Vacuum 97 (2013) 30e35

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Vacuum
journal homepage: www.elsevier.com/locate/vacuum

Cooling rate dependence of the icosahedral order of amorphous CuNi

alloy: A molecular dynamics simulation
Fatih Ahmet Celik*
Bitlis Eren University, Faculty of Arts and Sciences, Physics Department, 13000 Bitlis, Turkey

a r t i c l e i n f o a b s t r a c t

Article history: In this study, a molecular dynamics (MD) simulation is carried out to obtain glass formation and
Received 11 December 2012 icosahedral order for Cue%50Ni model alloy system with 10,976 atoms based on embedded atom model
Received in revised form (EAM) during the cooling processes. The structural development and icosahedral order of alloy system
3 April 2013
are analysed with the radial distribution function (RDF), the bond orientational order parameters and
Accepted 4 April 2013
HoneycutteAndersen (HA) bond-type index method. By looking into the amorphous-type bonded pairs
within the atomic clusters and by analysing bond orientational order parameters (icos Q6 and icos W c ),
6
Keywords:
the icosahedral order is investigated under different cooling processes for the model alloy system.
CuNi alloy
Molecular dynamic simulation
Ó 2013 Elsevier Ltd. All rights reserved.
HoneycutteAndersen (HA) bond-type index
method
Bond orientational order parameters

1. Introduction microscopic mechanism in formation and the structural properties

Amorphous materials are thermodynamically metastable and it
is important to understand the structural stability of these mate-
rials from both the fundamental and practical points of view [1e3].
The main problem for the stabilization of amorphous solids is
caused by the difficulty of controlling the cooling conditions, which
is conducted by optimizing the parameters of thermal process, such
as temperature and cooling conditions [4,5]. In the process of so-
lidification, the cooling rate and quenched conditions play a very
important role. If a material is quenched fast enough, the end
product will be an amorphous solid; if it is quenched slowly, the
end product will be a crystalline solid [6,7]. Especially, the CueNi
alloy is a type of solid solution alloy with infinite solubility which
has a large super-cooling tendency. It has a good level of sea-water
corrosion and halo bios adhesion resistibility. These properties of
the CueNi alloy are a result of the formation of a homogeneous film
during its exposure to sea-water [8].
Although the process of quenching of a metal from the liquid to
the amorphous phase has been investigated many times, the
liquideamorphous transition and the order of amorphous phase
have not been studied very well. In recent years, great effort has
been devoted to the understanding of the short-range order, the
* Tel.: þ90 (0434) 228 5270; fax: þ90 (0434) 228 5271.
E-mail address: facelik@beu.edu.tr.
of the amorphous metals. Especially, the nature of the icosahedral
order of amorphous materials has been of fundamental interest, but
it is poorly understood when compared to what is known about the
well-defined crystalline materials [9,10]. Recently, direct experi-
mental evidence about the icosahedral order has been obtained
from X-ray and neutron studies on levitated elemental and alloy
metallic liquids by using different techniques. The results of these
experimental observations are in agreement with the recent
modelling studies performed by means of the required parameters
obtained from the methods that are used in the present work [11].
Molecular dynamics (MD) simulations provide important com-
plementarities to the experimental investigations, helping to un-
derstand the short-range local atomic order and icosahedral order
that was set forth with recent detailed work [11]. The consistency of
the results obtained from the MD simulations with the experi-
mental values; depend tightly on the potential energy functions
which are used to model the relevant system. On the other hand,
the determination of the potential parameters, and especially of the
cross potential functions in the alloy systems, is still a problem [12].
One of the most useful potential energy methods is the embedded
atom method (EAM) based on the many-body interactions pro-
posed by Daw and Baskes [13]. In particular, the icosahedral order
of the amorphous phase has been estimated by means of bond
orientational order parameters and the HoneycutteAndersen (HA)
methods based on the MD simulation by using EAM. Recently, re-
searchers have investigated the cooling rate effect on icosahedral

