Acta Materialia 54 (2006) 99–104

www.actamat-journals.com

An application of irreversible thermodynamics to diffusional

phase transformations
Mats Hillert *

Department of Materials Science and Engineering, Royal Institute of Technology, Division of Physical Metallurgy, KTH SE-10044, Stockholm, Sweden

Received 20 June 2005; received in revised form 16 August 2005; accepted 19 August 2005
Available online 5 October 2005

Abstract

The method of transforming the set of flux equations for two simultaneous processes into a new set of processes is reviewed and
applied to diffusion in one-phase materials where the two primary equations describe the individual diffusion of the components and
the new ones describe the migration of Kirkendall markers and interdiffusion. It is then modified to apply to a two-phase material with
a diffusional transformation and the new equations then describe the migration of the phase interface and interdiffusion across the inter-
face. Comparison is made with previous attempts. In order to treat the transition from diffusion-controlled to partitionless growth it may
be necessary to introduce a third primary flux equation. It is possible to incorporate this third flux within the other two, in which case it
will contribute substantially to their cross-coefficients.
Ó 2005 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Diffusion; Entropy; Phase transformation; Irreversible thermodynamics; Trapping

1. Introduction transform them into the processes of interdiffusion and

Individual diffusion of the two components in a binary
solution by a vacancy mechanism has two effects, it mixes
the two components and it makes inert markers, so-called
Kirkendall markers, migrate through the system. The rela-
tion of these two processes to the processes of individual
diffusion was clarified by Darken [1] but the individual flux
equations have seldom been used. Most studies of diffusion
concentrate on the mixing of the components, often called
interdiffusion, and ignore the other one, the marker migra-
tion. On the other hand, in diffusional phase transforma-
tions the main interest is the migration of the interface
and one usually pays little attention to the interdiffusion
across the interface. In attempts to understand how the
new phase sometimes can grow with a composition inside
the two-phase field, so-called trapping, the author has tried
to start from the individual flux equations and formally
*
Tel.: +46 8 100411.
E-mail address: mats@mse.kth.se.
interface migration. This problem will now be reexamined
by starting from the treatment of diffusion by a vacancy
mechanism in a one-phase material, and irreversible ther-
modynamics will be used when transforming to a new set
of independent processes. The general procedure is well
established and the present treatment was inspired by a
presentation by Haase [2]. The same method will then be
applied to diffusional phase transformations.
2. Change of independent processes
The phenomenological equations for two simultaneous
processes are written as follows when the linear approxima-
tion is accepted:
J 1 ¼ a11 X 1 þ a12 X 2 ; ð1aÞ
J 2 ¼ a21 X 1 þ a22 X 2 ; ð1bÞ
where Ji is the rate of process i and is usually regarded as a
flux, and Xi is the thermodynamic driving force. The aij
parameters are the kinetic coefficients and according to
OnsagerÕs reciprocity relation aij = aji [3].

1359-6454/$30.00 Ó 2005 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actamat.2005.08.023
100 M. Hillert / Acta Materialia 54 (2006) 99–104

If Eqs. (1) are applied to the individual diffusion of two J 1 ¼ c11 J
1 þ c21 J
2 ; ð8aÞ
components in a binary A–B solution, J1 = JA and J2 = JB, J 2 ¼ c12 J
1 þ c22 J
2 . ð8bÞ
and if each component diffuses by a vacancy mechanism, it
may be assumed that they are two independent processes This system of equations can be solved for the new fluxes,
even though they may be coupled by the cross-coefficients, which take the form of Eq. (3) with the following relations
a12 and a21. One may like to transform the primary set of between coefficients:
two independent processes into another set of independent c11 c22  c12 c21 ¼ c22 =b11 ¼ c21 =b12 ¼ c12 =b21 ¼ c11 =b22 .
processes, interdiffusion and migration, by again assuming
linear relations ð9Þ

