Scripta METALLURGICA Vol. 26, pp.

443-448, 1992 Pergamon Press plc

et MATERIALIA Printed in the U.S.A. All rights reserved

ON THE GROWTH KINETICS OF PRIMARY GRAPHITE NODULES

IN HYPEREUTECTIC DUCTILE IRON MELTS

F.J. Bradley
Department of Materials Science and Engineering
University of Wisconsin-Madison, Madison, WI 53706
(Received August 29, 1991)
(Revised November 27, 1991)

Introduction
Micro-models of the solidification of ductile or nodular cast iron presented in the literature to date are based
on a 'graphite noduledaustenite shell' model of eutectic solidification [1-8]. Key assumptions of this model are that
very early in the solidification process graphite nodules are enveloped by an austenite shell, and that henceforth the
growth kinetics of the spherical equiaxed grain are determined by the rate of solid state diffusion of carbon through
the austenite shell to the graphite nodule. Based on a comparison of simulated and experimental cooling curves,
Stefanescu and Kanetkar [5] concluded that the diffusion-controlled 'graphite noduledaustenite shell' model is an overly
simplistic representation of ductile iron solidification behavior, with the model being highly sensitive to nodule density,
initial nodule size, and value of diffusivity of carbon in the austenite. Hummer [9], on the basis of dilatational and
cooling curve experiments, Stefanescu and Bandyopadhyay [10], on the basis of directional solidification studies, Beeri
and Weinberg [11], on the basis of quench and microprobe studies, and Engler and co-workers [12,13] all suggest
a somewhat more complex mode of solidification of eutectic ductile iron in which a significant portion of the 'eutectic'
austenite growth may occur in an uncoupled dendritic manner. Furthermore, according to Minkoff [14,15], graphite
growth during primary and eutectic solidification proceeds by mechanisms which are specific for a faceted material,
and the growth kinetics are controlled by interface attachment rather than diffusion kinetics.
Of practical significance is the fact much of commercial ductile iron production is of hypereutectic
composition, for which primary graphite solidification is expected prior to the start of the eutectic reaction. While
Weterfall, Fredriksson, and Hillert [1] have used a diffusion-controlled model to simulate the growth of primary
graphite nodules in direct contact with the melt, no comprehensive micro-model of the solidification of hypereutectic
ductile iron alloys has been presented in the literature. While the amount of latent heat liberated during primary
solidification is not expected to significantly influence the shape of the cooling curve of a hypereutectic alloy, the
precipitation of primary graphite nodules can impact on subsequent alloy solidification in a number of ways. Each
primary graphite nodule has associated with it a carbon depleted zone in the region of the graphite/liquid interface
which is potentially a favorable zone for austenite nucleation. Due to the large difference in density between the
graphite and liquid phases, the precipitation of graphite nodules is a driving force for convective flow, which is a
particularly important consideration in heavier section castings. The size at which a graphite nodules becomes
enveloped by an austenite shell during eutectic solidification will be determined by the extent of nodule growth in
direct contact with the melt during primary solidification. By significantly influencing the carbon distribution
throughout the melt during solidification, primary graphite solidification is expected to influence the nature of the
subsequent eutectic solidification. Since graphite and austenite precipitation are associated with expansion and
contraction, respectively, clarification of the mode of solidification of hypereutectic ductile iron alloys and accounting
for the distribution of carbon between the graphite, austenite, and liquid phases as solidification proceeds is
fundamental to the development of shrinkage prediction useful for the optimization of casting design.
In this paper a methodology for investigating the kinetics of the solidification of primary graphite nodules is
described. An approach is adopted which utilizes experimental cooling curve data obtained from thermal analysis of
a commercial hypereutectic ductile iron directly in a computer simulation of nodule growth during primary
solidification. The diffusion-controlled model of the growth of primary graphite nodules in direct contact with the

443
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Copyright (c) 1992 Pergamon Press plc
444 GROWTH OF GRAPHITE NODULES Vol. 26, No. 3

melt, which was first proposed by Weterfall, Fredriksson, and I-Iillert [1], is assessed. Results of numerical
simulations of the growth of graphite nodules for a number of cases are given. The ultimate goal of the research is
the development of a micro-model of solidification of commercial ductile irons which can be incorporated into a finite
element macro-model of solidification and applied to estimating the volume changes occurring during solidification
and to predicting the likelihood of shrinkage defects in castings.
Mathmnatical Formulation of Model of Growth of Prlnmrv Granhite Nodnl~
The case of diffusion-controlled growth of spherical graphite nodules during primary solidification in a
hypereutectic ductile iron melt is considered. Assuming equilibrium at the graphite/liquid interface, a carbon mass
balance at the graphite/liquid moving boundary (rffiRa) yields the following expression for the growth rate of the
graphite nodule
dR(; . D cL PL 1 ac
(I)
d, p o (c~L c ~ ) (~)r-.'o--

