Framework for

nanocomposites
by Richard A. Vaia* and H. Daniel Wagner†

Materials and material development are fundamental The nanoscale, and the associated excitement
to our very culture. We even ascribe major historical surrounding nanoscience and technology, affords
periods of our society to materials such as the stone unique opportunities to create these revolutionary
material combinations. These new materials promise
age, bronze age, iron age, steel age (the industrial
to enable the circumvention of classic material
revolution), polymer age, silicon age, and silica age
performance trade-offs by accessing new properties
(the telecoms revolution). This reflects how and exploiting unique synergisms between
important materials are to us. We have, and always constituents that only occur when the length scale of
will, strive to understand and modify the world the morphology and the critical length associated
around us and the stuff of which it is made. As the with the fundamental physics of a given property
21st century unfolds, it is becoming more apparent coincide. From a materials perspective, morphologies
that the next technological frontiers will be opened that exhibit nanoscopic features are necessary but far
from sufficient – the key opportunities are afforded
not through a better understanding and application
either when (i) the physical size of the material’s
of a particular material, but rather by understanding
constituents is engineered to coincide with the onset
and optimizing material combinations and their of nonbulk-like behavior, such as observed for the
synergistic function, hence blurring the distinction size-dependent light emission of quantum dots (QDs),
between a material and a functional device or (ii) when a structure-property relationship
comprised of distinct materials. approaches a singularity or depends nonlinearly on
aspects of the morphology, such as the internal
interfacial area.
Polymeric nanocomposites (PNCs) have been an area of
intense industrial and academic research for the past
20 years. No matter the measure – articles, patents, or R&D
*Air Force Research Laboratory,
Materials and Manufacturing Directorate, funding – efforts in PNCs have been exponentially growing
Wright Patterson Air Force Base,
OH 45433-7750, USA worldwide over the last ten years. PNCs represent a radical
E-mail: [email protected] alternative to conventional filled polymers or polymer blends
†Department of Materials and Interfaces, – a staple of the modern plastics industry. In contrast to
Weizmann Institute of Science,
Rehovot 76100, Israel conventional composites, where the reinforcement is on the

32 November 2004 ISSN:1369 7021 © Elsevier Ltd 2004

 REVIEW FEATURE

Fig. 1 Categorization of nanoparticles based on increasing functionality and thus, potential to increase functionality of the polymer matrix, which in turn is based on increasing spatial and
compositional precision in nanoparticle fabrication. Increased complexity and function require increased synthetic control. Nanoscale particles and clusters are polydisperse in size (σsize)
and composition (σcomp). One-dimensional elements are compositionally uniform, with narrow size dispersion in one dimension (δ1D), but polydisperse in the other two (σ2D). Three-
dimensional elements exhibit narrow size dispersion in all dimensions (δ3D). Rather than compositional uniformity, prescribed composition variation in three dimensions results in tailored
functionality, where proto-assembly of any of the aforementioned elements enables the creation of an infinite variety of tailored nanoparticles. Finally, the ultimate active and functional
nano-unit would embody the characteristics of a virus – prescribed size, composition, site-specific surface functionality, and dynamic responsivity leading to alteration of the particle’s
properties, composition, or size.

order of microns, PNCs are exemplified by discrete enabling greater retention of the inherent processibility and
constituents on the order of a few nanometers, ~10 000 toughness of the neat resin.
times finer than a human hair. The value of PNC technology Considering the plurality of potential nanoparticles,
is not solely based on the mechanical enhancement of the polymeric resins, and applications, the field of PNCs is
neat resin nor the direct replacement of current filler or blend immense. For example, Fig. 1 presents a hierarchy of
technology. Rather, its importance comes from providing nanoparticles based on increasing functionality and thus,
value-added properties not present in the neat resin, without the potential to increase the functionality of the polymer
sacrificing the resin’s inherent processibility and mechanical matrix.
properties, or by adding excessive weight. Traditionally, blend This issue provides a snapshot of the rapidly developing
or composite attempts at ‘multifunctional’ materials impose PNC field and a summary of two of the most investigated
a trade-off between desired performance, mechanical nanoparticles – layered silicates and carbon nanotubes.
properties, cost, and processibility. However, over and over Development of PNCs, as with any multicomponent material,
again, property suites comparable to, or improved beyond, must simultaneously balance four interdependent areas:
those common for traditional fillers are reported for PNCs constituent selection, cost-effective processing, fabrication,
containing substantially less filler (1-5 vol%) and thus and performance. For PNCs, a complete understanding of

