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COMPOSITES
SCIENCE AND
TECHNOLOGY
Composites Science and Technology 68 (2008) 329–331
www.elsevier.com/locate/compscitech

Short communication

On nanocomposite toughness
Malte H.G. Wichmann a, Karl Schulte a, H. Daniel Wagner b,*

a
Technical University Hamburg–Harburg, Hamburg 21073, Germany
b
Weizmann Institute of Science Materials and Interfaces, 76100 Rehovot, Israel

Received 10 April 2007; received in revised form 25 May 2007; accepted 28 June 2007
Available online 12 July 2007

Abstract

The structural toughness arising from conventional energy dissipation mechanisms has the potential to be much more significant in
nanocomposites than in composites containing conventional micron-size fibers. This is illustrated and discussed here using nanotube
pull-out as an example of such dissipation. While somewhat challenging conventional scaling arguments, this appears to concur with
current experimental observations.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: A. Nanostructures; B. Fiber/matrix bond; B. Fracture toughness; B. Interface

The fracture toughness of a solid reflects the amount of
energy that needs to be invested to propagate a crack in the
structure. There are increasing experimental indications
that the fracture toughness of composite materials consist-
ing of small amounts of high aspect ratio nanoparticles
(such as nanotubes or nanowires) finely dispersed in a poly-
mer matrix, is significantly enhanced, sometimes even well
above a simple rule of mixtures prediction. Concrete evi-
dence of increased toughness includes, inter alia, fracture
mechanics and impact test data [1–8]. The origin and mech-
anisms of such high toughness, however, are not clear. A
number of toughening mechanisms have been identified
in past research for micro-fiber based composites (for a
review, see Ref. 9, and a classic article by Kelly [10] and
may serve as a sound starting point for understanding
the toughness of man-made nanocomposites. However,
recent contradictory arguments make this assertion less
certain. Consider for example the fiber pull-out mecha-
nism, which has been shown to be the main source of
energy dissipation and thus toughness in carbon fiber
(CF) reinforced polymers [9] and may therefore be tenta-
*
Corresponding author. Tel.: +972 89342594; fax: +972 89344137.
E-mail address: daniel.wagner@weizmann.ac.il (H.D. Wagner).
tively considered to be so too in carbon nanotube (CNT)
based composites. A recently proposed scaling argument
[11] implies that toughness enhancements in CNT based
composites cannot be quantitatively justified by a nanotube
pull-out mechanism, in sharp contradiction with the affir-
mation by Fiedler et al. [3] that the high interfacial area
present in nanotube composites may lead to a significant
increase in fracture work due to nanotube pull-out. Then
what is the potential contribution of nanotube pull-out to
nanocomposite toughness, if any, and is there any experi-
mental evidence of its occurrence?
The following argument possibly resolves this confusing
state of affairs. Assuming with most other authors that
classical mechanics is valid at the nanoscale, the scaling
argument presented in Ref. [11] is based on a conventional
expression for the energy dissipated by fiber pull-out
(Gpull-out  rf r2f =si Þ, according to which the pull-out energy
significantly decreases when the fiber radius rf is scaled
down to the nanoscale. There is, however, an inherent
conceptual weakness with this argument: it is in fact not
possible to independently reduce the fiber diameter without
also affecting some of the other parameters (the fiber
strength rf, the interface strength si, the critical
length ‘c) because these are interrelated through the
Kelly–Tyson expression (‘c = rfrf/si). Actually, scaling

