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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


of polymeric nanocomposites. For this purpose, the
In recent years, many laboratories have launched projects manufacturing approach, i.e. distribution of preformed
on composites containing particles on the nanometre particles in a polymeric matrix with traditional com-
scale with varying success. For example, nanosized pounding techniques, should be considerably upgraded
inorganic particles have successively been added to to overcome the aforesaid shortcomings and to produce
polymers to improve their toughness and tribological nanocomposites with expected and forecasted excep-
performance.1 Owing to the ultrafine dimension of tional properties.
nanoparticles, a large fraction of atoms can reside at An ideal nanocomposite should be free of any
the interface, leading to strong interfacial interaction if a agglomerates, contain optimum filler content and
homogeneous dispersion of the nanofillers in the polymer maintain physicochemical characteristics of its indivi-
matrix is guaranteed. As a result, the nanocomposites dual components.2 So far, a series of methods have been
coupled with a great number of interfaces can be expected tried in two aspects: development of new compounding
to provide unusual performance. (dispersion) technique and surface pretreatment
However, it is very difficult to well disperse nanopar- approaches for nanoparticles. Because internanoparticle
ticles in polymers because the particles with high surface interaction is so strong that the shear force provided by
energy are easy to agglomerate. In addition, hydrophilic conventional mixing facilities often fails to break apart
nanoparticles and hydrophobic polymers are not com- the nanoparticle agglomerates in either polymer melt or
patible in nature, which will result in poor interfacial solution,3 research efforts should be laid on the latter
interaction. All these deficiencies obstruct effective aspect, which is more likely to give full play to the
utilisation of inorganic nanoparticles in polymer com- reinforcing effect of nanoparticulate fillers even though
posites. Physical mixtures of preformed inorganic a uniform dispersion in polymers is unavailable.
nanoparticles and polymers would weaken mechanical In microfiller/polymer composites, surface modifica-
or optical properties of the resultant materials owing to tion of the particles has already proved to be a wide
particle agglomeration. Because nanoparticle agglomer- applicable technique to minimise particle/particle inter-
ates are rather friable, they can hardly undertake stress action and to enhance particle/matrix interaction. With
and therefore are detrimental to the mechanical proper- the recent developments in nanoscience and nanotech-
ties of polymeric composites. nology, the correlation of polymer nanocomposites
From the viewpoint of mass production, nevertheless, properties with surface modification of nanoparticles is
incorporation of nanosize fillers into polymer melt or 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
Materials Science Institute, Key Laboratory for Polymeric Composite and presented on the surface modifications of nanoparticles
Functional Materials of Ministry of Education, Zhongshan University, and their influences on mechanical and tribological
Guangzhou 510275, China performance of polymer based nanocomposites as well
*Corresponding author, email cesrmz@zsu.edu.cn 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 (ii) the long polymeric chains can interfere with the
reagglomeration of the particles more effectively.
In general, surface modification of inorganic fillers However, it should be noted that hyperdispersants
means introduction of organic coatings onto the fillers, can only encapsulate nanoparticle agglomerates
which can be carried out by utilising physical and and can hardly diffuse into the agglomerates,
chemical interactions between the fillers and the owing to their long molecular feature.
modifiers. The resultant bonding is often a mixture of Relatively, encapsulation with in situ formed polymers
secondary and chemical bonds. Much understanding of might generate more uniform coverage. In the presence
treating techniques, interfacial characterisation and of nanoparticles, the polymer can be formed by either
interfacial effect on composites properties has been solution or emulsion polymerisation. Yoshinaga and co-
acquired for microcomposites.4 It is known that there is workers9 utilised radical polymerisation of vinyl mono-
no evident difference between the treatments of micro- mers to produce core–shell SiO2 particles. Because the
particles and nanoparticles except that it is quite difficult surfaces of silica colloid particles possess negative
for the modifiers to penetrate into the tightly bonded charges on the electric double layer, the initiator 2,29-
nanoparticle agglomerates, especially in the case of azobis(2-amidinopropane)dihydrochloride can be con-
physical treatments such as surfactant treatment and centrated and resulted in free radicals on the silica
polymer encapsulation. surface. A solvent with lower miscibility to the polymer
