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Acta Materialia 57 (2009) 3947–3954

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Phase field study of precipitate growth: Effect of misfit strain

and interface curvature
R. Mukherjee a, T.A. Abinandanan a,*, M.P. Gururajan b
a
Department of Materials Engineering, Indian Institute of Science, Bangalore 560 012, India
b
Department of Applied Mechanics, Indian Institute of Technology-Delhi, Hauz Khas, New Delhi 110 016, India

Received 1 March 2009; received in revised form 25 April 2009; accepted 29 April 2009
Available online 27 May 2009

Abstract

We have used phase field simulations to study the effect of misfit and interfacial curvature on diffusion-controlled growth of an iso-
lated precipitate in a supersaturated matrix. Treating our simulations as computer experiments, we compare our simulation results with
those based on the Zener–Frank and Laraia–Johnson–Voorhees theories for the growth of non-misfitting and misfitting precipitates,
respectively. The agreement between simulations and the Zener–Frank theory is very good in one-dimensional systems. In two-dimen-
sional systems with interfacial curvature (with and without misfit), we find good agreement between theory and simulations, but only at
large supersaturations, where we find that the Gibbs–Thomson effect is less completely realized. At small supersaturations, the conver-
gence of instantaneous growth coefficient in simulations towards its theoretical value could not be tracked to completion, because the
diffusional field reached the system boundary. Also at small supersaturations, the elevation in precipitate composition matches well with
the theoretically predicted Gibbs–Thomson effect in both misfitting and non-misfitting systems.
Ó 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Phase field modeling; Phase transformation kinetics; Precipitation

1. Introduction phase diagram, and the precipitate grows under a supersat-

In their classic study of diffusional growth of an isolated
precipitate into a supersaturated matrix, Zener [1] and
Frank [2] established the parabolic growth law: the square
of the precipitate size (radius) increases linearly with time.
They used what is now referred to as a ‘‘sharp interface”
model. Fig. 1 shows a schematic of a composition profile
in the precipitate p and matrix m phases during growth.
Local equilibrium at the (sharp) interface yields the matrix
interfacial composition, cmI , which is used as a boundary
condition for solving the diffusion equation; the far-field
composition, c1 is the other boundary condition. Neglect-
ing interface curvature (capillarity) effects, cmI is the same as
cme , the equilibrium matrix composition obtained from the
*
Corresponding author. Tel.: +91 8022932676; fax: +91 8023600472.
E-mail address: abinand@materials.iisc.ernet.in (T.A. Abinandanan).
uration of ðc1 –cme Þ.
The Zener–Frank (ZF) theory has been extended to
study diffusional growth problems in a variety of settings;
see Ref. [3] for a recent review. Laraia, Johnson and Voo-
rhees (LJV) extended the theory to diffusional growth of
elastically misfitting precipitates [4]; the work of LJV built
on the work of Eshelby [5,6], Larche and Cahn [7–10],
Johnson and Alexander [11], and Leo and Sekerka [12].
The main result of the LJV study is that the parabolic
growth law continues to be valid for precipitates with mis-
fit, but the growth coefficient depends on (i) misfit, (ii) the
elastic moduli of the two phases, (iii) interfacial stress and
(iv) compositional stress.
In the sharp interface model used by LJV, the effect of
dilatational misfit is to raise the matrix interfacial compo-
sition from cme to cmE , and therefore to decrease the supersat-
uration (by a constant factor) to c1 –cmE . Thus, neglecting
capillarity effects, the LJV theory predicts that the growth

