Computational Materials Science 47 (2009) 79–85

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Computational Materials Science

journal homepage: www.elsevier.com/locate/commatsci

Vibrational analysis of carbon nanotubes and graphene sheets using molecular

structural mechanics approach
K. Hashemnia, M. Farid *, R. Vatankhah
Department of Mechanical Engineering, Shiraz University, Molla Sadra, Shiraz, Iran

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

Article history: In this article, the vibrational properties of two kinds of single-layered graphene sheets and single-wall
Received 20 December 2008 carbon nanotubes (SWCNT) are studied. The simulations are carried out for two types of zigzag carbon
Received in revised form 14 June 2009 nanotubes (6,0), (12,0), armchair carbon nanotubes (4,4), (6,6) and zigzag and armchair graphene sheets
Accepted 17 June 2009
with free-fixed and fixed–fixed end conditions.
Available online 21 July 2009
Fundamental frequency is determined by means of molecular structural mechanics approach. In this
approach, carbon nanotubes (CNTs) and grapheme sheets are considered as space frames. By constructing
PACS:
equality between strain energies of each element in structural mechanics and potential energies of each
62.25.Jk
62.30.+d
bond, equivalent space frames can be achieved. Carbon atoms are considered as concentrated masses
62.25.g placed in beam joints (bond junctions).
62.20.x Results are presented as diagrams stating fundamental frequencies of nanotubes and graphene sheets
with respect to aspect ratios. The results indicate that fundamental frequency decreases as aspect ratio
Keywords: increases. So it is preferred to use nanotubes and graphene sheets with lower aspect ratios for dynamic
Graphene sheet applications in order to prevent resonance and dynamic damage. Fundamental frequency of nanotubes is
Molecular structural mechanics approach larger than that of graphene sheets. The results are in good agreement with results of previous
Nanotube
researches.
Vibrational analysis
Ó 2009 Elsevier B.V. All rights reserved.

1. Introduction
Carbon nanotubes are used in several areas such as medicine
and automotive industries [1]. The number of publications on CNTs
has grown very quickly since CNTs were discovered by Iijima [2].
Because of their size, shape, and remarkable physical properties,
nanotubes have drawn the attention of many researchers world-
wide. Large proportion of researches has been devoted to the
understanding of this area of science and technology in recent
years. Since 1991, the attempts to characterize, to investigate the-
oretically and to explore the properties of the nanotubes have risen
dramatically. Nanotubes have various properties depending on
their diameter, length and chirality. Their electronic, thermal and
structural properties have not fully been discovered yet and even
those discovered are disputable.
CNTs have very large Young modulus in their axial direction.
The Young modulus of SWCNTs lies close to 1 TPa as high as dia-
mond. Moreover they are tougher and five times stronger than
steel. The tensile strength of nanotubes can be up to 150 GPa,
* Corresponding author. Tel.: +98 711 6133013; fax: +98 711 6473511.
E-mail addresses: k_hashemnia@yahoo.com (K. Hashemnia), farid@shirazu.ac.ir
(M. Farid), ramin280@yahoo.com (R. Vatankhah).
around 50 times higher than that of the steels with highest ulti-
mate strength [3–6].
There are several methods which can be utilized to model CNTs
and graphene sheets in order to investigate their mechanical
behaviors. In Molecular Dynamic (MD) simulations, atoms are con-
sidered as particles interacting each other through several types of
potential fields. In this method the differential equations of mo-
tions of particles are coupled. Therefore this method is highly time
consuming and needs much computational effort. In molecular
structural mechanics approach (MSMA) atoms and bonds are con-
sidered as joints and beams, respectively. Therefore nanotubes, for
example, are substituted by space frames. Moreover, each nano-
tube can be modeled as a single continuous beam or shell for
simplicity. In this modeling, vibration equations of beams (e.g., Eu-
ler–Bernolli beam model) and shells are used as the equations of
vibration of nanotubes. MD simulations prepare results which
are more accurate than those of MSMA. However, they need more
computational effort and time. Modeling CNTs by MSMA is more
accurate than modeling by continuous beam or shell; but the for-
mer is slightly more time consuming.
Much effort has so far been devoted to the study of various as-
pects of nanotubes such as buckling, mechanical, chemical, and
electrical properties. However, vibrational characteristics of nano-
tubes have not been attracted the same amount of attention. Gao

