Surface modification of nanoscale fillers for

improving properties of polymer

nanocomposites: a review
M. Z. Rong*1, M. Q. Zhang and W. H. Ruan
Direct incorporation of inorganic nanoscale building blocks into polymers represents a typical
way for preparing polymeric nanocomposites. The most important aspect in preparation of
nanocomposites through dispersive blending is surface modification of the nanofillers. It is able to
increase hydrophobicity of the fillers, enhance interfacial adhesion via chain entanglement or
chemical bonding and eliminate the loosen structure of filler agglomerates. The present paper
reviews the state of the art of nanoparticles/polymer composites, including the specific surface
pretreatment techniques and their applications. Especially, the role of treated nanoparticles and
the mechanisms involved in the improvement of mechanical properties and wear resistance of the
composites are highlighted.
Keywords: Nanocomposites, Polymer matrix composites, Surface modification, Mechanical properties, Tribological performance

Introduction solution is still the most convenient way for preparation

In recent years, many laboratories have launched projects
on composites containing particles on the nanometre
scale with varying success. For example, nanosized
inorganic particles have successively been added to
polymers to improve their toughness and tribological
performance.1 Owing to the ultrafine dimension of
nanoparticles, a large fraction of atoms can reside at
the interface, leading to strong interfacial interaction if a
homogeneous dispersion of the nanofillers in the polymer
matrix is guaranteed. As a result, the nanocomposites
coupled with a great number of interfaces can be expected
to provide unusual performance.
However, it is very difficult to well disperse nanopar-
ticles in polymers because the particles with high surface
energy are easy to agglomerate. In addition, hydrophilic
nanoparticles and hydrophobic polymers are not com-
patible in nature, which will result in poor interfacial
interaction. All these deficiencies obstruct effective
utilisation of inorganic nanoparticles in polymer com-
posites. Physical mixtures of preformed inorganic
nanoparticles and polymers would weaken mechanical
or optical properties of the resultant materials owing to
particle agglomeration. Because nanoparticle agglomer-
ates are rather friable, they can hardly undertake stress
and therefore are detrimental to the mechanical proper-
ties of polymeric composites.
From the viewpoint of mass production, nevertheless,
incorporation of nanosize fillers into polymer melt or
Materials Science Institute, Key Laboratory for Polymeric Composite and
Functional Materials of Ministry of Education, Zhongshan University,
Guangzhou 510275, China
*Corresponding author, email cesrmz@zsu.edu.cn
of polymeric nanocomposites. For this purpose, the
manufacturing approach, i.e. distribution of preformed
particles in a polymeric matrix with traditional com-
pounding techniques, should be considerably upgraded
to overcome the aforesaid shortcomings and to produce
nanocomposites with expected and forecasted excep-
tional properties.
An ideal nanocomposite should be free of any
agglomerates, contain optimum filler content and
maintain physicochemical characteristics of its indivi-
dual components.2 So far, a series of methods have been
tried in two aspects: development of new compounding
(dispersion) technique and surface pretreatment
approaches for nanoparticles. Because internanoparticle
interaction is so strong that the shear force provided by
conventional mixing facilities often fails to break apart
the nanoparticle agglomerates in either polymer melt or
solution,3 research efforts should be laid on the latter
aspect, which is more likely to give full play to the
reinforcing effect of nanoparticulate fillers even though
a uniform dispersion in polymers is unavailable.
In microfiller/polymer composites, surface modifica-
tion of the particles has already proved to be a wide
applicable technique to minimise particle/particle inter-
action and to enhance particle/matrix interaction. With
the recent developments in nanoscience and nanotech-
nology, the correlation of polymer nanocomposites
properties with surface modification of nanoparticles is
also becoming a point of great interests. Although much
of the work is still continuing, some findings have shown
brilliant prospects. In the following sections, a review is
presented on the surface modifications of nanoparticles
and their influences on mechanical and tribological
performance of polymer based nanocomposites as well
as the interpretations of the results.

