Materials Science and Engineering A271 (1999) 116 – 121

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Computation of liquid Cu70Ni30 alloy structure using EAM in

rapid cooling and heating process
Li Hui a,*, Bian Xiufang a, Zhang Jingxiang b
a
The Institute of Material Science and Technology, Shandong Uni6ersity of Technology, Shandong, P.R. China
b
The Department of Information Engineering, Jinan United Uni6ersity, Jinan, P.R. China

Received 4 February 1999; received in revised form 9 April 1999

Abstract

A series of simulations of the glass transition of Cu70Ni30 alloy have been carried out based on the molecular dynamics
simulation technique under constant temperature and constant pressure. Atoms interact via semi-empirical many-body potential
EAM. The pair correlation function, pair analysis technique and bond orientation order parameters are used to reveal the
structural features of Cu70Ni30 alloy in a state of liquid, super cooled liquid and glass as well as structural evolution in the
process of the rapid solidification. In the quick heating of the amorphous metal obtained by the quick cooling method, the
ordering degree of the system is kept, to some extent, to the next stage. © 1999 Elsevier Science S.A. All rights reserved.

Keywords: Pair correlation function; Bond orientation order; Bonded pairs

1. Introduction Molecular dynamics (MD) simulation is widely used

The structural properties of liquid metals attract
more and more attention, for a large number of exper-
imental researches reveal that the macro properties of
metal materials are mostly defined by their micro struc-
ture. The micro structure is mainly determined by the
liquid structure of the metal before solidification and
the speed of the solidification. It is therefore very
important to research the variations of the structure of
liquid metals as the temperature changes.
Many solid materials, e.g. glass and crystalline, origi-
nate from their liquid state. Glass is usually considered
‘frozen liquid’. The amorphous phase in a large number
of metallic alloys can be prepared by the rapid solidifi-
cation technique because rapid cooling can prevent
crystallization by way of creating a kinetically unfavor-
able condition. In order to avoid the nucleation and
growth of the relatively stable crystalline phase, the
typical and traditional method is to keep the cooling
rate in a high range of 106 – 1012 K s − 1. However the
high cooling rate limits the use of the amorphous
technique in certain alloy systems.
* Corresponding author.
to research the glass transition [1–3]. Here we use this
method to study the features of liquid and amorphous
structure of Cu70Ni30 and its structural evolution from
liquid to glass. The structural evolution from glass to
liquid at a high heating rate has also been researched.
The result we derived from the research is that amor-
phous Cu70Ni30 is gradually formed in the rapid so-
lidification process.
The inter-atomic potential plays a key role in the
simulation. The first-principle liquid theory developed
by Car et al. [4] have been successfully applied to
calculate the active energy of simple liquid metals in
diffusion, but it cannot be applied to transition metals
because plane-wave basis sets are not suitable to de-
scribe their narrow d-bands. Recently Daw et al. [5]
proposed the embedded atom model (EAM) on the
basis of quasi atom concept and density function the-
ory. It is applicable to transition metals as well as
simple metals.
According to the EAM, the total energy of the
system containing N atoms is written as
1
Etot = %F(ri )+ %f(r) (1)
i 2 i

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PII: S 0 9 2 1 - 5 0 9 3 ( 9 9 ) 0 0 1 8 2 - 3
 L. Hui et al. / Materials Science and Engineering A271 (1999) 116–121 117

Table 1 thus ri can be expressed as the summation of local

The model parameters in the EAM many-body potential
electron density
Element Ec (eV) fe fe (eV) a b g
ri = % f(r) (2)
j"i
Cu 3.54 0.30 0.59 5.09 5.85 8.00
Ni 4.45 0.41 0.74 4.98 6.41 8.86 where ri is the electron density at atom i due to atom j
as a function of the distance between them. Both f(r)
and f(r) are given in form of Born–Mayor functions:

where F(ri ) is the energy to embed an atom into the

  n
f(r)= fe exp − b
r
(3)

  n
re − 1
local electron density provided by the remaining atoms;
f(r) is the pair potential representing an electron-static r
f(r)= fe exp − g (r5rc) (4)
interaction. We took Johnson’s empirical functions, re − 1

Fig. 1. The pair correlation function g(r) at different temperature.

