F E A T U R E A R T
Advances in Nanodielectric Materials
Over the Past 50 Years
Key words: nanodielectrics, nanocomposite, interface, colloid science, filler, agglomeration,
molecular tailoring
Introduction
DEIS was born in 1963. Nobody knew anything about nano-
dielectric materials at that time. Today “nano” is a buzz word!
Polymer composite research began in the early 1900s [1], and
clay-reinforced elastomers were patented in the 1950s. Only two
papers on nanodielectric materials were published in 2002, but
approximately 500 papers appeared in the following 10 years, as
many researchers became involved in the field. Much informa-
tion has been accumulated, and the applications of nanomateri-
als and nanotechnology are increasing rapidly.
Before Nanocomposites
The Good Old Times
DEIS was born two years before Moore’s law in microelec-
tronics was stated. People working in dielectrics were comfort-
able; progress was slow and steady. However, their scientific
lives became much less comfortable with the advent of nano-
composites.
The concepts of nanotechnology and nanodielectric materi-
als did not exist in the 1960s. Nanodielectric materials are now
included in what are generally called nanocomposites. Only 15
years have passed since the development of the first polyamide/
layered silicate nanocomposite in Japan, and it has been only
10 years since polymer nanocomposites or nanodielectrics were
first developed as dielectrics. Nevertheless, these developments
did not emerge suddenly but after an incubation period, perhaps
like an electrical tree before it starts growing! The incubation
period was approximately 50 years.
The Influence of Nanotechnology
on Nanocomposites
“There’s plenty of room at the bottom” said the famous Novel
laureate physicist Richard Feynman in 1959 [2]. A new world of
The first of a series of invited reviews
to be published during 2013 to mark
the 50th anniversary of DEIS.
10 0883-7554/12/$31/©2013/IEEE
I C L E
Toshikatsu Tanaka
Waseda University, Kitakyushu-shi, Fukuoka,
803-0135, Japan
Takahiro Imai
Toshiba Corporation, Fuchu-shi, Tokyo,
183-8511, Japan
Advances in polymer nanodielec-
trics over the past 50 years, using
colloid science, polymer composite
technology, and nanotechnology,
are reviewed. Despite rapid progress
during the past 10 years, interdis-
ciplinary investigation is needed to
yield additional benefit to society.
science and technology was expected. Norio Taniguchi used the
word “nanotechnology” in 1974 for the first time, in the context
of developments in microelectronics. During the period 1950 to
1970, much effort was directed toward miniaturization of mi-
croelectronics devices via micromachining technology. New
microminiaturized LSI devices were introduced almost every
day. According to Moore’s law (1965) the number of compo-
nents per unit area in integrated circuits would double every
year. Then a nanometer world emerged in which quantum me-
chanics rather than Newtonian mechanics applied. Drexler used
Feynman’s phrase to promote molecular nanotechnology in his
book Engines of Creation [3], which was based on a bottom-up
approach. Thereafter nanotechnology expanded rapidly. The in-
vention of the atomic force microscope in 1986 and the discov-
IEEE Electrical Insulation Magazine
ery of fullerenes in 1985 and carbon nanotubes in 1991 were two
gigantic milestones along the way. The National Nanotechnol-
ogy Initiative on nanoscale science, engineering, and technology
was adopted by the United States in 2000, calling for integration
and advancement of nano-related science and technology from
microelectronics to biomaterials. This has proved enormously
influential in accelerating the development of nanotechnology.
Nanotechnology has influenced specific academic-discipline
fields such as physics, chemistry, life science, and electrical
engineering, as well as the technical field of microelectronics.
The word now refers to a wide range of technologies dealing
with nanometer scale substances including nanodevices, nano-
composites, and nanomaterials. Nanodevices include integrated
microelectronics circuits and micro- and nano-electromechani-
cal systems (MEMS and NEMS). Nanocomposites loaded with
nanosized fillers include colloids, cosmetics, paints, battery
electrodes, food packaging, engineering plastics, and biomateri-
als. The new nanomaterials include fullerenes and carbon nano-
tubes.
We are interested in polymer nanocomposites, which are part
of the polymer/filler composites class. They were certainly influ-
enced by nanotechnology but were initially developed from mi-
crocomposites and filled resins. Nanocomposites have internal
interfaces between two kinds of substances, and those interfaces
are the dominant influence on their bulk properties. The natural
starting point in seeking to understand the interfaces is colloid
science, which has a long research history.
The Influence of Microcomposites
on Nanocomposites
Composites with superior and unique properties may be
formed when two or more different materials are combined.
The concept of composite materials is very old, e.g., mud and
straw for walls and buildings, and wood, bone, and animal glue
for bows. Modern composite technology was greatly advanced
by the discovery of plastics in the early 1900s. Plastics were
mechanically strengthened by other materials, but reinforce-
ment was needed to provide the strength and rigidity required
for structural applications. Fiberglass-reinforced plastics were
invented in 1935, and the fiberglass-reinforced plastics industry
expanded into military and consumer markets. Epoxy resin was
commercialized in 1946 as glue and was later mixed with inor-
ganic filler to create a structural composite substance.
The clay-reinforced elastomer was patented in 1950. The
composites industry began to mature in the 1970s and later de-
veloped strengthening materials such as aramid fibers (Kevlar).
The development of carbon fibers further stimulated composite
technology innovation.
