CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 50 (2015) 4958

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CALPHAD: Computer Coupling of Phase Diagrams and

Thermochemistry
journal homepage: www.elsevier.com/locate/calphad

Modelling precipitation kinetics: Evaluation of the thermodynamics of

nucleation and growth
Bastian Rheingans a,n, Eric J. Mittemeijer a,b
a
b

Institute for Materials Science, University of Stuttgart, Heisenbergstrasse 3, 70569 Stuttgart, Germany
Max Planck Institute for Intelligent Systems (formerly Max Planck Institute for Metals Research), Heisenbergstrasse 3, 70569 Stuttgart, Germany

art ic l e i nf o

a b s t r a c t

Article history:
Received 29 January 2015
Received in revised form
9 April 2015
Accepted 30 April 2015
Available online 4 May 2015

Modelling of (solid-state) precipitation kinetics in terms of particle nucleation and particle growth requires evaluation of the thermodynamic relations pertaining to these mechanisms, i.e. evaluation of the
nucleation barrier and of the GibbsThomson effect. In the present work, frequently occurring problems
and misconceptions of the thermodynamic evaluation are identied and a practical approach with regard
to kinetic modelling is proposed for combined and unied analysis of the thermodynamics of nucleation
and growth, based on the fundamental thermodynamic equilibrium consideration in a particlematrix
system. A computationally efcient method for numerical determination of the thermodynamic relations
is presented which allows an easy and exible implementation into kinetic modelling.
& 2015 Elsevier Ltd. All rights reserved.

Keywords:
GibbsThomson effect
Thermodynamics
CALPHAD
Precipitation kinetics
Modelling

1. Introduction
The dispersion of small second-phase particles within a parentphase matrix, e.g. as resulting from a solid-state precipitation reaction, strongly inuences the properties of the two-phase system.
In materials science, precipitation reactions are therefore widely
used as a method to enhance materials performance in numerous
elds of application [1]. Precise control of the reaction kinetics
allows to tailor the microstructure evolving upon precipitation and
thus to tune the material properties.
Upon precipitation, particles of a solute(s)-rich phase are
formed within an -phase matrix initially supersaturated in solute
(s), leaving behind a solute(s)-depleted -phase matrix. The
kinetics of the precipitation reaction, typically described in terms
of nucleation and growth of precipitate particles, strongly vary
with the degree of solute supersaturation, i.e., at constant temperature, with phase composition. In order to account for this effect in a model for precipitation kinetics the kinetics must be
coupled to the thermodynamics of the alloy system. The numerical
efciency of the kinetic model and the quality of its results are
therefore directly linked to the evaluation of the system's thermodynamics. Typical examples are models of KampmannWagner-numerical (KWN) type [2] (see e.g. [36] and Section 4): in this
frequently applied type of modelling approach, the evolution of
n

Corresponding author. Fax: 49 711 689 3312.

E-mail addresses: b.rheingans@is.mpg.de (B. Rheingans),
e.j.mittemeijer@is.mpg.de (E.J. Mittemeijer).
http://dx.doi.org/10.1016/j.calphad.2015.04.013
0364-5916/& 2015 Elsevier Ltd. All rights reserved.

the particle size distribution is computed on the basis of numerical

integration of a composition-dependent nucleation rate and a
size- and composition-dependent growth rate for discrete time
steps and discrete particle-size classes. Such models thus require
numerous evaluations of thermodynamic relations. Unfortunately,
up to now the current corresponding modelling practice often
involves usage of incompatible thermodynamic models for nucleation and growth and redundant thermodynamic evaluations
(see below). The present work proposes a practical route for the
thermodynamically correct and numerically efcient coupling of
kinetic model and thermodynamic description (for KWN-type
modelling).
In terms of thermodynamics, formation and stability of a precipitate-phase particle are (in the simplest case) dened by two
counteracting factors (see e.g. [7]): (i) The release of energy due to
the decomposition of the supersaturated matrix phase into solutedepleted matrix phase and solute-rich precipitate phase. This release of energy can be described as a difference of chemical Gibbs
energies Gcj (x j ) of the (homogeneous) phases j = , , dened by
their respective compositions xj. (ii) The increase in energy due to
the development of a particlematrix interface.1
In the rate equations for nucleation and growth as typically
used in KWN-type kinetic models, this stability consideration is
represented by two different concepts: the energy barrier for
1
Within the scope of this work, only the case of a, in the Gibbsian sense,
sharp interface, i.e. an interface with a width small compared to the size of the
particle will be considered.

50

B. Rheingans, E.J. Mittemeijer / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 50 (2015) 4958

nucleation and the GibbsThomson effect, affecting the growth

(rate) of a particle. In the classical theory of nucleation [8,9], the
rate of nucleation N is dominated by an energy barrier G* for
formation of a particle of critical size rn above which the particle is
stable:

G*
N exp
,
kT

(1)

where k and T denote the Boltzmann constant and the absolute

temperature, respectively.2 For the case of a precipitation reaction,
G* and rn are functions of the change in chemical Gibbs energy

gc (x ,m , x,p) upon nucleation (with gc (x ,m , x,p) being the

chemical driving force for nucleation) for given compositions
x ,m and x,p of the -phase matrix and the -phase precipitate,
respectively, and of the interface energy per unit area, i.e.
G* = G* (gc (x ,m , x,p) , ) and r * = r * (gc (x ,m , x,p) , ), thus reecting the two competing energy contributions. Growth of a
solute-rich particle leads to solute depletion of the surrounding
matrix; particle growth can then (in any case eventually) become
rate-controlled by solute diffusion through the solute-depleted
matrix towards the particle. The growth rate of a spherical particle
of radius r in a binary3 system AB is then often described by
[12,13]

dr
x ,m x ,int D
=
,
dt
kx,int x ,int r

(2)

with the diffusion coefcient D of the solute component in the

matrix and the atom fractions4 of solute x ,m in the -phase matrix
remote from the particle, and x ,int and x,int in the -phase matrix
and in the -phase particle at the particlematrix interface,
respectively; the factor k accounts for the difference in molar
volume of the phase and the phase. For x ,m > x ,int , i.e. for a
positive growth rate (considering precipitation of a solute-rich
phase, kx,int x ,int is generally positive), the particle is stable and
grows; for x ,m < x ,int , the particle is unstable and shrinks. x ,int
and x,int are often taken according to local establishment of
thermodynamic equilibrium at the interface.5 For a small particle
size, i.e. for a large ratio of interface area to particle volume, the
state of equilibrium between the -phase matrix and the -phase
precipitate can strongly deviate from the state of equilibrium
between the - and -bulk phases, i.e. the phase and the
phase in the absence of the interface. This is the so-called Gibbs
Thomson effect, which, in compliance with the two counteracting
contributions of composition-dependent chemical Gibbs energy
and interface energy, can be expressed by functions x ,int and x,int
depending on particle size (i.e. interface area) and interface energy
per unit area, i.e. x ,int = x ,int r, and x,int = x,int r, .