ß 2006 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 15 August 2005; accepted 28 November 2005
DOI 10.1179/174328406X101247 Materials Science and Technology 2006 VOL 22 NO 7 787
Rong et al. Surface modification of nanoscale fillers
Surface pretreatment techniques
In general, surface modification of inorganic fillers
means introduction of organic coatings onto the fillers,
which can be carried out by utilising physical and
chemical interactions between the fillers and the
modifiers. The resultant bonding is often a mixture of
secondary and chemical bonds. Much understanding of
treating techniques, interfacial characterisation and
interfacial effect on composites properties has been
acquired for microcomposites.4 It is known that there is
no evident difference between the treatments of micro-
particles and nanoparticles except that it is quite difficult
for the modifiers to penetrate into the tightly bonded
nanoparticle agglomerates, especially in the case of
physical treatments such as surfactant treatment and
polymer encapsulation.
Physical methods
Physical treatment (through covering the filler with a
low molecular weight surfactant or a high molecular
weight polymer) usually results in secondary forces (such
as van der Waals, hydrogen and electrostatic forces)
between particles and the modifier. A surfactant
contains one or more polar groups and a long aliphatic
chain. The principle of surfactant treatment is the
preferential adsorption of polar group of the surfactant
onto the high energy surface of the fillers by electrostatic
interaction. Ionic bonds can be formed under certain
circumstances. A typical example can be cited regarding
stearic acid treated CaCO3.5 It is proved that ionic
bonds were established between the surfactant molecules
and the filler surface. Therefore, a reduced surface
energy resulted from the shield made of C18 alkyl chains
on the filler surface. Alkyl dihydrogenphosphate, con-
taining functional groups such as olefine, chloro,
methacryloxy and mercapto, is another kind of effective
surface modifiers for calcium carbonate fillers.6 It was
shown that alkyl dihydrogenphosphate molecules can
react with CaCO3, resulting in a dibasic calcium salt of
phosphate. The products are deposited on CaCO3 and
provide CaCO3 with certain hydrophobicity, as con-
vinced by the good dispersibility in mineral oil.7 Besides,
treatment with alkyl dihydrogenphosphates always leads
to an increase in surface area of the treated particles.
This can be ascribed to surface erosion and/or to
calcium salt formation.
Another technique of physical treatment lies in
encapsulating inorganic fine particles with preformed
polymers or in situ formed polymers. In the former case,
a macromolecular dispersant, hyperdispersant, has been
successfully used.8 Similar to surfactants, polymeric
dispersants consist of two major components. One is
a functional group, such as –OH, –NH2, –NR3z,
–COOH, –COO2, –SO3H, –SO32 and –PO422, which
helps anchoring of the dispersants to the particles
surface through hydroxyl and electrostatic bonds. The
other is a solvable macromolecular chain, such as
polyolefine, polyester, polyacrylate and polyether, which
is appropriate to be dispersed in different media of low
to high polarity. Compared with traditional surfactants,
hyperdispersants have the following advantages:
(i) they are anchored to the particles surface more
strongly than surfactants and therefore, can
hardly be desorbed
788 Materials Science and Technology 2006 VOL 22 NO
(ii) the long polymeric chains can interfere with the
reagglomeration of the particles more effectively.
However, it should be noted that hyperdispersants
can only encapsulate nanoparticle agglomerates
and can hardly diffuse into the agglomerates,
owing to their long molecular feature.
Relatively, encapsulation with in situ formed polymers
might generate more uniform coverage. In the presence
of nanoparticles, the polymer can be formed by either
solution or emulsion polymerisation. Yoshinaga and co-
workers9 utilised radical polymerisation of vinyl mono-
mers to produce core–shell SiO2 particles. Because the
surfaces of silica colloid particles possess negative
charges on the electric double layer, the initiator 2,29-
azobis(2-amidinopropane)dihydrochloride can be con-
centrated and resulted in free radicals on the silica
surface. A solvent with lower miscibility to the polymer
was used to facilitate the attachment of the macro-
molecular chains to the particles. Encapsulation of small
inorganic particles by a polymer layer can also be
carried out by applying an emulsion polymerisation
process.10 Polymerisation occurs primarily at the surface
of unmodified particles owing to the adsorption of the
monomer on the surface, followed by polymerisation in
the adsorbed layer. The formation of an initial hydro-
phobic layer on the surface of the particles is crucial for
formation of the polymer shell, which can be introduced
by pretreating the particles with non-ionic surfactants,
amphiphilic block copolymers, etc.
Chemical methods
In comparison with physical methods, effect of surface
modification based on chemical interaction is more
significant because the covalent attachment modifier
avoids its desorption from the particles surface. Besides,
a fine adjustment of interfacial interaction in the
composites with chemically pretreated nanoparticles
can be completed by introducing modifiers containing
reactive groups, which helps construct chemical bonding
between the fillers and the matrix polymer.
Among the available techniques, coupling agent
treatment is the most popular and the easiest to be
applied. A variety of coupling agents, such as silane,
titanate and zirconate, have been used to improve the
adhesion between inorganic fillers and organic matrices.
Extensive information on reaction mechanisms and
effects of coupling agents is available for microfillers,
but fewer for nanoparticles. Gunko et al.11 studied the
features of fumed silica coverage with several kinds of
silanes from both experimental and theoretical aspects.
Depending on the pretreatment conditions, the attached
silanes can reduce the hydrophilic properties of silica to
different extents. However, it should be pointed out that
the uniform surface coverage of coupling agent on
nanoparticles is hard to realise by simple physical and
mechanical means.
Grafting macromolecules onto inorganic particles has
some advantages over modification by low molecular
surfactants or coupling agents. The polymer grafted
particles can possess desired properties through a proper
selection of species of graft monomers and the graft
conditions so that the interfacial characteristics between
the treated nanoparticles and the matrix can be tailor
made when manufacturing nanocomposites. Besides,
the fragile nanoparticle agglomerates become stronger
7

