applied

sciences
Article
Improvement of Interfacial Adhesion of Incorporated
Halloysite-Nanotubes in Fiber-Reinforced
Epoxy-Based Composites
Jin-Woo Lee 1 , Soo-Jeong Park 2 and Yun-Hae Kim 1, *
1 Department of Mechanical Engineering, Korea Maritime and Ocean University, Busan 49112, Korea;
zenith1179@naver.com
2 Department of Material Engineering, Graduate School, Korea Maritime and Ocean University, Busan 49112,
Korea; blue9069@kmou.ac.kr
* Correspondence: yunheak@kmou.ac.kr; Tel.: +82-51-410-4966

Academic Editor: David K. Mills

Received: 20 February 2017; Accepted: 22 April 2017; Published: 27 April 2017

Abstract: The heart of composite materials depends on the characteristics of their interface.
The physical properties of composite materials are often described by the rule of mixtures,
representing the average physical properties of the reinforcement and the matrix resin. However,
in practical applications there are situations which arise where the rule of mixtures is not followed.
This is because when an external energy applied to the composite material is transferred from the
matrix to the reinforcement, the final physical properties are affected by the interface between them
rather than the intrinsic properties of both the reinforcement and the matrix. The internal bonding
strength of the interface of these composites can be enhanced by enhancing the bonding strength
by adding a small amount of material at the interface. In this study, the mechanical properties were
evaluated by producing a carbon fiber-reinforced composite material and improved by dispersing
halloysite nanotubes (HNTs) and the epoxy resin using an ultrasonic homogenizer. The interfacial
bond strength increased with the addition of HNT. On the other hand, the addition of HNTs more
than 3 wt % did not show the reinforcing effect by HNT agglomeration.

Keywords: carbon fiber-reinforced composite; halloysite nanotube; ultrasonic homogenization;

interfacial adhesion; interfacial bonding strength; epoxy resin

1. Introduction
The interface of composite materials is the heart of composite materials. There is a significant
difference between the physical and chemical properties or the mechanical properties of the reinforcing
fibers and the matrix resin itself [1]. Therefore when the materials are combined, the nature of the
interface between the dissimilar materials can have a profound impact on the mechanical properties
of the composite material. The physical properties of composite materials are often described by the
rule of mixtures, which represent the average physical properties of the reinforcement and the matrix
resin. However, in practical applications, situations arise when the rule of mixtures is not followed.
This is because when an external energy is applied to the composite material, it is transferred from
the matrix to the reinforcement, affecting the final physical properties of the interface between them
rather than the intrinsic properties of both the reinforcement and the matrix. In addition, each matrix
or reinforcement forms strong internal chemical bonds, and their interface forms weak physical bonds.
Because of this, a force delivered from outside is dependent on the extent of the physical bonding [2,3].
In general, composite materials, which do not have any surface treatment of carbon fibers, are
known to show a low degree of interlaminar shear strength (ILSS) or critical stress intensity factor
(KIC ). This is due to the fact that carbon fiber, which is used as reinforcement, has a low wettability

