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Computational Mechanics
Solids, Fluids, Structures, Fluid-
Structure Interactions, Biomechanics,
Micromechanics, Multiscale Mechanics,
Materials, Constitutive Modeling,
Nonlinear Mechanics, Aerodynamics

ISSN 0178-7675

Comput Mech
DOI 10.1007/s00466-013-0908-x
Interface characteristics of carbon
nanotube reinforced polymer composites
using an advanced pull-out model
Khondaker Sakil Ahmed & Ang Kok
Keng
1 3
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Comput Mech
DOI 10.1007/s00466-013-0908-x
ORIGINAL PAPER
Interface characteristics of carbon nanotube reinforced polymer
composites using an advanced pull-out model
Khondaker Sakil Ahmed Ang Kok Keng
Received: 24 November 2012 / Accepted: 31 July 2013
Springer-Verlag Berlin Heidelberg 2013
Abstract An advanced pull-out model is presented to
obtain the interface characteristics of carbon nanotube (CNT)
in polymer composite. Since, a part of the CNT/matrix inter-
face near the crack tip is considered to be debonded, there
must present adhesive vander Waals (vdW) interactionwhich
is generally presented in the formof Lennard-Jones potential.
A separate analytical model is also proposed to account nor-
mal cohesive stress caused by the vdW interaction along the
debonded CNT/polymer interface. Analytical solutions for
axial and interfacial shear stress components are derived in
closed form. The analytical result shows that contribution of
vdW interaction is very signicant and also enhances stress
transfer potential of CNT in polymer composite. Paramet-
ric studies are also conducted to obtain the inuence of key
composite factors on bonded and debonded interface. The
result reveals that the parameter dependency of interfacial
stress transfer is signicantly higher in the perfectly bonded
interface than that of the debonded interface.
Keywords Polymer composites Stress transfer
Debonded interface Analytical pull-out model
van der Waals interaction
1 Introduction
Carbon nanotubes have stimulated extensive research activ-
ities devoted to smart materials including nanocomposites
and their applications in the wide range of engineering, mate-
rial science, physics and chemistry because of their excep-
tional properties [19]. It is well known that aspect ratio
K. S. Ahmed (B) A. K. Keng
Department of Civil &Environmental Engineering, National University
of Singapore, Singapore 117576, Singapore
e-mail: ceeksa@nus.edu.sg
(AR) and surface to volume ratio (SVR) of nanotubes are
higher in magnitudes than those of traditional composites.
Carbonnanotubes are alsoidentiedtohave great potential as
reinforcements of high strength and lightweight smart com-
posites [6, 10, 11]. The notable factors that affect the perfor-
mance of carbon nanotube (CNT) reinforced composites are
the mechanical properties of nanotubes, their purity, interac-
tions with host, dispersion, orientation of CNTs in the matrix
and CNT/polymer interface. Similar to conventional ber
reinforced composites, many research studies also suggested
that the performance of CNT reinforced composites depends
critically on the interfacial properties of the nanocomposite
[1216].
The main contributing factors for interfacial load trans-
fer between CNT and polymer are generally chemical bond-
ing, mechanical interlocking (friction), electrostatic force
and non-covalent bonding like van der Waals (vdW) inter-
actions [1719]. The presence of chemical bonding leads
the CNT/polymer interface to be perfectly bonded in which
other factors may be considered to be insignicant. Previous
research study also revealed that chemisorption to as little
as 5.0% carbon atoms of the nanotube increases the interfa-
cial shear stress by about 1,000% [20]. However, chemical
bonding at the CNT/matrix interface may be damaged due
to higher local stress intensity on CNT surface [21]. Chem-
ical bonding may also be defected due to excessive load-
ing, fatigue or improper manufacturing process that lead the
interface to debonded and the stress transferring ability of this
type of debonded interface is controlled by mechanical inter-
locking, thermal residual stress, Poissons contraction, vdW
interaction and electrostatic energy. Cohesive energy caused
by the vdW interaction contributes three orders higher in
magnitude than the electrostatic energy [22]. The inuence
of electrostatic interaction is thus considered to be neglected
in the debonded interface.
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Comput Mech
Pull-out tests have been widely used to measure inter-
face characteristics of conventional ber reinforced compos-
ites for many years [2326]. However, it is very difcult to
examine experimental investigation for CNT pull out test
from polymer matrix due to the challenges involved in grip-
ing, manipulation and stress, strain measurement. As pre-
liminary study, analytical studies on pull-out test can serve
the purpose by considering all practical factors involved at