1 Schematic drawing of polymer grafted from nanoparticles by using double bonds on particles
because they turn into a nanocomposite microstructure
comprising the nanoparticles, the grafted and the
ungrafted (homopolymerised) polymer. A series of work
has been carried out in this field of growing interest for
purposes of improving the dispersibility of the nano-
particles in solvents and their compatibility in polymers.
Mostly, the graft polymerisation is conducted via two
routes:
(i) monomers are polymerised from active com-
pounds (initiators or comonomers) covalently
attached to the inorganic surface (called ‘grafting
from’)
(ii) ready made polymers with reactive end groups
react with the functional groups on the particles
(called ‘grafting to’).
The latter benefits the control of the molecular weight of
the grafting polymer. But generally, the former
approach has advantage over the latter one because it
is more difficult for polymers to penetrate into the
particulate agglomeration than monomers. Besides, the
‘grafting to’ technique would lead to a polymer coating
on the particles, which might hinder the attachments of
other polymers.
With respect to ‘grafting from’ technique, there are
two routes initiating polymerisation from the particles.
One is surface modification with polymerisable groups,
for instance, by means of silane treatment (Fig. 1). The
other is surface modification with initiating groups
(Fig. 2). Comparatively, the former is easier while the
latter favours higher grafting percentage and grafting
efficiency. Espiard and Guyot12 firstly treated silica
nanoparticle surface with silane coupling agent contain-
ing a double bond, i.e. methacryloxypropyltrimethox-
ysilane (MPTMS). Then, the modified silica was grafted
with polyethylacrylate in emulsion solution. Oosterling
et al.13 grafted polystyrene (PS) and poly(styrene-
block-isoprene) onto nanosilica (,12 nm) by initiating
immobilised double bonds on the silica surface with
t-butylithium and then adding the monomers into the
reaction suspension. Rong et al.14,15 grafted the nano-
sized alumina and silicon carbide with PS and poly-
acrylamide (PAAm) using a similar route in solution.
Rong et al. Surface modification of nanoscale fillers
The same SiC nanoparticles were also grafted by
polyglycidylmethacrylate (PGMA) in a surfactant free
emulsion.16 The emulsion polymerisation loci have
proven to be located on the surface of SiC nanoparticles
owing to the higher number of nanoparticles and their
hydrophobic surface feature. This reaction mechanism is
particularly important to ensure effective encapsulation
and graft of PGMA surrounding the nanoparticles.
Surface initiated polymerisation can be achieved by
different mechanisms such as free radical, cationic,17
ring opening metathesis polymerisation (ROMP),18
atom transfer radical polymerisation (ATRP)19,20 and
anionic polymerisation.21,22 Tsubokawa and co-work-
ers23–28 systematically investigated the grafting of
various polymers onto ultrafine silica and carbon black
by polymerisation starting from the initiating groups
previously introduced onto the surfaces. They have
conducted anionic, cationic and radical graft polymer-
isation of various monomers initiated by potassium
carboxylate, acylium or benzylium perchlorate, and
peroxyester or azo groups already introduced onto
ultrafine silica respectively. For example, surface
anchored peroxide initiator was attached to the surface
by treatment of silica particles with thionylchloride to
obtain surface Si–Cl groups, which were then reacted
with tert-butylhydroperoxide or diisopropylbenzene
hydroperoxide to form the initiating groups. The azo
groups are usually introduced onto untrafine particle
surface by two ways. One is the reaction of 4,49-
azobis(4-cyanopentanoic acid) (ACPA) with surface
epoxide groups, which are introduced by the treatment
of the particle with c-glycidoxypropyltrimethoxysilane
(GPS).24 The other is the reaction of ACPA with surface
isocyanate groups, which are introduced by the treat-
ment of the particle with toluene di-isocyanate (TDI).25
In addition, by means of an amide bond formed between
ACPA and an amine containing silane coupling agent
on the silica, azo initiator can also be immobilised onto
silica substrates.26
Besides chemical grafting, graft polymerisation onto
nanoparticles can also be realised by c irradiation, which
is superior to chemical graft process in improving graft
Materials Science and Technology 2006 VOL 22 NO 7 789
Rong et al. Surface modification of nanoscale fillers
2 Schematic drawing of polymer grafted from nanoparticles by using initiators on particles
homogeneity, controlling pollution and simplifying
procedure. Under the high energy radiation, the surfaces
of the nanoparticles outside and inside the agglomerates
are equally activated. Therefore, the low molecular
weight monomers are allowed to react with the activated
sites of the nanoparticles throughout the agglomerates.29
In more recent studies, it was found that various
polymers can be successively grafted on the surface of
silica nanoparticles by this method under quite mild
condition (at air atmosphere).30 The key point might be
the highly active surface of the nanoparticles. Besides,
different silica exhibits different reactivity. The precipi-
tated silica performs better than fumed silica.31 Another
interesting result is that some metal nanoparticles, such
as iron, nickel and cobalt, can be grafted with polymers
under irradiation even though these particles contain
few hydroxyl groups,32 indicating that the reactive site
can be either the hydroxyl group or the surface
structural defect. Indeed, the double bonds introduced
to the surface of particles by silane are helpful for the
higher grafting percentage.33
Effects of interfacial interaction on
performance of polymer nanocomposites
Properties of composite materials are determined by
four factors: characteristics of the components, compo-
sition, structure and interfacial interactions. The effect
of interphase depends on its amount and characteristics.
That is, amount of the material bonded in the interphase
and the interaction strength influence the composites
790 Materials Science and Technology 2006 VOL 22 NO
ultimate properties. Recognition of the role of the main
factors influencing interfacial adhesion and proper
surface modification would lead to achievements in
nanocomposites development.
The general idea of nanocomposites is based on the
concept of creating a very large interface between the
nanosized building blocks and the polymer matrix.
However, very often homogeneous distribution of the
nanoparticles is problematic, i.e. the expected large
surface cannot always be created. Besides, tuning of
interfacial interaction or coupling of the components
presents additional problems. In the subsequent para-
graphs, the issues important for further development in
this field and the questions to be solved in the future are
discussed by analysing a few selected references.
Influence of coupling agent, surfactant and
dispersant
Chan et al.34 added nano-CaCO3 (44 nm) into poly-
propylene (PP) by melt mixing. The nanoparticles
produced an increase in elastic modulus and impact
strength of the PP matrix. The reverse effect was found
for yield stress and tensile strength of the composites.
Both of these quantities were highest for the neat PP and
decreased as the volume fraction of CaCO3 increased. In
a recent report by another group, however, simultaneous
enhancement of yield strength, elongation at break,
impact strength, flexural modulus and Vicat softening
temperature of polyvinyl chloride (PVC) was shown
by the addition of 0–15 phr nano-CaCO3 particles.35 It
is therefore believed that PP must have very poor
7