( )

( )

Kinetic modelling of nucleation and growth thus requires

evaluation of the thermodynamics of the system dened by chemical energy and interface energy. Usually, the interface energy
per area is taken as being constant within a certain range of
composition, particle size and morphology. This assumption effectively allows to reduce the evaluation of the thermodynamics
for the kinetic modelling to determination of (i) the nucleation
barrier as a function of the composition-dependent chemical
driving force for nucleation gc (x ,m , x,p) and (ii) the compositions x ,int (r ) and x,int (r ) as a function of particle size r (cf. Section
2

4
5

2 V 1
mol

x ,int (r ) = x r exp

RT r

(3)

for the composition of the matrix at the particlematrix interface,

where x (r ) is the solute concentration of the phase in the
reference state of equilibrium between the phase and the
phase with r , i.e. between the bulk phases in the absence of

the interface. Vmol

is the mean molar volume of the -phase and R
denotes the gas constant. Eq. (3) is based on the assumption that
the thermodynamic behaviour of the -matrix phase can be
described with the regular solution model and that the -precipitate phase is a pure phase, i.e. x,int (r ) = x r = 1. The

applicability of such analytical expressions can thus be severely

limited by the limited capability of the underlying simple solution
models to adequately describe the actual thermodynamic behaviour of the phase and the phase.
Hence, in recent years, direct numerical derivation of the relations gc (x ,m , x,p), x ,int (r ) and x,int (r ) from a comprehensive
thermodynamic assessment of the alloy system (which is typically
based on more complex solid solution models for the chemical
Gibbs energies) has become more frequently applied, especially for
multi-component systems (see, e.g., [5,6]). This trend is facilitated
by the increasing availability of such thermodynamic assessments,
e.g. in form of CALPHAD data, and commercial software for thermodynamic analysis (e.g. [15]). On the one hand, the numerical
determination of the chemical driving force for nucleation,
gc (x ,m , x,p), for a given composition x ,m of the matrix phase,
can be performed straightforwardly, for instance by application of
the parallel tangent/maximum chemical driving force approach
[16] (see Section 2). On the other hand, the numerical evaluation
of the GibbsThomson effect, i.e. the determination of the compositions x ,int (r ) and x,int (r ), is much more elaborate [1719],
since it requires the evaluation of a thermodynamic equilibrium
state including the energy contribution of the interface, e.g. by
minimisation of the total Gibbs energy [15]. In view of the correspondingly larger complexity and computational effort, direct
numerical evaluation of the GibbsThomson effect is in practice
often avoided and simple analytical expressions such as Eq. (3),
based on generally invalid solid solution models, are adopted instead. Obviously, problems of inconsistency arise when the relations gc (x ,m , x,p) for nucleation and x ,int (r ) and x,int (r ) for
growth are derived, analytically or numerically, by adoption of
differing, incompatible thermodynamic solution models for nucleation and for growth. This is a common shortcoming in kinetic
models of precipitation kinetics based on the KWN-approach (e.g.
[2,3]).6 The problem becomes even more aggravated when an
elastic strain energy contribution due to a precipitate/matrix mist
is taken into consideration only for nucleation but not for growth
(or vice versa) without more ado (e.g. [22,23]). As a consequence,
the kinetic model predictions may be strongly biased or

For a full expression of N according to classical nucleation theory, see e.g.

[10].
3

2). Analytical expressions for gc (x ,m , x,p), x ,int (r ) and x,int (r ),

based on simple thermodynamic solution models for the chemical
Gibbs energies of the and the phase, are an often used, numerically efcient way to implement thermodynamic data into the
numerical kinetic modelling. For instance, the GibbsThomson
effect in a binary system is often accounted for by application of
the equation [14]

For multinary systems, see e.g. [11].

For binary systems, the convention x j = xBj will be used.
cf. footnote at the end of Section 2.3.

6
Naturally, this problem does not appear in kinetic models without discrimination of nucleation kinetics and growth kinetics, as in cluster dynamics
models, cf. e.g. [20]. Also, in kinetic models involving a consideration of the total
(Gibbs) energy of the system [21], such problems are more readily avoided.

B. Rheingans, E.J. Mittemeijer / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 50 (2015) 4958

completely corrupted by the incongruent thermodynamic descriptions for nucleation and for growth.7
Against the above background, in the present work a generally
valid method for combined, inherently consistent, numerical
evaluation of nucleation barrier and GibbsThomson effect is
proposed which is founded on the Gibbsian treatment of nucleation and growth by fundamental consideration of thermodynamic
equilibrium in a particlematrix system [24,25]: starting from typically applied approaches for separate thermodynamic evaluations of nucleation and growth, it is rst shown how these approaches can be retraced to the same evaluation of thermodynamic equilibrium. Introducing assumptions typically made
upon coupling thermodynamics to kinetics (e.g. a constant interface energy per unit area), a computationally efcient method for
numerical evaluation of nucleation barrier, critical radius and
GibbsThomson effect is presented, which can be easily adapted to
practical cases of modelling transformation kinetics.

