International Journal of Cast Metals Research

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Microsegregation in mottled spheroidal graphite

cast iron

Jacques Lacaze, Gerardo Torres Camacho & Claude Bak

To cite this article: Jacques Lacaze, Gerardo Torres Camacho & Claude Bak (2003)
Microsegregation in mottled spheroidal graphite cast iron, International Journal of Cast Metals
Research, 16:1-3, 167-172, DOI: 10.1080/13640461.2003.11819577

To link to this article: https://doi.org/10.1080/13640461.2003.11819577

Published online: 29 Nov 2016.

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Microsegregation in mottled spheroidal graphite cast iron
*Jacques LACAZE1, Gerardo TORRES CAMACH01 , Claude BAK2
1 . CIRIMAT, UMR 5085, ENSIACET, 31077 Toulouse cedex 4, France
2. CRD, Pont-a-Mousson S.A., B.P. 109, 54704 Pont-a-Mousson cedex, France
When spheroidal graphite iron is cast on a chill,
a mottled structure is obtained because of the
rapid cooling conditions. More precisely, a
microstructure gradient may occur from the
outer surface in contact with the chill to the bulk
of the material. While the outer surface is
essentially white, the amount of cementite
decreases with the distance from the chill. The
number of nodules decreases generally in a
similar way. Accordingly, one may expect that
microsegregation of alloying elements, and thus
the composition of cementite, depends on the
location within the material. Experiments were
carried out with chill-cast spheroidal graphite
cast irons alloyed with low amounts of
substitutional elements (Cr, Cu, Mn, Ni).
Microanalyses made on cementite and on
austenite at various distances from the chilled
surface showed that segregation increases
slightly with the distance from the chill.
Calculation of the solidification path and of the
change in austenite and cementite composition
during solidification show a satisfactory
agreement with measurements.
© 2003 Maney Publishing
Keywords: Spheroidal graphite cast iron, microsegregation, stable
solidification, metastable eutectic, cementite
Introduction
When spheroidal graphite iron (SGI) is cast on a chill, a
mottled structure is obtained because of the rapid cooling
conditions. More precisely, a gradient of microstructure
may show up from the outer surface in contact with the
chill to the bulk of the material. While the outer surface
is essentially white, the amount of cementite decreases
with the distance to the chill. The number of nodules
decreases generally in a similar way. Because
partitioning of the elements between solid and liquid
differs during stable and metastable solidification, 1 one
may expect that microsegregation of alloying elements,
and thus the composition of eutectic cementite, may
depend on the location within the material. This study
reports an attempt to characterize such changes.
Microanalyses were made on cementite and on
austenite at various distances from the chilled surface in
SGI that solidified partly in the stable system and partly
in the metastable one. It has been shown previously that
* Author for correspondence
e-mail: Jacques.Lacaze@ensiacet.fr
DOl 10.1179/136404603225006855 International Journal of Cast Metals Research 2003 Vol. 16 Nos. 1-3 167
such mottled structures present segregation features
which are a mix of segregation due to both types of
solidification. 2 The present measurements are then used
to check the capability of predicting the effect of cooling
conditions and inoculation treatment on the solidification
path of low alloyed spheroidal graphite cast irons.
Calculations have been made by means of a model
developed previously. 3 The evolution of
microsegregation is finally discussed from the stand
point of its possible effect on the graphitization heat
treatment applied to the parts after casting.
Experimental details
Two highly inoculated spheroidal graphite cast irons
have been cast on a chill. Their composition and the
thickness of the castings are reported in Table I. Sections
perpendicular to the chill surface were taken from each
casting. Analyses and measurements were performed in
three locations across these sections, close to the
"chilled" surface (label "chilled"), in the "middle" of the
section (label "middle"), and finally near to the surface
opposite to the chill (label "inner"). Metallographic
samples were at first only polished for analysis of
graphite nodules. Then, the samples were etched with
Klemm's reageant which allows cementite to remain
white. For quantitative analysis, series of I 0 micrographs
0.4 mm apart were made along lines parallel to the chill
surface. Two such lines, distant by 0.4 mm from each
other, were used to characterize each location.
Quantitative informations were obtained from the
digitalized images by means of the APHELION
software. The measured surface nodule counts, NA, and
cementite fractions, gcem, are listed in Table 2, where is
also indicated the estimated standard deviation on each
average value.
Microanalyses were first performed on alloy S2 with a
wavelength dispersive spectrometer (WDS) by LINK
implemented on a CAMECA SXSO microprobe.
Measurements were made by implementing the probe in
IOxiO points 50 J.lm apart. Analysis of Cu, Cr, Mn, Ni
and Si was carried out by means of 20 s counting for
each species. In order to perform measurements on given
microstructural features, an energy dispersive
spectrometer (EDS) IMIX from PGT implemented on a
LEO scanning electron microscope (SEM) has also been
used. As cementite could not be differentiated from the
matrix on polished samples, neither in secondary nor in
back-scattered mode, areas to be analysed were first
marked with micro-indentation and photographed on
etched samples. The section was then re-polished in
order to eliminate the deposit due to etching and
analysed. On samples of both alloys, measurements were
made by means of X-ray maps with a total recording
time of 40 min while the SEM was operated under 15 kV
Microsegregation in mottled spheroidal graphite cast iron Lacaze, Torres Camacho, Bak

