Finite Elements in Analysis and Design 49 (2012) 13–18

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Finite Elements in Analysis and Design

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

Multiscale analysis of the core nanotube in a nanocomposite system

Vinu Unnikrishnan, J.N. Reddy n
Advanced Computational Mechanics Laboratory, Department of Mechanical Engineering, Texas A&M University, College Station, TX 77843-3123, USA

a r t i c l e i n f o abstract

Article history: Carbon nanotube reinforced polymer composites have novel properties that make them useful in a
Received 16 March 2011 wide variety of applications and there has been numerous studies to predict the overall bulk properties
Received in revised form of these nanocomposites. Theoretical studies to understand the properties of these nanomaterials
29 April 2011
consider the nanometer dimension of a nanotube and attempt to understand its interaction with a
Accepted 12 June 2011
Available online 1 October 2011
polymer chain thereby coupling the various length scales and time scales. In this paper, we estimate the
properties of the central nanotube (neat or functionalized) which is embedded in a matrix material. The
Keywords: investigation of mechanical behavior of nanostructure materials is carried out using molecular
Carbon nanotube dynamics (MD) simulations and these interactions are subsequently idealized into a homogenized
Nanocomposite
model. The interactions of the molecules of the nanotube with the matrix usually creates an interphase
Molecular dynamics
layer which has reduced mobility. This paper also discusses the variation of the effective properties of
Interphase
the interphase region in a carbon nanotube reinforced nanocomposite system.
& 2011 Elsevier B.V. All rights reserved.

1. Introduction between the components [11]. However, the presence of atom-

Polymer-based composites reinforced with carbon fibers have
been widely used in advanced structures, and the use of carbon
nanotubes as potential composite reinforcements has many
advantages over conventional fibers, primarily due to the
enhanced mechanical strength of the nanotubes. There have been
numerous experimental studies to find the mechanical strength
of nanotube-reinforced composite materials, and it has been
shown that there is a 25–40% increase in strength [1–3]. However,
very few theoretical works have been undertaken to ascertain the
effective properties of nanotube-based polymers. In a conven-
tional composite material analysis, the material/mechanical prop-
erties of the participating phases are widely studied and accepted.
This is, however, not the case with the nanofibers, where the
material properties are still being debated and even weak mole-
cular interactions between the fiber and the matrix drastically
alters the overall properties [4,5]. Estimation of the mechanical
properties of carbon nanotube reinforced composites (see Fig. 1)
can be carried out using a multiscale analysis—where the inter-
actions of the nanotube with the matrix molecules are captured
using an atomistic analysis [6–10] and a continuum based model
scales the atomistic properties to the higher scale of interest.
In most of the atomistic studies on nanotube-based compo-
sites it is implicitly assumed that strong bonds exist between the
nanotube and matrix molecules leading to a perfect load transfer
n
Corresponding author. Tel.: þ1 979 862 2417; fax: þ 1 979 845 3081.
E-mail address: jnreddy@tamu.edu (J.N. Reddy).
ically smooth nonreactive surface of nanotubes leads to weak
interfacial bonding that inhibits load transfer across the nano-
tube/polymer interface [12,13]. As the interfacial bond strength
depends on the type of polymer used, it is necessary to perform
individual analyses to capture the interaction of the carbon
nanotube with the polymers. Furthermore, by considering the
property of the surrounding interphase layer a greater accuracy
can be achieved in predicting the effective properties of the
composite structure. Experimental studies have shown that the
load transfer between the matrix and nanotube can be enhanced
by adding a substitution impurity (doping) [14] or by functiona-
lizing the nanotube (see Fig. 2). Functionalization provides the
nanotube multiple bonding sites to the polymer matrix and
thereby helps in improving the strength of the composite [15,16].
Studies on estimating the mechanical properties of nanotubes
are generally carried out using atomistic simulations like mole-
cular dynamics (MD) or ab initio methods. Despite the immense
success of MD simulations in the atomistic scale, computational
adaptations to model the macroscopic problems based on nano-
tubes are not completely established. The application of con-
tinuum mechanics principles to nanotube-reinforced composites
demands the bridging of the two or more scales of interest. From
a computational perspective, these techniques should efficiently
represent or provide solution to the fine-scale as well as the
macro-scale problems. This bridging of the spatial scales into a
continuum nanotube approximation can be carried out by volume
averaging of the constituent properties of the atomistic system.
This volume averaging can be carried out by using the equiva-
lence of the strain energy due to deformation of the continuum

