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Physica B 352 (2004) 156163

Simulation of Youngs modulus of single-walled carbon


nanotubes by molecular dynamics
Bao WenXing
a,b,
, Zhu ChangChun
a
, Cui WanZhao
a
a
School of Electronics & Information Engineering, Xian Jiaotong University, Xian 710049, PR China
b
The Second North-west Institute for Ethnic Minorities, Yinchuan 750021, PR China
Received 15 April 2004; accepted 13 July 2004
Abstract
Based on molecular dynamics (MD) simulation, the Youngs moduli of carbon nanotubes are studied. The inter-
atomic short-range interaction and long-range interaction of carbon nanotubes are represented by a second generation
reactive empirical bond order (REBO) potential and LennardJones (LJ) potential, respectively. The obtained potential
expression is used to calculate the total potential energies of carbon nanotubes. Three types of single-walled carbon
nanotubes (SWCNTs), armchair, zigzag and chiral tubules, are calculated, respectively. The computational results show
that the Youngs moduli of SWCNTs are in the range of 929.8711.5 GPa. From the simulation, the Youngs moduli of
SWCNTs are weakly affected by the tube chirality and tube radius. The numeric results are in good agreement with the
existing experimental results.
r 2004 Elsevier B.V. All rights reserved.
PACS: 61.48.+c; 62.20.Dc; 31.15.Qg
Keywords: Carbon nanotubes; Molecular dynamics; Youngs modulus; Potential function
1. Introduction
Since the rst report of carbon nanotubes
(CNTs) by Iijima [1], CNTs have got a lot of
attention because of their unique electronic and
mechanical properties. As a one-dimensional
structure, CNTs can be thought of as one sheet
or multiple sheets of graphene rolled into a
cylinder. They have single or multiple layers of
carbon atoms in the tube thickness direction,
called single-walled carbon nanotubes (SWCNTs)
or multi-walled carbon nanotubes (MWCNTs),
respectively. According to different chiral angles,
SWCNTs can be classied into zigzag (y=01),
armchair (y=301) and chiral tubule (01oyo
301) [2].
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doi:10.1016/j.physb.2004.07.005

Corresponding author. Institute of Vacuum Microelectro-


nics & Microelectromechanical System, School of Electronics &
Information Engineering, Xian Jiaotong University, Xian
710049, PR China. Tel.: +86-29-82668644; fax: +86-29-
82663957.
E-mail address: bwx71@163.com (B. WenXing).
There are some experimental studies of the
Youngs modulus of CNTs. Liu et al. [3] reported
the Youngs modulus of CNTs is 10.1 TPa with
the diameter increasing from 8 to 40 nm by
measuring resonance frequency of carbon nano-
tubes. Krishnan et al. [4] used TEM to observe the
vibration of an SWCNT at room temperature and
reported Youngs modulus of SWCNTs in the
range from 0.90 to 1.70 TPa, with an average of
1.25 TPa. Tombler et al. [5] used AFM to bend an
SWCNT and reported the Youngs modulus of
SWCNTs around 1.2 TPa. Yu et al. [6] conducted
nanoscale tensile tests of SWCNT ropes pulled by
AFM tips under a scanning electron microscope
and reported the Youngs modulus of SWCNT
ropes ranged from 0.32 to 1.47 TPa (mean
1002 GPa). Demczyk et al. [7] reported the
Youngs modulus of MWCNTs range from 0.8
to 0.9 TPa used TEM to bend an individual tubes.
There are also some theoretical studies for
predicting the Youngs modulus of CNTs. Lu [8]
used an empirical force-constant model to deter-
mine several elastic moduli of SWCNTs and
MWCNTs and obtained the Youngs modulus of
about 1 TPa. Li et al. [9] used molecular structural
mechanics method and obtained the Youngs
modulus of 1050750 GPa for MWCNTs. Jin et
al. [10] used MD and force-constant approach and
reported the Youngs modulus of SWCNTs to be
about 123677 GPa. Cornwell and Wille [11] used
the MD with the TersoffBrenner potential [12] to
obtain the Youngs modulus of SWCNTs about
0.8 TPa. Zhou et al. [13] used rst principles and
reported the Youngs modulus of SWCNTs to be
0.76 TPa. Vodenitcharova et al. [14] used con-
tinuum mechanics model to obtain the Youngs
modulus of SWCNTs about 4.88 TPa.
The objectives of this paper are to compute the
Youngs modulus of SWCNTs in detail using MD
simulation. MD simulations are the powerful tools
for investigation of the mechanical properties and
structural formation of carbon nanotubes. The key
to the MD simulation is to choose an exactly
potential energy model. A modied empirical
potential energy model is presented to describe
the bonding and nonbonding interaction. The
effects of carbon nanotubes structure, such as
tube radius and chirality on Youngs modulus of
SWCNTs, are examined. The accuracy and
stability of this method have been veried through
its application to several single layer and multi-
layer graphene sheets with different model sizes.
The computational results of the Youngs modulus
of SWCNTs are in good agreement with existing
experimental values. The organization of this
paper is as follows. In the second section, MD
simulation method and Verlet algorithm [15] are
described. The total potential energies and inter-
atomic forces are described in Section 3. The
expression of Youngs moduli of CNTs and
graphite are presented in Section 4. Results and
discussion are given in Section 5. The nal section
is the conclusions.
2. Molecular dynamics simulation method
In order to compare theoretical results with
experimental data, the ultimately investigated
model structures should represent stable or meta-
stable minimal energy congurations, which have
to be obtained by nite-temperature structure
optimization. The MD method has to rely on a
mathematical description of the total energy of the
system as a function of all atomic coordinates.
Focusing on the MD method, the Newtons
equation of motions for all atoms in the structure
has to be solved,
ma m
d
2
r
i
dt
2

