Materials Chemistry and Physics 198 (2017) 250e257

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Materials Chemistry and Physics

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

Superior interfacial mechanical properties of boron nitride-carbon

nanotube reinforced nanocomposites: A molecular dynamics study
Jin Zhang a, *, Xudong Peng b
a
Shenzhen Graduate School, Harbin Institute of Technology, Shenzhen 518055, China
b
Department of Mechanical and Industrial Engineering, University of Toronto, Toronto, Ontario M5S 3G8, Canada

h i g h l i g h t s

Composites reinforced by BN-CNTs have superior interfacial shear strength (ISS).

ISS of BN-CNT reinforced composites is larger than that of their CNT counterparts.

ISS of BN-CNT reinforced composites depends on the BN composition of BN-CNTs.

Superior ISS of the present composites is explained by classical friction theory.

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

Article history: The newly discovered hybrid boron nitride-carbon nanotubes (BN-CNTs) are very promising for the
Received 19 December 2016 innovative design of next-generation nanocomposites. In this work, molecular dynamics simulation-
Received in revised form based pull-out studies have been performed to characterise the interfacial properties of BN-CNT rein-
15 April 2017
forced polyethylene (PE) composites. Our results show that the interfacial shear strength (ISS) of BN-
Accepted 28 May 2017
CNT/PE nanocomposites strongly depends on the BN composition and the connecting pattern of the
Available online 7 June 2017
C/BN fragment in the embedded BN-CNTs. Specically, an ISS about 90% greater than that of the PE
composite reinforced by the conventional carbon nanotube (CNT) is detected in the composite reinforced
Keywords:
Boron nitride-carbon nanotube
by the BN-CNT with certain connecting pattern and BN concentration. Such a superior ISS in the BN-CNT/
Nanocomposite PE composites is found to mainly originate from the unique rough van der Waals surface of the BN-CNT
Interfacial shear strength and the greater binding interaction between the embedded BN-CNT and the PE matrix, both of which
Molecular dynamics contribute to enhancing the interface load transfer of nanocomposites. The enhanced ISS detected in the
composite reinforced by BN-CNTs suggests that, compared with the most commonly used CNT, the novel
BN-CNT can be a better reinforcement candidate in the design of nanocomposites.
2017 Elsevier B.V. All rights reserved.

1. Introduction
The discovery of carbon nanotubes (CNTs) has triggered great
scientic and engineering interest in the eld of one-dimensional
(1D) tubular nanomaterials. Besides CNTs, nanotubes of other ma-
terials have been studied experimentally and theoretically recently,
among which boron nitride nanotubes (BNNTs) have attracted
special attention [1e3]. It is proven that both CNTs and BNNTs have
exceptional mechanical properties [3,4]. For example, the Youngs
modulus of both CNTs and BNNTs was experimentally measured
and estimated to be in the order of 1 TPa [5,6]. The large Youngs
* Corresponding author.
E-mail address: jinzhang@hit.edu.cn (J. Zhang).
modulus and stiffness of CNTs and BNNTs were also detected in
theoretical studies [7,8]. Owing to their remarkable mechanical
properties, CNTs and BNNTs can be introduced as promising rein-
forcement materials for manufacturing lightweight polymeric
composite materials. Indeed, signicant enhancements in the
elastic modulus and strength of polymer composites with an
addition of small amounts of 1D tubular nanomaterials have been
observed in some recent experiments and simulations [9,10].
In contrast to their mechanical properties, the electronic prop-
erties of CNTs and BNNTs are vastly different. CNTs can be metallic or
semiconducting depending on the tube chirality and morphology
[11], while all BNNTs are permanent semiconductors [12]. In the
past decade, many efforts have been made in exploring the com-
binations of these component materials in order to develop novel
hybrid boron nitride-carbon nanotubes (BN-CNTs) with adjustable

