Current Opinion in Solid State and Materials Science 8 (2004) 3137

Carbon nanotube polymer composites

1
R. Andrews *, M.C. Weisenberger
Center for Applied Energy Research, University of Kentucky, 2540 Research Park Drive, Lexington, KY 40511-8410 USA
Received 7 October 2003; accepted 29 October 2003

Abstract
The state of research into carbon nanotube/polymermatrix composites for mechanical reinforcement is critically reviewed with
emphasis on recent advances in CNT composite toughness. Particular interest is also given to interfacial bonding of carbon nano-
tubes to polymer matrices as it applies to stress transfer from the matrix to the CNT. Potential topics of oncoming focus are
highlighted.
2003 Elsevier Ltd. All rights reserved.

1. Introduction However, after nearly a decade of research, their

Since the documented discovery of carbon nanotubes
(CNTs) in 1991 by Iijima [1] and the realization of their
unique physical properties, including mechanical, ther-
mal, and electrical, many investigators have endeavored
to fabricate advanced CNT composite materials that
exhibit one or more of these properties [2,*3,*4]. For
example, as conductive ller in polymers, CNTs are quite
eective compared to traditional carbon black micro-
particles, primarily due to their large aspect ratios [5].
The electrical percolation threshold was recently re-
ported at 0.0025 wt.% CNTs and conductivity at 2 S/m at
1.0 wt.% CNTs in epoxy matrices [6]. Similarly, CNTs
possess one of the highest thermal conductivities known
[*7], which suggests their use in composites for thermal
management [2]. The main focus of this paper, however,
will be on the use of CNTs as discontinuous reinforce-
ment for polymer matrices. The CNT can be thought of
as the ultimate carbon ber with break strengths re-
ported as high as 200 GPa, and elastic moduli in the 1
TPa range [8,**9]. This, coupled with approximately 500
times more surface area per gram (based on equivalent
volume fraction of typical carbon ber) and aspect ratios
of around 103 , has spurred a great deal of interest in
using CNTs as a reinforcing phase for polymer matrices.
*
Corresponding author. Tel.: +1-606-257-0305/859-257-0267; fax:
+1-606-257-0220/859-257-0220.
E-mail addresses: andrews@caer.uky.edu (R. Andrews), matt@
caer.uky.edu (M.C. Weisenberger).
1
Tel.: +1-859-257-0322; fax: +1-859-257-0220.
1359-0286/$ - see front matter 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.cossms.2003.10.006
potential as reinforcement for polymers has not been
fully realized; the mechanical properties of derived
composites have fallen short of predicted values. Yet
given the magnitude of the CNTs mechanical proper-
ties, signicant improvement on current composites
should be possible provided means to harness the CNTs
unique attributes exhibited at the nanoscale can be
transferred to the macroscale. This essentially denes
the fundamental challenge for applied CNT/polymer
composites research. How does one eectively manipu-
late nanoscale building blocks to assemble useful mac-
roscale materials? Some have suggested a bottom-up
approach possibly utilizing non-continuum eects at the
CNT-polymer interface [*10,*11,*12], while macroscale
composite synthesis typically utilizes more traditional
continuum ideas. A better understanding of the rela-
tionships between processing, interfacial optimization,
and composite properties is a major goal of this area of
research, which may lead to optimal reinforcement of
polymer matrices with CNTs.
The microscale analogue to the current nanocom-
posite material is a carbon ber/epoxy laminate: essen-
tially the same materials in dimensions 1000 times
larger. A 20 nm thick polymer/aligned CNT nano-
lamina may in fact be desirable, but currently extremely
dicult to scale-up or make reproducibly. Lacking di-
rect manipulation, when used as reinforcement in
polymers, CNTs are typically rst randomly dispersed in
a solvent or polymer uid/melt by sonication or shear
mixing followed by further processing to create the
composite. It should be noted that the energy input to
32 R. Andrews, M.C. Weisenberger / Current Opinion in Solid State and Materials Science 8 (2004) 3137
Abbreviations
CNT carbon nanotube
MWNT multiwall carbon nanotube
SWNT singlewall carbon nanotube
CNF carbon nanober
ISS interfacial shear strength
TEM transmission electron microscope
SEM scanning electron microscope
AFM atomic force microscope
XPS X-ray photoelectron spectroscopy
disperse the CNTs tends to break them into shorter
segments [2,*13] decreasing their aspect ratio in the nal
composite while simultaneously increasing their disper-
sibility. However, insucient dispersion is often cited as
a process limitation [14] and the key diminishing factor
[*11,*13,15] on the composites mechanical properties.
Eorts to improve CNT dispersion include: the use of
surfactants [**16], and the oxidation or chemical func-
tionalization of the CNT surface [17,18].
2. CNT functionalization
Recently, functionalization has been achieved via
exposure of vapor grown Pyrografe III carbon nano-
bers (Applied Sciences Inc.) to a CO2 /Ar plasma opti-
mized with respect to time, pressure, power, and gas
concentration resulting in 14.5 at.% oxygen in the rst 10
atomic layers [*19]. The presence of functionalities such
as hydroxyl, carbonyl, and carboxyl groups were de-
tected by XPS. In this case, surface defects in the curved
graphene planes of the nanobers may have increased
reactivity promoting the formation of the functionalities.
Nitric acid treatment has also been reported to success-
fully oxidize the surface of multiwall carbon nanotubes
(MWNTs) as detected using diuse reection infrared
Fourier-transform (DRIFT) spectroscopy [18]. Func-
tionalization of the CNT surface cannot only lead to
increased dispersibility of the CNTs in various organic
solvents and polymers [*4,*20], but also to increase the
strength of the interface between the CNT and the
polymer matrix [*20]. However, chemical functionaliza-
tion may disrupt the bonding of the graphene sheet, and
thereby reduce the mechanical properties of the func-
tionalized CNT in the nal composite.
3. CNT/polymer interfaces
Increasing attention is being focused on the CNT
surface, namely the interface between the CNT and
surrounding polymer matrix. From micro-mechanics, it
TGA thermal gravimetric analysis
PEB polyethylenebutene
PAN polyacrylonitrile
PS polystyrene
PMMA polymethylmethacrylate
PVA polyvinylalcohol
UHMWPE ultra-high molecular weight polyethylene
PMEMA methylethyl methacrylate copolymer
is through shear stress build-up at this interface that
stress is transferred from the matrix to the CNTs.
Numerous researchers have attributed lower-than-pre-
dicted CNT-polymer composite properties to a lack of
interfacial bonding [*4,15,21]. If one considers the sur-
face of a CNT, essentially an exposed graphene sheet, it
is not surprising that interfacial traction is a concern. It
is the weak inter-planar interaction of graphite that
provides its solid lubricant quality, and resistance to
matrix adhesion. This is exaggerated by the chemically
inert nature of graphene structures. A June 2002 publi-
cation on CNT composites noted In depth study on the
stress transfer mechanism of the nanotube composites
with dierent chemical and geometrical properties, ma-
trix environments and loading conditions are essential
. . . [8]. Since then, some interesting published results
have described progress on addressing this issue. The
pull-out force necessary to remove a given length of an
individual MWNT embedded in polyethylenebutene
using an AFM was measured [**22]. The calculated
average interfacial shear strength using a Kelly-Tyson
approach of 47 MPa (typical values for carbon ber/
epoxy are in the 3080 MPa range depending on ber
modulus and surface treatment [23]) was suciently
high to suggest that covalent bonding between defects in
the outer shell of the MWNT and the polymer was
occurring. It also suggested that the polymer chains
close to the interface behaved dierently than the bulk, a
logical result when considering the CNT outer diameter
is of similar magnitude to the radius of gyration for the
polymer. In a report corroborating an interfacial region
of non-bulk polymer, a sheathing layer of polycar-
bonate on pulled out MWNTs was imaged, which gave
further evidence of signicant interfacial interaction
between MWNTs and a polymer [**44]. It was also
found that chemical functionalization of the MWNTs
augmented the diameter of the polymer sheath sug-