with a beam current set at 1500 nA. Neither copper nor
nickel could be accurately measured by EDS and were
thus not considered in the analyses.
Figure I presents an optical micrograph and the
corresponding silicon EDS map as obtained on an as-cast
sample. Comparison of these two images allows to
identifY a graphite nodule, a cementite plate and a large
area of ledeburite. After the whole map has been
recorded, polygonal areas were defined in which EDS
spectra were averaged to provide composition of phases
or mixture of phases (see Figure I):
I) cementite, wf"m; 2) ledeburite, wled; 3) austenite
.
c Iose to the austemte-cementite. mtenace,
. " w iy I e<m ; 4)
austenite at half distance from graphite and cementite,
w 7; 5) austenite close to the austenite/graphite interface,
w (gra, where i stands for Cr, Mn or Si. The spectra
were then processed for correction with the phi-rho-z
type software provided by PGT. Estimates of the true
compositions were obtained by comparison to spectra of
pure elements obtained under the same operating
conditions. For each measurement, an interval ~Eos
related to the estimation of each species at a confidence
level of 98 % is also provided by the correction program.
Typical values of ~ms for cementite and austenite are
given in table 3. The corresponding confidence intervals
were about one fourth to one third of these values for the
WDS measurements.

Table 1: Composition (weight percents) of the SGI investigated during this work.

casting thickness (mm) c p Si Mn Cr Cu Ni

number
S1 5,1 3.77 0.05 2.05 0.40 0.01 0.01 0.02
S2 5,5 3.55 0.06 2.39 0.33 0.12 0.16 0.06

Table 2: Microstructural data with experimental standard deviation on the average value given between
brackets.

Castino number S1 S2
Location "chilled" "middle" "inner" "chilled" "middle" "inner"
2 1900 1670 630 730 670
NA(mm- ) 2040
I (120) I (175) I (140) I(11 o> (11Ql {110}
gcem (%) 20.6 15.6 10.9 26.8 14.7 13.6
I (1.5) I (2.8) I (1.2) I(1.7) (1.2) (1.5)

Fig. 1 Optical micrograph (right) and X-ray map of silicon (left) of sample 82, close to the chill surface.
Polygons superimposed to the X-ray map illustrate selected areas related to the various
microstructural features.