0042-207X/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.vacuum.2013.04.004
 F.A. Celik / Vacuum 97 (2013) 30e35 31

order for other systems such as Ni, Al, Ag, NieAl, AgeCu by using
the molecular dynamics simulation [14e17].
In the present work, my main aim is to investigate the cooling
rate effects on the structural properties and on the icosahedral
order of amorphous CueNi model alloy system by using bond
orientational order, HA method and radial distribution function
(RDF). The MD method proposed by Parrinello and Rahman for the
NPT ensemble is used to determine the rapid solidification of
amorphous CueNi binary alloy system. Cooling rate effects on the
structural properties and icosahedral order of the CueNi alloy
modelled by SuttoneChen type potential are also studied.
2. The method of calculations
2.1. Potential energy function
Inter-atomic potentials are very important for the systems
which have been modelling in the atomic scale. In the present study
an SCEAM potential function is used. The total energy of a crystal
with N atoms in the SCEAM methodology is given by [18,19]:
2 3
X X 1j X  
4 p ffiffiffiffi
ET ¼ Ei ¼ ε f rij  ci εii ri 5
i i
2 jsi ij
simulation method can be found from literature [22]. The sim-
ulations were performed with the system consisting of 10,976
atoms in a cubic box with periodic boundary conditions along all
the three directions. The fcc structure for the Cue%50Ni model
alloy systems has been chosen as the starting configuration for
the MD computer simulation. The potential functions were
truncated at a cut-off distance of 2.2 ACuCu. The temperature of
the system has been controlled by rescaling the atomic velocities
at every two integration steps. The equation of motion is
numerically integrated by the Gears’ 5th order predictore
corrector algorithm. The molecular dynamics time step was set
up as 5.509 fs.
The model alloy system is run for 50,000 MD step at 1400 K to
guarantee an equilibrium liquid phase to obtain the initial config-
uration for cooling processes. For the quenching conditions,
the temperature of system is decreased with three different
cooling rates of Q1 ¼ 1.8  1012 K/s, Q2 ¼ 1.8  1013 K/s and
Q3 ¼ 3.6  1013 K/s, respectively. In order to obtain the position and
velocity of particles as well as other parameters of the system, the
quenched systems have been further relaxed for 500 time steps at
each desired temperatures and the instantaneous spatial co-
ordinates of each atom are recorded for analysis below.
(1)
3. Structural analysis

where rij is the separation between atom i and j, c is a positive 3.1. Radial distribution function
dimensionless parameter, ε is a parameter with the dimensions of
energy. f(rij) is a pairwise repulsive potential Structural analysis is examined from the radial distribution
!n functions (RDF), g(r), which is given as
  Aij
f rij ¼ (2) *P +
rij   N
V i¼1 ni ðrÞ
g r ¼ 2 : (6)
N 4p r 2 Dr
between atoms i and j (arising primarily from Pauli repulsion be-
tween the core electrons), while the metallic bonding is captured in
Here r is the radial distance, ni(r) is the coordination number of
a local energy density, ri, associated with the atom i and defined as
atom i separated with r within Dr interval, and bracket denotes the
!m time average [22].
X   X Aij
ri ¼ r rij ¼ (3)
rij
jsi jsi 3.2. The HoneycutteAndersen (HA) method
Here A is a parameter with the dimensions of length; m and n
It is known that the pair analysis technique can be used to
are positive integers. The potential parameters for different types of
describe the local atomic arrangements and short-range order in
atoms in an alloy system can be calculated from LorentzeBerthelet
the structures [23]. In the technique the local structure is clas-
[20]:
sified by using a sequence of four integers (ijkl) which have the
Ai þ Aj ni þ nj mi þ mj following meanings; the first integer (i) is 1 when the atoms in
Aij ¼ Aji ¼ ; nij ¼ nji ¼ ; mij ¼ mji ¼ the root pair, selected atomic pair within a desirable cut-off dis-
2 2 2
tance, are bonded, otherwise it is 2. The second integer (j) is the
(4)
number of nearest neighbour atoms shared in common by the
pffiffiffiffiffiffiffiffiffiffi root pair. The third integer (k) is the number of next nearest
εij ¼ εji ¼ εi εj (5) neighbour bonds among the shared neighbours. The fourth
The potential parameters for CueCu, NieNi and CueNi atomic integer (l) is needed to differentiate between the cases when the
interactions have been given in Table 1 as seen in Ref [21]. first three indices are the same but the bond geometries are
different.
It is believed that this method is convenient to analyse the
2.2. Simulation and application process
geometric characteristics of an atomic cluster. If different two types
of atoms form a bond AeB, then the first index is i ¼ 1, otherwise
In the MD method used here, both the size and the shape of
i ¼ 2, A and B atoms represent root pair. For example, the 1551
the MD cell are variable. More detailed expositions of MD
bonded pairs represent the two root pair atoms with five common
neighbours that have five bonds forming a pentagon of nearest
Table 1 neighbour contact. In this case, some typical bonded pairs are
The SuttoneChen EAM potential parameters for CuNi model alloy system [21]. examined to understand the local structures of system. While the
Interaction A (
A) ε (eV) n m 1551 bonded pairs have five-fold symmetry, and the ratio of 1551
bonded pairs gives a measure of the degree of ideal icosahedral
CueCu 3.61 1.2382  103 9 6
NieNi 3.52 1.5707  103 9 6
(icos) order, the 1431 and 1541 bonded pairs are related to defective
icos [23].
32 F.A. Celik / Vacuum 97 (2013) 30e35