where DL is the diffusivity of carbon in the liquid; Po and DL are the densities of the graphite and liquid phases,
respectively; cOLis the concentration of carbon in the graphite phase in equilibrium with the anstenite (assumed to be
100%) and c ~ is the concentration of carbon in the liquid in equilibrium with graphite; and (8c/8r) at r=Ra is the
carbon concentration gradient in the melt at the graphite/liquid interface. In general, the notation ~ refers to the
concentration of species i in phase j at the interface between phases j and k, with concentration being expressed on
a per weight basis.
For the case of quasi-steady state diffusion of carbon in the liquid (assuming no impingement of the diffusion
fields of neighboring nodules), the governing differential equation and boundary conditions are, respectively,
v~ ~d (..2 ~de,
j -o (2)

~- ~ at , - Ro
(3)
o
C - C at r - ~,,

where c~ is the bulk concentration of carbon in the melt remote from the interface. Differentiating the solution for
the quasi-steady state case, which is
o R G ( c~ - Cct o ) (4)
c(r) - Cc -
r

and evaluating at r f Z o yields the following expression for the concentration gradient at the graphite/liquid interface

(dc),.~,dr c~ - Cc~ (5)

Ra

Substitution of equation (5) into equation (i) yields the following expression for the diffusion-controlled growth
kinetics of a primary graphite nodule
tire L PL ( c ~ - Cc
to) 1
- Dc . . . . . . . (6)
"~ p~ (c~L - c~) so

Primary solidification of graphite nodules in a hypereutectic ternary Fe-C-Si melt of initial composition %C ~c~
and %Siffic~ is considered. Based on the three points P1(4.26,0,1154), P2(4.63,0,1300) and P~0.37,3.74,1290),
where an arbi~ry point in the Fe-C-Si ternary phase diagram is represented by P(%C,%Si,T) with T in C, and
assuming a planar graphite liquidus surface, the equation of the liquidus surface is
Vol. 26, No. 3 GROWTH OF GRAPHITE NODULES 445

Tat - 394.6 % C + 130.0 %Si - 527.0 (7)

where TOL is graphite liquidus temperature. Points Pi and P2 are obtained from the binary Fv-C system [16] and P3
from the results of Chipman et. al. [17] on the solubilityof carbon in Fe-C-Si melts. The solidificationpath of a
hypereutectic ternary alloy is dependent on initialbulk composition of the melt. The equation giving the concentration
of carbon in the liquidin equilibrium with graphite, ~ during primary solidificationas a function of temperature and
initialbulk composition of the ternary melt, obtained by determining the line of intersectionbetween the graphite
liquidus surface and the verticalplane containing the point corresponding to the initialcomposition of the melt and
the ve~cal line representing the graphite vertex of the ternary system, is

1.336 + 0.002534 T - 33.01 ( - )

~. 100 - ~ (s)
4
I - 0.3301 ( - - )
O
100 - cc
Rearranging equation (7), the bulk carbon concentration of the melt ~ is expressed in terms of the equilibrium
graphite liquidus temperature corresponding to the initial concentration of the melt, ~L, and c~ as

c co . 1.336 + 0.002534 ~ t - 0.3301 c~ (9)

Substituting equations (8) and (9) into equation (6) would result in an expression for the growth kinetics of a primary
graphite nodule of the following form
dRo o AT
dt (lO)

where KVois a rate constant for primary graphite precipitation for the case of diffusion-oontrolled growth and AT is
the undercooling relative to the graphite liquidus temperature corresponding to the bulk concentration of the melt, i.e.

AT- ~t- T (11)

However, due to the complexity of the expressions, equation (10) is not easily obtained in explicit form.
Estimation of Rate Constant for the Growth of Primary Graahi~ Nodu|~
Cooling curve data obtained from thermal analysis is used in the computer simulation of nodule growth to
determine the time-dependent undercooling at each time step during primary solidification. Figure I shows the cooling
curve of a ductile iron thermal analysis specimen of composition %C--3.63 (4) and %Siffi2.54 (c~ for which the
carbon equivalent is CEffi4.48 based on CEffi%C+I/a%Si. The graphite liquidus temperature for this alloy
(~0L=1234.3 C), computed using equation (7), is indicated in Figure 1. Nucleation of No nodules per unit volume
is assumed to occur instantaneous at a specified undercooling ~T~ relative to ~OL, with growth of the primary graphite
nodules being simulated until the end of primary solidification, which is taken to be the start of eutectic solidification
TBtrr, which for ternary alloys is given by [18]

Tz~~. - 1154 + 4.0 %Si (12)

Thus, the start of primary solidification temperature is T~='PoL-AT~,and the range of primary solidification between
T ~ and Tmrr. The dashed line in Figure 1 is the eutectic temperature for a binary Fe-C alloy, ~ = 1 1 5 4 C.