2. Theoretical background

departs from a consideration of the change of Gibbs energy G (r )

of the system with size of the precipitate particle formed, i.e. in
case of formation of a spherical particle with radius r

4 3
r + 4 r 2 ,
3

(4)

adopting the sharp interface model (see footnote in Section 1) with a

constant (i.e. independent of r and composition), isotropic interface
energy per unit area. denotes the contributions to the Gibbs
energy change which scale with the volume of the particle. For
precipitation in the solid state, two contributions to (per unit
volume of particle) are typically taken into consideration: the (negative) change in chemical Gibbs energy gc upon formation of a particle
and an additional (positive) contribution of strain energy gel , arising
due to elastic accommodation of the particle/matrix mist (with
= gc + gel < 0). gc and gel are usually treated as constants
for a given matrix composition. The Gibbs energy change then shows a
maximum for dG (r ) /dr = 0 for r equal to the critical radius:

gc,mol
gc,mol
= gc,mol (x ,m , x,p)

xi,p c,i (x,p) xi,p c,i (x ,m).

(7a)

For the case of nucleation, it thus follows with Eq. (5):

gc,mol (x ,m , x,p) =

xi,p c,i (x,p) xi,p c,i (x ,m)

i

=
+ gel V mol
r*

(7b)

ordinate value of the tangent of the Gc,mol

(x )-curve drawn at x ,m
(the given composition of the matrix phase) and evaluated at x,p

(the composition of the nucleus), and the Gc,mol

x -curve at

( )

x = x,p . For a given matrix composition x ,m , Eq. (7b) does not

uniquely dene gc,mol (x ,m , x,p) for nucleation, since the composition of the nucleus x,p is not known a priori. In principle, for
given x ,m , the composition x,p of the precipitate nucleus may
assume any value for which gc,mol (x ,m , x,p) is negative. If x,p is

( )

chosen such that the tangent of the Gc,mol

x -curve drawn at x,p is

parallel to the tangent of the Gc,mol

(x )-curve (xed by the given
matrix composition x ,m ), the chemical driving force
gc,mol (x ,m , x,p) assumes a maximum value and is solely dened
by
the
composition
of
the
matrix
phase,
i.e.
max
max gc,mol (x ,m , x,p) = gc,mol
(x ,m ) and x,p = x,p x ,m . This

( )

is the so-called maximum chemical driving force approach or

parallel tangent approach [16,7], an originally graphical method to
determine the maximum chemical driving force for a binary
system which can be straightforwardly generalised to the multinmax
ary case to numerically determine gc,mol
(x ,m ) and

( )

x,p = x,p x ,m (see Fig. 2). Other methods for describing nuclea-

2
2
,
=

gc + gel

(5)

and with the nucleation barrier:

2
4
16
3
G* = G (r *) = r * =
.
3
3 (gc + gel )2

(6)

For evaluating the change gc in chemical Gibbs energy upon

particle formation, it is assumed that particle formation occurs
within an innitely large matrix phase (or that the particle is
negligibly small), implying a constant matrix composition x ,m
(and thus constant gc for certain composition x,p of the particle).
The change in chemical Gibbs energy per unit volume of the
particle is dened as the difference gc = gc gc of the chemical
Gibbs energy with gc being the chemical Gibbs energy of the
particle-forming components in the

( )

i in the (bulk) phase j = , , the chemical Gibbs energy change per

mol, gc,mol = gc,mol

, can be expressed as
gc,mol

Fig. 1). gc,mol (x ,m , x,p) is represented by the difference of the

Evaluation of nucleation thermodynamics, i.e. determination of

the nucleation barrier G* and the critical radius rn, classically

r* =

and gc being the chemical Gibbs energy of the same components

in the supersaturated -phase matrix of composition x ,m evaluated at the composition x,p of the nucleus (see Fig. 1, note that all
data presented for the binary case in Figs. 1(b) and 3 pertain to the
example given in Section 4).
Introducing the chemical potentials c,ji x j for the components

For a binary system, Eq. (7b) can be visualised in a diagram of

j
molar chemical Gibbs energy Gc,mol
(x j ) vs. composition xj (see

2.1. Nucleation barrier

G (r ) =

51

phase of composition

x,p

7
Such type of inconsistencies can in an extreme case lead to the unphysical
scenario that a particle of certain size generated by nucleation immediately experiences a negative growth rate due to (x ,m x ,int ) < 0 (cf. Eq. (2)), i.e. it would
be instantaneously, intrinsically unstable.

tion depart from setting x,p equal to the composition of the

phase corresponding with equilibrium between the - and -bulk
phases, thus inherently employing a lower chemical driving force;
in the following, x,p will always be identied with the composition of the phase pertaining to the maximum chemical driving
force. Use of the maximum chemical driving force is justied
recognising the strong dependency of the nucleation rate N on
gc,mol (x ,m , x,p) (Eqs. (1) and (6)), allowing to neglect nucleation
of particles of composition different from that corresponding with
the maximum chemical driving force [10].
2.2. GibbsThomson effect
Calculation of the growth rate requires evaluation of the Gibbs
Thomson effect, i.e. determination of the compositions x ,int (r ) and
x,int (r ) as a function of particle size (cf. Eq. (2)). This involves
analysis of the equilibrium state for the -phase particle embedded in the -phase matrix, accounting for the contributions of
the chemical energies, of the interface energy and of the elastic
mist-strain energy. Thermodynamic equilibrium, here at constant

52

B. Rheingans, E.J. Mittemeijer / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 50 (2015) 4958

Fig. 1. Chemical Gibbs energy curves Gc,mol

(x ) and Gc,mol
(x ) for the phase (matrix) and the phase (particle) in a binary system AB as a function of composition,
respectively: (a) schematic representation; (b) chemical Gibbs energy curves for the system CuCo at T = 763 K and p = 105 Pa [36], employed for the case study in Section 4
max

(A: Cu, B: Co, : fcc (Cu), : fcc (Co)). The chemical driving force gc,mol assumes a maximum value gc,mol
if the tangent on the Gc,mol
(x ) curve is parallel to the tangent

of Gc,mol
(x ) in x ,m , the given composition of the matrix (as shown here; parallel tangent/maximum driving force approach). This condition uniquely denes the composition x,p of the -phase particle.