Polymer nanocomposites, or simply nanocomposites, are an
offspring of microcomposites and have been strongly influenced
by nanotechnology. In the 1990s the Toyota research group de-
veloped the first polymer nanocomposites, namely clay/nylon-6
nanocomposites with improved thermal and mechanical perfor-
mances, for timing belt covers [4]. Lewis introduced the concept
of nanodielectrics in 1994, based on molecular tailoring and
molecular nanotechnology, and stressed the importance of inter-
faces [5]. In 2001 an attempt was made to describe comprehen-
January/February — Vol. 29, No. 1 11
sively the physical and chemical characteristics of polymer/filler
interfaces [6]. Following the Toyota work and Lewis’s sugges-
tion, two papers on fabrication and evaluation of nanodielectrics
appeared independently in 2002 [7], [8]. Since then much work
has been done on preparation, evaluation, and characterization
of novel nanodielectric materials. The first reviews of the field
appeared in 2004 [9], [10], followed by several others between
2006 and 2011 [11]–[14]. It was recognized that interfaces
played a dominant role in determining dielectric performance
and that self-assembly is a crucial process in the formulation of
nanocomposites [15].
Interfacial Forces in Colloids
Interface and colloid science dealt with nanometer-size sub-
stances long before nanotechnology emerged. Gold sols and
other nanomaterials with sizes down to 10 nm were studied in
the 1920s and Langmuir-Blodgett thin films with one or more
monolayers of organic material in the early 1950s. The first mea-
surement of surface forces was made in the early 1950s. The
characteristics of interfaces between mutually immiscible sub-
stances in colloids were also clarified. Colloid science reached
a significant level of maturity during the second half of the 20th
century. It is important to note that in colloid science, the forces
acting between particles and solvent are well understood for
both dilute and condensed phases. Various forces act between
colloidal particles, e.g., excluded volume repulsion, electrostatic
forces, van der Waals’ force, entropic forces, and steric forces.
Excluded volume repulsion, sometimes called Born repulsion,
is caused by the impossibility of overlap between hard particles.
Electrostatic forces surrounding a colloidal particle were ana-
lyzed in detail and clarified by Derjaguin, Landau, Verwey, and
Overbeek, resulting in the DLVO theory. There is a deep mini-
mum in the potential (attractive force) near the particle surface
and a shallow minimum (attractive force) far from the particle
surface, with a high maximum (repulsive force) in between. En-
tropic forces act between particles, increasing the entropy until
thermal equilibrium is reached. Steric forces arise between poly-
mer-covered surfaces, or in solutions containing nonadsorbing
polymer, producing an additional steric repulsive force (which
is predominantly entropic in origin) or an attractive force due
to depletion of counter ions. There are other more important
interfacial phenomena associated with the interaction between
particles and their environment. Physical and chemical adsorp-
tion is one of them. The former is related to hydrogen, hydro-
phobic or van der Waals bonding. The latter is caused by chemi-
cal bonding between adsorbate and adsorbent. Surface tension
appears on a soft surface, generated by the difference between
the free energies of surface and bulk. Wetting is the contact of
a solid surface by a liquid, and includes adhesion, spreading,
and immersion wetting. Knowledge of interfacial phenomena
in colloids has proved extremely useful in developing polymer
nanocomposites.
Bound Polymers: Suggested Interaction Zones
A bound polymer was discovered in the 1960s [16]–[18]. The
concept of a bound layer was suggested in 1969 to explain im-
provement of mechanical strength and increase of glass transi-
tion temperatures. The bound layer is immobile so that matrix

Figure 1. Model of a bound polymer layer.
molecules can be bound to surrounding inorganic fillers to form
the interface, and it becomes thicker as the interaction becomes
stronger, as shown in Figure 1. Its thickness was estimated as
several to several hundred nanometers in polyvinyl chloride
(PVC)/xonotlite and PVC/mica composites and several nano-
meters in rubber/carbon black composites; the thickness was too
small to measure in PVC/calcium carbonate composites. The
thickness depended on the type of matrix and filler, the method
of surface treatment, and the measurement technique, e.g., indi-
rect estimation from the glass transition temperature change, or
from the dissipation of vibrational energy through dynamic vis-
coelasticity, or direct measurement on bound polymer adsorbed
on the surface of the filler.
Initial Development of Nanocomposites
in the 1990s
Challenging Work by Toyota Group
Reference [19] seems to be the first paper published by the
Toyota research group. They recognized that clay/inorganic
complexes had various applications such as absorbents, addi-
tives for controlling rheological properties of organic solvents,
separators for optically active metal complexes, antioxidants for
rubber materials, and curing agents for synthetic resins. They
preferred a clay/polyamide composite, because they thought that
the mechanical properties of a polyamide were strongly affect-
ed by inorganic additives and that clay/polyamide interactions
had not been studied extensively. (Some work to which they re-
12 IEEE Electrical Insulation Magazine
ferred had already been done [20].) Smectic clay minerals, such
as montmorillonite, saponite, hectorite, stevensite, vermiculite,
and haloysite, were known to act as hosts of intercalated com-
pounds and to function as catalysts for various organic reactions.
Smectics were chosen because their properties depended upon
interlayer cations that were easily exchanged for inorganic or
organic cations.
After much investigation since then, a new type of polymer
nanocomposite named Nylon 6-Clay Hybrid (NCH) was devel-
oped for commercial use in the 1990s, in which clay mineral was
dispersed in a nylon 6 matrix at a molecular level. The dispersed
state of the clay in NCH was observed by transmission elec-
tron microscopy (TEM), and the molecular structure and crystal
structure of nylon 6 were analyzed by mass spectroscopy and
X-ray diffraction. The NCH showed good mechanical properties
and a high heat-distortion temperature, in spite of its low clay
mineral content. In addition, the NCH film had low gas perme-
ability. Comparing four NCH composites, one with montmoril-
lonite and three others with different clays, the montmorillonite
composite was superior in mechanical properties to the other
three. This was considered to be due to the strong ionic interac-
tion between montmorillonite and nylon 6, as revealed by 15N-
NMR results. The method of NCH synthesis was modified. The
diamine added to NCH controlled the laminated state of the clay,
and the one-pot synthesis shortened the synthesis process. The
NCH has been applied to automotive timing belt covers, the first
example of the use of a polymer nanocomposite as an engine
component. A comprehensive review on preparation and charac-
terization of polymer/layered silicate nanocomposites was pub-
lished in 2003 [21].