1359-6454/$36.00 Ó 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actamat.2009.04.056
3948 R. Mukherjee et al. / Acta Materialia 57 (2009) 3947–3954
(a)
(b)
Fig. 1. Schematic of the composition profile in the matrix and precipitate
phases during growth in (a) non-misfitting and (b) misfitting systems. The
solid curve in the matrix shows the profile considered in the theories of (a)
ZF and (b) LJV. Capillarity modifies the profile, as indicated by dashed
curve.
coefficient a in misfitting systems is the same as that in non-
misfitting systems with ðc1 –cmE Þ as the supersaturation.
This conclusion is valid for systems in which diffusivity is
independent of the state of stress; our study is restricted
to these systems (as already mentioned, LJV have studied
other stress-induced effects).
Direct experimental verification of the LJV results is
extremely difficult, not only due to the ‘‘isolated particle”
assumption, but also due to lack of reliable data on stress
effects on diffusion. Moreover, the assumption of isotropic
interfacial energy can also be difficult to realize experimen-
tally in crystalline alloys. Thus, simulations can act as ‘‘com-
puter experiments” for validating the LJV results, since their
parameters can be so tuned to make the computational
model resemble that used in the LJV theory as closely as
possible. Thus, the first goal of our study is a critical
comparison of the sharp interface results of LJV with those
from our simulations based on a (diffuse interface) phase
field model.
In ZF and LJV theories, which neglect the effect of inter-
face curvature, the diffusion fields at different times are self-
similar. This self-similarity is broken when capillarity effect
is included, since cmI (in Fig. 1a and b) is size dependent.
Capillarity, then, not only decreases the growth rate a,
but also renders it size-dependent. The second goal of this
study is to evaluate the extent of this reduction in a.
Our results also allow us to address two other issues:
1. Our simulation results on systems with low supersatura-
tion can be used to verify the predictions of Johnson and
Alexander [11] and of Leo and Sekerka [12] on the com-
position of a misfitting precipitate.
2. Many phase field models (including the one used in this
study) make use of a phase field variable g whose pri-
mary role is to help distinguish one phase from the
other. In some settings, such as precipitation of an
ordered phase, g may be associated with a long-range
order parameter. In other settings (e.g. in the present
work, or in solidification), g lacks a direct physical sig-
nificance, and its role in the model is justified through
mathematical convenience. In this study, we show first
that our computational model with a phase field vari-
able g reproduces well-known analytical results from
ZF theory in one-dimensional (1D) systems in which
capillary effects are absent.
Our study is organized as follows: Section 2 presents an
outline of our phase field model. In Section 3, we first
establish the essential correctness of the use of a phase field
variable g through a critical comparison of its results
against those of 1D ZF theory, in which capillarity and
elastic effects are absent. We then use the same model to
study the growth of non-misfitting and misfitting circular
precipitates, and critically compare our results with those
from ZF and LJV theories. These results are analyzed in
order to elucidate the elastic and capillarity effects. These
results are critically discussed in Section 4, followed by a
set of conclusions in Section 5.
2. Phase field model
2.1. Formulation
We consider a binary alloy at constant temperature; an
isolated precipitate of phase p grows into a matrix phase m.
We normalize compositions in such a way that the scaled
equilibrium compositions of m and p phases are cme ¼ 0
and cpe ¼ 1, respectively. A two-phase microstructure in this
alloy is described in terms of composition cðr; tÞ (conserved
variable) and order parameter gðr; tÞ (non-conserved vari-
able) in a periodic domain. The order parameter field g is
 R. Mukherjee et al. / Acta Materialia 57 (2009) 3947–3954 3949

