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Nanocomposite Creep

Control of Epoxy Creep Using Graphene

Ardavan Zandiatashbar, Catalin R. Picu,* and Nikhil Koratkar

The creep behavior of epoxy–graphene platelet (GPL) nanocomposites with different

weight fractions of filler is investigated by macroscopic testing and nanoindentation.
No difference is observed at low stress and ambient temperature between neat epoxy
and nanocomposites. At elevated stress and temperature the nanocomposite with the
optimal weight fraction, 0.1 wt% GPLs, creeps significantly less than the unfilled
polymer. This indicates that thermally activated processes controlling the creep rate
are in part inhibited by the presence of GPLs. The phenomenon is qualitatively
similar at the macroscale and in nanoindentation tests. The results are compared
with the creep of epoxy–single-walled (SWNT) and multi-walled carbon nanotube
(MWNT) composites and it is observed that creep in both these systems is similar to
that in pure epoxy, that is, faster than creep in the epoxy–GPL system considered in
this work.

1. Introduction and fatigue response of this material is of significant practical

importance.
Epoxy is a thermosetting polymer which is used in a wide range
Polymer properties can be modified by mixing with a
of applications as an adhesive, matrix material for various
second phase. In particular, the stiffness and strength of
composites, and for components with a structural role. Epoxies
thermosetting polymers can be increased by the addition of
are generally mixtures of a base resin and a crosslinker (hard-
stiff fibers, and their toughness can be enhanced by embed-
ener) and are molecular networks.[1,2] The average length of
ding rubber inclusions. Over the last decade, composites in
the resin molecule segment between crosslinks is on the nano-
which the second phase has nanoscale dimensions have been
meter scale and hence these network segments are rather stiff
studied extensively with the hope that synergies in the nano-
in both bending and axial deformation modes. This provides
scale material behavior can be exploited to lead to exceptional
significant strength and creep resistance to the network.
macroscale properties. In thermoplastics it was shown that
Since epoxies have a structural role in most applications,
strength and ductility can be increased simultaneously or at
their mechanical stability is essential. Their creep and resist-
least, one of these properties may be increased without com-
ance to fracture under repeated loading conditions (fatigue)
promising the other.[5] These effects have been attributed to
often control the equivalent properties of the structure in
the fact that the presence of fillers modifies the structure and
which they are used. For example, the ultimate failure of an
dynamics of polymeric chains, that is, the matrix material is
epoxy-matrix composite is usually controlled by delamination
modified by the presence of the second phase. This is a concept
and fracture of the epoxy matrix.[3] Similarly, the collapse of
fundamentally different from that controlling reinforcement
the ceiling of the Big Dig tunnel in Boston, MA, in 2006 was
in regular composites in which the properties of individual
traced to creep in epoxy.[4] Therefore, improving the creep
phases remain identical to those of the bulk, and reinforce-
ment is provided by the simple presence of inclusions.
Much more modest claims have been made so far
A. Zandiatashbar, Prof. C. R. Picu, Prof. N. Koratkar regarding improvements in nanocomposites with a thermo-
Department of Mechanical, Aerospace, and Nuclear Engineering setting matrix. The strength and ductility appear to be con-
Rensselaer Polytechnic Institute trolled by the molecular network of the matrix, which appears
Troy, NY 12180, USA
not to be modified significantly by the presence of nanoscale
E-mail: picuc@rpi.edu
inclusions. However, when the crosslinking density of the
matrix is modified by nanofillers, the macroscopic properties
DOI: 10.1002/smll.201102686 do change. It was shown, for example, that epoxy filled with

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Control of Epoxy Creep Using Graphene

pristine carbon nanotubes (CNTs) exhibits a slower crack Neat Epoxy

growth rate under fatigue loading conditions at small applied GPL/Epoxy 0.1%
3 GPL/Epoxy 0.3%
loads (stress intensity factor amplitudes), but loses these
GPL/Epoxy 0.5% 40 MPa
properties at high loads.[6,7] When the nanotubes are function-
alized to obtain a strong interface with the matrix, the fatigue

