ARCHIVES ISSN (1897-3310)

Volume 9
of Issue 3/2009

201 – 204
FOUNDRY ENGINEERING
Published quarterly as the organ of the Foundry Commission of the Polish Academy of Sciences
36/3

White and gray solidification

of the Fe-C eutectic
M. Trepczyńska-Łent*
Faculty of Mechanical Engineering, University of Technology and Life Sciences,
Kaliskiego 7, 85-796 Bydgoszcz, Poland
*Corresponding author. E-mail address: trema@utp.edu.pl

Received 20.04.2009; accepted in revised form 24.04.2009

Abstract
The mechanism of structure transition from stable to metastable eutectic is the object of the publication. The influence of micro-
segregation elements on forming different phase, growth undercooling and growth rates was determined. Also competitive growth
of both eutectic in alloys Fe-C was introduced.

Keywords: Solidification, Grey eutectic, White eutectic, Stable to metastable transition

where K1 and K2 are constants related to the material properties.

1. Introduction
It is well known that one of the most important types of
casting alloys, cast iron, solidifies in two different forms, gray
and white (figure 1):
Gray iron is predominantly obtained at low cooling rates. Its
eutectic phases, γ - iron and graphite, are the equilibrium ones.
White iron appears at high cooling rates and consists of γ –
iron and the metastable Fe3-C [2].
In order to model the grey/white structural transition, the
following phenomena should be described through appropriate
physical and mathematical models:
The nucleation and growth of both the stable and metastable
eutectic.
The growth competition between the same eutectics.
The change in equilibrium temperatures and solubility limits
because of the microsegregation of various elements occurring
during solidification [3].
Theoretical treatments of eutectic growth give relationships
between undercooling ΔT, lamellar spacing λ, and growth
velocity V of the general form :
K2
T K1 V (1)
Regular eutectics (like Fe-Fe3C) are assumed to grow at the
extreme, i.e. at maximum velocity or minimum undercooling.
This leads to the well known relationships [4]:
T 2 K1 K2 V K3 V (2)
K2
/ V K4 V (3)
K1
Growth of irregular eutectics (like Fe-C) is more
complicated. The growth kinetics (fig.2.)of the faceted phase
activates a defect mechanism for growth, which produces a very
anisotropic growth behavior.
This means that branching of graphite, which is needed for
growth at the optimum-lamellar spacing, is difficult. The
lamella of graphite will then grow straight in a converging or
diverging way, leading to a whole range of lamellar spacing
(corresponding to a range of undercooling given by eq. (1)). It
has been shown that growth cannot be achieved with a spacing
lower than the extreme one. Growth of converging lamella will
then stop when this spacing is reached. At the opposite, growth
of diverging lamella will be stable only as long as λ is less than
a critical spacing λbr where branching occurs, as shown in fig. 3.
It will be shown theoretically in a forthcoming paper that the

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relationships (2) and (3) (with different constants) are still valid
for irregular eutectics under usual conditions, with undercooling
2. Nucleation of stable and metastable
and lamellar spacing taken as average values over the whole eutectics
interface [4].
Figure 3 shows growth temperature versus solidification rate The grain density data used in the present model are as
for both Fe-C and Fe-Fe3C eutectics. The undercooling of grey follows:
(Fe-C) eutectic is much higher than the one for white (Fe- for the gray eutectic:
.
Fe 3 C) eutectic. This is so for two reasons:
The concentration difference between the two phases Ng(m-2)=1,0x105 + 3,3x104 T (4)
is much higher in Fe-C than in Fe-Fe3C (thus for the white eutectic:
.
requiring a higher diffusion flux of carbon).
The irregularity of growth is large in Fe-C, i.e. growth Nw(m-2)=5,0x105 + 1,0x104 T (5)
.
occurs at a larger mean spacing and therefore at a T is the cooling rate [3].
higher undercooling than the extreme one [4].

The research indicated that total number of nucleation was

given by N A ( T ) n where T is the undercooling with
respect to the equilibrium temperature of the phase
transformation, A and n are constants reflecting the inoculation
treatment. The nucleation rate is expressed as eq. (6), and the
number of nuclei appearing in liquid from calculation time t to
t+dt can be calculated by considering the available liquid
volume of nucleation with eq. (7):

dN d T
Fig. 1.Schematic of the iron-carbon phase diagram [1] nA( T ) n 1
(6)
dt dt

t dt d T (7)
Nt t dt
f1nA( T ) n 1
dt
t dt
where f1 is volume fraction of liquid (%) [6].

