Composite Structures 94 (2012) 2397–2406

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Composite Structures
journal homepage: www.elsevier.com/locate/compstruct

Improvements in mechanical and thermo-mechanical properties

of e-glass/epoxy composites using amino functionalized MWCNTs
M.M. Rahman a, S. Zainuddin b,⇑, M.V. Hosur b, J.E. Malone a, M.B.A. Salam a, Ashok Kumar c, S. Jeelani b
a
Department of Mechanical Engineering, Tuskegee University, Tuskegee, AL 36088, United States
b
Department of Material Science and Engineering, Tuskegee University, Tuskegee, AL 36088, United States
c
Construction Engineering Research Laboratory, US Army Engineer Research and Development Center, Champaign, IL 61821-9005, United States

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

Article history: The prime objective of this work is to optimize the mechanical and thermo-mechanical properties of
Available online 28 March 2012 e-glass/epoxy composites by utilizing amino-functionalized multi-walled carbon nanotubes
(MWCNTs–NH2) through a combination of dispersion method. At first, 0.1–0.4 wt.% of MWCNT–NH2
Keywords: was integrated into SC-15 epoxy suspension using a combination of ultra-sonication and calendaring
Functionalized MWCNTs techniques. E-glass/epoxy nanocomposites were than fabricated at elevated temperature with the mod-
Sonication ified resin using hand layup and compression hot press. 3-Point flexural and dynamic mechanical anal-
Calendaring
ysis (DMA) results demonstrated a linearly increasing trend in properties from 0 to 0.3 wt.% loading.
Mechanical and thermo-mechanical
properties
Micrographs of MWCNTs incorporated epoxy and e-glass/epoxy samples revealed uniform dispersion
of MWCNTs in epoxy, good interfacial adhesion between CNTs and polymer, and improved interfacial
bonding between fiber/matrix at 0.3 wt.% loading. An improved dispersion and hence an improved cross-
link interaction between MWCNT–NH2 and epoxy lead to the stronger shift of the mechanical and
thermo-mechanical properties of the composites.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction whereas it can reach 30% of the total volume in nanocomposites.

The high specific surface area of CNTs provide desirable interface
Glass fiber reinforced polymer (GFRP) composites are increas- for stress transfer but can introduce strong attractive forces in be-
ingly used in many structural applications replacing metallic mate- tween CNTs causing excessive agglomeration and produce un-
rials due to their low cost, high strength, high chemical resistance wanted stress concentrations which may act as a precursors for
and excellent insulating properties. In most of these GFRP applica- failure. However, multi-walled carbon nanotubes (MWCNTs) have
tions, fiber plays a major role in tensile load carrying capacity of a an approximate specific surface area of 200 m2/g or less which is
composite structure while compressive, bending, inter-laminar lower than SWNTs due to their much larger diameter and multiple
shear properties depend on the selection of matrix [1]. In a fiber/ graphene walls and thus exhibit better dispersibility.
matrix composite, matrix being the weakest component is first to One of the most important parameter in fabricating CNTs
fail upon such loading. Therefore, enhancement of matrix proper- reinforced composites is the dispersion of CNTs itself because of
ties is desired to enhance the overall performance of fiber rein- their strong tendency to re-agglomerate. Kim et al. have reported
forced polymer (FRP) composites under such loading. that degree of CNTs dispersion into epoxy strongly affected the
In past two decades, researchers have successfully tailored the matrix-dominated mechanical properties [7]. Various methods to
matrix properties by incorporating inorganic nanoparticles into disperse nanotubes in polymer resins, such as stirring, sonication
epoxy polymer and its fiber-reinforced composites [2–5]. Among and high shear mixing have been reported in literatures [8–10].
the nanoparticles, carbon nanotubes (CNTs) have emerged as po- Some researchers found that chemical functionalization of the
tential candidates for modification of matrix because of its excep- CNT surface improved interfacial interaction between CNTs and
tional strength and stiffness, high flexibility, diameter dependent matrix, and the dispersion of CNTs into the matrix [11–13].
specific surface area and high aspect ratio. According to Reynaud Previously, it has been shown that amino functionalization in CNTs
et al. [6], an interface of 1 nm thick represents roughly 0.3% of enhances the dispersibility in the epoxy matrix [14] and multi-
the total volume of the polymers in microparticle filled composites, walled carbon nanotubes (MWCNTs) exhibits better dispersion in
polymer than the single walled or double walled CNTs [1].
⇑ Corresponding author. Tel.: +1 334 724 4222; fax: +1 334 724 4224. In addition, interfacial adhesion between the CNTs and polymer
E-mail address: [email protected] (S. Zainuddin). is also a critical issue. In order to have sufficient stress transfer

