Computational Materials Science 17 (2000) 324330

www.elsevier.com/locate/commatsci

Monte-Carlo simulation of orderdisorder kinetics in 2D and

fcc binary alloys
A. Kerrache a, H. Bouzara a, M. Zemirli a, V. Pierron-Bohnes b,*, M.C. Cadeville b,
M.A. Khan b
a

Institut des Sciences Exactes, Universit

e M. Mammeri, Tizi-Ouzou 15000, Alg
erie, France
b
IPCM-GEMM, 23, rue du Loess, F-67037 Strasbourg, France

Abstract
The thermodynamic parameters that drive the atomic migration in 2D and 3D binary alloys are studied using
Monte-Carlo simulations. The model is based on a vacancyatom jump mechanism between nearest neighbour sites,
with a constant vacancy concentration, so that only the migration counterpart EM of the total activation energy
EA EM EF , where EF is the vacancy formation energy) is determined. The ordering kinetics are well described by
exponential like behaviours with one (respectively two) relaxation time in the 2D (respectively 3D) cases. The temperature dependence of the long relaxation time is an Arrhenius law yielding eective migration energies. Slowing down
of the relaxation is observed at the OrderDisorder transitions. In both cases, we observe a linear variation of the
eective migration energy with the OrderDisorder critical temperature. 2000 Elsevier Science B.V. All rights
reserved.
Keywords: OrderDisorder; Migration energy; Kinetics

1. Introduction
Monte-Carlo simulations were undertaken to
understand the ordering mechanism and the pertinent parameters that drive the atomic mobility in
ordered An Bm compounds, in order to compare
with experimental results. Let us recall that, when
considering ordering kinetics involving vacancy
atom jump mechanism (ABv), the activation
energy can be considered as a sum of two contributions: the vacancy average formation energy

Corresponding author. Tel.: 33-88-10-7066; fax: 33-88-107249.

E-mail address: vero@taranis.u-strasbg.fr (V. Pierron-Bohnes).

EF and the atomic average migration energy

(EM ). In our study, we keep the vacancy concentration constant, therefore we do not consider EF .
We report in this paper the results of Monte-Carlo
simulations in a square lattice and in the L12
structure. The square lattice calculations were intended as a test to see whether we obtain the same
results using long range order (LRO) and short
range order (SRO) parameters, as initially the
LRO was thought to be sensitive to anti-phase
domain formation.
2. Monte-Carlo model
The ABv model, initially developed to calculate
the long range order kinetics in equi-atomic AB

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A. Kerrache et al. / Computational Materials Science 17 (2000) 324330

phases of B2 structure [1], has then been applied to

other stoichiometries where B2 and DO3 coexist
[2]. We apply it now to structures ordered on the
fcc lattice as the L12 (present work and [3]) and
L10 structures [4].
The model is based on a vacancyatom jump
mechanism between nearest neighbour sites,
which is the most realistic microscopic process in
dense phases and not a direct atomic interchange
as in other Monte-Carlo simulations (as for example [5]). The elementary step is the following:
a vacancy (v) is chosen at random, then one of
its neighbours is randomly chosen. If this happens to be an other vacancy, the trial ends,

Fig. 1. Square lattice and L12 phase.

Fig. 2. LRO g and SRO a parameters (T 280 K, V2 5

meV).

325

otherwise the energy balance DE of the atomvacancy exchange is evaluated with an Ising
Hamiltonien, considering the two nearest neighbour shells of the initial and nal vacancy positions. DE can be considered as the driving force
of the jump mechanism. We have chosen to restrict our study to pair interactions with the
following relations: VvA VvB 0 (vacancyatom
interactions are neglected) and VAA VBB
VAB Vi (i equals to 1 and 2 for the nearest
and the next nearest neighbour shells, respectively). This approximation which is reasonable
for transition metal compounds is not restrictive
for the physical eects we treat here. Research
has gone beyond this approximation when
treating the Ni3 Al [3]. In all this study we xed
V1 20 meV to settle the temperature scale and
varied V2 /V1 . The jump probability is given by
the Glauber algorithm [6]


exp kDE
T
 B ;
P v () A or B
1 exp kDE
BT

Fig. 3. Variation of TC with V2 /V1 .

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A. Kerrache et al. / Computational Materials Science 17 (2000) 324330

Fig. 4. T/TC dependence of geq and aeq for three values of V2 (2, 2 and 5 meV).

Fig. 5. Arrhenius plots obtained using LRO and SRO parameters for three values of V2 .

where kB is the Boltzman constant and T the absolute temperature.

