CARBON 6 0 ( 2 0 1 3 ) 1 6 –2 7

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The effect of graphene dispersion on the mechanical

properties of graphene/epoxy composites

Long-Cheng Tang a,*, Yan-Jun Wan a, Dong Yan b, Yong-Bing Pei a, Li Zhao a, Yi-Bao Li c,
Lian-Bin Wu a,*, Jian-Xiong Jiang a, Guo-Qiao Lai a
a
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University,
Hangzhou 310012, China
b
Department of Polymer Engineering, College of Materials Science and Engineering, Beijing University of Chemical Technology,
Beijing 100029, China
c
College of Chemistry and Life Science, Gannan Normal University, Jiangxi 341000, China

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

Article history:
Received 24 September 2012
Accepted 23 March 2013
Available online 4 April 2013
The effect of dispersion state of graphene on mechanical properties of graphene/epoxy
composites was investigated. The graphene sheets were exfoliated from graphite oxide
(GO) via thermal reduction (thermally reduced GO, RGO). Different dispersions of RGO
sheets were prepared with and without ball mill mixing. It was found that the composites
with highly dispersed RGO showed higher glass transition temperature (Tg) and strength
than those with poorly dispersed RGO, although no significant differences in both the ten-
sile and flexural moduli are caused by the different dispersion levels. In particular, the Tg
was increased by nearly 11 C with the addition of 0.2 wt.% well dispersed RGO to epoxy.
As expected, the highly dispersed RGO also produced one or two orders of magnitude
higher electrical conductivity than the corresponding poorly dispersed RGO. Furthermore,
an improved quasi-static fracture toughness (KIC) was measured in the case of good disper-
sion. The poorly and highly dispersed RGO at 0.2 wt.% loading resulted in about 24% and
52% improvement in KIC of cured epoxy thermosets, respectively. RGO sheets were
observed to bridge the micro-crack and debond/delaminate during fracture process due
to the poor filler/matrix and filler/filler interface, which should be the key elements of
the toughening effect.
 2013 Elsevier Ltd. All rights reserved.

1. Introduction years, graphene sheets have been incorporated into a wide

Since the discovery of graphene using the simple Scotch tape
method [1], composites filled with graphene have been widely
investigated to achieve superior electrical, thermal, and
mechanical properties. The outstanding performance is
attributed to the large specific surface area of graphene and
its exceptional properties such as electrical conductivity, ther-
mal conductivity and Young’s modulus [2–4]. In the past few
range of polymer matrix, including epoxy [5], polystyrene
[6], polypropylene [7], polyethylene terephthalate [8], polyan-
iline [9], nylon [10] and polymethylmethacrylate [11] for vari-
ous functional applications.
In order to achieve optimal enhancement in the property
of graphene/polymer composites, several key issues should
be resolved, i.e., improved dispersion of graphene, alignment
of graphene in polymer and surface modification of graphene

* Corresponding authors: Fax: +86 571 28868905.