New World of Nanocomposite Engineering Plastics
Engineering plastics are generally defined as plastics that
show thermal and mechanical properties superior to those of
commodity thermoplastic materials. The latter include polyeth-
ylene, polypropylene, polystyrene, and PVC. Engineering plas-
tics include polyoxymethylene, polyamides, polycarbonates,
polybutylene terephthalate, polyethylene terephthalate, poly-
etheretherketone, and polyphenylene sulfide. It has been demon-
strated that nanocomposite technology can elevate commodity
plastics to engineering plastics. Nanocomposite technology has
produced commodity and engineering plastics with excellent
properties.
The term “nanocomposite engineering plastics” may be used
to indicate a group of plastics that have multifunctional char-
acteristics and properties superior to conventional (original)
plastics, thanks to nanofiller dispersion within them. This field
is burgeoning. After clay/nylon-6 nanocomposites were invent-
ed for automotive applications, other nanocomposites such as
clay/polyolefin nanocomposites were developed with potential
applications outside the automotive industry. One of the most
promising is drink packaging, using the superior barrier proper-
ties of polymer clay nanocomposites. Other potential applica-
tions include the use of polypropylene nanocomposites for fur-
niture, home appliances, and interior bulletin board substrates,
magnetic media, bone cement, filter membranes, aerogels, and
dye-sensitized solar cells. Polyether-ether-ketone/carbon nano-
fiber nanocomposites show promise for applications in the aero-
space and automotive industries. Polyether-ether-ketone is an
engineering polymer with superior mechanical properties such
as high melting temperature (380°C) and excellent resistance
to chemical corrosion. Carbon nanofibers function as three-
dimensional reinforcements. The nanocomposites are expected
to show improved mechanical properties, and electrical and
thermal conductivity, while conserving high melting point and
chemical resistance.
Thermosetting materials containing nanofillers are also
evolving rapidly. Epoxy-based and polyimide-based nanocom-
posites are typical. Epoxy/clay nanocomposites show thermal,
mechanical, and electrical insulation properties superior to those
of the base epoxy resin. Epoxy resin is a versatile material in
widespread use in products such as adhesives, coating materi-
als, insulation materials for industrial equipment, encapsulation
materials for LSI, and impregnation materials for the fiber-re-
inforced plastics. Epoxy-based nanocomposites are therefore
expected to be increasingly used as nanocomposite engineering
plastics.
From Colloids to Solid Composite
Dielectrics in the 1990s
Pioneering Work of T. J. Lewis
In 1994 T. J. Lewis [5] first suggested the concept of nano-
dielectric materials, as stated in the section titled The Influence
of Nanotechnology on Nanocomposites. The term nanometric
dielectrics, introduced later [22]–[24], had a broader meaning
than did nanodielectric materials [25]. The former includes the
latter and molecular devices such as those associated with elec-
tromechanical coupling (piezoelectric effect), electromechani-
cal/chemical coupling (polymer gels), and force coupling in bi-
ology. The importance of interfaces was emphasized in all cases.
An interface between a metal electrode and a polymer dielectric
substance consists of a Helmholtz layer and a Gouy-Chapman
layer, with dimensions in the nanometer range. The former can
be highly structured, while the latter is diffuse and often space
charged to form an electric double layer. Thus interfaces consist
of at least two layers and invariably have different properties
than do bulk materials. These properties can be analyzed us-
ing the Poisson and Boltzmann equations, and since they have
nanometric dimensions, quantum mechanics will also apply.
Computer simulation will be of great assistance in modeling the
dynamic behavior of molecular interfaces.
The concept of nanodielectric interfaces was developed by
Lewis in a follow-up paper in 2004 [22]. He used Figure 2 to
illustrate a nanointerface consisting of a Stern layer and a dif-
fuse layer.
There are several interfacial forces. They include hard-core
forces that are extremely short range, quantum mechanical, and
repulsive in nature. They arise from overlap interactions between
the electron clouds of individual atoms. All the other forces are
essentially attractive/repulsive electrostatic interactions involv-
ing negative electrons and positive nuclei in the system. Their
form depends on whether the individual atoms or molecules
are neutral or have a net charge, so that they become donor or
January/February — Vol. 29, No. 1 13
acceptor ions. In neutral form any asymmetric distribution of
electrons and nuclei in a molecule or atom will give rise to mul-
tipole forces, of which the dipole component will be dominant.
Several interactions are possible. Between ions the forces are
strongly Coulombic and long range. When permanent dipoles
are present there will be weaker ion-dipole and dipole-dipole
forces and a range of ion- and dipole-induced forces. Debye and
Keesom forces are in this category. All dipole-related polarizing
forces are of moderate range and generally attractive in nature
and are known collectively as van der Waals' forces. A particular
short-range electrostatic force, highly directional and therefore
of special structural importance, is the hydrogen bond between a
donor (a hydrogen atom covalently bonded to an electronegative
atom) and an acceptor electronegative atom. A flat interface is
assumed for simplicity (Figure 2), but for more rigorous analy-
sis a curved interface should be considered, since complicated
chemistry is involved in inducing polymer morphology forma-
tion in polymer-filler interfaces.