J
1 ¼ a
11 X
1 þ a
12 X
2 ; ð2aÞ
J
2 ¼ a
21 X
1 þ a
22 X
2 . ð2bÞ
In order to evaluate the new kinetic coefficients, a
ij , from
the old ones it is necessary to give the relations between
the old and new variables. Haase [2] chose to define the
two new processes by starting with
J
1 ¼ b11 J 1 þ b12 J 2 ; ð3aÞ
J
2 ¼ b21 J 1 þ b22 J 2 . ð3bÞ
Then the relations between the driving forces are also
known because the production of entropy, or the dissipa-
tion of Gibbs energy under constant temperature and
pressure, cannot depend on how one has chosen to de-
fine the independent processes. The following is
obtained:
T r ¼ J 1 X 1 þ J 2 X 2 ¼ J
1 X
1 þ J
2 X
2
¼ b11 J 1 X
1 þ b12 J 2 X
1 þ b21 J 1 X
2 þ J 2 X
2 . ð4Þ
The production of entropy is here denoted by r and Tr is
then the dissipation of Gibbs energy under constant tem-
perature and pressure. The following relations are obtained
from Eq. (4):
X 1 ¼ b11 X
1 þ b21 X
2 ; ð5aÞ
X 2 ¼ b12 X
1 þ b22 X
2 . ð5bÞ
Any set of new independent processes defined to satisfy
Eqs. (3) and (5) may be regarded as a set of conjugate pro-
cesses. By definition, such a set describes exactly the same
changes of the system as the primary set. Using the b coef-
ficients Haase could derive values for the new kinetic coef-
ficients, a
ij , from the old ones as we shall soon see. For a
different purpose, we need to solve Eq. (5) for the new driv-
ing forces
X
1 ¼ c11 X 1 þ c12 X 2 ; ð6aÞ
X
2 ¼ c21 X 1 þ c22 X 2 ; ð6bÞ
where the cij coefficients can be evaluated from
b11 b22  b12 b21 ¼ b22 =c11 ¼ b21 =c12 ¼ b12 =c21 ¼ b11 =c22 .
ð7Þ
These relations between the two sets of coefficients can be
used to test whether a given set of four equations actually
defines a set of two conjugate processes. If the set of two
new processes is instead defined through Eq. (6), one ob-
tains from an equation similar to Eq. (4)
Actually, Eqs. (7) and (9) are equivalent. Furthermore,
there may sometimes be a need to define the two new pro-
cesses through J
1 in Eq. (3a) and X
2 in Eq. (6b). From the
last part of Eq. (7) it is evident that only three of the four
coefficients b11, b12, c21 and c22 are independent, say b11, c21
and c22 with b12 = b11c21/c22. Instead, there must now be
a degree of freedom when deriving the remaining
coefficients and that is demonstrated by the fact that Eq.
(9) only yields a relation between c11 and c12, which may
be taken as
c11 c22  c12 c21 ¼ c22 =b11 ; ð10aÞ
c12 ¼ ðc11 c22  c22 =b11 Þ=c21 ¼ ðc11  1=b11 Þc22 =c21 . ð10bÞ
After having chosen the value of c11 one can evaluate c12
and the remaining b coefficients.
Finally, the two new processes may be defined by using
properties of only one of the new processes, e.g., by the use
of Eqs. (3a) and (6a). Eq. (7) then yields for the other
process
J
2 ¼ b21 J 1 þ b22 J 2 ¼ b22 ½ðb21 =b22 ÞJ 1 þ J 2 
¼ b22 ½ðc12 =c11 ÞJ 1 þ J 2 ; ð11aÞ
X
2 ¼ c21 X 1 þ c22 X 2 ¼ c22 ½ðc21 =c22 ÞX 1 þ X 2 
¼ c22 ½ðb12 =b11 ÞX 1 þ X 2 ; ð11bÞ
where b11, b12, c11 and c12, are known from Eqs. (3a) and
(6a). Furthermore, b22 and c22 are related by b22c22 =