Creep Strain (%)

crack growth rate is reduced by an order of magnitude over a
broad range of stress intensity factor amplitudes.[8] 2
Graphene, a single layer of carbon atoms sp2-bonded in a
hexagonal array, has attracted attention recently for its inter-
esting mechanical and transport properties.[9–11] Its use as a filler
material (in the form of platelets) in polymer nanocomposites 1
was also studied.[12] At present there is no efficient technique
20 MPa
to produce ideal, single-layer graphene sheets for use in nano-
composite applications.[13] This situation has directed attention
to the use of graphene platelets (GPLs), which are cheap and 0
0 30000 60000 90000 120000
easy to produce in large quantities.[12,14,15] The results discussed
to date indicate that while graphene affects the monotonic Time (sec)
mechanical properties weakly, it has a far more powerful effect Figure 1. Creep strain versus time for neat epoxy and epoxy–GPL of
on the fatigue crack growth behavior of the nanocomposite.[16] different filler contents, at stresses of 20 and 40 MPa and at room
A number of studies have addressed creep in nanocom- temperature.
posites. Zhang et al. studied the effect of CNT nanofillers on
the creep behavior of epoxy[17] and it is shown that single-
stress levels represent 35 and 70% of the yield stress, respec-
tively. The load is increased fast (σ⋅ = 200 MPa s−1) and then it
walled CNTs (SWNTs), unlike multi-walled CNTs (MWNTs)
and fullerene, lead to improved creep behavior of epoxies at
is held constant. The time at the beginning of the hold period
room temperature and low stresses, while they are not effec-
is considered the initial time for creep. The creep strain was
tive at higher stresses. Sheng et al. studied the creep behavior
recorded for 36 h. No necking or significant variation of the
of bisphenol E cyanate ester (BECy)–alumina nanocompos-
specimen cross-sectional area was observed during the test,
ites and observed an increase of the creep compliance rela-
so the effective stress is that prescribed throughout the entire
tive to neat BECy polymer at all temperatures between 190
test. Figure 1 shows the creep strain (total strain minus the
and 320 °C.[18] In another work it was shown that montmo-
elastic strain corresponding to the creep load) versus time for
rillonite-layered silicate (MLS) improves tensile mechanical
the four materials and for the two stress levels tested.
properties as well as the creep recovery of polyethylene.[19]
The creep behavior is essentially identical for filled and
Lam et al. studied creep in epoxy–nanoclay nanocompos-
pristine epoxy at the smaller load (20 MPa). However, at
ites using nanoindentation and concluded that 4 wt% is the
the larger stress the four materials respond differently. The
optimal filling fraction leading to the smallest creep strain.[20]
smallest creep strain is measured in the nanocomposite with
To our knowledge, the effect of graphene on creep in
0.1 wt% GPLs, which deforms significantly less than pristine
epoxies has not been studied to date. This is the objective of
epoxy. In fact, the strain at the end of the hold period (after
the present work. The time-dependent mechanical behavior
36 h) is 15% smaller in the 0.1 wt% GPL composite than in
is studied at the macroscopic scale by performing standard
pristine epoxy. The other composites (0.3 and 0.5 wt% GPLs)
creep tests, and at the nanoscale, by nanoindentation creep.
creep more than the unfilled polymer.
The results indicate significant creep rate reduction in the
The observation that the optimal properties are exhibited
nanocomposite with the optimal weight fraction of nano-
by the composite with 0.1 wt% GPLs is in agreement with
fillers. The effect depends on temperature and stress level,
previous work on this system, in which it was shown that the
being more pronounced at larger stresses and at elevated
composite with this weight fraction has the highest fracture
temperatures. For comparison, creep of epoxy filled with
toughness.[16] Specifically, the fracture toughness increases
SWNTs and MWNTs was also studied in the same range of
with increasing weight fraction of nanofillers up to 0.1 wt%,
stress and temperature and, consistent with previous work,[17]
after which it decreases. This behavior was associated with
it was observed that both epoxy–SWNT and epoxy–MWNT
the quality of filler dispersion. It has been observed that the
composites creep at the same rate as pure epoxy. Hence,
optimal dispersion obtained with this mixing method results
these additives do not improve the creep response relative to
in the 0.1 wt% GPL sample, while agglomeration is seen upon
that of pure epoxy.
increasing the filler fraction. Since GPLs bond to each other
only through van der Waals interactions, a cluster of GPLs
is quite weak when subjected to tension. If the cluster is not
2. Results and Discussion infiltrated by polymer, one may consider it as a nanovoid
from the mechanical point of view. Clearly, these large inclu-
2.1. Macroscopic Creep Behavior at Room Temperature sions should weaken the material rather than strengthen it.
To determine the distribution, the fracture surfaces in the
Creep tests were performed with a nominal stress of 20 and various materials studied were observed by scanning electron
40 MPa, in separate experiments, at room temperature. These microscopy (SEM) and the size of inclusions was estimated