0263-8223/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.compstruct.2012.03.014
2398 M.M. Rahman et al. / Composite Structures 94 (2012) 2397–2406

from the matrix to the CNTs and to efficiently use the potential of
CNTs as structural reinforcement, a strong interfacial adhesion be-
tween the CNTs and polymer is desired. The interfacial adhesion
between CNTs and matrix was reported to improve by functionali-
zing the CNTs. Tailored amino, carboxyl or glycidyl groups enable
covalent bonding between CNTs and epoxy resulting in improved
interfacial bonding. The positive effects of functionalized CNTs on
the mechanical properties are reported by various researchers
[9,15,16]. Kim et al. compared the effect of silane and acid treated
CNTs in carbon/epoxy composites and found 15% and 10%
enhancement in flexural strength and modulus [17]. Moniruzz-
aman et al. found an improvement of 10–15% in flexural properties
with 0.05 wt.% single-walled nanotubes (SWNTs) [18].
While numerous studies are conducted in the last two decades
on the CNT reinforced composites, effective dispersion of CNTs in
polymer is still a challenge and the experimental mechanical prop-
erties are still far below than the theoretical value. In addition,
studies on glass fiber reinforced polymer composites incorporated
with amino functionalized MWCNTs using a combination of soni-
cation and calendaring techniques is not yet been reported to the
best of our knowledge.
In this work, MWCNT–NH2 reinforced e-glass/epoxy nanocom-
posites were processed by combining sonication and calendaring
dispersion techniques, utilizing functionalized MWCNTs, combin-
ing fabrication processes and curing the composites at higher tem-
perature. Rheological, 3-point bend and dynamic mechanical
analysis tests were performed to investigate the effect of function-
alized MWCNTs on resin viscosity, flexural and thermo-mechanical
properties of e-glass/epoxy composites. Effect of combined sonica-
tion and calendaring techniques on MWCNTs dispersion in epoxy
suspension were investigated using transmission electron micro-
scope (TEM). In addition, effect of interaction of MWCNTs with
epoxide groups and fiber/matrix bonding were investigated using
scanning electron microscope (SEM). All results were compared
Fig. 1. SEM pictures of as-received MWCNTs at magnification of 500 (A) and
with the control (reference) epoxy composites results containing
10000 (B).
no MWCNTs.

2. Experimental pressure and temperature in the system, so the mixture was cooled
down to room temperature in a refrigerator cooler maintained at
2.1. Materials 5 °C. To further improve the dispersion of MWCNTs, the sonicated
mixture was then passed through three rollers as shown in Fig. 2.
SC-15 epoxy resin used in this study was supplied by Applied In this three roll process, roller 1 and 3 rotates in the same direc-
Poleramic Inc. It is a two part cyclo-aliphatic amine type epoxy re- tion whereas the roller 2 placed in between rotates in the opposite
sin (Part A: diglycidylether of bisphenol A, aliphatic diglycidyl and direction thereby inducing high shearing in the mixture. A varying
Part B: hardener). Multi-walled carbon nanotubes functionalized gap setting between the rolls and multiple passes of 20 lm (1st
using amino groups (–NH2) was purchased from Nanocyl Inc. These pass), 10 lm (2nd pass) and 5 lm (3rd pass) was used to induce
nanotubes were of diameter 10 nm, average length of several mi- high shear force in the mixture. The induction of high shear forces
crons and carbon purity >95%. Fig. 1 shows the scanning electron further de-agglomerates and improves the dispersion of CNTs in
micrographs of as received carbon nanotubes at different magnifi- resin. Roller speed of the three rolls was maintained at a ratio of
cations. High specific surface area and cotton-like entanglements 1:3:9 with a maximum speed of 200 rpm was maintained in all
caused the formation of agglomerates as reported by Reynaud the three passes.
et al. [6]. As reinforcement in composites, e-glass woven fabric
with a density of 2.58 g/cm3 and a single fiber diameter of 14– 2.2.2. Mixing of Part A and Part B
16 lm was procured from Fiber Glast Development Corporation. The hardener, Part B was added as per stoichometric ratio (Part
E-glass fibers were sized with 0.5 wt.% epoxy silanes to increase A: Part B = 10:3) to the modified mixture and mixed with a high
the compatibility and to have better adhesion between fibers and speed mechanical stirrer for 10 min at 800 rpm. The mixture was
epoxy matrix. then placed in a desiccator for 30 min to remove the volatile impu-
rities and entrapped air bubbles that were generated due to in-
2.2. Manufacturing process tense mechanical mixing.