the different types of interface. Pull-out model on CNT rein-
forced composite have been conducted by using molecular
dynamic (MD) simulations [16, 27]. Though MD simulation
is generallyacceptedtobe more accurate, it is however highly
time consuming and costly. Recently, some researchers have
proposed various pull-out models for carbon nanotube rein-
forced composites using continuum mechanics approach
[2831]. Some of these models consider either the case of
frictionally bonded interface that are valid only for weak
CNT/matrix interface or non-bonded interface without den-
ing the source of interface strength. The pull-out models pro-
posed by Tan and Kin [28] and Natsuki et al. [32] investi-
gated the interfacial shear stress transfer for multi-walled
carbon nanotubes (MWCNT) in composites. Though they
considered the inter-wall van der Waals interaction in the
MWCNT they ignored the major portion of vdW interac-
tion that actually arises between the nanotube and polymer.
The study carried out by Daniel Wagner [30], the interfacial
shear strength in polymer composites reinforced by SWNT
has been estimated using a modied KellyTyson approach
which however assumes the interfacial shear stresses to be
uniform all through the length.
In addition, most of the previous pull-out models are
developed based on the stress free end condition. However,
CNTembedded in polymer matrix having a perfectly bonded
interface condition should experience equal matrixs stress at
the embedded end of CNT. A perfectly bonded CNT/matrix
interface using RVE concept was considered by [35]. Their
study was however on a shear lag model which assumes the
CNT to be fully embedded within the matrix and is aimed at
estimating the average stress components of the matrix and
CNT. On the other hand, a pull-out test model is designed to
estimate the critical pull-out force, the mechanism of stress
transfer from CNT to matrix as well as the factors that inu-
ence the composite behavior. No complete research work
on CNT pull-out model considering vdW based debonded
interface near the crack tip and perfectly bonded interface
in the remaining embedded length has been reported in the
literature.
This study aims to develop a complete pull-out model in
order to illustrate the actual stress transferring mechanism
of CNT reinforced polymer composite. In nanotube pull-out
test, a portion of the interface near the crack tip of the embed-
ded ber is expected to be debonded due to generation large
interfacial shear stress at the tip. Previous pull-out models
also show that maximum interfacial shear stress generally
develops near crack tip [2831, 33, 34]. This study also con-
siders the interface to be debonded near the crack tip and per-
fectly bonded interface in the remaining part of the embedded
nanotube. In order to compute the cohesive stress caused by
the effect of vdWinteraction in the debonded region of inter-
face, a separate model has also been proposed using contin-
uum analysis. Closed form analytical solutions are derived
that can be used to determine different stress components of
the nanocomposite. Contribution of vdW interaction along
the length of the debonded interface has been investigated.
Aparametric study has also been conducted to determine the
effect of key composite parameters. In order to serve the pur-
pose of applying nanotube as reinforcement in wide range of
polymer composite, the proposed model is also expected to
provide the solution for any percentage of debonded length
which includes completely debonded interface as well.
2 Proposed analytical pull-out model
Aschematic diagramof the proposedpull-out model is shown
in Fig. 1. Acracked section showing the propagation of inter-
face crack along the length of nanotube in polymer composite
is presented in Fig. 1a. A 3D cylindrical representative vol-
ume element (RVE) selected from a cracked section of the
composite to dene the current pull-out model is presented
in Fig. 1b. The debonded CNT/matrix interface is presented
in Fig. 1c to represent the mechanical interlocking and van
der Waals interaction. The z and r coordinates are assigned
along the axial and radial directions of the CNT, respectively.
The pull-out model comprises of a CNT of radius a partially
embedded within a cylindrical matrix of radius b. L is the
total embedded length of CNT with a debond length l from
the free end. Thus, the remaining portion of embedded CNT
of length (L l) is considered to be perfectly bonded with
polymer. F is the axial normal force applied at the open end
of the CNT.
In this study, it is considered that the CNT be replaced by
aneffective solidber havingthe same lengthandouter diam-
eter. The modulus of the effective ber E
f
can be expressed
in terms of elastic modulus of the nanotube E
t
as follows
[2, 35, 36]
E
f
=
A
nt
A
ef
E
t
=
2at t
2
a
2
E
t
(1)
in which t denotes the thickness of the nanotube.
The governing equilibrium equations for the pull-out
problem in terms of polar coordinates (r, , z) may be writ-
ten as
d
rr
dr
+
d
r z
dz
+

