Composites: Part A 103 (2017) 1724

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Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa

The influence of N-doping types for carbon nanotube reinforced epoxy

composites: A combined experimental study and molecular dynamics
simulation
Hana Jung a,b, Hoi Kil Choi a, Soyoung Kim c, Hun-Su Lee a, Yonjig Kim b, Jaesang Yu a,
a
Multifunctional Structural Composite Research Center, Institute of Advanced Composite Materials, Korea Institute of Science and Technology (KIST), Chudong-ro 92,
Bongdong-eup, Wanju-gun, Jeollabukdo 565-905, Republic of Korea
b
Division of Mechanical Design Engineering, Chonbuk National University, Baekje-daero 567, Deokjin-gu, Jeonju 561-756, Republic of Korea
c
EZ Composites, Wonmanseong-ro 106, Deokjin-gu, Jeonju 561-202, Republic of Korea

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

Article history: In this study, nitrogen doped carbon nanotube reinforced epoxy nanocomposites were characterized
Received 24 March 2017 through experiments and molecular dynamics (MD) simulation. Carbon nanotubes were functionalized
Received in revised form 8 August 2017 by nitrogen inductively coupled plasma. They were made into a nanocomposite by a solvent-free mixing
Accepted 4 September 2017
method. The various characteristics of nanocomposites, including nitrogen doped carbon nanotubes were
Available online 8 September 2017
analyzed by the following experiments: a Raman spectra, an X-ray photoelectron spectroscopy (XPS),
quasi-static tensile tests, a scanning electron microscopy (SEM), and a transmission electron microscopy
Keywords:
(TEM). In addition, an MD simulation was performed to predict the mechanical properties of nanocom-
A. Nanocomposites
B. Mechanical properties
posites and the results were compared to the test measurements. It showed that the effective dispersion
C. Modelling of nitrogen doped carbon nanotubes was important to improve the mechanical characteristics of the
E. Surface treatments nanocomposites.
2017 Elsevier Ltd. All rights reserved.

1. Introduction and chemical kinetics in the nitrogen doped carbon structures.

The introduction of carbon nanotubes (CNTs) by Iijima [1] as a
reinforcement in polymer matrix composites (PMC) improves the
mechanical properties [25]. Recent research has extensively
focused on epoxy resin based CNTs nanocomposites because of
their wide applications in the electronics, aeronautics, and auto-
motive industries. The interfacial interaction between nanotubes
and polymer is an issue of nanocomposites. In particular, various
surface treatments of CNTs have been proposed to improve the dis-
persion of CNTs and interfacial interaction between nanotubes and
polymer [68]. Nitrogen doped CNTs may find extensive applica-
tion in composite design, due to their reactive surfaces, allowing
increased nanotube-matrix interaction [912]. The nitrogen in
the CNTs can be seen as regular defects that change the chemical
behavior of the tubes. Nitrogen doping plays a critical role in reg-
ulating electronic and chemical properties of carbon materials
due to the nitrogen doped carbon structures to form strong valence
bonds with carbon atoms [1315]. In addition, it is a challenge to
experimentally determine the exact locations of nitrogen atoms
Corresponding author.
E-mail address: jamesyu@kist.re.kr (J. Yu).
Molecular dynamics (MD) simulations have been employed to
prove the effects of functionalization. The goal of a MD simulation
is to trace the position of atoms as a function of time based on
Newtons 2nd law of motion [16]. Since MD simulations use an
atom based model, it has been widely used in studies for polymer
based composites including nanofiller. MD simulations have
demonstrated the potential for studying the local and bulk proper-
ties of cross-linked polymer networks as well as composites. Cho
et al. [17] investigated the elastic behavior of nanoparticle/polymer
composites and analyzed the size effect of nanoparticles. Mor-
tazavi et al. [18] investigated the effect of nitrogen doping and
vacancy on stiffness and strength of graphene. They can be applied
to nitrogen doped nanofiller. Many different types of nitrogen dop-
ing exist according to the functionalization methods. In this study,
we prepared epoxy based nanocomposites containing CNTs treated
by plasma under nitrogen gas. In order to improve the dispersion of
CNTs in the epoxy matrix, we used the dry method to functionalize
of CNTs by making use of the plasma. Moreover, this approach is a
solventfree method and easy to control by tuning key parameters
(exposure time plasma power, types of gases) in order to achieve
the desired functionalization level. The effects of nitrogen doping
on the structure of CNTs were studied experimentally by various