2.2.1. Dispersion of MWCNT–NH2 into epoxy resin 2.2.3. Manufacturing of fiber reinforced nanocomposites
At first, MWCNT–NH2 was mixed manually with epoxy resin E-glass/epoxy nanocomposites were fabricated by using a com-
Part-A as per calculated weight ratio. The mixture was then soni- bination of hand lay-up and compression hot press techniques. E-
cated at room temperature for 1 h at 35% amplitude and 40 s on/ glass woven fabric layers were properly stacked into seven plies
20 s off cycle pulse mode. Sonication process induces elevated and the orientation of fiber within the fabric was kept constant.
 M.M. Rahman et al. / Composite Structures 94 (2012) 2397–2406 2399

Sonicator probe

Cooling bath
Mixtures
Collection

3-roll shear mixing process

for further MWCNT

Dispersion of MWCNTs
in epoxy Part A using

Mechanical mixing of
modified mixtures and epoxy

Thickness
250 mm 3.25 mm

250

Consolidation of laminates Final e-glass/epoxy

in hot press laminates

Fig. 2. Schematic of MWCNTs dispersion and e-glass/epoxy composite fabrication.

Epoxy resin modified with MWCNTs was spread uniformly on each of 30 mm  30 mm  2 mm were cut from the panels and weighed
fabric layer and the laminate was consolidated by applying 133 kN precisely. The samples were then submerged into a bath of 80%
force in a hot press. The temperature of hot press was maintained concentrated nitric acid for about 5 h maintained at 75 °C. After
at 60 °C for 4 h for curing. Elevated temperature was selected to re- 5 h, once the matrix was digested completely, the fibers were taken
duce the curing period and thus production time as per recommen- out and washed several times by using acetone and distilled water.
dation of resin manufacturer. After completion of curing, the The fibers were then dried at 100 °C and weighed. The correspond-
temperature of the press was gradually reduced at a rate of 2 °C/ ing fiber volume, matrix volume and void volume fractions were
min to avoid any unwanted shrinkage in the laminate. Finally, calculated using the equations:
the cured panel was taken out and post cured in an oven for 5 h
W=F
at 100 °C. The final thickness of the panel was measured to be Fiber volume fraction; mf ¼  100 ð1Þ
w=C
3.25 mm. Fig. 2 shows the schematic of matrix modification and
e-glass/epoxy composite fabrication.
ðw  WÞ=M
Matrix volume fraction;mm ¼  100 ð2Þ
V
2.3. Material characterization
Void volume fraction; mv ¼ 100  ðmm þ mf Þ ð3Þ
2.3.1. Rheological properties
Rheology measurements were performed to observe the effect where W is the weight of fiber in the composite, w is the weight of
of increasing weight percent loading of MWCNTs on viscosity the initial composite specimen, F is the fiber density, M is the matrix
and the changes in viscosity as a measure of shear rate at constant density, V is the volume of composite and C is the composite
temperature. Measurements were performed with AR 2000 Rhe- density.
ometer in ETC control mode using parallel plate geometry at
1000 lm gap settings. Flow sweep was used to vary the shear rate 2.3.3. Mechanical and thermo-mechanical characterization
from 0.1 rad/s to 100 rad/s by keeping the temperature constant. Three point bend flexure test was conducted according to ASTM
D790-02 [20]. Samples were precisely cut to 52 mm  3.25 mm 
2.3.2. Calculation of fiber volume fraction and void content 12.25 mm dimensions to maintain span-length ratio of 16:1 and a
Matrix digestion test was conducted according to ASTM D 3171- minimum of seven specimens were tested. The test was performed
99(2004) to determine the fiber volume fraction and void content using a Zwick–Roell Z 2.5 testing machine in displacement control
of the fabricated composite panels [19]. Samples with a dimension mode with a crosshead speed of 1.2 mm/min. Load–deflection data
2400 M.M. Rahman et al. / Composite Structures 94 (2012) 2397–2406

