Composites Part B 217 (2021) 108872

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Composites Part B
journal homepage: www.elsevier.com/locate/compositesb

Impact resistance and interlaminar shear strength enhancement of carbon

fiber reinforced thermoplastic composites by introducing
MWCNT-anchored carbon fiber
Jinsil Cheon a, Minkook Kim b, *
a
Composites Convergence Reseach Center, Korea Textile Machinery Convergence Research Institute (KOTMI), 27 Sampung-ro, Gyeongsan-city, Gyeongbuk, 38542,
Republic of Korea
b
Institute of Advanced Composite Materials, Korea Institute of Science and Technology (KIST), 92 Chudong-ro, Bongdong-eup, Wanju-gun, Jeonbuk, 55324, Republic of
Korea

A R T I C L E I N F O A B S T R A C T

Keywords: Nano-fillers such as multi-walled carbon nanotubes (MWCNTs) are incorporated into composites to improve their
MWCNT mechanical and electrical properties; however, MWCNTs are not applicable to carbon fiber reinforced thermo­
Carbon fiber reinforced thermoplastic plastic polymer composites (CFRTPs) due to the high viscosity and melting temperature of the thermoplastic
composite (CFRTP)
resin. In this study, mass-producible MWCNT-anchored carbon fiber was developed and applied as a novel
Impact behavior
Interlaminar shear strength
incorporation into CFRTPs. Functional groups were introduced on the MWCNTs and carbon fiber through acid
and flame treatments, respectively, and were anchored by the esterification reaction of a coupling agent. The
tensile strength, Izod impact resistance and interlaminar shear strength (ILSS) of MWCNT-anchored CFRTPs were
investigated. An optimum concentration of and process method for MWCNT anchoring were suggested based on
the results of this work. The anchored MWCNTs increased the interfacial bonding between the PA6 matrix and
carbon fiber without increasing the viscosity of the thermoplastic resin. As a results, the impact resistance and
ILSS of the CFRTPs were significantly improved by the anchored MWCNTs on the carbon fiber.

1. Introduction
Carbon fiber reinforced polymer composites (CFRPs) are structural
materials commonly used in automobiles and aircraft due to their
promising mechanical properties, such as light weight, high specific ri­
gidity and strength, and excellent processability [1–4]. The polymer
matrix used in CFRP is divided into thermosetting polymers and ther­
moplastic polymers. In most cases, thermosetting resins are used for the
matrix of CFRP because they have a low viscosity and processing tem­
perature, allow good fiber impregnation, result in interfacial bonding
and are relatively inexpensive [5]. During the curing process, thermo­
setting polymer resin forms a complex three-dimensional network
structure with cross-links. CFRPs with a thermoset matrix are brittle,
with a low impact resistance and working temperature. Moreover, CFRP
cannot be recycled and reshaped by reheating due to the cross-links
formed.
To compensate for the disadvantages of thermoset matrix CFRP,
Carbon fiber reinforced thermoplastic polymer composites (CFRTPs)
have been widely researched because they have a thermoplastic resin
matrix that has a high impact resistance and that is recyclable [6,7]. It is
widely studied for application to structures require high impact resis­
tance and light weight. The main applications are electric vehicles that
require high impact resistance for battery protection and lightweight
aircraft such as unmanned aerial vehicles (UAVs) and drones [8,9]. In
particular, engineering thermoplastic with excellent mechanical and
thermal properties, such as PA6, PEEK, PPS and ABS, are being adopted
as the matrix of CFRTPs for automotive and aircraft applications.
However, the interfacial bonding strength and impregnation between
the fiber and matrix of a CFRTP is very low due to the poor interfacial
bonding strength (low surface free energy), the high melting tempera­
ture and the viscosity of the thermoplastic resin.
Multi-wall carbon nanotubes (MWCNTs) have been applied to
improve the mechanical properties of CFRPs, such as the impact resis­
tance, fracture toughness and interlaminar shear strength (ILSS),
because the fiber morphology and high aspect ratio are beneficial for
load transfer [10–14]. Simple mixing of MWCNTs with polymer resin is

* Corresponding author.
E-mail address: minkook@kist.re.kr (M. Kim).