small 2012, 8, No. 11, 1676–1682 © 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.small-journal.com 1677

full papers
Figure 2. a) Fracture surface of a sample with 0.1 wt% filling fraction showing individual GPLs and river pattern marks. b) Probability distribution
function of nanofiller size as observed on the fracture surface of nanocomposites with 0.1 and 0.5 wt% GPLs.
using the linear intercept method described in the ASTM
standard E112. Figure 2a shows a SEM image of the fracture
surface of a sample with 0.1 wt% GPLs. Inclusions having pro-
jected dimensions of approximately 1 μm are clearly visible,
along with river pattern marks produced during the fracture
process. The river pattern features are clearly distinct from
the inclusions. Large domains of this type were inspected. To
quantify clustering, Figure 2b shows a plot of the inclusion size
distribution in composites with 0.1 and 0.5 wt% GPLs. The
distribution is fairly broad in both cases, and shifts to larger
inclusion sizes as the GPL fraction increases. Agglomeration
is observed at all filling fractions (see the tail of the distribu-
tion), but it is more pronounced at higher filler loading. The
0.1 wt% composite has the largest fraction of inclusions with
projected dimensions below 1 μm, that is, individual GPLs.
The curves in Figure 1 can be approximated with a power
law function of time. Figure 3 shows the 40 MPa curves for
pristine epoxy and 0.1 wt% GPLs obtained at room tem-
perature in log–log coordinates. The curve is approximated
1 stress. It is interesting to investigate the effect of tempera-
Log (Creep Strain)
0.1
Neat Epoxy
GPL/Epoxy 0.1 wt%
10 100 1000 10000 100000
Log(Time)
Figure 3. Log–log plot of room-temperature creep strain versus time
for neat epoxy and epoxy–0.1 wt% GPL showing a power law creep
compliance function.
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A. Zandiatashbar et al.
by the function ε(t) ∼ t 1/q . The exponent q is 2.49 for epoxy
and 4.71 for the nanocomposite. This functional form of the
strain–time relationship results from a constitutive equation
of the form [Eq. (1)]:
 
∂  q σ (t) pq
ε(t) = (1)
∂t μc
for the viscoelastic body, where σ is the stress, and μc and
p are constants. Evolution equations of this type have been
used to represent the mechanical behavior of complex vis-
coelastic liquids and solids,[21] especially glasses,[22] and may
be expressed formally in terms of fractional calculus.[23] They
lead to slow, power law relaxation behavior and are indicative
of hierarchical relaxation processes taking place in the mate-
rial. Multiple molecular-scale mechanisms may lead to this
type of relaxation, but the specific mechanism taking place in
molecular networks is not entirely understood at present.
2.2. Macroscopic Creep Behavior at Elevated Temperatures
As shown in Figure 1, the nanocomposites creep identically
to the pristine epoxy samples at room temperature and low
ture on the creep response, while keeping the stress level low
(20 MPa). To this end we consider the 0.1 wt% GPL system.
Figure 4 shows the creep strain versus time for both pristine
and nanocomposite samples at room temperature and at T =
40 and 55 °C. At room temperature the curves corresponding
to the two materials overlap (see also Figure 1). However,
differences are seen as the temperature increases. At 55 °C
the epoxy creeps significantly more than the nanocomposite.
The difference is observed mostly in the transient part of
the creep curve, with the creep rates in the steady-state part
being relatively close to each other.
The data in Figure 1 and Figure 4 indicate that the
molecular mechanisms leading to differences between pris-
tine and filled epoxy, that is, those producing more deforma-
tion in unfilled epoxy, are activated by temperature (T) and
stress (σ). Let us consider that these thermally activated
small 2012, 8, No. 11, 1676–1682