for each sample was collected. Flexural modulus was calculated 100
from the slope of the tangent to initial straight line portion of
Control (Reference)
stress–strain plot. It was determined by the following equation: 0.1 wt. %
0.2 wt. %
Slope of tangent  ðspan lengthÞ2 0.3 wt. %
Flexure modulus ¼ ð4Þ 0.4 wt. %
4  width  ðthicknessÞ2

Viscosity (Pa. s)
10

The maximum stress at failure on the tension side of a flexural

specimen was considered as the flexural strength of the material.
Thus, using the homogeneous beam theory, the flexural strength
in a 3-point flexural test was determined using Eq. (5).
1
3  peak load  span length
Flexure strength ¼ ð5Þ
2  width  ðthicknessÞ2

Similarly, flexure strain to failure was calculated from the fol-

lowing equation:
1 10 100
6  maximum deflection at center  thickness Shear rate (1/s)
Flexure strain ¼
ðspan lengthÞ2 Fig. 3. Viscosity vs. shear rate response of control and NH2–MWCNTs incorporated
ð6Þ epoxy resin.

Dynamic mechanical thermal analysis (DMTA) was performed

according to ASTM D4065-01 [21] to study the viscoelastic behav- 3.2. Fiber volume fraction
ior of composite samples. It is also an effective way to investigate
the dispersion state of MWCNTs. In this test, the width of the sam- Fiber volume fraction and void content in control and 0.1–
ples was 12 mm and span length to thickness ratio was 10. Tests 0.4 wt.% MWCNTs e-glass/epoxy composites calculated by matrix
were conducted in dual cantilever beam mode with a frequency digestion test is summarized in Table 1. The average fiber volume
of 1 Hz and amplitude of 15 lm. The temperature was ramped fraction of the laminates was 58–60% with void content of 4–6%,
from 30 to 200 °C at a rate of 5 °C/min. A minimum of five speci- respectively. It can be seen that with increase of MWCNTs wt.%
mens of each type were tested. Storage modulus, loss modulus loading, the percentage of void content was also increased and
and glass transition temperature of samples were determined from can be attributed majorly due to increase of resin viscosity. With
the tests to evaluate the viscoelastic and damping properties of increasing CNTs wt.% loading, the resin viscosity increased in com-
control and MWCNTs incorporated e-glass/epoxy composites, parison to control resin shown in Fig. 3. The increase in resin vis-
respectively. cosity may hinder the removal of entrapped bubbles and volatile
impurities from the systems during processing.
2.3.4. Micrographic analysis
Dispersion state of MWCNTs in epoxy resin was investigated by 3.3. Flexural properties
transmission electron microscopy (TEM) using a Zeiss EM10 Trans-
mission Electron Microscope operated at 60 kV. The analysis of Typical stress–strain behavior obtained from the 3-point bend
fracture surfaces was carried out using a JEOL JSM-6400 scanning tests is shown in Fig. 4. Summary of the flexural test results and
electron microscope (SEM) at 5 kV accelerating voltage. Specimen the variation in properties as a function of MWCNTs content are
surfaces were coated with a thin gold film to increase their conduc- shown in Figs. 5a and b, respectively.
tance for SEM observation. The positive effect of MWCNT incorporation is clearly evident
from Figs. 5a and b. Flexural strength and modulus were improved
3. Results and discussion linearly with a maximum enhancement of 38% and 22% in 0.3 wt.%
samples in comparison to control (reference) samples as shown in
3.1. Rheological properties Fig. 5c. Likewise, flexural strain to failure was also found maximum
at 0.3 wt.% loading i.e. 27% higher in comparison to control sam-
Viscosity calculations were performed immediately after the ples. However a decrease in these properties was found at
degasification of mixture (Part A & B + MWCNTs). Fig. 3 shows vis- 0.4 wt.% MWCNTs loading.
cosity as a function of shear rate for control and 0.1–0.3 wt.% Fig. 6a and b shows the transmission electron micrographs
MWCNTs–NH2 loaded epoxy resin. Shear viscosity of a polymer (TEM) of 0.3–0.4 wt.% MWCNTs reinforced epoxy samples. An im-
is principally divided into Newtonian and shear thinning regions, proved dispersion of MWCNTs in matrix evident from Fig. 6a pro-
respectively. With increasing shear rate, a shear thinning behavior vides more sites facilitating higher chances for polymer and
was observed and a declining trend in shear viscosity was noticed. MWCNTs interaction. In addition, the amino functional groups
However, at high shear rate, a Newtonian behavior was observed in present on the outer ring of MWCNTs and epoxide group of epoxy
all the samples independent of shear rate. Viscosity of 0.1 wt.% resin causes the interfacial reaction resulting in strong covalent
MWCNTs reinforced epoxy sample remains at comparable range bond evident from scanning electron micrograph (SEM) shown in
with control resin. However, an increasing trend in viscosity was Fig. 7. Generally after mixing epoxy Part A and MWCNT–NH2, the
observed with increasing weight percent of MWCNTs content. Vis- interfacial reaction takes place between amine functional groups
cosity of 0.4 wt.% resin samples was found to increase more than of CNTs and epoxide groups of DGEBA resin which is consisted of
100% in comparison to control resin samples. This implies that ring opening reactions followed by a cross-linking reaction as
strong particle–particle interaction of CNTs is one major factor that shown in Fig. 8 [14]. This crosslink reaction creates interlocking
leads to an increase in shear viscosity with increasing CNTs content structure in the resin blend through the covalent bond which facil-
that may result in poor dispersion. itates impediment of the mobility of polymer chains in the system.
 M.M. Rahman et al. / Composite Structures 94 (2012) 2397–2406 2401