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Fig. 2 Schematic comparison of a ‘macro’-composite containing 1 µm x 25 µm ( x L) fibers in an amorphous matrix to that of a ‘nano’-composite at the same volume fraction of filler, but
containing 1 nm x 25 nm fibers. There are three main material constituents in any composite: the matrix (white), the reinforcement (fiber, red), and the so-called interfacial region
(green), which extends (z) into the matrix on the order of Rg, the radius of gyration of the polymer. Scanning electron micrograph shows E-glass reinforced polyolefin (15 µm fiber) and
transmission electron micrograph shows montmorillonite-epoxy nanocomposite (1 nm thick layers).

these areas and their interdependencies is still in its infancy, • Particle-particle correlation (orientation and position)
and ultimately many perspectives will develop, dictated by arising at low volume fractions (φC < 0.001);
the final application of the specific PNC. This article will • Large number density of particles per particle volume
sketch a general framework for PNCs, enabling connectivities (106-108 particles/µm3);
to be drawn between PNCs and material systems within the • Extensive interfacial area per volume of particles
broader soft-matter community, as well as posing key (103-104 m2/ml);
fundamental questions, which, when addressed, will have • Short distances between particles (10-50 nm at
broad impact to all types of PNCs. φ ~1-8 vol%); and
• Comparable size scales among the rigid nanoparticle
PNC framework inclusion, distance between particles, and the relaxation
The initial question when beginning to examine polymer volume of polymer chains.
nanocomposites is: how are these materials different from For spherical nanoparticles, the first two characteristics are
classic filled polymers or traditional composites? As not commonly observed because of the small aspect ratio of
anticipated, there is no simple answer; rather ‘they are the particle. Nevertheless, PNCs containing low-aspect ratio
related, but bring new opportunities, perspectives, and issues.’ nanoparticles are a critical bridge between conventional
Whether tubes (e.g. single- and multi-walled carbon micron-scale fillers and high-aspect ratio nanoparticles
nanotubes, SWNT and MWNTs, respectively) or plates where, from the nanoparticle perspective, size is reduced and
(e.g. exfoliated graphite, layered silicates), the nanoscopic number density is increased prior to the additional
dimensions and extreme aspect ratios inherent in these complexity of orientational correlations introduced by an
nanofillers result in six interrelated characteristics extreme aspect ratio. Note that the first two characteristics
distinguishing the resultant PNCs from classic filled systems: can manifest in spherical nanoparticles systems also, vis-à-vis
• Low percolation threshold (~0.1-2 vol%); innovative processing or proto-assembly of these

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nanoparticles. Overall, the key concept to answer ‘what is a

PNC’ is not specifically embodied within the shape of the
particle, but how do the characteristics of the particle provide
a means to ‘engineer and tailor morphology to achieve a
desired property suite from the PNC’.
To convey the origin and interrelation of these
distinguishing characteristics, Fig. 2 compares the dominant
morphological scale of a classic filled polymer containing
1 µm x 25 µm fibers in an amorphous matrix to that of a
nano-filled system at the same volume fraction of filler, but
containing 1 nm x 25 nm fibers. There are three main
material constituents in any composite: the matrix, the
reinforcement (fiber), and the so-called interfacial region. The
interfacial region is responsible for ‘communication’ between
the matrix and filler and is conventionally ascribed properties
different from the bulk matrix because of its proximity to the
surface of the filler. Nominally, the spatial extent of this
perturbed matrix is thought to extend into the bulk one to
four times the radius of gyration of the matrix, Rg, which has
a value of around tens of nanometers. For polymers, Rg is the
key spatial parameter to which the majority of the polymer’s
static and dynamic properties can be ultimately related. The
impact of the interface over a few Rg is substantiated by
extensive investigations on the behavior of thin polymer
films, as well as empirical observations in traditional
composites and filled rubbers. In the schematic of the classic
filled polymer, the relative volume fraction of this interfacial
region is exaggerated to convey its presence, but its
importance to ultimate mechanical properties is time and
again demonstrated in the literature. In contrast, because of Fig. 3 Logarithmic isolines of interfacial (surface) area / volume of particles
(µm-1 = m2/ml) with respect to the aspect ratio, α = H/R, and largest dimension of
the increased number density of particles, the distance particle (R = radius, H = height, length) based on approximating particles as cylinders
(area/volume = 1/H + 1/R). Aspect ratios greater than one correspond to rods
between particles in the nano-filled system is comparable to (length/diameter) and less than one to plates (height/diameter). Fully exfoliated and
the size of the interfacial region (10 nm) and, thus, the dispersed high aspect ratio plates or rods, such as montmorillonite or SWNTs, generate
internal interfacial area comparable to that of macromolecular structures, such as
relative volume fraction of interfacial material to bulk is dendrimers or proteins, and two to three orders of magnitude more than classic mineral
fillers. Comparison plots such as this draw similarities between different fillers, including
drastically increased as the size and homogeneity of the layered silicates (laponite, montmorillonite, fluorohectorite) with different degrees of
dominant morphological characteristics of the system exfoliation (N = number of layers per tactoid), roped SWNTs, carbon nanofibers, chopped
glass fibers, etc.
becomes smaller.
To quantify these arguments, Fig. 3 summarizes on a area per particle volume of 1-100 µm-1. In comparison, high-
log-log plot the dependence of the interfacial area per aspect ratio fibers and continuous fiber reinforcements with
volume of filler (µm-1 = m2/ml) on the aspect ratio (α) and 10-50 µm diameters and lengths greater than 100 µm
largest dimension of the filler (L, µm). Aspect ratios greater produce an interfacial area per particle volume of
than one correspond to rods (length/diameter) and less than 0.1-10 µm-1 – one to three orders of magnitude less than
one to plates (thickness/diameter). The vast majority of classic mineral fillers. Nano-fillers however, whether
classic mineral fillers exhibit low aspect ratios (0.2 < α < 5) nanotubes or nanoplates, generate one to three orders of
and cluster sizes between 0.1-10 µm, yielding an interfacial magnitude more internal interfacial area per particle than