interaction with the nanoparticles owing to its non-polar
character while the interfacial interaction should be much
more noticeable for the PVC composites. Evidently, the
interaction between the particles and the polymer matrix
plays a key role in composites performance.
To intensify interfacial interaction, surface modifica-
tion of fillers with surfactant or coupling agent, which
has been frequently utilised in making microcomposites,
is also expected to work in nanocomposites. However,
general solutions do not exist. A specific strategy must
be developed for each individual set of nanocomposites.
Zhang and Hua36 mixed CaCO3 (50 nm) with PP using a
twin screw extruder. The nanoparticles were pretreated
with a water soluble titanate coupling agent. In
comparison with fatty acid salt treated nano-CaCO3,
the coupling agent treated particles exhibit better
dispersion in PP. The impact strength of PP had an
increase of ,70% with the addition of 5–6 phr of
coupling agent pretreated nano-CaCO3 while only 50%
increase was measured for the fatty acid salt treated
nano-CaCO3 composites.
Home made phosphonate surfactants were also used
to modify nano-CaCO3 particles. Similarly, improve-
ment in Charpy impact strength of phosphonate treated
nano-CaCO3/PP composites was observed.37 In a work
by Ren and co-workers,38 the effect of a phosphonate
coupling agent was evaluated. The treated nano-CaCO3
can result in an increase in tensile and impact strength
while the untreated ones had nearly no reinforcing
effect. From the above discussion, it is possible to
extract the trend that various coupling agents, includ-
ing titanate, phosphate and aluminate,39 favour the
improvement of nanoparticle dispersion and mechanical
properties of polymer composites.
Usually, silane is not suitable for the surface
modification of CaCO3, but it is widely used in silica
treatment. Kruenate et al.40 reported such studies
related to the effects of commercial dispersant (Efka)
and silane coupling agent (thiocyanatopropyl-triethox-
ysilane) pretreatment of nano-silica on tensile properties
of PP. The tensile strength and modulus of PP mixed
with untreated nano-silica increased whereas the elonga-
tion to break decreased. Comparatively, treatment with
silane is more effective in improving the tensile strength
and modulus of PP/SiO2 composites (Table 1).
Actually, all commercial nano-CaCO3 particles have
been pretreated with stearic acid. Lazzeria et al.41 studied
the influence of stearic acid treatment on the mechanical
properties of precipitated CaCO3 (70 nm)/high density
polyethylene (HDPE) composites prepared by a twin
screw mixer–single screw extruder. The addition of
10 vol.-% nano-CaCO3 to HDPE caused a rise in
Young’s modulus and yield stress of its composites,
accompanied by a sharp drop in impact strength. The
employment of stearic acid slightly decreased both
Table 1 Mechanical properties of PP composites with treated and untreated nanosilica40
Material Elongation to break, %
PP 21.12¡2.43
PP/2%SiO2 13.19¡1.11
PP/2%SiO2/Efka 9.14¡2.38
PP/10%SiO2/Efka 10.12¡1.05
PP/2%SiO2/silane 11.80¡1.31
Rong et al. Surface modification of nanoscale fillers
3 Impact energy of stearic acid treated nano-CaCO3/PP
composites as function of filler content42
Young’s modulus and yield stress of the composites
compared with the uncoated CaCO3 composites while the
impact strength progressively increased.
The aforesaid surface pretreatment of nanoparticles is
usually completed by simply mixing the particles with
coupling agent or dispersant in a higher speed mixer
except for the wet treatment process (in water).
However, uniform surface coverage of nanoparticles is
hard to be achieved owing to the very low weight ratio
of coupling agent to nanoparticle agglomerates. To
solve this problem, an ultrahigh speed mixer has been
designed.42 The mixer has high speed (6000 rev min21),
special rotors that are designed to deal with nanopar-
ticles and atomiser by which the coupling agent is added.
It was demonstrated that the mechanical properties of
PP, especially the ductile properties, could be effectively
improved by introducing nano-CaCO3 modified by
stearic acid with the ultrahigh speed mixer (Fig. 3).
In most cases, nanoparticles were treated by coupling
agents or dispersants before compounding with poly-
mer. Because only the exterior nanoparticles of the
agglomerates can take part in the reaction, split of the
treated nanoparticle agglomerates during the subsequent
compounding with polymers would lead to an exposure
and reagglomeration of the unreacted interior particles.
Therefore, stabilisation of the split nanoparticles is
important. Wu and Ye43 firstly added HDPE into a two
