PHYSICAL REVIEW B 66, 153407 共2002兲

Nonlinear elastic properties of carbon nanotubes subjected to large axial deformations

T. Xiao* and K. Liao†
School of Mechanical and Production Engineering, Nanyang Technological University, Singapore 639798
共Received 25 July 2002; published 24 October 2002兲
Nonlinear elastic properties of single-wall carbon nanotubes subjected to large-scale tensile deformation
were investigated using the second-generation Brenner potential. The energy change of the nanotubes was
found to be a cubic function of tensile strains. In contrast to values of in-plane stiffness C based on small
strains reported previously in the literature, the present study showed that C is linearly dependent on axial
tensile deformation. C is also affected by the chirality of the tubes to some extent when axial strains are large.
Consequently, these tubes should be considered in the context of anisotropic elastic shell models in the event
of employing continuum mechanics in the analysis of nanotubes.

DOI: 10.1103/PhysRevB.66.153407 PACS number共s兲: 61.48.⫹c, 62.20.Dc

Since the discovery of carbon nanotubes 共CNTs兲 by Iijima
and Ichihashi1,2 in 1991, the prospect of their potential ap-
plications has initiated intensive research. Being the stron-
gest and stiffest among man made fibers, these nanowires are
anticipated to play a key role in future high-performance
nanocomposites. As such, better understanding and accurate
characterization of their mechanical properties are needed.
To study CNTs and their relatives, quantum mechanics cal-
culations are most reliable and accurate. However, at present,
ab initio method is merely available for relatively simple
atomic structures because of enormous amount of computa-
tions required. In most cases when CNTs with a large num-
ber of carbon atoms are concerned, molecular dynamics
共MD兲 simulations using empirical force fields are frequently
employed. For instance, Robertson, Brenner, and Mintmire3
have examined the energetics of a large number of single-
wall nanotubes 共SWNTs兲 using the Tersoff-Brenner
potential,4,5 and found that the strain energy per atom of a
SWNT is sensitive to its radius when the radius is small, but
it is insensitive to other aspects of the lattice structure. Ya-
kobson, Brabec, and Bernholc6 investigated morphological
pattern transformations of SWNTs also by means of the
Tersoff-Brenner potential, and showed that the shape change
of nanotubes corresponds to an abrupt release of energy.
Zhang, Lammert, and Crespi7 investigated the plastic defor-
mation of SWNTs using tight binding method, and found that
the elastic limit of SWNTs depends on chirality due to bond
rotation in the graphitic network, although their elastic prop-
erties are nearly independent of it. Srivastava, Menon, and
Cho8 calculated the strain energy of a SWNT under uniaxial
compression using both tight binding method9 and the
Tersoff-Brenner potential. Their study showed that at low
strain before any change of morphological pattern happens,
the two sets of results are in good agreement with each other.
At high-strain buckling occurs in the simulation with the
Tersoff-Brenner potential, and a deviation between them was
found, as had been analyzed in detail by Yakobson, Brabec,
and Bernholc.6
Although the aforementioned molecular simulations are
quite reliable in the investigations of nanostructures, inten-
sive processing time is required and large input and output
that result are hard to handle in engineering design. On the
other hand, continuum mechanics, which has been used con-
ventionally by engineers, are equivalently utilizable for ana-
lyzing CNTs. The larger the number of atoms in a CNT, the
more analogous it is to a continuum object. In this sense, the
advantages of continuum mechanics may compensate the
disadvantages of ab initio and other MD methods. Con-
tinuum mechanics has been employed in many occasions to
study the behavior of CNTs. Yakobson, Brabec, and
Bernholc6 proposed a continuum shell model with properly
chosen tubular parameters to explained the pattern transfor-
mations of SWNTs subjected to large axial compression,
such that the critical deformation at which buckling occurs
can be estimated. Tersoff10 introduced an approach of calcu-
lating energies of fullerene balls by viewing fullerenes as
distorted graphene sheets and applied an elastic cone shell
model to fullerene balls to approximate their energies. Ru,11
Govindjee and Sackman12 presented shell models for multi-
walled carbon nanotubes to study deformation and buckling.
It is demonstrated by all these works that continuum me-
chanics is particularly useful for the study of large-sized
atomic systems.
In this paper, we consider the situation of SWNTs sub-
jected to large-scale tensile deformation. Nonlinear elastic
properties of SWNTs that can be used in continuum descrip-
tion of their elastic response, were studied using the second-
generation Brenner potential.
In continuum mechanics, the constitutive relations, i.e.,
relations of load and deformation, have to been established
prior to solving a specific problem. If the material is homo-
geneous and isotropic, it becomes the problem of defining
two basic parameters,13 Young’s modulus Y and Poisson’s
ratio ␯. Suppose a material undergoes a uniaxial tension test,
Y is conventionally defined as
1 ⳵ 2E
Y⫽ , 共1兲
V ⳵␧2
where V is the volume of the material, E the total strain
energy under tensile deformation, and ␧ the tensile strain.
However, the definition in Eq. 共1兲 encounters difficulty in
CNTs because there is no translational invariance in the ra-
dial direction.14 For these hollow CNTs, different thicknesses
have been adopted,15 and the volume V is not properly de-
fined. Therefore, in-plane stiffness C which is independent of