0168-874X/$ - see front matter & 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.finel.2011.08.015
14 V. Unnikrishnan, J.N. Reddy / Finite Elements in Analysis and Design 49 (2012) 13–18

Hamiltonian represents the total energy of an isolated system

and is composed of the sum of the potential, kinetic energy and
the thermodynamic terms
1 X 2
HðrN ,pN Þ ¼ p þ Uðr N Þ ð1Þ
2m i i

where Uðr N Þ is the potential energy from intermolecular interac-

P
tions as a function of the spatial ordinate rN, ð1=2mÞ i p2i repre-
sents the momentum p of the particle i with mass mi , which is a
function of the absolute temperature called the kinetic energy.
The time derivative of the Hamiltonian gives

Fig. 1. Computational model of single walled nanotube surrounded by layers of dH 1X X @U

¼ p p_ þ r_ ¼ 0 ð2Þ
polyethylene matrix. dt m i i i i
@ri i

and with the spatial derivative we obtain the equation of motion

Fig. 2. Functionalized single walled carbon nanotube.
system and a corresponding change in the potential energy during
an iso-thermal mechanical straining process in an atomistic system
[17]. The main objective of this study is to analyze the effect of
surrounding polymer on the mechanical behavior of carbon nano-
tube. In this study, we take into consideration two factors that
would affect the stiffness of the composite: (a) change in the
property of the nanotube under the influence of the surrounding
polymer and (b) estimate the effect of imperfect load transfer during
a mechanical straining process of the composite.
This paper is organized as follows: Section 2 provides a
description of the MD simulation of nanotubes and also the
estimation of the mechanical properties of carbon nanotube.
The determination of the effective property of the nanocomposite
ensemble is discussed in Section 3.1 along with the homogeniza-
tion scheme used for the estimation of the nonlinear composite
system material properties. The paper concludes with a discus-
sion of the results in Section 4.
2. Analysis of carbon nanotubes
Carbon nanotubes are present mainly in three configurations:
single-walled carbon nanotubes, multiwalled carbon nanotubes,
and carbon nanotube bundles or ropes. They are many orders of
magnitude stronger, stiffer, conductive, and lighter than the best
available carbon fibers [4,9,18–23]. Single-walled nanotubes are
idealized as being formed by the folding of a graphene sheet into
a hollow cylinder, which is composed of hexagonal carbon ring
units referred to as graphene units [24–26,18]. Each of the carbon
atoms forming the tubules has three nearest neighboring bonds
and in a fully relaxed structure, the angles between these bonds
depend on the radius of the cylinder as well as on their orienta-
tion [24,18].
Studies on estimating the mechanical properties of nanotubes
were carried out atomistic simulations like molecular dynamics
(MD) or ab initio methods. In MD simulations the motion of
particles in an atomistic system is governed by the Hamiltonian,
which is a function of the position and momentum of the
particles, and the Hamiltonian equations of motion. The
dH @U
¼ ð3Þ
dr i @ri
The reliability of an MD simulation depends mainly on the
type of potential functions. Empirical bond-order potentials of the
Tersoff–Brenner type are found to be excellent for the simulation
of carbon based materials [27,28,4,11,22,21,7]. These types of
potentials are capable of describing the changes in the bonding in
a system but lacks in describing long range interactions, which
are often neglected [29]. In Tersoff type potentials the binding
energy of an atomic many-body system can be computed in terms
of pair-wise nearest-neighbor interactions modified by the local
atomic environment. In this work we use the Tersoff–Brenner
type of potential for the simulation of carbon–carbon interactions.
The total potential energy of an atom is given by
XX
U¼ fc ½aij Er ðrij Þbij Ea ðrij Þ ð4Þ
j j4i
Here Er ðrij Þ ¼ Aij elij rij represents the repulsive pair-wise potential,
such as the core–core interactions, of the potential function and
Ea ðrij Þ ¼ Bij emij rij represents the attractive part of the potential
function that represents the bonding due to the valence electrons.
The total potential of the nanotube structure is given by the sum
of valence bond energies and the nonbonding interactions
XX
U tot ¼ ½VijB þ VijNB  ð5Þ
j j4i
where VijB is the potential energy due to bonding and VijNB is the
potential energy due to nonbonding interactions. The force of
attraction and repulsion (Fab Þ experienced by each molecule is
obtained from the gradient of the potential field.
@U tot
Fab ¼  ð6Þ
@rab
The elastic constants can be obtained directly from the varia-
tion of the potential energy with respect to the spatial distance
[14,30,4] for nanotubes. The total potential energy due to the
strain which is the elastic strain energy can be expanded as a
Taylor series for small displacements, with the initial position
being represented by the equilibrium position. The elastic moduli
tensor can be written as
2 3
!
6 2 7
1 X6 6 d U  1 dU aa ab ag ad þ dbd 1 dU aa ag 7
7
Cabgd ¼ 6 2 ij ij ij ij ij ij 7 ð7Þ
2N Oa j a i 4 dr rij dr ij rij dr ij 5
ij |fflfflfflfflfflfflffl{zfflfflfflfflfflfflffl}
Aag ¼ 0
where Cabgd is the elastic moduli; U ¼ Uðrij Þ is the potential energy
as a function of the interatomic distance rij ; Aag is the internal
stress tensor, and at equilibrium is equal to zero; Oa is the
average volume of an atom and N is the number of atoms; dab
is the Dirac delta function and a, b, g, d are the spatial dimensions.
 V. Unnikrishnan, J.N. Reddy / Finite Elements in Analysis and Design 49 (2012) 13–18 15