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classic mineral fillers! For fully exfoliated and dispersed high PNCs. The validity of these relationships and their underlying
aspect ratio plates or rods, such as montmorillonite or assumptions are beginning to be reexamined by many
SWNTs, the amount of internal interfacial area generated is researchers in the light of the distinguishing characteristics
comparable to that of macromolecular structures such as of PNCs. Additionally, the idealized PNC shares topological
dendrimers or proteins. Note that full exfoliation is when the commonality with numerous mesostructured
mean distance between nanoparticles, <l>, becomes a macromolecular systems, such as semicrystalline polymers,
maximum for a given volume fraction. Addressing this block-copolymers, and liquid crystal polymers, whose
preponderance of the interface is critical to optimize PNC structure-property relationships are serving as guidance to
performance and is the source of many potentially novel ascertain the dynamic behavior of PNCs, as well as the
properties derived from the interface, such as impact of nanoparticle addition on order-disorder transitions
environmentally dependent mechanical damping. and phase behavior.
Similar comparison plots can be generated for the
dependence of particle number density or mean particle- PNC fabrication
particle separation on aspect ratio and largest dimension of Given the generalized framework that distinguishes PNCs and
the filler, leading to similar revelations. For example, fully draws analogies with other polymeric systems, is there a
exfoliated nanoscopic plates or rods generate four to six possibility for generalizing a framework guiding fabrication?
orders of magnitude more particles per volume than classic Unfortunately, an all-encompassing generalization of
mineral fillers. Also, for these extreme aspect ratios fabrication approaches is much less instructive because of the
(α > 100), the critical concentration, φ*, at which packing breadth of possible routes, ranging from melt dispersion of
considerations dictate orientation correlation between nanoscale inorganics in a polymer to in situ polymerization or
particles is ~10-3 for a plate and 10-4 for a rod. These low formation of the polymer or inorganic in the presence of the
volume fractions, which are substantially less than even other, and the diversity of final forms desired, including bulk,
commonly examined in nanocomposites, imply that PNCs are film, fiber, coating, thermoplastic, and thermoset. This
not fundamentally isotropic, but will have a tendency to diversity of innovative approaches implies the technological
exhibit anisotropic properties or a domain-like texture, impact of PNCs will be (and already has been) broad.
reminiscent of grains, that contain nanofillers with a local Generalizing in some instances may be instructive,
preferred orientation even though macroscopically the global however. For example, consider the dispersion of preformed
orientation is isotropic. Since the particle number density nanoparticles, which includes PNCs containing layered
may be comparable to lyotropic liquid crystal systems, such silicates and carbon nanotubes, encompassing the majority of
as the tobacco mosaic virus and rigid-rod polymers, similar current work in PNCs. In almost every case, nanoparticles are
phase behavior may even be present. Furthermore, the added to the matrix or matrix precursors as 1-100 µm
extreme aspect ratio implies transport phenomena derived powders, containing an association of nanoparticles – in
from percolated networks, such as electrical conductivity, will many instances these powders contain in excess of ten
show rapid enhancement at very low volume fractions of million nanoparticles. The overwhelming majority of the
nanoparticles. nanoparticles summarized in Fig. 1 can be grouped into two
As demonstrated in Fig. 3, the aforementioned categories based on this association: (i) low-dimensional
characteristics are not completely new. As an ideal form, crystallites and (ii) aggregates. Layered silicates, SWNTs, and
PNCs are most simply multicomponent systems where: other extreme aspect ratio, very thin (0.5-2 nm)
(i) <l>, the mean distance between nanoparticles (rigid nanoparticles exhibit translational symmetry within the
components), is on the order of Rg, the fundamental length powder. The alignment and close-packing results in the vast
scale of the matrix (soft component); and (ii) L, the size of majority of nanoparticle surface area being contained within
nanoparticle, is also on the order of Rg. Given this idealization the crystallite, leading to a very large cohesive energy per
and the associated implications, our understanding of particle that increases with aspect ratio. Surface
established structure-property relationships developed for functionalization generally relies on inclusion chemistry or
traditional composites may not be directly applicable to successive functionalization-removal cycles of nanoparticles

