Multiscale modeling of compressive behavior of carbon

nanotube/polymer composites
Chunyu Li, Tsu-Wei Chou
*
Department of Mechanical Engineering, University of Delaware, Newark, Delaware 19716, USA
Received 11 January 2006; accepted 12 January 2006
Available online 3 March 2006
Abstract
This paper reports a multiscale modeling of the compressive behavior of carbon nanotube/polymer composites. The nanotube is mod-
eled at the atomistic scale, and the matrix deformation is analyzed by the continuum nite element method. The nanotube and polymer
matrix are assumed to be bonded by van der Waals interactions at the interface. The stress distributions at the nanotube/polymer inter-
face under isostrain and isostress loading conditions have been examined. The buckling forces of nanotube/polymer composites for dif-
ferent nanotube lengths and diameters are computed. The results indicate that continuous nanotubes can most eectively enhance the
composite buckling resistance.
2006 Elsevier Ltd. All rights reserved.
Keywords: A. Carbon nanotube; Nanocomposites; B. Multiscale modeling; C. Buckling
1. Introduction
It has been theoretically and experimentally conrmed
that carbon nanotubes possess exceptional high stiness
and strength [15]. These properties as well as their high
aspect ratio and low density suggest that carbon nanotubes
may hold promise as the reinforcement for nanocomposites
[6,7]. The improvement in stiness and strength due to the
addition of carbon nanotubes in polymeric matrix materi-
als have been demonstrated [810]. For the eective utiliza-
tion of nanotubes as reinforcements in composites, various
attempts have been made regarding the dispersion and
alignment issues of nanotubes and well-dispersed and
well-aligned nanotube reinforced composites are now feasi-
ble [1115]. Meanwhile, some eorts have also been
devoted to the study of the load transfer between nano-
tubes and the matrix [9,10]. The transmission electron
microscopy study of Ajayan et al. [16] indicated weak inter-
facial bonding between the nanotubes and resin matrix.
The measurements of Schadler et al. [9] showed better load
transferring eciency when the composites are under com-
pression than tension. For enhancing the load transfer
capability, some researchers proposed the functionalization
of carbon nanotubes to form chemical bonds between
nanotubes and the matrix [17,18].
Due to the diculty in modeling nanotube reinforced
composites, analytical studies on the mechanisms of load
transfer between the matrix and nanotubes are still very
limited. Among the available literature, Lordi and Yao
[19] used force-eld-based molecular mechanics to model
the interactions between nanotubes and several dierent
kind of polymers. Wise and Hinkley [20] used molecular
dynamics simulation for addressing the local changes in
the interface of a single-walled nanotube surrounded by
polyethylene molecules. Odegard et al. [21] studied the
eect of chemical functionalization on the mechanical
properties of nanotube/polymer composites by using an
equivalent-continuum modeling technique. More recently,
Li and Chou [22] analyzed the stress distributions in carbon
nanotube/polymer composites under tension by combining
the atomistic molecular structural mechanics approach and
0266-3538/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2006.01.013
*
Corresponding author. Tel.: +1 302 831 6551; fax: +1 302 831 3619.
E-mail address: chou@me.udel.edu (T.-W. Chou).
www.elsevier.com/locate/compscitech
Composites Science and Technology 66 (2006) 24092414
COMPOSITES
SCIENCE AND
TECHNOLOGY
the continuum nite element method. There is still a lack of
extensive analytical studies of the behavior of nanotube/
polymer composites under compression.
In this paper, we examine the compressive behavior of
carbon nanotube/polymer composites using a multiscale
modeling approach. Following the technique of Ref. [22],
the nanotube is modeled at the atomistic scale by the
molecular structural mechanics method, and the matrix
deformation is analyzed at the macroscopic scale by the
continuum nite element method. The nanotube and poly-
mer matrix are assumed to be bonded by van der Waals
interactions at the interface. The load transfer at the inter-
face is considered rst, followed by an examination of the
buckling behavior of nanotube/polymer composites.
2. Modeling of nanotube/polymer composites
In this paper, we only considered nanocomposites rein-
forced by single-walled carbon nanotubes. Two cylindrical
unit cells, as shown in Fig. 1, are chosen as computational
models. One is the discontinuous reinforcement model where
the nanotube is entirely embedded in the matrix (Fig. 1a).
Another is the continuous reinforcement model, where the
length of the nanotube is assumed to be the same as the
length of the surrounding polymer matrix (Fig. 1b). The rst
model is used particularly for analyzing the stress distribu-
tion around the interface. Both models are used in comput-
ing the buckling force of nanotube/polymer composites.
2.1. Modeling of carbon nanotubes
As reinforcements in nanotube/polymer composites,
unlike traditional carbon bers, nanotubes are highly
size/structure dependent. The modeling of nanotubes at
the atomistic scale is necessary for nanotube-based com-
posites. But for the stress analysis of nanotube/polymer
composites, the application of extensively employed molec-
ular dynamics is time-consuming and unnecessary since the
task is essentially a static problem. Thus, the molecular
structural mechanics approach [23], which was developed
by the authors and was conrmed to be computationally
ecient, is adopted for modeling nanotubes. The main
concept of this approach is briey outlined below.
A single-walled carbon nanotube is viewed as a space
frame, where the covalent bonds are represented as con-
necting beams and the carbon atoms as joint nodes. Based
on the energy equivalence between local potential energies
in computational chemistry and elemental strain energies in
structural mechanics, we can determine the tensile resis-
tance, the exural rigidity and the torsional stiness for
an equivalent beam. The energy equivalence is schemati-
cally shown in Fig. 2. If the beam element is assumed to
be of round section, then only three stiness parameters,
i.e., the tensile resistance EA, the exural rigidity EI and
the torsional stiness GJ, need to be determined for defor-
mation analysis. By considering the energy equivalence, a
direct relationship between the structural mechanics
parameters and the molecular mechanics force eld con-
stants can be established [23], i.e.,
EA
L
k
r
;
EI
L
k
h
;
GJ
L
k
s
1
where k
r
, k
h
and k
s
are the force eld constants in molecu-
lar mechanics. Then, following the procedure of the struc-
tural mechanics technique, the nanotube deformation
under certain loading conditions can be readily solved.
2.2. Modeling of polymer matrix
Because the volume of the matrix is usually much
greater than that of the reinforcement, it is formidable to
simulate it using an atomistic modeling. Therefore, as a
compromise, the polymer matrix is treated as a continuous
medium and the nite element method is adopted for mod-
eling its deformation. Two kinds of three dimensional nite
elements are used in the meshing of the matrix: 20-node
isoparametric cubic element and 15-node isoparametric
wedge-shaped element. The 20-node element is used in
the circumferential region surrounding the nanotube,
whereas the 15-node element is used in the regions directly
above and below the nanotube.
2.3. Modeling of nanotube/polymer interface
Because the nanotube is modeled at the atomistic scale
and the polymeric matrix is treated as a continuum, the
modeling of the nanotube/polymer interface is rather di-
cult. Although some researchers have attempted to func-
tionalize the nanotube to establish its strong bonding
with the matrix, the bonding between the nanotube and
the matrix is in general by van der Waals interactions.
For simulations of van der Waals interactions at the
nanotube/polymer interface, a truss rod model, which
was introduced by the authors in Ref. [24], is adopted.
Fig. 3 illustrate the truss rods connecting carbon atoms
with nodes in nite elements. In this model, based on the
Lennard-Jones 612 potential, the van der Waals force
between interacting atoms is written as
Fig. 1. Computational models for nanotube/polymer composites: (a)
discontinuous tube cell; (b) continuous tube cell.
2410 C. Li, T.-W. Chou / Composites Science and Technology 66 (2006) 24092414
F r
dUr
dr
24
e
r
2
r
r