(i) the matrix phase is taken innitely large,

(ii) particle and matrix are separated by a sharp interface (see
above), with a size- and composition-independent, isotropic
interface energy per unit area ,
(iii) the elastic mist-strain energy gel per unit volume can be
reasonably well described by assumption of phases of constant compositions and of isotropic elasticity; the presence of
the interface has no effect on the state of stress (i.e. the effect
of interface stress is neglected, cf. [27,28,25]),
(iv) the particle is of spherical shape (a consequence of the elastic
isotropy and the isotropy of ; see (ii) and (iii) above),
(vi) the molar volume of the precipitate phase is independent of

composition (i.e. the partial molar volumes Vmol,

i of the
components of the phase have the same value).
These assumptions, all more or less implicitly already introduced
in the above discussion on the thermodynamics of nucleation,
allow expression of the equilibrium condition in terms of phase
composition and particle size on the basis of equality of the total
chemical potential of the components:

i ,m (x ,m , x,p , r ) = i,p (x ,m , x,p , r ),

Fig. 2. Chemical Gibbs energy surfaces Gc,mol

(x ) and Gc,mol
(x ) for the phase and
the phase in a ternary system ABC, respectively. Here, the parallel tangents of
the binary system correspond to parallel tangent planes (depicted in gray). Applying the parallel tangent/maximum chemical driving force method yields
gc,mol (x ,m ) (vertical red line) and the composition x,p (x ,m ) of the -phase par
ticle (for better visualisation, the Gc,mol
(x ) surface and the tangent planes were
plotted semi-transparent). (For interpretation of the references to colour in this
gure caption, the reader is referred to the web version of this paper.)

p and T, corresponds to equality of the (total ) chemical potentials

ij for each component i in all phases of the system j, i.e.

i ,m = i,p .

(8)

Elaboration of these equilibrium conditions for the system particlematrix in terms of size and shape of the second-phase particle,
composition (eld), elastic strain (eld) etc. can become extremely
cumbersome due to the interdependence of these parameters.
Therefore, without restricting the generality of the following discussion, several simplifying assumptions and boundary conditions
are introduced here:
8
Derived from the total energy function, i.e. in the present case the total Gibbs
energy incorporating the contributions of chemical Gibbs energy, interface energy
and elastic energy, see e.g. [26].

(9)

and also allow a separation of the contributions of interface energy, elastic energy and chemical energy to the (total) chemical
potential (cf. e.g. [7]), the latter then being the only contribution
depending on (variable) phase composition:

c,i (x ,m) = c,i (x,p) +

+ gel V mol,
i,
r

(10)

c,ji (x j )

with
being the chemical potential of component i in the
bulk phase j in the unstressed state, i.e. the chemical potential
pertaining to the composition-dependent chemical Gibbs energy
only (cf. Eq. (7)).9
Eq. (10) represents a system of equations (one equation for
each component i) which denes thermodynamic equilibrium for
the system particlematrix. For given values of the interface energy , the elastic strain energy gel and the partial molar volume

Vmol,
i , Eq. (10) allows to derive expressions for the compositions

x ,m (r ) = x ,int (r ) and x,p (r ) = x,int (r ) as a function of particle radius r employing suitable functions for the chemical potentials
c,ji (x j ) (i.e. employing suitable thermodynamic solution models
9
For r , the elastic energy contribution, in contrast to the interface energy
contribution, does not vanish, since both the chemical Gibbs energy and the elastic
energy contribution scale with the volume of the particle.

B. Rheingans, E.J. Mittemeijer / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 50 (2015) 4958

Gc,mol
(x ) and Gc,mol
(x ) for the and phases).
In case of binary systems AB, closed, analytical expressions for
x ,int (r ) and x,int (r ) can be obtained if very simple mathematical
expressions hold for the chemical potentials c,ji (x j ), i.e. if very
simple solid solution models are applicable (cf. Eq. (3)). For example, adopting the ideal solution model for the phase and
assuming a pure phase of the solute component B, the chemical

,0
j
potential c,B
(x ) = c,B
+ RT ln (x ), and
(x j ) is given by c,B

,0
, since x = x,p = 1 (the corresponding chemical poc,B
(x ) = c,B

tential

c,A

of component A in the

( (

,0
c,B
+ RT ln x r

)) =

,0
c,B

phase is not dened). Then,

V
2
mol,B
x ,m (r ) = x ,int (r ) = x (r ) exp
+ gel
.
RT
r

(11)

As compared to Eq. (3), this expression includes an additional

correction for the elastic energy contribution. Similar analytical
expressions for x ,int (r ) and x,int (r ), based on other (simplifying)
assumptions, can be found in numerous works (see e.g. [29,4] for
the case of gel = 0, and [28] including a consideration of elastic
mist-strain and interface stress for the special case of ideal solid
solutions).
For describing the GibbsThomson effect in the general case,
i.e. without resorting to specic simple solution models for the
and phases and without restriction to binary systems, Eq. (10)
has in principle to be evaluated numerically to obtain the (numerical) relationships x ,int (r ) and x,int (r ), see e.g. [17,18] or [19].
2.3. The equivalence of nucleation thermodynamics and growth
thermodynamics
Now considering the thermodynamics of both nucleation and
growth, as in case of kinetic modelling, separate analysis of nucleation thermodynamics (Eq. (7b)) and of growth thermodynamics (the GibbsThomson effect, Eq. (10)) is unnecessary:
both nucleation and growth thermodynamics are based on the
same thermodynamic stability consideration. In case of nucleation,
the critical size r * = r (g
(x ,m , x,p (x ,m )) , , g ) for stability of
el

a nucleus is determined, which, for given and gel , is dened by a

difference in chemical Gibbs energy (Eq. (7b)) and thus by the
compositions x ,m and x,p = x,p (x ,m )) of the -matrix phase and
the -precipitate phase, respectively. In case of growth, the compositions

x,int

( )
( ) of the -phase matrix and
(r, ) of the -phase precipitate particle, as dened

x ,int r , = x ,m r ,

(r, ) =

as presented above may be elucidated in the following way: from

Eqs. (9) and (10), the total molar Gibbs energy
,p
gmol
= i i,p (x,p, r ) x i,p of a precipitate particle with radius r and
composition x,p is given by (cf. Eq. (9))

i i,p (x,p , r ) xi,p = i,m (x ,m , r ) xi,p

(12)

and (cf. Eq. (10))