Why are interfaces important? Lewis [23] gives some rea-
sons. Interface properties become increasingly prominent if
phase A (see Figure 2) is a particle of finite size, surrounded by
phase B with an AB interface between them. The influence of
the interface can become very significant as the particle diameter
is reduced. If the interfaces are governed only by short-range
forces and are, say, about 0.5 nm thick, their volume exceeds
50% of the total volume when the particle size is below 5 nm.
If the interfaces are more than 10 nm thick, as they might be
when the interfaces are charged, they will be dominant when the
interparticle distance is less than 100 nm. Clearly the proper-
ties of the interface can strongly influence the overall dielectric
properties of the composite. This is a situation quite unlike that
assumed in traditional Maxwell-Wagner treatment of these sys-
tems.
Turning to the contribution from colloid science, the charge
distribution around a particle in a colloid is treated by the DLVO
Figure 2. A nanointerface: (a) diffuse electric double layer pro-
duced by charged particle phase A in matrix phase B containing
mobile ions; (b) resulting electrical potential distribution Ψ(r)
[22].
 theory of colloids, as explained in the section titled Interfacial
Forces in Colloids. This treatment was applied to the charge dis-
tribution around a nanoparticle in a polymer matrix/nanoparticle
system. Preparation of a nanodielectric composite frequently
involves the mixing of nanoparticles in a liquid phase of the
matrix. This is equivalent to a colloid. Two forces, namely an
attractive interparticle van der Waals' force and a screening dou-
ble layer force, act to stabilize the composite at a nanoparticle/
matrix spacing corresponding to the second energy minimum
of the DLVO theory. This situation is probable when the Debye
shielding length is large. Subsequent solidification of the matrix
is then likely to produce a homogeneous composite in which
the charges remain on the nanofiller and the surrounding double
layers and continue to stabilize the system. It is important to
realize that they also influence the dielectric properties of the
composite. The balancing of attractive polarization and repul-
sive double-layer forces to give a stabilizing energy minimum is
the essence of the DLVO theory of colloids.
To understand interfacial phenomena in nanocomposites in
greater depth, we need to apply conformational and morphologi-
cal polymer chemistry, chemical reaction kinetics and dynamics,
solid-state physics, thermodynamics, and quantum mechanics.
Early Study of Nanodielectrics
Eight years after Lewis’s 1994 paper, two papers on fabri-
cation and evaluation of nanodielectrics appeared [7], [8]. Re-
search on nanodielectrics was motivated by the development of
nanotechnology and engineering nanocomposite plastics. First,
study of epoxy/organically modified layered silicate nanocom-
posites [7] was inspired by the Toyota research group’s creative
work [19], [21] as stated in the section titled Challenging Work
by Toyota Group, and by other related results on epoxy/clay
nanocomposites intended for noninsulation applications in the
late 1990s. Second, investigation of epoxy/titania nanocompos-
ite [8] was encouraged by the concepts of nanometric dielectrics
[5] and nanodielectrics [22]–[25]. Previous work on these com-
posites had been directed mainly toward optical and mechanical
applications.
The term nanodielectrics appeared in 2001 [25]; [7] and [8]
were published in 2002. It was suggested in [25] that progress
in nanodielectrics would take place in three major fields, namely
imaging and measuring methods at the nanoscale level, molec-
ular machines, and molecularly tailored materials. It was also
suggested that polymer nanocomposites should be studied as
part of molecular tailoring.
Reference [7] dealt with epoxy/organically modified lay-
ered silicate nanocomposites, specifically their preparation;
their thermal, mechanical, and dielectric properties; and the
filler dispersion state. The layered silicate nanofillers were well
dispersed within intercalated and exfoliated structures and had
good affinity to epoxy resins. It was confirmed that nanocom-
posites exhibited enhanced thermal, mechanical, insulating, and
dielectric properties, compared with pure epoxy resin. Epoxy/
TiO2 nanocomposites were investigated [8], it being understood
that nanoparticles were the fundamental building blocks in the
creation of nanograined larger-scale structures with excellent
compositional and interfacial flexibility. Glass transition tem-
14 IEEE Electrical Insulation Magazine
peratures, dielectric properties, and space charge were evaluat-
ed, leading to the conclusion that nanometric fillers mitigate the
interfacial polarization characteristics of conventional materials,
reducing interfacial field strengths.
Synthesis and Analysis of Interaction Zones
Interfaces between polymer matrices and nanofillers are con-
sidered to play a dominant role in determining the properties of
nanodielectrics. A series of papers on interfaces [5], [22]–[24]
were published, leading to a deeper understanding of their prop-
erties (section titled Pioneering Work of T. J. Lewis). A multi-
core model was proposed in 2005 [26], using modification of
polymer morphology and charge transfer across interfaces to
explain the dielectric properties of polymer nanocomposites.
It is evident now that many factors should be included in
models of interfaces or interaction zones. These include silane
couplings, wettability and affinity, and hydrogen and covalent
bonding of polymers.
Silane couplings join organic polymers with inorganic sub-
stances (nanofillers in this case), as shown in Figure 3. In effect
two immiscible substances, e.g., organic and inorganic, are hy-
drogen bonded. Ionic and van der Waals forces also act between
two different substances. It is important to specify which kind of
force is exerted on the interface, in any specific case. The affinity
between two dissimilar materials in contact is a measure of the
ease with which they combine chemically and is important for
the wetting of interfaces. The force between the two materials,
exerted because of their affinity, may lead to the formation of a
bound polymer layer. It is suggested in [27], [28] that an inter-
facial hydrogen bonding layer can be enlarged when surface hy-
droxyl groups are generated by heating alumina nanoparticles,
and that the nanoparticle surfaces can be functionalized with
3-glycidoxypropyltrimethoxy-silane to form Al-O-Si bonds.