13

r
r

7

2
where r is the interatomic distance, e and r are the Lennard-
Jones parameters. For carbon atoms the Lennard-Jones
parameters are e = 0.0556 kcal/mole and r = 3.4 A

[25].
The activationof a truss rodis determined by the distance be-
tween an atom in the nanotube and a node in the nite ele-
ment. If the distance between an atom in the nanotube and
a node in the inner surface of the matrix is less than 2.5r, a
truss rod is activated. For convenience in computation, we
only consider the van der Waals interactions between the
nanotube and the inner surface of the polymeric matrix sur-
rounding the nanotube. The center of the atoms in the single-
walled nanotube is assumed to be located in mid-section of
the tube wall thickness, which is assumed to be 0.34 nm.
The inner surface of polymer matrix is assumed to be located
at the same position as the outer surface of the nanotube.
3. Elastic buckling of nanotube/polymer composites
Under compressive loading, one of the failure modes of
a structural component is elastic instability, namely, buck-
ling. For understanding the performance of nanotube/
polymer composites under compression, elastic buckling
is a fundamental issue that needs to be addressed. Accord-
ing to the theory of structural stability [26], the buckling
force of a structural element can be determined by the
eigenvalue analysis, which requires the consideration of
the geometrically nonlinear problem.
Assuming that the total elastic stiness matrix K
E
and
total geometric stiness matrix K
G
can be assembled fol-
lowing the conventional procedures in structural analysis,
the eigenvalue equations for determining the load factor
are expressed as
K
E
kK
G
U 0. 3
Here k is the loading factor and U is the vector of displace-
ments. By solving the above eigenvalue equations, the low-
est value k
min
can be obtained. Then the buckling force can
be given by
P k
min
P

