Acta Materialia 52 (2004) 4669–4676

www.actamat-journals.com

Modelling the overlap of nucleation, growth and coarsening

during precipitation
J.D. Robson *

Manchester Materials Science Centre, UMIST, Grosvenor Street, Manchester M1 7HS, UK

Received 29 March 2004; received in revised form 8 June 2004; accepted 11 June 2004
Available online 17 July 2004

Abstract

A modified version of the Kampmann and Wagner numerical precipitation model has been used to investigate the effect of
interfacial energy, solute supersaturation, and diffusivity on the kinetics of precipitation in binary alloys. It is predicted that overlap
occurs between nucleation and coarsening when the precipitate/matrix interfacial energy falls below a critical value or the super-
saturation increases above a critical value. Changes in diffusivity have no effect on the overlap. These predictions have been used to
produce a kinetic map showing the critical supersaturation at which nucleation and coarsening are predicted to overlap for different
alloy systems. This has important implications in the interpretation of the results of kinetic experiments.
Ó 2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Nucleation; Coarsening; Modelling

1. Introduction growth, and coarsening significantly overlap, in which

The precipitation of second phase particles is critical
to the properties of many industrially important alloys,
and modelling this precipitation has therefore been a
long standing interest in metallurgy. The decomposition
of a supersaturated solid solution by precipitation of a
new phase of a different composition is often considered
in terms of three distinct steps; nucleation of the new
phase through the random formation of supercritical
clusters of atoms, growth of these clusters by diffusional
transportation of atoms, and finally coarsening, which
involves the dissolution of small particles at the expense
of large ones, driven by an overall reduction in the in-
terfacial energy. Traditionally, these three processes
have often been considered in isolation with the implicit
assumption that one process is essentially complete be-
fore the next one begins. More recently, work on both
condensation of liquids from vapour [1] and precipitate
formation in solids [2–6], has demonstrated that this
assumption is often invalid. In many cases, nucleation,
*
Tel.: +44-161-200-3609; fax: +44-161-200-3586.
E-mail address: joseph.robson@umist.ac.uk (J.D. Robson).
case the evolution of both particle number density and
size depends on all three processes.
Several theoretical treatments that account for si-
multaneous nucleation, growth and coarsening have
been developed. Such a theory for droplet formation in
fluids was developed by Langer and Schwartz [1] and
later modified by Kampmann and Wagner to enable it
to be applied to precipitate formation in alloys (the
MLS model [7]). These models predict the evolution of
the mean precipitate parameters (e.g. radius) for an as-
sumed size distribution. More recently, Kampmann and
Wagner have developed a numerical model which does
not rely on such prior assumptions and is capable of
predicting the full evolution of the size distribution [8]
(the numerical, or KWN model). These models attempt
to predict the evolution of the precipitate size distribu-
tion without making arbitrary distinctions between nu-
cleation, growth and coarsening regimes. The numerical
framework used in the KWN model makes this ap-
proach particularly powerful and flexible. It is based on
classical theory for nucleation and growth, with the
particle size distribution evolved under the natural ac-
tion of these processes. This model has been successfully