Wettability is an important factor in achieving homoge-
neous mixing of two materials. To disperse inorganic nanofillers
through organic polymer matrices, the affinity between their sur-
Figure 3. Chemical structure of silane couplings.
faces in contact must be considered. Surface tension is a direct
measure of the affinity between two substances. It is necessary
to reduce the difference between the surface tensions of the two
materials to obtain homogeneous mixing. Common practice is
to use compatibilizers for polymer alloys and coupling agents
for polymer/inorganic composites. Surface tension is a force but
also involves free energy. The solubility parameter (SP) is often
used as a semi-quantitative measure of the affinity (degree of
miscibility) of polymers with organic modifiers and compatibil-
izers. It corresponds to the square root of the cohesive energy
density for the material in question, where the cohesive ener-
gy density is the energy needed to remove a molecule from its
nearest neighbors divided by the total volume of the removed
molecule. SP = (ΔE/V)1/2, where ΔE and V are, respectively, the
evaporation energy per mole required to form a gas at zero pres-
sure (infinite separation of the molecules), and the molar volume
[29], [30]. It can be calculated approximately, if the chemical
structure is known.
Several interfacial models have been proposed. Wilkes’s
model dates back to 1989 [31]. In it silica is partially distrib-
uted in the outer polymer region of the covalent bonding sys-
tem produced by the end cap method, and silica and polymer
combine to form a network structure in the hydrogen bonding
system produced by the direct mixing method. A comparative
study of silica-filled polystyrene and thin polystyrene films was
made using a two-layer model [32], each layer having a different
glass transition temperature. Tanaka et al. [26] have proposed a
generalized multicore model, in reality a three-layer model. The
core consists of a bonded layer (the first layer), a bound layer
(the second layer), and a loose layer (the third layer). In addi-
tion, an electric double layer, responsible for charge transfer and
triboelectricity, is present. The first layer is a region of chemical
bonding between inorganic fillers and organic polymer matri-
ces. The second layer is a region with special morphology, e.g.,
spherulites formed because of the influence of the first layer, or
a stoichiometrically cross-linked region. The third layer is a re-
gion with different morphology from the host polymer matrices
and is thought to be formed under the influence of the process
that forms the second layer. This is a region of incomplete stoi-
chiometrical cross-linking. A new model focusing on polymer
chain alignment was proposed in [33], specifically to explain the
effects of surface modification.
Various models have been proposed, but very little quanti-
tative matching has yet been demonstrated between any model
and experimental results. Computer simulation is awaited to
promote more quantitative investigation.
Difference Between Nanocomposites
and Nanomicrocomposites
To this point combination of pure polymers with filler sub-
stances has been discussed. In practice few pure polymers are
used, especially where mechanical strength is required. Instead,
microfilled polymers, usually called filled resins, are produced
for many applications. They are loaded with nanofiller to pro-
duce nanomicrocomposites or nanostructured microcomposites.
Layered silica and microsilica mixture composites have been
evaluated [34]. It was shown that a nano- and micro-filler mix-
January/February — Vol. 29, No. 1 15
Figure 4. Classification of composites based on the size of the
disperse phase.
ture improves electrical insulation properties and maintains low
thermal expansion. However, addition of nanoscale layered sili-
cates tends to increase resin viscosity and cost. It is necessary to
optimize the contents of layered silicates to improve their elec-
trical insulation properties. Nanostructured polymer microcom-
posites, using the same composites as in [34], were investigated
[35]. They were evaluated using thermal and stability analysis,
infrared spectroscopy, dielectric spectroscopy, breakdown char-
acteristics, partial-discharge (PD) resistance, space charge, and
conduction current. The results strongly support nanostructured
microcomposites using nanoclays as a viable technological op-
tion for electrotechnical applications. Composites with high
thermal conductivity and sufficient dielectric breakdown volt-
age have been synthesized. High thermal conductivity can be
achieved by loading polymers with microfillers such as boron
nitride. Nanofiller addition will improve dielectric breakdown
performance [36], [37].
Supercomposites with two or more functions are now a re-
search target. High-permittivity and low-loss composites, and
low-permittivity and high-breakdown-strength composites, are
awaited [38].
Classification of composites based on disperse phase size is
shown in Figure 4. A disperse phase such as an inorganic filler
with a diameter of several tens of micrometers is usually inserted
in the resins of microcomposites (filled resins). Before the advent
of nanocomposites, much work on polymer alloy materials was
done in the early 1990s. Polymer alloy materials are made by
blending two or more polymers. The size of the disperse phase is
generally in the submicron range. One of the biggest successes
is the development of materials composed of base polymer and
elastomer. These materials have a fracture toughness superior
to that of the base polymer, because of the submicron-scale
dispersed elastomer. Nanocomposites with a disperse phase on
the nanoscale represent an extension of polymer alloy materi-
als. Nanofiller development and ready availability of nanofillers
seem to have promoted nanocomposite research.
In nanomicrocomposites or nanostructured microcomposites,
the size of the disperse phase ranges from nanometers to mi-
crometers. Nanomicrocomposites have the properties attributed
 to the nanometer disperse phase (nanofiller) and to the microme-
ter disperse phase (microfiller). They are therefore materials that
originated in filled resins and were advanced by polymer-alloy
and nanocomposite technology. Composites are either super-
composites or multifunctional composites.