jai
fr
ij
; 1
where a is the acceleration of particle i, r
i
is the
position of particle i, r
ij
is the distance between
particle i and particle j, f is the total force acting on
the particle i and determined by the gradient of the
total potential energy of the system, f=rE
tot
. In
order to achieve control of the energy conserva-
tion, it would be desirable to determine the atomic
positions and velocities at each simulation time
step. Standard Verlet algorithm has the obvious
disadvantage that the positions and velocities are
not synchronized. Swope presented a method of
directly getting the positions and velocities at each
simulation time step , and provided an easy way of
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B. WenXing et al. / Physica B 352 (2004) 156163 157
calculating the velocities into Verlet algorithm [16],
rt h rt hvt h
2
at=2; 2
vt h vt h at h at =2; 3
where r is the position, v is the velocity, a is the
acceleration at time t and time t+h, respectively,
and h is the time step. As can be seen from Eq. (3),
to calculate the new velocities requires the accel-
erations at time t and time t+h, respectively.
Before going into any MD simulation, the basic
principles of the calculation of the total potential
energies and inter-atomic forces have to be described.
3. Total potential energies and inter-atomic forces
The reliability of MD simulations techniques
depend on the use of appropriate inter-atomic
energies and forces. Inter-atomic energies and forces
were calculated generally using an empirical bond-
order potential that describes the covalent bonding
within both small hydrocarbon molecules and
CNTs. It has been successfully used to study the
structure and mechanical properties of CNTs
[12,1719]. However, the empirical bond-order
potential is short-ranged and does not include
long-range nonbond interactions. For instance,
long-range nonbond interactions can be either
van-der-Waals or Coulomb interactions, or both.
Van-der-Waals interactions normally have a weak
inuence on the overall mechanical behavior among
the atomic interactions of the CNTs [20]. A long-
range LJ potential is added to model the van-der-
Waals interactions that exist in the SWCNTs. It
becomes activated only after the short-ranged
REBO potential goes to zero. The total potential
energy of the system may be described by summing
bonding energy and nonbonding energy, E
tot
=E-
bonding+Enonbonding
. For CNTs and graphite, the
bonding term can be described precisely by REBO
potential, and the nonbonding term is mainly the
energy of van-der-Waals force.
The van-der-Waals force is most often modeled
using the LJ 612 potential function [21]:
E
LJ
r 4
s
r
_ _
6

s
r
_ _
12
_ _
; 4
where r is the distance between interacting atoms,
and s are the LJ parameters, for graphite and
CNTs, 0:00239 eV and s 0:341 nm [22],
respectively. The cutoff distance of LJ potential
is 2:5s; no interactions are evaluated beyond this
distance.
Brenner (2002) [23] presented a second-genera-
tion reactive empirical bond order (REBO) poten-
tial energy expression for hydrocarbons. In the
REBO potential, the total potential energy of the
system is given by
E
REBO

ji1
E
R
r
ij


b
ij
E
A
r
ij

_
; 5
where r
ij
is the distance between pairs of nearest-
nearby atoms i and j,

b
ij
is a many-bond empirical
bond-order term between atoms i and j that is
derivable from Huckel electronic structure theory.
E
R
and E
A
are the repulsive and attractive pair
terms, respectively,
E
R
r f
c
r1
Q
r
A exp ar; 6
E
A
r f
c
r