E-mail addresses: lctang@hznu.edu.cn (L.-C. Tang), wulianbin@hznu.edu.cn (L.-B. Wu).
0008-6223/$ - see front matter  2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.carbon.2013.03.050
 CARBON 6 0 (2 0 13 ) 1 6–27
for good adhesion/interaction. As well known, due to the
entanglement of graphene produced by the synthesis and
the clusters of graphene caused by the intermolecular van
der Waals force, they are usually present in the form of
agglomerates [12]. Consequently, the dispersion and exfolia-
tion of graphene in a media becomes a challenge. Especially,
when they are mixed with a polymer, it will aggregate in ma-
trix. The poor dispersion and exfoliation of graphene not only
significantly lower their efficiency as reinforcement but also
would cause graphene to slip by each other when forces are
applied to the composites.
In recent years, a variety of processing methods e.g., in situ
polymerization, melt mixing and solution blending have been
proposed to disperse graphene into polymer matrix [13]. Gener-
ally, the vast interfacial area created by nanofillers can influ-
ence the behavior of the surrounding polymer matrix for
several radii of gyration even at extraordinarily low content
[14], producing a co-continuous network of greatly altered
polymer chains [15]. Accordingly, significant enhancements
in glass transition temperature (Tg), thermal stability and ulti-
mate strength were obtained for polymer matrix at low graph-
ene content such as 0.05 wt.% [16,17]. Notably, it is well
established that the different processing usually induces dif-
ferent dispersion levels of nanofillers in the matrix and thus re-
sults in different effects on the electrical properties of polymer
composites [18–20]. For example, Li et al. reported that the
nano-, micro- and macroscopic dispersion states of carbon
nanotubes (CNTs) in matrix obtained through employing dif-
ferent processing methods showed fundamental discrepancies
in the corresponding percolation thresholds of CNT/epoxy
composites [19]. Kim et al. found that three different processing
routes (in situ polymerization, melt compounding, and solvent
blending) caused different effects on the electrical conductivity
of graphene/polyurethane composites, which could be also
attributed to the different dispersion levels of graphene in the
thermoplastic matrix [20]. Therefore, the dispersion state of
graphene is crucial to determine the final performance of the
graphene/polymer composites, and it is necessary to under-
stand the effect of graphene dispersion on the properties of
the composites. Unfortunately, whether the different disper-
sion states of graphene can lead to a different impact on the
mechanical properties remains an important open question
in polymer composites.
In this study, two different specimens with the poorly and
highly dispersed graphene were prepared depending upon
whether a ball mill procedure was used during the dispersion
process or not. Discrepancies in the thermal, electrical and
mechanical properties of graphene/epoxy composites with
different graphene dispersion were examined with respect
to low weight loadings of graphene. Moreover, the fracture
behaviors were also characterized based on the microscopic
morphologies of the composites studied.
2. Experimental
2.1. Materials
The epoxy resin was standard diglycidyl ether of bisphenol-A
(DGEBA) (Wuxi Resin Factory of Bluestar New Chemical Mate-
17
rials Co., Ltd.). The curing agent was 4-methylhexahydroph-
tahlic anhydride (MHHPA, Puyang Huicheng Chemicals Co.,
Ltd.) accelerated with a trace of N,N-benzyldimethylamide
(Sinopharm Chemical Reagent Co., Ltd.). Natural graphite
flakes were supplied from Huadong Graphite Factory (Pingdu,
China). All materials for the oxidation of graphite flakes such
as concentrated sulfuric acid, concentrated nitric acid and
hydrochloric acid were purchased from Beijing Chemical Fac-
tory, China. Potassium chlorate was provided from Fuchen
Chemical Reagents (Tianjin, China).
2.2. Preparation of graphene sheets
Graphite oxide (GO) was prepared by completely oxidizing
natural graphite flakes in a solution of sulfuric acid, nitric
acid, and potassium chlorate for 96 h [21,22]. After drying in
a vacuum oven at 80 C for 24 h, the thermal exfoliation of
GO was achieved by placing the GO powder in a quartz tube.
The sample was flushed with argon for 10 min, and the quartz
tube was quickly inserted into a muffle furnace preheated to
1050 C for 30 s to get the graphene sheets (thermally re-
duced GO, RGO).
2.3. Fabrication of composites
Epoxy composites containing the highly dispersed RGO were
prepared by the following procedures. The RGO sheets were
first dispersed in ethanol by sonication at 60 C for 2 h.
The RGO/ethanol solutions with different RGO weight frac-
tions were then mixed with the epoxy by sonication at
50 C for 30 min. The blend (80 mL) was further processed
using a planetary ball mill (PM 400, Retsch) equipped with
four steel containers (125 mL) and three different types of
zirconia balls (3, 6, 11 mm in diameter and the corresponding
250, 50, 10 in number). The high shear stress applied by the
milling impact can break up the agglomerates of RGO sheets
and improve their exfoliations to generate the highly dis-
persed RGO/epoxy dispersions [23–25]. To avoid any intense
shock stress which could destroy the RGO structures, the
rotating tray was controlled at a low speed of 200 rpm to en-
sure that the shear stress is dominant [23]. Then, the mixture
was degassed at 80 C in a vacuum oven for 6 days to remove
the ethanol, followed by addition of the hardener with a re-
sin-to-hardener weight ratio of 185:170 by using mechanical
mixing (800 rpm for 30 min). After degassing (at 60 C for
20 min), the blend was poured into preheated steel molds
(60 C) and cured in an oven. A four-step curing procedure
was used: from room temperature to 90 C for 30 min, then
to 120 C for 60 min, afterwards to 140 C for 30 min and final-
ly to 160 C for 120 min. Fig. 1 shows the processing steps used
to fabricate the composite.
On the other hand, the epoxy composites with the poorly
dispersed RGO were prepared by sonication for 2 h in the eth-
anol at 60 C, while the ball mill procedure was not used
during the dispersion process. It was expected that, when
the high shear stress in the ball mill process was employed
in the dispersion process, the composites with highly dis-
persed RGO sheets could be obtained. But, without using the
high shear mixing, the aggregates of sheets could remain in
the epoxy matrix. Moreover, according to our recent work
18 CARBON 6 0 ( 2 0 1 3 ) 1 6 –2 7

Fig. 1 – Schematic of the preparation of RGO/epoxy composites.