b11c11 according to Eq. 7 and are thus trivial factors as long
as their product is equal to b11c11. It should be remembered
that the dissipation of Gibbs energy from the second new
process is J
2 X
2 and it thus depends on the product
b22c22, which is equal to b11c11 and that is known from
the first new process. By choosing one of the new processes
one has thus fixed the other one. For all these possibilities
of defining the new processes we may conclude the
following. In order for a new process to be part of a set
of conjugate processes it must be combined with a unique
partner.
When all the b coefficients are known, one can calculate
the new kinetic coefficients from, in turn, Eqs. (3), (1) and
(5). Generalized to any number of simultaneous processes
we obtain
X X X X X X
J
i ¼ bij J j ¼ bij ajk X k ¼ bij ajk blk X
l ;
j j j j k l
ð12Þ
XX
a
il ¼ ajk bij blk . ð13Þ
j k
 M. Hillert / Acta Materialia 54 (2006) 99–104
3. Diffusion in a binary solution
The general treatment given above will now be applied
to diffusion in a binary A–B solution phase. It is usually as-
sumed that atoms diffuse by jumping into vacant sites. One
could then apply Eq. (1) and identify J1 and J2 with the
fluxes of A and B in a lattice-fixed frame, JA and JB, and
X1 and X2 with the driving forces dlA/dz and dlB/dz,
where z is the length coordinate. Let us now change to a
new set of independent processes, the net flow of atoms
as indicated by the migration of inert Kirkendall markers
and the interdiffusion. The markers are supposed to be
fixed to the lattice and their migration relative to a num-
ber-fixed frame is then given by the net diffusion of vacan-
cies, which is equal to JA  JB, yielding
J
1 ¼ J A  J B ¼ J 1  J 2 .
The driving force for interdiffusion, i.e., diffusion of B in
exchange of A, is d(lA  lB)/dz and we shall write our sec-
ond condition as
dlA dlB
X
2 ¼  ¼ X 1 þ X 2 .
dz dz
Comparison with Eqs. (3a) and (6b) shows that we have
thus fixed the following coefficients, b11 = 1, b12 = 1,
c21 = 1, c22 = 1. It should be noted that these values sat-
isfy a requirement of Eq. (7), b12/c21 = b11/c22. We have
thus defined two new processes but in order to make them
conjugate we must also satisfy Eq. (10b), which yields
c12 = (c11  1/b11)c22/c21 = c11  1 or c11 + c12 = 1.
We may represent these coefficients with any composition,
i.e., c11 = xA and c12 = xB, where xA + xB = 1. Eq. (6a)
would then yield
dl dl
X
1 ¼ xA X 1  xB X 2 ¼ xA A þ xB B .
dz dz
It may be convenient to choose xA, xB as the local compo-
sition in the system because the Gibbs–Duhem relation,
Rxi dli = 0, can then be applied and it will make X
1 ¼ 0.
Eq. (9) will yield b22 = c11b11/c22 = c11(1)/1 = c11 = xA
and b21 = c12b11/c22 = c12(1)/1 = c12 = xB and from
Eq. (3b) we get, for the flux of interdiffusion
J
2 ¼ xB J A þ xA J B .
This is the well-known expression for the rate of mixing of
two components in the number-fixed frame. Both new
fluxes are thus expressed in the number-fixed frame. It
should be stressed that any other choice of xA, xB is for-