https://doi.org/10.1016/j.compositesb.2021.108872
Received 26 January 2021; Received in revised form 1 April 2021; Accepted 4 April 2021
Available online 14 April 2021
1359-8368/© 2021 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
J. Cheon and M. Kim Composites Part B 217 (2021) 108872

Table 1 viscosity of the resin [18,19]. The increased viscosity reduces the
Characteristic of the carbon fiber, polyamide 6 and MWCNT. impregnation and the interfacial bonding between the carbon fiber and
Carbon fiber, T700 matrix [20–22]. Compared with thermosetting polymer resin, thermo­
plastic polymer resin has a relatively high viscosity and low surface free
Tensile strength 4900 MPa
Tensile modulus 230 GPa energy, and the simple mixing of nanoparticles seriously reduces the
Strain at failure 2.1% resin flow and wettability during composite fabrication. In other words,
Diameter 7 μm a simple mixing method is difficult to apply for thermoplastic resin and
Density 1.8 g/cm3 CFRTPs.
Polyamide 6 The components of a CFRP (matrix, carbon fiber and nanofiller)
Tensile strength 60 MPa should be chemically or physically bonded to improve the interfacial
Tensile modulus 1.2 GPa bonding and ensure effective load transfer [23]. Regarding the
Particle size 150 μm connection between the carbon fiber and CNTs, CNT-grafted carbon
Melting point 224◦ C fiber has been developed by directly growing or synthesizing CNTs on
Processing temperature 260◦ C
the surface of carbon fiber [24–28]. However, the method of growing or
MWCNT synthesizing CNTs has obvious limitations in mass production and thus
Outer diameter 20–30 nm cannot be applied to actual CFRP structures. Vivet A. et al. [29] attached
Purity >95% MWCNTs on the surface of carbon fiber using a sizing agent. However,
Length 10–30 μm
the tensile strength of the carbon fiber was significantly reduced during
subsequent thermal treatment. To minimize damage to the carbon fiber,
electrophoretic deposition (EPD) or layer-by-layer (LBL) technology has
the basic method for fabricating MWCNT-incorporated CFRPs [15–17]. also been used to anchor MWCNTs on carbon fiber [30,31].
However, the simple mixing method of nanoparticles results in an un­ In this study, mass-producible MWCNT-anchored carbon fiber was
favorable nonuniform nanoparticle dispersion and greatly increases the developed and applied as a novel incorporation method of MWCNTs into

Fig. 1. Schematic drawing of (a) the MWCNT-anchored carbon fiber and (b) the fabrication process.

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J. Cheon and M. Kim Composites Part B 217 (2021) 108872

Fig. 2. SEM images of MWCNT-anchored CF surface with respect to the MWCNT concentrations in the MWCNT-dispersed water: (a) reference, (b) 1 wt.%, (c) 2 wt.
%, (d) 3 wt.% and (e) 4 wt.%.