[26], the density of the epoxy resin and curing agent was
determined to be 1.16 and 1.08 g/cm3, respectively. The
density of RGO sheets can be taken as 2.2 g/cm3, as reported
in previous work [27]. Thus, the estimated volume fraction
for 0.05%, 0.10% and 0.20% weight of RGO sheets then com-
putes to volume content of 0.025%, 0.051% and 0.102%
(Table 1).
2.4. Characterization
The microstructures of RGO and graphite and the composites
were examined by a transmission electron microscopy (TEM,
HITACHI H-7650). RGO sheets were dispersed in ethanol by
sonication for 15 min and some pieces were collected on car-
bon-coated 200-mesh copper grids for TEM observation. For
the RGO/epoxy composites, the samples were cut using an
ultramicrotome (LKB Nova) equipped with a diamond knife.
Thin sections, 100 nm in thickness, were cut from a mesa
of about 1 · 1 mm2 and collected on 200 mesh copper grids.
The thickness of RGO sheets was also identified by an atomic
force microscopy (AFM, Digital Instrument D3100). The dis-
persion of RGO in epoxy matrix was verified by using both a
transmission optical microscopy (TOM, Nikon Eclipse LV100
POL) and a scanning electron microscopy (SEM, HITACHI S-
4800). Raman spectra were recorded with SENTERRA Micro
Raman Spectroscopy (Bruker Instrument, Germany). The
excitation wavelength was 633 nm from He–Ne laser with a
laser power of ca. 15 mW at the sample surface. X-ray photo-
electron spectra (XPS) measurements were performed by VG
scientific ESCALab 220I-XL equipped with a hemispherical
electron analyzer and a Mg Ka X-ray source.
Direct current (DC) electrical conductivities of epoxy com-
posites with low conductivities than 106 S/m were measured
by a ZC-90G resistivity meter from Shanghai Taiou Electronics
(China) [28]. The samples with 88.0 mm in diameter and
2.0 mm in thickness were tightly pressed between two
cylindrical copper electrodes that had a diameter of 50 mm.
In order to provide stable values of the resistivity, the samples
were finely polished and tightly pressed between two cylin-
drical electrodes to ensure a good electrical contact. All of
the conductivity measurements were carried out at room
temperature. Dynamic mechanical thermal analysis (DMTA)
was made in tensile mode using a Dynamic Mechanical Ana-
lyzer (NETZSCH, DMA 242), which was performed at 1 Hz with
a constant heating rate of 3 C/min ranging from 30 to 200 C
in air atmosphere. The specimens’ dimensions were 15.0 mm
long · 4.0 mm wide · 0.5 mm thick. The ratio of applied dy-
namic stress to static stress was 1.5. The glass transition
temperature (Tg) of the studied materials was measured by
the temperature at which the loss factor curve showed a max-
imum peak.
Tensile and flexural tests were performed at room temper-
ature using an Ametek Ls100plus, following the ASTM D-638
and ASTM D-790, respectively. Standard dumbbell-shaped
specimens (80.0 mm long · 12.5 mm wide · 4.0 mm thick)
with the length of the narrow region of 28 mm were made
for tensile tests at a crosshead speed of 1.0 mm/min. Rectan-
gular specimens (80.0 mm long · 10.0 mm wide · 4.0 mm
thick) in flexural tests were loaded with a span of 64 mm at
a crosshead speed of 2.0 mm/min. At least five specimens
were tested for each set of conditions.
Quasi-static fracture toughness tests were performed fol-
lowing the ASTM D-5045 with compact tension (CT) speci-
mens (36.0 mm long · 36.0 mm wide · 7.0 mm thick). A pre-
crack was made by lightly tapping a sharp fresh razor blade
into the bottom of the saw slot in the specimen. The plane
strain fracture toughness (critical stress intensity factor, KIC)
can be calculated as follows:
Pmax f ða=WÞ
KIC ¼ ð1Þ
BW1=2
where Pmax is the maximum load of the load–displacement
curve for CT specimens, f(a/W) is related to the geometry of
the sample, B is the thickness of the specimen, W is the width

Table 1 – Glass transition temperature and electrical conductivity of neat epoxy and its composites with poorly and highly
dispersed RGO.