http://dx.doi.org/10.1016/j.compositesa.2017.09.005
1359-835X/ 2017 Elsevier Ltd. All rights reserved.
18 H. Jung et al. / Composites: Part A 103 (2017) 1724
characterization techniques: a Raman spectra, an X-ray photoelec-
tron spectroscopy (XPS), quasi-static tensile tests, and a scanning
electron microscopy (SEM). An MD simulation was performed to
estimate the effect of different nitrogen doping types (pyrrolic,
quaternary, pyridinic) on the mechanical properties of
nanocomposites.
2. Experiments
2.1. Materials
The multi-walled carbon nanotubes (MWCNTs) were produced
by a Catalytic Chemical Vapor Deposition (CCVD) process with a
purity of more than 95% carbon (JEIO Co., Ltd., Korea). The out
diameter and their lengths of the MWCNTs were less than 10 nm
and 520 lm, respectively. The bisphenol A based epoxy resin
EPON 826 (Momentive specialty chemicals Inc., USA) and the ali-
phatic diamine curing agent, Jeffamine D-230 (Huntsman Co., TX)
were used as a matrix. The viscosity of EPON 826 epoxy was about
6595 P (Poise) and the weight per epoxide was approximately
180 g/eq. In this experiment, a 50 wt% curing agent was mixed
with resin to form the matrix.
2.2. The plasma treatment of the MWCNTs
The plasma treatment was performed using a self-production
Inductively Coupled Plasma (ICP). The ICP discharged by an elec-
tromagnetic field induced by a radio frequency driven current
flowing through the coil around the reactor tube featured high
electron density and high electron temperatures at a low pressure
regime with respect to capacitively coupled plasma (CCP), one of
the most common types of discharge. The ICP chamber has no elec-
trode that is in direct electrical contact with the plasma. As a result,
ions in the plasma are not accelerated by as strong electric field as
in the CCP case. Therefore, the samples treated in the ICP process
experience less energetic ion bombardment with respect to those
in the CCP process. During these experiments the pressure was
set at 100 mTorr. The gas flow into the chamber was 10 sccm N2
(99.999%), and the power input was 100 W. The sample was placed
in the center of a Quartz tube and exposed to the plasma treatment
for 10 min.
2.3. Preparation of MWCNTs/epoxy composites
The epoxy nanocomposites containing 0.3, 0.6, and 1.0 wt% of
untreated pristine MWCNTs (P-MWCNTs) or nitrogen plasma trea-
ted MWCNTs (N-MWCNTs) were prepared. The EPON 826 resin
was put in a vacuum desiccator at a pressure of
80 kPa for 3 h
prior to mixing to remove entrapped air. P-MWCNTs or
N-MWCNTs were mixed with degassed epoxy using a high shear
mixer (ARE 310, Thinky Corp., Japan) at 1000 rpm and 2000 rpm
for 20 min. The mixture was stirred in bath-type sonicator (JAC-
3010, Kodo Technical Research Co. Ltd., Korea) for 30 min at
250 W. These solvent-free processing for fabricating epoxy based
nanocomposites were repeated twice to have the excellent disper-
sion of fillers. Additionally, in order to avoid overheating the
MWCNTs/epoxy mixture during sonication, the mixing beaker
was immersed in ice water and the mixture was maintained at
about 23 C. After the sonication, the curing agent was added to
the MWCNTs/epoxy mixture with shear mixing at 500 rpm and
1000 rpm for 20 min each. All resin systems were injected into a