Table 1
Matrix digestion test results of control and NH2–MWCNT incorporated e-glass/epoxy composites.

MWCNT weight percent content (wt.%) Control 0.1 0.2 0.3 0.4
Results of matrix digestion test
Fiber volume fraction (mf ) 59.54 ± 1.3 58.09 ± 1.6 58.35 ± 1.3 58.58 ± 2.7 58.19 ± 2.2
Void fraction (md ) 3.94 4.13 4.67 5.48 6.81

Increase w.r.t control or reference (%)

600 40
Control
0.1 wt.%
0.1 wt.%
0.2 wt.%
0.2 wt.% 35
500
Flexural stress (MPa)

0.3 wt.% 0.3 wt.%

0.4 wt.% 0.4 wt.%
30
400
25

300 20

15
200
10
100 5

0 0
Flexural strength Flexural modulus Flexural strain to failure
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Flexural strain (%) Fig. 5c. Improvement of flexural properties of e-glass/epoxy composites using
NH2–MWCNTs.
Fig. 4. Flexural stress–strain response of control and NH2–MWCNTs incorporated
e-glass/epoxy composites.

600 32

550 Strength
30
500
Flexural Strength (MPa)

Flexural Modulus (GPa)

450
28
Modulus
400

26
350

300
24
250

200 22
0.0 0.1 0.2 0.3 0.4
Weight Percentages (%)

Fig. 5a. Effect of NH2–MWCNTs content on flexural strength and modulus of e-

glass/epoxy composites.

2.6
Flexure strain (%)

2.4

2.2

2.0
Fig. 6. TEM micrographs of (a) 0.3 wt.% and (b) 0.4 wt.% loading of NH2–MWCNTs in
epoxy resin.

1.8
0.0 0.1 0.2 0.3 0.4
The noticeable increase in flexural strength and modulus from 0 to
CNT content (wt.%) 0.3 wt.% loading thus can be attributed to the better dispersion of
Fig. 5b. Effect of NH2–MWCNTs content on flexural strain of e-glass/epoxy
MWCNTs and better interfacial interaction between the amino
composites. functionalized MWCNTs and epoxy matrix. This improved
2402 M.M. Rahman et al. / Composite Structures 94 (2012) 2397–2406

