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IOP PUBLISHING NANOTECHNOLOGY
Nanotechnology 18 (2007) 185703 (5pp) doi:10.1088/0957-4484/18/18/185703

Creep mitigation in composites using

carbon nanotube additives
W Zhang1 , A Joshi2 , Z Wang1 , R S Kane2 and N Koratkar1,3
1
Department of Mechanical Aerospace and Nuclear Engineering, Rensselaer Polytechnic
Institute, 110 8th Street, Troy, NY 12180, USA
2
Department of Chemical and Biological Engineering, Rensselaer Polytechnic Institute,
110 8th Street, Troy, NY 12180, USA

E-mail: koratn@rpi.edu

Received 19 February 2007, in final form 14 March 2007

Published 5 April 2007
Online at stacks.iop.org/Nano/18/185703
Abstract
A major limitation of thermosetting epoxy based polymeric materials in
long-term structural applications is mechanical creep. Here it is demonstrated
that single-walled carbon nanotube additives in low weight fractions
(0.1–0.25%) are effective in limiting the load-induced re-orientation of epoxy
chains, resulting in a significant slowing of the creep response. Nanotube
additives could therefore be the key enabler for the long-term
higher-temperature application of polymeric structures which would
otherwise fail by excessive creep deformation.
(Some figures in this article are in colour only in the electronic version)

Over the past decade, carbon nanotube composites [1–7] have
been researched extensively for their thermal, mechanical,
electrical and optical properties. The mechanical proper-
ties that have been investigated include strength [8, 9], stiff-
ness [10, 11], buckling resistance [12], wear [13] and tough-
ness [14] as well as viscoelastic properties [15–19] such as
loss factor and loss modulus. However, as far as we are aware,
there are no reports in the literature on creep characterization
of carbon nanotube composite materials. Creep is the time-
dependent continued deformation of a structure under a persis-
tent load that is usually significantly lower than the material’s
yield stress. Materials with high creep resistance are critical
in long-term structural applications to ensure dimensional sta-
bility and load-carrying capability. In this paper a series of
creep characterization tests are performed for a carbon nan-
otube epoxy composite system, and a significant reduction in
creep is demonstrated with a relatively small weight fraction
(∼0.1%) of nanotube additives. To our knowledge, this is the
first reported demonstration of creep reduction in polymer sys-
tems by the use of carbon nanotube additives.
Thermosetting epoxy polymers were chosen for this study
since they are widely used in a variety of applications such as
paints, coatings, adhesives, industrial tooling and composites,
as well as in the semiconductor and electronics packaging
industries. Epoxies consist of long molecules that are cross-
linked and contain chains of atoms held together by covalent
3 Author to whom any correspondence should be addressed.
bonds. The chemical bonding is strong and directional along
the chains, but adjacent chains are bonded by weak Van der
Waals forces. Under persistent external loading, the molecular
chains are stretched and re-oriented to carry the load, resulting
in mechanical creep. The creep deformation is strongly
dependent on the stress level, the temperature and the micro-
structure of the materials. Some recent studies [20, 21] have
shown that the addition of nanoparticles into a polymer matrix
enhances its creep resistance at various stress and temperature
levels. In another study [22], the creep behaviour of
nanocomposites that incorporate layered silicate in the matrix
is investigated. A comprehensive review of carbon nanotube
epoxy composites, including stiffness and fracture toughness
characterization, is described in [27]. However, no systematic
study of the tensile creep behaviour of carbon nanotube filled
polymer composites is available in the literature. In the
following sections we describe the protocols used to fabricate
the nano-composite test coupons and the experiments that were
performed to characterize the creep behaviour of the nanotube–
epoxy composites.
The procedure used to disperse single-walled carbon nan-
otubes (SWNT) in the epoxy system is shown schematically
in figure 1(A) and described in the experimental section (ap-
pendix). The samples were tested using an MTS-858 servo-
hydraulic test system operating in constant-force mode. The
force is measured by the load cell of the MTS system and an in-
ternal feedback circuit is used to maintain constant stress in the

