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Contents lists available at SciVerse ScienceDirect

Physica B
journal homepage: www.elsevier.com/locate/physb

Crystallization analysis and determination of Avrami exponents of CuAlNi

alloy by molecular dynamics simulation
F.A. Celik a,n, S. Kazanc b
a
b

Bitlis Eren University, Faculty of Arts & Sciences, Physics Department, 13000 Bitlis, Turkey
Firat University, Faculty of Education, Physics Teaching Programme, 23119 Elazig, Turkey

a r t i c l e i n f o

abstract

Article history:
Received 16 May 2012
Received in revised form
14 September 2012
Accepted 15 October 2012

In this study, local atomic rearrangements of Cu%26.8Al%2.5Ni ternary alloys (3 A) are investigated
during their crystallization processes from amorphous phase using molecular dynamics (MD) simulations. These simulations are based on the SuttonChen type of embedded atom method (SCEAM) that
employs many-body interactions. In order to analyse the structural development obtained from MD
simulation, the simulation techniques are used as bond order parameter, radial distribution function
(RDF). Local atomic bonded pairs and short range order properties in the model alloy have been
analysed using the HoneycuttAndersen (HA) method. The kinetics of the crystallization is described by
Johnson, Mehl and Avrami (JMA) model, which has been analysed with MD method by using the
crystalline bonded pairs. The simulation results show that the structural variation of local atomic
bonded pairs is of great importance to understand the crystallization kinetics from amorphous phase to
crystal phase during the crystallization.
& 2012 Published by Elsevier B.V.

Keywords:
Crystal growth
Computer simulation
Nanostructures
Recrystallization
JohnsonMehl and Avrami (JMA) model

1. Introduction
Many studies of rapidly quenched amorphous alloys focus on
easy glass forming ability or the crystallization onset as a measure
of kinetic stability. In fact, the initial annealing response has been
used to distinguish between microcrystalline and amorphous
structures in terms of a continuous grain growth or a sharp onset
for a nucleation and growth [14]. Since amorphous alloys are not
in thermodynamic equilibrium, supplying such alloys with sufcient energy can promote a phase transformation from an
amorphous to a more stable crystalline phase during the annealing process [4,5]. In this process, nucleation plays a key role in
crystal growth, crystal formation, high quality single crystals and
its study is currently being stimulated by the development of new
experimental and theoretical techniques [69].
According to the classical nucleation theory, the nucleation
rate mostly depends on the nucleation energy barrier, diffusion
coefcient and free energy between solid and liquid. It is understood from these physical factors that the nucleation and crystal
growth are effective factors in amorphous structure stability
[1012]. On the other hand, the critical number of crystallinetype clusters occurred in the amorphous phase is an effective
factor in the stability of amorphous structure and crystallization
behaviours from amorphous phase to crystal phase [13,14].

Corresponding author. Tel.: 90 0434 228 5270; fax: 90 0434 228 5271.
E-mail address: facelik@beu.edu.tr (F.A. Celik).

Metallic alloys are especially popular due to their low costs

and relatively easy manufacturing. Especially, copper-based
alloys have been preferred in the technological and commercial
applications because of their good shape memory properties, easy
and low cost of production [15,16]. During amorphous phase to
crystal phase transformation process, it is quite difcult to
experimentally investigate the local order and nano-cluster characteristics determining the structural properties of the system at
a considerable level. Considering all of these, it is needed that
simulation studies should be conducted in order to determine the
internal dynamical properties of such transformations that have
an effect on the physical behaviours of the materials [1719].
Crystallization investigations of amorphous alloys are very
important to understand the mechanism of phase transformations and produce well-controlled nanostructures. Experimental
thermal analysis (TA) methods such as differential scanning
calorimetry are widely used for crystallization kinetics analysis
of amorphous alloys. This method recognizes three mechanisms,
i.e. nucleation, growth and impingement of growing new-phase
particles, and is applicable to both isothermal and non-isothermal
transformations [2022].
Cu-based alloys, such as CuAlNi, are attractive for fundamental
research of the thermo-mechanical properties of shape memory
materials (superelasticity, shape memory effect, twinning in
martensite) because the martensitic transformations in them are
fairly well known [23]. It can be said from our early studies that the
thermoelastic phase transformation at CuAlNi ternary alloy system
has been modelled by Sutton Chen type of embedded atom method