0927-0256/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.commatsci.2009.06.016
80 K. Hashemnia et al. / Computational Materials Science 47 (2009) 79–85

Nomenclature

a carbon–carbon bond length U vdw potential energy due to Van der Waals interaction
d Nanotube diameter UA strain energy for axial tension
L length of the equivalent beam UM strain energy for bending
h chiral angle UT strain energy for torsion
a0 length of unit vector in the direction of chiral vector UV strain energy for shear
a2~
~ a1 unit vectors xi natural frequencies
ks kr kh force field constants in molecular mechanics EA tensile stiffness
mc carbon nuclei mass EI bending stiffness
ra carbon atomic radius GJ torsional rigidity
rn radius of the carbon nucleus [K] element stiffness matrix
~
C chiral vector [M] element mass matrix
h
Ur potential energy due to bond stretching ff gi element force vector
Uh potential energy due to bond angle bending fUgi element displacement vector
U/ potential energy due to dihedral angle torsion ½Ka condensed stiffness matrix
Ux potential energy due to out-of-plane torsion ½Ma condensed mass matrix

et al. [7] found the vibrational modes of a series of (n,n) CNTs by
MSMA using the second derivatives of the potential energy surface.
Behfar and Naghdabadi [8] investigated the vibration of multilay-
ered graphene sheet embedded in an elastic medium using MSMA;
however, they did not include the cylindrical zigzag, armchair or
chiral nanotubes.
Vibration of embedded multi-all carbon nanotubes (MWCNTs)
was investigated by Yoon et al. [9]. Lu et al. [10] used non local
Timoshenko beam model in order to determine the wave proper-
ties such as natural frequency of SWCNTs and double wall carbon
nanotubes (DWCNTs).
There are some articles in literature related to vibration and
instability of CNTs conveying fluid such as [11–13]. Yan et al.
[14] investigated dynamical behaviors of fluid-conveyed MWCNTs.
Also, dynamical behaviors of DWCNTs conveying fluid with consid-
eration of small length scale effect were studied by Wang [15].
Wang et al. [16] studied the thermal effect on vibration and insta-
bility of CNTs conveying fluids. Lee and Chang [17] studied free
vibration of viscous fluid-conveyed SWCNTs embedded in an elas-
tic medium considering non local effects. Computational modeling
of the flow of viscous fluids in CNTs was studied by Khosravian and
Rafii-Tabar [18]. All of the above works [9–18] were done using
continuous beam or shell modeling. Furthermore, a review was
done on vibration of CNTs and their composites by Gibson et al.
[19].
Vibrations of CNTs are of considerable importance in a number
of nanomechanical devices such as oscillators, charge detectors,
clocks, field emission devices and sensors. In addition, CNT vibra-
tions occur during certain manufacturing processes (e.g., ultrason-
ication in nanocomposite processing) and as part of some
nondestructive evaluation processes (e.g., Raman spectroscopy).
Electron microscope observations of vibrating CNTs have also been
used to determine indirectly and nondestructively the effective
elastic modulii and other aspects of mechanical behavior of the
CNTs [19]. Therefore there is a considerable motivation for study-
ing the vibrational characteristics of CNTs. In this work, molecular
structural mechanics approach along with the finite element anal-
ysis is employed to determine the fundamental frequencies and
their corresponding modes for graphene sheets and two types of
nanotubes i.e., zigzag and armchair.
structure in which each carbon atom and its four nearest neighbors
are arranged in a tetrahedron, graphite has the form of a 2-D sheet
of carbon atoms arranged in a hexagonal array. In this case, each
carbon atom has three nearest neighbors.
The atomic structure of nanotubes can be described in terms of
the tube chirality, or helicity, which is defined by the chiral vector
~
C h and the chiral angle h. In Fig. 1, we can visualize cutting the
graphite sheet along the dotted lines and rolling the tube so that
the tip of the chiral vector touches its tail. The chiral vector, also
known as the roll-up vector, can be described by the following
equation:
~
C h ¼ n~
a1 þ m~
a2 ; ð1Þ
where the integers n and m are the number of steps along the zigzag
carbon bonds of the hexagonal lattice and ~ a1 and ~
a2 are unit vectors
illustrated in Fig. 1. The chiral angle determines the twist in the
tube. The chiral angles are 0 and 30 for the two limiting cases
which are referred to as zigzag and armchair, respectively (Fig. 2).
In almost all articles, the following formula has been considered
as nanotube’s diameter for various kinds (n,m) of nanotubes:
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
a0 ðm2 þ mn þ n2 Þ
d¼ ð2Þ
p
where a0 is the length of unit vector in the direction of chiral vector
[21].