mally permitted and there is an infinite number of sets of
conjugate processes satisfying Eqs. (14) and (16) but none
may be more convenient. We can now evaluate the new ki-
netic coefficients from Eq. (13), obtaining
a
11 ¼ a11 þ a12 þ a21 þ a22 ;
a
12 ¼ xB a11  xA a12 þ xB a21  xA a22 ;
a
21 ¼ xB a11 þ xB a12  xA a21  xA a22 ;
a
22 ¼ x2B a11  xA xB a12  xA xB a21 þ x2A a22 .
101
It is interesting to note that OnsagerÕs relation is obeyed for
the new set of coefficients, a
12 ¼ a
21 , if it is obeyed for the
primary set, a12 = a21. In fact, that is a well-known conse-
quence of satisfying Eq. (4) when introducing a new set of
conjugate processes. Eq. (2) now yields, because X
1 ¼ 0
due to the Gibbs–Duhem relation
J
1 ¼ a
12 X
2 ¼ ½xB ða11 þ a21 Þ  xA ða12 þ a22 ÞdðlA  lB Þ=dz;
ð19aÞ
J
2 ¼ a
22 X
2 ¼ ½x2B a11  xA xB ða21 þ a21 Þ þ x2A a22 dðlA  lB Þ=dz.
ð19bÞ
It is an interesting feature of Eq. (19) that both new pro-
cesses, marker migration and interdiffusion, are driven by
the same force, d(lA  lB)/dz. The marker migration is
thus driven only by its cross-term and it will not cause
ð14Þ
any dissipation of Gibbs energy because it would have been
evaluated from J
1 X
1 . It is evident that marker migration is
not a real process, in the sense that it has no driving force.
4. Role of cross-terms
ð15Þ
If the cross-terms turn out to be small or even vanish for
a particular set of conjugate processes with simple physical
interpretations, it may be taken as an indication that these
processes are actually the physical processes that are oper-
ating. As an example, it may be a reasonable approximation
to neglect the initial cross-coefficients, a12 and a21, and to
simplify Eq. (1), if it is assumed that the equilibrium content
of vacancies is maintained everywhere even during diffusion
J A ¼ J 1 ¼ a11 X 1 ¼ a11 dlA =dz; ð20aÞ
J B ¼ J 2 ¼ a22 X 2 ¼ a22 dlB =dz. ð20bÞ
ð16Þ On the other hand, this would result in an important cross-
coefficient for the new set of conjugate processes. It is the
only one predicting a marker migration through Eq.
(19a). Consequently, the fact that marker migration is of-
ten observed experimentally, when looked for, cannot be
taken as an indication that it is caused by its own physical
process, occurring by an exchange mechanism. That could
be justified only if it were caused by a dominating diagonal
ð17Þ term and its cross-term were small. It may be noted that the
cross-term in Eq. (19a) can vanish in special cases found by
putting a
12 and a
21 in Eq. (18b) and (18c) equal to zero,
e.g., when a12 = a21 = 0 and a11/xA = a22/xB. However, in
that case J
1 ¼ 0 in Eq. (19a) and there would be no marker
migration. This may actually happen for the vacancy mech-
anism, which is commonly assumed to give a11 as xAMA/Vm
and a22 as xBMB/Vm. Eqs. (19) could then be written as
dðlA  lB Þ
 J A  J B ¼ J
1 ¼ xA xB ðM A  M B Þ=V m  ;
dz
ð18aÞ
ð21aÞ
ð18bÞ
dðlA  lB Þ
ð18cÞ  xB J A þ xA J B ¼ J
2 ¼ xA xB ðxB M A þ xA M B Þ=V m 
dz
ð18dÞ ð21bÞ
102 M. Hillert / Acta Materialia 54 (2006) 99–104