roll mill preheated to 150uC. When the polymer was
thoroughly melted, both CaCO3 (40 nm) and stearic
acid at a desired composition were incorporated. It was
expected that the dispersed nanoparticles in the polymer
melt can be in situ activated by stearic acid and the
formation of larger nanoparticle agglomerates can be
prevented accordingly. Microstructural observation of
the fractured surfaces of the composites proved the
feasibility of their idea. That is, nearly no nanoparticle
agglomerates appeared when a proper dosage of the
Tensile strength, MPa Modulus, MPa
36.96¡0.40 1178.29¡42.18
40.21¡2.16 1376.46¡63.79
38.19¡1.44 1414.67¡10.40
33.60¡0.48 1603.31¡58.43
43.54¡1.85 1524.20¡45.57
Materials Science and Technology 2006 VOL 22 NO 7 791
Rong et al. Surface modification of nanoscale fillers
4 Izod impact strength of nano-CaCO3/PP composites as
function of filler content44
dispersing agent was applied. For the composites
containing 20 wt-% of nano-CaCO3 prepared in this
way, both impact strength and elongation to break of
HDPE were increased by .100%.
Influence of macromolecules encapsulation and
compatibiliser
In comparison with coupling agent, surfactant and
dispersant that belong to small molecules, encapsulation
with the high molecules, such as hyperdispersant, should
provide stronger interaction with polymer matrix for
nanoparticles owing to the enhanced interfacial entan-
glement. Li and Chen44 found that the hyperdispersant
CH-1A is more effective to improve impact strength of
PP/nano-CaCO3 composites than the conventional
dispersant and stearic acid (Fig. 4). Similar results were
presented in Ref. 39 for nano-CaCO3 reinforced low
density polyethylene (LDPE) composites. Both tensile
strength and elongation at break of LDPE composite
film filled by nano-CaCO3 treated with macromolecular
interfacial agent performed much better than the
composite containing nano-CaCO3 treated with alumi-
nate (Fig. 5). Zhang et al.45 also reported similar
behaviour for macromolecular dispersant pretreated
TiO2 (20 nm)/high impact polystyrene (HIPS) nano-
composites. When nano-TiO2 content is ,5 wt-%, not
only Young’s modulus, tensile strength and impact
strength, but also hardness of the composites are
enhanced.
Wang and Yan46 fabricated PP/CaCO3 nanocompo-
sites by melt blending where the CaCO3 nanoparticles
were pretreated with stearic acid or encapsulated by
poly(methylmethacrylate) (PMMA). The physical
encapsulation of nano-CaCO3 with PMMA was
obtained by in situ solution polymerisation. Their results
showed that the nano-CaCO3 particles covered by
PMMA were relatively homogeneously dispersed in PP
matrix. However, the PP composites containing either
stearic acid treated nano-CaCO3 or PMMA encapsu-
lated nano-CaCO3 gave similar mechanical perfor-
mance. Impact strength of PP composites was
improved by a factor of 2 as compared with that of
neat PP. In another work on PVC/nano-Sb2O3 nano-
composites, the researchers conducted surface modi-
fication of nano-Sb2O3 by in situ polymerisation of
methylmethacrylate (10 wt-% based on nano-Sb2O3
792 Materials Science and Technology 2006 VOL 22
5 Tensile strength of nano-CaCO3/LDPE composites as
function of filler content39
particles).47 The resultant PMMA shell covered on
nano-Sb2O3 particles strengthens the interaction
between the nanoparticles and the PVC matrix, leading
to breakdown of the nanoparticle agglomerates and
improved dispersion of the nanoparticles in PVC. As
a result, the treated nano-Sb2O3 particles stiffen,
strengthen and toughen PVC matrix with the maximum
effect at a loading of 2.5 wt-%. For PVC/CaCO3
nanocomposites, Wu et al.48 employed chlorinated
polyethylene (CPE) as an interfacial modifier when
preparing CPE/nano-CaCO3 (40 nm, titanate pre-
treated) masterbatch. Morphology investigation indi-
cated that the nano-CaCO3 particles in PVC matrix were
encapsulated with a CPE layer. Notched Izod impact
strength of the nanocomposites achieved a significant
improvement owing to the incorporation of CPE and
obtained the high value of 745 J m21.
Besides surface treatment of nanoparticles, incorpora-
tion of compatibiliser, such as PP grafted with maleic
anhydride (PP-g-MAH), was also demonstrated to be
capable of improving mechanical properties of nano-
composites. Zhang et al.49 studied the effect of PP-
g-MAH as interfacial modifier in PP/nano-CaCO3
composites. PP-g-MAH was synthesised by means of
solid phase graft copolymerisation. The addition of PP-
g-MAH improved notched impact strength (Fig. 6),
flexural strength and tensile strength of PP/nano-CaCO3
6 Effect of PP-g-MAH on notched impact strength of
nano-CaCO3/PP composites49
NO 7