0921-4526/$ - see front matter & 2012 Published by Elsevier B.V.

http://dx.doi.org/10.1016/j.physb.2012.10.015

Please cite this article as: F.A. Celik, S. KazancPhysica B (2012), http://dx.doi.org/10.1016/j.physb.2012.10.015

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F.A. Celik, S. Kazanc / Physica B ] (]]]]) ]]]]]]

based on many-body interaction [24,25]. On the other hand, we want

to emphasize that the goal of this study is to investigate the crystallization behaviours of amorphous CuAlNi alloy during isothermal
annealing by MD method and recrystallization process of ternary
alloy nanoclusters of Cu, Al and Ni in the nano-size range. In this
purpose, rst, MD simulation method proposed by Parrinello and
Rahman was used to study the crystallization process of amorphous
in CuAlNi (Cu%26.82Al%2.47Ni atomic percentage) ternary alloy
system during isothermal annealing. The nucleation and growth
mechanisms at the microscopic level were investigated by HA
analysis method based on the bonded pairs and bond orientational
order parameter for the model alloy system by using MD method at
different annealing temperatures. Second, we determine the Avrami
exponents based on the experimental thermal analyses of the ternary
model alloy system by using crystalline atomic bonded pairs obtained
from MD simulation results.

2. Potential energy function

Interatomic potentials are very important for the systems
which have been modeling in the atomic scale. PEF which are
used for modeling of binary alloy systems have been used for
modelling ternary alloys systems as well [26]. In the present
study a SCEAM potential function is used. The total energy of a
crystal with N atoms in the SCEAM methodology is given by [27]
2
3
X
X 1X
 
p
4
ET
1
Ei
eij f rij ci eii ri 5
2 jai
i
i
where rij is the separation between atom i and j, c is a positive
dimensionless parameter, and e is a parameter with the dimensions of energy. f(rij) is a pairwise repulsive potential
 n
 
A
f r ij ij
2
r ij
between atoms i and j (arising primarily from Pauli repulsion
between the core electrons), while the metallic bonding is
captured in a local energy density, ri, associated with the atom
i and dened as
X   XAij m
ri r r ij
3
r ij
jai
jai
here A is a parameter with the dimensions of length; m and n are
positive integers.
The potential parameters representing the interaction
between different type atoms can be written from Lorentz
Berthelet as follows [17];
Ai Aj
,
2
p

Aij Aji

eij eji

nij nji

ni nj
,
2

ei ej

mij mji

mi mj
2

4
5

3. Calculations methods
3.1. The simulation technique
In the MD method considering the variation of MD cell in
shape and size, the lengths of the MD cell axis are described with
three vectors A(t), B(t) and C(t) as a function of time. More detailed
expositions of MD simulation method can be found from literature [28,29].
The simulations were performed on three dimensional arrays
of 30  30  30 unit cells (54,000 atoms). The ideal crystal DO3