2. Structural characteristics of carbon nanotubes

SWCNT can be viewed as a graphene sheet rolled into a tube.

Unlike diamond, which can be assumed to be a 3-D crystal Fig. 1. Schematic diagram of a hexagonal graphene sheet [20].
 K. Hashemnia et al. / Computational Materials Science 47 (2009) 79–85 81

X X X X
U¼ Ur þ Uh þ ðU / þ U x Þ þ U vdw ; ð5Þ

where U r is bond stretching, U h is bond angle bending, U / is dihe-

dral angle torsion, U x is out-of-plane torsion, and U vdw is Van der
Waals interaction. From a structural mechanics viewpoint, the
deformation of a space frame results in the change of strain energy.
The strain energy for a beam element is given by
X X X X
U¼ UA þ UM þ UT þ UV ; ð6Þ

where U A , U M , U T and U V are strain energies for axial tension,

bending, torsion and shear force, respectively. If the atomistic
beam is assumed to be of round cross-section, then only three stiff-
ness parameters, i.e., tensile stiffness (EA), bending stiffness (EI)
and torsional rigidity (GJ), need to be determined for deformation
analysis (Fig. 3). In Eqs. (5) and (6), it can be seen that U r and U A
represent stretching energies, U h and U M represent bending ener-
gies, and U s ¼ U / þ U x and U T represent torsional energies. By
considering the energy equivalence between Eqs. (5) and (6), a di-
Fig. 2. Schematic diagram of (a) an armchair and (b) a zigzag nanotube [20].
rect relationship between the structural mechanics parameters and
the molecular mechanics force field constants can be established
In this research, according to the nanotubes’ geometry, two new [20] as
formulas are suggested and used for their diameter. These formu-
EA EI GJ
las are: ¼ kr ; ¼ kh ; ¼ ks ; ð7Þ
L L L
3a
d¼   ð3Þ where kr , kh and ks are the force field constants in molecular
sin 180
n
mechanics, and L is the length of the equivalent beam [22].
cos 30
d¼a   ð4Þ
sin 90
n
4. Eigenvalue problem and calculation of fundamental
frequency
Eqs. (3) and (4) represent armchair(n,n) and zigzag(n,0) nano-
tubes’ diameter, respectively. In these equations, parameter a rep- By considering negligible radius of the carbon nucleus
resents each element length (carbon–carbon bond length). By rn = 2.7  105 Å) in comparison with carbon atomic radius
using these formulas, the length of all elements becomes the same, (ra = .67 Å), concentrated masses are adopted to simulate carbon
which is the advantage of our suggested formulas. atoms. The concentrated masses i.e., carbon nuclei masses
ðmc ¼ 1:9943  1023 gÞ are positioned at the end of the beams
3. Application of structural mechanics approach to carbon representing joints of the covalent bonds. It is assumed that the
nanotubes mass of the electrons is not significant in comparison with the nu-
cleus [23].
The idea of molecular structural mechanics stems from the Young and shear modulii are considered 1000 Gpa and 450 Gpa
observation of the geometrical similarities between nanoscopic for CNTs, respectively. These modulii are 1060 Gpa and 430 Gpa for
fullerenes and macroscopic frame structures [20]. In a carbon graphene sheets, respectively [22,24].
nanotube, each atom is bounded covalently with three nearest The frequencies and their corresponding modes of a structure
neighbors. Then it is logical to consider nanotubes as 3-D space can be determined using finite element method. In this method,
frame-like structures with beams connecting the carbon atoms. the frequencies, xi , can be obtained from relation (8).
When a nanotube is subjected to external forces, the positional
changes of atomic nuclei are constrained by the covalent bonds. ð½K  x2i ½MÞfUgi ¼ ff gi ð8Þ
Thus, the deformation of the nanotube structure can be viewed
similar to the deformation of a frame structure composed of con- where ½K, ½M, fUgi and ff gi are the element stiffness matrix, ele-
necting beams. In essence, we utilize the aspects of computa- ment mass matrix, displacement vector and force vector, respec-
tional chemistry to model the covalent bond between the tively. The stiffness matrix, ½K and the mass matrix ½M are
carbon atoms as an equivalent structural beam. Using concepts symmetric and are given by
of molecular mechanics, a linkage between the great differences " # " #
K ii K ij Mii Mij
in length scales of these structures was established based on ½K ¼ ; ½M ¼ ð9Þ
the concept of energy equivalence. Using the energy equivalence K Tij K jj M Tij M jj
between local potential energies in computational chemistry and
elemental strain energies in structural mechanics, we can deter- where the sub-matrices, K ii , K ij , K jj and Mii , Mij and M jj are given by
mine the tensile stiffness, bending stiffness and torsional rigidity 2 3
for an equivalent beam. Once these beams are connected together EA=L 0 0 0 0 0
as a nanotube, we can then utilize computationally efficient 6 0 12EIx =L 3
0 0 0 6EIx =L 7
2
6 7
6 3 2 7
structural mechanics techniques to solve the resulting nanotube 6 0 0 12EIy =L 0 6EIy =L 0 7
K ii ¼ 6
6
7;
deformation [20].
6 0 0 0 GJ=L 0 0 7 7
From the viewpoint of molecular mechanics, the general 6 7
4 0 0 6EIy =L2 0 4EIy =L 0 5
expression of total potential energy is a sum of energies due to va-
lence or bonded interactions and non-bonded interactions 0 6EIx =L2 0 0 0 4EIx =L
82 K. Hashemnia et al. / Computational Materials Science 47 (2009) 79–85