gesting chemical augmentation of interfacial bonding.
Acid oxidation of MWNTs was again reported to attach
carboxylic groups on the surface, which were then re-
acted with epoxide-terminated molecules up to12 wt.%
by TGA [*20]. These types of functionalized tubes could
 R. Andrews, M.C. Weisenberger / Current Opinion in Solid State and Materials Science 8 (2004) 3137
enhance reinforcement of epoxy resins. Carboxylated
tubes have also been reported to augment the cure rate
of epoxy resins at lower temperatures [18]. Unfortu-
nately, direct and indirect measurement of polymer
CNT interfacial shear strength suggesting good bonding
exists conict with other reports which often cite
clean pull-out of CNTs and poor interfacial bonding
[*4,15,*24]. The magnitude of CNT strength (>10 times
that of typical carbon ber) may preclude embedded
CNT tensile failure in large numbers resulting in the
dominant failure mode to be CNT pull-out. Order of
magnitude increases in interfacial shear strength may be
required for the most ecient strengthening of polymers
with CNTs. Optimizing the polymerCNT interface for
nanoscale mechanical reinforcement remains unclear,
but the evidence available indicates that chemical means
can be eective, and this is likely to be a major focus in
the near term.
Theoretical treatments of CNT pull-out were recently
reported [*24,25]. Including one in which a 10; 10 sin-
glewall carbon nanotube (SWNT) pulled out from a
polyethylene matrix was modeled via molecular dynam-
ics simulations, and quite a low eective viscosity of 0.2
cP was found for interfacial sliding [*24]. A force of
approximately 0.1 nN was required for pull-out to initi-
ate for a single tube.
4. Embedded CNT strain characterization by micro-
Raman spectroscopy
Earlier publications have associated Raman peak
shifting up (to higher wavenumbers) or down (to lower
wavenumbers) from the peak near 2700 cm1 with
compressive and tensile strain in the CNT respectively
[26,27]. A recent report monitored tensile load transfer
to MWNTs in a UHMWPE matrix by the Raman peak
shifting at 2691 cm1 [**28], and found four regions of
strain behavior outlined in Table 1. Another report [*29]
related the Raman peak shift at 1594 cm1 to the axial
strain in SWNTs embedded in epoxy by:
Dx1594 cm1
c1  ms ez 1
x0
Table 1
Raman shift (2691 cm1 ) vs. percent tensile strain in a MWNT/UHMWPE composite
Region %e Shift
1 01 Clear shift down
2 110 Much less apparent or intense shift down
3 1015 Somewhat more apparent shift down
4 >15 A shift up
Four regions of behavior were found for D* Raman band shifting as a function of applied tensile strain to an ultra-high molecular weight
polyethylene/MWNT composite lm. Data and interpretation from [**28].
33
where the Gruneisen parameter c 1:24 and the Pois-
son ratio ms 0:28.
5. CNT reinforcement of polymers
Signicant toughening of polymer matrices through
the incorporation of CNTs has been reported [*4,**16,
**28]. A loading of 1 wt.% MWNTs, randomly distrib-
uted in an ultra-high molecular weight polyethylene lm,
was reported to increase the strain energy density by
150% and increase the ductility by 140%. Secondary
crystallites, which nucleated from the MWNTs, were
attributed a higher mobility and hence the increase in
strain energy [**28]. A similar eect was found in aligned
MWNT/polyacrylonitrile bers containing 1.8 vol.%
MWNTs with an approximately 80% increase in energy
to yield and energy to break [*4]. A process of spinning
60 wt.% SWNT/polyvinylalcohol bers with pre-drawn
energy absorbing capacity nearly 3.5 times spider silk
(165 J/g) was reported [**16]. Slippage between SWNT
bundles was suggested as the mechanism responsible for
the enhancement in the toughness. The addition of
1 wt.% MWNTs to isotactic polypropylene (iPP) was
shown to aect crystal nucleation from dierential
scanning calorimetry and X-ray diraction measure-
ments [*30]. Compared with neat iPP, there was an in-
crease in crystallization rate for the composite material
with evidence of brillar crystal growth rather than
spherulite growth (Fig. 1). These modications in the
morphology of a polymer matrix combined with the
energy required for CNT debonding and pull-out suggest
CNTs may augment the energy absorption or toughness
characteristics of the composite.
A twofold increase in the tensiontension fatigue
strength for an aligned SWNT/epoxy composite was
found in comparison to typical carbon ber/epoxy
composites (Fig. 2) [*31]. Embedded CNTs may eec-
tively prolong the formation of and/or bridge micro-
cracking/crazing that can propagate and lead to fatigue
failure. CNT reinforced polymer composites are seen as
a potentially fruitful area for new, tougher or fatigue-
resistant materials. Further investigations into the
toughness and fatigue properties of these composites are
Interpretation
Tensile loading of MWNTs Elastic response
Interfacial stick and slip yielding matrix
Tensile loading of MWNTs; MWNT knots preventing further
PE chain stretching
Compressive loading of MWNTsElastic recovery from local
matrix failure
34 R. Andrews, M.C. Weisenberger / Current Opinion in Solid State and Materials Science 8 (2004) 3137
Fig. 1. SEM images crystalline morphology of isotactic polypropyl-
ene. The dierence in crystalline morphology for (a) neat isotactic
polypropylene (iPP), and (b) iPP/1 wt.% MWNT composite is shown
in these SEM images. Fibrillar morphology is observed for the com-
posite while the neat iPP has a spherullite morphology [*30, p. 525,
526]. Nucleation Ability of Multiwall Carbon Nanotubes in Polypro-
pylene Composites, Assouline E, Lustiger A, Barber AH, Cooper CA,
Klein E, Wachtel E, Wagner HD, Copyright (2003) Wiley Periodicals
Inc., Reprinted by permission of John Wiley and Sons Inc.
Fig. 2. SWNT fracture surface bridging. SWNT ropes are observed
bridging a fatigue fracture surface in an epoxy matrix. Twofold in-
creases in tensiontension fatigue strength over typical carbon ber/
epoxy composites were observed [*31, p. 2178]. Reprinted form Car-
bon 41, Ren Y, Feng L, Cheng HM, Liao K, TensionTension Fatigue
Behavior of Unidirectional Single-Walled Carbon Nanotube Rein-
forced Epoxy Composite, pg 217779, Copyright (2003) with permis-
sion from Elsevier.
needed to understand the reinforcing mechanism at
work.
Tensile strength and modulus enhancements are
continually reported [3234]; very little of the data
achieve reinforcement predicted by a rule-of-mixtures
approach especially at loadings beyond 10 vol.%
[*4,17,*35] (For aligned, discontinuous ber reinforce-
ment, the HalpinTsai model [36] is often used, which
approaches the rule of mixtures for large Ef =Em or l=d).
For ENT =Em 100 and l=d 500, the HalpinTsai ap-
proach is 95% that of the rule of mixtures for aligned
composites. An eective l=d of the CNT, deduced from
these sort of comparisons, can shed light on stress
transfer to the CNTs [37]. Some have oered new
explanations and factors contributing to understanding
this discrepancy between experimental and predicted
results. In a two paper series using nite element analysis
and micro-mechanical methods, it was proposed that
observed curvature of embedded CNTs or waviness
signicantly reduced their reinforcement capabilities (by
factors from 50 to 200) compared to straight CNTs
[*12,*35]. It was also noted that other indistinguishable
factors contribute to the low values measured in ex-
perimental data: including weak interfacial bonding,
insucient dispersion, and degradation of the CNTs due
to processing [*35]. At very low strains, it was suggested
that the eect of poor interfacial shear strength should
not aect the composites modulus, implying a mea-
surable elastic response below the strain detrimental to
the CNT interface [*10]. It was also suggested that the
diameter distribution of embedded MWNTs would have
Fig. 3. Eect of MWNT outer diameter on aligned MWNT composite
tensile modulus. The tensile modulus of a MWNT composite is
modeled as a function of embedded MWNT outer diameters for var-
ious MWNT lengths and volume fractions. The strong dependency on
MWNT outer diameter results from using an eective MWNT mod-
ulus that accounts for only the outer shell carrying any of the tensile
load [*10, p. 581]. Thostenson ET, Chow TW, On the Elastic Prop-
erties of Carbon Nanotube-Based Composites: Modelling and Char-
acterization, Copyright (2003) IOP publishing limited, Reprinted with
permission.
 R. Andrews, M.C. Weisenberger / Current Opinion in Solid State and Materials Science 8 (2004) 3137 35