super lattice structure of the 3 A model alloys was chosen as the

starting conguration for the MD computer simulation. The initial
velocities were derived from random number generator so as to
conrm a Maxwell Boltzmann distribution at a given temperature initially. The temperature of the system has been controlled
by rescaling the atomic velocities at every two integration steps.
The equation of motion is numerically solved by using the Gears
ve order predictor-corrector algorithm. Each molecular dynamics
time step corresponds to about 6.64 fs.
Structural analysis is examined from the radial distribution
functions (RDF), g(r), which is given as
*P
+
N
V
i 1 ni r
g r 2
6
4p r 2 Dr
N
Here r is the radial distance, ni(r) is the coordination number of
atom i separated with r within Dr interval, and bracket denotes
the time average [29].
The atomic conguration depends on the degree W of longrange order. For the B2 type ordered (CsCl type) phase, there are
two sublattices. In the perfect B2 type order state (WB2 1),
sublattice I is occupied by Cu atoms while sublattice II is occupied
by Al, Ni and the remaining Cu atoms. In the A2 type disordered
state (WB2 0) the occupations of the two sublattices are the
same. CCu, CNi and CAl are the atomic fractions of Cu, Ni, Al atoms,
respectively, (CCu CNi CAl 1); then the fractions of each atom
in CuAlNi alloys on sublattices I and II are those listed in Table 1
[30].
For the DO3 type (or more accurately L21 type) ordered phase,
above mentioned sublattice II is divided further into two sublattices, i.e. sublattice 3 and 4. In the perfect L21 type order state
(WL2 1), all Ni atoms lie on sublattice 3 while Al atoms lie on
sublattice 4. The ordering state with WL2 0 corresponds to that
with WB2 1. Therefore, we have the atom occupation fractions
for L21 type ordered CuAlNi alloys as listed in Table 2 [30].
In order to investigate the crystallization process of the model
alloy system from amorphous to crystalline phase, the equilibrated model in the structure of DO3 type super lattice at 500 K
temperature was, rst, heated up to 1100 K at intervals of 100 K
starting from 500 K. Later, the system was quenched up to 300 K
temperature at intervals of 100 K (1  1013 K/s). It was observed
that the system was stable at amorphous phase in all these
holding time and that the transformation to crystalline phase
was not realized. The model alloy system was held at amorphous
phase and following this it was heated up to the annealing
temperatures of 400 K and 500 K starting from amorphous phase
(300 K).
3.2. The HoneycuttAndersen (HA) method
It is known that the pair analysis technique can be used to
describe the microscopic local structure and short-range order in
the structures [31]. In this technique the local structure is
classied by using a sequence of four integers (ijkl) which have
the following meanings, the rst integer (i) is 1 when the atoms in
the root pair are bonded, otherwise it is 2. The second integer (j) is
the number of near-neighbour atoms shared in common by the
root pair. The third integer (k) is the number of nearest-neighbour
Table 1
Atom occupation fractions in sublattices I and II of B2  type ordered phases [30].
Atom

Sublattice I

Sublattice II

Cu
Al
Ni

1  (1  WB2) (CAl CNi)

(1  WB2) CAl
(1  WB2) CNi

1  (1 WB2) (CAl CNi)

(1 WB2) CAl
(1 WB2) CNi

Please cite this article as: F.A. Celik, S. KazancPhysica B (2012), http://dx.doi.org/10.1016/j.physb.2012.10.015

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Table 2
Atom occupation fractions in sublattices III and IV of DO3-type ordered phases
[30].
Atom

Sublattice III

Sublattice IV

Cu
Al
Ni

2CCu  1 2WDO3 (CAl  CNi)

(1 WDO3) 2CAl
(1 WDO3) 2CNi

2CCu  1 2WDO3 (CNiCAl)

(1 WDO3) 2CAl
(1  WDO3) 2CNi

3.3. Measuring the order parameter

The calculation of the bond orientational order parameters
has, recently, been used to determine the local structures of the
atoms in the MD cell [32,33]. The formalism is basically running
such that the nearest neighbours of each atom in the MD cell,
which constitute a cluster, is determined from a cut-off distance
taken from the minimum of the RDF between the rst and second
peaks. The spherical coordinates of each bond in the cluster is
calculated from
Q lm r  Y lm yr, fr

where Ylm(y,f) are spherical harmonics, and y(r) and f(r) are the
polar and azimuthal angles of the bond measured with respect to
some reference frame. The local structure around particle i is
given by
N i

Q lm i 

b
1 X
Q r
Nb i j 1 lm

where the sum runs over all Nb(i) bonds that particle i has with its
neighbours. On the other hand, the global orientational order
parameters can be obtained from the average of Q lm i over all N
particles, i.e.,
PN
1 N b i Q lm i
Q lm i P
9
N
i 1 N b i
The second-order invariants (Ql) is determined from the
relations,
"
#1=2
l
X


4p
 Q lm 2
Ql 
10
2l 1 m  l

Fig. 1. Black atoms (A and B) represent pair atoms (root pair); white atoms
represent neighbour atoms with root pair. Straight thick line denotes the bond
between A and B, dotted lines denote near-neighbour bond numbers of root pair,
dashed lines denote bond among neighbours. (a) 1421 bonded pair in fcc cluster
(b) 1441 bonded pair in bcc cluster (c) 1422 bonded pair in hcp cluster (d) 1551
bonded pair in icos cluster.