3
n1
B
n
e
b
n
r
; 7
where the parameters Q, A, a; B, b are used to t
the pairs terms, the values for all the parameters
are given in Ref [23]. The function f
c
is a cutoff
function, and is given by
f
c
r
1; roR
min
;
1 cos
prR
min

R
max
R
min

_ _ _ _
=2; R
min
oroR
max
;
0; r4R
max
_

_
8
where R
max
R
min
denes the distance over the
function goes from one to zero, for graphite
and CNTs, R
max
=0.26 nm and R
min
=0.17 nm,
respectively.
4. Expression of Youngs modulus
Youngs modulus is one of the important
characterizations of mechanical properties of
materials. In classical mechanics the Youngs
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B. WenXing et al. / Physica B 352 (2004) 156163 158
modulus is dened as
Y
s


F=A
DL=L
0
; 9
where s is the axial stress, is the strain, F is the
axial tensile force acted on the object, A is the
cross-sectional area of object, L
0
is the initial
length and DL is the elongation under the force F.
The load conditions of CNTs and graphite are
illustrated in Fig. 1, respectively.
After putting the tensile force on CNTs or
graphite in axial direction and calculating the
variation of the total potential and length, we can
get the Youngs moduli of CNTs or graphite.
5. Results and discussion
In this study, Youngs moduli of graphite and
SWCNTs are simulated using our molecular
dynamics simulation program. The MD simula-
tion program can run on FreeBSD 4.6 and
Windows 2000 platform. The simulation time step
is 1 fs. The Langevin thermostats are applied to
simulate and maintain temperature at 300 K. MD
simulation was performing approximately 5000
steps when the energy attained a constant mini-
mum value. A periodic boundary condition has
been used along the axial direction to mode the
tubes under axial loading.
5.1. Youngs modulus of graphite
The Youngs modulus of graphite is calculated
to verify the feasibility of the present method.
These calculations can provide useful information
for CNTs. In Eq. (9) the crossing-sectional area of
graphite is expressed as A NWdR; N is number
of graphene layers, W is width of graphite, the
interspacing between graphene layers dR are
assumed to be 0.34 nm.
The computational results of Youngs moduli of
graphite are showed in Tables 1 and 2, respec-
tively. There is a negligible difference of Youngs
modulus in Table 1 between the single layer of
graphite and multi-layers of graphite, and the
results in Table 2 are weakly affected by model size
of graphite. The average of Youngs modulus of
graphite is 1026.176 GPa, it is very close to the
experimental value of 1025.0 GPa [24,25]. Fig. 2
shows the variation of Youngs modulus of
graphite with number of graphene layers.
5.2. Youngs modulus of SWCNTs
Based on this method, the Youngs moduli of
SWCNTs are studied. Eq. (9) is still used for
calculating the Youngs modulus, the cross-sec-
tional area A of SWCNTs is 2pRdR; where R
stands for the tube radius and dR stands for the
wall thickness with a value of 0.34 nm [5,8]. Three
types of SWCNTs, armchair, zigzag and chirality,
are considered. By scaling atomic positions along
the axial direction, the variation of the total energy
and variation of tube length are calculated.
The stressstrain curve of armchair (8, 8)
SWCNTs is obtained and given in Fig. 3. It is
seen in the gure that the elastic limit is at the
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Fig. 1. Load conditions of graphite and SWCNTs.
B. WenXing et al. / Physica B 352 (2004) 156163 159
strain value of 0.08. Beyond the elastic limit, the
stress-strain curve deviate from a straight line.
Computational results of Youngs modulus of
SWCNTs for different tube radius are shown in
Fig. 4. There is a slight difference between the
trends of variation in Youngs modulus of arm-
chair and zigzag SWCNTs in Fig. 4. The Youngs
modulus of chiral SWCNTs is slightly lower than
those values of armchair and zigzag. The differ-