1359-6454/$30.00 Ó 2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actamat.2004.06.024
4670 J.D. Robson / Acta Materialia 52 (2004) 4669–4676
used to predict precipitate evolution in a wide range of
model alloy systems, including Cu–Co, Ni–Al, Al–Sc
and Fe–Ni [8–10].
These predictions, in conjunction with experimental
evidence, confirm that for certain alloys and heat
treatment conditions, there is a large overlap between
nucleation and coarsening. However, it is also possible
to find combinations of conditions for which nucleation
is complete before the onset of coarsening. This is im-
portant, because studies of nucleation that focus on
counting the increase in particle number density during
the early states of precipitation rely on the assumption
that changes in the number density can be wholly at-
tributed to nucleation. If the number density of particles
is complicated by coarsening however, such an analysis
will be invalid. Aaronson and LeGoues [6] have dis-
cussed this in detail and introduced the concept of a
‘‘nucleation window’’, which defines the conditions for
which the nucleation rate is large enough to be detect-
able while avoiding overlap between nucleation and
coarsening. However, a quantitative determination of
the nucleation window for the alloy systems commonly
used for nucleation studies has yet to be performed.
The KWN model provides a useful tool for system-
atically studying the effects of kinetically important pa-
rameters, such as supersaturation, diffusivity and
interfacial energy on nucleation, growth, coarsening and
the overlap between these processes, within the limita-
tions of the classical theory on which the KWN model is
based. These limitations are discussed in more detail
later. In this paper, a modified KWN model has been
used to investigate the effect of these parameters on
precipitation and, in particular, investigate their effect
on the overlap between nucleation and coarsening.
These calculations are used to identify the nucleation
window for different alloy systems.
2. The model
2.1. Kinetics model
The Kampmann and Wagner numerical (KWN)
model for precipitate evolution has been described in
detail elsewhere [8,11,12]. The essential features of this
model are:
(1) The continuous time evolution of the particle distri-
bution is considered in terms of discrete time steps.
(2) The continuous size distribution of the particles is
discretised into a large number of size classes.
(3) The number of new particles in each time step is
calculated using classical nucleation theory. The
exchange of particles between size classes is calcu-
lated assuming solute diffusion is the rate limiting
process and a spherical growth morphology. The
Gibbs–Thomson relationship is used to calculate
the modified interfacial compositions for each size
class at each time step.
(4) The change in matrix solute level due to precipitate
formation or dissolution is calculated at each time
step using the mean field approximation.
The resultant model is capable of predicting nucle-
ation, growth and coarsening within the classical
framework without artificial constraints, whether these
processes occur concommitantly or sequentially. Details
of the implementation of the model used in this work,
and in particular the adaptive time step routine to en-
sure sufficient numerical accuracy, can be found else-
where [10].
2.2. Nucleation
Classical nucleation theory gives the equation for
time dependent, homogeneous nucleation, as [8,5]

  s
4pcr
2
I ¼ Nv Zb
exp exp  ; ð1Þ
3kT t
where Nv is the number of nucleation sites per unit
volume (and will be discussed below), Z is the Zeldovich
factor (which accounts for the decay of some of the
supercritical clusters), c is the interfacial energy of the
nucleus (which is assumed to be isotropic and size in-
dependent), r
is the critical radius a cluster must reach
to become a nucleus and s is the incubation time for
nucleation (the time taken to establish the initial cluster
distribution). k and T have their usual meanings. A well
known feature of classical nucleation theory is the high
sensitivity of the nucleation rate to the interfacial en-
ergy. Furthermore, interfacial energies are difficult to
directly determine experimentally. Small differences in
the interfacial energy can therefore lead to large varia-
tions in the predicted nucleation rate, and this consti-
tutes one of the main sources of error in the KWN
model.
The critical radius depends on the driving force for
transformation and the interfacial energy. Ignoring
strain energy, the critical radius may be written as
2c
r
¼ ; ð2Þ
DGv
where DGv is the chemical volume free energy change
driving nucleation. For a cluster to reach this critical
radius it must overcome an energy barrier of height G
,
where
4
G
¼ pr
2 c: ð3Þ
3
Using the assumption of a spherical nucleus, the Z, b
and s values may be written [5,13,14]
 J.D. Robson / Acta Materialia 52 (2004) 4669–4676
Va DG2v
Z¼ pffiffiffiffiffiffiffiffiffiffi ; ð4Þ
8p c3 kT
16pc2 cD
b
¼ ; ð5Þ
DG2v a4
8kT ca4
s¼ ; ð6Þ
Va2 DG2v Dc
where Va is the volume per atom in the matrix, c is the
concentration (atomic fraction) of solute in the matrix, a
is the lattice constant of the product phase and D is the
diffusivity of the solute in the matrix.
The number of nucleation sites per unit volume, Nv is
an important factor in Eq. (1). In Russell’s analysis [13],
Nv for homogeneous nucleation was set equal to the
total number of atoms per unit volume in the system, on
the basis that any atom in the system can act as a nu-
cleation site. However, as Stowell has discussed [15], this
assumption can lead to physically meaningless results,
since it ignores the fact that the cluster population is
limited by the availability of solute atoms. More realistic
results emerge using the assumption that Nv is equal to
the number of solute atoms per unit volume [15]. This
modification was therefore used in this work.
The volume chemical free energy change on forming
a nucleus was calculated using the dilute solution ap-
proximation, so that DGv can be written in terms of
compositions as [16]