Fig. 3. Modeling of carbon–carbon bond with beam by molecular structural mechanics approach [20].

2 3
EA=L 0 0 0 0 0 3000

natural frequency (GHz)

6 0 12EIx =L3 0 0 0 6EIx =L2 7
6 7 y = 4934.8x-1.7019
6 7 2500
6 0 0 12EIy =L3 0 6EIy =L2 0 7 R2 = 0.9987
K ij ¼ 6
6
7;
6 0 0 0 GJ=L 0 0 7 7 2000 free-fix
6 7
4 0 0 6EIy =L2 0 2EIy =L 0 5 Pow er
1500
2
0 6EIx =L 0 0 0 2EIx =L
1000
2 3
EA=L 0 0 0 0 0 500
6 0 12EIx =L3 0 0 0 6EIx =L2 7
6 7 0
6 7
6 0 0 12EIy =L3 0 6EIy =L2 0 7 0 1 2 3 4 5 6
K jj ¼ 6
6
7;
7
6 0 0 0 GJ=L 0 0 7 aspect ratio (nm/nm)
6 7
4 0 0 6EIy =L2 0 4EIy =L 0 5
Fig. 4. Fundamental frequency vs. aspect ratio for zigzag (6,0).
2
0 6EIx =L 0 0 0 4EIx =L
2 3
mc 0 0 0 0 0 12000
natural frequency (GHz)

6 y = 12622x-1.3849
6 0 mc 0 0 0 077
6 7 10000 R2 = 0.9981
6 0 0 mc 0 0 07
M ii ¼ Mjj ¼ 6
6
7; fix-fix
6 0 0 0 0 0 077
8000
6 7 Power (fix-fix)
4 0 0 0 0 0 05 6000
0 0 0 0 0 0 4000