steel mold and cured in a preheating oven (JEIO TECH Co., Ltd.,
Korea) at 80 C for 18 h.
2.4. Surface analysis and characterization
The X-ray photoelectron spectroscopy (XPS, K-Alpha, Thermo
Fisher Scientific, Inc., USA) was carried out with a monochromatic
Al ka source. 100 lm spot size was selected to determine the nitro-
gen doping concentration and examine the nitrogen doping effects.
In addition, the structural defects of the N-MWCNTs and compos-
ites were investigated using Raman spectroscopy (Renishaw Invia
Raman microscope, Renishaw, England). The second order band
of nanotubes (G0 ) was used to monitor the stress level of carbon
nanotubes [19]. The tensile properties of MWCNTs/epoxy compos-
ites were determined by quasi-static tensile tests in accordance
with ASTM D 638 [20]. Five specimens were prepared for each
specification. They were well-polished to minimize the adverse
effect of surface roughness on the resulting data. The tensile tests
were conducted at room temperature with 1mm/min cross-head
speed by using a universal testing machine (Unitech-M, R&B,
Korea). The choice of this quite low loading rate was due to the
hardening of the composites [21]. The strain was measured
through an extensometer with a gage length of 50 mm (Model
3542, Epsilon Tech. Corp., USA). All data was presented by the aver-
age values and reported the related error bars by taking into
account the data scattering. A scanning electron microscope (FE-
SEM, Nova NanoSEM 450, FEI Corp., OR, USA) was used to observe
the dispersion level of the MWCNTs and fracture surface of the
composites. The fractured surfaces were coated with platinum
using a sputter coating machine (Ion Sputter E-1030, Hitachi High
Technologies, Tokyo, Japan) for 120 s in a vacuum. The ultra-thin
films were cut from sample blocks using an ultramicrotome,
equipped with a diamond knife and observed by the transmission
electron microscopy (TEM, TITANTM, FEI Corp., OR, Netherland) at
300 kV.
3. Molecular dynamics simulations
3.1. Potential equations
All-atom based molecular dynamics (MD) simulations were
performed to estimate the effect of nitrogen doped CNTs on the
mechanical behavior of nanocomposites. The COMPASS II force
field in the commercial software, Materials Studio 8.0 package
for all-atom MD simulations, was adopted to calculate the total
free energy exactly. The potential energy equations in the COM-
PASS II force field can be expressed as [22]
X 2 3 4
U total bk2 b
b0 k3 b
b0 k4 b
b0 c
stretch
X
k2 h
h0 2 k3 h
h0 3 k4 h
h0 4 
angle
X
k1 1
cos / k2 1
2 cos / k3 1
cos 3/
bending
"    0 6 # X 1
X X r 0ij
9
r
k2 v
v0
2 qi qj
k5 2 r
3 rij r ij
ij ij
torsion v dW electro
X X
0 0
k6 b
b0 b
b0 k6 b
b0 h
h0
s;s0 s;a
X X
k6 b
b0 1
cos / k6 h
h0 h0
h00
s;b a;a0
where Utotal is the total potential energy of molecular model, b is the
bond length, h is the angle variation, / is the bending angle, v is the
torsional angle, r is the distance between non-bonding atoms, q is
the quantity of electric charge. k is the forcefield constant for corre-
sponding energy term and 0 means value on initial position. The
proposed equations have been widely used to simulate a potential
for complex structure of amorphous polymers.
 H. Jung et al. / Composites: Part A 103 (2017) 1724 19