0957-4484/07/185703+05$30.00 1 © 2007 IOP Publishing Ltd Printed in the UK

Nanotechnology 18 (2007) 185703 W Zhang et al

A C

D
B

Figure 1. Creep characterization of nano-composite and pure epoxy samples. (A) Schematic showing the fabrication protocol used to disperse
the single-walled carbon nanotube additives into the epoxy matrix. The exact same fabrication steps were also repeated to prepare the baseline
epoxy samples without the nanotube additives. (B) Measured creep strain as a function of time. The room-temperature creep response of the
0.1 wt% nano-composite is significantly lower than the pure epoxy. After 50 h of continuous testing at 10 MPa stress, the nano-composite
shows a reduction of over 30% in the creep deformation. (C) Results for percentage reduction in creep strain for nano-composite compared to
pure epoxy sample after 50 h of testing at 10 MPa stress for different weight fractions of nanotube additives. The weight fractions for
minimum creep response lie in the 0.1–0.25% range. (D) Scanning electron microscopy characterization of microstructure of the 0.1 wt% (top
images) and 1 wt% (bottom images) samples. The 1 wt% nano-composite sample shows significantly larger agglomeration of the nanotube
additives.

sample. The time-dependent strain response of the sample is
measured using an extensometer (MTS 632.26E-20) attached
to the sample. First, a nano-composite sample with 0.1 wt% of
SWNT additives was tested at a constant stress of 10 MPa and
its creep response was compared to that of a pure epoxy sam-
ple. The results are shown in figure 1(B); the nano-composite
exhibits a significant reduction in creep strain compared to the
pure epoxy. After 50 h of continuous testing, the creep strain
for the nano-composite (∼0.9%) is over 30% lower than the
baseline epoxy material (∼1.3%). Next, samples with differ-
ent weight fractions (0%, 0.001%, 0.01%, 0.1%, 0.25% and
1%) were tested to study the effect of nanotube weight fraction
on the material creep response. Figure 1(C) shows the percent-
age reduction in creep strain for the nano-composite compared
to the baseline epoxy sample after 50 h of continuous load-
ing at a constant stress of 10 MPa. For a small weight frac-
tion of SWNT additives (e.g. 0.001 wt%), no noticeable reduc-
tion in creep strain over the pure epoxy is observed. When
the SWNT weight fraction is increased to 0.01%, a reduction
of about 13% in creep strain compared to the pure epoxy is
observed. On further increasing the SWNT weight fraction to
0.1%, the reduction in creep strain improves to 30%. The creep
performance improvement then plateaus with increasing nan-
otube weight fraction (e.g. for 0.25% SWNT weight fraction,
the creep reduction levels off at ∼27%). However, when the
SWNT weight fraction was raised to 1%, the creep strain after
50 h of testing showed ∼90% degradation (figure 1(C)) com-
pared to the pure epoxy. Therefore it appears that the desir-
able SWNT weight fraction for minimum creep response is in
the 0.1–0.25% range, with associated creep reduction of about
30% compared to the baseline. To investigate the reason for the
loss in creep performance for the 1 wt% SWNT sample, scan-
ning electron microscopy (SEM) characterization of the frac-
ture surface (figure 1(D)) of the nanotube–epoxy samples was
performed. The dispersion quality of SWNT in the 0.1 wt%
sample is quite uniform, as seen in the fracture surface image

2
Nanotechnology 18 (2007) 185703 W Zhang et al

A B

C D

Figure 2. Effect of applied stress and operating temperature on the creep response: (A) creep strain deformation for the 0.1 wt%
nano-composite and pure epoxy sample at an applied stress of 20 MPa and room temperature. (B) Corresponding results at an applied stress
of 30 MPa and room temperature. At the higher stress level the response of the 0.1 wt% nano-composite and pure epoxy samples are identical.
(C) Creep strain deformation for the 0.1 wt% nano-composite and pure epoxy sample at an operating temperature of 40 ◦ C. The applied stress
is 10 MPa for both samples. (D) Corresponding results at an operating temperature of 55 ◦ C. Temperature dramatically increases the creep
deformation of the baseline epoxy material but it does not significantly affect the ability of the nanotube additives to reduce the creep
response.