Appl. Sci. 2017, 7, 441; doi:10.3390/app7050441 www.mdpi.com/journal/applsci

Appl. Sci. 2017, 7, 441 2 of 8

level with the matrix and the surface itself is smooth, and thus the interfacial bonding strength is
weakAppl.
[4].Sci. 2017, 7, 441
Therefore, the interfacial bonding strength of carbon fiber-reinforced composite material 2 of 8
can
be improved
(KIC). Thisby twotomethods.
is due (i) carbon
the fact that first removing
fiber, whichimpurities
is used ason the surface has
reinforcement, of the carbon
a low fiber with
wettability
surface treatment methods such as vapor phase oxidation, liquid phase oxidation,
level with the matrix and the surface itself is smooth, and thus the interfacial bonding strength anodic oxidation,
is
and plasma treatment. After that the number of functional groups (carboxyl,
weak [4]. Therefore, the interfacial bonding strength of carbon fiber-reinforced composite material carbonyl, and hydroxyl)
enhancing the bonding
can be improved force
by two with the
methods. (i) matrix, is increased
first removing [5]; on
impurities (ii)the
thesurface
interfacial
of thebonding
carbon fiberstrength
with can
surface treatment
be improved be adding methods
tracesuch as vapor
amounts of phase
other oxidation,
materialsliquid
such phase
as SiCoxidation, anodic
[6] and TiO 2 oxidation,
[1] between the
and plasma treatment.
carbon fibers and the matrix. After that the number of functional groups (carboxyl, carbonyl, and hydroxyl)
enhancing the bonding
In this research, carbonforce with the matrix,composite
fiber-reinforced is increased [5]; (ii) the
materials interfacial
were bonding
produced strength canHNTs
by dispersing
be improved be adding trace amounts of other materials such as SiC [6] and TiO 2 [1] between the
and expected to enhance the interfacial bonding strength between the carbon fibers and the matrix,
carbon fibers and the matrix.
and epoxy resin using an ultrasonic homogenizer. In order to analyze the mechanical behavior in
In this research, carbon fiber-reinforced composite materials were produced by dispersing HNTs
the presence
and expected of added HNTs
to enhance theto carbon fibers
interfacial bonding and the matrix,
strength betweenfirstthe the mechanical
carbon fibers and behavior
the matrix,of the
HNT/matrix-based
and epoxy resin using an ultrasonic homogenizer. In order to analyze the mechanical behavioron
composites was observed by dispersing HNTs in the matrix. Based this, the
in the
mechanical
presenceproperties
of added were HNTsevaluated
to carboninfibers
accordance
and thewith the interfacial
matrix, bonding strength
first the mechanical behavioraccording
of the to
the addition of particlescomposites
HNT/matrix-based with varying was HNT content.
observed by dispersing HNTs in the matrix. Based on this,
the
Also,mechanical properties were
mode II interlaminar evaluated
fracture in accordance
toughness with theand
was measured interfacial
evaluatedbonding strength the
to investigate
according to the addition of particles with varying HNT content.
fracture phenomenon at the interface of carbon fiber reinforced composite with nanoparticles. In order
Also, the
to investigate mode II interlaminar
interfacial fracture toughness
reinforcement was measured
effect of HNTs, nanoparticlesand evaluated to investigate
were dispersed theepoxy
only in
fracture phenomenon at the interface of carbon fiber reinforced composite with nanoparticles.
resins, and mechanical properties were evaluated to compare the reinforcing effect in the resin and the
In order to investigate the interfacial reinforcement effect of HNTs, nanoparticles were dispersed only
theoretical and experimental properties of the layered composite material.
in epoxy resins, and mechanical properties were evaluated to compare the reinforcing effect in the
resin and the theoretical and experimental properties of the layered composite material.
2. Experimental
2. Experimental
2.1. HNT Particle Dispersion
2.1. HNT Particle
In order Dispersion
to prevent the agglomeration of the epoxy resin and the HNT (DOORICHEM,
Seoul, Korea)
In ordernanoparticles,
to prevent the the additives were
agglomeration of the dispersed
epoxy resin using
and theanHNT ultrasonic
(DOORICHEM, dispersion device.
Seoul,
The cavitation effect as shown
Korea) nanoparticles, in Figure
the additives were1dispersed
is generated
usingby high-intensity
an ultrasonic ultrasound.
dispersion device. TheWhen ultrasonic
cavitation
waveseffect
are as shown in Figure
introduced into the 1 issolution,
generatedaby wavehigh-intensity
forms andultrasound.
propagates When ultrasonic
through waves are
the liquid. At this
point, positive pressure is generated in the direction the wave is moving, instantlypositive
introduced into the solution, a wave forms and propagates through the liquid. At this point, leaving the
pressure
negative is generated
pressure behind.inThisthe difference
direction thein wave is moving,
pressure creates instantly
waves, and leaving the negative
as these pressure
get larger, millions of
behind. This difference in pressure creates waves, and as these get larger, millions of microcavities of
microcavities of microscopic vacuum bubbles are generated. The bubbles easily form in hollows or
microscopic vacuum bubbles are generated. The bubbles easily form in hollows or cavities and
cavities and implode violently due to the change in the pressure of the ultrasonic waves. At this point
implode violently due to the change in the pressure of the ultrasonic waves. At this point a strong
a strong
shock shock
wavewaveforms forms
causedcaused
by strongbyliquid
strong jetsliquid jets and
and swirls. Theswirls.
collapseThe
of thecollapse of the occurs
microcavities microcavities
in
occurs in microseconds (s), taking place many million times in a very small
microseconds ( s), taking place many million times in a very small area. Pressures of more than area. Pressures of more
than 10
10 GPa
GPaand andtemperatures
temperatures ofof 5000
5000 KK areare reached
reached [4,7].
[4,7]. TheThe force
force generated
generated at time
at this this time is powerful
is powerful
enough to corrode
enough to corrode thethe
propeller
propellerofofa aship
shipor or generate noise.ByByapplying
generate noise. applying thethe cavitation
cavitation effecteffect
to theto the
composite
composite material,
material, thethe penetrationofofthe
penetration thepolymer
polymer resin
resininto
intothe
thecarbon
carbon fiber waswas
fiber facilitated.
facilitated.