Control of Epoxy Creep Using Graphene
Neat Epoxy
GPL/Epoxy 0.1wt%
30
25
20
Creep Strain (%)
15
10
5 o
0 0.00
0 15000 30000 45000 60000
Time (sec)
Figure 4. Creep strain versus time for neat epoxy and epoxy–0.1 wt%
GPL at a stress level of 20 MPa and temperatures of 23, 40, and 55 °C.
processes can be described by an Arrhenius expression,
ε⋅ ∝ exp(−E a (σ )) kB T ), where Ea is the stress-dependent
activation energy and kB is the Boltzmann constant. At σ =
20 MPa, the activation energy for creep in epoxy is 1.05 eV,
while in the nanocomposite it becomes 1.12 eV. Given that
the difference between the creep of pure epoxy and that of
the nanocomposite depends strongly on temperature, the dif-
ference in activation energy reported here is significant and
outside of the measurement noise. The atomistic/molecular
mechanisms leading to this difference are not fully under-
stood at this time, but it is conjectured that the good bonding
between GPLs and epoxy (as shown in Reference [22]) has a
contribution. Another indication that individual GPLs bond
well with epoxy is provided by the nanoindentation tests dis-
cussed in Section 2.4. The comparison with data obtained for
epoxy–SWNT and epoxy–MWNT (Section 2.3) also sheds
light on this issue.
It is appropriate to inquire if these differences are due
to the variation of the glass transition temperature, Tg, in
the nanocomposite relative to epoxy. Tg was measured using
differential scanning calorimetry (DSC) for neat epoxy and
nanocomposites of 0.1, 0.3, and 0.5 wt% GPLs. Samples were
heated and cooled in two cycles between room temperature
and 180 °C with a heating/cooling rate of 10 °C min−1 and
5-min hold periods between heating and cooling cycles. Tg
was measured in the second heating cycle. The values range
between 73 and 79 °C for all these materials. While the mean
values of Tg seem to increase with the filler content, the
experimental noise is rather large (±2 °C) and a clear state-
ment cannot be made. However, the difference observed in
Figure 4 cannot be due to the small difference of Tg between
the various materials, primarily because this argument pre-
dicts the opposite trend relative to the experiment. At a given
temperature, the nanocomposite is closer to its Tg than the
unfilled epoxy, which suggests that more creep should be
observed in epoxy–GPL.
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o Neat Epoxy
T = 55 C
GPL/Epoxy 0.1wt%
1E-5
Strain Rate (1/s)
o
T = 40 C
1E-6
T = 55 C
o
T = 40 C
o 1E-7
T = 23 C
0.05 0.10 0.15 0.20 0.25 0.30 0.35
Strain
75000
Figure 5. Strain rate versus strain for neat epoxy and epoxy–0.1 wt% GPLs
at temperatures of 40 and 55 °C. Tests were performed at 20 MPa.
The strain rate versus strain plots corresponding to the
higher-temperature curves in Figure 4 are shown in Figure 5.
As the temperature increases, the strain rate differential at
given strain between the nanocomposite and pristine epoxy
increases. At larger strains, the strain rate of the composite is
more than an order of magnitude smaller than that of epoxy.
The difference between the two curves at T = 55 °C increases
even more with time. This is a significant reduction of the
creep rate in conditions in which creep resistance is more
critical (higher temperatures and stresses).
2.3. Comparison with the Creep of Epoxy–Carbon
Nanotube Composites
The comparison of the results reported in the previous sec-
tion with the creep behavior of epoxy–CNT composites is of
interest. To this end, samples of epoxy–SWNT and epoxy–
MWNT were processed using the method employed for
epoxy–GPL. The filling fraction was selected as 0.1 wt% to
allow direct comparison with the GPL composite exhibiting
optimal mechanical performance.
Figure 6 shows the creep strain versus time for neat epoxy
and epoxy–GPL, epoxy–SWNT, and epoxy–MWNT compos-
ites subjected to 20 MPa load at 55 °C. The curves for neat
epoxy and epoxy–GPL are identical to those in Figure 4. It
is observed that the curves corresponding to the epoxy–CNT
systems are very close to that for neat epoxy. The epoxy–GPL
composite creeps significantly less than all other composites
studied. Differences are largely observed during the tran-
sient part of creep, with the creep rates in the steady-state
regime being relatively close to each other at a given time.
This behavior is similar to that described previously[17] and
is attributed to the fact that the bonding between the CNTs
and epoxy is weaker than that between GPLs and epoxy.[24]
While the CNTs used in this work (and in Reference [17])
are pristine, the GPL surface is functionalized[16] by the pres-
ence of oxygen and OH groups, which enhance the interac-
tion with the epoxy matrix. The warped configuration of most
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full papers A. Zandiatashbar et al.