Fabrication Methods
Nanofillers should be homogeneously dispersed, microscopi-
cally and macroscopically, in a polymer matrix and should be
tightly bound to the surrounding polymer. It is recognized that
surface treatment will bring about more homogeneous disper-
sion. Carefully chosen glue is necessary to bind organic poly-
mers and inorganic fillers that are totally immiscible. Tight bind-
ing has not yet been achieved consistently.
Nanofiller agglomeration tends to occur in the process of fab-
ricating a composite, and it is necessary to reduce or eliminate
it. Techniques have been borrowed from chemistry, including
intercalation methods, sol-gel methods, hydrothermal methods,

Figure 5. Three main nanocomposite fabrication methods.

16 IEEE Electrical Insulation Magazine

sonicator methods, mechanical mixing methods, and high-pres-
sure-orifice methods. Masterbatches of uncured resins loaded
with nanofillers are now available.
There are three main nanocomposite preparation methods, as
shown in Figure 5. Preparation of clay nanocomposites uses the
intercalation method. The first nanocomposite (Nylon-6 Clay
Hybrid) produced by the Toyota group was prepared using this
method and polymerization. Polymerization requires a chemi-
cal plant to polymerize the monomer dispersed with organically
modified clays, while melt blending has the advantage that clay
nanocomposites can be made relatively easily using thermo-
plastic resins. A low-cost manufacturing method in which un-
modified clays are dispersed in polyamide (Nylon) using a wa-
ter slurry technique has been developed [39]. The intercalation
method for producing clay nanocomposites has been improved
for industrial materials.
In the sol-gel method, the reactions forming the base poly-
mer and the nanofillers occur simultaneously. The latter are
formed by the hydrolysis and condensation reactions of alkox-
ides. Nanocomposite preparation using the sol-gel method was
originally unsuitable for industrial manufacture. However it has
been improved recently and is now widely accepted in industry.
The direct dispersion method is the simplest of the three. As
mentioned above, it is difficult to disperse nanofillers homoge-
neously. However, recent improvement of mixing devices and
surface treatment techniques has helped [40], [41].
The Last 10 Years of Research
on Nanodielectric Materials
General Trend
During the period 2000 to 2005 many kinds of polymer nano-
composites were prepared, and their properties were encourag-
ing further research. Polymer matrices such as epoxy, polyethyl-
ene, polypropylene, and ethylene vinyl acetate have been favored
because they are conventional insulating materials. Nanofillers
such as layered silicate, SiO2 (silica), TiO2 (titania), Al2O3 (alu-
mina), and MgO (magnesia) have been favored because some
of them have been used as conventional filled resins in industry.
Recently, in the early 2010s, combinations of silicone elasto-
mers with silica have attracted attention. These elastomer com-
posites are nanomicrocomposites by nature.
Figure 6 shows the number of papers on nanocomposite
dielectrics published in the IEEE Transactions on Dielectrics
and Electrical Insulation and the number of insulation-related
conferences each year since 1994. As stated above, one paper
predicting the future appeared in 1994, but no papers presenting
experimental data were published until 2002, when two confer-
ence papers appeared. A special issue of IEEE Transactions on
Dielectrics and Electrical Insulation on nanocomposites was
published in 2008. In addition, 26 papers (written in English)
were published in a special issue of IEEJ Transactions on Fun-
damentals and Materials in 2006. These papers are not included
in Figure 6.
It might be claimed that Figure 6 shows that the nanocompos-
ite bubble burst in 2010. Has interest in nanocomposites waned?
It probably has not; 18 IEEE Transactions on Dielectrics and
January/February — Vol. 29, No. 1 17
Figure 6. Number of papers on nanocomposite dielectrics pub-
lished in IEEE Transactions on Dielectrics and Electrical In-
sulation (TDEI) and number of insulation-related conferences
including CEIDP, ISEI, ICSD, ICPADM, and ISH.
Electrical Insulation journal papers were published in the first
half of 2012. It is important to strive for a better understanding
of the fundamentals and to find more industrial applications.
Characterization of Nanocomposites
Polymer nanocomposite materials prepared for research are
characterized by conventional advanced analytical methods
such as
(1) wide-angle X-ray diffraction,
(2) small-angle X-ray scattering,
(3) energy-dispersive X-ray spectroscopy,
(4) scanning electron microscopy,
(5) field-emission scanning electron microscopy,
(6) TEM,
(7) atomic force microscopy,
(8) electron spin resonance, and
(9) positron annihilation spectroscopy.
Scanning electron microscopy and TEM micrographs are fre-
quently used to evaluate the dispersion of nanofillers in polymer
matrices, as shown in Figure 7. Unfortunately such micrographs
provide limited information. An image analyzer can also help
to quantify particle dispersion. Trials were carried out using the
public-domain software ImageJ (National Institutes of Health,
Bethesda, MD, USA) [44] and the commercial software ImageA
(A-zokun, Asahi Kasei Engineering, Minato-ku, Tokyo, Japan)
[45]. The former was applied to TEM images of 12.5 wt% nano-
silica/cross-linked polyethylene (XLPE) nanocomposites, with
and without vinyl treatment, while the latter was applied to scan-
ning electron microscopy images of epoxy/silica nanocompos-
ites with different nanosilica loadings.
Energy-dispersive X-ray spectroscopy may be used to ana-
lyze distributions of atoms within composites. Silica SiO2 was
detected in epoxy resins filled with layered silicate (0.45 wt%)
and microsilica (60 wt%) [35], while several different atoms
such as Fe and Mg, in addition to C, O, and Si, were found
in polyamide/layered silicate nanocomposites [46] and epoxy/
layered silicate nanocomposites [47]. Atomic force microscopy
 Figure 7. Transmission electron microscopy micrographs of layered silicates and nanosilica dis-
persed in polymer matrices [42], [43].
can give information of nanoscale roughness on surfaces; it was
used to study nanocomposite surfaces roughened by PDs [48].