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J. Cheon and M. Kim
Table 2
Parameters of CFRTP specimens and MWCNT Concentrations.
Reference specimen
Reinforcement Pristine carbon fiber
Matrix Pure PA6 powder
MWCNT-mixed CFRTP
Reinforcement Pristine carbon fiber
Matrix MWCNT mixed PA6
powder
MWCNT concentrations (wt.%) in the PA6 Matrix 1, 3 and, 5 wt.%
MWCNT-anchored CFRTP
Reinforcement MWCNT-anchored carbon
fiber
Matrix Pure PA6 powder
MWCNT concentrations (wt.%) in the MWCNT 1, 2, 3 and 4 wt.%
dispersed water
CFRTPs to improve the impact resistance and interlaminar shear
strength of CFRTPs. A CFRTP was fabricated using a polyamide 6 (PA6)
matrix and plain-woven carbon fiber fabric (CF) reinforcement. The
MWCNTs were anchored on the carbon fiber through an esterification
reaction between the acid-treated MWCNTs and carbon fiber using the
silane coupling agent. This MWCNT anchoring method is advantageous
for mass production because it used only simple surface treatment of the
MWCNT and carbon fiber, and esterification reaction. To compare this
incorporating method with the traditional simple mixing method, a
CFRTP was also fabricated by simply mixing MWCNTs with PA6 using
cryogenic pulverization. The mechanical properties of the CFRTPs were
investigated by tensile tests, Izod impact tests and short beam shear tests
with respect to the incorporation method and amount of MWCNTs.
1.1. Materials
CFRTP specimens were fabricated with a 12-k yarn plain-woven
carbon fabric (T700, Toray Advanced Materials, Japan) and poly­
amide 6 (PA6) (Nylon6 Chip, KP Chemtech, Republic of Korea). PA6 is
an affordable engineering plastic with excellent mechanical properties
and a relatively low processing temperature of 260◦ C [32]. In addition,
PA6 has polar functional groups (–CO–NH-) in the polymer chain to
form hydrogen bonds with polar materials containing hydroxyl groups
(-OH) or carboxyl groups (-COOH). Pellet-type PA6 was cryogenically
pulverized to enhance impregnation into the carbon fiber. The particle
size of the PA6 powder was controlled to under 150 μm using a sieve
with a 150 μm mesh after cryogenic pulverization. The MWCNTs and the
PA6 powder were also simply mixed by the cryogenic pulverization
process. The average diameter and length of the MWCNTs (KRU4309,
Korea Nanomaterials, Republic of Korea) were 20–30 nm and 10–30 μm,
respectively. CFRTPs with MWCNTs simply mixed with the PA6 matrix
were fabricated with different concentrations of MWCNTs in the PA6
matrix: 1, 3, and 5 wt.%. Table 1 shows the characteristic of the carbon
fiber, PA6 and MWCNT.
1.2. MWCNT-anchored carbon fiber
The process for MWCNT anchoring on the carbon fiber was
sequentially performed by the desizing the carbon fiber, coating the
coupling agent, dipping the carbon fiber into the MWCNT dispersed
solution, and waiting for the hydrolysis reaction, as shown in Fig. 1.
First, the commercial sizing agent on the carbon fabric was desized by a
flame treatment, which also increased the oxygen functionalities on the
surface of the carbon fiber [33]. Then, the flame-treated carbon fabrics
were dipped into a 0.5 wt.% epoxy-terminated silane coupling agent
aqueous solution. An epoxy-terminated silane coupling agent
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Composites Part B 217 (2021) 108872
(KBM-403, Shin-Etsu Silicone, Japan) was applied to improve the
chemical bonding between the carbon fiber and the MWCNTs. The
acidity of the aqueous solution was controlled to pH 4 by using acetic
acid to promote the solubility of the epoxy-terminated silane coupling
agent in distilled water. The silane coupling agent-coated carbon fabric
was dried at 120◦ C for 2 h in a convection oven to accelerate the hy­
drolysis reaction between the carbon fiber and the silane coupling agent.
MWCNT-anchored carbon fabric was fabricated by dipping coupling
agent-coated carbon fabric into MWCNT-dispersed water. The surface of
the MWCNTs was acid-treated with a 3 M nitric acid and 30% hydrogen
peroxide in aqueous solution to enhance the dispersibility of the
MWCNTs in the distilled water [34]. The acid-treated MWCNTs were