We have chosen the Glauber algorithm in order
to ensure that at high temperature or when
DE 0, a jump has the same probability to occur

and not to occur. Moreover, no jump has a

probability equal to 1 as long as DE remains nite.
In order to account for the existence of an energy
barrier between the two positions of the vacancy
(or of the jumping atom) before and after the
jump, a saddle point energy depending on the
jumping atom but independent of its neighbours,
can be introduced. As we are mainly interested in
the ordering energy eects and as it has been
shown that the two eects are additive [1], we
studied the OrderDisorder kinetics without saddle point energy. Finally, the jump will only take
place if P(v () A or B) is less than a randomly
generated number.
The OrderDisorder kinetics were performed
on a square lattice 400  400 unit cells with 10
vacancies, initially distributed randomly in the
lattice) and in L12 structure (64  64  64 unit
cells with a single vacancy) using the periodic
boundary conditions.
The 2D structure can be described by two sublattices I and II which are occupied by A and B

A. Kerrache et al. / Computational Materials Science 17 (2000) 324330

327

Fig. 6. Correlation between EM and TC for 2D structure.

atoms, respectively (Fig. 1). The A atoms have 4 B

nearest neighbours and 4 A next nearest neighbours. The long g and the short a range order
parameters are given by:
I

g2
a1

and

NP
;
Z  CA  1 CA  N
I

Fig. 7. Phase diagram for three values of V2 .

II

NA NA
N

II

where NA and NA are the number of A atoms in I

and II sub-lattices, N the total number of sites in a
square lattice, NP is the number of rst neighbour
AB pairs and Z is the coordination number of the
lattice.
The L12 structure can be described by four
interpenetrating simple cubic sub-lattices a; b; c
and d (Fig. 1), three of them b; c; d being occupied by B atoms, the fourth one a by A atoms,
that have 12B neighbours and six A next nearest

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A. Kerrache et al. / Computational Materials Science 17 (2000) 324330

neighbours. The long range order parameter

gL12 is given by
4
a
gL12  PA CA ;
3

Fig. 8. gL12 for (T 300 K, V2 0:002 eV).

where PA is the occupation probability of the

a sub-lattice.

3. Results on a square lattice

For a given concentration (50%) and for various temperatures we calculate g and a at regular
time intervals, as described in [1], until they reach
their equilibrium values geq ; aeq . In Fig. 2, the
g and a values corresponding to V2 /V1 0.25,
T 280 K are plotted versus the Monte-Carlo
time. The temperature dependence of geq and aeq
was then obtained and the critical temperature TC
was deduced from the rst derivative of geq (T) and
aeq (T). TC is determined within 10 K, the transition region being crossed with a temperature step
of 20 K. This accuracy is sucient as we are not
investigating the critical region. We obtain a linear
variation of TC with V2 /V1 (Fig. 3). In Fig. 4, geq
and aeq and values corresponding to three values
of pair potentials V2 2, 2 and 5 meV) are

Fig. 9. T/TC dependence of gL12 for ve values of V2 .

A. Kerrache et al. / Computational Materials Science 17 (2000) 324330

329

Fig. 10. Arrhenius plots for ve values of V2 .

plotted versus the reduced temperature T =TC . It

can be noticed that the various curves of geq T =TC
and aeq T =TC overlap. All the kinetics are well
tted with an exponential yielding the relaxation
times s1 and s2 corresponding to the LRO and
SRO parameters, respectively. Arrhenius plots of
s1 and s2 (Fig. 5) lead to the eective migration
energies. A least-square t gives a variation of EM
with TC of 0.65 eV/1000 K for both LRO and SRO
parameters (Fig. 6).
Finally, we have determined some phase diagrams (Fig. 7) around AB stoichiometry for the
same values of V2 .
4. Results in L12 structure
For a given concentration (25%) and for various temperatures, following the same procedure as
in the 2D case, we calculate the long range order

parameter gL12 at regular time intervals, until it

reaches its equilibrium value geq . In Fig. 8, we
represent the gt values for (V2 2 meV,
T 300 K). The critical temperature is determined
within 0:5 K, the transition region being crossed
with a temperature step of 1 K. In Fig. 9, the geq
values corresponding to ve values of
V2 1; 2; 4; 8; and 10 meV) are plotted
in the reduced temperature scale. All the kinetics
are well tted with two exponentials, yielding two
relaxation times sL and sS . The temperature dependence of the long relaxation time sL follows an
Arrhenius law. In Fig. 10, we show Arrhenius
plots for ve values of V2 =V1 , corresponding to TC
ranging between 490.5 and 1019.5 K. The slopes of
the Arrhenius plots at high temperature give the
migration energies whose critical temperature dependence is represented in Fig. 11. A least-square
t gives a linear variation of EM with a slope of
0.28 eV/1000 K, which is the contribution of the

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A. Kerrache et al. / Computational Materials Science 17 (2000) 324330

migration energy to the total activation energy.

This is small compared to the experimental EA
value  1 eV=1000 K) obtained in Ni1x Mx 3 Al
compounds (M Cr, Mn, Fe) [7].
References
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A239240 (1997) 784789.
[3] P. Oramus, R. Kozubski, M.C. Cadeville, V. PierronBohnes, W. Pfeiler, Mat. Res. Soc. Symp. Proc. 527 (1997)
185.
[4] A. Kerrache et al. (paper in progress).
[5] C. Frontera, E. Vives, A. Planes, Phys. Rev. B 55 (1997).
[6] R.J. Glauber, J. Math. Phys. 4 (1963) 294.
[7] R. Kozubski, J. Soltys, M.C. Cadeville, V. Pierron-Bohnes,
T.H. Kim, P. Schwander, J.P. Hahn, G. Kostorz, Intermetallics 1 (1993) 139150.

Fig. 11. Correlation between EM and TC .