Wide-angle X-ray diffraction and small-angle X-ray scattering
are often used for material characterization but rarely in dielec-
trics. One example has been published [46] that analyzed deg-
radation of a nanocomposite by PDs. Electron spin resonance
was used in an attempt to identify lone pairs of electrons, i.e.,
trapped electrons or holes in XLPE and in 12.5 wt% of vinylsi-
lane-treated SiO2 nanoparticles in XLPE [49]. Positron annihi-
lation spectroscopy will yield the free volume size in nanocom-
posites, e.g., in styrene-butadiene rubber/montmorillonite clay
nanocomposites [50]. In [51] various physical and chemical
methods are critically reviewed as possible tools for character-
izing nanocomposites.
Verified Dielectric Properties of Nanocomposites
Dielectric properties include PD resistance, treeing lifetime,
dielectric breakdown strength, space-charge density, tracking
resistance, permittivity, and dc conductivity. Approximately
500 journal and conference papers have been published on
nanocomposites (nanodielectric materials) in the past 10 years.
Much valuable knowledge has been accumulated. Some brief
comments follow.
Polymer matrices or hosts of interest include epoxy resins,
polyethylene, XLPE, polypropylene, ethylene vinyl acetate,
Table 1. Qualitative Improvement of Some Characteristics of Polymer Nanocomposites.
Property Improvement
Partial-discharge resistance Enhancement
Treeing lifetime Prolongation
Space charge Reduction
Tracking resistance Enhancement
Breakdown strength Increase/No change
Permittivity Increase/Decrease
Dielectric loss Complicated
dc conductivity Increase/Decrease
18 IEEE Electrical Insulation Magazine
polyester, polyimide, polyimide-amide, polyester-imide, and
silicone elastomers. Nanofillers of interest include layered sili-
cate (natural and synthetic clays, montmorillonite), silica (SiO2,
fume fused, precipitated types), titania (TiO2), silicon carbide
(SiC), alumina (Al2O3), boehmite (AlOOH), magnesia (MgO),
zinc oxide (ZnO), zirconia (ZrO2), barium titanate (BaTiO3),
and polyhedral oligomeric silsesquioxane (POSS). Nanofillers
are often surface treated with silane coupling agents. Silicone
nanocomposite is a late comer that has been intensively investi-
gated recently.
Nanofillers may be homogeneously dispersed in polymer
matrices as described in the section titled Fabrication Methods.
Various dielectric properties of the resulting nanocomposites
are of interest. How can they be improved? There is no doubt
that PD resistance, treeing lifetime, and space charge can be
significantly improved by loading the matrices with appropriate
nanofillers (Table 1). Surprisingly, permittivity decreases when
a high-permittivity filler such as titania is incorporated, even
at low filler content. Breakdown strength is also an important
engineering characteristic, and it seems to be sensitive to fac-
tors such as filler dispersion, complex interfaces, and polymer
morphological characteristics associated with ions, dipoles, and
traps. The tracking properties of polymer insulators intended for
outdoor use are important. Improvement of these properties is
expected. At present, silicone rubber containing nanosilica filler
Remarks
Nanosegmentation of base polymers
Especially under moderate field
Elevated threshold for charge injection
Similar to partial-discharge resistance
Coupling and impurity effects
Increase under limited conditions
Complicated interface structures
Roles of ion traps and impurities
is of considerable research interest; the filler particle size may
vary from several nanometers to several micrometers. Recently,
great progress has been made in increasing tracking resistance
of silicone rubbers by nanosilica loading.
CIGRE activities have led to three interesting papers [51]–
[53]. The first is a comprehensive review of contemporary
knowledge on nanodielectric materials. The other two are based
on work done on the same samples by many investigators. The
XLPE and XLPE/fumed silica nanocomposite samples were
supplied from one source [52], and epoxy, epoxy/silica nano-
composite, and epoxy/silica nanomicrocomposite samples were
supplied from another [53].
Computer Simulation
Computer simulation of the mechanical properties of com-
posites is popular [54], [55]. It includes molecular dynamics
simulation, Monte Carlo simulation, and ab initio computation.
It would also be useful for clarifying dynamic behavior such
as the formation of interfaces and dispersion of nanoparticles
in polymer matrices. Some phenomena and performances have
been qualitatively explained [56]–[61], but the technique is still
maturing in the context of nanocomposites.
Molecular dynamics simulation of thermosetting resins in-
corporating nanofillers [58], [60] has demonstrated several char-
acteristics. First, the distribution of created bonds is changed by
the asymmetrical interaction between monomer and surface, and
the affinity of the hardener brings about an increase in the number
of near-surface bonds. Second, the segmental motion of reacted
resins is not affected by the surface affinity in regions far from
the surface, but it changes drastically near the surface. It was
suggested that the state of interfaces is correlated with the mul-
ticore interfacial model, as stated in the section titled Synthesis
and Analysis of Interaction Zones. In an ab initio computational
study [59] the theory of local dielectric permittivity was applied
to understand variations of static and optical dielectric constant
across idealized Si-SiO2, Si-HfO2, and SiO2-polymer interfaces
over interatomic distances. These variations have been corre-
lated with the chemistry of the interfaces, e.g., dangling bonds
and multiple oxidation states. The layer decomposed density of
states approach has been used to compute the electronic struc-
ture variation across Si-HfO2 and SiO2-polymer interfaces and
to elucidate band bending, band offsets, and the creation of trap
states at interfaces. Filler dispersion in a polyamide-imide/silica
nanocomposite system has been studied by molecular dynamics
simulation [61]; adhesive fracture energy at the interfaces be-
tween silica and solvents was calculated, and Brownian motion
of the silica particles was simulated to clarify their dispersion. It
was found that the colloidal state of silica is maintained by cov-
ering the silica surface with a new low-hygroscopicity solvent,
and the chemical structure of the polymer influences the disper-
sion of the silica. It was claimed that the method is useful when
attempting to determine the optimum conditions for good filler
dispersion in nanocomposite systems.