dispersed in distilled water with a surfactant (Triton X-100, Daejung
Chemicals and Metals, Republic of Korea) in a 1:0.3 weight ratio. The
silane coupling agent coated carbon fabric was dipped into
MWCNT-dispersed water. Finally, the MWCNT-coated carbon fabric was
dried at 120◦ C for 2 h in a convection oven. MWCNT-CF was prepared
with different concentrations of MWCNTs from 0 to 4.0 wt.% in the
MWCNT-dispersed water.
Fig. 2 shows the surface topography of the MWCNT-CF as a function
of the MWCNT concentration. The MWCNTs covering the surface of the
fiber were entangled and tightly bound by the coupling agent after the
anchoring process. It was found that the amount and thickness of the
anchored MWCNTs increased with the MWCNT concentration.
1.3. Composite fabrication
The CFRTPs were fabricated with two different types of carbon fabric
(pristine CF and MWCNT-anchored carbon fiber) and PA6 (pristine PA6
and MWCNT-mixed PA6) using the powder spreading method. The
CFRTP was fabricated by compressive molding at 250 ◦ C under 20 MPa
(Appendix A). The closed mold cavity size was 120 mm × 120 mm.
CFRTPs were prepared with two different thicknesses for the tensile test
(0.75 mm; 3 plies of CF), Izod impact test and short beam shear test (3
mm; 12 plies of CF). Table 2 summarizes the specimen parameters ac­
cording to the weight percentage of the MWCNT concentrations in the
PA6 matrix (MWCNT-mixed CFRTP) and MWCNT-dispersed water
(MWCNT-anchored CFRTP).
Fig. 3 shows the cross section images of the MWCNT-anchored
CFRTPs respect taken with a digital microscope (VHX-900F, Keyence,
Japan). Regardless of the concentration of the anchored MWCNT, there
were no measurable sized voids or pores in CFRTPs. This proves that the
fabrication process including the PA6 powder size, spreading method,
mold design, fabrication temperature and pressure were adequate to
minimized the porosity of the CFRTPs.
1.4. X-ray photoelectron spectroscopy and FE-SEM analysis
To confirm the changes in the functionalities of MWCNTs and each
step of the carbon fiber treatment, X-ray photoelectron spectroscopy
(XPS, Thermo Fisher Scientific, U.S.A.) was performed for O1s
(525.08–545.08 eV) and C1s (279.08–298.08 eV) by using an Al–K alpha
gun source. The spot size and energy step size for each scan in the
analysis are 200 μm and 0.05 eV, respectively.
A field-emission scanning microscope (NOVA NanoSEM 450, FEI,
USA) was used to observe the anchored formation of MWCNTs on the
surface of the carbon fiber and fractured surface after the IZOD impact
test and the ILSS test. Each sample was uniformly coated with platinum
for 180 s by the sputtering method. Topographical analysis was per­
formed to define the role of anchored MWCNTs as a load-transferring
bridge in the CFRP on the interaction between PA6 and CF.
J. Cheon and M. Kim
Fig. 3. Cross section images of the MWCNT-anchored CFRTPs with respect to the MWCNT concentrations: (a) w/o MWCNT, (b) 1 wt.%, (c) 2 wt.%, (d) 3 wt.% and
(e) 4 wt.%.
1.5. Mechanical properties measurement
The tensile strength, interlaminar shear strength (ILSS) and Izod
impact strength of the CFRTP were measured with respect to the
MWCNT concentration and incorporation method (Appendix B). Seven
tests were performed for each CFRTP specimen. The test specimens were
machined by a water jet cutting system (T500-3015, TOPS waterjet,
Republic of Korea) with a cutting speed of 650 mm/min. The nozzle size
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Composites Part B 217 (2021) 108872
and the pressure of the water jet are 0.82 mm and 70,000 psi, respec­
tively. The specimen dimensions and stacking number of plies were
determined to satisfy the ASTM standard.
The tensile strength of the CFRP was measured by using a universal
testing machine (Instron 5985, Instron, U.S.A.) following the ASTM
D3039 standard. The tensile test specimen dimensions were 0.75 mm ×
15 mm x 120 mm, and the test speed was 1 mm/min. To identify the ILSS
of the CFRTP, the short beam shear test was performed by using a
J. Cheon and M. Kim Composites Part B 217 (2021) 108872