Figure 1. The ultrasonic dispersion of nanoparticles in the base material using the cavitation behavior.
Figure 1. The ultrasonic dispersion of nanoparticles in the base material using the cavitation behavior.
 Appl. Sci. 2017, 7, 441 3 of 8

Appl. 2.2.
Sci. Production
2017, 7, 441 of Test Specimens and Interfacial Properties Evaluation 3 of 8

In this study, HNTs were used as the additive for a carbon fiber-reinforced composite for
reinforcing
2.2. Production ofeffect. Two types and
Test Specimens of test specimen
Interfacial were produced
Properties with HNT/matrix and HNT/carbon
Evaluation
fiber/matrix material. SK-N300 fiber was used in this study as the carbon fiber and supplied by SK
In this study,
Chemicals, Korea;HNTs were
its basic usedproperties
physical as the additive
are listedfor a carbon
in Table 1a. fiber-reinforced composite for
reinforcing effect.
Among theTwo
widelytypes
usedofmatrix
test specimen were an
in the industry, produced with
epoxy resin HNT/matrix
with and HNT/carbon
superior physical properties
was selected as the matrix. To disperse the nanoparticles, KFR-120 epoxy resin
fiber/matrix material. SK-N300 fiber was used in this study as the carbon fiber and supplied with low viscosity
by SK
from Kukdo Chemical Co., Ltd. (Seoul, Korea) was used. KFH-160
Chemicals, Korea; its basic physical properties are listed in Table 1a. was used as a hardener at a 100:30
weight ratio. The basic physical properties of the epoxy and hardener are listed in Table 1b.
Table 1. Mechanical properties of main materials used in this study.
Table 1. Mechanical properties of main materials used in this study.

(a) Carbon Fiber Used as the Reinforcement

Properties
Tensile Strength Density Elastic Modulus Diameter
Value
Carbon fiber 4694 MPa 300 g/m2 26.2 GPa 1115 m
(b) Epoxy Resin Used as the Matrix
Equivalent Weight
Properties Density (g/mL) Viscosity (cps) Total Amine Value
(g/eq, EEW)
Value DIN EN ISO 1675 DIN EN ISO 2555 (mgK OH/g)
DIN EN ISO 3001
KFR-120 170180 1.01.2 10001500 -
KFH-160 - 0.81.0 550 400600

The tensile strength of HNT was measured at 0, 0.5, 1, 2, 3, 5, 8, and 10 wt % to take into account
Among the widely used matrix in the industry, an epoxy resin with superior physical properties
the cohesion of HNT and understand the range of cohesion of HNT in a matrix with viscosity and its
was phenomenon.
selected as the matrix. To disperse the nanoparticles, KFR-120 epoxy resin with low viscosity
The test specimens with HNT added to the carbon fiber composite material were
fromprepared
Kukdo Chemical Co.,nanoparticles
by dispersing Ltd. (Seoul, Korea) was resin
in an epoxy used.using
KFH-160 was used
an ultrasonic as a hardener
dispersing machineat aand
100:30
weight ratio. The basic physical properties of the epoxy and hardener are listed
then preparing prepregs directly. The prepared prepreg resin was subjected to vacuum bagging to in Table 1b.
The tensile
prepare strength
a test piece. of
ToHNT was the
evaluate measured
results,atthe
0, 0.5, 1, 2,test
tensile 3, 5,and
8, and 10 wt % to
interlaminar taketest
shear intowere
account
the cohesion
performedofaccording
HNT and to understand
ASTM D5766-2002 the range of cohesion
strandard of HNT
test method in a matrix
for open-hole withstrength
tensile viscosity ofand
polymer matrixThe
its phenomenon. composite laminateswith
test specimens and ASTM
HNT D2344
addedstandard test method
to the carbon fiber for short-beam
composite strength
material were
of polymer matrix composite materials and their laminates. The DCB test specimens
prepared by dispersing nanoparticles in an epoxy resin using an ultrasonic dispersing machine and were prepared
thenby laminating
preparing six sheets
prepregs of prepregs
directly. with nanoparticles
The prepared prepreg resinaddedwas andsubjected
adding a to Teflon
vacuumsheetbagging
to the to
middle of the prepregs to form a first crack. The DCB test specimens were tested according
prepare a test piece. To evaluate the results, the tensile test and interlaminar shear test were performed to ASTM
D 6671 standard test method for mixed mode I-mode II interlaminar fracture toughness of unidirectional
according to ASTM D5766-2002 strandard test method for open-hole tensile strength of polymer matrix
fiber reinforced polymer matrix composites. In all tests, 10 test specimens were produced and the
composite laminates and ASTM D2344 standard test method for short-beam strength of polymer
average of 8 test specimens excluding the maximum and minimum values was obtained.
matrix composite materials and their laminates. The DCB test specimens were prepared by laminating
six sheets of prepregs
3. Results with nanoparticles added and adding a Teflon sheet to the middle of the prepregs
and Discussion
to form a first crack. The DCB test specimens were tested according to ASTM D 6671 standard test
Tensile strength was investigated to evaluate the effect of HNTs on the tensile strength of carbon
method for mixed mode I-mode II interlaminar fracture toughness of unidirectional fiber reinforced
fiber-reinforced composite material. The respective mean value of the eight sets was calculated
polymer matrix composites. In all tests, 10 test specimens were produced and the average of 8 test
excluding the minimum and maximum values. These results are shown in Figure 2a. The tensile
specimens
strengthexcluding
of the testthe maximum
specimens and minimum
increased values
in accordance was
with theobtained.
added amount of HNT content up
until 1 wt %. However, the tensile strength tended to decrease after 1 wt % HNT content. In particular,
3. Results and Discussion
the specimen with an HNT content of >5 wt % had a smaller tensile strength than the specimens with
no addedstrength
Tensile HNT. Inwastheinvestigated
case where the content ofthe
to evaluate theeffect
HNTofincreased
HNTs onbeyond a certain
the tensile level,ofitcarbon
strength is
believed that by increasing the cohesion of the HNT, the tensile strength decreased
fiber-reinforced composite material. The respective mean value of the eight sets was calculated according to the
stress concentration
excluding the minimum in the
andagglomerated HNT. These results are shown in Figure 2a. The tensile
maximum values.
The interlaminar shear test was carried out to evaluate the interfacial properties of carbon
strength of the test specimens increased in accordance with the added amount of HNT content up
fiber/epoxy composite with added HNTs. The ILSS with varying amount of HNTs is shown in
until 1 wt %. However, the tensile strength tended to decrease after 1 wt % HNT content. In particular,
Figure 2b. The ILSS of carbon fiber-reinforced epoxy composite without any added HNT was ~26.29 MPa,
the specimen with an HNT content of >5 wt % had a smaller tensile strength than the specimens
which was even lower than the test specimen with 10 wt % HNT showing the smallest strengthening
witheffect
no added HNT.
with the In theofcase
addition HNTs.where the content
The ILSS improved of by
theadding
HNT increased beyond when
HNTs. In addition, a certain level, it is
the added
believed that by increasing the cohesion of the HNT, the tensile strength decreased according to the
stress concentration in the agglomerated HNT.
The interlaminar shear test was carried out to evaluate the interfacial properties of carbon
fiber/epoxy composite with added HNTs. The ILSS with varying amount of HNTs is shown in
Figure 2b. The ILSS of carbon fiber-reinforced epoxy composite without any added HNT was
~26.29 MPa, which was even lower than the test specimen with 10 wt % HNT showing the smallest
Appl. Sci. 2017, 7, 441 4 of 8