Rg T b lnðci Þ b lnð1  ci Þ
DGv ¼  ce þ ð1  c e Þ ; ð7Þ
Va lnðcae Þ lnð1  cae Þ
where Va is the molar volume of the precipitating phase
and ci is the instantaneous concentration of solute in the
matrix. This is the far field matrix concentration, strictly
speaking an infinite distance from the precipitate/matrix
interface. cae is the concentration of solute in the matrix (a)
in equilibrium with the precipitate (b) and cbe is the equi-
librium concentration of solute in the precipitate phase.
2.3. Growth and coarsening
In the case of diffusion controlled growth of spherical
particles, and providing the dispersion of precipitates is
sufficiently dilute so that each particle may be treated as
being effectively isolated, the growth rate is given by [17]
dr D ci  car
¼ ; ð8Þ
dt r cbe  car
where r is the particle radius, car is the concentration of
solute in the matrix at the interface (which depends on
the particle radius due to the effect of capillarity) and it
is assumed that the precipitates have the equilibrium
composition cbe . car is calculated from ca1 (the equilibrium
concentration of solute in the matrix for a planar in-
terface) using the Gibbs–Thomson equation
4671
 
2cVm 1
car ¼ ca1 exp ; ð9Þ
Rg T r
where c is the interfacial energy of the growing (or
shrinking) particles. A key assumption used in the KWN
model is that a single value of interfacial energy can be
applied to particles undergoing nucleation, growth and
coarsening. This assumption will only be strictly valid
when the interfacial energy is independent of the particle
radius.
Coarsening arises naturally in the KWN model. As
the fraction of solute in the matrix decreases during
precipitation, the driving force for nucleation and
growth of the precipitate particles decreases and the
critical particle radius increases. Particles in the size
distribution which have a radius <r
will have a negative
growth rate according to Eq. (8) and will thus start to
shrink. Particles with a radius >r
will retain a positive
growth rate and will continue to increase in size. When
the size of a group of shrinking particles reaches zero
they are removed from the size distribution. Note that
this treatment is only a reasonable approximation in
systems where the precipitate volume fraction is small.
In alloys with a high precipitate volume fraction, inter-
actions between particles, that are not accounted for in
this model, become important and coarsening will not
be correctly predicted.
3. Results
Versions of the KWN model have been successfully
applied to a wide range of alloy systems (e.g. Fe–Ni,
Cu–Ti, Ni–Al, Al–Sc [8,9]). In each case, a comparison
of prediction and experiment has shown that the model
is capable of accurately reproducing the observed pre-
cipitation kinetics. Recently, an implementation of the
model similar to that described here was used to predict
precipitation in the Cu–Co system [10], and was shown
to reproduce experimental data reasonably well (to
within an order of magnitude). Therefore, no further
experimental validation of the model is reported in this
paper. Rather, the model is used as a tool to investigate
the effects that changes to individual physical parame-
ters have on the precipitate evolution predicted by
classical theory, from nucleation to coarsening, and in
particular the overlap between these processes. One of
the advantages of a model is that it allows changes in
parameters to be investigated individually, something
that is often not possible experimentally.
For a fixed temperature, analysis of the nucleation
and growth equations show that the three most critical
system dependent variables are the interfacial energy,
supersaturation, and solute diffusivity. The effect of
changing each of these variables will be investigated in
turn.
4672 J.D. Robson / Acta Materialia 52 (2004) 4669–4676
3.1. Effect of interfacial energy
A critical parameter controlling precipitate evolution
is the interfacial energy. The critical nucleus size and
hence nucleation rate are very sensitive to this parame-
ter. Interfacial energy also influences precipitate growth
through the capillarity effect and drives the coarsening
process. The interfacial energy of precipitates in different
alloy systems varies markedly, even when the interface
type is the same (e.g. fully coherent). For example, the
interfacial energy of coherent Ni3 Al particles precipi-
tating in Ni–Al alloys is ’0.014 J m2 [18], which is over
an order of magnitude less than the interfacial energy of
Co precipitating in the Cu–Co system (0.22 J m2 [15]).
The effect of changing interfacial energy over the
range 0.05–0.3 J m2 on precipitate evolution was pre-
dicted using the KWN model. The predicted evolution
of precipitate number density is shown in Fig. 1. This
calculation was performed using data for the Cu–