35 o represents the mean of nine indentation measurements and

T = 55 C
the error bars indicate the variability (standard deviation)
30 from indentation site to indentation site. As on the macro-
scopic scale, the nanocomposite creeps less than the unfilled
25 polymer. The inset shows the same data in logarithmic coor-
Creep Strain (%)

dinates indicating that, as in Figure 3, the variation in time

20 of the creep response can be described by a power law, t1/q,
with exponent q = 1.23 ± 0.05 for epoxy and 1.33 ± 0.18 for
15 the nanocomposite. The indicated variability is associated
with the response measured at different points on a given
10 Neat Epoxy sample. The discrepancy between the values of q measured
SWNT / Epoxy 0.1 wt% at the macroscopic and nanoscale is attributed to the fact that
MWNT / Epoxy 0.1 wt%
5 the indentation creep tests can only last for a relatively short
GPL / Epoxy 0.1 wt%
time (1000 s).
0 The indentation displacement, d(t), obtained with a flat
0 15000 30000 45000 60000 75000 punch can be related to the creep compliance of the viscoe-
Time (sec) lastic material, J(t), via the relation [Eq. (2)]:[25]
Figure 6. Creep strain versus time for neat epoxy, epoxy–0.1 wt% GPLs,
4a
epoxy–SWNT, and epoxy–MWNT at a stress level of 20 MPa and 55 °C. J (t) = d(t) (2)
(1 − ν)P0

GPL inclusions is also a factor which may contribute to the where a, ν, and P0 are the contact radius, Poisson’s ratio, and
slowing down of creep in this system. the indentation load, respectively. Hence, this nanoscale test
allows identification of a material property which is usually
accessible only in macroscopic uniaxial tests. Due to this
2.4. Nanoscale Creep Response equivalence, we may interpret the power law fit to J(t) in the
same way as discussed in conjunction with the macroscopic
The macroscopic creep behavior is compared next with the local, test, that is, this indicates that small strain deformation (incip-
nanoscale creep response. This is determined using nanoinden- ient creep) is controlled by hierarchical processes without a
tation. The indenter is brought into contact with the surface and single, dominant relaxation time.
the load is increased at a constant load rate up to 2 mN. The The variability is more pronounced in the nanocomposite,
load is then held constant for 1000 s and the penetration of the as expected; however, the difference in these fluctuations
probe is monitored. The creep time and creep displacement are between the composite and unfilled epoxy is not very large.
measured relative to the beginning of the hold period. Multiple This is due to the fact that the flat punch diameter (50 μm) is
indentations are performed in each material, in arrays of 3 × 3 more than one order of magnitude larger than the inclusion
indentation points with 200 μm distance between them. size (see Figure 2).
Figure 7a shows the indentation displacement versus creep It is interesting to note that significant variability is
time for pristine epoxy and the 0.1 wt% GPL nanocomposite observed in pristine epoxy when probed on this length scale.
obtained using a flat punch (50 μm in diameter). Each curve Generally, one considers epoxy to be homogeneous down to