In this work, the gray and white transformation under their

equilibrium temperatures, Tstable and Tmetastable respectively, was
considered and they were calculated by literature:

Tstable(oC ) 1154 4( Si %) 2( Mn%) 30( P%) (8)

o
Tmetastable ( C ) 1148 15( Si%) 3( Mn%) 37 ( P%) (9)
Fig. 2.Schematic of the growth kinetics of gray and white
iron eutectics [1]
where (Si%), (Mn%), and (P%) are weight percents of silicon,
manganese, and phosphorus of liquid [6].
It is widely accepted that the nucleation of cementite
eutectic is rather sluggish, requiring a certain degree of
undercooling to temperatures in which Tc < Tmst . Below Tc, both
graphite and cementite eutectic grow simultaneously, interfering
with each other in giving rise to the final structure. The real
volume fractions of graphite (fg) and cementite (fc) eutectics can
be described by:
f ge
fg {1 exp[ ( f ge f ce )]} (10)
f ge f ce

f ce
fc {1 exp[ ( f ge f ce )]} (11)
f ge f ce

Fig. 3. Schematic diagram showing growth temperatures

for white and gray eutectic [4, 5]

202 ARCHIVES of FOUNDRY ENGINEERING Volume 9, Issue 3/2009, 201 -204

where fge and fce are the extended volume fractions of graphite t t
and cementite eutectics, which, in turn, can be given by: X gray
and X white
are concentrations of X element in
t
4 4 4 gray and white eutectic at time t, X is partition
f ge NR 3 N (u g t ) 3 N[ g (Ts T ) 2 t ]3 (12) gray
3 3 3 coefficient of X element in liquid and gray eutectic and
4 4 4 t
f ce N c Rc3 N c (u c t ) 3 N c [ c (Tmst T ) 2 t ]3 (13) X is partition coefficient of X element in liquid and
3 3 3 white
t
Equations (12) and (13) assume spherical geometry, where R
white eutectic, and X 1...
is content of X element in liquid at
and Rc are the mean radii of either the graphite or cementite time t [5].
cells; N and Nc are the numbers of graphite and cementite Neglecting macro convection, the total content of an
eutectic cells, respectively, per volume or cell densities; and t is element of any mesh was assumed unchanged (Eq. (18)), and
the time. Equations (10) and (11) are only valid for fge/fce = then the concentration of an element in liquid was determined
constant. After solidification, fg +fc = 1; this, in turn, indicates by Eq. (19):
that the exponential components in eqs. (10) and (11) tend to
zero. Thus, eqs. (10) and (11) can be rewritten as: t
t t
t
t t
X gray gray df gray X white white df white (18)
t 0 t 0
f ge t
fg (14) X f t
X
f ge f ce 1 1 1 0 1

t
f ce X
t t
df gray
fc (15) gray gray
f ge f ce t t t 0 t (19)
X 1
X o
/f 1 t
/ f
1 1
t t
In order to estimate the fractions of graphite and cementite
X white white df white
t 0
eutectics, it is assumed as a first approximation that isothermal
conditions prevail for the eutectic transformation (figure 3) and where X o
is initial content of X element in the melt, t
df gray
that the nucleation of eutectic cells is instantaneous, with a
constant density ratio of N/Nc= 10 [7]. and df white
t
is volume increase of gray and white eutectic at
calculation time t respectively [6].
The partition coefficients k Si, g and k Si,w are calculated
3. Microsegregation using the following relationships:

Many researchers have done significant effort to describe k Si, g 1,70 0,31c Si 2,05c Si2 (20)
the microsegregation behavior during solidification of different
alloys including SG iron. It was proved that microsegregation of k Si,w 0,88 0,05c si (21)
various elements had a significant effect on stable to metastable
transition as well as the solid-state transformation or heat where cSi is the silicon concentration expressed in weight
treatment. The microsegregation behavior is quite different percent [1].
among various elements, for example, silicon segregates The eutectic temperatures of gray and white iron eutectics
negatively during stable while positively in metastable are obtained by:
solidification; manganese segregates positively in both
reactions, which makes the content of manganese in liquid Tg 1135,06 13,89cSi 2,05cSi (22)
increase during solidification. Therefore, stable and metastable
eutectic equilibrium temperature must be calculated as a 2
Tw 1147,2 6,93(cSi 2,5c p ) 1,717 c Si 2,5c p (23)
function of silicon and manganese concentration in the liquid.
At any time t, the distribution of the element X in liquid, gray
where cp is the concentration of phosphorus, which is assumed
and white eutectics was approximately given by eqs. (16) and
to be constant [1].
(17):

t t
X K X , gray X (16)
gray 1... 4. Growth rates
t t
X white
K X ,white X 1...
(17)
The growth rates for graphite eutectic (ug) and cementite
eutectic (uc) can be related to the degrees of undercooling
where through eqs. (24) and (25), according to theoretical treatments
on eutectic growth:

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ug Tg2 (24) graphitizinq effect) and decrease the hysteresis (if
g
K 3g and Tnc are unchanged).
uc c Tc2 (25)
The growth undercooling of grey eutectic is markedly
where: influenced by the growth conditions of graphite (i.e.
Tg Ts T (26) Gibbs-Thomson coefficient and branching
mechanism). Increasing K 3g decreases Vg w and
Tc Tmst T (27)
Vw g without changing the hysteresis. This
In eqs. (24) through (27), ΔTg is the undercooling for graphite carburizing effect is due to growth kinetics.
eutectic and ΔTc is the undercooling for cementite eutectic, and The undercooling necessary to nucleate the cementite
μg and μc are their respective growth coefficients; and Ts and Tmst phase depends on the existence of clusters or
are the stable and metastable equilibrium temperatures of the heterogeneous phases in the liquid. In case of
graphite and cementite eutectics, respectively [7].
One notices from figure 3 that there is a critical difficulties in nucleating cementite, Tnc will
solidification rate Vc where the growth temperatures of white increase, thus increasing Vg w but leaving Vw g
and grey eutectics are equal. It can be thought that the system unchanged [4].
will try to choose the eutectic which has - the minimum
undercooling (or the maximum growth rate), i.e. grey as long as
the growth rate is less than Vc and white for faster velocities. In
fact, transitions from grey to white and white to grey exhibit a 5. Conclusions
large hysteresis due to the difficulty of nucleation of the new
phase. There are then two distinct critical velocities: with Transitions from grey to white and white to grey exhibit
increasing growth rates, a grey eutectic will remain stable until a large hysteresis due to the difficulty of nucleation of the new
the critical velocity Vg w is reached. This growth rate is phase.
It was found that neglecting silicon microsegregation, if
associated with an undercooling Tnc required for the meta-stable transformation was advantageous to stable, the
nucleation of cementite. At the opposite, transitions from white simulated carbide fraction is higher, and vice versa.
to grey occur at a solidification rate Vw g and an undercooling

Tng . Note that the undercooling Tnc and Tng are defined References
with respect to the eutectic temperature of γFe-cementite (white)
and γFe-graphite (grey) [4]. [1] A. Jacot, D. Maijer, S.Cockcroft: A two-dimensional
As the white to gray transition occurs very close to the model for the description of the columnar-to-equiaxed
critical velocity Vc, Vw g will then be set equal to Vc in the transition in competing gray and white iron eutectics and
its application to calender rolls. Metallurgical and
subsequent analisys. From figure 2, one can deduce from
Materials Transactions A, vol. 31a, August 2000.
geometrical considerations the following relationships:
[2] P. Magnin, W. Kurz.: Competitive growth of stable and
metastable Fe-C-X eutectics. Part I. Experiments.
2
Te Tnc Metallurgical Transactions A, vol. 19A, August 1988.
Vg w
(28) [3] L. Nastac, D.M Stefanescu: Modeling of stable to
K 3g metastable structural transition in cast iron. Advanced
2 Materials Research vol. 4-5, 1997.
Te (29) [4] P. Magnin, W Kurz: Transition from grey to white and
Vw g
K 3g white to grey on Fe-C-X eutectic alloys, Met. Res.
Soc.Symp. Proc. Vol 34, 1985.
where ΔTe is the difference between stable and metastable [5] P. Magnin, W. Kurz: Competitive growth of stable and
eutectic temperatures. The transition velocities are then a metastable Fe-C-X eutectics. Part II. Mechanisms.
function of the three parameters ΔTe , K 3g and Tnc . Metallurgical Transactions A, vol. 19A, August 1988.
Modifications of these parameters by an alloying addition have [6] H. Zhao, B. Liu: Modeling of stable and metastable
different effects: eutectic transformation of spheroidal graphite iron
ΔTe is a measure of the thermodynamic stability of casting, ISIJ International, vol. 41, no 9, 2001.
cementite with respect to graphite. An increase in ΔTe [7] E. Fraś, M. Górny, H. F. Lopez: The transition from gray
by alloying will raise both Vg w and Vw g (i.e to white cast iron during solidification: Part I.
Theoretical background, Metallurgical and Materials
Transactions A, vol. 36A, November 2005.

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