rr

r
= 0 (2a)
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Fig. 1 A schematic diagram of
the pull-out model for
imperfectly bonded interface
d
zz
dz
+
1
r
d(r
r z
)
dr
= 0 (2b)
where,
zz
,
rr
,

,
r z
are the axial, radial, hoop and shear
stress components, respectively and
rr
,
zz
,

,
r z
their
corresponding strain components, respectively.
Considering the material is isotropic and obeys Hookes
law, the constitutive equations may be written as

zz
=
1
E
{
zz
(
rr
+

)} (3a)

rr
=
1
E
{
rr
(
zz
+

)} (3b)

=
1
E
{

(
rr
+
zz
)} (3c)

r z
=

r z
G
(3d)
where E, G and are the Youngs modulus, shear modulus
and Poissons ratio, respectively.
The strain-displacement relationships may be written as

rr
=
du
dr
(4a)

zz
=
dw
dz
(4b)

=
u
r
(4c)

r z
=
du
dz
+
dw
dr
(4d)
where w, u the axial and radial displacements, respectively.
It is to be noted that Eqs. (2), (3) and (4) are valid for both
the effective solid ber and matrix.
The mechanical equilibriumequation at any section of the
reinforced region in the RVE can be written as
a
2
=
a
_
0

f
zz
(2r) dr +
b
_
a

m
zz
(2r) dr (5)
where (= F/a
2
) denotes the average stress applied in the
effective ber at z = 0 and the superscripts f and m refers
to the effective ber and matrix, respectively. The average
axial stresses of CNT and matrix can be expressed as

f
zz
=
2
a
2
a
_
0

f
zz
rdr (6a)

m
zz
=
2
b
2
a
2
b
_
a

m
zz
rdr (6b)
The boundary conditions of the pull-out model are

f
zz
(0) = (7a)

f
zz
(L) =
m
zz
(L) (7b)

f
zz
(l) =
f
l
(7c)

m
rr(a)
=
f
rr(a)
(7d)

m
zz
(b) = 0 (7e)

m
rr
(b) = 0 (7f)

f
r z
(a) =
m
r z
(a) =
i
(7g)

m
r z
(b) = 0 (7h)

m
r z
(b) = 0 (7i)

f
z(a,z)
=
m
z(a,z)
(7j)
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=
m

(7k)
u
m
r(a)
= u
f
r(a)
(7l)
w
f
z
(a) = w
m
z
(a) (7m)
where
f
l
is the axial stress of CNT at z = l and
i
is the
interfacial shear stress of the CNT.
Upon integrating Eq. (2b) with respect to r from 0 to a
and applying the boundary conditions given in Eq. (7g) for
the effective ber, we obtain
d
f
zz
dz
=
2
a

i
(8)
2.1 Interfacial shear stress in CNT/polymer debonded
interface
Since the stress transferring ability in the debonded inter-
face is controlled by mechanical interlocking, thermal mis-
match, Poissons contraction and van der Waals interactions,
the interfacial shear stress at this type of interface may be
presented as

i
= (q
0
q
1
+q
2
) (9)
where is the coefcient of friction at the nanotube matrix
interface to represent the mechanical interlocking at the
debonded CNT/matrix interface. q
0
, q
1
and q
2
are the resid-
ual stress due to differential thermal contraction, the radial
stress due to Poissons contraction and the cohesive stress
caused by vdW interaction acting as pressure normal to the
CNT surface at the non-bonded interface, respectively.
2.1.1 Thermal residual stress (q
0
)
This radial (compressive) stress (q
0
) is caused by the matrix
shrinkage due to differential thermal contraction of the con-
stituents upon cooling fromthe processing temperature. This
residual stress acts as a uniform pressure over the entire
interface, which can be estimated directly through experi-
mental investigation. This uniform radial stress can also be
determined by using the experimental value of temperature
change, thermal contraction, volume fraction, Poissons ratio
and Youngs modulus of the constituents as follows [37]
q
0
=
E
m

m
2
_
1 +v
f
+
(v
m
v
f )
f
E
f
E
_
_

f

m
_
T
_
_
_
1
_
1
Em
E
f
_
(1v
f )
2
+

m(v
m
v
f )
2

_
E
m
E
f
_ _
v
f
+
(v
m
v
f )
f
E
f
E
_
2
_
_
_
(10)
where T is the change of temperature after thermal cooling;

m
,
f
are the volume fractions of matrix and ber, respec-
tively;
f
,
m
are the thermal coefcients of expansion of
CNT and matrix, respectively; E the axial modulus of elas-
ticity of composite which is approximated by
E =
m
E
m
+
f
E
f
(11)
2.1.2 Radial stress due to differential Poissons ratio (q
1
)
The radial stress due to Poissons contraction is generally
formed at the interface due to the fact the ber has a smaller
Poissons ratio than matrix. When an axial tensile stress is
applied at the remote end of the RVE, contraction takes place
at the CNT/polymer interface and hence a compressive radial
stress generates at the interface acting normal to the ber. The
radial compressive stress caused by this contraction, q
1
may
be written as given by [38]
q
1
=

f

f
zz
(a, z)
m

m
zz
(a, z)

_
1
f
_
+1 +
m
+2
(12)
where
=
a
2
b
2
a
2
(13)
= E
m
/E
f
(14)
2.1.3 van der Waals interaction
One of the major challenges of this study is to account the van
der Waal interaction at the debonded CNT/polymer interface
using continuum based approach. The major difculty arises
in calculating each atominteraction because RVEmodel typ-
ically involves billions of atoms or even more. To meet this
challenge, this study assumes that the carbon nanotube is
placed in an innite polymer as proposed by [18] and esti-
mates total cohesive energy caused due to vdW interaction
at the CNT/matrix interface. In order to account individual
atoms interaction accurately, this study simplies the com-
putation by considering the number of atoms per unit sur-
face area of CNT and number of molecules per unit volume
of polymer. The vdW interactions between two non-bonded
atoms is usually represented by the Lennard-Jones potential
V (r) as follows
V (r) = 4
_