(a) log(t) (b)

100 1000
300 250
Neat Epoxy
GPL/Epoxy 0.1%
log(d)

250 100
200
Creep Displacement, d (nm)
Creep Displacement, d (nm)

200
150

150
100
100

50
50 Neat Epoxy
GPL/Epoxy 0.1%

0 0
0 200 400 600 800 1000 0 200 400 600 800 1000
Time (sec) Time (sec)

Figure 7. Nanoindentation creep data obtained with a) a 50-μm-diameter flat punch, and b) a Berkovich tip. The creep displacement versus time
curves obtained with the flat punch can be approximated with a power law (inset in (a)).

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Control of Epoxy Creep Using Graphene
length scales of a few tens of nanometers, where the effect of
the underlying molecular network structure should become
visible. Studies of material homogeneity have been con-
ducted using transmission electron microscopy (TEM) and
swelling experiments.[26] Density fluctuations were observed
in TEM,[26] but later those were discarded as artifacts. We
did not perform TEM studies of the pristine material, but the
present probing indicates that the mechanical behavior is not
uniform throughout the sample.
Figure 7b shows similar indentation data obtained with
the Berkovich indenter. The trends are similar, but the dif-
ference between the pristine and filled materials is more pro-
nounced. The distinct response obtained with the Berkovich
tip is due to the tip geometry, which mandates that the
volume of material probed increases continuously during
indentation, and to the fact that this tip is much smaller than
the flat punch. It is interesting to observe that in all indenta-
tion experiments, with the flat punch and with the Berkovich
tip, the initial creep response of the composite and the pris-
tine epoxy are identical.
3. Conclusion
A set of epoxy-based nanocomposites with 0.1, 0.3, and
0.5 wt% GPLs was studied in this work. When tested for
creep, the nanocomposite with 0.1 wt% GPLs creeps less
than all other materials, including the neat epoxy. The differ-
ence is small at small stress levels and room temperature, but
increases with increasing stress and temperature. An order of
magnitude difference between the creep rates of neat epoxy
and 0.1 wt% GPLs is observed at 55 °C and 20 MPa. The
creep strain versus time curves can be fitted with a power
law function with exponents larger than 1. This indicates that
hierarchical deformation processes control creep deforma-
tion. Furthermore, the increase of the difference between
the neat polymer response and that of the nanocomposites
with increasing temperature and, to a smaller extent with
increasing stress, indicates that thermally activated processes
which are active in neat epoxy are inhibited by the presence
of GPLs. The creep of the epoxy–GPL system was compared
with that of epoxy–SWNT and epoxy–MWNT and it was
concluded that epoxy–CNT systems creep at the same rate as
neat epoxy at elevated temperatures. The epoxy–GPL creeps
significantly less, which is interpreted as being a consequence
of the stronger bond between GPLs and the epoxy.
4. Experimental Section
GPL Preparation: GPLs were produced by the thermal reduc-
tion of graphite oxide. In this method, graphite oxide was first
prepared from natural graphite flakes by oxidation in a solu-
tion of nitric acid (68%), sulfuric acid (95–98%), and potassium
chlorate (99.5%) for 96 h. For thermal exfoliation, graphite oxide
(≈200 mg) was placed in a quartz tube (inner diameter: 200 mm,
length: 1 m). The tube was sealed at one end with an inlet and
outlet for argon flow and the other end was closed by a rubber
stopper. The graphite oxide was flushed with argon for ≈10 min
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and the tube was placed in a tube furnace (Thermolyne 79300,
Thermo Fisher Scientific Inc., USA) immediately. The furnace was