118 L. Hui et al. / Materials Science and Engineering A271 (1999) 116–121

1. At 2000 K, the liquid state of Cu70Ni30 is well

equilibrated by MD runs of time intervals from
initial random configuration.
2. The equilibrated liquid was gradually cooled to 400
K at a cooling rate of 4× 1013 K s − 1.
3. The liquid state at 400 K was gradually heated to
2000 K again at a heating rate of 4× 1013 K s − 1.
4. Finally, the structure and its evolution were profiled
in a rapid solidification and heating process.
The atomic configurations were recorded at each
fixed temperature interval in each cooling and heating,
The structure of three states (liquid, super cooled liquid
and glass) was analyzed using the pair correlation
function (PCF) and pair analysis (PA) techniques. The
PCF was obtained after 6×103 time intervals of com-
putations for each configuration. The results by PA
were averaged over 20 configurations.

Fig. 2. The bond orientation order parameter Q6 at different temper-

ature. 3. Structural functions

where fe, fe, a, b, g are model parameters respectively 3.1. Pair correlation function [12]

@ A
to be suitable to the bulk solid properties, rc is cut-off
distance, re is the nearest separation between two atoms The partial PCF g(r) is conventionally defined by
at equilibrium. By use of Rose relation [6], we can Ni

obtain the embedded function F(r) as % naj (r)

  n  
l3 a=1
gij =
a r r a/b
r g/b
Ni Nj 4pr 2Dr
F(r)= − Ec 1− ln −fe (5)
b re re re
 