Composite Poorly dispersed RGO Highly dispersed RGO

wt.% vol.% Tg (C) C (S/m) Tg (C) C (S/m)
11
0 0 146.3 ± 1.7 (6.91 ± 1.69) · 10 146.3 ± 1.7 (6.91 ± 1.69) · 1011
0.05 0.025 149.8 ± 2.1 (1.68 ± 0.52) · 1010 152.9 ± 1.9 (9.23 ± 1.85) · 1010
0.10 0.051 149.7 ± 1.5 (3.25 ± 1.06) · 1010 154.3 ± 2.2 (4.57 ± 1.13) · 109
0.20 0.102 148.1 ± 1.6 (6.92 ± 1.75) · 1010 157.4 ± 1.8 (1.47 ± 0.41) · 108
 CARBON 6 0 (2 0 13 ) 1 6–27
of the specimen, and a is the sharp crack of length which
should be between 0.45W and 0.55W. For CT samples, f can
be expressed as:

a a a  a 3
f ¼ 2þ ð0:086 þ 4:64  13:32ð Þ2 þ 14:72
W W W W
 a 4  a 3=2
5:6 1 ð2Þ
W W
The tension of CT specimens was also accomplished on
Ametek Ls100plus at a crosshead speed of 1 mm/min. At least
five specimens of each composition were tested, and the aver-
age values were reported. The microcopy analysis of fracture
surfaces of CT samples were sputtered with gold for 20 s and
observed under SEM.
3. Results and discussion
3.1. Morphology and characterization of RGO sheets
In order to investigate the morphology and structure of RGO
sheets, SEM, TEM and AFM have been utilized. A representa-
tive SEM image of RGO powder in Fig. 2a exhibits that the
sheets are highly agglomerated powder with a ‘‘fluffy’’ struc-
ture, as reported in [29,30]. The dimensions of RGO sheets
are from submicron to several micrometers, and, as shown
in Fig. 2b, a relatively large sheet is approximately 4 · 7 lm2.
The surface of RGO exhibits the bumpy texture in which
many corrugations with several hundred nanometers can be
discernible (Fig. 2c). The isolated oxygen reaction sites and
the resultant defects during thermal reduction of the GO
[31], as well as extremely small thickness of the resulting
graphene, casue a wrinkled topology of RGO at nanoscale
(Fig. 2d) [32,33]. Selected area electron diffraction of those
stacks display only weak and diffuse rings, suggesting the
loss of long range ordering [34], though it is not as perfect
as pristine monolayered graphene. This is in agreement with
Fig. 2 – Micrographs of (a) a SEM image, (b), (c) and (d) typical TEM images of RGO (inset: the measured electron diffraction
pattern and the cross-section of RGO), (e) a typical TEM image of graphite, (f) a typical AFM image of RGO.
19
the work where the blurry hexagonal symmetry of the graph-
ene was also maintained [35]. Comparatively, the graphite
which is composed of many graphene held together by van
der Waals forces shows relatively smooth features without
the corrugated morphology (see the black arrows in Fig. 2e).
Furthermore, the typical TEM image of the core section of
RGO (see the inset in Fig. 2d) presents 3.5 nm in thickness,
indicating that many sheets are composed of 3–6 such
stacked single-layer sheets. After sonication, however, the
AFM image in Fig. 2f indicates that the thickness of a small
RGO sheet is only 1.23 nm, which is consistent with the val-
ues of well exfoliated graphene [36–38], implying that some of
the few-layer graphene stacks are exfoliated into individual
sheets in the solvent.
Raman spectra of graphite, GO and RGO are shown in
Fig. 3a. The Raman spectrum of the pristine graphite displays
a prominent G peak as the feature at 1581 cm1, correspond-
ing to the first-order scattering of the E2g vibration mode and
a 2D band at 2684 cm1 due to the second-order two-phonon
mode. A weak D band adsorption at 1335 cm1 indicates the
presence of defects inherent in the graphite and the edge ef-
fect of graphite (A1g mode). The significant structure changes
during the oxidation from graphite to GO; the G band is broad-
ened and shifted to high frequency, and the D band becomes
higher relative intensity, showing an increased G/D intensity
ratio of 0.846 indicating the distortion of the bonds and
destruction of symmetry possible due to the reduction in size
of the in-plane sp2 domains caused by the extensive oxida-
tion. When GO transformed to RGO, the G band slightly
shifted back to the location of the G band in graphite. An in-
creased G/D intensity ratio of 0.915 compared to GO reflects a
slight increase in the average size of the sp2 domains upon
reduction of GO [39]. The XPS data can offer more information
about the chemical compositions of pristine graphite, GO and
RGO. As shown in the scan (Fig. 3b), pristine graphite is com-
posed of a rich C and a small trace of O and the atomic ratio of
20 CARBON 6 0 ( 2 0 1 3 ) 1 6 –2 7

(a) Graphite 1581 (b) Graphite C1s

O1s
D band G band 2D band

Intensuty [a.u.]