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BRIEF REPORTS PHYSICAL REVIEW B 66, 153407 共2002兲

any shell thickness, is defined as an alternative measurement

of the mechanical characteristic of nanotubes,

1 ⳵ 2E
C⫽ , 共2兲
S ⳵␧2
where S is the surface area of the nanotube.
A graphene sheet, which possesses a two-dimensional
hexagonal structure, is isotropic in the case of small
deformation.13 Since a single CNT can be viewed as a
graphene sheet rolled up into a cylindrical tube with a con-
stant radius,16 CNTs are isotropic as well when tension de-
formation is small, and they can be characterized by a uni-
form cylindrical shell model with only two elastic
parameters. This argument has been confirmed by the results
of Sanchez-Portal, Artacho, and Soler,17 which showed that
stiffness C does not vary significantly with the radii and
chirality of SWNTs. Other results18 –20 also showed that the
strain energy per atom is insensitive to the lattice structures
of CNTs. If a representative thickness h is defined for a
graphene sheet or a single CNT,6,19,21 then their volume is
V⫽Sh, and the representative Young’s modulus is
C
Y⫽ . 共3兲
h and zigzag group from 共7, 0兲 to 共20, 0兲, plus 共22, 0兲 and 共25,
The lattice constants of a perfect graphite were experi-
mentally determined,22,23 with a 0 ⫽0.2462 nm and c 0
⫽0.6707 nm, so that the specific volume per atom V 0
⫽0.0088 nm3 and the specific area per atom S 0
⫽0.02624 nm2 . The interplanar separation h 0 ⫽c 0 /2
⫽0.335 nm, is defined as the representative thickness of the
graphite. The unit of energy per atom for graphite, 1 eV/
atom, is equal to 6.1 J/m2.
Divergence exists in the values of the in-plane stiffness C
or representative modulus Y.3,8,17–20,24,25 Among them the
maximum value3 is C⫽59 eV/atom⫽360 J/m2 , the mini-
mum value24 is C⫽220 J/m2 . Typically C⫽342 J/m2 is ex-
pected for SWNTs.14 The differences, possibly attributed to
the simulation methods employed or different ways of load
applications, are in general within an acceptable range of
same order of magnitude.
Although different values of stiffness are reported, all of
them are assumed to be constants. It will be shown later that
the in-plane stiffness C may not be treated as a constant in
general, it is dependent on the strain ␧ of the CNTs, and can
only be approximated as a constant when ␧ is very small. It
has been known that CNTs are remarkably resilient,6 able to
retain their elastic behavior when strained to 15% when the
material yields. Under large-scale deformation, nonlinear
elastic response of CNTs becomes more obvious, and there-
fore it must be taken into account.
In many cases3,6,24,26 –30 the Tersoff-Brenner potential4,5 is
used in molecular mechanics simulations to study the behav-
ior of carbon-based structures. This potential function accu-
rately describes the bonding energies of graphite phase of
carbon atoms, and the results are in good agreement with
those of ab initio calculations.3 Recently Brenner presented a
second-generation potential energy function31 for solid car-
FIG. 1. Energy change per atom of nanotube 共10, 10兲 under
axial tension. Crosses are simulation results using the second-
generation Brenner potential, and solid line is the regression curve
using Eq. 共4兲.
bon and hydrocarbon molecules, which provides a better de-
scription of bond energies and length for carbon nanotubes.
Here this second-generation Brenner potential is adapted to
compute the strain energy E of CNTs in Eq. 共2兲. The ener-
getics of two groups of SWNTs subjected to axial tension
were examined: arm-chair group from 共4, 4兲 to 共15, 15兲,32
0兲. The values of the in-plane stiffness C of SWNTs were
determined by Eq. 共2兲. Analyzing the computational results
of each SWNT, it is found that for every SWNT the relation
between ⌬E, the energy changes per unit area, and the ap-
plied strain ␧ can be nearly perfectly fitted into a cubic poly-
nomial function with two coefficients, a and b, as follows:
⌬E⫽a␧ 2 ⫺b␧ 3 , 共4兲
where values of a, b are determined by regression analysis.
The energy change per atom ⌬E of a 共10, 10兲 SWNT with
respect to applied strain ␧ subjected to axial tension, is illus-
trated in Fig. 1. Regression analysis showed that a
⫽25.6 eV/atom, b⫽48.2 eV/atom, with a multiple correla-
tion coefficient R⬎0.999, and the estimated standard error
less than 0.005. Similar high-R values and low-standard er-
rors were also obtained for other SWNTs from simulations of
tensile response.
The force per unit circumference acting on the ends of a
SWNT, T, is the first derivative of Eq. 共4兲:
⳵E
T⫽ ⫽2a␧⫺3b␧ 2 共5兲
⳵␧
and the in-plane stiffness C is the second derivative of Eq.
共4兲. According to Eq. 共2兲, we have
1 ⳵ 2 E ⳵ 2 ⌬E
C⫽ ⫽ ⫽ ␣ ⫺ ␤ ␧, 共6兲
S ⳵␧2 ⳵␧2
where ␣ ⫽2a, ␤ ⫽6b. The coefficient ␣ reflects the initial
in-plane stiffness of the tube, and ␤ the influence of ␧ on the
in-plane stiffness C. It is seen from Eq. 共4兲 that coefficients a
and b reflect the linear and nonlinear properties of the tube,
respectively. At small deformation when ␧ approaches 0, C