where gij is the probability of finding an atom in the
VB 1/2 range from r to r+ Dr, l is the cell length of the box in
a=3 , (6) the simulation. Ni and Nj are the respective number of
Ec
atoms i and j in the system and Naj is an averaged
Ec number of j-type atoms around i-type atoms in the
fe = , (7)
V sphere shell ranging from r to r+Dr, Dr is the step of
Ec computation.
f= (8)
6
3.2. Bond orientation order parameters [13]
where Ec is the coherent energy, and the model parame-
ters in this paper are listed in Table 1 [7,8] In this paper, the bond orientation order parameters
are adopted to measure both local and extended orien-
tation symmetries in computer-generated models of
2. The simulation process dense liquid and glass. Our analysis starts from associ-
ating a set of spherical harmonics with every bond
MD simulation method under constant pressure and joining an atom to its near neighbors. The ‘bonds’ we
constant temperature was adopted [9]. The internal define here are not chemical bonds but lines that come
pressure can be obtained from the Virial theorem [10]. from some convenient assignation of near neighbors.
The simulation was performed in a cubic cell of 500 Any bond is assigned a set of numbers.
atoms at zero external pressure. Periodic boundary
Qlm = Ylm (u(r),f(r))
conditions were assumed to simulate the bulk geometry.
The equations of motion were solved by the Verlet where the Ylm (u,f) are spherical harmonics, u(r) and
algorithm [11] with a time interval of 5 ×10 − 15 s. Here f(r) are the polar angles of the bond measured in some
the damped-force method was used to decrease temper- reference coordinate system.
ature by forcing bath temperature to change linearly at In our numerical studies, we shall often consider
every time interval. In our study, we have researched averaged quantities, for example, Qlm =ŽQlm (r),
the following types of computation on liquid Cu70Ni30 where the average is taken over some suitable set of
alloy. bonds in the sample. The first non-zero averages (other
 L. Hui et al. / Materials Science and Engineering A271 (1999) 116–121
than Q00) occur for l =4 in samples with cubic symme-
try and for l =6 in icosahedrally oriented systems.
Because for a given l, the Qlm can be scrambled drasti-
cally by changing to a polar coordinate system, it is
important to consider rotationally invariant combina-
tions, such as, Ql = (4p/(2l +1))lm = − 1 Qlm 2 n
1/2
. The
Ql is the key parameter to some cluster ‘shape spec-
troscopy’ in liquid and glass.
3.3. Pair analysis technique [14,15]
Structural analysis by the PA technique is also
demonstrated in our work. In this technique, pairs of
atoms are classified first, by whether or not they are
near neighbors and secondly, by the numbers of near-
neighbor relations among the shared neighbors. Two
atoms are regarded as the near neighbors if they are
within a certain cut-off distance and they are called a
bond pair. Here the cut-off distance is that between the
first minimum in the PCF and the origin.
Honeycut and Anderson used four parameters i, j, l,
and m to distinguish bonded pairs. If any atom system
A –B forms a bond, i= 1; otherwise i is 2. The j denotes
the number of near neighbors which form bonds with
both atom A and atom B. The l represents the number
of bonds formed among near neighbors which form
bonds with both atom A and atom B. The m represents
the way in which bonds are formed between near
neighbors which form bonds with both atom A and
atom B. That is, if these bonds link in turn, m= 1
otherwise m = 2. Based on the PA formula, the five-fold
symmetry bond, plus other different kinds of bond, can
be obtained by computer. The 1551 bonded pairs repre-
sent the two root pair atoms with five common neigh-
Fig. 3. The relative number of bonded pairs at different temperature.
119
bors that have five bonds which form a pentagon of
near neighbor contacts. Similar analysis holds for 1441
bonded pairs,1661 bonded pairs, etc. It is necessary to
point out that the number of 1551 bonded pairs in
liquid is a direct measurement of the degree of icosahe-
dral ordering. The relative number of 1541 and 1431
bond pairs are used to describe the characterization of
short range order in the liquid, super cooled liquid and
amorphous state. The 1441 and 1661 bonded pairs are
corresponding to bcc crystalline structure. The 1421
bonded pair are characteristic of fcc-type, 1421 and
1422 bonded pairs are characteristic of hcp-type
crystalline.
4. Result and discussion
The structure of the system in the cooling and heat-
ing can be checked by examining some appropriate
physical properties. The first physical property which
comes to mind is the PCF g(r) of atomic positions. The
partial and total g(r) in cooling and heating are shown
in Fig. 1. Obviously, in the rapid cooling process,
gCu – Cu(r) (as shown in Fig. 1a) reaches maximum which
lies between those of gCu – Ni(r) (Fig. 1b) and gNi – Ni(r)
(Fig. 1c). The first peaks of gNi – Ni(r) are much lower
than those of gCu – Ni(r) and gCu – Cu(r). This means that
there is a small possibility that Ni atoms occupy the
near-neighbor coordination shell around the Ni atom.
As the temperature becomes lower, the second peaks of
g(r) split into two sub-peaks. The lower the tempera-
ture becomes, the more distinctly the splitting shows.
This indicates that the system is in a glassy state below
800 K. In the quick cooling, the height of the first peaks
of g(r) at high temperature is less than those of the first
120 L. Hui et al. / Materials Science and Engineering A271 (1999) 116–121
peaks of g(r) at a low temperature. The lower the
temperature, the higher the peak.
It means that the ordering degree of the liquid
metal becomes greater as the temperature decreases.
In the heating process from 400 to 2000 K the height
of the peak of g(r) in quick heating becomes greater