0.5at.% Co system at a temperature of 450 °C. The
equilibrium solubility of Co in Cu was taken from Setna
[19] and diffusion coefficient of Co in Cu from D€ ohl [20].
These conditions are used throughout this paper as a
reference set of input parameters.
It can be seen that changing the interfacial energy has
a marked effect on the shape of the number density
evolution curves. At low interfacial energy values, there
is no plateau when the number density reaches its
maximum value. This is because there is an overlap
between nucleation and coarsening. At the point where
the addition of new particles by nucleation has effec-
tively stopped, coarsening is already dissolving the
smallest particles, reducing the number density. A stea-
dy state number density is therefore never obtained
during precipitation.
0.1 0.15
1 lead to LSW coarsening behaviour.
σ= 0.05Jm-2
Number Density (normalized)
0.8
0.6
0.4
0.2
0 overlap occurs, a significant number of particles in the
1 2 3 4
10 10 10 10
Time / s
Fig. 1. Predicted evolution of precipitate number density with time for
a range of interfacial energies (all other input parameters correspond
to the Cu–Co system at 450 °C).
When the interfacial energy reaches 0.2 J m2 how-
ever, a plateau appears at the maximum number density.
This corresponds to a case where there is a delay be-
tween the time at which the nucleation rate has fallen to
zero and the onset of a reduction in number density due
to coarsening, i.e. there is no overlap between nucleation
and coarsening.
Further calculations were performed for selected in-
terfacial energies, covering the range over which nucle-
ation and coarsening start to overlap. Fig. 2(a) shows
the predicted variation in true number densities with
time (on a logarithmic scale). The strong dependence of
the maximum number density on the interfacial energy
can be seen, as can the onset of the plateau at the
maximum number density as the interfacial energy in-
creases. Fig. 2(b) shows the corresponding predicted
variation in particle radius. It can be seen that there is
also a plateau in the particle radius evolution, which
becomes more pronounced as the interfacial energy in-
creases. This corresponds to a time interval in which the
particle number density and volume fraction are con-
stant, and the reduction in radius mean due to small
particles shrinking balances the increase in mean radius
due to large particles growing. Fig. 2(c) is a plot for two
of the interfacial energies, one for which model predicts
that nucleation and coarsening overlap (0.18 J m2 ), and
one for which they do not (0.26 J m2 ), showing the
evolution of the critical and mean radii. For larger in-
terfacial energy there is an extended period over which
the mean radius of the particles is increasing steeply
whilst the critical radius is increasing only slowly. When
the interfacial energy is reduced, this period is consid-
erably shorter. Note that the classical LSW theory of
coarsening [21,22] only applies in the regime where the
mean and critical radii are equal. However, any given
particle will begin to shrink due to coarsening as soon as
the critical radius exceeds its particle radius, and this
may occur well before the onset of the conditions that
0.2 0.25
To explain why there is significant overlap between
nucleation and coarsening for low interfacial energy
values, but not at higher values, it is useful to consider
the particle size distributions (PSDs) at a time corre-
sponding to the peak in the particle number density. The
0.3 PSDs for two cases, one where there is overlap (0.18
J m2 ) and one where there is no overlap (0.26 J m2 ),
are shown in Fig. 3. Also marked on these plots are the
instantaneous values of the critical radius at the time
when the number density reaches its maximum value. It
can be seen that for the low interfacial energy, where
5
10 size distribution are below the critical radius size when
the peak number density is reached. These particles will
therefore be dissolving, confirming that the coarsening
process has begun. For the higher interfacial energy, all
particles are larger than the critical radius, Therefore,
 J.D. Robson / Acta Materialia 52 (2004) 4669–4676 4673

25 22
10 x 10
10

-3
Number density /m
-2 -2
σ = 0.18 Jm σ = 0.18 Jm

24 0.20
10 5
Number Density /m-3

0.22
23 0
10 0
0.24 r* 1 2 3 4 5
(a) Radius / nm

22 0.26 x 10
20
10
15

Number Density /m-3

-2
σ = 0.26 Jm
10
21
10
2 3 4 5 6 7
10 10 10 10 10 10 5
(a) Time / s

0
6 0 r* 1 2 3 4 5
(b) Radius / nm
5 0.26
Mean Particle Radius / nm

Fig. 3. Predicted particle size distribution when the particle number

density reaches its maximum value. The critical radius at this point is
4 also marked. (a) Interfacial energy 0.18 J m2 . (b) Interfacial energy
0.26 J m2 .