153407-2
BRIEF REPORTS
FIG. 2. Tensile force of nanotube 共10, 10兲 versus axial tensile
strain. The solid line is the curve of Eq. 共5兲, crosses on the curve
correspond to those in Fig. 1. The dash line is the tangent line of the
curve at the origin, T⫽2a␧, depicting the specific condition of Eq.
共5兲 when the material is considered linear at small deformation.
approximates to ␣. The in-plane stiffness C reported in the
literatures to date conceptually corresponds to the coefficient
␣, a constant.
Variation of tensile force T with the strain ␧ of a 共10, 10兲
SWNT according to Eq. 共5兲 is illustrated in Fig. 2, where the
in-plane stiffness C is the initial slope of curve. In Fig. 2 it is
seen that when ␧ is small 共less than 0.02兲, the curve coin-
cides with its tangent at the origin 共dash line兲, suggesting that
the nonlinear constitutive relation may be simplified into
Hooke’s law. The nonlinear response becomes apparent with
increasing ␧. The force-strain curve tends to flatten out, im-
plying that the material is gradually softening, until the point
when the tangent of the curve is leveled, that is, ⳵ T/ ⳵ ␧⫽0 or
C⫽0, at which point the tensile force reaches its maximum
T max :
T max⫽2a␧ max⫺3b␧ max
2
, 共7兲
where ␧ max is the elastic strain limit for CNTs under tensile
deformation, ␧ max⫽␤/␣.
From our simulation results, ␧ max is 15% and 17% for
zigzag and arm-chair group, respectively. And both groups
have identical maximum force (T max) around 27 N/m, be-
yond which CNTs will collapse. Previous MD
simulations6,8,33 performed for similar tubes showed only lin-
ear elastic deformations to ␧ max . Although at present the ten-
sile failure strain for CNTs is still unsettled, various experi-
mental results,34,35 suggest that it rarely exceeds 10%, which
is smaller than our simulation results.
One possibility is that while the CNTs simulated here are
defect-free and under ideal loading condition and therefore
deformed elastically until failure, defects exist in real CNTs
that could substantially reduce their failure strain. Moreover,
it is demonstrated by several theoretical studies7,33,36 that at
high strain structural defects of CNTs due to bond rotation or
bond reconstruction8 could occur, result in plastic deforma-
tion. Taking the bond rotation effect into account, Zhang,
Lammert, and Crespi7 reported a maximum elastic limit of
about 173 nN/nm per tube radius for group of zigzag tubes
共which equals 27.5 N/m per tube circumference, in agree-
153407-3
PHYSICAL REVIEW B 66, 153407 共2002兲
FIG. 3. Variation of coefficients a and b with the increase of
tube diameter, of 12 armchair-type tubes from 共4, 4兲 to 共15, 15兲, and
16 zigzag-type tubes from 共7, 0兲 to 共20, 0兲, plus tube 共22, 0兲 and
tube 共25, 0兲. The solid lines are used as guides to the eye.
ment with our result of T max⫽27 N/m). That value is nearly
twice that of arm-chair tubes, suggesting that the onset of
plastic response depends on chirality of the tubes. Here we
focus on defect-free CNTs under completely elastic deforma-
tion, with no structural rearrangement during loading, so that
the elastic strain limit and the force limit are insensitive to
chirality.
Coefficients a and b versus different tube diameters from
simulations of two groups of SWNTs under axial tension are
depicted in Fig. 3. It is found that coefficient a of the two
groups of CNTs are close to each other, indicating that at
small deformation the in-plane stiffness C 共at the moment
C⫽2a⫽ ␣ ) is insensitive to chirality. That coefficient b of
the two groups of CNTs are distinct, indicates that at large