7 Tensile strength of nano-SiO2–GPTS/PP and nano-
SiO2–GPTS–H20–C19/PP composites as function of
filler content53
composites. Fourier transform infrared (FTIR) proved
that PP-g-MAH had reacted with CaCO3, resulting in
reactive compatibilisation. In Ref. 50, a more compli-
cated manufacturing procedure to produce PP/nano-
CaCO3 composites was reported. Silane coupling agent
KH-570 treated nano-CaCO3 was encapsulated by
polymerised organic monomers in emulsion; meanwhile,
PP-g-MAH was prepared by a similar process. Through
melt mixing PP, PP-g-MAH and encapsulated CaCO3,
PP based nanocomposites were prepared. It was found
that Izod impact strength of the composites increased
two times over that of neat PP. By cross-experiments for
the effects of the filler/encapsulating polymer ratio and
the contents of PP-g-MAH and filler, the optimum
composition was determined as filler/encapsulating poly-
mer 10 : 1, PP-g-MAH 10 wt-% and CaCO3 5 wt-%.
Huang et al.51 carried out in situ graft polymerisation of
acrylic acid when preparing PP/nano-CaCO3 master-
batch, which was then diluted with PP by an extruder
and injected into nano-CaCO3/PP composite specimens.
It is shown that tensile strength and modulus of the
nanocomposites can be remarkably improved by this
measure while impact strength varies in reverse trend.
Epoxy has been used as a processing aid and a
dispersing agent for fumed nanosilica in producing melt
mixed polyethersulphone (PES) composites.52 Having
dispersed in matrix polymer, epoxy component was
polymerised to recover its mechanical properties. It was
found that strong interaction between the polar groups
of epoxy and the silanol groups on nanosilica helped to
disperse the particles into PES. Improvement in barrier
resistance to diffusion of solvents such as methylene
chloride, heat deflection temperature and impact
strength over neat PES was observed.
Influence of graft polymerisation and reactive
compatibilisation
Very interesting results were obtained by Xu et al.,53
who prepared a series of PP/silica grafted hyperbranched
polyester nanocomposites. The silane 3-glycidoxy pro-
pyltrimethoxysilane (GPTS) pretreated silica (30 nm)
was grafted by hyperbranched polyester (Boltorn H20),
which was then terminated by octadecylisocyanate (C19)
groups after the graft reaction. The incorporation of
silica grafted modified Boltorn H20 (3–5 wt-%SiO2)
greatly enhanced notched impact strength (Fig. 7) as
Rong et al. Surface modification of nanoscale fillers
well as tensile strength of the composites. The mould
flow index of PP composites increased when the silica
grafted modified Boltorn H20 particles were added, as
compared with PP/SiO2 or PP/SiO2–GPTS composites.
Because nanoparticles are very small, agglomeration
in nanocomposites is practically unavoidable. It has
been demonstrated that nanoparticle agglomerates
usually do not possess sufficient strength.54 As a result,
under the applied force, the agglomerates would easily
fracture leading to premature failure of the entire
composite. In consideration of this, Rong et al.30
performed a unique set of experiments with SiO2
nanoparticles in PP matrix with and without the
addition of grafting polymers (either PS or PMMA),
which have the ability to facilitate the dispersion of
nanoparticles, improve the interfacial interactions
between the particles and the matrix and especially
enhance the agglomerates strength. The coverage of
grafting polymer around SiO2 helps to increase tensile
strength of the nanocomposites, but nearly has no effect
on elastic modulus. The strain to failure was lower in the
untreated systems than that of neat PP. In the treated
system, however, the parameter increased with content
of the nanoparticles up to 2 vol.-%. At the same filler
loading, PP composites with grafted nano-SiO2 has an
impact strength 3–4 times higher than that of neat PP.
The above concept of strengthening nanoparticle
agglomerates by grafting polymer also works in making
antiwearing nanocomposites. A systematic research
carried out by Shi et al.55 evaluated the sliding wear
behaviour of epoxy containing nano-Al2O3 particles
with different pretreatments. In this work, nano-Al2O3
was grafted with acrylamide, styrene and ethylacrylate
by irradiation polymerisation respectively. It has been
proven that the amide groups of polyacrylamide take
part in the curing of epoxy resin, greatly enhancing the
interface interaction.56 Encapsulation of nano-Al2O3
with polystyrene or polyethylacrylate is believed to be
able to significantly increase the hydrophobicity of the
particles and therefore the compatibility with the
polymer matrix. As shown in Fig. 8, the high wear rate
of unfilled epoxy owing to the three-dimensional cross-
linking network is greatly reduced by adding nano-
Al2O3 particles, especially when treated nano-Al2O3 is
incorporated.57 Besides, the nanoparticles also reduce
frictional coefficient of epoxy and the composites with
treated nanoparticles have lower frictional coefficients.
For example, the frictional coefficient of Al2O3-c-
PAAM/epoxy is 0.35 that amounts to 61% of the value
of unfilled epoxy and 69% of the value of untreated
nano-Al2O3/epoxy.
Recently, Friedrich et al.58 combined chemical graft
approach of nanoparticles and reactive compatibilisa-
tion for nanocomposites preparation. That is, reactive
groups (epoxide or amine groups) were firstly introduced
onto nanoparticles by chemical graft polymerisation,
which was then melt blended with PP at different
compositions. Meanwhile, differently functionalised PP,
such as maleic anhydride grafted polypropylene (PP-
MAH), amine functionalised PP (PP-NH2) and epoxide
functionalised PP (PP-GMA), was added respectively so
as to build up chemical bonding at the filler/matrix
interface during the composites manufacturing. It was
shown that the reactive compatibilisation is capable
of providing better dispersion of the nanoparticles,