Appl. Sci. 2017,

strengthening 7, 441
effect with the addition of HNTs. The ILSS improved by adding HNTs. In addition, 4 of 8

when theSci.added
Appl.
HNT content was up to 3 wt %, the ILSS increased with added amount, and starting at
HNT2017, 7, 441was up to 3 wt %, the ILSS increased with added amount, and starting at 3 wt %,
content 4 of
as8the
3 wt %, as the content was increased, the ILSS decreased. When more than a certain amount of HNTs
content was increased, the ILSS decreased. When more than a certain amount of HNTs was added,
wasHNT
added,
contentthe effect
was up oftothe addition
3 wt wasincreased
%, the ILSS found towith
be small.
addedIn the case
amount, where
and a comparatively
starting at 3 wt %, as thehigh
the effect of the addition was found to be small. In the case where a comparatively high amount was
amount was
content wasadded to
increased,the epoxy
the ILSS resin, even
decreased. when
When dispersed,
more than a the HNTs
certain
added to the epoxy resin, even when dispersed, the HNTs clumped together and were clumped
amount of HNTstogether
was and were
added,
not uniformly
the effect
not uniformly of the
disperseddispersed addition was found to be small.
by visual observation.
by visual observation. In the
It was
It was surmised case where
thatsurmised a comparatively
that stress due
stress concentration high
concentrationamount
duewasto such
to such agglomeration
added
agglomeration to the epoxy
decreased
decreased the strength. resin, even
the when
strength. dispersed, the HNTs clumped together and were not uniformly
dispersed by visual observation. It was surmised that stress concentration due to such agglomeration
decreased the strength.

(a) Tensile test (b) Interlaminar shear test

Figure 2. Comparison of tensile strength (a) and interlaminar shear strength (b) of carbon
(a) Tensile teststrength (a) and interlaminar shear(b) Interlaminar shear test
Figure 2. Comparison of tensile strength (b) of carbon fiber-reinforced
fiber-reinforced composites according to HNT content.
composites according to HNT content.
Figure 2. Comparison of tensile strength (a) and interlaminar shear strength (b) of carbon
fiber-reinforced
The left sidecomposites
in Figureaccording
3 shows to HNT
the content.
SEM image of a test specimen with a fracture cut from the
The left
front side
side in the
after Figure 3 showsshear
interlaminar the SEM
test ofimage of afiber-reinforced
the carbon test specimen composite
with a fracture cut from
with added HNTs.the
A The
front sidetest left
after side inwith
the
specimen Figurean 3HNT
interlaminar shows
shear the SEM
test of
content 10image
of the %,of
carbon
wt a test specimen
fiber-reinforced
compared with a fracture
composite
to the test specimen cut3from
with
with wt %the
added HNTs.
HNT
front side after
content, had the
theinterlaminar
maximum shear test
shear of the carbonforming
strength fiber-reinforced composite with added HNTs.
A test specimen with an HNT content of 10 wtvalue,
%, comparedatosignificant interlaminar
the test specimen withshear
3 wtfracture,
% HNT
A test
and specimen
the damagedwith an
side HNT
of thecontent of
fractured 10 wt
surface %, compared
was seen to to
be the test
smooth. specimen with 3 wt % HNT
content, had the maximum shear strength value, forming a significant interlaminar shear fracture, and
content, had the maximum shear strength value, forming a significant interlaminar shear fracture,
the damaged side of side
and the damaged the fractured surface
of the fractured was seen
surface to betosmooth.
was seen be smooth.