12
d
12


6
d
6
_
(15)
where d is the distance between non-bonded pair of atoms or
molecules; the characteristics bond length between CNT
and CH
2
units of the polymer;

2 is the equilibrium
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Fig. 2 An analytical model to determine cohesive stress caused by
vdW interaction
distance between the atoms and the bond energy at the
equilibrium distance.
A 2D CNT/polymer model is proposed to determine the
cohesive stress due to vdW interaction as shown in Fig. 2. In
the model, h is the equilibrium distance of the matrix with
respect to CNT in the innite polymer and O
i
the average
interface gap beyond equilibrium distance. Therefore, the
cohesive energy stored in an area d A of single walled nan-
otube embedded in a polymer volume dV due to the van der
Waals interaction can be written as

d A
= n
c
d A
_
V (d) n
p
dV (16)
where n
p
, n
c
are the number of polymer molecules per unit
volume and number of atoms per unit area of nanotube,
respectively. By substituting Eq. (15) into Eq. (16), and then
integrating over the entire volume, the total cohesive energy
can be simplied as follows

=
2
3
n
c
n
p

3
_
2
9
15 (h + O
i
)
9


3
(h + O
i
)
3
_
(17)
Now, differentiating Eq. (17) with respect to O
i
, the normal
cohesive stress due to van der Waals interactions may be
presented as follows [18]
q
2
=
d

dO
i
= 2n
p
n
c

2
_

_
1
_
0.4
1
6
+
O
i

_
4

0.4
_
0.4
1
6
+
O
i

_
10
_

_
(18)
Substituting q
1
and q
2
from Eq. (12) and Eq. (18) respec-
tively, into Eq. (9) leads to

i
=
_
q
0

f

f
zz
(a, z)
m

m
zz
(a, z)

_
1
f
_
+1 +
m
+2
+2n
p
n
c

2
_

_
1
_
0.4
1
6
+
O
i

_
4

0.4
_
0.4
1
6
+
O
i

_
10
_

_
_
_
_
(19)
Substituting Eq. (19) into Eq. (8) and then using Eq. (5), the
governing differential equation may be obtained as
d
f
zz
dz
=
2k
a

f
zz

2k
a
_
q
o
k


m

v
f
+ v
m
+
2n
p
n
c

2
k
_

_
1
_
0.4
1
6
+
O
i

_
4

0.4
_
0.4
1
6
+
O
i

_
10
_

_
_

_
(20)
where
k =
v
f
+ v
m

_
1 v
f
_
+1 +v
m
+2
(21)
2.1.4 Solution for debonded interface (0 z l)
The solution of the differential equation in the debonded
region (0 z l) can be obtained by using the bound-
ary condition as stated in Eq. (7). Thus the average axial
stress of CNT in debonded region may be obtained as,

f
zz
=
_
_
_
q
0
k
+
2n
p
n
c

2
k
_

_
1
_
0.4
1
6
+
O
i

_
4

0.4
_
0.4
1
6
+
O
i

_
10
_

v
f

v
f
+ v
m
_

_exp
2kz
a
(22)
Upon differentiating Eq. (22) with respect to z and substi-
tuting its derivative into Eq. (8), we obtain interfacial shear
stress as follows,

i
= k
_
_
_
q
0
k
+
2n
p
n
c

2
k
_

_
1
_
0.4
1
6
+
O
i

_
4

0.4
_
0.4
1
6
+
O
i

_
10
_

v
f

v
f
+ v
m
_

_exp
2kz
a
(23)
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2.2 Formulation for the perfectly bonded interface
In view of perfectly bonded interface that the matrix shear
stress (
m
r z
) has to be compatible with interfacial shear stress
(
i
) and the fact that the outer surface of matrix cylinder is
stress free,
m
r z
at any radial distance r can be derived by
integrating Eq. (2b) to give

m
r z
=
a
b
2
a
2
(b
2
r
2
)
r

i
(24)
As
du
dz
<<
dw
dr
, we may consider
du
dz
+
dw
dr

dw
dr
. Therefore,
Eq. (4d) may be rewritten as

r z
=
dw
dr
(25)
In view of Eqs. (25) and (3d) for both the ber and matrix
may then be rewritten as

f
r z
=
E
f
1 +
f
dw
f
dr
(26a)

m
r z
=
E
m
1 +
m
dw
m
dr
(26b)
By substituting Eq. (26b) into Eq. (24), we obtain
E
m
1 +
m
dw
m
dr
=

a
(b
2
r
2
)
r

i
(27)
By integrating Eq. (27) over a to b, we obtain

i
=
a

E
m
_
w
m
b
w
m
a
_
(1 +
m
)
_
b
2
ln
b
a
a
2
/2
_ (28)
Finally, by substituting Eq. (28) into Eq. (27) and integrating
over a to b, we obtain
w
m
(r, z) = w
m
a
+
_
b
2
ln
r
a
(r
2
a
2
)/2
_ _
w
m
b
w
m
a
_
_
b
2
ln
b
a
a
2
/2
_
(29)
In view that the axial stress is the predominant stress compo-
nent, we may assume that
rr
+