bonds among the shared neighbours. The fourth integer (l) is

needed to difference between the cases when the rst three
indices are the same but the bond geometries are different.
It is believed that the method is convenient to analyze the
geometric characteristics of an atomic cluster. If any atom system
AB forms a bond, i 1, otherwise i2, A and B atoms represent
root pair. For example, the 1551 bonded pairs represent the two
root pair atoms with ve common neighbours that have ve
bonds forming a pentagon of near-neighbour contact. In this case,
some typical bonded pairs are examined to understand the local
structure of systems. The 1551 bonded pairs have vefold
symmetry, and the ratio of 1551 bonded pairs gives a measure
of the degree of ideal icosahedral (ICOS) order. The 1421 and 1422
bonded pairs are characteristic bonded pairs for fcc and hcp
crystal structures, respectively. The 1661 and 1441 bonded pairs
are the characteristic bonded pairs for bcc crystal structure [31].
The pair fractions shown here are normalised so that the sum
over all cases for the nearest neighbours is summed to unity. The
1541 and 1431 bonded pairs are characteristic disordered ICOS
order. The 1201, 1331, 1321, 1311 bonded pairs represent the
rhombus symmetrical features of short-range order. An example
displaying four integers in some atomic clusters is given by HA
method in Fig. 1.

Since the lowest non-zero Ql is common with the ICOS and

crystal cubic symmetry corresponds to l6, it has been argued by
several authors that the value of Q 6 is very sensitive to any kind of
crystallization and increases signicantly when order appears
[34,35].
3.4. Crystallization kinetics
The kinetic study of crystallization was performed by using
JohnsonMehlAvrami (JMA) [36,37] isothermal analyses for
volume fraction x transformed as a function of time t based on
the following equation:
n

ln12x k t

11

Eq. (11) can be written as

ln2ln12x nlnk nlnt

12

where k is effective rate constant, x is the crystallized volume

fraction and n is the Avrami exponent. The Avrami plot of
ln[  ln(1 x)] versus ln(t), yields a straight line with slope and
intercept n ln(k). n may be 4, 3, 2 and 1, which are related to
different crystallization mechanism [20]: n 4, volume nucleation
and three dimensional growth; n 3, volume nucleation and two
dimensional growth; n 2, volume nucleation and one dimensional growth; n 1, surface nucleation and one dimensional
growth.

4. Results and discussion

In this study, the validity of the PEF and its parameters for the
model system were determined before investigating phase transformations. To determine the stable lattice structure of the model
system, the variation of cohesive energy with volume was

Please cite this article as: F.A. Celik, S. KazancPhysica B (2012), http://dx.doi.org/10.1016/j.physb.2012.10.015

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calculated for three different lattice structures such as disorder

B2, DO3 and disorder A2 lattices. The variation of cohesive energy,
which we have obtained from SCEAM approach, with compressing volume for these different structures is shown in Fig. 2. The
value of cohesive energy for order B2, DO3 and disorder A2
structures was determined as 3.41 eV, 3.43 eV and 3.38 eV,
respectively. It is well known that the stable structure of a system
corresponds to the minimum enthalpy. As a result, it can be said
that the DO3 type super lattice structure for 3 A model system is
the most stable structure for our MD study.
The effect of annealing temperatures on the crystallization
process at the 3 A model alloy system was performed as seen
from Fig. 3. From this gure, the variations (or changes) of the
structural quantities, are observed such as the cohesive energy (E)
during the crystallization process. At the annealing temperature
of 400 K, cohesive energy decreases very slowly and a nearly
constant energy during the crystallization processes, which
means that amorphous state is conserved without crystallizing
during the process. Therefore, at the annealing temperature of
400 K, there is only some structural relaxation. At the annealing
temperature of 500 K, the energy drops during the crystallization
process. This means that there are some crystalline embryos which
grow in the amorphous matrix, and therefore crystallization has

-3.0

E (eV)

-3.1

-3.2

-3.3
A2
B2

-3.4

DO3
-3.5
0.8

1.0

1.2
V / V0

1.4

Fig. 2. The cohesive energy against the variation of volume for order B2, DO3 and
disorder A2 structures of 3 A model alloy system.