,p

+ gel V mol,
=
i xi

i c,i (x,p) +

c,i (x ,m) xi,p

i

(13a)

holds for equilibrium between the

bulk phases, i.e. in the absence of interface and mist strain. Applying Eq. (10) for the equilibrium between the -phase matrix
and the -phase precipitate in this case then leads to a Gibbs
Thomson-type equation:

c,mol

53

x,p

by a difference in chemical Gibbs energy (c.f. Eq. (10)), are evaluated for a particle of certain size r stable in an -phase matrix.
Thermodynamic analysis in both cases thus breaks down to an
evaluation of the equilibrium state for an -phase matrix of certain
composition containing a -phase particle of certain composition
and certain size r, associated with a certain interface energy and
elastic strain energy. As such, this is a consideration of thermodynamic equilibrium in a heterogeneous system with counteracting contributions to the total energy scaling differently with
size of the second-phase domain (see [24], p. 252 ff., for a discussion of particle formation/nucleation and stability in a onecomponent system ensuing from a consideration of thermodynamic equilibrium, there in terms of the variables size and
pressure).
The equivalence of the nucleation and growth thermodynamics

c,i (x,p) xi,p + 2 + gel V mol

=
i

c,i (x ,m) xi,p ,

i

(13b)

,p

with i Vmol,
and i x i,p = 1. In a diagram of molar
= Vmol
i xi
chemical Gibbs energies vs. composition of a binary system, Eq.
(13b), under the constraint of satisfying Eq. (10),10 for each
component i, represents a construction of two parallel tangents,

one of the Gc,mol

(x ) curve and one of the Gc,mol
(x ) curve, with a

, since this additional term to

vertical offset of 2 /r + gel Vmol

each c,i is independent of composition. Eq. (13b), under the

constraint of satisfying Eq. (10) for each component, thus is
identical with Eq. (7) derived specically for nucleation, provided
the latter is evaluated according to the parallel tangent/maximum
chemical driving force approach (see discussion below Eq. (7)).
Hence, evaluation of nucleation thermodynamics by combination
of Eq. (7) with the maximum chemical driving force approach
represents an evaluation of the thermodynamic equilibrium of the
system particlematrix as a function of the variables x ,m , x,p and r
and thus comprises both nucleation thermodynamics and growth
thermodynamics.11
Irrespective of the simplifying assumptions introduced above,
equivalence of nucleation thermodynamics and growth thermodynamics generally holds as long as nucleation is treated as occurring via a critical state for which the particle is in an unstable
equilibrium with the matrix and growth is treated as involving
local establishment of thermodynamic equilibrium at the particle
matrix interface (see Section 1).12 Separate evaluation of nucleation thermodynamics and growth thermodynamics is then generally unnecessary, as will be illustrated in the next section.
Despite the fundamental nature of the equivalence of nucleation thermodynamics and growth thermodynamics [24], it is frequently disregarded for analysis of the thermodynamics of nucleation and growth with respect to kinetic modelling (but, cf. e.g.,
[27,28,16,7,4]) a possible reason may lie in typical textbook
treatments of nucleation thermodynamics in terms of an energy
change (cf. Eq. (4)), and of growth in terms of compositions only
(instead of, e.g., activities; cf. Eq. (2)) [14]. Moreover, its implications for thermodynamic evaluation upon kinetic modelling based
on a modelling approach as outlined in Section 1 have, to the
10
Eq. (13b) is only a necessary condition, while Eq. (10) is a sufcient
condition.
11
Eq. (7) results from a maximisation of the system energy change as a function
of the radius r. Combined with a maximisation of the chemical driving force as a
function of the composition x at given x ,m , this corresponds, under the present
assumptions, to the determination of equilibrium as a function of r and x (the
function G (r , gc,mol (x = x ,m, x )) shows a saddle-point at r = r*, x = x,p ). Indeed, the maximum chemical driving force/parallel tangent method is derived from
a consideration of thermodynamic equilibrium [16].
12
In case these assumptions do not hold, e.g. in the (very) early stages of
particle growth before particle-growth kinetics become rate-controlled by longrange volume diffusion of solute only (i.e. for an, in comparison, low interface
mobility), an approach must be chosen which does not use this point of departure;
see here, e.g., [21] and, more generally, [30] and [31].

54

B. Rheingans, E.J. Mittemeijer / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 50 (2015) 4958

authors knowledge, up to now not been utilised at all.

3. Usage of the common stability consideration upon numerical evaluation of nucleation and growth thermodynamics
Modelling of nucleation and growth kinetics requires numerous evaluations of the corresponding thermodynamic relations, i.e.
nucleation barrier and GibbsThomson effect (cf. Section 1). In this
situation, the equivalence of nucleation thermodynamics and
growth thermodynamics as presented in the previous section allows, for the typically made assumption of a constant interface
energy and a constant elastic energy contribution gel , to devise
a convenient method for computationally efcient analysis of
thermodynamic data.
For nucleation, numerical evaluation of the chemical driving
force can be performed straightforwardly by application of the
maximum chemical driving force approach: for given matrix
max
composition x ,m , gc,mol
(x ,m ) can be directly evaluated from the

chemical Gibbs energy functions Gc,mol

(x ) and Gc,mol
(x ), for example

by rst calculating the tangent (plane) T of Gc,mol

(x ) in x ,m , i.e.
T (x ,m , x ) = i xi c,i (x ,m ), and then nding the maximum of
max