Counts [a.u.]
GO GO O1s
1588 C1s

RGO 1586 RGO C1s

O1s

500 1000 1500 2000 2500 3000 250 260 270 280 290 300 520 530 540 550
Raman Shift [ cm-1 ] Binding Energy [eV]

Fig. 3 – (a) Raman spectra and (b) XPS survey scans of graphite, GO, and RGO.

C/O is 8.1 calculated by the peak area of C1s to O1s. While
the peak intensity of O 1s (ca. 533 eV) is significantly in-
creased relative to the C 1s peak (ca. 286 eV) after oxidation
to GO, and the atomic ratio of C/O is 2.0. In contrast to GO,
RGO sheets show two peaks, which is similar as those of
graphite. The C/O ratio is raised to 7.3, consistent with re-
ported values for highly reduced GO [40]. These Raman and
XPS results as well as TEM images reflect the fact that some
defects still remain in the restored graphitic structure result-
ing from the removal of oxygen functionalities of GO [38],
which may lead to a deterioration of the electrical properties
of RGO sheets.
3.2. Dispersion level of RGO sheets in epoxy resin
The aggregates of the prepared RGO shown in Fig. 2 would be
obstacles to obtain a good dispersion of graphene and were
hardly broken into individual flake in the epoxy resin. The
solution mixing was usually employed to disperse the graph-
ene sheets in previous work [31,41–45]. Fig. 4 shows TOM
images of epoxy dispersions with 0.2 wt.% RGO before curing.
Clearly, the well dispersed RGO can be obtained through using
the sonication process (Fig. 4a), although many small and
black clusters of RGO in the epoxy matrix are still found in
Fig. 4b. Comparatively, the dispersion level of RGO does not
change obviously after the ball mill process (compare Fig. 4a
with Fig. 4c), but the aggregate size indeed becomes smaller
(see Fig. 4d). It suggests that the exfoliation degree of RGO
sheets seems to be highly improved after the high shear mix-
ing process as previously reported in the literature [23].
After curing the epoxy composite samples, the dispersion
of RGO sheets in the matrix in Fig. 5 shows obvious differ-
ences. The RGO sheets dispersed in the epoxy resin without
using the ball mill process are in the form of agglomerates
(see Fig. 5a). While, after using the ball mill process, the
sheets present a relatively good dispersion in the matrix
(Fig. 5b). These phenomena are quite different from the RGO
dispersion before curing shown in Fig. 4, suggesting the re-
agglomeration of RGO during curing of resin. Similar phe-
nomenon was also found in the CNTs/epoxy composites

Fig. 4 – TOM images of epoxy suspensions filled with 0.2 wt.% RGO before curing prepared (a), (b) without and (c), (d) with
using the ball mill process.
 CARBON 6 0 (2 0 13 ) 1 6–27
Fig. 5 – TOM and TEM images of cured epoxy composites filled with 0.2 wt.% RGO prepared (a), (c) without and (b), (d) with
using the ball mill process.
[46]. It is expected that the re-agglomeration of RGO sheets
could be more limited at highly dispersed/exfoliated state
probably because the interfacial area created by graphene
are enhanced significantly. The TEM graphs of RGO/epoxy
composites can demonstrate this. It is clearly seen that the
agglomerates and closely packed RGO are prevalent in the
sample without using the ball mill process (Fig. 5c), which be-
came significantly exfoliated and highly dispersed after the
high shear mixing (Fig. 5d).
3.3. Glass transition temperature and electrical
conductivity
Fig 6 shows the dynamic mechanical properties of neat epoxy
and its composites. One can recognize that the incorporation
of RGO sheets results in the increase of the storage modulus
in the whole temperature range (Fig. 6a and b), compared to
that of neat epoxy. This can be well explained by the reinforc-
ing effect of the nanofiller leading to increased stiffness. In
comparison, the slightly more modulus enhancement ap-
pears to occur for highly dispersed RGO than that for the
poorly dispersed ones. On the other hand, the changes in Tg
in epoxy composites are particularly important, not only be-
cause they yield insights into the fundamental changes in
polymer chain dynamics, but also because the associated
gains in thermal stability are critical for many applications
[47]. Determined from the midpoints of glass transition re-
gions of the damping curves, the Tgs of RGO/epoxy compos-
ites are listed in the Table 1. It can be found that the Tg
values for the composite with the poorly dispersed RGO
sheets are slightly enhanced by about 2–3 C (Fig. 6c and
21
Table 1). Interestingly, the Tg data for the composite with
the highly dispersed RGO is particularly striking: an unprece-
dented shift of nearly 11 C occurs at only 0.2 wt.% of the RGO
sheets (Fig. 6d and Table 1). As reported in our recent work
[48], although CNTs were well distributed in the matrix and
well-wetted by the epoxy resin, no significant shift of Tg
was observed even at 1.0 wt.% loading. It suggests that the
RGO sheets are much more effective to increase the Tg value
of epoxy resin than the CNTs, which is consistent with the
previous results [47,49].
Several reasons are probably ascribed to the above phe-
nomena. First, for the epoxy composites with pristine CNTs,
localized clustering leads to nanotube-rich and nanotube-
poor regions [48], which make the polymer molecules to move
easily and thus decreased or remained the Tgs [50]. Similar
phenomenon should be also occurred in the epoxy compos-
ites with the poorly dispersed RGO and thus results in a slight
change in Tg value (Table 1). Second, although no clustering of
the CNTs was observed in some CNT/epoxy systems, the
nanotubes are curled up and thicker, resulting in a decrease
of the surface area in contact with the polymer and a smaller
Tg shift compared to the highly dispersed graphene [47]. Note
that, in some epoxy composites with functionalized CNTs,
the decreased degree of cross-linking induced by partial
absorption/reaction of the curing agent even led to a drop in
Tg [51,52]. Furthermore, the nanoscale surface roughness of
graphene with many corrugated morphology could be an-
other key factor. As shown in Fig. 2, both the wrinkled
structure and large specific surface area of RGO sheets likely
induce strong interfacial interactions with polymer chains
and substantially larger influence on the thermal properties
22 CARBON 6 0 ( 2 0 1 3 ) 1 6 –2 7