The radius of a graphite nodule at the end of primary solidification P~ is computed as follows. At each time
step in the primary solidification range the nodule growth rate (dl~dt) is determined using equations (6) and (8) and
the appropriate temperature obtained from the cooling curve. Once the growth rate is determined, the new value of
Ro is computed using the Runge-Kutta technique to solve the ordinary differential equation, and dP.o/dt, AT, and Ro
446 GROWTH OF GRAPHITE NODULES Vol. 26, No. 3

sC-3.63
A . llSi,-2.54
CE-4.48

& T&
E

11000 20I I I I
40 (608) 8O IO0
Time

FIG. 1 Cooling Curve of a Hypereutectic Ductile Iron Thermal Analysis Specimen

are stored for each time step during the simulation, which is terminated when T='P~w. An estimate of the rate
constant for a particular simulation is obtained by linear regression of (dRo/dt) versus (AT/Ro).
Discussion of Results
The thermal analysis specimen corresponding to the cooling curve in Figure 1 was sectioned in the vicinity
of the thermocouple and the graphite nodule distribution was characterized using image analysis. The largest observed
nodule diameter was 62 #m (so that P,~=31 #m), with 94.4% of the observed diameters being less than 35 #m.
Number of nodules per unit volume and volume fraction of graphite were found to be Nv=9.7xl06 nodules/era 3 and
fa=0.133, respectively. On the basis of quenching experiments, Wetterfall, Fredriksson, and Hillert [1] noted that
graphite nodules nucleate continuously during primary and euteetie solidification in the case of hypereutectie alloys.
In order to estimate the volume fraction graphite fo and the average concentration of carbon in the liquid c~Q at the
end of primary solidification, it is assumed that the 5.6% of the nodules with diameters greater than 35 #m nucleate
instantaneously at undercooling ATe. For all of the simulation results presented, the number of primary graphite
nodules per unit volume is taken as 1~o=5.4x105 nodules/era 3, and the volume fraction of graphite at the end of
primary solidification, fro, is calculated using
4 p .3
- -~ ~ N~ R a (13)

Average carbon concentration in the liquid at the end of primary solidification is computed on the basis of mass
conservation of carbon between the No graphite nodules of radius P~ and the liquid phase. Since an iron of eutectic
composition is defined by the relationship [18]
%C + 0.31%$i - 4.26 (14)
a value of %C~Q--3.40 is expected for the case being considered. Assuming diffusion-controlled kinetics, the ratio
of P~ to P-~ can be approximated by the uluare root of the ratio of primary solidification time to total solidification
time (approximately 15% for the specimen being considered), so that the radius of a graphite nodule at the end of
primary solidification would be approximately 12 pm.
Table I contains results of numerical simulations of the growth of graphite nodules based on the diffusion-
controlled model for various values of ATe. The initial radius of the graphite nodule at the start of primary
solidification is taken as 1 ~tm. Other data used to evaluate equation (6) include DLcffi6xl0"s cm2/s [19], PL=6.85
g/cm 3, and Po =2.05 g/cm 3. From the results in Table I, it is apparent that the computed radius of the graphite nodule
at the end of primary solidification decreases with increasing ATe. This trend is primarily associated with the
corresponding reduction in time of primary solidification, r~. As expected, volume fraction graphite and average
carbon concentration of liquid at end of primary solidification vary inversely as dictated by conservation of carbon.
The rate constant for diffusion-controlled growth is essentially independent of ATe, and the values of the regression
Vol. 26, No. 3 GROWTH OF GRAPHITE NODULES 447

coefficient R support the validity of the general form of the kinetics expression given in equation (10). The results
in Table I suggest that unreasonably large values of ATrN are required in order to obtain reasonable values of R~, fo,
and %C~Q, indicating that the rate constant K~ for diffusion-controlled growth, which represents a limiting case, is
too large.
TABLE I
Graphite Nodule Radius, Solidification Time, Volume Fraction Graphite, Average Carbon
Concentration of Liquid at End of Primary Solidification, and Rate Constant
for Diffusion Controlled Growth Model for Various Undercooling
AT~ P-~ r; fo %C~ K~ xl0 ' R
(oc) 0t) (s) (cm21s/C)