Gc,mol
(x ) T (x, x ,m ) = gc,mol
(x ,m ) and the corresponding

composition x = x,p (x ,m ) of the -phase particle (Figs. 3 (a,b) and

4). Upon kinetic modelling, for given values of and gel , the
max
critical radius r * = r (gc,mol
(x ,m ) , , gel ) = r (x ,m , , gel ) can be
computed using Eq. (5) (see Figs. 3(c) and 5). During the actual
computation process, the numerical relation r * = r (x ,m , , g )
el

can then be accessed rapidly for certain x ,m , e.g. via a table look-up.
For growth, the equilibrium of the particlematrix system (i.e.
the GibbsThomson effect) has to be evaluated [1719] for given
values of radius r, interface energy and elastic energy gel based
on Eq. (10) (see Section 2; or in Eq. (13), see e.g. [18], the additionally required constraint (see below Eq. (13)) can then e.g. be
obtained by introduction of the GibbsDuhem equation). Now,
instead of either (numerically) evaluating Eq. (10) (see, e.g., [17
19]) or adopting some approximate description of the Gibbs
Thomson effect (as Eq. (11); see, e.g.[2,3,23]), the equivalence of
evaluating the thermodynamics of nucleation and of the treatment
of thermodynamic equilibrium of the particlematrix system can
be
utilised:
values
for
the
matrix
composition
x ,int = x ,m (r , , gel ) as a function of the radius can simply be
obtained by inverse evaluation of the relation r * = r (x ,m , , g )
el

as already determined for nucleation, e.g. via an inverse table lookup. The corresponding composition x,int of the precipitate phase
can then be derived from the relation x,p (x ,m ) (see Figs. 3(a),
(c) and 5).With the thermodynamic relations for nucleation and
for growth thus based on the same thermodynamic analysis,
(i) any inconsistencies of the thermodynamic descriptions for
nucleation and growth are inherently excluded and (ii) separate
evaluation of the GibbsThomson effect [1719] is rendered
obsolete.13
In binary systems, for a given radius r, the inverse evaluation
method
provides
a
unique
set
of
compositions
x ,int = x ,m (r , , gel ) and x,int = x,p r , , gel = x,p (x ,m ) (this

13
The critical radius and the so-called no-growth radius rc, the radius for
which x ,int (r ) equals the current composition x ,m of the matrix and the growth
rate (Eq. (2)) then equals zero, are then inherently identical (compare e.g. [22]).
Arguably, the thermodynamics of nucleation and of growth may be different: for
example, after nucleation of a particle, the mist strain generated by the particle
can be relaxed in the further course of its growth, e.g. via vacancy condensation or
introduction of mist dislocations. The kinetics of such additional mechanisms
should then be explicitly introduced into the kinetic model.

Fig. 3. (a) Composition x,p (x ,m ) of the -phase particle and (b) maximum change in
max
molar chemical Gibbs energy gc,mol
(x ,m ), both as a function of the -matrix composition x ,m , as derived from the chemical Gibbs energy curves of the and phases
(see Fig. 1(b)) by application of the maximum chemical driving force method. The
contribution of the elastic energy is represented by the dotted line in (b). For
max
gc,mol
(x ,m ) = 0 , i.e. zero chemical driving force, x ,m and x,p assume the composition
values for equilibrium between bulk phases in the absence of interface energy and
elastic energy (indicated by the dashed vertical lines in (a), (b) and (c)). For
gc,mol (x ,m ) + gel = 0 , x ,m and x,p assume the values for the so-called coherent
equilibrium of the bulk phases (indicated by the solid vertical lines in (a), (b) and (c)).
max
(c) The relation r (gc,mol
(x ,m ), , gel ) as a function of the matrix composition x ,m
(black curve), calculated by use of Eq. (5) (for and gel see Section 4). For nucleation,
this relation can be evaluated for given matrix composition x ,m in order to obtain the

max
critical radius r = r (gc,mol
(x ,m ), , gel ). For growth, the same relation can be evaluated inversely for given radius r of the precipitate-phase particle in order to obtain the
corresponding equilibrium composition of the matrix x ,int = x ,m (r ) as a function of
the particle radius. The composition x,int = x,p (r ) of the phase can then be derived
via the relation x,p (x ,m ) shown in (a). The gray curve in (c) represents the relation
x ,int (r ) as derived from the classical GibbsThomson equation (3), i.e. neglecting the
elastic energy contribution gel and using a highly simplied thermodynamic solution
model (note that when using the classical GibbsThomson equation, x,p = 1 is assumed). For r , the composition of the matrix in the rst case (exact treatment)
approaches the composition for coherent equilibrium (i.e. the solid vertical line), in the
second case (the approximate GibbsThomson equation) the composition for incoherent equilibrium (i.e. the dashed vertical line). All numerical results shown in this
gure pertain to the example case considered in detail in Section 4.

B. Rheingans, E.J. Mittemeijer / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 50 (2015) 4958

max
Fig. 4. Maximum change in chemical Gibbs energy gc,mol
(x ,m ) as a function of
the matrix concentration x ,m for a ternary system ABC with phases and (a
surface in this gure; cf. Fig. 2). The corresponding composition relation x,p (x ,m )
between the -precipitate phase and the -matrix phase is here represented as a
plot of the surface gc,mol (x,p (x ,m )) . Each composition pair (x,p, x ,m ) is related by
a tie-line (the dashed red line represents the tie-line for the case depicted in Fig. 2).
For gc,mol (x ,m ) = 0 , i.e. zero chemical driving force, the ternary equilibrium between the - and -bulk phases is obtained (cf. Fig. 3). (For interpretation of the
references to colour in this gure caption, the reader is referred to the web version
of this paper.)

corresponds to the existence of a single tie-line at given p and T

relating one pair of compositions (x ,m , x,p), analogous to equilibrium between bulk phases in a binary system, cf. Fig. 3). Starting
from a composition x,p (x ,m ) = x,int of the particle dened by the
composition of the matrix x ,m = x ,int at the moment of its nucleation, the compositions x ,int and x,int then evolve upon particle
growth (see, e.g., Eq. (2)) according to x ,int = x ,m (r , , gel ) and