3.2. Constant strain simulation

To simulate the mechanical behaviors of nanocomposites, Con-

stant strain simulations were performed in the MD models. It is
used to calculate elastic properties, such as Youngs modulus, shear
modulus, and Poissons ratio. Constant normal and shear strain
increments of 0.25% were uniformly applied along each direction
on the molecular models and updating the position of atoms. Aver-
age stress in the molecular model is defined by calculating virial
stress between the atoms as follows [23]
!
1X N
1X N
rij
k
 i uk

mk ui
u 
j
uj
l k kl
x
xi f j 2
V k1 2 l1 i
where rij is a stress tensor, V and m are volume and mass, N is the
number of atoms. ui, xi, fi are velocity, position, and force vector of
kth or lth atom, respectively. The process was stopped when a value
of strain reached 1.0%. Stress-strain curves were determined by
plotting the recoded data points to obtain elastic properties.

3.3. Simulation details

To compare with experimental results, MD models can be made

of nanocomposites with three different N-MWCNTs: pyrrolic, qua-
ternary, and pyridinic types. The MWCNTs in experiments were
modified as zigzag (7, 0) single walled nanotubes (SWCNTs) in
MD simulations because the nitrogen is only functionalized on a
surface of the outer most layer of MWCNTs. Fig. 1 shows three dif-
ferent N-doping types on SWCNTs. Their diameters and lengths
were 5.48 and 25.56 , respectively. Two components, the epoxy
(EPON 826) and curing agent (Jeffamine D-230), were used to form
a matrix, and the weight ratio of the epoxy to curing agent is iden-
tical to that in experiments. To exclude the influences of a cross
linking ratio, a cross linking ratio of the two components in a
matrix is 100%. Weight fractions of P-MWCNTs and N-MWCNTs
were 1.0 wt%. A periodic boundary condition was adopted on every
model. The percentage of N-doping was set to 5.0%, which equaled
the maximum value by ICP. To stabilize the MD models, a constant
volume and isothermal (NVT) ensemble was performed to room
temperature. After the NVT ensemble, models were equilibrated
in an isothermal and isobaric (NPT) ensemble at 300 K and 1 atm
until a density of MD model was conversed in a tolerance of
10
3 g/cm3.
Fig. 1. Various nitrogen doping types: (a) pyrrolic, (b) quaternary, (c) pyridinic. (For
4. Results and discussion interpretation of the references to colour in this figure legend, the reader is referred
to the web version of this article.)