than that of g(r) in quick cooling at the same temper-
ature. The splitting of the second peaks of g(r) in the
quick heating is more distinct than that in the quick
cooling at the same temperature. The third peaks g(r)
at 600 and 800 K begin to split into two sub-peaks in
the quick heating. This is the result of the relaxation
of the amorphous.
The bond orientation order parameters are used to
describe the symmetry of the liquid. The result is dis-
played in Fig. 2. In the cooling process, the orienta-
tion order parameter Q6 (solid line) takes monotonic
increase until the temperature drops to 400 K corre-
sponding to the glass transition. It means that the
degree of the icosahedral ordering is strengthened un-
der the quick cooling conditions. However, when the
amorphous at a temperature of 400 K is heated to
2000 K in the case of a heating rate of 4 × 1013 K
s − 1, the value of the Q6, icos drops to zero at a tem-
perature of 600K and the value of Q6, icos keeps con-
stant zero from a temperature of 600 – 2000 K. It
means that the quick heating process destroys the
icosahedral ordering degree in the amorphous. The
value of the Q6, tol and Q6, def increases to 0.5 or so at
a temperature of 600 K and then begins to drop until
the temperature increases to 2000 K. Except for the
value of the Q6, icos, the values of the Q6, tol and Q6, def
possess larger values under the quick heating condi-
tions than those under the quick cooling conditions.
Various bonded pairs, such as 1551,1541,1421,1422
and 1661,1441 were counted in the system under con-
sideration. The number of other bonded pairs is small
enough to be disregarded. In terms of PA formula,
these results are displayed in Fig. 3. In the case of a
cooling rate of 4×1013 K s − 1, this relative number of
1551 bonded pairs takes monotonic increasing until
the temperature drops to1200 K and then begins to
drop until the temperature reduces to 400 K. The two
rela-tive numbers of 1541 and 1431 bonded pairs in-
crease as the temperature drops although there are
some slight fluctuations in general.
In the case of the quick heating conditions, the
relative number of bonded pair 1551 at a temperature
of 400 K falls suddenly to about zero and then begins
to increase at a temperature of 600 K until the tem-
perature increases to 2000 K. The two relative num-
bers of 1541 and 1431 bonded pairs at a temperature
of 400 K drop respectively to 7.5 and 3.5 or so at a
temperature of 800 K and then begins to increase.
The result of Fig. 3a illustrates that the quick heating
process does not prefer the existence of the 1551, 1541
and 1431 bonded pairs. On the contrary, the quick
heating process prefers the increasing of the 1661 and
1441 bonded pairs corresponding to bcc crystalline
structure. The total relative numbers of 1661 and 1441
come up to 70% at a temperature of 600 K. It is
demonstrated that the bcc crystalline structure is in
predominant position in the system when the system
has been quick heated.
It can also be seen that the relative number of 1421
bonded pair corresponding to fcc crystalline structure
increases as the temperature decreases in the quick
cooling. However, in quick heating the glass, the rela-
tive number of 1421 bonded pair jumps suddenly to
45% or so at 600 K and then falls to zero at a
temperature of 800 K. There are no dramatic changes
in the following heating process. The relative number
of 1422 bonded pair characteristic of hcp-type crys-
talline structure has the same inclination as the 1421
bonded pair characteristic of fcc-type crystalline struc-
ture. The Fig. 3c proves that quick heating process
has no serious effect on the micro structure of the
system.
5. Summary
It can be concluded from the result of Fig. 1 that
the ordering degree of the liquid or glassy system is
higher under the conditions of quick heating than it is
under the conditions of quick cooling. That is to say,
some features of ordering degree showing at a lower
temperature will be kept to the following process of
the quick heating at a higher temperature.
The quick heating process prefers existence of bcc-
type cluster and does not prefer the existence of bond
pairs 1551and 1541.
The pair correlation function reveals the distribu-
tion and packing of the atoms in the quick cooling
and heating. In addition, the PA technique gives a
detailed description concerning the structure of liquid,
super cooled liquid and amorphous of Cu70Ni30 al-
loy.
The micro-structure configuration of liquid metal is
affected by temperature and rates of cooling or heat-
ing. In order to obtain high-quality material, we
should pay serious attention to the liquid structure
and its cooling and/or heating conditions.
References
[1] S.D. Chen, T. Egami, V. Vitek, Phys. Rev B37 (1988) 2440.
[2] D.T. Kulp, G.J. Ackland, M. Sob, V. Vitek, T. Egami, Model
Simul. Mater. Sci. Eng. 1 (1993) 315.
[3] T. Tomida, T. Egami, Phys. Rev. B52 (1995) 3290.
[4] R. Car, M. Parrnello, Phys. Rev. Lett. 55 (1985) 2471.
[5] M.S. Daw, M.I. Baskes, Phys. Rev. B29 (1984) 6443.
 L. Hui et al. / Materials Science and Engineering A271 (1999) 116–121 121

[6] J.H. Rose, J.R. Smith, F. Guinea, J. Ferrante, Phys. Rev. B29
(1984) 2963.
[7] R.A. Johnson, Phys. Rev. B39 (17) (1989) 12554.
[8] J. Mei, J.W. Davenport, G.W. Fernando, Phys. Rev. B43 (6)
(1991) 4653.
[9] D.J. Evans, G.P. Morriss, Chem. Phys. 77 (1983) 63.
[10] L.D. Laudul, E.M. Lifshitz, Statical Physics, Pergamon, Oxford,
1970.
[11] M.P. Allen, Tildeley, Computer Simulation of Liquids, Oxford
University Press, Oxford, 1987.
[12] Y. Waseda, The Structure of Non-crystalline Materials, Liquid
and Amorphous, McGraw-Hill, New York, 1980.
[13] P.J. Steinhardt, D.R. Nelson, M. Ronchetti, Phys. Rev. B28 (2)
(1983) 784.
[14] D.R. Nelson, T. Toner, Phys. Rev. B24 (1981) 363.
[15] J.D. Honeycutt, H.C. Anderson, J. Phys. Chem. 91 (1987) 4950.