http://dx.doi.org/10.1016/j.matchemphys.2017.05.064
0254-0584/ 2017 Elsevier B.V. All rights reserved.
 J. Zhang, X. Peng / Materials Chemistry and Physics 198 (2017) 250e257
electronic properties [13e15]. Generally, BN-CNTs can be treated as
the doping of BN segments into different CNT segments with a
suitable formation proportion [16,17]. Theoretical studies show that
the electronic properties of BN-CNTs can be tailored by adjusting
their forming pattern or BN concentration [18]. In addition, our
recent studies [19,20] prove that the Youngs modulus and stiffness
of BN-CNTs are between those of pristine CNTs and BNNTs. In other
words, the mechanical properties (Youngs modulus and strength)
of BN-CNTs are comparable to those of their pristine CNT and BNNT
counterparts (see Ref. [20]). Similar to their CNT and BNNT coun-
terparts, the superior mechanical properties of BN-CNTs to some
extent suggest that the BN-CNT can also be an ideal material
candidate to serve as the reinforcing agents in nanocomposites.
Motivated by this idea, it is of great interest to quantify the me-
chanical properties of the nanocomposites reinforced by BN-CNTs.
Specically, it is known that the effective load transfer at the
interface between the embedded nanoller and the surrounding
polymer matrix is an important design parameter to maximize the
contribution of the polymer adsorption layer [21e29]. Thus, the
interface load transfer ability of the nanocomposites, which is
characterised by the interfacial shear strength (ISS), is critical for the
mechanical properties of the nanocomposites [21e29].
In this paper, we use molecular dynamics (MD) simulations to
investigate the ISS of the BN-CNT reinforced nanocomposites
through the pull-out test, in which an external load is applied on
the embedded BN-CNT to pull the nanotube out from the polymer
matrix. This pull-out technique has been widely utilized in previous
experiments and simulations to measure the ISS of CNT and BNNT
reinforced polymer composites [21e29]. In the present pull-out
studies, a superior ISS is detected in composites reinforced by the
BN-CNT with certain connecting pattern and molar fraction of BN
atoms. Some efforts are also made to reveal the mechanism of the
enhanced ISS observed in the present BN-CNT/PE composites.
2. Simulation method
In the present study, we considered a (8, 0) zigzag BN-CNT with
a helicoidal arrangement of the BN and C stripes (see Fig. 1a). To
form this hybrid structure, the C or BN hexagons at the boundaries
of the BN and C stripes were doped by one impurity atom (see
Fig. 1a). BN-CNTs with this forming pattern were motivated by the
existence of helical wrapping patterns in composite nanotube
systems [30] and have been proven to be energetically favourable
by previous theoretical studies [16,17,30]. The composition of these
BN-CNTs was represented by the molar fraction of BN atoms c,
which was taken as the ratio of the number of BN atoms to the total
number of atoms in the BN-CNT system. As for the matrix, we chose
the polyethylene (PE) as an example (see Fig. 1a). The PE, a chain
containing 20 monomers eCH2eCH2e, was chosen as the matrix
here because its structural simplicity can effectively reduce the
computational cost. Moreover, as a representative polymer matrix,
PE can give a general picture of the possible interfacial behaviours
of various other nanotube/polymer nanocomposites.
In this study, classical MD simulations were adopted to perform
the pull-out test on the BN-CNT reinforced PE nanocomposites,
which contain three distinct components: BN-CNT, polymer matrix
(PE) and interface. In the MD model the atoms are usually treated as
point-like masses that interact with one another according to a
given potential energy. In the present simulation, the hybrid
adaptive interactive reactive empirical bond order (AIREBO)-Tersoff
potential was used to describe the BN-CNT. Specically, the in-
teractions between C atoms of the BN-CNT were described by the
AIREBO potential, while the B-N, C-B and C-N interactions were
described by the Tersoff potential. The values of the parameters in
this hybrid AIREBO-Tersoff potential were taken from Refs. [31e33]
251
(a)
BN-CNT
Polyethylene
(b)
30
70
z
y
x
Fig. 1. (a) The molecular structure of a single PE chain and a (8, 0) BN-CNT. (b)
Equilibrated structure of the simulation cell for the BN-CNT/PE nanocomposites.
and have been widely used to reveal the optimal morphology of
hybrid BN-CNTs [34] and BN-C nanosheets [35]. The PE chains were
described by the modied AMBER potential function [22]. The pa-
rameters of the AMBER potential function used for the PE were
taken from Ref. [22]. The nonbonded van der Waals (vdW) inter-
facial interaction between the BN-CNT and the PE matrix was
modelled by the 12-6 Lennard-Jones (LJ) potential. The parameters
of the LJ potential used in the present study were calculated based
on Lorentz-Berthelot mixing rules [36] together with the LJ co-
efcients for C, H, B and N atoms in Refs. [37,38].
In the present simulation, a BN-CNT with a length L of ~70 was
initially created using the lattice constant of CNTs, and then relaxed
to a local minimum energy state using the conjugate gradient al-
gorithm. Subsequently, the obtained BN-CNT was placed in the
centre of a model box. Meanwhile, 59 PE chains were placed into
the model box randomly using the Packmol software [39]. Since
Packmol treats molecules as rigid bodies, the size of the model box
was initially enlarged to accommodate all PE chains and the BN-
CNT. To increase the density of the PE matrix to an experimen-
tally measured value of 0.92 g/cm3 [40], the conjugate gradient
method was adopted to compress the model box gradually from its
initial dimension to the targeted size of 30  30  70 (see
Fig. 1b). After the volume reduction, to distribute the molecules
evenly, the compressed box was then equilibrated for 2 ns with the
time step 1 fs in the isothermal-isobaric (NPT) ensemble at the
temperature of 300 K and pressure of 1 atm. The Nose -Hoover
thermostat algorithm [41] was implemented in this equilibration
process. The obtained equilibrated structure of the representative
volume element of the BN-CNT reinforced PE nanocomposites was
thus ready for the pull-out test. The pull-out simulations of the BN-
CNT from the PE matrix were implemented by moving the atoms at
the right end of the BN-CNT along the x direction (see Fig. 2a). To
reach this goal, the outermost atoms at the right end of the BN-CNT
were frozen to maintain the quasi-static pull-out process by a step-
by-step movement of these outermost atoms. At the same time, in
252 J. Zhang, X. Peng / Materials Chemistry and Physics 198 (2017) 250e257