; 4
where P
*
stands for the reference loading.
For the nanotube modeled by the molecular structural
mechanics approach, the element stiness matrix K
e
, which
contributes to the total elastic stiness K
E
, is given by
K
e

K
e
ii
K
e
ij
K
eT
ij
K
e
jj

; 5
where K
e
ii
, K
e
ij
and K
e
jj
can be found in Ref. [23], and K
eT
ij
is
the transpose of K
e
ij
. The element geometric stiness matrix
K
g
, which contributes to the total elastic stiness K
E
, is gi-
ven by [27]
K
g

K
g
ii
K
g
ij
K
gT
ij
K
g
jj

; 6
where K
g
ii
, K
g
ij
and K
g
jj
are listed in the Appendix [29] and
K
gT
ij
is the transpose of K
g
ij
.
For the nanotube/polymer interface, the forcedisplace-
ment relationship of a truss rod is nonlinear. The nonlinear
relationship of the truss rod can be expressed in the same
form as the geometric stiness matrix, Eq. (6). Its submatri-
ces are as follows:
K
vdw
ii
K
vdw
jj

A 0
33
0
33
0
33

; K
vdw
ij
K
vdw
ii
; 7
where
A
a 0 0
0 0 0
0 0 0

; a 24
e
r
2
26
r
r

14
7
r
r

8

; 0
33

0 0 0
0 0 0
0 0 0

.
8
Fig. 2. Modeling of nanotubes by the molecular structural mechanics approach.
Fig. 3. Illustrations of truss rods connecting nodes in nite elements with
carbon atoms: (a) on the nanotube lateral surface and (b) on the nanotube
end cap region.
C. Li, T.-W. Chou / Composites Science and Technology 66 (2006) 24092414 2411
For the polymer matrix, the general expressions for the
elemental elastic stiness matrix and geometric stiness
matrix are [28], respectively,
K
e
m

V
B
T
DBdV ; 9
K
g
m

V
G
T
MGdV ; 10
where B and D are, respectively, the strain matrix and the
elasticity matrix for three dimensional nite elements, and
the superscript T indicates transpose. The matrices G and
M are
G
oN
1
ox
I
33
oN
2
ox
I
33

oNn
ox
I
33
oN
1
oy
I
33
oN
2
oy
I
33

oNn
oy
I
33
oN
1
oz
I
33
oN
2
oz
I
33

oNn
oz
I
33

; 11
M
r
xx
I
33
r
xy
I
33
r
xz
I
33
r
yx
I
33
r
yy
I
33
r
yz
I
33
r
zx
I
33
r
zy
I
33
r
zz
I
33