ence between maximum and minmum Youngs
modulus values is about 30 GPa. The effect of the
chiral angle on the Youngs modulus of SWCNTs
is shown in Fig. 5. With the variation of chiral
angles, the Youngs modulus value is slightly
uctuated from 904 to 935 GPa. The effect of tube
radius and tube chirality on Youngs modulus of
SWCNTs is very weak.
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Table 1
The variation of Youngs modulus of Graphite with number of
graphene layers
Number of
graphene layers
Y (GPa) (present
prediction)
Y (GPa)
(experimental
value)
1 1030.530
2 1032.033
3 1033.771 1025.000
4 1022.156
5 1012.390
Average 1026.176
Model size: height is 10.508 nm, width is 1.107 nm.
Table 2
The variation of Youngs modulus of graphite with model size
Height (nm) Width (nm) Y (GPa)
16.898 2.336 1012.230
8.378 0.861 1061.025
33.938 1.107 1036.707
16.898 1.107 1033.246
10.508 1.107 1030.530
Fig. 2. Youngs modulus of graphite.
Fig. 3. The curve of variation of axial stress s with the axial
strain (armchair (8,8)).
Fig. 4. Youngs modulus of SWCNTs for different tube radius.
B. WenXing et al. / Physica B 352 (2004) 156163 160
In order to compare numerical results with
other predictions of Youngs modulus, all the
computational results in this study are given in
Tables 3 and 4, respectively. Table 3 lists the
values of Youngs modulus of armchair, zigzag,
chiral SWCNTs with different tube radius. Table 4
lists the values of Youngs modulus for different
chiral angers. The present approach gives slightly
lower values of Youngs modulus than those of
reported in [810,26]. The average of Youngs
modulus of SWCNTs is 929.8711.5 GPa and
agrees very well with the existing experiment
values [35]. Comparisons between numerical
results and experimental results and other theore-
tical prediction of Youngs modulus of SWCNTs
listed in Table 5.
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Fig. 5. The effect of the chiral angle on the Youngs modulus of
SWCNTs.
Table 3
Youngs modulus of SWCNTs for different tube radius
(n, n) Number of atoms Radius (nm) Length (nm) Y (GPa)
Armchair
(8,8) 1168 0.542 8.854 934.960
(10,10) 1460 0.678 8.854 935.470
(12,12) 1752 0.814 8.854 935.462
(14,14) 2324 0.949 10.084 935.454
(16,16) 3040 1.085 11.560 939.515
(18,18) 3924 1.220 13.281 934.727
(20,20) 5000 1.356 15.250 935.048
Average 935.80570.618
Zigzag
(14,0) 840 0.548 6.230 939.032
(17,0) 1360 0.665 8.362 938.553
(21,0) 1890 0.822 9.428 936.936
(24,0) 2400 0.939 10.500 934.201
(28,0) 3080 1.096 11.563 932.626
(31,0) 3720 1.213 12.621 932.598
(35,0) 4900 1.370 14.757 933.061
Average 935.28772.887
Chirality
(12,6) 1344 0.525 9.023 927.671
(14,6) 1896 0.696 11.367 921.616
(16,8) 2240 0.828 11.279 928.013
(18,9) 2520 0.932 11.279 927.113
(20,12) 3920 1.096 14.921 904.353
(24,11) 3844 1.213 13.215 910.605
(30,8) 4816 1.358 14.792 908.792
Average 918.309710.392
Average 929.8711.5
The length-to-radius ratio is greater than 10.
B. WenXing et al. / Physica B 352 (2004) 156163 161
As can be seen in Table 5, the values of Youngs
modulus obtained by different researchers is
different. The reasons and effect of geometric
structure of SWCNTS of elastic moduli can be
given in the following:
(i) Different wall thickness values were used to
calculate the Youngs moduli: in Refs.
[810,26,27] and this present prediction, dR
0:34 nm was used, and obtained the values of
Youngs modulus ranging from 0.9 to
1.26 TPa. But in Ref. [14] dR 0:0617 nm
was used, and the obtained values of Youngs
modulus was 4.88 TPa. Compared with the
CC bond length of CNTs, 0.0617 nm the
magnitude of wall thickness seems too small.
To use dR 0:34 nm calculated the values of
Youngs modulus were closed to experimental
values than Ref. [14] in Table 5.
(ii) Difference in the tube model sizes: in Refs.
[2730], the length-to-radius ratio is smaller than
10. Therefore, the edge effects may have effect