M ij ¼ ½066 ð10Þ 2000

[K] and [M] are computed for each individual element and then 0
through an assemblage process, the global assembled matrices for 0 1 2 3 4 5 6 7
the whole structure are calculated. Natural frequencies can be
aspect ratio (nm/nm)
determined from the following eigenvalue problem:
Fig. 5. Fundamental frequency vs. aspect ratio for armchair (4,4).
ð½Ka  x2i ½Ma ÞfUgi ¼ f0g ð11Þ
where ½Ka and ½Ma are the condensed stiffness matrix and mass
matrix after satisfying boundary conditions, respectively. Above 6000
natural frequency (GHz)

homogenous linear algebraic equations have non-trivial solution if

-1.3191
and only if 5000 y = 6162.9x
2
 a  R = 0.9995
½K  x2 ½Ma  ¼ 0 ð12Þ 4000
i
fix-fix
Then natural frequencies will be determined. Each eigenvector, 3000 Power (fix-fix)
fUgi in Eq. (11), consists of 12 degrees of freedom including three
translational DOF’s and three rotational DOF’s at each node. 2000

1000
5. Results
0
The results are presented as diagrams stating fundamental fre- 0 1 2 3 4 5
quencies of nanotube and graphene sheet with respect to aspect aspect ratio(nm/nm)
ratios. In this article normal mode vibration of two kinds of arm-
chair nanotube (armchair(4,4) and armchair(6,6)) and two kinds Fig. 6. Fundamental frequency vs. aspect ratio for zigzag (12,0).
 K. Hashemnia et al. / Computational Materials Science 47 (2009) 79–85 83

2500 10000

natural frequency (GHz)

natural frequency (GHz)
9000 free-fix
-1.63
y = 2529.8x fix-fix
2000 2 8000
R = 0.9979 Power (fix-fix)
7000
Power (free-fix)
1500 6000
free-fix 5000
1000 Power (free-fix) 4000
3000
500 2000
1000
0 0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
aspect ratio (nm/nm) aspect ratio (nm/nm)
Fig. 7. Fundamental frequency vs. aspect ratio for armchair (6,6). Fig. 11. Fundamental frequency vs. aspect ratio for zigzag (6,0).

600 3000

natural frequrency (GHz)

natural frequency (GHz)

-1.9592
y = 765.98x free-fix
500 2 2500
R =1 fix-fix
400 2000 Power (free-fix)
free-fix
Power (fix-fix)
300 Power (free- 1500
200 1000
100
500
0
0
0 0.5 1 1.5 2 2.5 3 3.5 0 0.5 1 1.5 2 2.5
aspect ratio (nm/nm) aspect ratio (nm/nm)
Fig. 8. Fundamental frequency vs. aspect ratio for armchair graphene sheet.
Fig. 12. Fundamental frequency vs. aspect ratio for zigzag graphene sheet.

4000 4000
natural frequency (GHz)
natural frequency (GHz)

armchair(4,4) armchair(6,6)
3500 3500
armchair armchair(4,4)
3000 3000
graphene
Power
2500 Power 2500 (armchair(6,6))
(armchair(4,4))
Power
2000 Power (armchair 2000 (armchair(4,4))
graphene)
1500 1500
1000 1000
500 500
0 0
0 1 2 3 4 5 6 7 0 1 2 3 4 5 6 7
aspect ratio (nm/nm) aspect ratio (nm/nm)

Fig. 9. Fundamental frequency vs. aspect ratio for armchair (4,4) and armchair Fig. 13. Fundamental frequency vs. aspect ratio for armchair CNT with free-fixed
graphene sheet. end condition.

10000
natural frequency (GHz)

zigzag(6,0)
12000 9000
natural frequency (GHz)

free-fix 8000 zigzag(12,0)