0.0 33.1 25.2 0.0823 1.13 56.8 0.984305

10.0 32.9 22.6 0.0803 1.19 57.7 0.997836
20.0 32.1 19.8 0.0749 1.37 56.9 0.999487
30.0 30.7 16.6 0.0653 1.68 56.1 0.999865
40.0 28.3 13.0 0.0512 2.13 55.5 0.999963
50.0 24.7 9.2 0.0341 2.64 55.1 0.999991
60.0 18.9 5.0 0.0153 3.20 54.8 0.999998

According to Minkoff [14,15], the growth mechanisms of the graphite phase in the Fe-C system are determined
by the crystallography and defect structure which are specific for a faceted material, rather than by diffusion kinetics.
Instabilities in the growth of grapMte lead to different forms as single phases. For example, it is suggested that the
flake graphite form grows from the steps of rotation boundaries; the compacted graphite form grows by the
development of pyramidal forms on the crystal surface from steps of screw dislocations; and the spheroidal graphite
form grows by repeated instability of pyramidal surfaces forming a radial array. Each growth mechanism has
associated with it a distinctive undercooling at which it becomes operative. With regard to the growth of the
compacted and spheroidal forms of graphite, Minkoff notes that the reactive elements Mg and Ce significantly
influence the kinetic undercooling of the melt, and that it is the kinetic, rather than the constitutional, undercooling
which changes the mode of growth of these forms of graphite. On the basis of experimental observations, it has been
reported that the growth of the spheroidal graphite form occurs at a total undercooling of approximately 30 C [14].
Figure 2, a plot of P,~ versus rate constant K o for AT~=30 C, was obtained by solving equation (6) for
various values of D L and then back-calculating the rate constant by regressing (dRddt) versus (AT/Ro). As expected,
P~ varies directly with the magnitude of Ko. The open circle in Figure 2 highlights the result for the case of
diffusion-control using the literature value of DLc in equation (6), for which K~ffi56. lx10 t cm2/s/C, IQ=30.7/zm,
%CuQ=1.68, and ~--0.0653 (see Table I). The results in Figure 2 indicate that a more reasonable simulation
prediction of the radius of graphite nodule at the end of primary solidification is obtained if a rate constant of
I% = 9x10 -t cm2/s/C is used in the diffusion-controlled kinetics model, which is approximately a factor of six less
than Kv6, assuming that 1~-- 12/~m is good estimate of the actual radius of graphite nodule at the end of primary
solidification, which is likely since R=~-31
o~_ #m. In addition, the value of %CuQ-3.50 obtained from the carbon
mass balance is much more reasonable than that obtained for the case of KVo=56.1x10 l cm2/s/C. Thus, the
numerical simulation results suggest that rate of growth of primary graphite nodules is significantly slower than
kinetics associated with diffusion-control based on literature values of the diffusivity of carbon in iron melts.

Summary
A numerical-simulation based methodology for investigating the kinetics of the solidification of primary
graphite nodules which utilizes experimental cooling curve data and the measured nodule size distribution in the
vicinity of the thermocouple has been described and applied to assessing the diffusion-controlled model of the growth
of primary graphite nodules in direct contact with the melt proposed by Weterfall, Fredriksson, and Hillert. On the
basis of a comparison of computed graphite nodule radius at the end of primary solidification with estimates based
on measurements of graphite nodules observed in the thermal analysis specimen, it appears that the kinetics of primary
graphite precipitation are significantly influenced by the crystallography and defect structure of the faceted graphite
448 GROWTH OF GRAPHITE NODULES Vol. 26, No. 3

28

v
2 tt

I
m

Ko x 10 ' (cm~/s/C)
FIG. 2 P.~ and C~Q Versus Ka for the Case of ATe=30 C

phase, as suggested by Minkoff. While no micro-model of primary graphite solidification based on interface
attachment kinetics which utilizes a phenomonological formulation different than equation (6) has been presented in
the literature, the methodology for estimating the rate constant is in principle generally applicable given an appropriate
phenomonological representation of the kinetics. An approach to micro-model development based on microstructure
prediction provides a better means of model assessment than simply comparing simulated and experimental cooling
curves, as is typically done, because rather small adjustments in the large number of parameters in heat transfer
models facilitate good simulation predictions of cooling curves. Microstructure prediction, on the other hand, requires
the simultaneous satisfaction of conservation of energy and mass. Research is underway to develop a phenomonolog-
ical kinetics model of graphite precipitation that appropriately accounts for the role of atom attachment at the graphite-
liquid interface.

The author gratefully acknowledges the support of National Science Foundation Grant No. DDM-9102682.

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