168 DOl 10.1179/136404603225006855 International Journal of Cast Metals Research 2003 Vol. 16 Nos. 1-3
Lacaze, Torres Camacho, Bak Microsegregation in mottled spheroidal graphite cast iron

Experimental results manganese and chromium contents of ledeburite are right

in between the data measured for the matrix and
The graphs in figure 2 present the relationship between cementite. As can be seen by comparing the data for the
the silicon content on the one hand and the chromium or two alloys at given location, the amount of Cr and Mn in
manganese contents on the other hand for both alloys and cementite, ledeburite and matrix, increases with the
for the three locations considered. WDS measurements nominal content of the alloy in any of these species. This
made on the "chilled" and "inner" locations of alloy S2 is in accord with the extensive study by Sandoz. 4
appear as elongated clouds of points at decreasing Cr However, the most interesting feature shown in Figure 2
(crosses) and Mn (plus signs) values with increasing Si is related to the change of the Cr and Mn contents in
values. EDS measurements have been plotted on the cementite according to the location. For each alloy, one
graphs with closed symbols refering to manganese and may note increasing Cr and Mn contents in cementite
open symbols to chromium. Data at zero Cr or Mn value from the "chilled" to the "inner" locations. This
correspond to measurements for which the estimated observation is confirmed by the WDS measurements. A
content was lower than ~Eos (and was thus set to zero by last point further discussed below is the large range of Cr
the acquisition software). Comparison of EDS data to and Mn contents in cementite which is seen from the
WDS ones shows a good agreement on the average EDS measurements, while not visible in the WDS data.
trends, although the former appears much more scattered.
EDS measurements allowed to differenciate data Table 3: Typical values of the interval DEos at a 98
according to the silicon content : cementite contains less % level of confidence for the indicated
than 0.2-0.3 wt % Si, ledeburite lies in between I and 2 compositions.
wt % Si, and higher silicon contents are related to
austenite. Some very high silicon values, up to 5 wt %, Typical -EDS
composition
were measured in the matrix close to cementite. These
Species Si Mn Cr Si Mn Cr
values agree with previous measurements~ and are in line 0.10
w~em
0.60 0.32 ±0.04 ±0.15 ±0.13
with observations made by Charbonnier and Margerie. 1 It I
is worth emphasising that the differences between the 2.63 0.31 0.14 ±0.10 ±0.10 ±0.12
values related to the various microstructural features are w'!I
highly significative when considering the standard
deviation corresponding to silicon. It is noted that the

1.5

Sl-<!billed I Sl-middle Sl-lnner

I
*! I
I
L
i
•
~ I •
8
• I
• • •
~ ••
~ 0.5 • ••
• • • • ..
u •• • ....
0
[J
•
Em•'
D
D
'• 0

183
D

"
I
•.,.
Qi' I
0 3 4 6 0 I 4
Silicon content (WI%) Silicon content (WI o/o) Silicon content (wt %)

1.5

52-middle
1i
!
J!l
scc
8
0.,
..c 0.5
c
:::1!
"+
+

.
ii<x
•

D
•
•'iJ
...
~~
•• •
0
0 2 3 4 5 6 0 5 6
Silicon content (WI%) Silicon content (wt o/o) Silicon content (WI%)

Fig. 2: Relation between the silicon content and the chromium (open symbols for EDS measurements and
crosses for WDS data) and manganese (closed symbols for EDS measurements and plus signs for
WDS data) contents. Measurements are reported for the three locations within the section of the samples,
"chilled", "middle" and "inner".

DOl 10.1179/136404603225006855 International Journal of Cast Metals Research 2003 Vol. 16 Nos. 1-3 169
Microsegregation in mottled spheroidal graphite cast iron Lacaze, Torres Camacho, Bak