Materials Science and Technology 2006 VOL 22 NO 7 793
Rong et al. Surface modification of nanoscale fillers
8 Specific wear rate (testing configuration: block on
ring) ẇs of neat epoxy and its composites filled with
nano-Al2O3 before and after surface modification:57
Al2O3-c-PAAM denotes that Al2O3 nanoparticles are
grafted by PAAM without removing homopolymers
generated during graft polymerisation while Al2O3-g-
PAAM represents that Al2O3 nanoparticles are accom-
panied only with unextractable grafting polymers
stronger interfacial adhesion and improved mechanical
properties. Such reactive compatibilisation has also been
successfully applied in SiC/epoxy nanocomposites for
obtaining higher wear resistance.59 In this work, PGMA
was chemically grafted onto silane pretreated nano-SiC
particles by means of soapless emulsion polymerisation.
Compared with untreated nano-SiC particles, the
grafted versions exhibited improved dispersibility.
Besides, they are able to form chemical bonding between
the fillers and the epoxy matrix through reaction
between the epoxide groups and the curing agent.
Owing to these advantages, the epoxy composites filled
with PGMA grafted nano-SiC particles possess rather
high sliding wear resistance and low frictional coefficient
at low filler loading, which cannot be observed in
untreated SiC nanoparticles/epoxy system.
Micromechanical models
In contrast to the experimental studies in the area of
nanocomposites, only a few micromechanical models
have been developed which are in agreement with the
behaviour of nanocomposites. Chaberta et al.60 pre-
dicted the elastic response of polymer nanocomposites
based on a mean field approach or a discrete simulation.
Two micromechanical models were proposed to account
for the short range interactions between filler particles: a
self-consistent scheme introducing a third rigidifying
phase of matrix immobilised on the surface of filler
particles and a discrete model of sphere assembly taking
into account the local contacts between filler/filler and
matrix/filler. The physical bases are the same in the two
models, but they were differently treated: in homo-
genisation scheme, the thickness of interphase (or
effective volume of filler) is the key parameter whereas
in the discrete simulation, the surface of contact (or
interaction forces) between filler particles rules the
mechanical behaviour. Therefore, it is necessary to
increase considerably the effective fraction of filler in
the self-consistent model to account for the observed
reinforcement whereas in discrete simulation, a slight
794 Materials Science and Technology 2006 VOL 22 NO
volume of immobilised matrix confined between filler
particles leads to a significant increase of the modulus. A
nanocomposite consisting of submicronic rigid PS
particles randomly dispersed in a soft polybutylacrylate
(PBA) matrix was used to verify the above models. In
addition to the good agreement with the experimental
results, the discrete model highlighted the importance of
filler–filler interactions on the reinforcement above the
percolation threshold.
Starr et al.61 carried out molecular dynamic simula-
tions covering the polymer–nanoparticle interactions,
the structure and dynamics of the polymer melt
containing nanoparticles. They found that the chains
near the nanoparticle surface are elongated and flat-
tened; as a result, the glass transition temperature Tg of
the melt can be shifted to either higher or lower
temperatures owing to the gradual change of the
polymer dynamics approaching the nanoparticle sur-
face. That is, the changes in surface dynamics give rise to
the expectation that attractive interactions will increase
Tg while very weak interactions can suppress Tg. If the
bound polymer region is thin (very few layers), Tg will
probably increase with attractive monomer–particle
attractions. For a larger thickness of bound polymers
(many layers), where outer layers of monomer relax far
more quickly than that of inner monomers, Tg will
probably decrease.
Conclusions
In an attempt to understand how nanosized inclusions
affecting properties of polymer nanocomposites, a
selection of representative and recent literature was
reviewed to highlight the key issues related to surface
modification of nanoparticles and their influence on the
mechanical behaviour of nanocomposites.
As discussed above, some trends are observed but no
universal patterns can be deduced for the moment.
Table 2 summarises the polymer nanocomposites dis-
cussed in the present paper in terms of component
species, filler treatment and ultimate properties of the
composites. It is seen that coupling agent (including
surfactant and dispersant) effectively operates in most
cases to enhance the mechanical performance of
polymer nanocomposites, but can scarcely bring about
remarkable improvement in overall properties. This is
reasonable because uniform coverage of coupling agent
around nanoparticles is hard to attain. Comparatively,
macromolecules encapsulating nanoparticles have super-
ior effects than the small molecules owing to the
stronger interface entanglements.
To intensify the fragile nanoparticle agglomerates,
chemically induced graft polymerisation from nanopar-
ticles surface proves to be a favourable way. Especially,
when reactive groups are introduced into the grafting
chains, reactive compatibilisation between the grafted
nanoparticle and the matrix polymer would further
benefit interfacial adhesion.
In general, even though various treatments and
modification techniques are applied, agglomeration of
nanoparticles can be rarely avoided when preparing
nanocomposites with traditional compounding facilities
and techniques. For the moment, every effort has to be
made to decrease in its amount to the greatest extent.
It is worth noting that mechanical performance of
polymer nanocomposites is dependent not only on
7
 Rong et al. Surface modification of nanoscale fillers