preheated to 1050 °C and the tube was held in the furnace for
40 s. The high heating rate of more than 2000 °C min−1 leads to
the exfoliation of graphite oxide to GPLs, as demonstrated in Ref-
erences [12,15]. The GPLs obtained by this method had residual
hydroxyl groups on the surface, which helped their dispersion in
polar solvents.[27–30]
Nanocomposite Sample Preparation and Processing: A ther-
mosetting bisphenol A blend epoxy resin (Epoxy 2000) and a
curing agent (2120 Epoxy Hardener), both from Fibreglast, USA,
were used for preparing the nanocomposites. To disperse the
graphene fillers in the epoxy resin the following procedure was fol-
lowed.[16,31] A suitable amount of GPLs was dispersed in acetone,
which is recognized as a polar solvent (100 mL acetone per each
0.1 g GPLs), using an ultrasonic probe sonicator (Sonics Vibracell
VC 750, Sonics and Materials Inc., USA) at high amplitude for 1 h.
The epoxy resin was added to the suspension of GPLs/acetone
and the ultrasonication procedure was repeated for one more
hour. After this, acetone was removed from the mixture of epoxy
resin and GPLs by heating the mixture while stirring using a Teflon-
coated magnetic bar on a magnetic stir plate for 3.5 h at 70 °C. The
mixture was then placed in an oven for 8 h at 70 °C to insure that
all the solvent had been removed. Cooling was performed before
adding the curing agent to avoid any curing at higher than ambient
and uncontrolled temperature. The hardener was then added and
mixing was performed using a high-speed shear mixer (ARE-250,
Thinky, Japan) at 2000 rpm for 4 min. The mixture was degassed
in a vacuum chamber for ≈20 min and poured into silicone molds.
The resulting samples were cured in the mold under 90 psi pres-
sure, at room temperature for 24 h. This was followed by 4 h of
post-curing at 90 °C.
Herein, we consider pure epoxy and epoxy–GPL nanocompos-
ites with 0.1, 0.3, and 0.5 wt% GPLs. Unfilled epoxy samples were
prepared for the purpose of these tests as described above, that is,
by using the same procedure as with the nanocomposite samples.
SWNTs (diameter ≈1–2 nm, length ≈1–3 μm) and MWNTs
(diameter ≈10–20 nm, length ≈10–30 μm) were purchased from
Nanostructured & Amorphous Materials Inc. Composites of epoxy–
0.1 wt% SWNTs and epoxy–0.1 wt% MWNTs were produced by
using the method described for epoxy–GPL.
Mechanical Creep Testing: Macroscopic tensile creep tests
were conducted in load control using an MTS-858 (MTS Systems
Corp., MN, USA) and dog-bone tensile test samples with gauge
length 25 mm and thickness 4 mm. The strain was measured using
an extensometer (MTS 632.26E-20). In tests performed at elevated
temperature, an environmental chamber was used and the tem-
perature was controlled with ±1% accuracy.
Nanoscale Creep Testing: Nanoscale creep tests were per-
formed with a NanoTest nanoindenter (Micro Materials Ltd.,
Wrexham, UK) under load control. The load was increased at a
rate of 0.01 mN s−1 up to 2 mN and then held constant. Two
types of probes were used: a flat punch with diameter 50 μm
and a Berkovich diamond tip. The nanoindentation tests were
performed in a temperature-controlled chamber at 27 °C.
The samples used for the nanoscale testing were obtained
from the same batches as the samples used for macroscopic
experiments.
www.small-journal.com 1681

full papers
Supporting Information
Supporting Information is available from the Wiley Online Library
or from the author.
Acknowledgements
We gratefully acknowledge the support from the US National Sci-
ence Foundation through grant CMMI-0900188.
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Received: December 20, 2011
Published online: February 29, 2012
small 2012, 8, No. 11, 1676–1682