3 0.24
ceeding the size of the smallest particles in the distri-
2 bution which will then dissolve and disappear, at which
0.22 -2
point the number density decreases.
σ = 0.18 Jm
0.20 It is noteworthy that the critical radius when the
1
number density reaches its peak is greater when the in-
terfacial energy is less. This can be understood by a
0 simple consideration of the nucleation equation. The
3 4 5 6 7
10 10 10 10 10
(b) Time / s nucleation rate is very sensitive to the energy barrier, G
.
As the solute in the matrix falls, G
increases until it
7 reaches a value at which the nucleation rate is effectively
zero. This value will be the same regardless of the in-
6 Mean radius terfacial energy. Eq. (3) shows that if the interfacial
Critical radius -2 energy is increased, then the critical radius required to
5 σ= 0.26Jm
reach the fixed value of G
at which nucleation stops will
Radius / nm

4
be less. r
itself also depends on the interfacial energy
0.18 (Eq. (2)). Therefore, if the interfacial energy is increased,
3 not only is a smaller increment in r
required before
nucleation stops, but this increment can be achieved
2 through a smaller decrease in the driving force for nu-
cleation (DGv ) and therefore a smaller level of solute
1 depletion. Essentially, as the interfacial energy increases,
the nucleation rate becomes more sensitive to solute
0 depletion, and falls to zero earlier, relative to the time
2 3 4 5 6 7
10 10 10 10 10 10
(c) for completion of precipitation.
Time / s
This is not a new observation, but its implications to
Fig. 2. (a) Predicted evolution of number density with time for a se- the overlap of nucleation, growth and coarsening do not
lected range of interfacial energies. (b) Predicted evolution of mean appear to have been considered before. In the case of
particle radius with time. (c) Predicted evolution of mean particle ra-
high interfacial energy, a small level of solute depletion
dius and critical radius for the highest and lowest interfacial energies.
results in a rapid reduction in the nucleation rate.
even once nucleation has stopped, all particles will However, there is still sufficient solute left for growth of
continue to grow. As further solute is removed from the all the precipitates. In the case of low interfacial energy,
matrix, the critical radius will increase, eventually ex- a greater level of solute depletion can be tolerated before
4674 J.D. Robson / Acta Materialia 52 (2004) 4669–4676
nucleation stops, by which point the critical radius has
increased above the size of the smallest particle, and
coarsening has begun.
3.2. Effect of supersaturation
Supersaturation is a critical parameter in determining
the driving force for precipitation, and hence the nu-
cleation and growth rates. Supersaturation can be de-
fined as the ratio between the instantaneous and
equilibrium matrix solute concentration, ci =cae . The ef-
fect of the initial supersaturation on the overlap between
nucleation, growth and coarsening was predicted by
performing calculations for the reference Cu–Co system
(using an interfacial energy 0.22 J m2 ). The initial su-
persaturations used were calculated as multiples of that
for the reference system (Cu–0.5at.% Co at 450 °C).
A plot of the predicted evolution of the number density
as a function of the relative supersaturations is shown in
Fig. 4. As expected, as the supersaturation increases, the
kinetics of the transformation are accelerated and
the peak number density is reached at a shorter time.
The maximum number density (Nmax ) is also very sen-
sitive to the supersaturation. For example, for a super-
saturation 10 greater than reference, Nmax is predicted
to be 1.1  1026 m3 , which is over 100 greater than
Nmax for the reference supersaturation (8.2  1023 m3 ).
Although the actual Nmax values may be expected to be
in error (by up to an order of magnitude based on past
application of this model to the Cu–Co system [10]) the
predicted trend is expected to be accurate.
In addition to a change in kinetics, a change in su-
persaturation can also been seen to change the shape of
the number density versus time plot. For low supersat-
28
10
x10
26
10
Number Density /m-3
x2
24 x1
10
x0 .5
22
10
20
10
0 2 4 6
10 10 10 10
Time /s
Fig. 4. Predicted evolution of precipitate number density with time for
variation in supersaturation, given as multiples of the reference su-
persaturation (corresponding to Cu–0.5at.% Co at 450 °C).
urations, there is a plateau at the maximum number
density, which, as discussed, occurs when there is no
overlap between nucleation and coarsening. As the su-
persaturation is increased, the plateau disappears as
nucleation and coarsening start to overlap. This is sim-
ilar to the effect observed when the interfacial energy is
increased, and its origins are also similar. Nucleation is
more sensitive to supersaturation than growth. If the
initial supersaturation is small, then even a small re-
duction in the matrix solute level is sufficient to cause
nucleation to effectively stop. At this point, the critical
radius has not increased sufficiently to exceed the size of
the smallest particles, and so coarsening has not begun
and there is no overlap.
If the initial supersaturation is large, a significant
nucleation rate is retained even when a substantial
proportion of the solute has been removed from the
matrix into the precipitates. This level of solute removal
is sufficient to cause the critical radius to increase above
the smallest particle size, at which point coarsening will
begin to dissolve these particles. There is therefore an
overlap between nucleation and coarsening.
3.3. Effect of diffusivity
Both the nucleation and growth rates depend on the
diffusivity of the solute species. In the classical nucle-
ation rate Eq. (1) the diffusivity enters into both the b