defined in such a way that g ¼ 0 in the m-phase and g ¼ 1 Table 1

in the p-phase; see Eq. (6) below. Parameters used in the simulations.
The microstructural evolution in our system is governed Parameter type Parameters Non-dimensional values
by the Cahn–Hilliard equation [13] and the Allen–Cahn Elastic parameters G m
800
equation [14]: m 0.3
d 0.5, 1.0 and 2.0
@c eT 0.01
¼ r  Mrl; ð1Þ
@t /ðgÞ g3 ð10  15g þ 6g2 Þ  12
@g dðF =N V Þ bðgÞ g3 ð10  15g þ 6g2 Þ
¼ L ; ð2Þ C ijkl
eff
1 ijkl ijkl
2 ðC m þ C p Þ
@t dg
Simulation parameters Dx 0.4
where M is the atomic mobility, l is the chemical potential Dy 0.4
and L is the relaxation coefficient for the order parameter. Dt 0.2
Chemical potential l is defined as the variational derivative System size 20000 in 1D
1024  1024 in 2D
of the total free energy per atom, F, with respect to the lo-
Allowed error 6 108
cal composition c, in displacements
dðF =N V Þ
l¼ : ð3Þ
dc
rel and el are elastic stress and strain tensors, respectively,
The total free energy of the system F is assumed to be and e0 is the the position-dependent eigenstrain (misfit
given by the sum of a chemical contribution F ch and an strain). The total strain eij is:
elastic contribution F el :  
1 @ui @uj
F ¼ F ch þ F el : ð4Þ eij ¼ þ ; ð12Þ
2 @rj @ri
The chemical contribution F ch is given by the following
where ui is the the displacement field.
functional:
Z Assuming both the m and p phases to be linear elastic,
2 2
F ch ¼ N V ½f ðc; gÞ þ jc ðrcÞ þ jg ðrgÞ dX; ð5Þ we have:
X
rel el
kl ¼ C ijkl eij ; ð13Þ
where f ðc; gÞ is the bulk free energy per atom, jc and jg are
the gradient energy coefficients for gradients in composi- where C ijkl is the elastic modulus tensor.
tion and order parameter, respectively, and N V is the num- The stress field rel ij obeys the equation of mechanical

ber of atoms per unit volume. equilibrium:

The bulk free energy density f ðc; gÞ is given by, rel
ij;j ¼ 0: ð14Þ
2
f ðc; gÞ ¼ f m ðcÞð1  W ðgÞÞ þ f p ðcÞW ðgÞ þ P g2 ð1  gÞ ; ð6Þ The eigenstrain e0ij and the elastic moduli C ijkl are
where P, a constant, sets the height of the free energy bar- assumed to depend on the order parameter as follows:
rier between the m-phase and p-phase. e0ij ðgÞ ¼ bðgÞeT dij ; ð15Þ
In Eq. (6), f m ðcÞ and f p ðcÞ stand for free energies of m
(matrix) and p (precipitate) phases, respectively. In our C ijkl ðgÞ ¼ C eff
ijkl þ /ðgÞDC ijkl ; ð16Þ
work, they are assumed to take the following simple forms: where eT is a constant that determines the strength of the
eigenstrain, dij is the Kronecker delta, bðgÞ and /ðgÞ are
f m ðcÞ ¼ Ac2 ; ð7Þ
scalar (interpolation) functions, where C eff ijkl is an ‘‘effective”
p 2
f ðcÞ ¼ Bð1  cÞ ; ð8Þ modulus, C pijkl and C mijkl are the elastic moduli tensor of the
p and m phases, respectively, and DC ijkl ¼ C pijkl  C mijkl . All
with positive constants A and B. In Eq. (6), W ðgÞ is an the model parameters used in our simulations are listed
interpolation function [15], given by: in their non-dimensional form in Table 1. Our non-dimen-
8 sionalization procedure is the same as that used in Ref.
< 0;
> for g < 0;
[16].
W ðgÞ ¼ g3 ð10  15g þ 6g2 Þ; for 0 6 g 6 1; ð9Þ For a configuration at time t, the equation of mechani-
>
:
1; for g > 1: cal equilibrium, Eq. (14), is solved using an iterative Fou-
rier spectral technique with periodic boundary conditions
The elastic contribution to the free energy is:
Z (described in detail in Gururajan and Abinandanan [16];
1 see also Refs. [17–21]) to yield the elastic stress and strain
F el ¼ rel ; el dX ð10Þ
2 X ij ij fields; these, in turn, are used to integrate the Cahn–Hil-
where liard (Eq. (1)) and Allen–Cahn (Eq. (2)) equations over a
time step Dt to yield the configuration at t þ Dt. For this
0
eel
ij ¼ eij  eij ; ð11Þ time integration step, we use a semi-implicit Fourier
3950 R. Mukherjee et al. / Acta Materialia 57 (2009) 3947–3954

spectral technique, due to Chen and Shen [22]; the Fourier (a)
transforms are performed using the freeware called FFTW,
developed by Frigo and Johnson [23]. Microstructural evo-
lution is simulated through a repeated application of this
procedure on the new configuration at the end of each time
step.