-3.56
400K
-3.57

E (eV)

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F.A. Celik, S. Kazanc / Physica B ] (]]]]) ]]]]]]

500K

-3.58

-3.59

-3.6
1

1.2

1.4

1.6
Time (ns)

1.8

Fig. 3. The variation of potential energy during annealing process for different
temperatures.

happened at higher annealing temperatures because of the rapid

growth of the crystalline phase.
Fig. 4(ac) shows the RDFs results for different annealing times
during crystallization at 400 K, 500 K and 600 K annealing temperatures. It can be seen that the annealing process starts form
amorphous phase (0 ns), which means that a splitting can be seen
in the second peak at 300 K, which is a characteristic of the
metallic glass as stated in [7,10]. At 400 K annealing temperature,
about at the time of 3.6 ns, the crystallization process starts from
amorphous phase due to the splitting of the second peak becoming less obvious. Since the peaks of RDF at certain atomic
positions are not very sharp, it can be said that it only starts with
the surface crystallization in the amorphous phase and a stable
crystalline structure does not appear. At 500 K annealing temperature and the time of 0.82 ns, the crystallization process starts
from amorphous phase and the curves obviously show that the
transition occurs from amorphous structure to crystalline structure due to the nucleation of crystalline phase in amorphous
phase. After 0.82 ns, the peaks are sharper and this indicates that
the degree of crystalline order of the system has increased and
that a stable crystalline structure has appeared obviously. This
implies that the crystallized phase undergoes coarsening with
increasing annealing time at high annealing temperature. At the
time of 2.1 ns, the peaks of RDF become sharper compared with
400 K annealing temperature; the RDF curves show the feature of
more stable crystal structure due to the rapid growth of the
crystal grains. At annealing temperature of 600 K, we note that
the model structure is in liquid phase for all annealing times. The
crystal phase does not occur and the atoms are distributed in
more disordered.
It is also known that it is necessary to investigate the atomic
bonded pairs to determine small sized embryos structures [14].
These atomic groups are yet embryos at amorphous phase and
these embryos reach the critical number depending on the
structural rearrangements of different types of atomic bonded
pairs being within a system because of nucleation. During the
transformation process from amorphous phase to crystal phase,
the structural properties of bonded pairs (these pairs will be
called as embryos) have determined from HA method and their
effect on nucleation and growth process has been investigated in
this study.
Fig. 5 shows the variation of the number of crystal-type
bonded pairs (total number of 1421, 1422, 1441 and 1661 bonded
pairs) during from amorphous phase to crystal phase at 400 K and
500 K annealing temperatures for the model system. It can be
seen that from beginning of annealing time to t1, the number of
crystal bonded pairs increases slowly. This time period may be
interpret as the crystal nucleation in the amorphous phase. From
t1 to t2 the number of crystal bonded pairs increases very fast, and
this time period may be related to the crystal growth during the
crystallization process. After time of t2, the number of crystal
bonded pairs goes to constant values and the crystal phase remain
stable with the time. In brief, it can be said that the structural
relaxation in the amorphous phase, the nucleation of crystalline
clusters and crystal embryos growth occur during this annealing
process. The results lead to the increasing of number of crystal
bonded pairs forming crystalline grains which occur faster at the
high annealing temperature. This case is in agreement with the
theories based on the classical crystallization kinetics [9,11].
Fig. 5b shows the variation of amorphous-type bonded pairs
(total number of 1551, 1541, 1431 bonded pairs) during from
amorphous phase to crystal phase at 400 K and 500 K annealing
temperatures for the model system. The curves clearly show that
the total number of the crystal bonded pairs increases, while the
total number of the amorphous bonded pairs decreases correspondingly. This result clearly shows that the amorphous phase

Please cite this article as: F.A. Celik, S. KazancPhysica B (2012), http://dx.doi.org/10.1016/j.physb.2012.10.015

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400K

500K

600K

0 ns

g (r)

0.82 ns

2.1 ns

3.6 ns

3.7 ns

4
5
r ()

0 ns

0 ns

0.82 ns

0.82 ns

2.1 ns

2.1 ns

3.6 ns

3.6 ns

3.7 ns

3.7 ns

4
5
r ()

4
5
r ()

Fig. 4. The RDF curves at different annealing times and temperatures during the crystallization process.