deformation, C 共now C⫽ ␣ ⫺ ␤ ␧) is not only being affected
by ␧, but also sensitive to chirality. Moreover, the values of a
and b seem to approach their limits at large tube radii. This is
expected because CNTs are constructed conceptually by roll-
ing up a single sheet of graphene,16 in the limit of infinite
radius, coefficients a and b become that of a graphene sheet
in specific directions. As shown in Fig. 3 limiting values a 2
⫽28.3 eV/atom, b 2 ⫽60 eV/atom. for zigzag-type 共n, 0兲
tubes, and limiting value a 1 ⫽25.5 eV/atom, b 1
⫽47.2 eV/atom for armchair-type 共n, n兲 tubes. Using the
limiting values a 2 , b 2 , and Eq. 共6兲, we get the in-plane
stiffness C 2 ⫽56.6– 360␧ eV/atom along the direction per-
pendicular to vector 共n, 0兲 in graphene. Similarly, using the
limiting values a 1 , b 1 , and Eq. 共6兲, we get the in-plane
stiffness C 1 ⫽51– 283␧ eV/atom along the direction perpen-
dicular to vector 共n, n兲 in graphene. Because a 2 ⬎a 1 , 共n, 0兲
tubes have higher initial stiffness, but since b 2 ⬎b 1 the stiff-
ness of the 共n, 0兲 tubes decreases faster than that of the 共n, n兲
tubes. Consequently the elastic strain limit of zigzag 共n, 0兲
tubes, are about 2% lower than that of the arm-chair 共n, n兲
tubes. When ␧ is small, the second term in the expressions of
C 1 and C 2 can be neglected, the graphene is now treated as
an isotropic material with an average in-plane stiffness C
⫽(C 1 ⫹C 2 )/2⫽53.8 eV/atom⫽328 J/m2 . This value is in
good agreement with C⫽342 J/m2 for graphene, reported
recently.14
BRIEF REPORTS
Our results suggest that the in-plane stiffness of CNTs is
dependent on diameters of the tubes when they are small.
Yao and Lordi37 predicted that Young’s modulus increases
significantly with decreasing tube diameter for smaller diam-
eter, whereas the calculation of Hernandez et al.18 predicted
that the in-plane stiffness decreases slightly with decreasing
tube diameter for smaller diameter, and the results of Lu19
showed that stiffness is almost completely independent of the
tube size. These divergences are believed to attributed to
different effects of the curvature on the bonding of tubes
from various MD methods. In Fig. 3, coefficient b increases
slightly with a decrease in tube diameter while coefficient a
is almost unchanged, suggesting that the initial stiffness of
CNTs are less sensitive to the diameter of the tubes, but the
nonlinear properties depend somewhat on tubes with smaller
diameters.
*Email address: mtxiao@ntu.edu.sg
†
Corresponding author. Email address: askliao@ntu.edu.sg
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153407-4
PHYSICAL REVIEW B 66, 153407 共2002兲
In sum, we have simulated the tensile elastic response of
two groups of SWNTs under large-scale deformations by
means of the second-generation Brenner potential. It is found
that the energy change of the tubes per unit area is a two-
coefficient cubic function of applied tensile strain. Therefore,
the in-plane stiffness C of the tubes, which is linearly related
to the applied strain, characterizes the nonlinear elastic re-
sponse of CNTs. C is also dependent on the chirality of the
tubes when the tensile strain is large. This anisotropy is due
to the fact that the molecular structure of CNTs lost their
symmetry at large deformations. When strain is less than
0.02, the values of C reduce to a constant, and it is insensi-
tive to chirality. The diameters of the tubes also affect the
value of C to some extent when radii are small while at large
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