3. Results

In our simulations, we place a small particle of initial

radius Ro and composition cpe at the centre of our simula-
tion cell with periodic boundary conditions; the initial
composition outside the particle is set to c1 everywhere;
with the normalizing scheme we have used, c1 is numeri-
cally the same as the supersaturation (or equilibrium vol-
ume fraction): n ¼ ðc1  cme Þ=ðcpe  cme Þ. As the simulation
proceeds, we track the particle radius, operationally (b)
defined as the distance from the centre where g ¼ 0:5,
and hence the growth coefficient a. The simulations end
when either the diffusion field or the elastic stress field from
neighbouring simulation cells begin to overlap; the values
of a obtained just before the simulations end are used in
the plots. They are also listed in Table 1 along with Rf ,
the final precipitate radius, and nE ¼ ðc1 –cmE Þ=ðcpe –cme Þ, the
effective (i.e. elasticity-corrected) supersaturation.

3.1. Zener–frank theory

We first compare our 1D simulation results with those

from the ZF theory. In Fig. 2, we have plotted the growth
coefficient a against matrix supersaturation n. The data
points from our 1D simulations are in excellent agreement
with the analytical results of ZF theory for 1D systems (the
lowest curve) for all supersaturations. This agreement is
not just in the growth coefficient, but also in the composi-
tion profile in the matrix phase in Fig. 3a.
Fig. 3. A comparison of scaled composition profiles in (a) a 1D and (b) a
2D system with n ¼ 0:4. The dashed curve in the matrix is from the ZF
sharp interface theory, while the solid and dotted curves are from phase
field simulations at two different particle sizes. The distance on the x-axis
is scaled by the instantaneous particle size. In the legend, S and P stand for
sharp interface theory and phase field simulations, respectively.

1D Thus, this excellent agreement in the baseline case— the

1.6
2D one without interface curvature and without misfit
3D
1D strains—is our main evidence for the essential correctness
2D
of the use of a phase field variable g in our model.
1.2 Fig. 2 also displays a comparison of the 2D growth coef-
ficients from the ZF theory and our simulations. Values of
a from our simulation are in excellent agreement with those
α

0.8 from ZF theory for a supersaturation of n ¼ 0:4 (within

0.4% at a final particle size of Rf ¼ 60), but become less
so at lower supersaturations. At n ¼ 0:1, growth coeffi-
0.4
cients from ZF theory and our simulations differ by about
13% at Rf ¼ 21. The main conclusion from these results is
0 that particles of smaller size, which experience a stronger
0 0.2 0.4 0.6 0.8 effect due to interface curvature, grow slower than pre-
ξ dicted by ZF theory.
As shown in Fig. 1a, the curvature effect may be
Fig. 2. Dependence of growth coefficient a on matrix supersaturation n.
The three curves are from the ZF (sharp interface) theory for 1D, 2D and
explained using the elevation of matrix interfacial composi-
3D growth. The data points are from our 1D and 2D phase field tion from cme from zero to cmI , which results in a reduced
simulations. supersaturation. Since the reduction in supersaturation
 R. Mukherjee et al. / Acta Materialia 57 (2009) 3947–3954 3951