Modelling solid fraction is identical for both locations only at the

beginning of solidification, i.e. as long as bulk deposition
Build-up of microsegregation during solidification has of the stable eutectic has not started. Also, the set-up of
been simulated using a model previously developed. 3 the metastable solidification is clearly evidenced on the
This model has been applied to Fe-C-Si-(Mn) alloys with graph by the sharp slope change on the curves of the
either grey, mottled or white structure, 2 and was extended solid fraction, with a related recalescence for the "inner"
during the present work to account for other location. It is worth noting that the temperature at which
substitutional elements. All data needed for the cementite starts to develop decreases slightly when the
calculations were given in the two former papers, apart cooling rate is increased. This is due to the related
for the distribution coefficients of substitutional species change of microsegregation build-up during earlier
other than silicon and manganese. For the present study, solidification of the stable eutectic. As soon as cementite
the distribution coefficients between austenite and liquid has nucleated, it grows so rapidly that most of the
and between cementite and liquid have been calculated residual liquid is readily transformed. Please, note that
by means of the THERMOCALC software and the the end of solidification corresponds to a final solid
SGTE databank. 5 Calculations were performed at two fraction lower than one because of solidification
temperatures, namely 1100 oc and 1200 °C, for various shrinkage (the reference volume is defined in the liquid
silicon contents and given amount (either 0.5 or 1.0 wt state).
%) of other substitutional species (Cr, Cu, Mn, Ni). Use
has been made of the capability of the software to
perform calculations on metastable phases, and all data
are given for a liquid composition on the austenite
liquidus surface. Copper and silicon were assumed not to
enter in cementite. The data thus obtained are shown in
the graphs of figure 3, where it is seen that the partition
coefficients vary both with temperature and silicon
content in the liquid in the case of austenite, but only
with silicon content in the case of cementite. Polynomial
expressions of the partition coefficients for austenite and .,
'E
cementite have been obtained from these data which ~ 0.4
were then introduced in the simulation programme. 8
Simulations have been carried out assuming a constant j 0.2
a
cooling rate for the "chilled" surface and a heat flux ~
condition for "middle" and "inner" locations. Given the 2 4 6 8 10
cooling conditions, the nodule count, Nv, may vary in Silicon content (wt %)
each location from one melt to another because of the
inoculation treatment. This is accounted for in the model "C
·:;
by varying the nucleation constant A in the equation g
"C
relating the undercooling of the melt with respect to the fij 4
graphite liquidus, ~Tf , to Nv: N v = A.~Ttra, which ~c:
3

., Cr
has been found to be valid for well inoculated SGI. 6 The
appropriate parameters for cooling conditions and
~ 3 0

inoculation treatment have been determined so as to

reproduce the microstructural informations, i.e. the
nodule count and the fraction of cementite. The values of
A which were found to apply in the present case are 1400
and 350 K- 1.mm-3 for alloys Sl and S2 respectively.
Conversion from surface to volume nodule counts were
made by means of the relation proposed by Castro: 7
Nv =3.46(NA)t. 5 • when NA and Nv are expressed in O'--"-~__._j~~......_j_~~-'-..l.~~...._l_~~.._j

square and cubic millimeteres respectively. A cooling
rate at the chill surface of 1000 °C.min- 1 has been found
adequate, while the selected heat flux conditions lead to a
cooling rate at 1000 oc about 300 °C.min- 1 and 150
°C.min- 1 in locations "middle" and "inner" respectively.
Figure 4 compares the evolution of the nodule count
and of the overall solid fraction with temperature during
solidification of alloy S2 in the locations "chilled" and
"inner". Calculated results related to the middle of the
section lie in between. Because this alloy is of slightly
hypoeutectic composition, one may note that the solid
fraction starts to increase before nucleation of graphite
nodules. The evolution of the nodule count and of the
0 2 3 4 5
Silicon content (wt %)
Fig. 3: Calculated partition coefficients between
austenite and liquid (a) and between
cementite and liquid (b). Solid and dotted
lines are for calculations made at 11 00 oc
and 1200 oc
respectively.
Figure 5 shows the evolution of the liquid content in
Cr, Cu, Mn and Si with temperature for location
"chilled", again in the case of alloy S2. On each curve, a
sharp slope change is observed at about Ill 0 oc when
the white eutectic starts to grow. In agreement with