Fig. 4. XPS spectra results of the MWCNT and the carbon fiber following the MWNCT anchoring processes: (a) Acid treated MWCNT, (b) pristine CF, (c) flame treated
CF, (d) silane coupling agent treated CF and (e) MWCNT-anchored CF.

universal testing machine (Instron 5567A, Instron, U.S.A.) following the
ASTM D2344 standard. The span-to-depth ratio of the specimen was 4:1,
and the width was 2 times the specimen thickness. The dimension of the
ILSS test specimen were 3 mm × 6 mm x 18 mm, and the span length was
12 mm. The ILSS test speed was 1 mm/min. The load cells used in the
tensile tests and ILSS tests were ±30 kN load cell (2525–810, Instron, U.
S.A.) and ±2 kN load cell (2525–818, Instron, U.S.A.), respectively. The
sensibility of both load cells are 2 mV/V at full static rating and the error
at indicated force is smaller than 0.1%.
The Izod impact strength of CFRP was measured by using a low-

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J. Cheon and M. Kim Composites Part B 217 (2021) 108872

Table 3 1.6. Chemical bonding between the MWCNT and CF

Atomic composition of the MWCNT and carbon fiber (CF) following the MWNCT
anchoring processes. To investigate whether the MWCNTs were properly anchored on the
Specimen Atomic Composition (%) Atomic carbon fiber, the functional groups of the carbon fiber and MWCNT
Ratio (%) surfaces were analyzed by XPS analysis following the process. The O1s
Carbon Oxygen Silicone O/C Si/C (525.08–545.08 eV) and C1s (279.08–298.08 eV) XPS spectra results are
(C) (O) (Si) deconvoluted by using Gaussian fitting, as shown in Fig. 4 and Table 3.
Acid treated 93.5 6.5 0.0 0.07 0.00 In accordance with the information provided about the composition
MWCNT of the pristine MWCNTs (over 98% carbon) f], the surface carbon
Pristine CF 67.3 25.3 7.4 0.38 0.11 composition was reduced by over 4.5% by the acid treatment. The O1s
Flame treated CF 74.3 20.2 5.5 0.27 0.07 spectra for the acid-treated MWCNTs were deconvoluted into four
Silane treated CF 64.8 27.0 8.1 0.42 0.13
MWCNT-anchored 93.2 6.9 0.0 0.07 0.00
binding energies at 532.0 eV (-C-O-, 60.4%), 532.9 eV (O– – C-, 21.6%),
CF 533.8 eV (O–– C–OH, 8.4%) and 536.1 eV (chemisorbed water, 9.6%), as
shown in Fig. 4-(a). The MWCNTs underwent surface oxidation though
acid treatment, and the C1s spectra deconvoluted into six binding en­
energy pendulum impact tester (IT 504, Tinius Olsen, U.K.) with a ergies: 284.3 eV (C–C sp2, 66.6%), 284.7 eV (C–COOH, 14.5%), 285.9
pendulum energy of 15 J, following the ASTM D256 standard. The di­ eV (C–C sp3, 8.4%), 287.0 eV (C– – O, 4.4%), 288.5 eV (COOH, 4.0%),
mensions of the impact specimen were 3 mm × 12.5 mm x 63.5 mm, and and 290.3 eV (π- π, 2.1%). As a result, oxygen-containing functional
the 2.5 mm deep notch was machined by an impact specimen notcher groups were formed by the acid treatment.
(Model 899, Tinius Olsen, U.K.). The atomic composition of the carbon fibers was dramatically
changed by the flame treatment and silane coupling agent coating
process. The flame treatment reduced the oxygen and silicone contents

Fig. 5. Chemical mechanism of the MWCNT anchoring on the surface of carbon fiber.