1.8 No Misfit, S
c∞ = 0.1 , S
c∞ = 0.4 , S Misfit, S
1.6 1.6 Misfit, P
c∞ = 0.1 , P
c∞ = 0.4 , P
1.4
1.2
1.2

α
α

0.8
0.8

0.6
0.4
0.4

0.2
0
0 0 0.2 0.4 0.6 0.8
0 10 20 30 40 50 60 70
R ξ

Fig. 4. Effect of capillarity on instantaneous growth coefficient a, plotted
as a function of instantaneous particle radius R in 2D, non-misfitting
systems. The horizontal lines are from the ZF sharp interface theory
(without considering capillarity effects), and the data points are from our
2D phase field simulations.
Fig. 5. Dependence of growth coefficient a on matrix supersaturation n in
a misfitting system with d ¼ 0:5. The dashed curve is for LJV sharp
interface theory in 2D, and the data points are from 2D simulations. The
solid curve, from the 2D ZF theory for non-misfitting precipitates, is also
shown for comparison.

for a given particle size is a larger fraction of the original
supersaturation in a less concentrated matrix, the curvature
effect on growth coefficient is much higher at n ¼ 0:1 than
at n ¼ 0:4. Thus, in Fig. 4, in which the instantaneous val-
ues of growth coefficient are plotted against instantaneous
particle size, the data points from our simulations are much
closer to the ZF result in the latter, even at a particle size of
R ¼ 20. We return to a discussion of the curvature effect in
Section 4.
Similar to the 1D case in Fig. 3a, the composition profile
in the matrix at two different sizes obtained from our sim-
ulations show good agreement, in Fig. 3b, with that from
the ZF theory for a matrix composition of n ¼ 0:4.
3.2. Effect of a misfit strain: LJV theory
and simulations is about 18% at Rf ¼ 21. Thus, the com-
bined effect of misfit and capillarity in Fig. 5 mimics that
of capillarity alone in Fig. 2.
In Fig. 6, we find a good agreement between the simu-
lated (scaled) composition profile for two different times
with that for the LJV model. This agreement is similar to
that for the non-misfitting case in Fig. 3b.
3.3. Effect of interface curvature
A more detailed assessment of the role of capillarity is
possible by considering cpI , the precipitate interfacial com-
position.
 In the  sharp interface model, the difference

DcpI ¼ cpI  cpe , is proportional to DcmI ¼ cmI  cme :

In these simulations, we have used a dilatational misfit

of 1%. The precipitate and matrix phases are elastically iso- S
1 time R 35, P
tropic, with a Poisson’s ratio of 0.3. The shear moduli of R 55, P
the two phases, however, can be different. We have consid- 0.8
ered three different cases with ðGp =Gm Þ ¼ d ¼ 0:5, 1.0 and
2.0, though, for the sake of clarity, we present our plots
0.6
only for d ¼ 0:5.
c

As we mentioned in Section 1, if curvature effects are

0.4
neglected, the growth coefficient vs. supersaturation curve
(dashed curve in Fig. 5) from the LJV theory for the misfit-
0.2
ting case is obtained by shifting the ZF curve (solid curve,
for the non-misfitting case) to the right by cmE .
0
In Fig. 5, the growth coefficients a from our simulations
are plotted against supersaturation, along with the LJV 1 2 3
result for a system with elastically soft precipitates Scaled Distance
ðd ¼ 0:5Þ. The agreement is quite good at high supersatura-
Fig. 6. A comparison of scaled composition profiles in a 2D misfitting
tions (with a difference of just 0.1% at a particle size of
system with n ¼ 0:4. The dashed curve in the matrix is from the ZF sharp
Rf ¼ 57 in an alloy with n ¼ 0:4Þ. With decreasing solute interface theory, while the solid and dotted curves are from phase field
concentration, however, the agreement becomes worse; at simulations at two different particle sizes. The distance on the x-axis is
n ¼ 0:1, for example, the difference between the LJV theory scaled by the instantaneous particle size.
3952 R. Mukherjee et al. / Acta Materialia 57 (2009) 3947–3954