(Eq. (5)) and incubation time (s, Eq. (6)) terms. If the
incubation time is short compared to the time to reach
the peak number density, then the exponential term
containing s in Eq. (1) will rapidly approach 1. The
steady state nucleation rate then becomes directly pro-
portion to an increase in D (assuming all other variables
are fixed). Similarly, the growth rate (Eq. (8)) is also
proportional to D.
The effect of changing the diffusivity on the overlap
between nucleation and coarsening was investigated by
varying D over several over orders of magnitude (and
keeping all other variables as for the Cu–Co reference
system). The resultant number density versus time
curves are shown in Fig. 5. Each curve corresponds to a
different value of D, given as a multiple of the reference
value (that for Co in Cu at 450 °C). It can be seen that,
as expected, an increase in diffusivity accelerates the
kinetics and reduces the time to reach the peak number
density. However, a change in D does not change the
maximum number density reached, and importantly
does not change the shape of the plot.
Theoretical treatments that derive analytical expres-
sions for the maximum number density show that this
8
10 important parameter depends on the ratio of the nu-
cleation rate to diffusivity (I=D) [15]. As discussed, when
the incubation time is negligible, the nucleation rate
increases in proportion to D, so that I=D is independent
of D. The prediction of the present model, that the
 J.D. Robson / Acta Materialia 52 (2004) 4669–4676
23
x 10
10
x100 x10 x1 x0.1 x0.001
8 technique used to identify newly nucleated particles, in
Number Density /m-3
6 tions, in this work the end of nucleation is arbitrarily
4
2
0
1 3 5 7
10 10 10 10
Time / s
Fig. 5. Predicted evolution of precipitate number density with time for
variation in diffusion coefficient (at constant temperature), given as
multiples of the reference diffusion coefficient for Co in Cu at 450 °C).
maximum number density is independent of D, is
therefore consistent with these analytical models.
The observation that changing D does not change the
shape of the number density evolution plot arises from
the prediction that D does not influence the extent of
overlap between the nucleation, growth and coarsening
processes. This is because changing D effects both nu-
cleation and growth rates in the same way (unlike
changes in supersaturation or interfacial energy), and
therefore only acts to scale the kinetics. This observation
is consistent with predictions Kampmann and Wagner
performed for the Cu–Ti system [8].
3.4. Kinetic map
As shown above, the interfacial energy and initial
supersaturation are both critical parameters in deter-
mining whether the nucleation and coarsening processes
overlap. As Aaronson and LeGoues have noted [6],
many studies of nucleation may have been contaminated
by coarsening. To avoid this it is necessary to chose a
condition where there is no overlap between these pro-
cesses, whilst obtaining nucleation kinetics that are
sufficiently rapid to be measurable over practical time-
scales.
Using the model, it is possible to calculate a ‘‘kinetic
map’’, showing regions where nucleation and coarsening
are predicted to overlap, and regions where they do not,
as a function of supersaturation and interfacial energy.
The boundary between ‘‘overlap’’ and ‘‘no overlap’’
regions is defined by the set of conditions for which
nucleation stops exactly at the time when the first par-
ticle disappears from the distribution due to coarsening.
4675
Since the nucleation rate never reaches exactly zero, it is
necessary to define a cut off at which nucleation is ef-
fectively considered complete. In practice, this value of
this cut off will be determined by the measurement
particular the minimum resolvable particle size and the
volume of material analysed. To avoid these complica-
considered as the point where the nucleation rate falls
below 1% of its steady state value. Predictions made