4.1. Surface morphology and chemistry of MWCNTs

The chemical nature of the MWCNTs surface before and after
nitrogen plasma treatment was investigated by XPS. The plasma
treatment not only affected the percentage of nitrogen incorpo-
rated in the N-MWCNT structures, but it also varied the type of
the nitrogen incorporation (N-types). There were at least four dif-
ferent N-types that could be found in the N-MWCNT structures.
The peaks obtained from the XPS could be assigned to the pyridinic
nitrogen (398.3399.8 eV), pyrrolic nitrogen (400.1400.5 eV),
quaternary nitrogen (401.0401.4 eV) and to nitrogen oxide spe-
cies and/or intercalated nitrogen molecules (404.0405.6 eV)
[24]. Fig. 2 shows XPS N1 s spectra of N- MWCNTs samples with
nitrogen concentrations from 4.0 atom (at)%. The spectra can be fit-
ted with component peaks labeled N1, N2, and N3 at 399.02,
400.11 and 401.25 eV, respectively. Pyridinic nitrogen with a bind-
ing energy of 399 eV constituted 48% of the total N1s signal. Pyrro-
lic and quaternary nitrogen groups with a binding energy of 400 eV
and 401 eV constituted 36%, 16% of the total N1s signal. The survey
spectra of P-MWCNTs only revealed the presence of carbon; in par-
ticular, no traces of nitrogen were observed. There is a clear differ-
ence in the magnified N1s spectra range as shown in Fig. 2(bc).
Nitrogen plays an important role in forming the bamboo-like struc-
ture of the CNx nanotubes [25]. Increasing the amount of nitrogen
greatly affects the alignment of the CNTs lattice. From the XPS
spectra, it was confirmed that nitrogen has been doped into the
MWCNTs. It corresponds to an increase of intensity area ratio of
the D to G bands, ID/IG, obtained by Raman (ID/IG determined a
qualitative measure of functionalization level). The Raman spec-
troscopy was carried out to analyze the microstructure and defect
densities of the N-MWCNTs and N-MWCNTs/epoxy composites.
The graphitic crystal structures of the MWCNTs have a characteris-
tic peak at 1593 cm
1 (the G band) and a peak at 1368 cm
1
(the D band). The G band indicates a good arrangement of the
hexagonal lattice of graphite (i.e., crystallinity of the sample, pris-
tine arrangement of atoms). The D band gives an indication of
defects in MWCNTs (i.e., carbonaceous impurities with sp3 bond-
ing, broken sp2 bonds in the sidewall). The Raman spectra of the
MWCNTs before and after the plasma treatment are shown in
Fig. 3. The intensity area ratio of the D to G bands serves as a
standard to measure the defects of CNTs [26]. The higher the
20 H. Jung et al. / Composites: Part A 103 (2017) 1724
Fig. 2. XPS analysis (a) spectra survey from MWCNTs before and after nitrogen
plasma treatment, (b) Raw level of P-MWCNTs, and (c) N1s core level of N-
MWCNTs. (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)
ID/IG, the more defects present, which indicates more groups
appear on the surface of MWCNTs. Compared with the intensity ratio
of P-MWCNTs (ID/IG = 1.27), the ratio of N- MWCNTs was increased
to 1.48. This result indicated that considerable defects were pro-
duced on the surface of N-MWCNTs so that nitrogen-containing
groups were already attached on the side walls of MWCNTs.
4.2. Interface quality between MWCNTs and matrix
The nitrogen plasma treatment is expected to improve the
interface adhesion between MWCNTs and an epoxy matrix. Substi-
Fig. 3. Raman spectra of both pristine and nitrogen (N-) doped MWCNTs. (For
interpretation of the references to colour in this figure legend, the reader is referred
to the web version of this article.)
tutional N-doping may effectively enhance the surface energy and
a surface reactivity of graphitic carbons with the minimum loss of
material properties. The improved surface energy and a chemical
activity can be utilized for a facile synthesis of robust composite
structures with various matrix materials. The Raman spectroscopy
reflects the interface quality between MWCNTs and polymer
matrix when the composites are subjected to stress [27]. As well
established, the G band of MWCNTs is very sensitive to stress
levels loaded on them. It shifts to a lower wavenumber when the
MWCNTs are subjected to tension while they shift to a higher
wavenumber in compression [28]. The neat epoxy sample has no
Raman bands in the vicinity of G band (Fig. 4a). For the P-
MWCNTs/epoxy composites, their G band value is about
2683 cm
1. Otherwise the G band value becomes 2701 cm
1
(Fig. 4b) when the N-MWCNTs are added to the epoxy resin. The
G band values of nanocomposites containing N-doped CNTs fur-
ther increase compared to those of composites containing pristine
CNTs. The value means a tight interface between CNTs and an
epoxy resin as well shown as SEM images in Fig. 8(d) and (e). In
this case, the MWCNTs were subjected to compression stresses
due to the resin shrinkage during the curing process. Thus, after
nitrogen plasma treatment the stress can transfer more effectively
from the matrix to MWCNTs. It means the N-MWCNTs have stron-
ger interfacial bonding with an epoxy resin in comparison to that