(a)

x
(b)
300

BN-CNT
Energy (Kcal/mol)

200 CNT

100

0
0 20 40 60 80 100
o
Pull-out distance (A)
Fig. 2. (a) Setup of the pull-out test of BN-CNT from the PE matrix using MD simulations. Here, the gray boxes show the x edges. (b) Change in the potential energy of the BN-CNT/
PE and the CNT/PE composites with the pull-out distance during the pull-out process.

order to prevent the simultaneous drift of the PE with the BN-CNT
during the pull-out process, all sides except the right edge of the PE
matrix were constrained. It is noted here that, throughout the pull-
out process, the simulation was conducted in the canonical (NVT)
ensemble at room temperature (300 K). In the present study, all MD
simulations were conducted using a large-scale atomic/molecular
massively parallel simulator (LAMMPS) [42] with the periodic
boundary conditions in the y and z directions.
3. Results and discussion
Based on the MD technique proposed above, we have conducted
the pull-out test for a BN-CNT (c 0.5) from the PE matrix.
Meanwhile, for the purpose of comparison, we also performed
similar simulations on nanocomposites reinforced by the pristine
CNT with the same geometric size of the BN-CNT considered.
During the pull-out process, the change in the potential energy (U)
of the nanotube/matrix system is plotted in Fig. 2b with respect to
the pull-out distance d. We can see from 2b that U keeps growing
with the increase of d before the nanotubes are totally separated
from the polymer matrices (d < 70 ). However, after the nanotube
is completely pulled out from the PE matrix (d > 70 ), U remains
almost unchanged since there is no interaction between the
nanotube and the PE. The constant U after the complete pull-out
process is called the pull-out energy, which is noted as Up in the
present paper. Since the work required to pull out the nanotube is
attributed to the shear force between the nanotube and the matrix,
the pull-out energy Up can be related to the ISS as follows [21e27]:
ZL
Up 2pr tL  ddd:
0
Here, r is the radius of nanotubes and equals to ~3.2 for the (8,
0) nanotubes considered in the present study; t is the ISS. Similar to
the methodology in Refs. [21e29], the ISS was obtained by calcu-
lating its average value from Eq. (1). The average ISS t obtained
from Eq. (1) can be written as
Up
t : (2)
prL2
From Fig. 2b we can see that the pull-out energy of the BN-CNT/
PE system is much larger than that of the CNT/PE system, which
denotes that the ISS of the BN-CNT/PE composite should be much
greater than that of its CNT/PE counterpart. Indeed, the ISS of the
BN-CNT/PE composite calculated from Eq. (2) is 39.2 MPa, which is
87% larger than 21 MPa obtained in the CNT/PE composite. The
value of the ISS of the CNT/PE system obtained in the present study
agrees well with the results reported in the existing literature
[24,26,27]. The higher ISS detected in the BN-CNT/PE system sug-
gests that, in terms of the interface load transfer ability, the BN-CNT
can be a better reinforcing nano-agent in the composites when
compared to the conventional CNT.
To further understand the enhanced ISS of the BN-CNT/PE sys-
tem, we have conducted a series of pull-out simulations for BN-
CNTs with various molar fractions of BN atoms c. In Fig. 3 we
show the change in the potential energy of nanocomposites rein-
forced by these BN-CNTs during the pull-out process. Based on the
pull-out energy in Fig. 3 and the relationship between the pull-out
energy and the ISS in Eq. (2), Fig. 4a shows the ISS of the composites
reinforced by BN-CNTs whose c increases from 0 to 1. The corre-
sponding molecular structures of these BN-CNTs after the full
structural relaxation are presented in Fig. 4b. We can see from
(1)
Fig. 4a that when c increases from 0 (i.e., pristine CNTs) to 0.5, the
ISS gradually increases from 21 MPa to 39.27 MPa. When c keeps
 J. Zhang, X. Peng / Materials Chemistry and Physics 198 (2017) 250e257 253