(a) HNT = 3 wt %

(a) HNT = 3 wt %

(b) HNT = 10 wt %

Figure 3. Internal image of the damaged(b)zone

HNT(left) and
= 10 wt % a fracture (right) of HNT carbon fiber-
reinforced composites taken using SEM equipment.
Figure 3. Internal image of the damaged zone (left) and a fracture (right) of HNT carbon fiber-
Figure 3. Internal image of the damaged zone (left) and a fracture (right) of HNT carbon fiber-reinforced
reinforced composites taken using SEM equipment.
composites taken using SEM equipment.
Appl. Sci. 2017, 7, 441 5 of 8

Appl.
Appl. Sci.
Sci. 2017,
2017, 7,
7, 441
441 55 of
of 88
An image of the fractured surface, which was taken to evaluate the fractures shape is shown in
An
Ansideimage
image of
of the
the fractured
fractured surface,
surface, which
which was
was taken
taken to
to evaluate
evaluate the
the fractures
fractures shape
shapewas is
is shown
shown in
in
thethe rightright side ofofFigure
Figure 3.3.With
With anan HNT
HNT content
content of
of 3 wt
3 wt %, %, thepull-out
the pull-out phenomenon
phenomenon was relatively
relatively
the right side of Figure 3. With an HNT content of 3 wt %, the pull-out phenomenon was relatively
small
small in the entire fractured surface, and the epoxy resin was was alsoobserved
observed tobebeadhering adhering well to
small in in thethe entire
entire fractured
fractured surface,
surface, and and the the epoxy
epoxy resin
resin was also also observed to to be adhering well well to to
thethe surface of the carbon fiber. In addition, at an HNT content of 10 wt %, the pull-out phenomenon
the surface
surface of of the
the carbon
carbon fiber.fiber. InIn addition,
addition, at at an
an HNT
HNT content
content of of 10
10 wt
wt %,%, the
the pull-out
pull-out phenomenon
phenomenon
suchsuch asasthe white part ininthe SEM image of the test specimen
specimenappeared appearedininevery every aspect of the fiber,
such as the white part in the SEM image of the test specimen appeared in every aspect
the white part the SEM image of the test aspect of of the
the fiber,
fiber,
and and in particular, delamination appeared near or at the the fiber-resininterface.
interface. It isbelieved believed that the
and in in particular,
particular, delamination
delamination appeared appeared near near or at the fiber-resin
fiber-resin interface. ItIt is is believed that that thethe
reason
reason delamination
delamination appears
appears locally
locally is
is because
because ofof
thethe stress
stress concentration
concentration
reason delamination appears locally is because of the stress concentration from the agglomeration of from fromthe the agglomeration
agglomeration of
of the
the HNTs.
the HNTs.
HNTs. In In order
In orderto
order to prevent
to preventthe
prevent theagglomeration
the agglomerationof
agglomeration ofofthetheepoxy
the epoxyresin
epoxy resin
resin andand
and thethe
the HNTHNT
HNT nanoparticles,
nanoparticles,
nanoparticles,
itit was
it was was dispersed using an ultrasonic dispersion device. An ultrasonic dispersion device was
dispersed
dispersed using
using anan ultrasonic
ultrasonic dispersion
dispersion device.
device. An
An ultrasonic
ultrasonic dispersion
dispersion device
device waswas usedused
used to
to to
incorporate
incorporate the the cavitation
cavitation effect
effect into
into the
the
incorporate the cavitation effect into the composite material. composite
composite material.
material.
Figure
Figure
Figure 44 shows
4 shows
shows thethe graph
thegraph
graphof of mode
ofmode
modeII II shear
shear modulus
IIshear modulus with
modulus withvarying
with varyingHNT
varying HNTcontent
HNT content
content to evaluate
toto evaluate
evaluate mode
modemode
II
II interlaminar
II interlaminar
interlaminar fracture
fracture
fracture toughness
toughness
toughness of of
of carbon
carbon
carbon fiber
fiber reinforced
reinforced
fiber reinforced composite
composite
composite with
withwithHNT. HNT.
HNT.TheThe interfacial
interfacial
The interfacial bond
bond
energy energy increased up to 3 wt % of HNT, but decreased