3.3. Bond orientational order parameter 8

(a)
In addition, recently, the calculation of the bond orientational
order parameters has also been used to determine the local struc- 1400 K
tures of the atoms in the MD cell [24,25]. The formalism is basically 6
300 K
based on that the nearest neighbours of each atom in the MD cell,
which constitute a cluster, is determined by using a cut-off distance
taken from the minimum of the RDF between the first and second.
The spherical coordinates of each bond in the cluster is calculated

g(r)
from 4

Qlm ðrÞhYlm ðqðrÞ; fðrÞÞ (7)

where Ylm(q,f) are spherical harmonics, and q(r) and f(r) are the
polar and azimuthal angles of the bond measured with respect to 2
some reference frame. The local structure around particle i is given
by
Nb ðiÞ
 1 X
Q lm i h Qlm ðrÞ (8) 0
Nb ðiÞ 2 3 4 5 6 7
j¼1
r10/nm
where the sum runs over all Nb(i) bonds that particle i has with its 5
neighbours. On the other hand, the global orientational order pa- (b)
rameters can be obtained from the average of Q lm ðiÞ over all N
particles, i.e., 1400 K
4
PN   300 K
i¼1 Nb i Q lm i
Q lm ¼ PN (9)
i¼1 Nb ðiÞ
3
The second-order invariants (Ql) and third-order invariants (Wl),
g(r)

respectively, are determined from the relations

" #1=2
4p X
l  2
Ql h Q  (10) 2
lm
2l þ 1
m ¼ l

X  
l l l
Wl h  Q lm1 Q lm2 Q lm3 ; 1
m1 m2 m3
m1; m2; m3
m1 þ m2 þ m3 ¼ 0
(11) 0
2 3 4 5 6 7
where the parameters in square brackets are the Wigner 3j-sym- r10/nm
bols. The reduced order parameters are independent strictly on the 5
definition of the nearest neighbours, and can be calculated from (c)

c h" Wl 1400 K
W l #3=2 (12) 4
Pl  2 300 K
Q 
m ¼ l lm

Here since l takes only even values spherical harmonics are 3

c are much less sensitive
invariant under inversion. The values of W l
g(r)

to definitions of the nearest neighbour cut-off than that of Ql.

However, it is appreciated that the two-bond order parameters Q6
and Wc are generally convenient to identify icosahedral clusters 2
6
accurately [26e29].

1
4. Results and discussions

Fig. 1a demonstrates the RDF curves at 1400 K and 300 K under

the quenching condition Q1. At the highest temperature, the system 0
shows the typical features of a liquid phase. At the lowest tem- 2 3 4 5 6 7
perature, it can be seen clearly from the RDF curves that the system r10/nm
shows the typical features of a crystal phase. Hence, the first peak of
Fig. 1. The RDF curves at 300 K and 1400 K temperatures. (a) Q1 cooling rate; (b) Q2
g(r) becomes higher and a new peak appears between the first and cooling rate; and (c) Q3 cooling rate.
 F.A. Celik / Vacuum 97 (2013) 30e35 33

Table 2 IcosQ6
The values of bond order parameters of ideal some typical clusters or their bulk 0,65 IcosW6 -0,10
systems.