7
J. Cheon and M. Kim
Fig. 6. Tensile strength and stiffness of the CFRTPs with respect to the MWCNT concentration: (a) the MWCNT-mixed CFRTPs, (b) the MWCNT-anchored CFRTP and
(c) stress-strain curves.
on the fiber surface because the commercially sized layer was elimi­
nated. In contrast, the epoxy-terminated silane coupling agent increased
the oxygen and silicone functional group, as shown in Fig. 4-(c) and (d).
The functional groups of the MWCNT-anchored carbon fiber were the
same as those of the acid-treated MWCNTs without the silicone func­
tional group and were not detected from the O1s and C1s spectra, as
shown in Fig. 4-(e). Because the penetration depth of the X-ray source
used in XPS is limited below 1000 Å [35], the MWCNTs completely
covered and anchored to the surface of the carbon fiber, as shown in the
SEM images of the MWCNT-anchored carbon fiber in Fig. 2.
The MWCNT anchoring mechanism on the surface of carbon fiber
can be described by tracing the functional groups of the acid-treated
MWCNTs and the carbon fiber based on the XPS analysis results, as
shown in Fig. 5. Oxygen-containing functional groups such as the hy­
droxyl (-OH) and carboxyl (-COOH) groups were formed on the MWCNT
surface due to the acid treatment, and these carboxyl groups bond with
the epoxy groups and form ester linkages (-C-O-C-) by esterification
[36]. The epoxy-terminated silane coupling agent was chemically
bonded by esterification with the hydroxyl and carboxyl groups of the
flamed-treated carbon fiber. As a result, the acid-treated MWCNTs
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Composites Part B 217 (2021) 108872
anchored on the surface of the carbon fiber by esterification between the
epoxy groups on the carbon fiber surface and the carboxyl and hydroxyl
groups on the acid-treated MWCNTs.
2. Results and discussion
2.1. Tensile strength
As shown in Fig. 6, The tensile strengths and stiffness of the CFRTPs
showed similar values of approximately 1100 MPa and 50 GPa,
respectively, regardless of the incorporation methods and concentra­
tions of the MWCNTs. The ‘reference’ label indicates the CFRTP fabri­
cated with pristine CF and PA6 matrix. The tensile strength and stiffness
of the CFRTPs is the same as that of a T700 carbon/epoxy CFRP, which
proves that the CFRTPs were properly fabricated by cryogenically pul­
verized PA6 powder and compressive molding.
The tensile stiffness of the CFRPs are predominantly determined by
the carbon fiber properties and volume fraction. However, the inter­
laminar strength between the carbon fiber and matrix can be inferred
through the difference between the stress-strain curve (S–S curve) and
J. Cheon and M. Kim
Fig. 7. Inter-laminar shear strength (ILSS) and the shear stress-displacement curves of the CFRTPs with respect to the MWCNT concentration: (a) MWCNT-mixed
CFRTP and (b) MWCNT-anchored CFRTP.
the failure mode. In case of the MWCNT-mixed CFRTPs and, delami­
nation occurred during the tensile test and the slope decreased when the
strain was 0.02 mm/mm as shown in Fig. 6-(c). The main failure mode of
the MWCNT-mixed CFRTPs under the tensile was delamination between
carbon fabric layers. In contrast, MWCNT-anchored CFRTPs showed the
tensile failure and fiber pull-out failure modes, and the slope decrement
of the S–S curves were not noticeable (Appendix C). There was no sig­
nificant difference in tensile strength and stiffness of the CFRTPs, but it
was confirmed that the interlaminar strength of the CFRTPs were
improved by the MWCNT-anchoring on the carbon fiber.
2.2. Interlaminar shear strength
Fig. 7 shows the ILSS and the shear stress-displacement curves of
CFRTP with respect to the MWCNT incorporation method and concen­
tration. The ILSS results are consistent with the results inferred from the
SS curve and failure mode of tensile test. The ILSS of the MWCNT-mixed
CFRTP was reduced from 35 MPa to 28 MPa by mixing the MWCNTs, as
shown in Fig. 7-(a), although it was clear that the matrix properties were
improved by the MWCNTs [37–41]. The ILSS for laminated FRP was
affected by the interfacial bonding of the fiber and polymer matrix and
the wettability of the polymer matrix. The resin viscosity of the polymer
was increased by incorporating the MWCNTs. This drastically reduced
the resin flow and infiltration into the carbon fabric reinforcement
during the fabrication process. Therefore, the interfacial bonding be­
tween the matrix and fiber deteriorated, and resin-rich areas were
generated between the laminated fabrics. This reduction in the ILSS was
detrimental to CFRTPs in which thermoplastic resin with high viscosity
and poor interfacial bonding was used. In the case of the reference
CFRTP, delamination occurred in the PA6 matrix, as shown in Fig. 8-(a)
and Fig. 9-(a). The delamination crack gradually propagated by the slip
on PA6 matrix layer, the shear stress curves of the reference and
MWCNT-mixed CFRTP showed no obvious drop and peak point [42] as
shown in Fig. 7-(a).
The ILSS of the MWCNT-anchored CFRTP was increased by up to
34%, a maximum of 46.7 MPa, with a 1 wt.% MWCNT concentration
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Composites Part B 217 (2021) 108872
and decreased with increasing MWCNT amount. With the 1 wt.%
MWCNT anchoring on the carbon fiber surface, the coupling agent layer
teared-off from the carbon fiber as shown in Fig. 8-(b). The teared-off of
coupling agent layer proved that the MWCNTs formed mechanical and
chemical interlocking between the PA6 matrix and the coupling agent
layer on the carbon fiber. Therefore, the delamination also occurred
between the carbon fiber and the coupling agent layer, as described in
Fig. 9-(b). The ILSS decreased to 24 MPa with 4 wt.% MWCNT
anchoring, less than the reference.
With 2 and 3 wt.% MWCNT concentrations, the MWCNT fully
covered the carbon fiber surface and delamination occurred in the PA6
matrix layer over the MWCNT layer, as described in Fig. 9-(c). There was
no teared-off of the coupling agent layer, but the MWCNT entangling
and pull-out effect increase the ILSS of the CFRTP as shown in Fig. 8-(c)
and (d). The delamination crack of the MWCNT-anchored CFRTPs
rapidly propagated when the entangled MWCNTs were pulled out,