300
c = 0 (CNT)
c = 0.25
250 c = 0.50
c = 0.75

Energy (Kcal/mol)
200 c = 1 (BNNT)

150

100

50

0
0 20 40 60 80 100
o
Pull-out distance (A)
Fig. 3. Change in the potential energy of nanocomposites reinforced by BN-CNTs with various molar fractions of BN during the pull-out process.

increasing to 0.75, the ISS is found to drop to 28.9 MPa. However,
when c ultimately increases to 1 (i.e., pristine BNNTs), the ISS is
found to grow to 31.92 MPa. From Fig. 4a we can conclude that the
ISS of the BN-CNT/PE system strongly depends on the molar frac-
tion of BN atoms of the embedded BN-CNTs and possesses a
maximum value when c is 0.5. In addition, the ISS of the BN-CNT/PE
system is found to be larger than that of the conventional CNT/PE
system, irrespective of the molar fraction of BN atoms. Moreover,
when c is 0.5 the ISS of the BN-CNT/PE system can even be larger
than that of the BNNT/PE system. In the present study, attention is
mainly focused on the ISS of nanocomposites reinforced by pristine
nanotubes. However, defects such as vacancy and Stone-Wales
(SW) defects may appear during the fabrication of nanotubes
[43]. In recent MD studies on the CNT reinforced composites, the
vacancy defect of the embedded CNT is found to decrease the ISS of
the nanocomposites, while the SW defect is found to promote
greater ISS [44,45]. It is expected that these defects may have
similar effects on the ISS of the nanocomposites reinforced by BN-
CNTs, since the existence of C, B or N vacancies in BN-CNTs will
reduce their interaction to the surrounding polymer matrix, while
the SW defects in both C and BN domains can improve the binding
energy between BN-CNTs and foreign atoms [46,47]. Indeed, an
accurate measurement of ISS of the composites reinforced by
defective BN-CNTs deserves a detailed study in the near future to
give a comprehensive understanding of the effect of defects.
Moreover, as we noted above, the ISS obtained based on Eq. (2) is an
averaged quantity. According to the shear lag theory [25,28,29,48],
the ISS actually holds a maximum value at the nanotube entry
position. Such a maximum ISS is another important parameter
characterising the interfacial mechanical property of nano-
composites [25,28,29]. In the shear lag model the maximum ISS tm
can be related to the average ISS t through the following equation

(a) 50 (b)
Average
40 Maximum
ISS (MPa)