<<
zz
. Equation (3a)
may therefore be rewritten as

f
zz
= E
f
dw
f
dz
(30a)

m
zz
= E
m
dw
m
dz
(30b)
Equation (30b) in view of Eq. (29) becomes

m
zz
(r, z) =
m
zz
(a, z)
+
_
b
2
ln
r
a
(r
2
a
2
)/2
_ _

m
zz
(b, z)
m
zz
(a, z)
_
_
b
2
ln
b
a
a
2
/2
_ (31)
Upon substituting Eq. (31) into Eq. (5) and after rearranging,
we obtain

m
zz
(b, z) =

_

f
zz

_

+
_
1
1

m
zz
(a, z) (32)
where
=
b
2
(1 + )ln
b
a
(3b
2
a
2
)/4
_
b
2
ln
b
a
a
2
/2
_ (33)
Now, by substituting Eq. (28) into Eq. (8), we obtain
d
f
zz
dz
=
2

E
m
_
w
m
b
w
m
a
_
(1 +
m
)
_
b
2
ln
b
a
a
2
/2
_ (34)
By differentiating Eq. (34) with respect to z and making use
of
m
zz
(b, z) given in Eq. (32), we obtain the following second
order differential equation
d
2

f
zz
dz
2
=
2
(1 +
m
)

f
zz

m
zz
(a,z)

_
b
2
ln
b
a
a
2
/2
_ (35)
Since we consider that this part of the CNT/polymer interface
is perfectly bonded, i.e.
f
z
(a) =
m
z
(a), the stress strain
relationship given in Eq. (3a) reduces to

m
zz
(a, z) =
f
zz
(36)
Now, by substituting
m
zz
(a, z) from Eq. (36) and from Eq.
(33) into Eq. (35) and after rearranging, we obtain
d
2

f
zz
dz
2
=
2
a
2

2
(1 +
m
)
( + )
f
zz
_
b
a
_
4
ln
b
a
(3b
2
a
2
)/4a
2

(37)
which may be simplied and written as
d
2

f
zz
dz
2
C
1

f
zz
+C
1

+
= 0 (38)
where
C
1
=
2
a
2

2
(1 +
m
)
_
+
_
b
a
_
4
ln
b
a
(3b
2
a
2
)/4a
2

_
(39)
2.2.1 Solution for perfectly bonded region (l < z L)
This governing differential equation can be solved by using
boundary conditions given in Eq. (7) and hence axial stress
of CNT in perfectly bonded region is obtained as

f
zz
=
_
_
1
_
_
_
_
1
1+
_
sinh
_
C
1
(z l)
_
+
_
1
(+ )


f
l
_
sinh
_
C
1
(L z)
_
_
_
_
_
sinh
_
_
C
1
(L l)
_
_
_

+
(40)
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Comput Mech
Interfacial shear stress of CNTin the perfectly bonded region
can be obtained by using Eq. (8) and Eq. (40) as

i
=
_
_
_
_
1
1+
_
cosh
_
C
1
(z l)
_

_
1
(+ )


f
l
_
cosh
_
C
1
(L z)
_
_
_
_

C
1
2( + )sinh
_
C
1
(L l)
_ (41)
3 Analytical results and discussions
The axial and interfacial shear stress of the CNTcan be deter-
mined by using Eqs. (40) and (41), respectively for the per-
fectly bonded interface. On the other hand, the axial and
interfacial shear stress of CNT for the debonded interface
can be determined by using Eqs. (21) and (22), respectively.
The derived analytical solutions are valid to determine stress
components for any percentage of debonded length from
the crack tip. It is observed from the closed form solutions
that stress transferring of CNT in perfectly bonded region is
relatedtothe mechanical andgeometric properties of the con-
stituents as well as applied pull-out stress. In the debonded
interface, both ber residual stress and cohesive stress due
to vdW force act as pressure normal to embedded CNT. The
cohesive stress by vdW interaction may uctuate over the
length due to the fact that this cohesive stress is a function of
interface displacement, (O
i
). This interface displacement is
a function of relative radial displacement of CNT and poly-
mer matrix that results due to external loading. Since both
the stress components and cohesive stress due to vdW are
interrelated in the debonded interface, it becomes compli-
cated to determine stress components accurately. In order to
solve the problem, an iterative approach is used to account
the relative radial displacement as well as cohesive stress due
to vdW interaction and hence correct stress components are
obtained. Since the model is symmetric with respect to its
length, it is to be noted that the radial displacement is same
along the circumference of the tube at a certain value of z.
Available experimental data that has been used to obtain ana-
lytical results from the derived solution are given in Table 1.
The analytical results are compared with existing pull-out
model for CNT reinforced composite [31, 39]. The contribu-
tion of vdW interaction is also determined along the length
of the debonded interface.
3.1 Comparison with previous study
In order to compare the results with existing models, the
CNT/matrix interface of the proposed pull-out model is con-
sidered to be completely debonded, i.e. the case l = L is
considered. Figure 3a shows the average axial stress of CNT
along the embedded length of the CNT. It can be seen from
Table 1 Values of the different parameters for the pull-out model
Parameter Value
F 125.6 nN
a 2.0 nm
b 12nm
L 50 nm
E
m
25 Gpa
E
t
1, 000 GPa