. 12
In Eqs. (11) and (12), I
33
denotes the 3 3 identity matrix,
N
i
(i = 1, 2, . . ., n) is the shape function of n-node nite ele-
ments, r
ij
(i, j = x, y, z) is the stress component at the
Gaussian integral point resulted from the applied load.
4. Results
Using the molecular structural mechanics approach and
nite element method, The computational modeling of a
continuous nanotube- and a discontinuous nanotube-rein-
forced polymeric matrix composite has been carried out.
The matrix is assumed to be an epoxy polymer with Youngs
modulus and Poisson ratio of 2.41 GPa and 0.35, respec-
tively. The nanotube is assumed to be zigzag type with end
caps.
We consider two cases of loading, i.e., isostress and iso-
strain conditions, for the analysis of stress distribution.
Due to the symmetry of the problem, only top halves of
the computational cells are considered. The nite element
nodes at the symmetry plane of the matrix are assumed
to be constrained in the axial direction for both cases.
Under the isostress and isostrain conditions, a uniform
stress and a uniform displacement are imposed, respec-
tively, on the nite element nodes at the top surface the
matrix. For the computation of buckling force, the whole
computational cell is considered.
The stress distributions in the nanotube/polymer com-
posite are examined using the computational cell with a
discontinuous nanotube. The normalized axial and shear
stresses in the polymer matrix are shown in Figs. 4 and 5,
respectively for both isostrain and isostress loading condi-
tions. The stresses are normalized by either the magnitude
of the uniform applied stress (isostress case) or the applied
strain multiplied by the Youngs modulus of the matrix
(isostrain case). Since the stress distribution is axially sym-
metric, only one quarter of the matrix material is shown in
a radial section through the nanotube centerline.
The axial stress distribution in the matrix given in Fig. 5
shows that high stress concentration exists at the vicinity of
the nanotube cap. The overall trends of axial stress distri-
bution for isostrain and isostress conditions are similar,
but the magnitude of stress concentration under isostrain
condition is higher than that under isostress condition.
Fig. 6 shows that the maximum shear stresses occur at
the vicinity of nanotube ends rather than nanotube caps,
for both isostrain and isostress conditions, and the shear
stresses vanish at the middle section of the nanotube, as
expected. Again, the maximum shear stress in the isostrain
case is larger than that of the isostress case.
The buckling behavior of nanotube-reinforced polymer
composites is studied for both of the computational cells of
Fig. 1. For the model with a discontinuous nanotube, several
nanotube length/diameter ratios are considered. The volume
fraction of nanotubes ranges from 2.5% to 6.2%.
Fig. 7 displays the buckling force of nanotube-rein-
forced polymer composites under uniform compression at
Fig. 4. Element meshes for computational cells: (a) discontinuous
nanotube (b) continuous nanotube.
Fig. 5. Normalized axial stress distribution in the polymer matrix.
2412 C. Li, T.-W. Chou / Composites Science and Technology 66 (2006) 24092414
one end while the other end is xed. It can be seen that the
buckling force is dependent on the volume fraction of
nanotube, and increases with increasing nanotube length.
But a dramatic increase of the bucking force appears when
the nanotube approach to the same length as the matrix,
i.e., the case of continuous nanotube. The higher local
stress concentrations at the nanotube ends may be the main
reason that the discontinuous nanotube is not as eective
as the continuous nanotube in improving the load bearing
capability of nanocomposites.
5. Conclusions
In this paper, a multiscale modeling of carbon nano-
tube/polymer composites under compression is presented.
The nanotube is modeled at the atomistic scale, and the
matrix deformation is analyzed by the continuum nite ele-
ment method. The nanotube and the polymer matrix are
assumed to be bonded by van der Waals interactions at
the interface. The simulations revealed the stress distribu-
tions at the nanotube/polymer interface under isostrain
and isostress loading conditions. The buckling forces of
nanotube/polymer composites for dierent nanotube
lengths and diameters are also computed. The results indi-
cate that continuous nanotubes can most eectively
enhance the composite buckling resistance.
Acknowledgements
This work is supported by the Army Research Oce
(Grant No. DAAD 19-02-1-0264, Dr. Bruce LaMattina,
Program Director) and the National Science Foundation
(NIRT Program, Grant No. 0304506, Dr. Ken P. Chong,
Program Director).
Appendix
The submatrices of the geometric stiness matrix from
Yang and Kuo [29] are as follows:
K
g
ii

a 0 0 0 d e
b 0 d g k
c e h g
f i l
sym. j 0
m

; A:1
K
g
ij

a 0 0 0 n o
0 b 0 n g k
0 0 c o h g
0 d e f i l
d g h i p q
e k g l q r

; A:2
K
g
jj

a 0 0 0 n o
b 0 n g k
c o h g
f i l
sym. j 0
m

; A:3
where
a
F
xb
L
; b c
6F
xb
5L

12F
xb
I
AL
3
; d
M
ya
L
;
e
M
za
L
; f
F
xb
J
AL
; g
M
xb
L
;
h k
F
xb
10

6F
xb
I
AL
2
; i
M
za
M
zb
L
;
j m
2F
xb
L
15

4F
xb
I
AL
; l
M
ya
M
yb
6
; n
M
yb
L
;
o
M
zb
L
; p r
F
xb
L
30

2F
xb
I
AL
; q
M
xb
L
;
A:4
Fig. 7. Buckling force of nanotube-reinforced polymer composites (R
nt
and R
m
denote, respectively, nanotube diameter and matrix cylinder
diameter. L is the matrix cylinder length).
Fig. 6. Normalized shear stress distribution in the polymer matrix.
C. Li, T.-W. Chou / Composites Science and Technology 66 (2006) 24092414 2413
and F
xb
, M
xb
, M
ya
, M
yb
, M
za
and M
zb
are internal forces in
a beam element and shown in Fig. 8.
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