30

20

10

0
0.00
CNT 0.25 0.50 0.75 BNNT 1.00
Concentration of BN atoms
Fig. 4. (a) The average and maximum ISS of BN-CNT/PE composites as a function of the concentration of BN atoms of the embedded BN-CNT. (b) Molecular structures of BN-CNTs
with different molar fractions of BN atoms after the equilibration.
254 J. Zhang, X. Peng / Materials Chemistry and Physics 198 (2017) 250e257
[25,28]:
bL
tm t : (3)
tanhbL
p
In Eq. (3) b 2G=Er 2 ln a is a shear lag constant, where G is
the shear modulus of the matrix, E is the Youngs modulus of
q N) atom and a C atom is larger than that between two C atoms.
nanotubes, r is the radius of nanotubes, and a p=4Vf is a
parameter related to the nanotube volume fraction Vf [25]. In Fig. 4a
we show the maximum ISS tm of the present BN-CNT/PE composite,
which was calculated from Eq. (3). In the present calculation, the
shear modulus of PE was taken as G 0:7 GPa [49]. Meanwhile, the
Youngs modulus of BN-CNTs was E cEBN 1  cEC with
EBN 802 GPa and EC 894 GPa respectively being the Youngs
modulus of BNNTs and CNTs [20]. From Fig. 4a we can see that the
impact of the BN-CNT on the maximum ISS tm is qualitatively
similar to that on its average counterpart. For example, an enhanced
tm is detected in the composites reinforced by the BN-CNT. tm of the
BN-CNT reinforced composites is strongly dependent on c of the BN-
CNT and reaches its maximum value when c is 0.5.
Theoretically, in the nanotube reinforced polymer composites
the interfacial shear force mainly originates from the friction be-
tween the (vdW) surface of the nanotube and the inner (vdW)
surface of the polymer matrix, since the nanotube and the polymer
in the composites are connected through the nonbonded vdW
interaction. From the classical friction theory [50] we know that the
friction force between two surfaces is proportional to (1) the
normal force exerted by each surface on the other and (2) the co-
efcient of friction, which is related to the roughness of the surface,
i.e., rougher surfaces tend to have higher effective values. In terms
of these two factors that may affect the friction between the rein-
forcement and matrix, in what follows we will attempt to reveal
some possible reasons responsible for the enhanced ISS of the
nanocomposites reinforced by BN-CNTs and its dependence on the
molar fraction of BN atoms of the embedded BN-CNT. Actually, the
classical friction theory has been proven to be able to capture the
major features of the nanoscopic friction in previous studies [51]
and also widely accepted in analysing the pull-out process of the
nanotube reinforced composites [50,52].
First, we will study the possible inuence of the normal inter-
action force between the BN-CNT surface and the inner surface of
the PE matrix, which is determined by the intermolecular inter-
action energy between the BN-CNT and PE structures. To this end,
we have conducted a simulation on the wrapping of a single PE
chain around a BN-CNT whose molar fraction of BN atoms c is 0.5. In
comparison, similar wrapping simulation was also performed for
pristine CNTs. During the wrapping process we recorded the evo-
lution of the interaction energy Eint between the nanotube and the
single PE chain with respect to the simulation time. Here, the
interaction energy was calculated from Eint Epot  ENT  EPE ,
where Epot is the potential energy of the entire nanotube/PE system,
ENT is the energy of the nanotube without the PE chain and EPE is
the energy of the PE chain without the nanotube. The recorded
results in Fig. 5a show that the PE chain reacts spontaneously to the
binding interaction with the nanotube surface and reaches a steady
interaction energy state within a very short time. The interaction
energy of the steady state is found to be about 56.42 kcal/mol for
the CNT and about 79.55 kcal/mol for the BN-CNT. The negative
interaction energy indicates that the PE molecule moves towards
the surfaces of nanotubes due to an attractive force. In Fig. 5b we
show the nal conformation of the adsorbed PE chain on the sur-
faces of the BN-CNT and the CNT. From Fig. 5b we see that the PE
chain folded and moved toward the nanotubes until the equilib-