Table 2
Selected mechanical properties of CNT/polymer composites
CNT Matrix Conc. (%) Loading Modulus Yield Strength Tough- Max. strain ISS Ref.
stress ness (Mpa)
MWNT None 100 Tensilea 910 GPa 150 GPa [**9]
MWNT None 100 Tensileb 270950 GPa 11200 GPa 12% [39]
MWNT PAN 1.8 vol.% Tensile +36% +46% +31% +80% [*4]
SWNT PVA 60 wt.% Tensile 80 GPa 1.8 GPa 570 J/g 100% [**16]
MWNT PS 5 wt.% DMA +49% [17]
(25 C) (aligned) + 10%
(random)
MWNT PEBc AFMc 47 [**22]
MPa
MWNT UHMWPE 1 wt.% Tensile +25% +48% +25% +150% +60 to +140% [**28]
SWNT PAN 4 wt.% AFMd  +100% [14]
CNF PMMA 5 wt.% Tensile +50% +200%e )37.5% [34]
MWNT PMEMA 1 wt.% DMA +200% [33]
(+/)) indicates an enhancement/diminishment from the neat matrix. Recently reported mechanical property enhancements for various CNT/polymer
composites are presented with additional information on the method used to collect the data. Experimentally measured values of MWNT mechanical
properties are also presented.
a
In situ TEM tensile testing of individual MWNTs via a micro-fabricated device.
b
In situ SEM tensile testing of individual MWNTs via dual AFM tips.
c
In situ AFM pull-out of individual MWNT from PEB lm.
d
Moduli measured using an AFM nanoindentation technique.
e
Compressive strength via loop test.