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30
400K

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24

t2


70
500K

60
50
40

t1


30

400K

60

The number of amorphous bonded pairs (%)

The number of crystal bonded pairs (%)

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500K

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20

20

10
0.8

1.2

1.6

0.8

Time (ns)

1.2

1.6

Time (ns)

Fig. 5. Variation of various bonded pairs during annealing times (a) crystal bonded pairs (b) amorphous bonded pairs.

transforms to crystal phase during crystallization process. On the

other hand, the number of disordered structural units, such as
1201, 1211, 1301, 1311 and 1321 only amounts to 8.81% and
6.01% at 400 K and 500 K annealing temperatures, respectively as
seen Table 3. The relative bonded pairs, such as 1431, 1551, 1541,
1311 and 1321 which are corresponding to disorderly system can
preserve the structures from amorphous phase to crystal phase
during annealing process because of under the high quenching
from liquid phase. 1331, 1211 and 1301 bonded pairs are not
found or found in a very small amount in crystal phase because
there are not only internal relations but also structural and range
order differences between liquid and crystal phase. On the other
hand, super cooled liquids contain many disorderly structural

Table 3
The various bonded pairs at 400 K and 500 K annealing temperatures.
400 K
Pairs

Percentage
(%)

500 K
Pairs

Percentage
(%)

1301
1311
1321
1331
1211
1201
1101
Total

0.67
5.27
1.84
0
0.45
0.36
0.22
8.81

1301
1311
1321
1331
1211
1201
1101
Total

0.4
4.25
0.88
0
0.11
0.24
0.13
6.01

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units not in solids such as clusters 1221, 1331, etc. The existence
of various clusters in liquid manifests the variety of microstructural in liquid or amorphous metal. Under slow annealing conditions, various types of clusters in amorphous metal will be
rearranged in a particular order to form metal crystal during
crystallization process. As the annealing temperature increases,
the relative numbers of crystal-type bonded pairs increase
slightly and disordered bonded pairs (other pairs) tend to be
removed from the system.
Moreover, it is known that the bond orientational order
parameters are also very important parameters to detect the
crystalline order during crystallization process. In particular, since
the values of Q 6 are very sensitive to crystallization [35], the
values increase signicantly indicating the order of crystalline
phase. In the process of transition from the amorphous to crystalline phase, rearrangement of the atoms in the system can be
assessed by examining the variation in global bond orientational
order parameter values. During any phase transition, global bond
orientational order parameter values have considerable variations. As previously established, particularly in the crystallization
process, a sudden increase in the numerical values of the Q 6
parameter indicates a transformation into the crystalline phase or
ordering. In this case, the variation of Q 6 value for the model
ternary alloy obtained at annealing temperatures of 400 K and
500 K starting from amorphous phase with the time interval is
shown in Fig. 6. The order parameter Q 6 has very weak values in
the amorphous phase and with the time; it has much larger
values in the crystal phase at two annealing temperatures. As
seen in Fig. 6, a sudden change (increase) was observed in the
numerical values of the Q 6 parameter in time at the annealing
temperature of 500 K. On the other hand, at 400 K, no suddenly or
sharply change of Q 6 values was observed in time. This result
shows that the model system of alloys has a better crystallization
and crystal growth process at high annealing temperatures.
One of the most well known statements regarding nucleation
and growth kinetics is the JohnsonMehlAvrami (JMA) kinetics.
The Avrami exponent n provides the characteristics of nucleation
and growth during the crystallization mechanisms at any temperature. In this study, the effect of the number of bonded pairs

representing the crystal structures determined via MD method on

the nucleation and growth process was investigated. The crystallized volume fraction in a given time during crystallization was
determined by measuring the percentage of crystalline bonded
pairs for system.
With the above HA analysis, all crystalline embryos (or nuclei)
in the system can be conrmed, and the number of crystalline
bonded pairs can be calculated. Fig. 7 shows the evolutions of the
crystallized volume fraction of crystal phases during the relaxation process of amorphous alloy at 400 K and 500 K annealing
temperatures. The crystallized volume fraction (x) in a given time
during crystallization is determined by crystalline bonded pairs
for which corresponding results are shown in Fig. 8. Plotting
ln[ ln(1  x)] versus ln(t) using data x%, the isothermal JMA
plotted at different annealing temperatures for model alloy
system are obtained. The Avrami exponents n are calculated by

0.8

500K
0.7
0.6
0.5

400K
0.4
0.3
0.2
0

Time (ns)
Fig. 7. Crystallized volume fraction x as function of annealing time for model alloy
system.