now X
1 > 0. It may further be noted that there is now a

and a
12 would vanish if MA = MB. However, this seems un-
cross-term in the equation for the interdiffusion, the first
likely except for tracer diffusion and careful experimental
term in Eq. (23b). It should finally be noted that the driving
studies might show some marker migration, at least in
force for the migration of the interface, xADlA + xBDlB, is
metallic systems. It should then be possible to rule out
formally the driving force for a diffusionless transfer from b
the exchange mechanism of diffusion by studying marker
to a of material with the composition xA, xB.
migration.
The present manipulations of the equations for diffusion
6. Previous treatments
in a one-phase material were used to illustrate how to
change the set of conjugate processes and the importance
Baker and Cahn [4] started from the phenomenological
of analyzing the physical interpretation of the new pro-
flux equations in the form of Eq. (1) and introduced new
cesses was demonstrated. It may also form a basis for the
processes in two different ways. With A and B inserted
treatment of diffusional phase transformations to be pre-
for components 1 and 2 in Eq. (1), they first defined the
sented in the next section.
new processes through the equations

5. Diffusional phase transformations J A ¼ J
1 ¼ xaA ðJ A þ J B Þ; ð24aÞ

JB ¼ J
2 ¼ xaB ðJ A þ J B Þ. ð24bÞ
For fluxes across an a/b interface it may be convenient
However, they did not modify the driving forces. Thus,
to express the potential gradient dli/dz as Dli/Dz, where
X
1 ¼ X 1 and X
2 ¼ X 2 . The dissipation by the initial pro-
Dz is the thickness of the interface and could be included
cesses in the lattice-fixed frame is
in the kinetic coefficient. Dli is the discontinuous jump in
chemical potential from a to b at the interface and, in real- T r ¼ J AX 1 þ J BX 2. ð25Þ
ity, it would be possible to treat cases where that jump is For the new set of processes the dissipation will be
much higher than between two atomic planes within a
phase. The driving forces in Eq. (1) would thus be defined T r ¼ J
1 X
1 þ J
2 X
2 ¼ ðJ A þ J B ÞðxaA X 1 þ xaB X 2 Þ. ð26Þ
as This reduces to the result of Eq. (17) by insertion of Eq.
X 1 ¼ DlA ; ð22aÞ (24) and the requirement for a set of conjugate processes
was thus fulfilled so far. For another new set of processes
X 2 ¼ DlB . ð22bÞ
they chose
All the derivations for introducing a new set of conjugate
J


1 ¼ J A þ J B; ð27aÞ
processes in a one-phase material are still valid except that
X
1 does not disappear because the Gibbs–Duhem relation J


2 ¼ J

a
1 ðxB  xbB Þ ¼ ðJ A þ J B ÞðxaB  xbB Þ ð27bÞ
cannot be applied when there is an appreciable discontinu-
and in order not to change the dissipation they here chose
ous change at the interface. It does not help how we use the
the following driving forces:
freedom to choose c11 and c12, i.e., the composition xA, xB.
b b
It is not self-evident what choice of xA, xB should now be X


1 ¼ xA X 1 þ xB X 2 ; ð28aÞ
preferred in Eq. (16) but it would affect the flux of the con- X


2 ¼ X 1 þ X 2 . ð28bÞ
jugate process, which is still driven by X2  X1 according to
Eq. (15). It concerns interdiffusion across the interface and It can easily be confirmed that this set also yields the same
its flux depends on the choice of xA, xB, which will be in- dissipation under steady state conditions where
serted not only in Eq. (16) but also in the flux equation, J A =xaA ¼ J B =xaB ¼ J


1 .
Eq. (17). Introducing the kinetic coefficients from Eq. T r ¼ J








1 X1 þ J2 X2
(18), we obtain for a phase transformation
b b b
¼ J

a
1 ½xA X 1 þ xB X 2 þ ðxB  xB ÞðX 1 þ X 2 Þ
J
1 ¼ a
11 X
1 þ a
12 X
2 ¼ ða11 þ a12 þ a21 þ a22 ÞðxA DlA þ xB DlB Þ
¼ J

a a
1 ðxA X 1 þ xB X 2 Þ ¼ J A X 1 þ J B X 2 . ð29Þ
þ ½xB ða11 þ a21 Þ  xA ða12 þ a22 ÞðDlA  DlB Þ; ð23aÞ
J
2 ¼ a
21 X
1 þ a
22 X
2 ¼ ½xB ða11 þ a12 Þ  xA ða21 þ a22 Þ Then Baker and Cahn evaluated the new kinetic coeffi-
2
 ðxA DlA þ xB DlB Þ þ ½ðxB Þ a11  xA xB ða12 þ a21 Þ þ ðxA Þ a22  2 cients, in principle by using Eq. (13), and tested whether
it would be possible to make the cross-coefficients of the
 ðDlA  DlB Þ. ð23bÞ
new set of processes vanish if they vanish for the original
The important fact is that according to Eq. (23a) is no J
1 processes, i.e., when a12 = a21 = 0. However, they found
longer dependent only on the cross-term. The diagonal that the new cross-coefficients were not even equal to each
term now appears and will most likely have a dominating other as they should be according to Onsager. They con-
effect on J
1 , which still represents the net flow of atoms cluded that in order to satisfy his reciprocity relation it is
but is no longer related to the migration of Kirkendall not sufficient to keep the dissipation the same when a
markers but of the interface, i.e., the progress of the phase new set of processes is defined. That is true and the failure
transformation, and it will dissipate Gibbs energy because of the cross-coefficients to be equal is simply caused by the
 M. Hillert / Acta Materialia 54 (2006) 99–104
two fluxes in Eqs. (24) or (27) not being independent, all
being equal to or proportional to JA + JB. That is another
requirement for OnsagerÕs relation to apply. Furthermore,
Eq. (7) can be used to show that the set of processes defined
by Eqs. (24) and (25) or by Eqs. (27) and (28) are not con-
jugate to the set of phenomenological equations.
Even though the two simultaneous processes according
to the second choice by Baker and Cahn do not make a
set of conjugate processes, they make a very useful set of
processes. In fact, these processes were directly postulated
in a successful attempt to model trapping of carbon in
the transformation of Fe–C austenite to ferrite [5,6]. The
definition of J