(a) 3000 (b) 3000

Poorly dispersed Highly dispersed
2500 2500

Storage modulus [MPa]

Storage modulus [MPa]

2000 2000

1500 1500

1000 0 wt% 1000 0 wt%

0.05 wt% 0.05 wt%
500 0.10 wt% 500 0.10 wt%
0.20 wt% 0.20 wt%
0 0
40 60 80 100 120 140 160 180 40 60 80 100 120 140 160 180
o o
Temperature [ C] Temperature [ C]

(c) 1.4 Poorly dispersed

(d) 1.4 Highly dispersed

1.2 1.2

1.0 0 wt% 1.0 0 wt%

Tan Delta
Tan Delta

0.05 wt% 0.05 wt%

0.8 0.8
0.10 wt% 0.10 wt%
0.6 0.20 wt% 0.6 0.20 wt%

0.4 0.4

0.2 0.2

0.0 0.0

40 60 80 100 120 140 160 180 40 60 80 100 120 140 160 180
o o
Temperature [ C] Temperature [ C]

Fig. 6 – Dynamic mechanical properties of cured epoxy composites containing: (a) and (c) poorly dispersed RGO; (b) and (d)
highly dispersed RGO.

of the matrix [53], even probably affect the curing reaction
rate by changing the maximum exothermic heat flow temper-
ature [54]. Such an effect has been suggested by the previous
molecular dynamics studies in which the polymer mobility
was altered due to geometric constraints at nanofiller sur-
faces [55]. Hence, in the graphene/epoxy composites, good
dispersion of the sheets leads to a substantial interphase
zone around each sheet in which the mobility of the matrix
polymer chains is constrained [47]. Therefore the dispersion
state of graphene in the matrix is better, which should result
in an increase of the surface area in contact with the polymer
matrix and a larger Tg shift.
The electrical conductivity, C, of the epoxy composites
with poorly and highly dispersed RGO sheets are shown in Ta-
ble 1. An electrical conductivity of 1011 S/m was measured
for the neat epoxy resin, which is typical for such a polymer
[56]. As expected, the electrical conductivity of the compos-
ites containing highly dispersed RGO sheets is one or two or-
ders of magnitude higher than that of the composites with
poorly dispersed sheets (see Table 1), although both systems
still exhibit high electrical resistance at low RGO content. It
is well established that electrical properties of the polymer
composites depend on the microstructures such as filler dis-
persion state, filler geometry and content, as well as filler-fil-
ler interaction [18]. In this work, the geometry, content and
interaction of the conductive RGO are almost same in both
the composite systems studied. Thus, the dispersion level of
RGO is crucial to determine the final electrical properties of
epoxy composites. The good dispersion levels of RGO in the
cured composites can produce the formation of an effective
network for electron path transmittance (see Fig. 5) [57],
which should be responsible for the higher electrical conduc-
tivity obtained in the highly dispersed RGO/epoxy composites
(Table 1). Apparently, more research is needed to construct
the effective percolating network in the graphene/epoxy com-
posites, and it is beyond the scopes of this study.
3.4. Tensile and flexural properties
Fig. 7 shows the tensile and flexural properties of the RGO/
epoxy composites. The elastic and flexural moduli increase
with the increase of RGO loading regardless of the dispersion
level (see Fig. 7a and c). However, the ultimate strength of the
composites with the highly dispersed RGO has no significant
change for both tensile and flexural tests, but those of the
composite with the poorly dispersed RGO decreases dramati-
cally (see Fig. 7b and d). Similar results can be found in other
graphene/epoxy systems [49,58]. The graphene agglomerates
in the epoxy composites can lead to cracks to initiate and
propagate easily and, consequently, produce the reduced
strength of the composites [57]. Comparatively, the highly dis-
persed graphene fillers are more efficient than the aggregated
ones in transferring applied load [17,41].
In general, the tensile and flexural properties of the graph-
ene/polymer composites are slightly improved, but not en-
ough as expected [41,44,57], especially for the elastic
modulus. Three reasons may explain the mild enhancement
in these properties of the graphene/epoxy composites. First,
a strong interfacial bond between the graphene sheet and
the surrounding matrix is crucial to determine the properties
of the polymer composites [20,59]. However, the interfacial
bond between the RGO sheets and the polymer resin in this
 CARBON 6 0 (2 0 13 ) 1 6–27 23