f
0.28

m
0.34
0.3825 nm
0.48
T 250

C
n
p
3.1 10
28
m
3
n
c
3.82 10
19
m
2
O
i
0.25
the gure that the maximum axial stress occurs at z = 0 and
then gradually decreases towards the end. The gure shows
that the current axial distribution is close to the earlier work
done by Natsuki et al. [31] but a clear deviation from the
work done by Xiao and Liao [39]. The current study pre-
dicts higher axial stress over the full length of the embedded
ber than other two studies. This may happen because cur-
rent study accounts vdWs interaction in full order in which
each atoms or molecules are taken into consideration where
the other two study account vdW interaction linearly as well
as inter-wall interaction only. The deviation between pull-out
model proposed by Xiao and Liao [39] and other two may
be explained as their double derivative removes the thermal
residual stress. As a result, their solution becomes indepen-
dent of thermal residual stress though they considered ther-
mal residual effect in their modeling assumption. However,
in friction based model, there should be an effect due to ther-
mal residual stress unless thermal coefcients of ber and
matrix are not equal at same temperature.
Figure 3b shows the comparison of interfacial shear stress
distribution along the normalized length (z/L) of the embed-
ded CNT with the previous models. As can be seen from the
gure, the shear stress gradually increases towards the end
starting from an initial value at z=0. The interfacial shear
stress distribution also shows that the prediction of the cur-
rent model is close tothe previous model proposedbyNatsuki
et al. [31]. It is interesting to note that the interfacial shear
stress distribution of all models coincides nearly at a distance
60 % of the embedded ber.
3.2 Contribution of vdW interaction
Before presenting the contribution of the vdW interaction,
the cohesive energy produced by vdW force is veried with
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0
1
2
3
4
5
6
7
8
9
10
0 0.2 0.4 0.6 0.8 1
A
x
i
a
l

s
t
r
e
s
s

o
f

C
N
T

(
G
P
a
)
z/L
(a)
(b)
Current Study
Natsuki et al. (2007)
Xiao and Liao (2004)
100
120
140
160
180
200
220
240
260
280
300
0 0.2 0.4 0.6 0.8 1
I
n
t
e
r
f
a
c
i
a
l


s
h
e
a
r


s
t
r
e
s
s

(
M
P
a
)
z/L
Current Study
Natsuki et al. (2007)
Xiao and Liao (2004)
Fig. 3 a Comparison of axial stress distribution of CNT with existing
models. b Comparison of interfacial shear stress distribution of CNT
with existing models
the molecular mechanics model proposed by Liao and Li
[14]. They found that 0.24eV adhesive energy was produced
mainly due to van der Waals force and a minor portion from
electro static force for 2 nm long and 1.334 nm diameter
CNT fully surrounded by 80 molecule polystyrene polymer.
Using the same geometric data in Eq. (17) of the current study
shows that the total cohesive energy by vdW interaction is
0.25eV, which is very close to the value obtained by Liao
and Li [14]. The small difference in results may be attributed
to the fact that the current model considers the CNT in an
innite polymer where Lian and Lis study considers a nite
length of CNT and a limited number of polymer molecules.
Note that the vdW interaction between neighbour atoms is
six orders larger than that between the non-bonded atoms
located at distant.
Variation of normal cohesive stress along the length of the
embedded CNT caused by vdW interaction is presented in
Fig. 4. In this estimation, the interface is considered to be
completely debonded (i.e. l = L). It can be seen from the
gure that this normal cohesive stress due to vdWinteraction
146
148
150
152
154
156
158
160
162
164
166
0 0.2 0.4 0.6 0.8 1
N
o
r
m
a
l

c
o
h
e
s
i
v
e

s
t
r
e
s
s

(
M
P
a
)