(a) S In simulations using diffuse interface models, interfacial

1.08
c∞ = 0.1, P compositions cpI and cmI cannot be measured, as the compo-
c∞ = 0.4, P
sition changes continuously across an interface region of
finite width. However, if we assume that the chemical
potential gradients are negligible inside the precipitate,
1.06
the composition anywhere in the precipitate should be
the same as cpI .
p

In Fig. 7, we have plotted cpI , obtained from simulations

cI

1.04
against the inverse of particle size R in (a) non-misfitting
and (b) misfitting systems. In Fig. 7a, the straight line rep-
resents the Gibbs–Thomson result (Eq. (18) without the
1.02
stress and strain terms), and the data points from our sim-
ulations are compositions at the centre of the precipitate;
for clarity, we have presented data only for two supersatu-
1 rations: n ¼ 0:1 and n ¼ 0:4. This figure shows that, in a
0 0.02 0.04 0.06 0.08 0.1
growth setting, particles growing in more concentrated
1/R
alloys display a smaller Gibbs–Thomson effect.
(b) In Fig. 7b, we compare the theoretical value of cpI (the
dashed line) with those from simulations for n ¼ 0:1 and
1.08
n ¼ 0:4. This figure also shows that the Gibbs–Thomson
effect is less completely realized for more supersaturated
alloys, leading to a better match between a from simula-
1.06
tions and that from theory (see Figs. 2 and 5).
Thus, Fig. 7 reveals yet another reason for the closer
cIp

agreement between ZF theory and our 2D simulations for

1.04
1.02
S precipitate experiences a large part of the Gibbs–Thomson
P, c∞ = 0.1
P, c∞ = 0.4
1 ulations (at Rf ¼ 21) matches well with the theoretical result
0 0.02 0.04 0.06 0.08
1/R
Fig. 7. Dependence of precipitate composition on particle radius in (a)
non-misfitting and (b) misfitting systems. The straight line is for cpI ,
precipitate composition at a curved interface, given by the Gibbs–
Thomson effect (see Eqs. (17) and (18)). The data points represent the
composition at the centre of the precipitate in simulations with n ¼ 0:1
(open circles) and n ¼ 0:4 (filled circles).
Wm
DcpI ¼ p DcmI
W the LJV theory of elastic stress effects during precipitate
where W ¼ ½@ 2 f =@c2 ce in the designated phase, and DcmI is
given by the generalized Gibbs–Thomson effect [24]:
rmij ðemij  epij Þ þ ½rpij ðepij  eT dij Þ  rmij emij =2
vc
DcmI ¼ þ p
ðcpe  cme ÞWm ðce  cme ÞWm
In the above equation, rij and eij are the stresses and
strains, respectively, in the designated phase, eT is the dila-
tational eigenstrain and v is the mean interface curvature.
In our 2D simulations, v ¼ 1=R; from Eqs. (7) and (8) (with
the parameter values of A ¼ B ¼ 1), we get Wm ¼ Wp ¼ 2.
For the values of misfit, shear modulus and Poisson’s ratio
used in this study (see Table 1), the (constant) elasticity
contribution to DC mI —the first term on the right-hand side
of Eq. (18)) — is 0.044, 0.056 or 0.066 for systems with
d ¼ ðGp =Gm Þ ¼ 0:5, 1.0 or 2.0, respectively.
more concentrated alloys: Gibbs–Thomson effect is less
completely realized in systems with a higher supersaturation.
At n ¼ 0:1, even though our results were obtained in a
growth setting, the small supersaturation ensures that the
effect. Thus, in the misfitting case, DcpI ¼ 0:066 from our sim-
0.1
of DcpI ¼ 0:067 calculated from Eq. (18). This agreement in
Fig. 7b may be taken as an indirect verification of the predic-
tions of Johnson and Alexander [11] and Leo and Sekerka
[12] on the phase compositions across a sharp interface.
4. Discussion
As we mentioned in Section 1, the primary aim of this
article is to use our ‘‘computer experiments” to validate
ð17Þ
growth. The following features of our phase field model
make it resemble closely the alloy model used in the LJV
theory: isotropic interfacial energy, isotropic atomic mobil-
: ð18Þ ity, constant atomic diffusivity in the matrix (and in the
precipitate too, though this is not an essential part of the
LJV theory), isotropic elastic moduli, and constant misfit
in the precipitate phase. While the LJV theory includes
cases where composition gradients may engender stress,
our model parameters are such that they do not.
However, interfacial curvature (and hence the Gibbs–
Thomson effect) is one feature which is always present in
phase field simulations (except in 1D), but absent in the
LJV and ZF theories. Its primary consequence is to
dampen the growth rate. However, this dampening effect
keeps decreasing with increasing particle size, and the
 R. Mukherjee et al. / Acta Materialia 57 (2009) 3947–3954 3953