of P-MWCNTs.
4.3. Mechanical properties and fracture surface analysis
Fig. 5 shows SEM images of the fracture surfaces of P-MWCNTs/
epoxy and N- MWCNTs/epoxy composites. These are used to ana-
lyze both the effectiveness of the stress-transfer and the dispersion
of the N-MWCNTs. The N-MWCNTs were uniformly better dis-
persed, even well dispersed at the highest loading. The TEM images
(Fig. 6b) demonstrated a relatively good dispersion of N-MWCNTs.
In contrast, P-MWCNT aggregates were observed in Fig. 6(a). The
doped specific functional groups can contribute not only to the
uniform dispersion but also to the enhanced interfacial bonding.
One of the most effective functionalization is to dope nitrogen
groups to surfaces owing to the polarity effect. This covalent bond-
ing provides much stronger interfacial bonding than van der Waals
forces. N-doped CNTs possess advantages in several aspects:
reduced work-function [29], increased, high dispersibility [30],
and produced band gap energy. This is due to the nitrogen groups
on the N-MWCNTs improving the dispersibility of the MWCNTs as
well as their interfacial bonding.
 H. Jung et al. / Composites: Part A 103 (2017) 1724
Fig. 4. Raman spectra (a) a typical neat epoxy matrix and (b) 1.0 wt% MWCNT/
epoxy composites. (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)
It is known that the nitrogen doping of MWCNTs in nanocom-
posites may improve their mechanical properties. Tensile tests
were conducted to evaluate the effect of nitrogen doping on the
mechanical properties of the composite. The typical stress-strain
curves of the tensile test are shown in Fig. 7. The addition of
MWCNTs in the epoxy enhances the elastic modulus due to the
incorporation of rigid components into the relatively soft epoxy
matrix as shown in Fig. 7(b). Epoxy resins are classified as brittle
material because these materials usually fail in tension at rela-
tively low values of strain. Fig. 7(a) shows that the neat epoxy com-
posite fails with a small elongation after the proportional limit is
exceeded. The specimens failed after the tensile stress reached
the maximum value. However, there is no obvious yielding point
was found in the curves. Fig. 7(b) shows that the composites con-
taining N-MWCNTs exhibited high elastic modulus without reduc-
ing its strength even at 1.0 wt% content. Table 1 reports the tensile
properties as a function of MWCNT contents for the different N-
doping type, together with P-MWCNTs. Among the P-MWCNTs/
epoxy nanocomposites, the best increase in tensile properties
was found from the epoxy with 0.3 wt% P-MWCNTs. The elastic
modulus and the tensile strength was increased by 8.2% and
9.8%, simultaneously. However, the addition of 1.0 wt% P-
MWCNTs decreased the tensile strength by 11.8%. Although its
elastic modulus increased up to approximately 8.6% compared to
the neat epoxy, these increases are lower than that of the 0.6 wt%
P-MWCNTs/epoxy nanocomposites. The dispersion of P-MWCNTs
in the epoxy matrix becomes poor at the higher weight fraction
of MWCNTs. Thus, the increases in the tensile properties for the
N-MWCNTs/epoxy nanocomposites were consistently higher than
21
Fig. 5. FE-SEM images of the fracture surfaces of the epoxy composites containing
the 1.0 wt% MWCNTs: (a) pristine, (b) nitrogen doped.
those for P-MWCNTs. The tensile strength of composites contain-
ing N-MWCNTs was 7.9%, 13.5% higher than those of the P-
MWCNTs composites data at 0.6 and 1.0 wt%, respectively. Simi-
larly, the elastic moduli of composites containing N-MWCNTs were
higher than the P-MWCNTs composites data. Fig. 8 shows SEM
images of the fracture surfaces of epoxy nanocomposites contain-
ing P-MWCNTs and N-MWCNTs after the tensile tests. The neat
epoxy has cleavage planes showing a relatively flat and smooth
fracture surface which is characteristic of brittle materials (Fig. 8
(a)). The fracture surfaces of the epoxy filled with 0.3 wt% P-
MWCNT and N-MWCNTs (Fig. 8(b) and (c)) appeared rough com-
pared to that of the neat epoxy. This is because the crack propaga-
tion was deflected by the presence of MWCNTs. Many P-MWCNTs
were visibly pulled out of the epoxy matrix suggesting poor adhe-
sion (Fig. 8(d)). In contrast, it is well evident the good interfacial
adhesion of N-MWCNTs, Fig. 8(e) that are well embedded in the
matrix. This suggests excellent interfacial bonding between the
N-MWCNTs and epoxy matrix. From the above results, it can be
concluded that the nitrogen groups on the surface of the MWCNTs
introduced by the plasma treatment improved both the dispersion
of the MWCNTs and the interfacial bonding with the epoxy matrix,
which leads to the profound improvement in the mechanical prop-
erties of the N-MWCNT nanocomposites.
4.4. MD simulations: Effects of N-doping
In Table 1, the elastic modulus of a 1.0 wt% P-MWCNT/epoxy
composite calculated by an MD simulation was 37.1% higher than
that of experimentally measured value. Also, the elastic modulus of
22 H. Jung et al. / Composites: Part A 103 (2017) 1724