55

Fig. 5. The relation r (x ,m, , gel ) as a function of the matrix composition x ,m in a

ternary ABC system with phases and , calculated from the maximum change
max
in chemical Gibbs energy gc,mol
(x ,m ) as shown in Fig. 4 by use of Eq. (5), with
arbitrarily chosen values for and gel (for gel = 0 , this gure corresponds to the
so-called GibbsThomson phase diagram as presented in [18]). The corresponding composition relation x,p (x ,m ) is represented by a plot of the surface
r (x,p (x ,m ), , gel ). Corresponding relations pertaining to different values of and
max
(x ,m )-data via Eq. (5). When congel can be easily re-obtained from the gc,mol

sidering nucleation, the critical radius r = r (x ,m, , gel ) and the composition of
the nucleus x,p (x ,m ) can directly be obtained from r (x ,m, , gel ) , equivalent to
the binary case (cf. Fig. 3). In case of growth, direct inverse evaluation of
r (x ,m, , gel ) in order to determine x ,int (r ) and x,int (r ) is not possible (in contrast
to the binary case, Fig. 3 (c)): For a given value of r, an innite number of composition pairs (x,p, x ,m ) exists (equivalent to equilibrium between bulk phases, i.e.
for r and gel = 0 ). For modelling of particle growth in a multi-component
system under assumption of equilibrium at the particlematrix interface, particle
radius and as well as compositions must therefore be tracked. Size and compositions then follow coupled trajectories on the r (x ,m, , gel ) and
r (x,p (x ,m ), , gel )-surfaces dened by the diffusion kinetics of the different
components in the matrix phase.

x,int = x,p r , , gel .

In a multinary system, however, equilibrium is not uniquely
dened by the value of the particle radius r (the system of Eqs. (10)
would then be an underdetermined system), i.e. the composition
of the phases cannot be determined directly via the inverse evaluation method (this corresponds to the existence of multiple tielines at given p and T relating multiple pairs of compositions
(x ,m , x,p), analogous to phase equilibrium between bulk phases in
a multinary system; cf. Figs. 4 and 5). Starting from the, also for the
multinary case, known compositions x ,int = x ,m (r , , gel ) and

x,int = x,p r , , gel = x,p (x ,m ) of matrix and particle at the

moment of nucleation, upon particle growth the generally differing diffusivities of the components in the matrix can then lead to a
continuous change of the compositions in addition to the size effect. Modelling of the growth kinetics in a multi-component system considering the GibbsThomson effect therefore requires
treatment of the coupled evolutions of particle radius and of phase
compositions under the equilibrium constraint provided by Eq.
(10) (see e.g. [11]). This constraint corresponds to subjecting the
size-composition trajectory of the particle to the relations
r (x ,m , , gel ) and x,p (x ,m ) obtained via the inverse evaluation
method (Fig. 5): particle size and the compositions at the interface

then follow a path, which is governed by the particle-growth kinetics in the multi-component system [11], on the size-composition surfaces determined by thermodynamics (i.e. the r (x ,m )and
r (x,p) surfaces in Fig. 5; cf. [5,6]).
The equivalence of nucleation and growth thermodynamics in
principle also allows application of a reverse procedure to obtain
the thermodynamic relations between particle size and phase
compositions: in a rst step, the evaluation of the growth thermodynamics via Eq. (10) could be performed for chosen values of r
to determine x ,int = x ,m (r , , gel ) and x,int = x,p (r , , gel ), for
given interface energy and elastic energy contribution gel . Then,
in a second step, the corresponding relation r * = r (x ,m , , gel ),
required for description of the nucleation kinetics, could be obtained by inverse evaluation. However, upon assumption of constant and gel , determination of the thermodynamic relations as
presented above is much more convenient that this reverse procedure: evaluation of the thermodynamics of growth as a rst step
would require a complete evaluation of thermodynamic equilibrium via Eq. (10) for each value of , gel and r [1719]. The approach via nucleation thermodynamics, by contrast, allows to split

56

B. Rheingans, E.J. Mittemeijer / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 50 (2015) 4958

the thermodynamic evaluation into two independent steps: once

max
the chemical driving force for nucleation gc,mol
(x ,m ) and the
relation x,p (x ,m ) have been derived from the thermodynamic
assessment of the system (determination of critical, equilibrium
phase compositions), the numerically simple Eq. (5) can be easily
(re-)evaluated for given values of and gel to obtain the numerical relation r (x ,m , , gel ) pertaining to these values (determination of critical, equilibrium particle size). The method
proposed in this paper, with evaluation of the nucleation thermodynamics as a rst step, thus represents a potent and numerically efcient way of handling the numerical thermodynamic
data and allows for instance to use the interface energy as a t
parameter in a computational algorithm (see [32]) or to efciently
incorporate a size dependency of the interface energy14 = (r ).
The proposed treatment builds on the separability of the chemical Gibbs energy contribution, the interface energy contribution
and elastic energy contribution (Eqs. (9) (10)), which allows
application of the maximum chemical driving force method to
independently determine the chemical contribution. Accordingly,
the presented approach breaks down as soon as interface energy
and elastic energy (and the molar volume of the precipitate phase)
show a composition dependency which cannot be neglected, thus
prohibiting application of the maximum chemical driving force
method [16]. Analysis of the thermodynamics of nucleation and
growth would then require determination of equilibrium on the
basis of a more general consideration of the total energy (cf. Eq.
(8)). However, the fundamental equivalence of the thermodynamics of nucleation and of growth, as two aspects of the same
fundamental thermodynamic equilibrium principle, still remains
intact and allows inverse evaluation of the thermodynamic relations, thus avoiding inconsistent, unnecessarily separate thermodynamic evaluations of nucleation and growth.

4. Application example
To visualise the usage of the inverse evaluation method upon
modelling the kinetics of precipitation reactions, thus avoiding
inconsistent thermodynamic descriptions for nucleation and
growth, the precipitation kinetics were simulated for a binary AB
model system (using for the kinetics a KWN-type approach as
frequently employed for practical applications; for details on the
kinetic modelling, see [32]).
The properties of the AB system were chosen to mimic the
system CuCo, a classical model system for precipitation reactions
(see e.g. [3335]): upon annealing of supersaturated Cu-rich alloys, spherical Co-rich precipitate particles of fcc structure are
formed which are (initially) fully coherent with the fcc Cu-rich
matrix phase. Thermodynamic data was taken from a recent
CALPHAD assessment of the system CuCo [36] at T = 763 K (and
p = 105 Pa ): from the chemical Gibbs energy curves (Fig. 1(b)),
employing the maximum chemical driving force method,
max
gc,mol
(x ,m ) and the precipitate particle composition x,p (x ,m )
were derived as a function of the matrix composition x ,m (Fig. 3).
Due to the small lattice mist between fcc Cu and fcc Co [37], the
elastic energy contribution gel is relatively small (but not negligible, cf. [38]): at the chosen alloy composition of Cu 0.5 at% Co,
gel (here calculated using Eshelby's model [39]) amounts to about
14 % of the initial maximum chemical driving force. Further
parameters employed for kinetic modelling are given in Table 1.
The precipitation kinetics were simulated for two different
14
Note that in this case, Eq. (5) (and, correspondingly, also Eq. (10)) does not
hold in the usual form as given in Section 2; it must be derived from Eq. (4) with
= (r ) .