1 in Eq. (27a) shows that it represents the
rate of the interface migration and its driving force accord-
ing to Eq. (28a) is the driving force for diffusionless transi-
tion of material from b with its composition xbA ; xbB into a.
It would not yield a phase with the correct composition but
that is compensated by interdiffusion across the interface
driven by X1 + X2 = DlA  DlB according to Eq. (28b)
and with a flux according to Eq. (27b), which has exactly
the magnitude needed to adjust the composition to
xaA ; xaB of the flux J


1 for the diffusionless transition.
Caroli et al. [7] examined the trapping problem and
again started from Eq. (1) and defined a new process by
choosing
J
1 ¼ J A þ J B ð30Þ
in agreement with Eq. (27a). Then they mentioned the
expressions for interdiffusion inside any of the two phases,
writing them as
J ec ¼ xeA J B  xeB J A ; ð31Þ
where e represents a or b. Without any argument they then
accepted the same expression for interdiffusion across the
interface and by combination with Eq. (30) for the interface
migration they showed that the correct dissipation would
thus be obtained if combined with the following driving
forces:
X
1 ¼ xeA X 1 þ xeB X 2 ; ð32aÞ
X
2 ¼ X 1 þ X 2 . ð32bÞ
For both alternatives, e = a or b, one can derive the coef-
ficients in Eqs. (32) from those in Eqs. (30) and (31),
using Eq. (7). In both cases, the two new processes are
thus a conjugate set and the new kinetic cross-coefficients
obey OnsagerÕs rule if they are equal for JA and JB. In
fact, in Section 3 it was already shown that any choice
of the composition xA, xB in Eqs. (31) and (32a) is al-
lowed although Caroli et al. only mentioned the two
cases e = a or b. They did not really explain why they
chose to represent the interdiffusion across the interface
with the expression for interdiffusion inside one of the
phases. Later they argued that Eq. (32a) with e = a
should be used when there is no diffusion inside the
growing a phase, which was also the case for the steady
state conditions considered by Baker and Cahn in their
first new set of processes.
103
Caroli et al. then discussed what values the kinetic coef-
ficients in Eq. (1) should have in order to account for trap-
ping and finally they introduced a new set of conjugate
processes, assuming that the material is transferred across
the interface as two different groups, A + pB and B + qA,
and without any cross-terms. They showed how the initial
aij coefficients should be related to the new a
11 and a
22 in
order not to give cross-terms.
The author [6] again considered the problem of trapping
but now accepted to start from the phenomenological flux
equations. As did the others, he chose Eq. (27a), which is
identical to Eq. (30), and he chose Eq. (17), which is identical
to Eq. (31) with e = b. He also examined if it would be pos-
sible to describe these two processes as independent and
without any coupling, i.e., with a
12 ¼ a
21 ¼ 0, but contrary
to Caroli et al. he gave the necessary relation between the ki-
netic aij coefficients in the primary set of equations, Eq. (1).
7. Discussion
In order to describe a diffusional phase transformation
in a binary alloy one must consider at least two processes.
In one case [6] they were postulated to be a diffusionless
phase transition and chemical diffusion (here called inter-
diffusion) across the interface in order to attain the correct
composition of the growing phase. Instead, Baker and
Cahn [4] and Caroli et al. [7] started from the fundamental
flux equations for the individual components but trans-
formed them into the ones for diffusionless transition and
interdiffusion across the interface. The similarity between
their approaches has been demonstrated but it should be
emphasized that their results are not only valid for e = a
or b. They are special cases of the treatment given in
Section 5, which holds for any choice of the composition
xA, xB.
It is evident from Eq. (23) that in order for the cross-
coefficients to be zero for the two flux equations giving
the rates of interface migration and interdiffusion across
the interface, they cannot be zero for the individual flux
equations for each component. The two sets of processes