rium was achieved, which nally makes the PE molecule helically
wrap on the surface of the nanotube. This phenomenon is observed
in both CNT and BN-CNT. Similar helical wrapping patterns are also
observed in other nanotube reinforced composite systems, e.g., CNT
or BNNT wrapped by polyglycolide, polystyrene, polythiophene
[53] and so on [29,54]. Moreover, as for the case of the BN-CNT, we
see from Fig. 5b that most part of the PE chain is adsorbed on the BN
domain of the BN-CNT, since the vdW interaction between a B (or
Since the vdW interaction is the main reason of nanotube-polymer
interaction, the existence of B and N atoms instead of C atoms in the
BN-CNT increases the vdW interaction and thus enhances the
interaction between the BN-CNT and the polymer. Accordingly, the
larger interaction energy (or interaction force) between the BN-
CNT and the PE is a possible reason for the greater ISS observed
in the BN-CNT/PE composites when compared with their pristine
CNT counterparts.
On the other hand, if the increased interaction energy in the BN-
CNT/polymer system is the only main reason for the enhanced ISS
of the BN-CNT/PE composites, the ISS of the BN-CNT/PE should
monotonously increase as the molar fraction of BN atoms c in-
creases and reach its maximum value when c is 1 (i.e., the BNNT
reinforced PE composites). However, we can see from Fig. 4a that
the largest ISS of the BN-CNT/PE system occurs actually when c is
0.5. The discrepancy between the simulation result and the theo-
retical prediction implies that, in addition to the increased inter-
action energy in the BN-CNT/PE composites, some other factors
may also greatly contribute to enhancing ISS in the BN-CNT/PE
system. Thus, we will turn our focus to the other factor, the coef-
cient of friction between the nanotube surface and inner surface
of the PE matrix. We can see from Figs. 1a, 4b and 5b that, as for a
BN-CNT whose c is 0.5, after the full structural relaxation its mo-
lecular structure is screwy, helicoidal and cyclical, like the structure
of deoxyribonucleic acid molecule. Such a unique wavelike prole
of the BN-CNT along the axial direction probably originates from
the lattice mismatch between the C domain and the BN domain
[34]. Similar unique structure was also observed in the recent rst-
principles calculations for the similar zigzag BC2N nanotubes
[16,17]. The rough surface of the present BN-CNTs is in contrast to
the smooth surface of their pristine CNT and BNNT counterparts.
According to the classical friction theory, this rough surface may
increase the coefcient of friction and accordingly the friction force
between the nanotube and the matrix, resulting in the enhanced
ISS of the BN-CNT/PE system. To prove this prediction, we have
conducted the pull-out test for two types of BN-CNT, who have the
same molar fraction of BN atoms (c 0.5) but different connecting
patterns at the boundaries between the C and BN stripes. In the BN-
CNT considered above, the C and BN hexagons at the frontier be-
tween the C and BN stripes have one impurity atom, i.e., a C atom
at a B/N site of otherwise pure BN hexagons and an N/B atom at
otherwise pure C hexagons (see Fig. 6a). In the present study, we
note this type of BN-CNT as type 1 BN-CNT. In addition to type 1 BN-
CNT, the BN-CNT also has another connecting pattern at the
boundaries between the C and BN stripes, where all hexagons are
composed uniquely by C (BN) atoms (see Fig. 6b). Here, we term
this type of BN-CNT as type 2 BN-CNT. After the full structural
relaxation, the molecular structures of type 1 and type 2 BN-CNTs
are illustrated in Fig. 6a. Different to the rough tube surface
observed in type 1 BN-CNT, in Fig. 6a we see that type 2 BN-CNT
holds a smooth surface similar to the pristine CNT and BNNT.
Since type 2 BN-CNT has the same molar fraction of BN atoms as its
type 1 counterpart but a different smooth surface, after replacing
type 1 BN-CNT by its type 2 counterpart we can consider the same
inuence of the increased interaction energy but meanwhile can
exclude the inuence of the rough surface. Thus, through
comparing the results of type 1 BN-CNT with those of its type 2
 J. Zhang, X. Peng / Materials Chemistry and Physics 198 (2017) 250e257 255