form in the resin blends. Dı´ez-Pascual et al. reported that shear

slippage of individual nanotubes within these bundles may occur
[23]. Due to this factor, a reduction in load transfer capability be-
tween CNTs and matrix systems may be occurred and hence the
properties may have decreased at 0.4 wt.% loading. So the flexural
properties were improved in small loadings as long as it is dis-
persed in the matrix properly and as well in case of higher loading
systems, uniform dispersion of CNTs into the matrix is very diffi-
cult. Moreover incorporation of higher weight percent loading in-
creased the viscosity of matrix which may have impeded the
dispersion [3]. Song et al. also performed rheological study and sta-
ted that poorly dispersed CNTs within epoxy have a higher viscos-
ity than that of uniformly dispersed suspensions [24]. In addition,
high viscosity of the resin resulting from poor dispersion may
cause poor wetting of the glass fiber during laminate fabrication
and hence poor adhesion between glass fiber and matrix [25]. This
Fig. 7. SEM micrograph showing the interfacial adhesion between MWCNTs and
epoxy resin. may be another factor of getting a decrease in strength, strain and
modulus s at 0.4 wt.% loading of MWCNTs.
A gradual increase in strain to failure was also observed in e-
interfacial interaction may have facilitated in stress transfer during glass/epoxy composites from 0 to 0.3 wt.% loading. It was reported
loading and thus resulting increase in flexural properties. Similar that polymer matrix added with amino-functionalized MWCNTs
reasons for improvement in epoxy/matrix incorporated with can increase the fracture energy as crack propagation can be re-
MWCNTs were also reported previously [22,23]. sisted by bringing up the crack faces of nanotubes [22]. Zhou
However, a decrease in flexural properties at 0.4 wt.% loading et al. reported that the crack propagation changes direction as it
can be attributed to strong attractive forces between MWCNTs crosses CNTs during failure process due to bridge effect which pre-
leading to excessive agglomeration. Due to poor dispersion evident vents crack opening [5]. As a result, crack initiation and propaga-
from Fig. 6b, MWCNTs remains in small bundles or agglomerates tion becomes difficult in the laminates reinforced by CNTs than

(a) Reaction of epoxide group (DGEBA) with primary amine of functionalized MWCNT
H O
MWCNT N C CH
H H2
MWCNT N + H 2C C
OH
H
H
Epoxy molecule # 1

(b) Reaction of epoxide group (DGEBA) with primary amine of functionalized MWCNT
OH

O H2C C
MWCNT N C CH
H H2 H
+ MWCNT N
H2C C H
OH
H H2C C

Epoxy molecule # 2
OH

(c) Cross-linking reaction between epoxy and MWCNT OH

OH O C CH
H2
O
H2C C H2C C
H H
MWCNT N + H 2C C MWCNT N
H H H
H2C C H2C C
H
OH Epoxy molecule # 3 & 4 O C C
H2
OH

Fig. 8. Schematic representation of interfacial reaction between DGEBA (Part A) and MWCNT–NH2.
 M.M. Rahman et al. / Composite Structures 94 (2012) 2397–2406 2403

Table 2
Flexural strain energy of NH2–MWCNT incorporated e-glass/epoxy composites.

Specimen
Control 0.1 (wt.%) 0.2 (wt.%) 0.3 (wt.%) 0.4 (wt.%)
Flexural strain energy (J) 1.03 1.49 1.65 1.97 1.40
% gain/loss – +44.66 +60.19 +91.26 +35.92

that of without reinforced CNTs. It may be one of the reasons due

1400
to which the flexural strain to failure in the composites was in-
creased. Carbon nanotubes have a high aspect ratio and shows 1200 Control
0.1% CNT
highly flexible elastic behavior during loading [26]. Because of

Loss Modulus, Mpa

0.2% CNT
the strong interfacial bonding with this reinforcement, the nan- 1000 0.3% CNT
0.4% CNT
ophased resin systems exhibited higher absorption of energy evi- 800
dent from Table 2. Average flexural strain energy calculated from
the area of load–deflection curves showed an increase in strain en- 600
ergy with increase in MWCNTs from 0 to 0.3 wt.% loading. The in-
400
crease in strain energy thus can be attributed to increase in strain
to failure in MWCNTs incorporated e-glass/epoxy composites. 200