(a) 3.3 (b) 70

Poorly dispersed
3.2 Highly dispersed

Tensile strength [MPa]

Elastic modulus [GPa]
60
3.1

3.0 50

2.9
Poorly dispersed 40
2.8 Highly dispersed

2.7 30
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
RGO content [wt%] RGO content [wt%]

(c) 3.1 (d) 180

Poorly dispersed
3.0 Highly dispersed
160
Flexural modulus [GPa]

Flexural strength [MPa]

2.9

2.8 140

2.7
120
2.6
Poorly dispersed 100
2.5
Highly dispersed
2.4
80
2.3
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
RGO content [wt%] RGO content [wt%]

Fig. 7 – Tensile and flexural properties of cured RGO/epoxy composites: (a) and (c) modulus; (b) and (d) strength.

work is weak and the load transfer from the polymer to the Poorly dispersed
0.8 Highly dispersed
sheets should be not large enough for the sheets to be broken
under loading. There is evidence of the debonding of the RGO
KIC [MPa.m ]

0.7
1/2

which can be observed by SEM as shown in the later section.

The second reason may be related to the structure of graph-
0.6
ene because the weak van der Waals forces exist between
individual shells of the graphene agglomerates [60], slipping
0.5
between the shells will occur. Finally, most of the RGO sheets
in epoxy show significant curvature (see Fig. 2). Upon loading,
0.4
the sheets need to extend and rotate first along the tensile 0.00 0.05 0.10 0.15 0.20
direction to maximize their improvements on the tensile RGO content [wt%]
modulus. Accordingly, the relative reinforcement effect is
Fig. 8 – Fracture toughness of cured epoxy composites as a
limited for the composites with the wrinkled graphene.
function of RGO content.

3.5. Fracture toughness

The KIC values of the composites with RGO content are plotted
in Fig. 8. In the composite with the highly dispersed RGO, the
KIC value increases with the sheet content. While, in the com-
posite containing the poorly dispersed RGO, the KIC increases
first with the increase of sheet content but saturates at
0.1 wt.% (see Fig. 8). At a given filler content, the gains in KIC
values are 24% i.e., from 0.493 ± 0.048 MPa m1/2 for neat epoxy
to 0.611 ± 0.039 MPa m1/2 for the composite with 0.2 wt.%
poorly dispersed RGO; while the gains become 52%
(0.748 ± 0.038 MPa m1/2) for the composite with 0.2 wt.%
highly dispersed RGO. It indicates that the well dispersed
RGO sheets are much more effective on toughening epoxy re-
sin than the poorly dispersed sheets.
The morphologies of CT fracture surfaces of the neat
epoxy and its composites with 0.2 wt.% RGO are presented
in Fig. 9. As shown in Fig. 9a, the fracture surface of the neat
epoxy is featureless with a typical brittle fracture process, and
it is very smooth (see the inset in Fig. 9a), revealing its nature
of weak resistance to crack initiation and propagation [26]. In
the case of the composite containing the poorly dispersed
RGO, the fracture surface exhibits relatively rough with some
river-like structures (Fig. 9b). It should be noted that the RGO
sheets dispersed in the epoxy just using the sonication exist
in the form of agglomerates, which is consistent with the
TOM and TEM observations in Fig. 5. The RGO rich region indi-
cated by a black square in Fig. 9b is magnified and shown in
Fig. 9c in order to verify existence of the RGO sheets (see
the black arrows). Comparatively, the composite with the
highly dispersed RGO exhibits a rougher fracture surface
(Fig. 9d), and numerous tortuous and fine river-like structures
with hackles and ribbons can be observed (see the black ar-
rows in the inset). Normally, the improved surface roughness
is accompanied by the creation of matrix plastic deformation,
24 CARBON 6 0 ( 2 0 1 3 ) 1 6 –2 7

Fig. 9 – SEM images of CT fracture surfaces: (a) neat epoxy; (b), (c) and (e) 0.2 wt.% poorly dispersed RGO/epoxy; (d) and (f)
0.2 wt.% highly dispersed RGO/epoxy. (The long white arrows at the bottom right corners indicate the crack growth
direction.).