(top SEM images of figure 1(D)); similar results were also ob-
served for the 0.25 wt% SWNT–epoxy sample. In contrast,
for the 1 wt% SWNT–epoxy sample, there appears to be a sig-
nificant agglomeration of SWNT, as observed in the bottom
SEM images of figure 1(D). These agglomerations decrease
the number of nanotube–epoxy interfacial contacts and create
voids/defects in the material which could cause the creep rate
to increase, as observed in the experiments. Note that the static
Young’s modulus for all the samples was measured prior to the
creep tests, and there was no significant difference in Young’s
modulus between the samples with and without nanotube addi-
tives in the 0.001–0.25 wt% fraction range. However, the creep
modulus of the nano-composite showed significant difference
compared to the pure epoxy, as evidenced by the creep strain
data shown in figure 1.
Next, the effect of the material stress level on the creep
deformation response was investigated. For this test the
SWNT–epoxy nano-composite with 0.1 wt% of nanotube
additives was tested at three different stress levels (10, 20
and 30 MPa); the test results are shown in figures 1(B), 2(A)
and (B). At the relatively lower stress level of 10 MPa, the
creep strain reduction for the SWNT–composite after 50 h
is ∼30%. However, with an increase in stress, the creep-
resistant behaviour of the SWNT composite slowly diminishes.
At 20 MPa stress, the creep strain reduction for the SWNT
composite over the pure epoxy is only 17% (figure 2(A)). At
a relatively larger stress level of 30 MPa, there is virtually
no change (figure 2(B)) in the observed creep strain response
of the SWNT composite and the pristine epoxy material.
This result provides an important clue towards understanding
the underlying mechanism for creep reduction in our system.
The ability of the nanotube additives to reduce creep appears
to be strongly related to the nanotube matrix interfacial
bonding. At the low stress levels, this interfacial bonding
holds and the nanotube additives form an infiltrating network
of cross-linking elements that interconnect the epoxy chains,
thereby increasing their effective cross-linking density and
restricting the localized re-orientation and disentanglement
of epoxy chains under mechanical stress. At the higher
stress levels, the nanotube–polymer interfaces are prone to
failure [15–19, 23–26] and, as a consequence, the ability of