a very strong eect on the composites modulus (Fig. 3)
[*10]. In the case of MWNTs, an eective modulus was
deduced assuming that the outer shell carries essentially
all the load [26] such that its modulus, ENT , was reduced
in proportion to the ratio of the area of the annular
outer shell thickness to the total cross-sectional area. A
MWNT diameter distribution was therefore essential for
accurate prediction of the composites modulus [*10].
In another study, increased inter-tube friction of
SWNT bundles by the introduction of twist, which
served to atten the SWNTs, was predicted by molec-
ular mechanics modeling to have increased the bundles
load carrying capacity [38]. Some recent mechanical
property results for CNT/polymer composites are sum-
marized in Table 2.
experimentally measured values up to 150 GPa for
MWNTs [**9]. These high strengths imply break strains
of approximately 10% with even higher break strains
reported in the literature [8,41,42]. Recent reports indi-
cate that tensile failure of MWNTs that carry all of the
load within the outer shell is initiated by the formation
of a StoneWales defect in which 2 CC bonds are
broken and 2 new CC bonds are formed such that a
pair of pentagons and a pair of heptagons results (Fig.
4) [41,42]. Increasing numbers of these dislocations leads
to necking and ultimately, failure of the CNT [42].
Often, however, in a polymer/CNT composite a reduc-
tion in strength is observed suggesting that the CNTs