b
y

v
d
W
z/L
Fig. 4 Variation of normal cohesive stress due to vdW interaction
along the length of CNT/polymer debonded interface
gradually increases towards the embedded end of the CNT.
This may be explained as with the application of load on the
open end of the CNT, both CNT and matrix are displaced in
both axial and radial direction. The relative radial displace-
ment of CNT with respect to matrix also changes along the
length of the embedded CNT. Since the relative radial dis-
placement that inuences the interface displacement is higher
near the crack tip, relative smaller normal cohesive stress is
observed at z = 0. The result shows that the minimum and
maximum cohesive stresses are found to be around 146 and
165 MPa, respectively, which also ensure that the contribu-
tion of vdW interaction is quite signicant all through the
debonded interface.
4 Parametric study
Usingthe analytical solutions of the proposedpull-out model,
parametric studies are alsoconductedfor different percentage
of debonded interface, CNT/matrix Youngs modulus ratio
and CNT/polymer radius ratio to obtain their inuences on
axial and interfacial shear stress of CNT.
4.1 Inuence of debonded length
Figure 5a, b show the average axial stress of CNT and inter-
facial shear stress, respectively along the length for different
percentage of debonded length. It can be observed from the
Fig. 5a that the axial stress of CNT decreases towards the end
after starting from a peak value at z=0. The axial stress dis-
tribution also shows that the trends are linear in the debonded
region but a stress saturation zone is found at the middle of
the embedded length. In addition, the gure shows that with
the increase of debonded length axial stress also increases.
This can be illustrated as larger percentage of debond length
which in fact represents longer length of frictionally bonded
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0
1
2
3
4
5
6
7
8
9
10
A
x
i
a
l

s
t
r
e
s
s

o
f

C
N
T

(
G
P
a
)
z/L
(a)
(b)
Debond Length =20%
Debond Length =10%
Debond Length =0%
0
100
200
300
400
500
600
700
800
0 0.2 0.4 0.6 0.8 1
0 0.2 0.4 0.6 0.8 1
I
n
t
e
r
f
a
c
i
a
l

s
h
e
a
r

s
t
r
e
s
s

(
M
P
a
)
z/L
Debond Length =20%
Debond Length =10%
Debond Length =0%
Fig. 5 a Axial stress of CNT along the length for different percentage
debond length. b Interfacial stress along the length of CNT for different
percentage of debond length
interface ensures less stress transfer than that would happen
for perfectly bonded interface and thus more stress is to be
carried by CNT. For an example 0 % debond length means
perfectly bonded interface that insures smallest axial stress
which indicates maximum stress transfer though interface
and hence a larger shear stress is also observed in the Fig. 5b.
It can be seen from the gure that a jump of shear stress
is occurred at the end of debond zone. It is interesting to
note that the shear stress decreases up to 50 % length of the
embedded nanotube and then increases towards the end for
all three cases.
It is important to note from the Fig. 5a that the stress
transferring of CNT is higher in the case of perfectly bonded
interface than the debonded interface. This can be claried
by the comparison of the axial stress distribution for 0 and
10 % debonded length. It is clear from the gure that the
difference in axial stress for 0 % (which in fact represents
perfectly bonded interface) and 10 % debonded interface is
very signicant which ensure that perfectly bonded interface
is capable to transfer more stress than the debonded inter-
face. The result also shows that the difference of axial stress
0
1
2
3
4
5
6
7
8
9
10
0 0.2 0.4 0.6 0.8 1
A
x
i
a
l

s
t
r
e
s
s

o
f

C
N
T

(
G
P
a
)
z/L
(a)
(b)
Em/Ef=0.025
Em/Ef=0.05
Em/Ef=0.10
0
100
200
300
400
500
600
700
800
0 0.2 0.4 0.6 0.8 1
I
n
t
e
r
f
a
c
i
a
l

s
h
e
a
r

s
t
r
e
s
s

(
M
P
a
)
z/L
Em/Ef=0.025
Em/Ef=0.05
Em/Ef=0.10
Fig. 6 a Axial stress of CNT along the length for different Youngs
modulus ratio. b Interfacial shear stress along the length of CNT for
different Youngs modulus ratio
between 0 and 10 %debond length are much higher than that
between 10 and 20 % debond length. Similar observation is
also found in the interfacial shear stress distribution. How-
ever, the deviation is comparatively smaller in the debond
region for 10 and 20 % and very small is in the perfectly
bonded zone. Thus, it can be concluded that the stress trans-
ferring of CNT signicantly reduces due to the presence of
debonding particularly near the open end of the CNT.
4.2 Inuence of CNT/matrix Youngs modulus ratio
Figure 6a, b show the average axial stress and interfacial
shear stress along the length of CNT, respectively for dif-
ferent matrix/nanotube Youngs modulus ratio. Both of the
stress distributions showthat the trends are linear up to initial
20 %of the debond length but a stress saturation zone is found
at the remainingpart of the embeddedlength. Axial stress dis-
tribution shows that as the Youngs modulus ratio increases,
axial stress of CNT decreases. This happens because higher
E
m
/E
f
indicates stronger matrixas well as stronger interface
which can transfer more stress to matrix and hence smaller
axial stress results in CNT. Figure 6b shows that interfacial
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0
1
2
3
4
5
6
7
8
9
10
0 0.2 0.4 0.6 0.8 1
A
x
i
a
l