3.4. Viscoelastic/thermo-mechanical properties 0

20 40 60 80 100 120 140 160 180 200
Temperature,°C
Dynamic mechanical thermal analysis (DMTA) was performed
to observe e-glass/epoxy samples stiffness behavior as a function Fig. 10. Loss modulus vs. temperature response of e-glass/epoxy composites.
of temperature and analyze the effect of NH2–MWCNTs on ther-
mo-mechanical performance. Figs. 9–11 show the variation in dy-
namic measurements of storage modulus, loss modulus and loss
tangent as a function of temperature obtained from DMTA. A stron- 0.20 Control
ger influence of amino-functionalized CNTs was observed in the 0.1% CNT
0.2% CNT
dynamic mechanical properties evident from Fig. 12a and b show- 0.3% CNT
0.15
ing the mean storage modulus, loss modulus and glass transition 0.4% CNT
Tan Delta

temperature plotted as a function of CNTs content. The improve-

ment as obtained in the DMTA test is shown in Fig. 12c. 0.10
Storage modulus of laminates in the glassy regions and vicinity
of the glass transition temperature was increased upon incorpora-
0.05
tion of MWCNTs from 0 to 0.3 wt.% loading. However, the addition
of nanotubes to the composite laminates was observed to have a
slight influence in rubbery region. This behavior can be attributed 0.00
to the improved dispersion and interaction between the MWCNTs
and epoxy due to the formation of covalent bonds between them. 20 40 60 80 100 120 140 160 180 200
The interfacial interaction reduces the mobility of epoxy polymer Temperature, deg C
chain around the nanotubes which leads to stronger shift of elastic
Fig. 11. Tan delta vs. temperature response of e-glass/epoxy composites.
properties in final composites below the rubbery region. Above the
glass transition temperature i.e. in rubbery region, a slight increase
of storage modulus was observed. This can be attributed to the rel- state the molecular motion and its amplitude remains high and the
atively higher molecular motion and higher amplitude of this mo- macromolecule is not practically in contact with particles for
tion in the rubbery region. Montazeri et al. reported that in rubbery which no shear force act between them [27]. This increase in stor-
age modulus was found from 0 to 0.3 wt.% loading of CNTs. How-
14000 ever, a decrease in storage modulus was observed when the
Control nanotube loading was increased to 0.4 wt.% loading. It might be
0.1% CNT
12000 0.2% CNT due to the incapability of de-agglomeration which facilitates the
Storage Modulus, Mpa

0.3% CNT molecular motion and movement of chain.

0.4% CNT
10000 Loss modulus of MWCNTs reinforced e-glass/epoxy samples
was also found to increase in comparison to control samples. Loss
8000 modulus of composites indicates the energy used to deform the
material that is dissipated into heat and can be used as a measure-
6000
ment of viscous component or unrecoverable oscillation energy
dissipated per cycle. The good dispersed nanotubes must dissipate
4000
energy due to resistance against viscoelastic deformation of the
2000 surrounding matrix [28]. Vlasveld et al. reported that covalent
bond between amino-functionalized CNTs and epoxy improve the
20 40 60 80 100 120 140 160 180 200
efficiency of load transfer from matrix to fillers resulting in an
Temperature,°C increase in loss modulus due to more energy dissipation in com-
posites [29]. So the decrease of loss modulus at 0.4 wt.% nanotube
Fig. 9. Storage modulus vs. temperature response of e-glass/epoxy composites. contents can be ascribed to increasing inclination of agglomeration
2404 M.M. Rahman et al. / Composite Structures 94 (2012) 2397–2406

14000 1400

a
13000 1300

12000 1200

Storage modulus (MPa)

Loss Modulus (MPa)

11000 1100

10000 1000

9000 900

8000 800

7000 700

6000 600
0.0 0.1 0.2 0.3 0.4
Weight percentages (%)

114

112 b
Glass Transition Temperature (deg C)

111.62 ºC

110 110.55 ºC

108.55 ºC
108

106
106.08 ºC
104

102
101.66 ºC

100
0.0 0.1 0.2 0.3 0.4
Weight Percentages (%)

Fig. 12a and b. Effect of NH2–MWCNTs content on viscoelastic properties of e-glass/epoxy composites.