resulting in a drop in the shear stress was dropped and showed peak, as
shown in Fig. 7-(b). And it can be confirmed from the slope difference of
the shear stress-displacement curves in Fig. 7-(a) and (b), that the shear
stiffness of MWCNT-anchored CFRTPs relatively higher than that of
MWCNT-mixed CFRTPs. In other words, the anchored MWCNTs on the
carbon fiber effectively prevent the shear deformation by entangled with
the PA6 matrix.
With 4 wt.% MWCNT anchoring, however, smooth delaminated
surfaces were observed after the ILSS test, as shown in Fig. 8-(e). The
anchored MWCNTs thickly covered the carbon fiber surface and formed
an MWCNT layer on the surface of the carbon fiber, as shown in Fig. 2-
(e). There was no chemical bonding between the MWCNTs and it was
hard to fully impregnate the aggregated MWCNT with the PA6 matrix.
Therefore, the MWNCT entangling effect reduced and the delamination
easily occurred between the anchored MWCNT layers as described in
Fig. 9-(d). The interfacial bonding between the carbon fiber and polymer
matrix can be weakened by increasing the thickness of the anchored
MWCNT layer [43] because it becomes difficult for the resin to
completely impregnate between the MWCNTs. The tensile strength of
the MWCNT-anchored CFRTP also decreased due to the reduction in the
J. Cheon and M. Kim
Fig. 8. Delaminated surface of the MWCNT-anchored CFRTP after the ILSS test
with respect to the MWCNT concentrations: (a) Reference (w/o MWCNT), (b) 1
wt.%, (c) 2 wt.%, (d) 3 wt.% and (e) 4 wt.%.
ILSS [42,44,45]. As a result, MWCNTs can be incorporated into CFRTP
without increasing the viscosity of the thermoplastic resin through the
use of MWCNT-anchored carbon fiber.
2.3. Izod impact resistance
Fig. 10 shows the Izod impact resistance results of the MWCNT-
mixed CFRTP and the MWCNT-anchored CFRTP with respect to the
MWCNT concentrations. The impact resistance increased as the
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Composites Part B 217 (2021) 108872
incorporated amount of MWCNTs increased. The Izod impact resistance
of MWCNT-mixed CFRTP was increased by 24% from 191 kJ/m2 to 231
kJ/m2 with a MWCNT concentration of 3 or 5 wt.%. When the impact
was applied to the CFRP, delamination started at the impacted site and
propagated along the reinforced fiber. The impact energy was absorbed
by delamination, matrix cracking, fiber breakage and fiber pull out. In
the case of carbon nanofiller mixing in a polymer matrix, the impact
resistance was increased by the matrix toughening effect [46–49].
However, the matrix toughness (impact resistance) did not increase
beyond the critical value, even when the MWCNT amount increased,
because the MWCNTs started to aggregate and acted as defects [50,51].
The Izod impact resistance of the MWCNT-anchored CFRTP
dramatically increased with respect to the MWCNT concentration, as
shown in Fig. 10-(b). The impact resistance of the MWCNT-anchored
CFRTP was increased by 91% to356 kJ/m2 with the optimum MWCNT
concentration of 3 wt.%. The improved interfacial bonding between the
fiber and matrix increased the impact energy propagation and energy
consumed by delamination. Moreover, the MWCNT anchoring on the
surface of the carbon fabric increased the inter-yarn friction of the
woven fabric and interfacial bonding between the fiber and the matrix.
In other words, the toughness of the reinforced fabrics and the impact
energy absorption by the fiber pull-out were improved [52], in addition
to the ILSS and matrix toughness. As a result, the impact resistance of the
MWCNT-anchored CFRTP was dramatically enhanced compared with
that of MWCNT-mixed CFRTP. Without MWCNT anchoring, the CFRTPs
were fractured by the mainly delamination under the Izod impact as
shown in Fig. 11-(a). On the contrary, in case of the MWCNT-anchored
CFRTPs, the fracture mainly occurred by fiber breakage and fiber
pull-out due to the improved ILSS, as shown in Fig. 11-(b) & (c). As a
result, the impact energy absorption (Izod impact resistance) of the
CFRTPS were also improved significantly.
Fig. 12 shows the fracture surfaces of the MWCNT-anchored CFRTP
after the Izod impact test with respect to the MWCNT concentrations. In
the case of the reference CFRTP, the fracture mainly formed by the
debonding between the PA6 matrix and the carbon fiber. The debonding
fracture proved that the impact load transfer between fibers was not
sufficient. The fracture mode of the MWCNT-anchored CFRTP changed
from debonding to PA6 matrix rupture with increasing MWCNT con­
centration, as shown in Fig. 12-(b)~(d). The interlocking between the
fiber and matrix was increased by the addition of the MWCNTs, and the
carbon fiber and PA6 matrix remained partially bonded even after the
impact test. In the case of the CFRTP based on a thermoplastic resin with
excellent impact resistance, the improvement in impact resistance was
maximized by increasing the ILSS, unlike the case of the CFRTP based a
brittle thermoset resin. However, the impact resistance of MWCNT-
anchored CFRTP with the 4 wt.% MWCNT concentration was largely
decreased, and the fracture occurred by debonding and delamination
again, as shown in Fig. 11-(d) and Fig. 12-(e). The thickening of the
anchored MWCNT layer on the surface of the fiber reduced the ILSS and
impacted the energy transfer.
3. Conclusion
In this work, mass producible MWCNT-anchored carbon fibers were
developed to improve the impact resistance and interlaminar shear
strength of CFRTPs. Simply mixing MWCNTs with the PA6 matrix using
cryogenic pulverization increased the Izod impact resistance of the
resulting CFRTP; however, it decreased the corresponding ILSS due to
the increased resin viscosity. Therefore, it is difficult to simultaneously
increase the impact resistance and ILSS of a CFRTP by simply mixing the
nanofiller with the thermoplastic matrix.
The MWCNTs were chemically anchored on the carbon fiber rein­
forcement through an esterification reaction between the MWCNTs and
the carbon fiber using a silane coupling agent instead of mixing with the
thermoplastic matrix. Functional groups from the esterification reaction
were introduced on the MWCNTs and the carbon fiber through acid and
J. Cheon and M. Kim Composites Part B 217 (2021) 108872