Table 2 Variation in mechanical performance of some polymer nanocomposites manufactured through melt mixing as
compared with unfilled polymers

Properties variation*

Polymer Young’s Tensile Elongation Impact

Nanosized fillers Filler pretreatments matrix modulus strength to break strength References

CaCO3 (44 nm) Stearic acid coated PP z 2 2 zz 34

CaCO3 (45 nm) Stearic acid coated PVC N/A z zz z 35
CaCO3 (50 nm) Titanate v. Stearic acid PP N/A 2 N/A z 36
CaCO3 (50 nm) Phosphonate PP N/A 2 2 z 37
CaCO3 (80 nm) Phosphonate PP z z N/A zz 38
CaCO3 (30 nm) Macromolecular surfactant v. aluminate LDPE N/A z z N/A 39
SiO2 Dispersant v. silane PP z z 2 N/A 40
CaCO3 (72 nm) Stearic acid HDPE z z N/A 2 41
CaCO3 (70 nm) Stearic acid PP zz 2 N/A zz 42
CaCO3 (40 nm) Stearic acid HDPE N/A N/A zz z 43
CaCO3 (80 nm) Hyperdispersant v. stearic acid PP N/A z N/A zz 44
TiO2 (20 nm) Macromolecular dispersant HIPS z z z z 45
CaCO3 (40 nm) PMMA encapsulated PP, PVC z z zz z 46, 47
Sb2O3 (40 nm)
CaCO3 (40 nm) CPE encapsulated PVC z 2 zz zz 48
CaCO3 PP-g-MAH compatibiliser PP N/A 2 N/A z 49
SiO2 (30 nm) Grafted with hyperbranched polyester PP N/A zz 2 zz 53
SiO2 (7 nm) Irradiation graft PP z z z zz 30
SiO2 (10 nm) Chemical graft and reactive compatibilising PP z z 2 z 58
*The symbol ‘z’ corresponds to a moderate rise in the properties and ‘zz’ a prominent improvement while ‘2’ describes a moderate
decrease in the properties.

interfacial characteristics, but also on many variables
such as crystallinity, amorphous nature of polymer
matrix and multimorphologies. On the basis of a
systematic consideration of every possibility (actually,
many techniques for modifying nanoparticles, as inten-
sively reviewed previously, have not yet been applied to
nanocomposites manufacturing), the positive effect of
nanoparticles might be brought into full play in polymer
matrix, leading to much higher properties than those
ever reported.
Acknowledgements
The authors are grateful to the support of the Natural
Science Foundation of China (Grants Nos. 50273047,
50133020 and 50473019), the Key Program of the
Science and Technology Department of Guangdong,
China (Grants Nos. 2004A10702001 and 2003C50107),
the Team Project of the Natural Science Foundation of
Guangdong (Grant No. 20003038), the Program of the
Science and Technology Department of Guangzhou,
China (Grant No. 2004Z3-D2061) and the project of
Guangdong Economic and Trade Commission, China
(Grant No. 20040112).
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