55 tan delta vs. temperature curve as shown in Figs. 11 and 12b. This
0.1 wt.%
50 0.2 wt.% gain in thermo-stability can again be interpreted as a reduction in
Increase w.r.t control or

45 0.3 wt.%
0.4 wt.% mobility of epoxy matrix around the nanotubes by interfacial
40 interactions. Because this interaction induces different cross-link-
reference (%)

35 ing regions in epoxy matrix which will eventually reduce the poly-
30
mer chain motion, a strong shift of glass transition temperature in
25
nanocomposites was observed. In contrast, agglomeration of
20
MWCNTs was observed in case of 0.4 wt.%. During impregnation
15
with fiber, these MWCNTs agglomerates at the fiber interfaces
10
could alter the flow behavior of the matrix which results in nano-
5
meter scale porosities [30]. As a result, free volume may be created
0
Storage modulus Loss modulus Glass transition temp. due to these porosities between polymer molecules which facili-
tates in polymer chain motion. So these may be a reason for drop
Fig. 12c. Improvement of thermo-mechanical properties of e-glass/epoxy compos- in glass transition temperature of e-glass/epoxy samples contain-
ites using NH2–MWCNTs.
ing 0.4 wt.% MWCNTs.

3.5. Fracture surface analysis

resulting less energy dissipating in the system under viscoelastic
deformation. Fracture surfaces of neat and nanophased glass fiber reinforced
The addition of MWCNTs in epoxy resulted in shift of glass tran- composites were investigated by SEM to explore the reason for
sition temperature of e-glass/epoxy samples. The glass transition enhancement in mechanical and viscoelastic properties of compos-
temperature was shifted from 101 °C for control samples to ites. Fig. 13a and b shows the SEM micrographs of fractured single
111 °C for 0.3 wt.% loading MWCNTs obtained from the peak of fiber of control and 0.3 wt.% samples at higher magnification after
 M.M. Rahman et al. / Composite Structures 94 (2012) 2397–2406 2405

Fig. 13. SEM micrographs of fractured single fiber of (a) control and (b) 0.3 wt.% Fig. 14. SEM micrographs of fractured surface of (a) control and (b) 0.3 wt.%
MWCNTs e-glass/epoxy composites. MWCNTs e-glass/epoxy composites.

3-point flexural test. As evident from these micrographs, the fiber 4. Conclusion
in 0.3 wt.% sample contains considerable amount of epoxy resin
residue and rougher fracture surface in comparison to control In this study, functionalized MWCNTs were incorporated in e-
samples. glass/epoxy composites to enhance the flexural and viscoelastic
Fig. 14a and b shows the SEM micrographs of fracture surfaces properties. Based on the experimental and micrographic results,
of control and 0.3 wt.% e-glass/epoxy samples taken at a magnifica- the following conclusions are reached:
tion of x300. As evident from Fig. 14a, control samples exhibited
poor fiber–matrix bonding as fiber breakage with distinct pullout (1) MWCNTs incorporation at low concentrations in e-glass/
scene or interface debonding of fiber–fiber tows. In contrast, no epoxy composites increased flexural property and thermal
sharp fiber pullout or interface debonding was observed in stability of composites. In terms of mechanical and
0.3 wt.% samples. thermo-mechanical properties, 0.3 wt.% MWCNTs loading
The epoxy silane present on the surface of e-glass fibers may was found optimum.
have also reacted with amino groups of MWCNTs in addition to (2) Flexural test results of 0.3 wt.% MWCNTs incorporated e-
its reaction with epoxy matrix functional groups shown in Fig. 8. glass/epoxy samples showed a maximum improvement in
This improved chemical reactivity leading to a strong covalent strength, modulus and strain to failure by 37%, 21% and
bonding may have resisted the crack propagation and increased 21%, respectively in comparison to control samples.
the fiber/matrix bonding in 0.1–0.3 wt.% MWCNTs samples. Thus (3) Dynamic mechanical thermal analysis (DMTA) results of
presence of matrix residue and rougher fracture surface is an indi- 0.3 wt.% samples showed a maximum improvement of 41%
cation of good adhesion between fiber and matrix contributing to in storage modulus, 52% in loss modulus and an increase
the improvement in properties of 0.1–0.3 wt.% composites. This in- of 10 °C in glass transition temperature in comparison to
crease in matrix residue and rougher surface is an indication of control samples.
good adhesion between fiber and matrix which may have contrib- (4) Improvement at optimum loading of 0.3 wt.% explores a
uted to the improvement in e-glass/epoxy composite flexural and good interfacial interaction and effective load transfer
viscoelastic properties. between CNTs and epoxy system due to better dispersion.
2406 M.M. Rahman et al. / Composite Structures 94 (2012) 2397–2406

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