10000 7000
fix-fix
6000 Power
8000 Power (free-fix) (zigzag(6,0))
5000
Power (fix-fix) Power
6000 4000
(zigzag(12,0
3000
4000 2000
1000
2000
0
0 0 1 2 3 4 5 6
0 1 2 3 4 5 6 7 aspect ratio (nm/nm)
aspect ratio (nm/nm)
Fig. 14. Fundamental frequency vs. aspect ratio for zigzag CNT with fixed–fixed end
Fig. 10. Fundamental frequency vs. aspect ratio for armchair (4,4). condition.
84 K. Hashemnia et al. / Computational Materials Science 47 (2009) 79–85
Fig. 15. Fundamental frequency of nanotubes with free-fixed and fixed–fixed end condition [20].
of zigzag nanotube (zigzag(6,0) and zigzag(12,0)) and two types of
graphene sheets (armchair and zigzag) are studied.
Aspect ratio is defined as the length to diameter ratio for nano-
tubes and length to width ratio for graphene sheets.
Fundamental frequency decreases as aspect ratio increases in
all diagrams.
The equations of curves (y) fitted on data points and related cor-
relation coefficients ðR2 Þ can be seen in all diagrams. These curves
are fitted well on data points (correlation coefficients are from .99
to 1). Therefore power curves nearly show the fundamental fre-
quency trend in normal mode vibration analysis of nanotubes
and graphene sheets (Figs. 4–8).
Fundamental frequency of nanotubes is larger than that of
graphene sheets. For example fundamental frequency of arm-
chair(4,4) is 7.5 times that of armchair graphene sheet in aspect ra-
tio 2.7. This value for zigzag(6,0) is 11.5 times that of zigzag
graphene sheet in aspect ratio 1.94 (Fig. 9).
As expected from modal analysis of Euler–Bernolli beam theory,
fundamental frequency of nanotubes and graphene sheets with
fixed–fixed end condition is greater than that of nanotubes and
graphene sheets with free-fixed end condition. For example this
value for zigzag(6,0) with fixed–fixed end condition is 4.5 times
that of with free-fixed end condition in aspect ratio 3.3. This value
for armchair(4,4) with fixed–fixed end condition is 4.5 times that
of with free-fixed end condition in aspect ratio 3.6 (Figs. 10–12).
Fundamental frequency decreases as nanotube’s diameter in-
creases. It indicates that mass increasing is more effective than
stiffness increasing as nanotube’s diameter increases. For example
this value for zigzag(12,0) is .49 times that of zigzag(6,0) with free-
fixed end condition in aspect ratio 2.8. This value for armchair(6,6)
is .63 times that of armchair(4,4) with free-fixed end condition in
aspect ratio 2.7 (Fig. 13).
These results are true for nanotubes with fixed–fixed end con-
dition, too. For example this value for zigzag(12,0) is .44 times that
of zigzag(6,0) with fixed–fixed end condition in aspect ratio 2.8.
This value for armchair(6,6) is .60 times that of armchair(4,4) with
fixed–fixed end condition in aspect ratio 2.7 (Fig. 14).
Therefore, it is preferred to use nanotubes and graphene sheets
with lower aspect ratios for dynamic applications in order to pre-
vent resonance and dynamic damage.
Also it is suggested to use nanotubes with larger diameters and
fixed–fixed end condition because of the above reason.
The results are in good agreement with results (in the aspect ra-
tio range from 5 to 7) of Li and Chou research [20] (Fig. 15). Their
research was done on nanotubes with free-fixed and fixed–fixed
end conditions for aspect ratios larger than 5. But the present work
is done on nanotubes and graphene sheets for aspect ratios from 1
to 7. Another difference of these two works is the formulas used for
calculation of nanotubes’ diameters.
Another work done on this subject belongs to Mir et al. [25]. The
order of fundamental frequencies in that paper differs from those
of the present work and Li and Chou [20]. Fundamental frequencies
in that paper [25] are in the order of megahertz while ours similar
to those of [19] are in the order of gigahertz. It is worth noting that
the nanotubes’ kinds investigated in [25] are different from those
of reference [19] and the present work. This difference may be be-
cause of the assumption of uniform distribution of mass along
beam element (bond length) in their work. Their assumption can
be seen from the element mass matrix introduced by them which
is not correct from the chemical point of view. This is why almost
total mass of an atom is concentrated in its nucleus.
7. Conclusion
The vibrational properties of two kinds of single-layered graph-
ene sheets and SWCNT (zigzag and armchair) are studied in the
present research. Obtained results are compared with results of
previous researches. They are in good agreement with some of
them. Results show that fundamental frequencies of nanotubes
are greater than those of graphene sheets. Also, fundamental fre-
quencies of nanotubes and graphene sheets with fixed–fixed end
condition are larger than those of nanotubes and graphene sheets
with free-fixed end condition. It can be observed that fundamental
frequency decreases as nanotube’s diameter increases.
MSMA is less accurate than MD simulation. Therefore MSMA
cannot be used for problems requiring very accurate results.
Vibrational analysis of multi-wall carbon nanotubes (MWCNT)
can be done in future.
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