ‘Modern steelmaking
and casting technology’, Toronto, Canada, August 1994, The
Metallurgical Society of CIM, 19–28.
11. N. Yuki, F. Shibata and T. Emi: ISI J. Int., 1998, 38, 317–323.
12. A. V. Dub, F. Tsukihasi and N. Sano: ISI J. Int., 1991, 31, 1438–
1440.
13. K. Oikawa, K. Ishida and T. Nishizawa: ISI J. Int., 1997, 37, 332–
338.
14. T. Sawai, M. Wakoh, Y. Ueshima and S. Mizoguchi: ISI J. Int.,
1990, 30, 605–611.
15. T. Skaland: ‘A model for graphite formation in ductile iron’, PhD
thesis, The Norvegian Institute of Technology, Trondheim,
Norway, 1992.
16. ‘Cast iron inoculation booklet’, ELKEM Foundry Products
Division, Oslo, Norway, 2007, available at: www.foundry.elkem.-
com.
17. ‘Preseed preconditioner booklet’, ELKEM Foundry Products
Division, Oslo, Norway, 2007, available at: www.foundry.elkem.-
com.
18. I. Riposan, M. Chisamera, S. Stan, C. Ecob and D. Wilkinson:
World Foundry Org. (WFO) Tech. Forum, Dusseldorf, Germany,
June 2007, WFO, Poster Session, Paper P1.
19. I. Riposan, M. Chisamera, S. Stan, P. Toboc, C. Ecob and G.
Grasmo: Proc. 68th World Foundry Cong., Chennai, India,
February 2008, WFO, Paper 53.
NO 1–4