Table 2 instabilities are promoted at larger sizes. In order to test

Comparison of growth coefficients from theory ðat Þ and simulations ðas Þ. the role of fluctuations in our system, we introduced a ran-
System n nE Rf at as 100  ðas  at Þ=at dom noise of magnitude 0:05% in both c and g at each time
No misfit 0.1 0.1 21 0.369 0.321 13.0 step in our 2D simulations with a circular particle. At the end
0.2 0.2 35 0.628 0.604 3.8 of these simulations the particle remains circular, indicating
0.3 0.3 48 0.897 0.885 1.3 that the fluctuations have not had any effect on particle shape
0.4 0.4 60 1.199 1.194 0.4
in the size regime explored in this study.
Misfit, d ¼ 0:5 0.1 0.056 21 0.246 0.202 17.9
0.2 0.156 32 0.514 0.502 02.3
5. Conclusions
0.3 0.256 44 0.775 0.776 +0.1
0.4 0.356 57 1.061 1.060 0.1
Misfit, d ¼ 1:0 0.1 0.044 19 0.208 0.145 30.3
0.2 0.144 31 0.482 0.469 02.7
(1) Using a our phase field simulations as computer
0.3 0.244 43 0.742 0.744 +0.3 experiments, we have validated the LJV theory of
0.4 0.344 56 1.023 1.031 +0.8 growth of misfitting particles in systems in which
Misfit,d ¼ 2:0 0.1 0.034 16 0.178 0.068 61.8
composition differences do not engender stress.
0.2 0.134 30 0.458 0.444 3.1 (2) Capillarity effects decrease instantaneous growth
0.3 0.234 42 0.717 0.722 +0.7 rate; this dampening effect is more pronounced at
0.4 0.334 55 0.996 1.003 +0.7 smaller sizes and at smaller supersaturations.
(3) At constant particle size, capillarity has a smaller
effect in alloys with larger supersaturations, because
instantaneous growth coefficient keeps rising towards the the Gibbs–Thomson effect is less completely realized.
theoretical values (e.g. Fig. 4). It is clear from Figs. 2 and (4) At low supersaturations, the Gibbs-Thomson effect is
5 that capillarity has a larger dampening effect on a at more completely realized, and our results on precipi-
lower supersaturations. In misfitting systems, the available tate compositions are in agreement with those pre-
(effective) supersaturation nE ¼ ðc1  cmE Þ=ðcpe  cme Þ is dicted from the theory of thermodynamics of
smaller when the precipitate is stiffer (see Table 2). Thus stressed solids.
we find that a values from simulations are smaller than the-
oretical values by 18%, 30% and 62%, when d ¼ 0:5; 1:0
Acknowledgements
and 2.0, respectively, in systems with n ¼ 0:1.
Our 2D simulations (with and without misfit) show that
The authors thank the Volkswagen Foundation for
the Gibbs–Thomson effect is only partially realized during
financial support for this work. They also thank Prof. V.
growth, especially at large supersaturations. Since the
Jayaram and Dr. H. Ramanarayan for discussions.
Gibbs–Thomson effect dampens the growth rate, its partial
realization helps bring the growth rate closer to the theoret-
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