170 DOl 10.1179/136404603225006855 International Journal of Cast Metals Research 2003 Vol. 16 Nos. 1-3
Lacaze, Torres Camacho, Bak Microsegregation in mottled spheroidal graphite cast iron

previous report, 1 calculations show that : i) Cu segregates between Cr and Mn contents in cementite to
as does Si, i.e. negatively during stable solidification and experimental measurements taken again from Fig. 2.
positively during metastable solidification ; ii) Cr and
Mn segregate positively during stable solidification, and --chilled
Cr segregates negatively when cementite deposits while ~
Q
...... oo. inner
Mn still presents a positive segregation. Calculated ~ • Mn, chilled
0.8
evolutions in the two other locations and for the three c •
0 Cr, chilled
locations of alloy S I presented similar overall features.
~
c • • Mn, inner
0
.,
u
• •• • 0 Cr, inner
.,"'c 0.6
j
.
gb
c
E 0.4 0
:.
f•
••
8 10
4
0.8
"0
.
c
E
• ~
:I
"e ·e 0.2
a
.s 6 10
4
0.6 ..c
e
c:I Cll
£.
u Cr
0 0
0.:
.,u 0 2 3 4 5 6 7 8
:; 4 10
4
0.4 ~
"0 !?. Silicon content (WI%)
z
0 o·
:I

4
2 10 0.2
X --chilled
inner
000000000

0 10° 0 ~ 0 chilled
Q
1050 1100 1150 1200
Temperature (°C) I X
X inner
c X X X
Fig. 4: Simulation of the solidification of alloy S2 : ~0 X
u
0.5
evolution of the nodule count and solid E xxxxx»<
xo

o~tfx
fraction with temperature in locations :I
·e
"chilled" (solid lines) and "inner" (dotted e
..c
xO •••••• X
X

u ~X •• •••
lines). 0 X Xx •• •••
X

1.5 8
b ><x
X X X
7 0
0 0.5 1.5
~
Q
.. 6 Manganese content (WI%)
~ 1.0
~
;::;·
c~ 5 0
c
:I
(")
Fig. 6: Comparison of simulated change of
0
·. 0
composition during white solidification with
~
u
c ...
' ·~..
J 4
:I
~
a measurements in the case of alloy S2: a) Si
' '
J: i
"0
c content versus Cr and Mn content in
0.5 silicon
"' '\...... ··················· ::!( austenite close to cementite, lines are
' ' ------ ------
:I
u Q

calculated, solid symbols refer to Mn and

d
'\ manganese
COf!l?er
0.0
.-(
1050 1100 1150
Temperature (°C)
Fig. 5: Simulation of the solidification path of alloy
S2: evolution of the Cr, Cu, Mn and Si
content in the liquid with temperature in
location "chilled".
As the build-up of microsegregation changes the
composition of the remaining liquid, it also affects that of
the phases which deposit. Graphs in Figure 6 provide a
comparison of predicted compositional changes with
EDS measurements. Figure 6-a compares the calculated
evolution of the Cr and Mn contents versus the silicon
content in austenite during solidification of alloy S2 to
the experimental w 11cem values taken from Fig. 2.
Similarly, figure 6-b compares the calculated correlation
open symbols to Cr; b) Mn content vesus Cr
content in cementite for locations "chilled"
chromium
0 and "inner".
1200
The experimental austenite data shows a postttve
correlation between silicon and manganese contents, a
negative one between chromium and silicon data.
Although the spreading of the experimental data is large,
these correlations are somehow reproduced by
simulation. Because of the low Cr contents, the
correlation between Cr and Si values does not appear to
vary with the location considered. On the contrary,
experimental data shows that the manganese content
increases more steeply with the silicon content for the
"inner" location than for the "chilled" one. These
observations are supported by calculations. Figure 6-b
illustrates both the large scatter of the data on cementite
and the fact that this phase presents higher Mn and Cr
average values in the "inner" location than in the other
locations. This is effectively predicted by calculations.