6. A look forward

The ultimate goal remains macroscale CNT/polymer

composites that are optimally reinforced. Increases in
composite moduli are almost always observed even for
very low loadings of CNTs. It should be feasible to in-
crease the modulus of a polymer/CNT composite up to
and beyond that achievable with high modulus graphite
ber. Alignment of CNTs has been achieved in poly-
meric matrices most often by means of shear or elon-
gational ow [*4,14,**16,17,**28], and recently by a
magnetic eld [40] resulting in lm and ber geometries. Fig. 4. A StoneWales defect. A representation of a StoneWales
defect in the graphitic structure of a CNT under tensile stress shows the
However, strengthening of polymer/CNT composites is
rearrangement of the hexagonal graphitic structure into two pairs of
less commonly reported. Due to the small number of heptagons and pentagons [42, p. 115401-1]. Wei C, Cho K, Srivistava
defects per unit length, the most impressive mechanical D, Physical Review B 67, 115407, 2003, Copyright (2003) by the
property of the CNT is its tensile strength with recent American Physical Society, Reprinted with permission.
36 R. Andrews, M.C. Weisenberger / Current Opinion in Solid State and Materials Science 8 (2004) 3137
may promote crystalline defects in the matrix or, con-
sidering their size, act as defects themselves. This sug-
gests a critical volume fraction of CNTs is required for
hindering matrix strain allowing strengthening to occur
as typically observed in composites. Classically this re-
sults from the composites failure criterion being ber
rupture at the ber break strain, which is typically
smaller than the matrix break strain. It remains to be
seen whether or not a 10% elastic tensile strain can be
transferred to CNTs embedded in a polymer, fully
exploiting their load carrying capacity, and at this
strain, most polymeric matrices will have begun to ow
plastically. Furthermore, many authors report higher
loadings of CNTs in a composite do not perform as well
as lower loadings [*4,34] suggesting an increase in voids
or other defects as the loading of CNTs increases, likely
due to the diculty of homogeneously dispersing con-
centrated CNT/polymer melts or solutions. All this begs
the question as to what is the failure criterion applicable
to CNT/polymer composites, a question complicated by
CNT misalignment, debonding and pull-out, end-eects
and dispersion, to name a few. Strengthening a polymer
matrix with CNTs may best be realized in an aligned
concentrated CNT nano-lamina, where all polymer is
near a CNT interface [*43], provided the interphase
polymer does indeed have higher mechanical properties
than the bulk. In situ TEM tensile testing of these nano-
lamina could provide insight into this issue. Lay-up of
nano-lamina, or perhaps self-assembly could lead to
optimally reinforced macroscale CNT/polymer com-
posites.
Acknowledgement
The authors wish to acknowledge nancial support
from the NSF MRSEC Grant DMR-9809686.
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