bond energy increased up to 3 wt % of HNT, but decreased at 5 wt % HNT content. The binding of
increased up to 3 wt % of HNT, but decreased at 5 wt at% 5 wt
HNT % HNT
content. content.
The The
binding binding
energy
HNT energy
energy of
of HNT
increased HNT forincreased
3 wt % atfor
increased the33interface,
for wt
wt % % atat thebutinterface,
the at 5 wtbut
interface, %, at
but at 5
the 5 wt
wt %,
binding%, the binding
energy
the bindingof HNT energy
energy wasof HNT
HNT was
ofconcentratedwas
concentrated
dueconcentrated
to the concentration due to
due to the the
of HNT.concentration
concentration
To evaluate of HNT.
of theHNT. To evaluate
To evaluate
interfacial the interfacial
the interfacial
bond energy bond
of HNTreinforced energy
bond energy of
of
carbon
HNTreinforced
HNTreinforced carbon
carbon fiber
fiber reinforced
reinforced composites
composites and
and the
the strengthening
strengthening effect
effect of
of HNT
HNT addition,
addition,
fiber reinforced composites and the strengthening effect of HNT addition, HNT was added to the
HNT
HNT was
wasto added
added to
to the epoxy
thetheepoxy resin
resin to to evaluate
evaluate the strengthening effect of epoxy
epoxy resin by
by HNT. Figure 5
epoxy resin evaluate strengthening effect the strengthening
of epoxy resin byeffect
HNT.ofFigure 5resin
shows HNT. Figure
the result of 5the
shows
shows the result
the result of the tensile
of the tensile strength by adding HNT to the epoxy resin. The strength of the epoxy
tensile strength by adding HNTstrength
to the epoxy by addingresin.HNT to the epoxy
The strength of theresin.
epoxy Theresinstrength of theHNT
without epoxy was
resin
resin without
without HNT
HNT was
was 22
22 MPa,
MPa, and
and the
the addition
addition of
of HNT
HNT strengthened
strengthened the
the effect
effect by
by two
two to
to three
three
22 MPa, and the addition of HNT strengthened the effect by two to three times, confirming remarkable
times,
times, confirming
confirming remarkable
remarkable epoxy
epoxy resin strengthening effect by the
the addition of HNT, and
and the
epoxy
increase
resin strengthening effectby by theresin
addition strengthening
of HNT, effect
and the by
increase addition
in the of HNT,strength
tensile theby
increase in the tensile strength by addition increased the content of HNT to 5 wt %. In 5 wt % of
in the tensile strength addition increased the content of HNT to 5 wt %. In 5 wt % of test
test
addition
specimens, increased the content of HNT to 5 wt %. In 5with wt % of test specimens, the strengthening
specimens, the the strengthening
strengthening effect effect gradually
gradually decreased
decreased with addition. addition.
effect gradually decreased with addition.

Figure
Figure 4.4.
Figure Mode
ModeIIIIIIshear
4.Mode shear modulus
modulus of
shearmodulus of CFRP
of CFRP according
CFRP accordingto
according toHNT
to HNTaddition.
HNT addition.
addition.

Figure 5. Comparison
Figure of tensile strength of
of HNTadded
added epoxywith
with HNTcontent.
content.
Figure 5.
5. Comparison
Comparison of
of tensile
tensile strength
strength of HNT
HNT added epoxy
epoxy with HNT
HNT content.
Appl.Sci.
Appl. Sci.2017,
2017,7,7,441
441 66of
of88

In order to investigate the correlation between the strengthening effect of HNT in epoxy resin
and theorder
In to investigate
mechanical propertiesthe of
correlation
carbon fiber between the strengthening
reinforced effect by
composite material of HNT in epoxy
the addition of resin
HNT
and the mechanical properties of carbon fiber reinforced composite material by
by the improvement of interfacial bonding energy based on the results obtained above, the strength the addition of HNT
by the improvement
characteristic value ofofthe
interfacial bonding
epoxy resin energy
reinforced based
with HNT, on and
the results obtained
the strength above, the of
characteristics strength
carbon
characteristic value of the epoxy resin reinforced with HNT,
fiber were obtained by the theoretical strength of the composite material.and the strength characteristics of carbon
fiber were obtained by the
The displacement andtheoretical
the strainstrength of the composite
of the composite laminatematerial.
under load are different from those
of theThesingle
displacement and the strain
layer composites, of theof
because composite laminatebetween
the interaction under load the are different
layers. from
In the those of
composite
the single layer composites, because of the interaction between the layers. In the composite
laminate, the lamination angles are different for each layer, so the stiffness and strength are different laminate,
the
for lamination angles areforce.
the same external different
Thefor eachand
force layer, so the stiffness
moment appliedand strength
to the are different
laminate can be for the same
obtained by
external force. The force and moment applied to the laminate can be obtained
integrating different forces and moments for each layer depending on the laminate thickness. by integrating different
forces
Assumingand moments
the planarfor eachstate
stress layerofdepending on the
the laminates, thelaminate thickness.
forces and moments Assuming
appliedthe planar
to the stress
laminates
state
are asoffollows.
the laminates, the forces and moments applied to the laminates are as follows.