on the results. In this present case and Ref. [10],
the length-to-radius ratio is greater than 10 to
ensure that edge effects can be ignored.
(iii) Different accuracy of theoretical approach: ab
initio, DFT and tight-binding are quantum-
mechanical-based methods, the results ob-
tained are reliable than other methods, but
the computational model is only composed of
several ten to several hundred atoms [2630].
MD methods can be used to model several
thousand to several million atoms and the
results are more close to real CNT. Used
accurate potential model, the simulation
results of MD method are very closer to
experimental data.
(iv) The effect of endcap on Youngs modulus of
SWCNTs: There are two different models,
open-ended SWCNTs [810,26,28,29] and
close-capped SWCNTs [27], respectively. From
Table 5 we see that the Youngs modulus of
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Table 4
Youngs modulus of SWCNTs for different chiral angle
(n,n) Angle (deg) Radius (nm) Y (GPa)
(35,0) 0.0 1.370 933.061
(20,2) 4.715 0.825 918.019
(12,2) 7.589 0.514 920.674
(8,2) 10.893 0.359 913.530
(12,4) 14.920 0.565 919.823
(10,4) 16.100 0.489 912.852
(14,6) 17.000 0.696 921.616
(18,9) 19.106 0.933 927.113
(20,12) 21.780 1.097 904.353
(24,18) 25.284 1.430 907.028
(20,20) 30.0 1.356 935.048
Table 5
Comparisons between numerical results and experiment results and other theoretical prediction of Youngs modulus of SWCNTs
Methods Wall thickness value (nm) Y (GPa) Ref.
Armchair Zigzag Chirality
MD 0.34 935.8 935.3 918.3 This present
Empirical force-constant model 0.34 972.0 975.0 973.0 [8]
Molecular structural mechanics model 0.34 1050750 1080720 [9]
MD and Force approach 0.34 123677 [10]
Continuum mechanics model 0.0617 4880 [14]
Tight-binding 0.34 12201250 12201260 12401250 [26]
Tight-binding 0.28 950 [29]
Ab initio 0.34 1060 11401180 1030 [27]
Ab initio 1000 [28]
DF-TB 0.34 11002800 [30]
Measuring resonance frequency
a
1001000 [3]
TEM
a
9001700 [4]
AFM
a
1200 [5]
a
Experimental methods.
B. WenXing et al. / Physica B 352 (2004) 156163 162
open-ended SWCNTs in this present prediction
and other prediction is similar to close-capped
SWCNTs [27]. From Ref. [27], a tube with long
structures are expected to avoid the inuence
of endcap effects.
(v) The effect of tube radius and tube chirality on
Youngs modulus of SWCNTs: most studies
[810,14,2629] show that the values of Youngs
moduli of SWCNTs are independent of tube
radius and tube chirality, except for Ref. [30].
This is also validated by this present work.
6. Conclusions
Using MDmethod, we study the Youngs moduli
of graphite and SWCNTs in detail. The Verlet
algorithm, which was improved by Swope in MD
method, was used to obtain atomic positions and
velocities at each simulation time step. Based on the
modied empirical potential function models, the
van-der-Waals forces in SWCNTs are taken into
account. The results show that the average of
Youngs modulus of graphite is 1026.176GPa,
which is very well closed to the experiment value.
The average of Youngs modulus of SWCNTs is
929.8711.5 GPa, which is slightly lower than the
Youngs modulus of graphite. It is also in good
agreement with the existing experimental ones. The
results show that the Youngs moduli of SWCNTs
are independent of the tube radius and tube
chirality. All these illustrate the simulation of
Youngs modulus of SWCNTs with MD and
modied potential energy model is quite workable
and reliable. It is expected that the present model
will be further developed to model other covalent-
bonded materials and analyze the mechanical
properties of nanotube-based composites.
Acknowledgements
The research is supported by the National Natural
Science foundation of China (Grant No. 60036010)
and China Doctoral foundation of National Educa-
tion Bureau (Grant No. 2000069823).
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