using different values of this cut off showed that the
position of the boundary on the map was not very
sensitive to the precise value chosen.
Fig. 6 shows the map calculated by the model on the
basis of the criterion outlined above. This map can be
used to help to interpret the behaviour in different alloy
9 systems. Also shown on Fig. 6 are the interfacial ener-
10
gies of common systems for which measurements of
nucleation kinetics have been made [8]. As the interfacial
energy of the precipitates decreases, the maximum su-
persaturation that can be tolerated whilst avoiding
overlap of nucleation and coarsening is greatly reduced.
Therefore, in systems such as Ni–Al, nucleation and
coarsening are predicted to become overlapping even for
small supersaturations. However, for both the Cu–Co
and Fe–Cu systems there is a usefully wide range of
supersaturations that fall within the nucleation window.
Note however that as the interfacial energy is increased,
so is the tendency for heterogeneous rather than ho-
mogeneous nucleation. This is not considered in the
present KWN model. If heterogeneous nucleation
0.4
-2
Interfacial Energy / Jm
0.3
No overlap
Fe Cu 2 2
1
Cu Co
0.2
Overlap
0.1
Cu Ti
0.05 3 4
5 Ni Al
0 1 2
10 10 10
Supersaturation
Fig. 6. Map showing the region of supersaturation and interfacial
energy where nucleation and coarsening overlap, and the region where
they do not. The interfacial energies of some common systems used for
kinetic studies are marked on the plot. The experimental conditions
used by (1) Aaronson, LeGoues [6], (2) Kampmann, Wagner [23], (3)
von Alvensleben, Wagner [24], (4) Eckerlebe et al. [25] and (5) Wendt,
Haasen [26] are also marked.
4676 J.D. Robson / Acta Materialia 52 (2004) 4669–4676
occurs, the boundary in Fig. 6 would be expected to be
shifted.
Marked on the figure are the ranges of conditions
used by various researchers investigating nucleation and
precipitation kinetics in a number of alloy systems. It
can be seen that of all these investigations, only the work
of Aaronson and LeGoues was performed under con-
ditions where there is predicted to be no overlap between
nucleation and coarsening. This re-emphasises the point
that Aaronson and LeGoues themselves made; that in
many kinetic studies, it is highly likely that even during
the early stages of precipitation, measurements of the
increment in particle number density will be contami-
nated by coarsening, and cannot be used as a direct test
of nucleation theory alone. As can be seen, this is par-
ticularly the case for alloy systems where the precipitate
interfacial energy is low.
4. Conclusions
The KWN model has been applied to independently
predict the effect of supersaturation, interfacial energy
and solute diffusivity on the overlap between nucleation,
growth and coarsening during precipitation under the
constraints of classical theory.
(1) The extent of overlap depends strongly on the inter-
facial energy of the precipitate. When the interfacial
energy exceeds a critical value, nucleation is com-
plete before coarsening begins (i.e. there is no over-
lap).
(2) The extent of overlap also depends on the solute su-
persaturation. For low solute supersaturations there
is no overlap.
(3) The solute diffusivity does not effect the extend of
overlap, since it influences both nucleation and
growth in the same way. An increase in diffusivity
therefore simply accelerates the transformation.
(4) An alloy independent kinetic map has been pro-
duced, showing the critical combinations of interfa-
cial energy and supersaturation for which nucleation
and coarsening begin to overlap. For alloy systems
such as Ni–Al, where the interfacial energy is rela-
tively low, there is overlap even at small supersatu-
rations. For alloy systems with a higher interfacial
energy, such as Cu–Co, there is a useful range of su-
persaturations for which there is no overlap.
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