(a) 50
Neat epoxy

40

MPa]
30

Tensile stress [
20

10

0
0 1 2 3 4 5 6
Strain [ , %]

(b) 50
P0.3 wt%
P0.6 wt%

Tensile stress [ , MPa]

40 P1.0 wt%
N0.3 wt%
N0.6 wt%
30
N1.0 wt%

20

10

0
0 1 2 3 4 5 6
Strain [ %]

Fig. 7. Typical quasi-static tensile stress-strain curves for (a) neat epoxy and (b) P-,
N-MWCNTs/epoxy composites. (For interpretation of the references to colour in this
figure legend, the reader is referred to the web version of this article.)

Table 1
Tensile properties of epoxy nanocomposites.

Sample (or Elastic Increase Tensile strength Increase

molecular model) modulus (GPa) (%) (MPa) (%)
Neat epoxy 2.57 0.05 37.53 0.05
Pristine MWCNTs/epoxy
Fig. 6. TEM images of the fracture surfaces of the epoxy composites containing the 0.3 wt% 2.78 0.08 8.2 41.2 1.5 9.8
1.0 wt% MWCNTs: (a) pristine, (b) nitrogen doped. 0.6 wt% 2.83 0.19 10.1 35.3 1.4
5.9
1.0 wt% 2.79 0.09 8.6 33.1 1.1
11.8
1.0 wt% (MD) 3.83 49.0
1.0 wt% N-MWCNTs/epoxy obtained from experiments was lower
N-doped MWCNTs/epoxy
27.3%, 38.8%, and 34.6% than those of the predicted 1.0 wt% N- 0.3 wt% 2.97 0.09 15.6 42.9 1.2 14.3
MWCNTs/epoxy composites containing pyrrolic, quaternary, and 0.6 wt% 2.94 0.02 14.4 38.1 4.8 1.5
pyridinic nitrogen groups, respectively. This result was due to the 1.0 wt% 2.97 0.05 15.6 37.6 2.1 0.2
aggregations of P-MWCNTs or N-MWCNTs in the epoxy matrix 1.0 wt% (MD*1) 3.78 47.1
1.0 wt% (MD*2) 4.12 60.3
which existed only in experiments. Every MD model in this study *3
1.0 wt% (MD ) 3.99 55.3
had a uniform dispersion of MWCNTs. Therefore, a good dispersion
*
is essential in improving the mechanical properties of nanocom- 1: pyrrolic type model, *2: quaternary type model, *3: pyridinic type model.
posite containing P-MWCNTs or N-MWCNTs. In the MD simulation
results, the calculated elastic moduli of 1.0 wt% N-MWCNTs/epoxy
composites containing quaternary and pyridinic nitrogen groups content. This explains its more favorable formation at a higher
were 7.8 and 4.5% higher than that of the predicted 1.0 wt% P- nitrogen content [31]. On the other hand, a pyrrolic nitrogen group
MWCNTs/epoxy composite. The calculated elastic modulus of a including pentagon defects is shown to lower energy in carbon
1.0 wt% N-MWCNTs/epoxy composite containing pyrrolic nitrogen nanostructures. Thus, the increased concentration of pyrrolic nitro-
groups was 1.0% lower than that of the predicted 1.0 wt% P- gen group induces more defects on carbon nanostructures. These
MWCNTs/epoxy composites. When a nitrogen atom is added to results show that the pyrrolic nitrogen groups on N-MWCNT
the carbon nanostructure, it disrupts the normal bonding configu- decreased the mechanical properties of nanocomposites unlike
ration between carbon atoms. This trend is observed for the corru- quaternary and pyridinic nitrogen groups. Therefore, it is a critical
gated carbon nanostructure, which is closely related to the issue to determine the elastic moduli of nanocomposites contain-
pyridinic nitrogen group formation. As a result, the pyridinic nitro- ing N-MWCNTs for controlling the nitrogen doping groups in their
gen group exhibits a low disrupted energy of formation at nitrogen surface treatment.
 H. Jung et al. / Composites: Part A 103 (2017) 1724
Fig. 8. FE-SEM images of the fracture surfaces of nanocomposite: (a) neat epoxy, (b) 0.3 wt% P- MWCNTs/epoxy, (c) 0.3 wt% N-MWCNTs/epoxy at low magnification 1000,
(d) 1.0 wt% P-MWCNTs/epoxy, and (e) 1.0 wt% N-MWCNTs/epoxy at high magnification 100,000.
5. Conclusion
Epoxy based composites containing pristine (P-) MWCNTs and
nitrogen (N-) doped MWCNTs were prepared. The N-doped
MWCNTs improved their dispersion in a matrix. In addition, better
interfacial adhesion to an epoxy matrix was found in comparison
to that of pristine MWCNTs. This led to an improvement in the
mechanical properties of epoxy nanocomposites containing
MWCNTs. In particular, the elastic modulus of a nanocomposite
containing 1.0 wt% N-doped MWCNTs was increased by 15.6%
compared with those of experimentally measured values of the
neat epoxy. MD simulations were performed to compare the
effects of nitrogen doping on the structure of MWCNTs for
mechanical properties of nanocomposites. Ideal dispersion of N-
doped and P- MWCNTs in the MD simulations improved the
mechanical properties of nanocomposites compared with experi-
mental results. Nanocomposite models containing quaternary
and pyridinic nitrogen doping types showed higher mechanical
properties than that of an MD model containing P-MWCNTs. How-
ever, the mechanical property of an MD model containing pyrrolic
type MWCNTs was decreased. Thus, for enhancing the mechanical
characteristics of nanocomposites containing N-doped MWCNTs, it
is required to increase the percentage rate of quaternary and pyri-
dinic types of N- MWCNTs instead of pyrrolic type in composites.
Acknowledgements
This study was supported by Korea Institute of Science and
Technology (KIST) Institutional Program. This study is also sup-
23
ported by the WPM (World Premier Materials) Program, Project
No. 10037878, Ultralight Structural Nano Carbon Composites,
funded by the Ministry of Trade, Industry and Energy (MOTIE,
Korea), and Space Core Technology Development Program (No.
2017M1A3A3A02016310) through the National Research Founda-
tion of Korea (NRF).
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