are thus inconsistent with each other in a physical sense
although not mathematically. As already emphasized, the
set of two processes with the smallest cross-coefficients
according to measurements are more likely to be those that
are actually operating during the reaction.
On the other hand, it seems quite possible that the two
mechanisms of interface migration, by diffusion of each
component individually or by a diffusionless transfer,
may operate simultaneously. In that case it would be most
transparent to start with three flux equations, two for indi-
vidual diffusion as Eq. (1), and a third one for the diffusion-
less transfer. For all three it should be reasonable to neglect
the cross-terms but they should not be regarded as indepen-
dent because the contribution from the third process could
then be split into two parts that depend on DlA or DlB,
respectively, and be added to the two individual flux equa-
tions. Then the other set of conjugate processes, governed
104 M. Hillert / Acta Materialia 54 (2006) 99–104
by the interface migration and interdiffusion, could be de-
rived if preferred. The primary problem would be to decide
on the net composition for the diffusionless transfer. A pos-
sibility would be to take the mean value of the composi-
tions on the two sides of the interface.
There has been much discussion regarding the migration
mechanism of grain boundaries and phase interfaces. For
diffusional transformations, where the diffusion within the
two phases occurs by a vacancy mechanism and thus by
individual diffusion of the components, it seems natural
to accept that the same is true also for the transfer of atoms
across the phase interface. On the other hand, for partition-
less transformations it is necessary that one of the compo-
nents is transferred across the interface in a direction
against its driving force. It is thus necessary that there is
some cooperative process by which that component is
trapped when the other component is transferred. It thus
seems difficult to avoid the introduction of three primary
flux equations although they can then by manipulation
be changed into two with important cross-terms.
8. Summary
The method of redefining two simultaneous processes by
linear combinations without changing the production of
entropy has been reviewed. The possibility of defining
one of the two new processes through its flux but the other
one through its driving force has been examined. For that
particular case, there is a degree of freedom.
When applied to diffusion in a binary solution phase, the
vacancy flux can be introduced as a new process and it cor-
responds to the migration of Kirkendall markers or of a
phase interface. For diffusion inside a phase the degree of
freedom can be used to eliminate the driving force for the
vacancy flux but it will be driven by coupling to the inter-
diffusion process. The migration of Kirkendall markers can
thus be calculated together with interdiffusion, which will
be the other new process.
With a modification, the formalism for diffusion inside
a phase can be applied to the migrating interface in a
phase transformation. The driving force for the vacancy
flux can no longer be eliminated and now it controls
the rate of interface migration if the individual jumps of
A and B atoms are the only simultaneous processes.
The degree of freedom can be used to introduce the
net composition of the material crossing the migrating
interface.
Previous attempts to treat diffusion in connection with
trapping of solute atoms have now been discussed using
the framework of the present approach. It was explained
that the failure of the treatment by Baker and Cahn to obey
OnsagerÕs relation is caused by their two new processes not
being independent although they predict the correct the en-
tropy production.
For phase transformations it is proposed that one
should start with three primary equations, two representing
diffusion of the individual components and the third one
representing diffusionless transfer of both components.
Acknowledgement
Thanks are due to Professor John Ågren for valuable
discussions.
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