Structure Q4 Q6 c
W c
W 0,60 -0,11
4 6

ICOS 0 0.66332 0 0.16975

0,55 -0,12

IcosW6
IcosQ6
0,50 -0,13
the second peaks when compared with that of the highest tem-
perature. Fig. 1b and c show the RDF curves at 1400 K and 300 K
0,45 -0,14
under the quenching condition Q2 and Q3. As shown in the figures,
the system behaves as if it is in the amorphous phase when the
temperature reaches 300 K. The splitting of the second peak at 0,40 -0,15

300 K was also observed in earlier studies on metallic glass, which

was defined as a common feature of the amorphous materials [30].
This indicates that no momentous structural change takes place
under the faster cooling rate and the rearrangement of atoms is
inclined to be in short-range order. This situation was also agreed in
earlier studies [31e34]. However, it should be noted that the RDF
cannot provide an accurate identification of the structural changes
as it only provides a general description of the cooling processes
based on the liquid structure. In this study, the local structure and
the rearrangement of atomic bonded pairs were observed together
with the bond orientational order parameters were observed using
the HA method in order to identify the structural changes during
the cooling processes.
It is also known that bond orientational order parameters,
especially Q6 and Wc , are important to detect the icosahedral order.
6
The values of these order parameters are given in Table 2 for an
ideal icosahedral cluster [24].
The quantity of icos Q6 has an important role in terms of the
c is a sensitive value of orienta-
shape of the cluster, while icos W
6
tional order of symmetry for an ideal icosahedral cluster. Bond
orientational order parameters are plotted as a function of tem-
perature during the three cooling conditions in Figs. 2e4. In the Q1
cooling process, the absolute values of the bond orientational order
parameters of icos Q6 and icos W c increase with the decreasing
6
temperature. At the temperature of 800 K, the values of these pa-
rameters suddenly change and reach zero below this temperature
as seen in Fig. 2. This means that no icosahedral order can be
observed at low temperatures because the system has been
transformed into the crystal phase under the slow quenching
process. During the Q2 cooling process, the absolute values of icos
Q6 and icos Wc increase with the decreasing temperature. While a
6
few icosahedral clusters appear in the liquid phase during the
0,35 -0,16
200 400 600 800 1000 1200 1400
T(K)
Fig. 3. Bond orientational order parameters as a function of temperatures during Q2
cooling process.
cooling process, many more clusters are observed with the
decreasing temperature as the fast cooling rate leads to increasing
icosahedral order. The values of Q6 and W c 6 are 0.6633
and 0.169754 for an ideal icosahedral cluster, respectively. As can
be seen in Fig. 3, both the values of icos Q6 and icos W c 6 are very
close to an ideal icosahedral order at 300 K in the amorphous phase.
c6
In the Q3 cooling process, the absolute values of icos Q6 and icos W
increase with the temperature decreasing, but these values are not
very close to an ideal icosahedral order at 300 K in the amorphous
phase as seen from Fig. 4. This indicates that with a faster cooling
rate the number of ideal icosahedral clusters in the system becomes
much less when compared to the number of defective icosahedral
clusters and other non-crystal structures.
For a more reliable description of the mechanism of the struc-
tural transformation and the icosahedral order during the cooling
process, a quantitative evaluation of the atomic structure is
required. A local arrangement achieved with a short-range order
analysis technique, i.e. HA analysis, has been used in this study for
this purpose.
Fig. 5 shows the relative numbers of 1551, 1541, 1431 and 1331
for bonded pairs as a function of the temperature during the
cooling process Q1 (slow quenching condition). It can be seen from
Fig. 5 that the 1551, 1541, 1431 and 1331 bonded pairs which are

0,7 0,02 0,58

IcosQ6 IcosQ6
IcosW6 0,56 IcosW6 -0,10
0,6 0,00
0,54
-0,02
0,5 -0,11
0,52
-0,04
0,4 0,50 -0,12
-0,06
0,48
IcosW6

IcosW6
IcosQ6

IcosQ6

0,3
-0,08 -0,13
0,46
0,2 -0,10 0,44
-0,14
-0,12 0,42
0,1
0,40
-0,14 -0,15
0,0
0,38
-0,16
-0,1 0,36 -0,16
200 400 600 800 1000 1200 1400 200 400 600 800 1000 1200 1400
T(K) T(K)

Fig. 2. Bond orientational order parameters as a function of temperatures during Q1 Fig. 4. Bond orientational order parameters as a function of temperatures during Q3
cooling process. cooling process.
34 F.A. Celik / Vacuum 97 (2013) 30e35