36 November 2004
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from the crystallite exterior inward. In contrast, the initial plies and weaving – thus transforming ‘nano-filled systems’
state of slightly larger, more polydisperse nanoparticles, such to ‘nanocomposite systems’. In parallel, PNCs are moving
as MWNTs and nanosilica, are disordered with at least equal beyond commodity plastic applications to critical
amounts of nanoparticle surface area readily accessible to components of active devices, such as fuel cell membranes,
vapor or liquid medium as bound-up in nanoparticle- photovoltaics, sensors, and actuators.
nanoparticle contacts. The disordered state and more facile PNCs have great potential, especially when viewed with
access to surface area imply that these systems are generally respect to the explosion of available functional nanoparticles,
easier to disperse and amenable to a broader range of surface enabling never-before-realized properties to be generated
modification approaches. In all cases, although engineering within plastics. The underlying framework of PNCs implies
the correct interfacial chemistry between nanoparticle and that the physics and chemistry of these systems parallels
medium is critical, it is not sufficient to transform the many macromolecular systems, not just filled polymers. By
micron-scale compositional heterogeneity of the initial considering the idealized framework, examination of the
powder into nanoscale homogenization of nanoparticles underlying principles defining structure-property relationships
within a PNC. Mechanical mixing (compounding, sonication, can begin, and the potential pitfalls arising from
shear) is necessary – and the efficiency is dependent on the extrapolating structure-property relationships of classic filled
medium viscosity and reactivity. Increasing nanoparticle systems can be considered and addressed. The necessary
separation without sufficient mechanical mixing only foundation and tools to address system-specific complexities
produces hybrid micron-scale reinforcing particles. These and process-history dependencies, such as nonequilibrium
‘hybrid’ particles exhibit an internal structure that simply phenomena including irreversible aggregation, nanoparticle
reflects that of the initial low-dimensional crystallite or network association, percolation, and ultra-long relaxation
aggregate swollen by the polymer. Compositional times of process-induced orientation (glass-like behavior), are
heterogeneities on the micron scale still exist and are beginning to evolve. The topological similarities between
topologically similar to that of conventional filled systems, PNCs and other mesoscale polymer systems, such as
but in this case the ‘hybrid’ filler is comprised of polymer- semicrystalline polymers, block-copolymers, liquid crystals,
nanoparticle associates. Uniform nano-reinforcement in a and colloids, are the impetus for many of these current
PNC implies that the dominant length scale of efforts, providing significant guidance toward understanding
heterogeneities is nanoscopic and that nanoparticle- the role of processing on structure control and the ultimate
nanoparticle distances are at a maximum. impact on properties.
So, is the full realization of PNCs technologically here? No,
Conclusions but it is a viable option today when considering the selection
Today, nanocomposites are really nanofilled plastics, where of filled or blend polymer systems. Will PNCs deliver the
the total internal interfacial area becomes the critical potential currently ascribed? That is still to be determined,
characteristic rather than simply the relative volume fraction especially since realistic estimates of the ultimate potential,
of constituents. The use of the moniker nano-‘composites’ which are based on fundamental understanding of the physics
invokes parallels to traditional fiber-reinforced composite at these scales, are still in development. However, the
technology and the ability to spatially ‘engineer, design, and possibilities are engaging communities worldwide, and the
tailor’ materials performance for a given application. scientific literature is being enriched at an increasing rate
Currently, the realization of ‘compositing’ PNCs is over the with works that show great promise and are beginning to
horizon. For the vast majority of investigations, the challenge establish a pervasive fundamental understanding of PNC
is still to achieve single-particle dispersions and the structure-property relationships. MT
subsequent PNCs are treated much as an isotropic, filled
polymer. Only recently have examples emerged that consider
cost-effective approaches to provide spatial and orientational Acknowledgments
control of the hierarchical morphology with a precision We are very grateful for E. Manias for insightful discussions, L. Drummy for micrographs,
and partial support from the Air Force Office of Scientific Research and the Air Force
comparable to that conventionally obtained through fiber Research Laboratory, Materials and Manufacturing Directorate.

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