Fig. 10 – TEM images of RGO/epoxy composites: (a) the delamination and (b) the crack bridging of RGO sheets.

and thus much fracture energy is likely dissipated [61,62].
Therefore the better dispersion state of RGO in matrix could
lead to an increase of the energy dissipation during the frac-
ture process and a higher fracture toughness value as shown
in Fig. 8.
In order to further investigate the fracture behaviors of the
RGO/epoxy composites, the high magnified SEM graphs of CT
fracture surfaces were observed. As shown in Fig. 9e and f, the
wrinkled morphology of RGO can be seen for the composites
with the poorly or highly dispersed RGO (see the white ar-
rows). However, some gaps between RGO sheet and matrix
can be also found on the surface (see the black arrows in
the figures), indicating that the sheet/matrix interface is still
weak in both these two systems. As a result, the debonding
 CARBON 6 0 (2 0 13 ) 1 6–27
of RGO occurs and thus induces many river-like structures on
the fracture surface. More experimental evidence about the
debonding of RGO sheets can be observed under TEM. As
can be seen in Fig. 5c and d, the gap between the sheet and
matrix can be also clearly observed. Normally, the diamond
knife used in ultramicrotome would induce a relatively high
stress during the preparation of TEM specimen. Under such
high stress field, the few-layer graphene agglomerates usually
delaminates or slips by each other during the fracture process
due to the weak adhesion between both the sheet/sheet and
sheet/matrix (see the black arrows in Fig. 10a). Some voids ob-
served in the RGO rich region on the CT fracture surface also
support for this hypothesis (see Fig. 9c). In addition, a rela-
tively large 2D sheets can bridge micro-crack, as observed
and arrowed by the black arrow in Fig. 10b, which can stabi-
lize and stop developing into large and harmful cracks to
the composites. With the micro-crack propagating, however,
the poor filler/matrix interface results in the pull-out of
graphene sheets when the stress exceeds the filler/matrix
interfacial strength [63]. The debonding/delamination or
pull-out of graphene was able to trigger and promote the local
plastic deformation of matrix such as shear banding to dissi-
pate fracture energy [64], which is evidenced by the highly
scale-like rough fracture surface in Fig. 9b and d.
The above findings suggest that the debonding/delamina-
tion and crack bridging of RGO should be the key elements of
the toughening effect in the epoxy composites. Note that the
interfacial quality between RGO and matrix is still very weak
in both epoxy systems. It may be required that the RGO/ma-
trix interface be improved and become strong with the matrix
to fully realize the benefit of graphene reinforcement in epoxy
resin.
4. Conclusion
This work investigated the influence of RGO dispersion on the
mechanical properties of epoxy resin. A better dispersion of
RGO in epoxy matrix was obtained after using the ball mill mix-
ing process. It is found that the highly dispersed RGO resulted
in higher strength and fracture toughness of epoxy resin than
the poorly dispersed RGO, although no significant differences
in both the tensile and flexural moduli was observed regardless
of the dispersion level. The gains in KIC values are 24% and 52%
for the composite with 0.2 wt.% poorly and highly dispersed
RGO sheets, respectively. In addition, the well dispersed RGO
fillers are much more effective in improving the Tg and electri-
cal conductivity of epoxy resin than the poorly dispersed RGO.
SEM and TEM images showed that the debonding/delamina-
tion and crack bridging of RGO sheets should be the key ele-
ments of the toughening effect in the graphene/epoxy
composites. It was also found that the highly dispersed RGO
resulted in much more tortuous and fine river-like structures
on the fracture surface to consume fracture energy in
comparison with the poorly dispersed RGO.
Acknowledgements
We acknowledge the financial support of the National Natural
Science Foundation of China (No. 51203038), the Starting
25
Foundation for Scholars of Hangzhou Normal University (No.
2012QDL022) and the Scientific Research Fund of Zhejiang Pro-
vincial Education Department (No. Y201224314), as well as the
Youth Natural Science Foundation of Jiangxi Province
(20122BAB213008). L. C Tang wishes to thank Dr. Y Bai (Hangz-
hou Normal University) for his help with Raman measurement.
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