25 15 25 22

20 24 20

10 18
15 23

% 1551

% 1551
% 1431

% 1431
16
10 22
5 14
5 21 12

0 0 20 10
15 0.8 24 1

22 0.8
0.6
10 20
% 1541

% 1331

% 1541

% 1331
0.6
0.4 18
0.4
5 16
0.2
14 0.2

0 0 12 0
200 400 600 800 1000 1200 1400 200 400 600 800 1000 1200 1400 200 400 600 800 1000 1200 1400 200 400 600 800 1000 1200 1400
T(K) T(K) T(K) T(K)
Fig. 5. Relative number of amorphous-type bonded pairs during Q1 cooling process. Fig. 7. Relative number of amorphous-type bonded pairs during Q3 cooling process.

amorphous-type are dominant at 1400 K. But, the relative numbers

of these bonded pairs decrease with the decreasing temperature. At
a temperature of 800 K, the relative numbers of these bonded pairs
descend dramatically all of a sudden, and tend to become zero with
a further decrease in temperature. This indicates that the system
has been transformed into crystal phase and therefore neither an
ideal nor a defective icosahedral order appears in the system.
Figs. 6 and 7 show how the relative number of various
amorphous-type bonded pairs in a model alloy system can change
with the temperature during the cooling processes Q2 and Q3 (fast
quenching conditions). It can be seen from Fig. 6 that above the
temperature 800 K, there is a relative number of 1551 bonded pairs,
which corresponds to a gradual increase in the ideal icosahedral
clusters as the temperature drops. But, below the temperature
800 K the number of 1551 bonded pairs decreases suddenly as the
temperature drops. On the other hand, while there are relative
numbers of 1431 and 1541 bonded pairs, which correspond to an
increase in the defective icosahedral clusters, the 1331 bonded
pairs tend to be removed from the system during the cooling
process Q2. Fig. 7 shows the relative numbers of various bonded
pairs as a function of temperature during the cooling process Q3. It
can be seen from Fig. 7 that below the temperature 500 K while the
relative numbers of 1541 and 1431 bonded pairs increase, the
relative number of 1551 bonded pairs decreases. On the other hand,
the relative number of 1331 bonded pairs also moves to zero with
the temperature decreasing.
Besides this, at the end of the Q2 cooling process and at 300 K,
while the 1541 and 1431 bonded pairs consist 20.65% and 20.94% of
the total number of the clusters in the system, respectively, the rate
of 1551 bonded pairs is only about 13.65%. But at the end of the Q3
cooling process and at 300 K, while the rates of 1541 and 1431
bonded pairs in the system become 22.67% and 24.88%, respec-
tively, the rate of 1551 bonded pairs becomes approximately
10.84%. This indicates that the amount/percentage of the ideal
icosahedral order decreases in the system with an increase in the
cooling rate at the amorphous phase. This result is in good agree-
ment with the change of the bond orientational order parameters
observed in Figs. 3 and 4.

22 22 5. Conclusion
20
We have performed an MD simulation to study the transition
18 from the liquid state to the crystal and amorphous states of the Cue
% 1551
% 1431

21 Ni model alloy system. The icosahedral order can be determined by

16
using the radial distribution function, the bond orientational order
14 parameters and the HA pair analysis method under different
cooling rates (slow and fast quenched). The present simulations
20 12 have demonstrated that the cooling rate plays a crucial effect on the
22 0.8 icosahedral order at the temperature of 300 K. The absolute values
of icos Q6 and icos Wc bond order parameters are zero at 300 K
6
20
0.6 under a slow cooling rate (Q1) and, correspondingly, amorphous-
type bonded pairs do not appear at this temperature. Under fast
% 1541

% 1331

18
0.4 quenched conditions (Q2 and Q3), the absolute values of icos Q6 and
16 icos Wc bond order parameters decrease with the increasing
6

14
0.2 cooling rate. In addition to this, the number of 1551 bonded pairs,
which correspond to the ideal icosahedral clusters, decrease with
12 0 the increasing cooling rate. After all the results were examined, it
200 400 600 800 1000 1200 1400 200 400 600 800 1000 1200 1400
was concluded that the ideal icosahedral order decreases with the
T(K) T(K)
increasing cooling rate under a fast cooling condition at the
Fig. 6. Relative number of amorphous-type bonded pairs during Q2 cooling process. amorphous phase.
 F.A. Celik / Vacuum 97 (2013) 30e35
We believe that the methods used and the parameters provided
in this study will be very useful when similar studies are conducted
in different fields such as material science and the modelling of
nanostructured systems.
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