3
Nanotechnology 18 (2007) 185703
A composite (figure 2(C)) is 28% lower than the pristine epoxy,
B
Figure 3. Effect of filler geometry on the creep response. (A) Creep
strain deformation versus time for pure epoxy sample and epoxy
samples with 0.1 wt% of SWNT, MWNT and C60 additives. The
tests are performed at room temperature and the applied stress is
10 MPa. (B) Measured creep strain after 3 h of continuous testing for
the pure epoxy and nano-composite samples. For the same weight
fraction (0.1%), the SWNT additives offer significantly better creep
resistance compared to the MWNT and the C60 additives.
the nanotubes in providing a barrier for the polymer chain
movement is negated.
The effect of operating temperature on the creep behaviour
of the nano-composite was also investigated. For this test,
the 0.1 wt% SWNT–epoxy composite and the pure epoxy
sample were tested at three different operating temperatures
(23, 40 and 55 ◦ C) and at a constant stress level of 10 MPa.
Note that addition of as-received (i.e. non-functionalized)
nanotubes in low weight fractions (<0.5%) does not change
the glass transition temperature of the epoxy significantly,
as shown in several studies [28–30]. The test results after
50 h of testing at 40 and 55 ◦ C are shown in figures 2(C)
and (D); corresponding results for the room-temperature case
(23 ◦ C) were shown previously in figure 1(B). The results
indicate that the creep rate of the baseline epoxy increases
significantly at the elevated temperatures; for example, the
creep strain of the pure epoxy sample after 50 h of testing
at 10 MPa stress is ∼1.3% at room temperature, and this
increases to ∼4.75% at 40 ◦ C and ∼17.5% at 55 ◦ C. This
result is expected, since increased polymer chain mobility at
the elevated temperatures will facilitate the re-orientation and
disentanglement of the polymer chains, causing the creep to
increase. However, the ability of the SWNT additives to
reduce creep is not significantly diminished at the elevated
temperatures. For example, at 40 ◦ C, the creep for the SWNT-
4
W Zhang et al
and a similar reduction can also be observed for the 55 ◦ C
test case (figure 2(D)). This indicates that the nanotube–matrix
interfaces are not weakened significantly by increasing the
temperature and, as a consequence, the ability of the nanotube
cross-linking elements to limit epoxy chain re-orientation is
not adversely affected by the temperature, which makes such
systems attractive for high-temperature structural applications.
The bump observed in figure 2(C) after ∼104 s of testing could
be caused by a temperature-dependent morphological change
or relaxation of the epoxy, which causes a sudden change in
the creep compliance. However, since this effect is felt equally
for both the pure epoxy sample and the nano-composite, the
comparison between the two is still valid.
Tests were also performed to compare the performance
of multi-walled carbon nanotubes (MWNT) and C60 fullerene
additives with that of the single-walled nanotube (SWNT)
results shown previously. In all cases, the exact same
fabrication protocols (figure 1(A)) were used and the weight
fraction of the additives was held constant at 0.1% for all the
samples. Figure 3(A) shows the creep strain time history at
an applied stress of 10 MPa, while figure 3(B) compares the
measured creep strain for the different samples after 3 h of
testing. The creep testing was limited to 3 h in this case, since
this time period is sufficient to compare the material creep
response of the various nano-composite samples. Clearly, the
SWNT additives outperform both the C60 and the MWNT
additives. For the MWNT additives, only the outer shells are
in contact with the epoxy chains while the inner concentric
cylinders play no role in increasing the effective cross-linking
density within the nano-composite. Therefore, for the same
weight fraction of additives we expect that the SWNT fillers
will offer significantly higher resistance to the re-orientation of
epoxy chains than the MWNT fillers, as was confirmed by our
results. Our results also indicate that, for 0.1% filler weight
fraction, SWNT additives provide a significant improvement
(figures 3(A) and (B)) in creep resistance compared to C60
additives. This effect may be related to the filler geometry;
SWNT have significantly higher aspect ratios compared with
spherical fullerene additives.
To summarize, we have shown that the addition of well-
dispersed single-walled carbon nanotube additives into an
epoxy host matrix significantly reduces the creep deformation;
a reduction of up to 30% in the creep strain after only 50 h
of testing is demonstrated. Increasing the weight fraction
of nanotubes in the 0–0.1 wt% range improves the creep
response; however, for larger weight fraction (∼1%) the
creep performance deteriorates rapidly due to poor-quality
dispersion of the nanotubes in the epoxy resin. With an
increase in the applied stress, the creep resistance of the
SWNT additives is significantly reduced. We expect that
this is due to the failure of the polymer–SWNT interface at
the high stress levels. However, increasing the temperature
does not significantly impact the ability of the nanotube
additives to reduce the creep response of the nano-composite.
SWNT additives also showed markedly higher creep strain
reduction compared to both MWNT and fullerene additives. In
conclusion, carbon nanotube-reinforced polymer composites
might play an important role in enabling the long-term higher-
temperature application of polymeric structures which would
otherwise fail through excessive creep deformation.
Nanotechnology 18 (2007) 185703
Acknowledgment
This work was funded by the US National Science Foundation
through the Faculty Early Career Development Award (CMS-
0347604) to Nikhil Koratkar.
Appendix. Experimental details
Figure 1(A) shows the procedure used to disperse the single-
walled carbon nanotube (SWNT) additives in the epoxy
system. The SWNT are purchased from CNI with a purity of
over 95 wt%, length of 5–30 µm and diameter of 1–2 nm. The
epoxy system is a two-part room-temperature-cured system
with a glass transition temperature of 90 ◦ C. The required
amount of SWNT (from 0.001 to 1.0 wt%) was first weighed
and mixed with 300 mg of the dispersion surfactant BYK-9076
obtained from BYK Chemie Company. Next, 2.0 ml of acetone
was added to the mixture; the mixture was stirred at 200 rpm
for 15 min and was then placed into a room-temperature batch
sonicator for 30 min. The mixture was added to epoxy (Epoxy
2000 from Fibreglast Inc.), stirred manually for 10 min and
then placed in the batch sonicator for a further 10 min. De-
gassing was then performed by heating the sample in a vacuum
oven at 50 ◦ C for 10 h; this step was essential to evaporate and
remove the acetone in the mixture. The sample was then cooled
and 75 mg (0.5 wt%) of an air-releasing agent (BYK A-500)
was added to the mixture. The mixture was stirred manually for
10 min and then de-gassed under vacuum at room temperature.
Next, low-viscosity curing agent 2120 (from Fibreglast Inc.)
was added and blended into the epoxy using a high-speed
mixer (Model ARE-250 from Thinky Corporation) at 2500 rpm
for 4 min. The mixture was then placed in vacuum again for a
final de-gassing stage for 15 min and was poured slowly into
silicone rubber molds. The epoxy composite was cured at room
temperature and a pressure of 90 psi for 24 h, followed by 2 h
of post-cure at 80 ◦ C. The high-pressure curing was necessary
to prevent the formation of micro-bubbles in the composite
samples. Once the samples were cured, they were removed
from the mold and then polished using a 600-grid sandpaper
for a smooth surface finish.
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