Fig. 9. Schematics for the delamination behavior of MWCNT anchored CFRTP with respect to the MWCNT concentrations: (a) Reference (w/o MWCNT), (b) low
concentration (~1 wt.%), (c) middle concentration (2, 3 wt.%) and (d) high concentration (4 wt.%).

Fig. 10. Izod impact resistance with respect to the MWCNT concentration: (a) MWCNT-mixed CFRTP and (b) MWCNT-anchored CFRTP.

Fig. 11. Fractured specimen images of the MWCNT-anchored CFRTPs after the Izod impact test with respect to the MWCNT concentrations: (a) Reference (w/o
MWCNT), (b) 1 wt.%, (c) 3 wt.% and (d) 4 wt.%.

flame treatment. This MWCNT anchoring method is advantageous for matrix and carbon fiber. As a result, MWCNTs were effectively incor­
mass production because it used only simple surface treatment of the porated into CFRTPs and the impact resistance and ILSS of the CFRTPs
MWCNT and carbon fiber, and esterification reaction. The ILSS and the were significantly improved by the anchored MWCNTs on the carbon
impact resistance of the MWCNT-anchored CFRTP were increased by fiber.
34% and 91%, respectively, with optimum MWCNT-anchoring con­
centrations. The anchored MWCNTs resulted in mechanical and chem­
ical interlocking and increased the interfacial bonding between the PA6

11
J. Cheon and M. Kim
Fig. 12. Fractured surface of the MWCNT-anchored CFRTP after the Izod
impact tests with respect to the MWCNT concentrations: (a) w/o MWCNT, (b) 1
wt.%, (c) 2 wt.%, (d) 3 wt.% and (e) 4 wt.%.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
This work was supported by the technology innovation program
(No.20010735) funded by the Ministry of Trade, Industry & Energy
12
Composites Part B 217 (2021) 108872
(MOTIE, Korea) and the Korea Institute of Science and Technology
(KIST) institutional Program (No. 2Z06050).
Appendix A. Supplementary data
Supplementary data related to this article can be found at https://do
i.org/10.1016/j.compositesb.2021.108872.
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