aij is the undeformed value of rij , where uij ¼ rij aij , and ubij ¼ aaij eab ,
eab is the homogenous infinitesimal strain tensor applied between
atoms i and j. The application of any thermostat in the MD
simulations should therefore be carried out before the straining
process and hence extraction of the elastic properties can be
carried out at various temperatures as an equivalent continuum
(EC) [8,31].
3. Interphases in nanocomposites
Numerous experiential works have predicted an increase in
the stiffness of the resulting polymeric composite reinforced with
nanotubes [18,1,32,7,25,3]. The large surface area and the nan-
ometer dimensions of the nanotube increase the quantum of
molecular interactions between the molecules of the surrounding
polymer and the atoms of the nanotube and has been experi-
mentally observed especially in the works of Ding et al. [33] and
Sandler et al. [34] and Barber et al. [35]. These experiments
categorically prove that the interfacial strength of nanotube–
polymer interface is strong for an effective load transfer and
The stress components ðsij Þ are given as sij ¼ @C=@eij , where eij
are the strain components. The components of deformation
gradient tensor F are given by Fij ¼ @xi =@Xj , where Xj and xi are
the components of the material and spatial coordinates, X and x,
respectively. In a composite material with two or more partici-
pating phases (e.g., matrix, fiber, interphase, etc.), the elastic
response is assumed to result from the contributions of the
individual phases and their interactions. Therefore, the strain
energy function of the composite C ~ can be divided into three
parts, namely
~ ¼ Cm þ Cf þ Cfm
C ð10Þ
where C represents the strain energy and the superscripts m,f ,fm
denote the contributions due to the matrix phase, fiber phase and
fiber–matrix interactions respectively. The strain-energy density
function can be expressed as a linear combination of the strain
invariants (I1 ,I2 ,I3 ) functions of the left Cauchy–Green strain
tensor
X
n
C¼ ck ðI1 ,I2 ,I3 Þ ð11Þ
k1