0266-3538/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2007.06.027
330 M.H.G. Wichmann et al. / Composites Science and Technology 68 (2008) 329–331
down is conceptually possible only with a similar fiber, thus
a fiber whose material properties are all the same, which is
certainly not the case when comparing CFs and CNTs. As
a matter of fact, to compare the pull-out energy of a single
nanofiber with that of a single microfiber grossly underes-
timates the true toughening potential of nanofibers: a fairer
approach would consist in comparing the pull-out energy
dissipated by a single microfiber of a given volume and crit-
ical length (composite toughness is known to be maximized
when the fiber length is equal to the critical length) with the
pull-out energy dissipated by a large number of nanofibers
with their own critical length and a total volume equivalent
to that of the microfiber. In so doing, an upper bound for
the pull-out energy can be obtained by assuming that the
volume of all CNTs is redistributed so as to form a parallel
array and undergo pull-out, as shown in Fig. 1. Thus we
compare the pull-out energy dissipated by a single fiber
of a given (cylindrical) volume Vf and critical length ‘cf
with the pull-out energy dissipated by a large number n
of CNTs with their own critical length ‘cCNT and a total
volume nVCNT equivalent to that of the fiber. This volu-
metric equivalence, Vf = nVCNT, leads to
r2f ‘cf
n¼ 2
ð1Þ
rCNT ‘cCNT
The critical lengths of the fibers and the CNTs are
r f rf rCNT rCNT
lcf ¼ and lcCNT ¼ : ð2Þ
sif siCNT
Classically, for a fiber-based composite with optimum (for
toughness) fiber length ‘c, the fiber length pulled out at
fracture will vary between 0 and ‘c/2. The average pull-
out energy per fiber is then [10]:
1 matrix deformation (such as -but not limited to- crazing)
Gf ¼ prf si ‘2c ð3Þ
12
Eqs. (1)–(3) can now be used to compare the pull-out en-
ergy of a carbon fiber, Gf, with the pull-out energy nGCNT
Fig. 1. Schematic view of a crack propagating in a composite: (a) through
a microfiber (carbon fiber) of given volume VCF and critical length ‘cCF;
(b) through a series of nanotubes (CNTs) of total volume equivalent to the
volume of the microfiber in (a), and of critical length ‘cCNT.
of an array of n nanotubes with critical length and with a
volume equivalent to that of a single fiber:
nGCNT nrCNT sCNT ‘2cCNT rCNT
¼ ¼ ð4Þ
Gf rf sf ‘2cf rf
Carbon fibers have strengths of the order of 1–7 GPa,
whereas CNTs have experimental strengths of the order
of 30–50 GPa [12] (and computer simulations provide val-
ues of 100 GPa [13]. Thus the above ratio is anywhere
between 4 and 100, which shows that CNT pull-out poten-
tially represents a substantial source of toughness for com-
posites. Concrete evidence of CNT pull-out has just
recently been presented [6,14–16], and laboratory measure-
ments, albeit technically difficult [14,15], are of necessity.
This straightforward model, which can easily be further
modified to account for the fact that CNTs are hollow
rather than full fibers [17], illustrates the potential advan-
tage of nanoscale reinforcing fibers provided that a pull-
out mechanism is indeed active in such materials. Other
mechanisms such as nanoparticle debonding and off-frac-
ture plane processes may contribute significantly to the
toughening of nanomaterials [18] although particular
toughening mechanisms may be active only in specific
nanomaterials, depending on the nature and geometry of
the nanometric component, and the surrounding matrix
[19]. In the three-dimensional process-zone in front of the
crack tip, more nanofibers/nanotubes will be involved in
toughening processes such as debonding and bridging of
microcracks. The pull-out contribution of nanotubes,
nanowires and nanofibers should therefore be most pro-
nounced when a large process-zone is developing in the
composite and if, additionally, localized and extreme
occurs as a failure mechanism. Another energy dissipation
mechanism, the work done due to nanotube extension over
a distance on either side of – and within – the matrix frac-
ture plane, which generally is unimportant in traditional
brittle fiber based composites, may become important as
well because of the high flexibility (strain to failure of
10% or more) of carbon nanotubes. This ‘bridging’ behav-
iour, which reflects the significant extensibility of carbon
nanotubes, leads to nanotube strains that are indeed much
higher than the failure strain of both the surrounding
matrix and of typical carbon fibers. A visualisation of this
mechanism can be found in Fig. 2 [20]. While in Fig. 2a the
classical pull-out mechanism is illustrated, Fig. 2b depicts
the mechanism of partial debonding and bridging, which
could be promoted by a localized functionalisation of the
carbon nanotube ends.
From a practical viewpoint it is currently hard to prepare
nanocomposites with high tube contents similar to those of
fibers in today’s advanced composites (of the order of 0.60–
0.70 or so), because the mixing procedures quickly lead to
extremely high viscosities, nanotube agglomerations and
so on. Therefore the toughness comparison presented here
for an equivalent volume of tubes and fibers is theoretical
 M.H.G. Wichmann et al. / Composites Science and Technology 68 (2008) 329–331
Fig. 2. Potential toughening mechanisms of CNTs in a polymeric matrix
[20]. (a) Pull-out caused by CNT/matrix debonding, (b) partial debonding
and bridging, enabled by local bonding at the tube ends.
only, and will remain so until the technical difficulties are
resolved. A possible clue towards a solution is the fact that
self-assembled anisotropic nanocomposites with high filler
contents do exist in nature, bone being a typical example
consisting of nanometer-size high aspect ratio apatite-based
ceramic platelets in collagen fibrils. Typically, natural nano-
composites possess very high reinforcement content, high
alignment, high interface strengths, structural hierarchies,
and therefore high toughness, the source of which is thus
radically different from those currently made by man. As
noted by Windle [11], this means that radical changes are
needed in the preparation of nanocomposites.
Acknowledgements
Support from the NOESIS European project on ‘‘Aero-
space Nanotube Hybrid Composite Structures with Sens-
331
ing and Actuating Capabilities’’, and from the G. M. J.
Schmidt Minerva Centre of Supramolecular Architectures
at the Weizmann Institute, is acknowledged. H.D. Wagner
is the recipient of the Livio Norzi Professorial Chair.
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