(a)
0

Energy (Kcal/mol)
-50 CNT+PE

BN-CNT+PE

-100
0 200 400 600 800 1000
Time (ps)
(b)

Fig. 5. (a) Interaction energy evolution for CNT/PE and BN-CNT/PE composites during the wrapping process. (b) MD snapshots of the nal conformation of the adsorbed PE chain on
the BN-CNT and CNT.

(a) (b)
300
Type 1
Type1
Type2

200
Energy (Kcal/mol)

Type 2

100

0
0 50 100
o
Pull-out distance (A)
Fig. 6. (a) Molecular structures of BN-CNTs with different connecting patterns at the boundaries between the C and BN stripes. (b) Change in the potential energy of the nano-
composites reinforced by BN-CNTs with different connecting patterns during the pull-out process.

counterpart we can quantitatively measure the contribution of the
rough surface of the BN-CNT to the enhanced ISS detected in the
above studies. In Fig. 6b we present the change in the potential
energy of the type 2 BN-CNT/PE system during the pull-out process.
In comparison, the result of its type 1 counterpart is also presented
in Fig. 6b. Since the rough surface of type 1 BN-CNT will raise the
interlocking effect with the surrounding molecules and thus
enhance the load transfer between the nanotube and the matrix,
the pull-out energy (Up) of the type 1 BN-CNT/PE system is found to
be larger than that of the type 2 BN-CNT/PE system. Furthermore,
the ISS of the type 2 BN-CNT/PE system calculated from Eq. (2) is
27.28 MPa, which is 30% smaller than the value of the type 1 BN-
CNT/PE system. Based on this nding, we are able to conclude
that the rough surface of the BN-CNT is another major factor that
can contribute to enhancing the ISS of the nanocomposites rein-
forced by type 1 BN-CNT. Actually, in the previous studies
256 J. Zhang, X. Peng / Materials Chemistry and Physics 198 (2017) 250e257
[24,26,27,55,56] articially raising the surface roughness of the
embedded nanollers through some chemically surface function-
alization methods was treated as an efcient avenue to enhance the
ISS of nanocomposites.
Inspired by the nding that the surface roughness of the
nanotube is an important factor that can affect the ISS of nano-
composites, we will turn back to give some possible explanation for
the nonmonotonic relationship between the ISS and the molar
fraction of BN atoms c of the embedded BN-CNTs (see Fig. 4a). In
Fig. 4b we show the molecular structures of type 1 BN-CNTs with c
respectively being 0.25, 0.5 and 0.75. We can see from this gure
that when c increases from 0.25 to 0.75, the roughness of the BN-
CNTs rstly increases and reaches its maximum at c 0.5. After
that, the roughness of the nanotubes begins to decrease when c
keeps increasing. This complex roughness-to-smooth sequence can
be understood by the strain sharing theory proposed recently for
the BN-CNTs with the parallel forming pattern [34]. Since the BN-
CNT with c 0.5 holds the roughest surface, the BN-CNT/PE sys-
tem may have the strongest load transfer between the BN-CNT and
the PE and thus the largest ISS when c of the embedded BN-CNT is
0.5. This theoretical analysis result is consistent with our MD
simulation result illustrated in Fig. 4a. As the enhanced ISS detected
in the present BN-CNT/PE composites is essentially attributed to the
rough surface of BN-CNTs and the increased vdW interaction due to
the existence of B and N atoms instead of C atoms in BN-CNTs, it is
expected that the BN-CNT reinforcement may have similar impact
on the ISS of nanocomposites with other polymer matrices, e.g.,
epoxy, aramid, poly(methyl methacrylate) and so on.
4. Conclusions
In this paper, we have studied the interfacial properties of the
hybrid BN-CNT reinforced nanocomposites and explored the po-
tential of such novel 1D nanomaterial as the reinforcement for
polymers. In doing this, MD simulations were performed to
conduct the pull-out test of the helically symmetric BN-CNT from
the PE matrix. The results show that the ISS of the BN-CNT/PE
system strongly depends on the composition of the BN atoms and
the connecting pattern of the BN-CNTs. Specically, an ISS which is
87% greater than that of the CNT/PE system is detected in the
composite system reinforced by type 1 BN-CNT (as illustrated in
Fig. 6a) with the molar fraction of BN atoms being 0.5. Such a su-
perior ISS detected in the BN-CNT/PE system mainly originates
from (1) the enhanced binding interaction between the BN-CNT
and the PE due to the existence of B and N atoms instead of C
atoms in the BN-CNT and (2) the rough vdW surface of the BN-CNT
induced by the lattice mismatch between the C domain and the BN
domain in the BN-CNTs. Both of these two factors can enhance the
interface load transfer ability and thus increase the ISS of the
nanocomposites. Moreover, as CNTs and BNNTs possess signi-
cantly different contact electrical and thermal resistances [57,58], it
is expected that the electrical and thermal properties of the BN-CNT
reinforced composites can be tuned by changing the molar fraction
of BN atoms of the hybrid BN-CNTs [59,60]. The superior ISS
together with the tunable electrical and thermal properties of the
BN-CNT reinforced composites suggests that the novel BN-CNT
structure is a better reinforcement candidate in the design of
nanocomposites when compared with the most commonly used
CNTs.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (No. 11602074) and Harbin Institute of Tech-
nology (Shenzhen Graduate School) through the Scientic Research
Starting Project for New Faculty.
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