Nx
N Z Z
k
x
N( =
) = ( )y
y dz (1)
(1)


Nxy k=1
= 1
Z 1
k 1 xy

Mx x


N Z Zk
M(y ) =
= ( ) zdz (2)
Z1 (2)

y



Mxy
=1
k =1 k 1
xy
where N
where Nijij is
is the
the applied
applied force
force per
per unit
unit length
length of
of the
the laminate
laminate and
and M
Mijij is
is the
the applied
applied force
force per
per unit
unit
length of the laminate. Figure 6 is the moment applied per unit length of
length of the laminate. Figure 6 is the moment applied per unit length of the laminates. the laminates.

Figure6.6. Positive
Figure Positive resultant
resultantforces
forcesand
andmoment.
moment.

Here,the
Here, theaverage
averagestress
stressofofthe
thecomposite
composite material
material is given
is given by by
thethe following
following equation,
equation, andand t is
t is the
the total
total thickness
thickness ofcomposite
of the the composite laminate.
laminate.

=Nij (3)
ij = (3)
t
To compare
To compare the strength
the strength of the theoretically
of the theoretically strengthenedstrengthened
composite composite
with the with
actualthe actual strength,
strength, the fiber
the fiber volume fraction was calculated to investigate the strength
volume fraction was calculated to investigate the strength of the theoretical composite material.of the theoretical composite
The
material. The fiber contents of composite specimens were tested in accordance
fiber contents of composite specimens were tested in accordance with ASTM D 3171, and determined with ASTM D 3171,
and determined
using the following using the following formula.
formula.
m33m11
M iber =
f =100100m m (4)
(4)
22 11
where m
where m11,, mm22,, m are the
m33 are the initial
initial mass (g) of
mass (g) of the
the dried
dried container only, the
container only, the mass
mass of
of the
the container
container (g)
(g)
containing the dried test specimen, and the mass of fiber (g), respectively.
containing the dried test specimen, and the mass of fiber (g), respectively. The volume content The volume content of
of the
the fibers
fibers measured
measured by by each
each method
method was~62%,
was ~62%,and andthetheweight
weightofofthe theadded
added HNT
HNT waswas calculated
calculated byby
assuming that the HNT was dispersed in the
assuming that the HNT was dispersed in the epoxy resin. epoxy resin.
Figure
Figure 77shows shows thethegraph
graphcomparing
comparing the the theoretical
theoretical strength
strength obtained
obtained byby calculation
calculation with
with the
the
carbon
carbon fiber reinforced composite material and interlaminar fracture toughness energy added with
fiber reinforced composite material and interlaminar fracture toughness energy added with
HNT.
HNT.The Thetheoretically
theoreticallycalculated
calculatedvalues
valueswere
were~20 ~20 MPa
MPa higher
higher than
than the
the test specimens without
test specimens without HNT.
HNT.
The difference in the strengthening effect due to the additive content was insufficient in the
Appl. Sci. 2017, 7, 441 7 of 8

The Appl.
Appl.
Sci. 2017, 7, 441
difference
Sci. 2017,in the strengthening effect due to the additive content was insufficient in the theoretical
7, 441
7 of 8
7 of 8
calculation. Theoretically, the calculation of the strength of a composite material does not seem to have
theoretical calculation. Theoretically, the calculation of the strength of a composite material does not
theoretical
any seem
effecttoonhave calculation.
the Theoretically,
theoretically calculated the calculation
value because of it
theisstrength
dominatedof a composite material
is adoes not
any effect on the theoretically calculated value because it isby fiber, which
dominated by fiber,reinforcing
which
seem to
material, havethan
rather any effect on the
a known theoretically
resin. However, calculated value becauseofit HNT
is dominated by fiber, which
is a reinforcing material, rather than a known the measured
resin. However,valuethe measured wasvaluetheof highest
HNT was at the
5 wt %
HNT,is abecause
reinforcing the material,
binding rather
force than
at thea known resin.
interface However,
increased theincreasing
with measured value
amount of HNT
of was the
added HNT.
highest at 5 wt % HNT, because the binding force at the interface increased with increasing amount
highest
Moreover, at 5 wt
it isHNT. % HNT,
considered because
that the the binding force at the interface increased with increasing amount
of added Moreover, it isaddition of HNT
considered which
that the is not calculated
addition of HNT whichtheoretically is due to the
is not calculated
of added HNT. Moreover, it is considered that the addition of HNT which is not calculated
interfacial adhesion
theoretically is duestrengthening effect.
to the interfacial adhesion strengthening effect.
theoretically is due to the interfacial adhesion strengthening effect.