hence mathematical simulations with perfect load transfer con- where ck are convex scalar functions. The invariants of the strain
ditions are acceptable. The emphasis of this study however is on deformation tensor B is given by
the characterization of polymer layer immediately surrounding 2 2 2
the nanotube, called the interphase, which is found to have an I1  trðBÞ ¼ l1 þ l2 þ l3
altered effective property which is not related to the bulk of the 2 2 2 2 2 2
material. Ding et al. [33] have observed that the total effective I2  12ðI12 trðB2 ÞÞ ¼ l1 l2 þ l2 l3 þ l3 l1
diameter of the multiwalled nanotube embedded in a polycarbo-
2 2 2
nate polymer is larger the actual diameter of the nanotube and I3  detðBÞ ¼ l1 l2 l3 ð12Þ
this indicates that there exists strong interaction between the T
where B ¼ FF is the left Cauchy–Green strain tensor and
surrounding polymer molecules. According to Fisher and Brinson fl1 , l2 , l3 g are the principal stretches. For an incompressible
[1] the interphase thickness is of the order of the diameter of the material the stress–strain relationship is given by
nanotube.
@W
The effect of the interphase cannot be completely eliminated sij ¼ pdij þ ð13Þ
in the analysis of the effective properties of the composite. @eij
Interphase analysis of fiber matrix composites due to various where p is the pressure. In a nonlinear elastic material, the body
effects considers the variation of the interphase property based on recovers its original position upon removal of the external forces
Wacker et al.’s [36] mathematical model given by causing deformation, but the relationship between the stress and
  strain is not linear. The strain energy function for a compressible
r r n
Ei ¼ ðaEf Em Þ i þ Em ð8Þ neo-Hookean material in the reference configuration is given by
ri rf
m k
where Ei,f ,m is the modulus of the interphase, fiber and matrix W¼ ðJ 2=3 I1 3Þ þ ðJ1Þ2 ð14Þ
2 2
phases respectively and 0 r a r1, and n ¼ 2; 3, . . .. The effective
where J ¼ detðFÞ and
average transverse modulus of the interphase is given by
Ee Ee
ri rf m¼ and k¼ ð15Þ
Ei ðrÞ ¼
R ri 1
ð9Þ 2ð1þ ne Þ 3ð12ne Þ
rf E ðrÞ dr Here Ee denotes Young’s modulus of the homogenized material in
i
the mesoscale and ne is the corresponding Poisson’s ratio. When
the material is incompressible J¼1 and the second term in the
3.1. Homogenization of hyperelastic nanocomposite strain energy density function vanishes.

Let us now consider a homogenous and hyperelastic composite

system comprising the matrix and fiber phases along with the
interphases. Such hyperelastic materials can be characterized as
materials that can undergo large elastic strains with essentially
small compressibility. The deformation characteristic can then be
defined by the strain energy function C [37–39], which is
assumed to be objective, isotropic and strongly elliptic (rank
one convex) functions of the deformation gradient F. Considering
O0  R3 to be the reference configuration of a deformable body
with no discontinuities, let the current position of a point X be
X A O0 , which refers to the material position in the body. Under
the action of external or internal forces, the point X moves to the
position x in the current (deformed) configuration such
that x ¼ X þu, where u is the displacement vector and the motion
(or deformation mapping) is defined by the mapping fðX,tÞ.
4. Results and discussion
In this work, MD simulations of carbon nanotube of finite
length using Tersoff–Brenner potential were carried out for a Zig-
Zag (17,0) nanotube ensemble at 300 K with periodic boundary
conditions. A maximum of eight layers of polyethylene matrix
layers are distributed equally around the nanotube (see Fig. 1) in
a nanocomposite system. To exclude the boundary effect the
atoms of the nanotube for about one diameter length from the
edge were restrained [4,11,22]. The nanotube–polymer ensemble
is equilibrated to 300 K over a sequence of temperature incre-
ments and total energy at this state is taken as the ground
potential energy. The nanotube–polymer units are now strained
at a constant rate to a maximum of 5% strain followed by each
16 V. Unnikrishnan, J.N. Reddy / Finite Elements in Analysis and Design 49 (2012) 13–18