Plausible Applications
Some of the possible applications of nanocomposites lie in
motor windings (synthetic enamel) [62], [63], generator wind-
ings (epoxy) [64], switchgear spacers (epoxy) [65], capacitors
January/February — Vol. 29, No. 1 19
(polypropylene) [66], ac and dc cable insulation (polyethylene
and XLPE) [67]–[69], silicone elastomers for outdoor use [70],
[71], and microelectronics PWB (printed wiring board) and
packaging (epoxy) [72].
Plausible applications of nanocomposites in the electric pow-
er field are summarized in Figure 8 [73]. They seem to offer
advantages of higher efficiency, longer service life, and reduced
size of equipment. At present, energy consumption is increasing
around the world, and global warming is becoming more serious
every year. Energy saving and environmental friendliness are in-
ternational concerns. Nanocomposites have the potential to help
solve these problems.
When the use of nanotechnology and nanocomposites is
widespread, one might reasonably be concerned about potential
nanohazards in work places and in homes [74]–[76]. Important
as it is, that topic is beyond the scope of this article.
The Next 50 Years
We have looked back on 50 years of nanodielectric material
history. We see that polymer nanocomposites or nanodielectric
materials are promising as near-future high-performance materi-
als, but unfortunately the materials themselves have not yet been
fully developed. In which directions should research proceed?
We should address areas such as optimization of material
fabrication methods, basic understanding of interfaces, clarifica-
tion of dielectric characteristics, computer simulation, and in-
dustrial applications. In the foreseeable future, multifunctional
supercomposites, essentially extensions of nanocomposites, will
demand attention. As a current example, fiberglass-reinforced
plastics are multifunctional materials, lightweight, strong, and
transparent at radio frequencies. Thus they are used to shield ra-
dar equipment. Nanocomposites show considerable promise as
multifunctional and high-performance materials. We need new
nanocomposites that can withstand high voltage and which offer
other properties such as low thermal expansion coefficient, high
thermal conductivity, high or low permittivity, varied perme-
abilities, and high-temperature endurance. The search for such
materials is already underway.
There are two ways to see our future, first through advanc-
es in science and technology and second through concerns for
a sustainable society. The first is driven essentially by human
curiosity. Molecular tailoring will probably be the key. In rela-
tion to the second, we are now facing crucial global issues such
as population growth and an increase of energy consumption,
as shown in Figure 9. These will give rise to difficult problems
such as increase in petroleum demand, lack of metal resources,
and global warming. These will demand extensive innovation in
materials science to create sustainable materials. In that context
nanocomposites can be expected to serve our society well, be-
cause they will have high mechanical and electrical performance
and the ability to function as metal substitutes, bio-mimetic sys-
tems, reusable systems, and carbon-neutral systems, all in an
environmentally friendly way.
Interdisciplinary investigations are necessary. Electrical engi-
neers, physicists, chemists, biologists, computer scientists, and
people working in industry need to cooperate. There is plenty of
room for nanodielectric materials!
 Figure 8. Plausible applications of nanocomposites in the electric power field [73].

Figure 9. Nanocomposites as sustainable materials.

20 IEEE Electrical Insulation Magazine

Acknowledgments
The authors are much indebted to Dr. R. J. Fleming, Co-
Editor-in-Chief EIM, for his help in improving the English ex-
pression and quality of the manuscript, and to Dr. C. W. Reed for
his kind encouragement and valuable suggestions.
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 Toshikatsu Tanaka (SM ’95, F ’00) was
born in Tokyo, Japan, in 1939. He is pres-
ently Research Fellow at IPS Research
Center of Waseda University. He received
the PhD degree from Osaka University in
1968. He worked at CRIEPI for 38 years,
the last six as vice president, and then at
IPS Graduate School, Waseda University,
until March 2009. He was visiting lecturer
at Salford University in the UK (1970–1972), visiting associate
professor at Rensselaer Polytechnic Institute and General Elec-
tric in the United States (1975–1976), and visiting professor at
Kyushu University in Japan (1993–1997). He was a recipient of
the Ministry of Science and Technology Prize (Japan) in 2000,
IEEJ Technology Progress Award in 1988, IEEE Whitehead Me-
morial Lecture Award in 2001, and IEEE Dakin Award in 2002.
He is active in IEEJ, IEEE, and CIGRE. He is an IEEE Fellow
and an IEEJ Life Fellow.
January/February — Vol. 29, No. 1 23
Takahiro Imai (M ’12) was born in Gifu
Prefecture, Japan, in 1972. He received the
BEng and MEng degrees in applied chemi-
cal engineering from Waseda University in
1996 and 1998, respectively, and DEng in
materials science in 2006. He joined the
Toshiba Corporation in 1998. Presently he
is engaged in developing electrical insula-
tion materials and systems for switchgear
in the Power and Industrial Systems R&D Center of Toshiba
Corporation. He received the IEE of Japan (IEEJ) Distinguished
Paper Award in 2006. He is a member of the IEEJ and the Soci-
ety of Polymer Science, Japan (SPSJ).