Figure
7. A7. A graph
of of the relationshipbetween
between the theoretical
theoreticaltensile
tensilestrength, thethe
experimental tensile
Figure
Figure 7.graph
A graph the
of relationship
the relationship between the
the theoretical tensile strength,
strength, experimental
the experimental tensile
tensile
strength, and the interlaminar fracture toughness of CFRP according to the HNT content.
strength, and the interlaminar fracture toughness of CFRP according to the HNT
strength, and the interlaminar fracture toughness of CFRP according to the HNT content. content.

The cohesion of the HNT in the carbon fiber reinforced composite material was investigated by
TheThe
SEM.
cohesion
cohesion of of
thethe
Figure 8 shows
HNT
HNT
the ininthe
thecarbon
photograph
carbon fiber
fiber reinforced
of specimens
reinforced composite
taken at 5composite
material was
wt % HNTmaterial was
having the
investigated by
investigated
highest tensile by
SEM.SEM. Figure
Figure 8 8 shows
shows the the photographofofspecimens
photograph specimens taken
taken at
at55wt
wt %%HNT
HNT having thethe
having highest tensile
highest tensile
strength value, and at 8 wt %, the tensile strength decreases with increasing content. The photograph
strength value,
strength and
at88atwt
8 wt %, thetensile
tensile strength decreases
decreases with increasing content. The photograph
of thevalue,
sampleand
with wt %%, the
HNT shows astrength
considerable amount with increasing
of agglomerated content.
HNTs. The photograph
of the sample with 8 wt % HNT shows a considerable amount of agglomerated HNTs.
of the sample with 8 wt % HNT shows a considerable amount of agglomerated HNTs.

(a) HNT = 5 wt % (b) HNT = 8 wt %

(a) HNT = 5 wt % (b) HNT = 8 wt %
Figure 8. Scanning electron micrographs of EP/CF/HNT composites.
Figure 8. Scanning electron micrographs of EP/CF/HNT composites.
Figure 8. Scanning electron micrographs of EP/CF/HNT composites.
4. Conclusions
4. Conclusions
4. Conclusions
In this study, the interfacial bonding strength between carbon fibers and epoxy resins of the
In this study, the interfacial bonding strength between carbon fibers and epoxy resins of the
composite test specimens
In this study, with bonding
the interfacial added HNTs was between
strength measured. The added
fibersHNT
and was expected to the
composite test specimens with added HNTs was measured.carbon
The added HNT epoxy resins of
was expected to
enhance
composite the interfacial bonding strength between carbon fibers and epoxy resins. The conclusions of
enhancetest
thespecimens with added
interfacial bonding HNTs
strength was measured.
between Theand
carbon fibers added HNT
epoxy wasThe
resins. expected to enhance
conclusions of
this study are as follows.
the interfacial bonding
this study are strength between carbon fibers and epoxy resins. The conclusions of this study
as follows.
are as follows.
Appl. Sci. 2017, 7, 441 8 of 8

(1) The addition of HNT reinforced the tensile strength of the composite material, and the tensile
strength had a greater effect on the bonding force between the fiber and the resin than the effect
on the resin.
(2) Where the added amount of HNTs was up to 3 wt %, the tensile strength of the carbon
fiber-reinforced composite material increased, but for higher content than that, strength decreased.
In the case of the addition of higher content, this is considered to be due to the cohesive strength
of HNTs decreasing the stress concentration.
(3) The addition of HNTs showed a steady increase in the strength until the addition of 3 wt % of
nanoparticles, but after that the ILSS decreased with increasing HNT content. This is probably
because of the inherent nature of HNTs, where an increase in content leads to agglomeration of
the HNTs, decreasing the strength values due to local stress concentration.
(4) The size of GIIC due to the addition of HNT increased up to 3 wt %, but decreased thereafter.
With increasing HNT content, the aggregated part due to the dispersion of HNT is locally acting
as a stress concentration, decreasing the fracture energy.
(5) According to the GIIC size based on the interlaminar fracture toughness evaluation of HNT, the
nanoparticles with very low cohesive strength are thought to have the highest interlayer energy at
~3 wt %, and the content of nanoparticles depends on the cohesive force. The strengthening effect
was insignificant according to the addition amount because of the reduction in the fracture energy.

Acknowledgments: This research was supported by the Ministry of Trade, Industry & Energy (MOTIE), Korea
Institute for Advancement of Technology (KIAT) through the IDEA FACTORY Research Grant of N0001410.
Author Contributions: Jin-Woo Lee and Yun-Hae Kim conceived and designed the experiments; Jin-Woo Lee
and Soo-Jeong Park performed the experiments; Jin-Woo Lee analyzed the data; Yun-Hae Kim contributed
reagents/materials/analysis tools; Jin-Woo Lee, Yun-Hae Kim and Soo-Jeong Park wrote the paper.
Conflicts of Interest: The authors declare no conflict of interest.

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