minimization and the potential energy is determined at the end of

each increment cycle. The difference in the potential energy,
indicates the strain energy in the system and the second deriva-
tive of this strain energy with respect to the axial strain gives the
elastic modulus. In the analysis, pristine individual nanotubes are
referred to as ‘‘neat’’ and as ‘‘embedded’’ when the nanotube is
embedded in a polymer matrix. In a typical multiscale analysis we
are interested in understanding the effect of an embedded
nanotube on the overall mechanical properties of a composite
system. In this manuscript we study the effect of the surrounding
polymer on the overall effective property of a nanotube. Due to
these molecular interactions between the atoms of the nanotube
and the surrounding polymer, the effective properties of the
surrounding polymer undergoes change in its mechanical char-
acteristics that are not related or independent of the bulk proper-
ties of the polymer. This altered mechanical property needs to be
estimated to characterize the overall effective property of the
composite system by considering the interphase layer as an
independent phase.
A ‘‘functionalized’’ carbon nanotube with ethylene chains as
the functional group is shown in Fig. 2. The sites of substitution
are chosen randomly along the length of the nanotube and
therefore no specific order is used in the creation of the functio-
nalized nanotube and the ethylene chain is of sufficient length to
be attached to the surrounding polymer. After minimization of Fig. 4. Variation of elastic stiffness of core single walled nanotube with the
the functionalized nanotube ensemble, tensile strains are applied number of layers of polyethylene matrix.
incrementally, followed by a relaxation cycle. The change in the
elastic modulus (TPa) of the functionalized nanotube is compared
with a neat nanotube (Fig. 3) and is in good agreement with
published results [11,20]. When strain is applied on a composite
material with a functionalized nanotube, the chemical attach-
ment usually breaks at the fiber wall and the bonded chain gets
sufficient time to get disentangled from the surrounding matrix.
The corresponding movement of the attached polymer helps in
dissipating the energy during deformation thereby increasing
the overall resistance of the material to failure [40]. The effect
of the surrounding polymer on the overall effective property of a
neat nanotube is shown in Fig. 4 for different polymer layers. The
significance of this paper lies in the fact that we estimate
the effect of the polymer on the nanotube as well as understand
the effect of the nanotube on the polymer layer surrounding the
nanotube.
Considering the interphase property of the nanotube polymer
systems, it has been reported that for purely polyethylene based
composites, the value of a in Eq. (8) is around 0.21 with the value
of n fixed. In this work, the elastic modulus of polyethylene
matrix is taken as 610 MPa and the value of n is taken as 2 [7].
Since this model takes into consideration the polymer based

Fig. 5. Variation of axial stiffness along the radius of the composite in the
interphase region for neat and functionalized carbon nanotube systems.

composite systems, the direct application of the load transfer

Fig. 3. Elastic properties of various single walled nanotube ensembles.
mechanism into the molecular regime can be implicitly assumed.
Thus, we are able to model the effective properties of the
interphase based on the properties of the surrounding matrix in
the outer layer and the effective property of the nanotube which
forms the inner core. The effective axial stiffness of the interphase
is calculated from Wacker et al.’s model [36] in the longitudinal
direction for nanotube-polymeric systems having neat and func-
tionalized nanotubes. The significance of such an approach is that
we choose the modified modulus of the nanotube, due to the
effect of the surrounding polymer, to estimate the overall effec-
tive property of the interphase. In a nanotube reinforced nano-
composite system (with an incompressible polymer), the elastic
property of the interphase can be obtained from Fig. 5. At the
 V. Unnikrishnan, J.N. Reddy / Finite Elements in Analysis and Design 49 (2012) 13–18
Fig. 6. Variation of bulk and shear modulus of interphases with neat, functionalized and embedded nanotubes.
mid-section of the interphase for neat nanotube systems, the
homogenized elastic modulus is obtained as 0.5 TPa from Eq. (8),
and the corresponding shear and bulk modulus are obtained as
0.17 TPa and 8.4 TPa respectively using Eq. (15). The shear and
bulk modulus for functionalized and embedded nanotubes are
shown in Fig. 6. It should be noted that the homogenized shear
and bulk modulus of the matrix phase could also be estimated
using homogenization schemes for use in the multiscale model.
5. Conclusions
For the accurate and reliable estimation of the properties of
nanocomposites, an efficient multiscale modeling strategy is
imperative. In this paper, we determine the effect of the sur-
rounding polymer on the mechanical properties of the central
nanotube and also on a nanocomposite system using a multiscale
approach. In this study, we also estimate the effect of chemical
functionalization and imperfect load transfer on the stiffness of
nanotubes along the axis of the nanotube. The estimated proper-
ties of the nanotube are subsequently used in an interphase
model for the estimation of the interfacial property. The novelty
of the present approach lies in the fact that the overall effective
property of the hyperelastic nanocomposite system can be esti-
mated using the homogenized properties of the nanostructures.
Acknowledgment
The authors acknowledge the support of this study by the
Oscar S. Wyatt Endowed Chair account at Texas A&M University.
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