s
t
r
e
s
s

o
f

C
N
T

(
M
P
a
)
z/L
(a)
(b)
b/a=4
b/a=5
b/a=6
0
200
400
600
800
1000
1200
1400
0 0.2 0.4 0.6 0.8 1
I
n
t
e
r
f
a
c
i
a
l

s
h
e
a
r

s
t
r
e
s
s

(
M
P
a
)
z/L
b/a=4
b/a=5
b/a=6
Fig. 7 a Axial stress of CNT along the length for different radius ratio.
b Interfacial stress along the length of CNT for different radius ratio
shear stress increases in a very mild slope in the debonded
region and a downward jump of shear stress is observed at the
point of intersectionof bondedanddebondedinterface before
reaching a minimum peak nearly at 60 % of the embedded
length and then sharply increases towards the end.
It is interesting to note that interfacial shear stress
increases as the Youngs modulus ratio increase in debonded
interface but opposite trends are foundinthe perfectlybonded
interface. This can be explained as with the increase of
E
m
/E
f
, the thermal residual stress which is function of
matrix Youngs modulus also increases and hence interfa-
cial shear stress in the debonded region also increases.
4.3 Inuence of radius ratio, b/a (volume fraction)
Figure 7a, b show the average axial stress and interfacial
shear stress along the length of CNT, respectively for dif-
ferent radius ratio which in fact represents the volume frac-
tion of CNT in polymer composites. It can be seen from the
Fig. 7a that the axial stress decreases linearly in the debonded
region before gradually decreases towards the end. It can be
observed from the Fig. 7b that the shear stress distribution
is nearly constant in the debonded interface before resulting
an upward jump of stress at the intersection of perfectly and
debonded interface. In the perfectly bonded region, shear
stress sharply decreases before reaching a minimum peak
and then increases sharply towards the embedded end of the
CNT. It is also observed that all the shear stress distribu-
tions coincide nearly at the 75 % length of embedded nan-
otube. In addition, the gure shows that as the radius ratio
increase shear stress decreases at z = l but opposite behav-
ior is observed at the embedded end i.e. large shear stress is
found at z = L. However there is a certain limit of inter-
facial shear stress after which crack propagation starts to be
enhanced. Fromthis result, it is understood that if the volume
fraction is increased, the interface crack will start to propa-
gate from the embedded end rather than from the vicinity of
the debonded zone.
It has been clearly observed from both of the gures that
stress distributions in the debond region are nearly indepen-
dent of radius ratio. However, the inuence of the volume
fraction of the CNT is found to be signicant in the perfectly
bonded interface. In this region, with the increase of radius
ratio axial stress of CNTalso increases. This can be explained
by the fact that higher radius ratio indicates smaller volume
fraction of CNT that ultimately results comparatively more
stress transfer of CNT in the perfectly bonded interface.
5 Conclusion
An analytical pull-out model has been proposed to evaluate
the stress transfer of CNT in polymer matrix by using con-
tinuum mechanics approach. Closed form analytical solu-
tions are also obtained for the axial and interfacial shear
stresses along the length of CNT. The accuracy of the pro-
posed analytical model is veried by comparing with the
available results from existing models in the case of com-
pletely debonded interface. Current analytical result shows a
good agreement with the recent pull-out model proposed by
[31]. The analytical results also shows that vdW interaction
of CNT with polymer chains contributes signicantly at the
debond region and hence enhances stress carrying potential
of CNT. This study suggests that vdW interaction should be
taken into account in investigating debonded interface which
are generally common in CNT reinforce polymer compos-
ites. To demonstrate the applications of the newly developed
model, parametric studies of sample cases are alsoconducted.
The parametric study reveals that stress transfer of CNT is
signicantly higher in the perfectly bonded interface than
that of debonded interface. The results also show that the
length of debonded interface, modulus ratio and relative size
of RVE (i.e. volume fraction) are controlling factors for nan-
otube reinforced composites in the perfectly bonded region.
In contrast, the analytical results show that interfacial shear
stress transfer is nearly independent on the volume frac-
1 3
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tion of nanotube in the debonded interface of the polymer
composite.
This present work is a preliminary attempt to evaluate the
interface characteristics of CNT reinforced composites for
overcoming the great difculty in conducting their experi-
mental investigation on a single CNTpull-out test. This study
can also be used as an alternate of molecular mechanics or
MDs simulation which are not only time consuming but also
costly as well as the incapability to execute billions of atoms.
Therefore, the proposed pull-out model can play a signif-
icant role in designing CNT as reinforcement in polymer
composite.
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