0.4

0.39

500K
400K

500K

0.38

0.36

ln (-ln (1-x))

0.37

Q6

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F.A. Celik, S. Kazanc / Physica B ] (]]]]) ]]]]]]

Volume fraction (x)

400K

-0.4

0.35

-0.8
0.34

0.33

-1.2
1

3
Time (ns)

Fig. 6. Variation of the bond order parameter at 400 K and 500 K temperatures
during annealing.

0.5

1
ln (t)

1.5

Fig. 8. Isothermal JMA plots of crystallization at different annealing temperatures

for model system.

Please cite this article as: F.A. Celik, S. KazancPhysica B (2012), http://dx.doi.org/10.1016/j.physb.2012.10.015

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the slope of curves and our most simulation results are located at
these tted curves. Under the isothermal condition, the Avrami
exponent at 400 K annealing temperature is obtained as 0.48. This
value smaller than 1, which indicates that the crystallization is
governed by one dimensional growth from surface to the inside
and only surface nucleation. At high annealing temperature of
500K, the value of Avrami exponent is 2.78. This value is larger
than 2.5 and close to value of 3, which indicates that volume
nucleation and two dimensional growths with an increased
nucleation rate. At low temperatures, because of random packed
atomic conguration and a multi-component system of amorphous phase, mobility of atoms in such atomic conguration is
very difcult. The formation of new crystalline nuclei needs the
atomic rearrangements and mobility. The number of crystalline
bonded pairs increases with increasing annealing temperature as

exhibited in Fig. 5. At higher temperature, growth of critical

crystalline embryos leads to change the composition in their
neighborhood and as a result the crystal growth increases
because of the easy mobility of atoms as seen in Fig. 3. On the
other hand, it is considered that since the model alloy system is
subsequently heated to a high annealing temperature, the structural defects such as slipping of atomic planes and stacking faults,
in the transformed regions may be removed or alternatively
rearranged at nucleating recrystallized grains in congurations
of lower energy during isothermal annealing processes. With noncrystalline bonded pairs decreasing in the amorphous phase
during annealing, the crystallized bonded pairs or atomic groups
are particularly efcient at nucleating these grains. From the
simulation results, the necessary time for formation of stable
crystal phase and completion of recrystallization decreases with
increasing temperature as seen in Figs. 5, 6 and 8, which is
consistent with the nucleation theory [9,11,12]. On the other
hand, since form a stable crystal phase from amorphous phase,
the most ideal annealing temperature for model alloy system is
determined as 500 K with MD method.
Fig. 9 shows snapshots of atomic conguration during crystallization at 400 K and 500 K annealing temperatures. Fig. 9a shows
the atomic conguration at 400 K and it can be said from this
image that some crystal nuclei are formed in the amorphous
phase nucleate from the amorphous phase. Fig. 9b shows the
atomic congurations of the nal crystallization at the annealing
temperature of 500 K. The ordered crystalline structure is almost
completely formed, namely the crystal embryos have grown
forming stable crystal phase after growth and the grain coarsening can be clearly observed. As it is obviously seen in the gures
that some areas possess disordered structures in this atomic
conguration, which are also in agreement with Fig. 5.

5. Conclusion
The EAM potential for the CuAlNi alloy system was performed
to study the crystallization process of the amorphous alloy during
isothermal annealing. The transition from amorphous structure to
crystal structure of the system at different annealing temperatures is a continuous process, associated with the sharp variations
in the RDF, bond order parameter, the number of bonded pairs by
using HA method. The simulation results also show that the
higher the annealing temperature, the faster the crystallization
process. These simulation results are consistent with experimental ndings and nucleation theory. On the other hand, the Avrami
exponent of about 3 implied that the crystallization process of the
bulk amorphous alloy is a three dimensional growth and volume
nucleation at high annealing temperature. At low annealing
temperature, the value of Avrami exponent is smaller than 1.
This value is consistent with a surface nucleation mechanism
according to which the crystallization occurs mainly from the
glass surface and crystal growth proceeds into the interior. We
calculate Avrami exponents at different annealing temperatures
by using crystallized volume fraction of CuAlNi model alloy
system estimates from present MD simulation.

Acknowledgement

Fig. 9. Snapshots of the atomic conguration at different annealing temperatures

of model system. (a) 400 K and (b) 500 K.

This work is supported by the Research Foundation of Firat

University contact grant-number: FUBAP 1496. In addition to, the
authors wish to thank Professor Jamal Beraktar from MartinLuther-University for supplying the researches.

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