DOl 10.1179/136404603225006855 International Journal of Cast Metals Research 2003 Vol. 16 Nos. 1-3 171
Microsegregation in mottled spheroidal graphite cast iron
Discussion-Conclusion
Boeri and Weinberg8 investigated experimentally the
partitioning and build-up of microsegregation of various
substitutional elements during the stable solidification of
SGI. Their results are in agreement with previous
studies' and show in particular that the Mn and Cr
contents in the liquid increase with the overall solid
fraction. Thus, if cementite was to deposit before
completion of a solidification which processed mainly in
the stable system, its Mn and Cr contents would be
higher the larger the fraction of stable eutectic. This is
what was noticed in the present work in relation with
Figure 2. Moreover, as expected from solidification
theory, the absolute content in the residual liquid of
substitutional solutes which partition positively (direct
segregation) was shown to increase with the nominal
content of the alloy. 8 This is expected to lead to higher Cr
and Mn content in cementite as effectively observed
from the present experimental results. Such conclusions
could have been also drawn from analysis of the
experimental results by Liu and Loper on carbides
composition in heavy section SGI castings. 9
The scatter of the data related to the matrix close to
cementite (see Fig. 6-a) comes partially from the analysis
method (EDS) but could well be also due to variations in
cementite composition. Such variations may be related to
the solidification process itself, i.e. to the fact that
microsegregation builds up also during white
solidification as demonstrated experimentally by
Charbonnier and Margerie. 1 Another source of scatter
could be found in the intrinsic variability of the
microstructure and in the clustering of the eutectic
spheres. Such a clustering has ben studied by
metallographic means by Sikora et al. in the case of
hypoeutectic alloys where primary austenite dendrites
appear to have a particular importance. 10 Also, it has
been reported that the shape of cementite, either as plates
or associated in ledeburite, corresponds to slight
compos1t10na I d"f"
0 0
1 1erences. I ·II In the present approach,
deposition of cementite plates was not considered and
only growth of ledeburite was accounted for in the
calculations. Nevertheless, apart for the highest Cr values
which could be related to the very first growth stage of
cementite, it has been seen that the modelling approach
proposed is able to reproduce most of the observed
segregation features.
One feature of particular interest is counter-segregation
of Cr and Mn during growth of ledeburite. As white
solidification processes, the sum of Mn and Cr contents
in the liquid, and thus in the cementite which deposits
from it, remains roughly unchanged. For latter
graphitisation heat treatment of alloys containing these
two elements, any cementite deposit would thus behave
quite similarly, i.e. the dissolution process of cementite
would not depend on local composition. Redistribution
of alloying elements during graphitisation has been
studied and is described elsewhere. 12
172 DOl 10.1179/136404603225006855 International Journal of Cast Metals Research 2003 Vol. 16 Nos. 1-3
Lacaze, Torres Camacho, Bak
Acknowledgements
One of the authors (GTC) wishes to thanks the
CONACyT for the provision of a grant. WDS analyses
were carried out at the Service commun d'analyse de
I'Universite Paul Sabatier a Toulouse.
References
I Charbonnier J., Margerie J.-C., "Nouvelle contribution
a !'etude generale des microsegregations dans les
alliages fer carbone du type fonte", Mem. Sci. Rev.
Metal/., 1967,64,345-57
2 Selig C., Lacaze J., "Study ofmicrosegregation build-
up during solidification of spheroidal graphite cast
iron", Metal. Mater. Trans. B, 2000,318, 827-36
3 Lacaze J., "Solidification of spheroidal graphite cast
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mater., 1999, 47, 3779-3792
4 Sandoz G., "The effects of some alloying elements on
the decomposition of cementite and graphitization
kinetics in cast irons", Proceedings of the seminar
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Merchant, Gordon and Breach, New-York, 1968,
509-550
5 Sundman B., Jansson B., Andersson J.O., CALPHAD,
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9 Liu P.C., Loper C.R., "Segregation of certain elements
in cast irons", AFS Trans., 1984,92,289-295
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