Table 1
Data employed for simulation of the precipitation kinetics in a binary model system
AB mimicking a Cu0.5 at% Co alloy at T = 763 K . : interfacial energy; Q, D0: activation energy for diffusion, corresponding pre-exponential factor (used for both
nucleation and growth); Vmol : molar volume; E: Young's modulus (elastic isotropy
approximation), G: shear modulus.
Parameter

Value

220 mJ m2

Q
D0

214 kJ
4.3

Source, remark
(assessed)

mol1

105

m2 s2

[40]
[40]

A (fcc Cu)
Vmol

7.3 106 m3 mol1

[37]

18.1 1010 Pa

[41], T = 750 K

6.6 1010 Pa

[41], T = 750 K

B (fcc Co)
Vmol

6.8 106 m3 mol1

[37]

31.1 1010 Pa

[42], T = 710 K

11.0 1010 Pa

[42], T = 710 K

scenarios: (i) Consistent scenario: use of the relation r (x ,m , , gel )

as determined via Eq. (5) from the maximum chemical driving
max
force gc,mol
(x ,m ) (Fig. 3(b), (c)) and of the relation x,p x ,m
(Fig. 3 (a)) for both nucleation and growth via the inverse evaluation method (consistent thermodynamic model). (ii) Inconsistent scenario: use of the relations r (x ,m , , gel ) and x,p x ,m
for particle nucleation only; description of the GibbsThomson
effect for growth, i.e. of x ,int (r ), by use of Eq. (3). The composition
of the particle x,int (r ) = x,p (r ) is then equal to 1, and the contribution of elastic energy is neglected for particle growth (inconsistent thermodynamic model).
The resulting precipitation kinetics according to both scenarios
are shown in Fig. 6. Pronounced differences of the results for both
scenarios can be observed: only in the very early stages, the mean
matrix composition x ,m (t ), the mean radius r (t ), the critical radius
r * (t ) and the no-growth radius r c (t ) (i.e. the particle radius for

( )
( )

which x ,int (r ) = x ,m (t ) and dr /dt = 0, Eq. (2)), and the particle

number density N(t) show a relatively similar evolution for both
cases. Note that for scenario (ii), due to employing an inconsistent
thermodynamic model, the critical radius and the no-growth radius are not identical: an existing particle of size equal to the
critical particle size, or even of somewhat smaller size, still exhibits a positive growth rate (see footnote in Section 1), whereas a
nucleating particle of critical size is in (unstable) equilibrium with
the matrix. Application of the classical GibbsThomson equation
in scenario (ii) thus results in an acceleration of the growth kinetics
as compared to scenario (i). As a consequence, towards later
stages, the enhanced growth kinetics in scenario (ii) lead to a
markedly faster decrease of x ,m (t ) and thus to a deceleration of
the nucleation kinetics and a lower particle number density N(t).
When the mean matrix composition x ,m (t ) approaches the limiting composition of the so-called coherent equilibrium (i.e. accounting for the elastic energy contribution gel , see Fig. 3), in
scenario (i) the critical radius for nucleation rn and the no-growth
radius r c (which are in this case identical) continuously increase
and eventually approach the mean particle radius r , correlated
with the onset of distinct particle coarsening, i.e. dissolution of
particles with r < r c = r *. In scenario (ii), by contrast, x ,m can fall
below the matrix composition for coherent equilibrium, which is
now only limiting for particle nucleation. Consequently, the critical
radius for nucleation rn rst strongly increases and is then no
longer dened when x ,m falls below this composition value. The
kinetic model of inconsistently coupled nucleation and growth
thus degenerates to a model of particle growth (and coarsening)

B. Rheingans, E.J. Mittemeijer / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 50 (2015) 4958

57

and the inconsistent scenario pertain to the real case CuCo, a

model system of only modest mist strain development. Pronounced cases of large(r) mist abound and can lead to much
larger discrepancies.

5. Conclusions

 Current practice of modelling precipitation kinetics frequently

involves inconsistent and redundant evaluations of the thermodynamics of nucleation and growth. As demonstrated in this
work, inconsistent thermodynamic modelling (manifested by,
e.g., the non-identity of rn and r c ) results in inadvertent, articial enhancement or attenuation of either nucleation or
growth, accompanied by a breakdown of the model of initially
coupled nucleation and growth. It has been exemplary shown
here how typical approaches for separate evaluation of nucleation barrier and GibbsThomson effect can in fact be retraced to a single thermodynamic equilibrium consideration
common to both mechanisms [24].
On this basis, a general approach for a single, consistent numerical evaluation of nucleation barrier and GibbsThomson
effect is proposed which (i) inherently excludes the corruption
of kinetic modelling by incongruent description of thermodynamics and (ii) renders separate evaluation of, e.g., the
GibbsThomson effect obsolete.
For typical assumptions made upon kinetic modelling, a numerically efcient method for coupling thermodynamic data,
as e.g. derived from a CALPHAD database, and kinetic model is
presented which reduces access to the thermodynamic database to a minimum and allows to easily incorporate a (composition-independent) contribution of elastic energy for both
nucleation and growth, or a size-dependent interface energy.

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Fig. 6. Simulation of the precipitation kinetics in a binary AB model system (Cu

0.5 at% Co, T = 763 K , p = 105 Pa ) as a function of time for two different cases of
thermodynamic modelling of nucleation and growth (cf. Fig. 3 (c)): (i) consistent
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nucleation and growth thus degenerates to a model of particle growth only.

only, with x ,m slowly approaching the limiting matrix composition for incoherent equilibrium.
Finally, above discussed discrepancies between the consistent

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