was used to facilitate the attachment of the macro-
Physical methods molecular chains to the particles. Encapsulation of small
Physical treatment (through covering the filler with a inorganic particles by a polymer layer can also be
low molecular weight surfactant or a high molecular carried out by applying an emulsion polymerisation
weight polymer) usually results in secondary forces (such process.10 Polymerisation occurs primarily at the surface
as van der Waals, hydrogen and electrostatic forces) of unmodified particles owing to the adsorption of the
between particles and the modifier. A surfactant monomer on the surface, followed by polymerisation in
contains one or more polar groups and a long aliphatic the adsorbed layer. The formation of an initial hydro-
chain. The principle of surfactant treatment is the phobic layer on the surface of the particles is crucial for
preferential adsorption of polar group of the surfactant formation of the polymer shell, which can be introduced
onto the high energy surface of the fillers by electrostatic by pretreating the particles with non-ionic surfactants,
interaction. Ionic bonds can be formed under certain amphiphilic block copolymers, etc.
circumstances. A typical example can be cited regarding
stearic acid treated CaCO3.5 It is proved that ionic Chemical methods
bonds were established between the surfactant molecules In comparison with physical methods, effect of surface
and the filler surface. Therefore, a reduced surface modification based on chemical interaction is more
energy resulted from the shield made of C18 alkyl chains significant because the covalent attachment modifier
on the filler surface. Alkyl dihydrogenphosphate, con- avoids its desorption from the particles surface. Besides,
taining functional groups such as olefine, chloro, a fine adjustment of interfacial interaction in the
methacryloxy and mercapto, is another kind of effective composites with chemically pretreated nanoparticles
surface modifiers for calcium carbonate fillers.6 It was can be completed by introducing modifiers containing
shown that alkyl dihydrogenphosphate molecules can reactive groups, which helps construct chemical bonding
react with CaCO3, resulting in a dibasic calcium salt of between the fillers and the matrix polymer.
phosphate. The products are deposited on CaCO3 and Among the available techniques, coupling agent
provide CaCO3 with certain hydrophobicity, as con- treatment is the most popular and the easiest to be
vinced by the good dispersibility in mineral oil.7 Besides, applied. A variety of coupling agents, such as silane,
treatment with alkyl dihydrogenphosphates always leads titanate and zirconate, have been used to improve the
to an increase in surface area of the treated particles. adhesion between inorganic fillers and organic matrices.
This can be ascribed to surface erosion and/or to Extensive information on reaction mechanisms and
calcium salt formation. effects of coupling agents is available for microfillers,
Another technique of physical treatment lies in but fewer for nanoparticles. Gunko et al.11 studied the
encapsulating inorganic fine particles with preformed features of fumed silica coverage with several kinds of
polymers or in situ formed polymers. In the former case, silanes from both experimental and theoretical aspects.
a macromolecular dispersant, hyperdispersant, has been Depending on the pretreatment conditions, the attached
successfully used.8 Similar to surfactants, polymeric silanes can reduce the hydrophilic properties of silica to
dispersants consist of two major components. One is different extents. However, it should be pointed out that
a functional group, such as –OH, –NH2, –NR3z, the uniform surface coverage of coupling agent on
–COOH, –COO2, –SO3H, –SO32 and –PO422, which nanoparticles is hard to realise by simple physical and
helps anchoring of the dispersants to the particles mechanical means.
surface through hydroxyl and electrostatic bonds. The Grafting macromolecules onto inorganic particles has
other is a solvable macromolecular chain, such as some advantages over modification by low molecular
polyolefine, polyester, polyacrylate and polyether, which surfactants or coupling agents. The polymer grafted
is appropriate to be dispersed in different media of low particles can possess desired properties through a proper
to high polarity. Compared with traditional surfactants, selection of species of graft monomers and the graft
hyperdispersants have the following advantages: conditions so that the interfacial characteristics between
(i) they are anchored to the particles surface more the treated nanoparticles and the matrix can be tailor
strongly than surfactants and therefore, can made when manufacturing nanocomposites. Besides,
hardly be desorbed the fragile nanoparticle agglomerates become stronger

788 Materials Science and Technology 2006 VOL 22 NO 7


Rong et al. Surface modification of nanoscale fillers

1 Schematic drawing of polymer grafted from nanoparticles by using double bonds on particles

because they turn into a nanocomposite microstructure The same SiC nanoparticles were also grafted by
comprising the nanoparticles, the grafted and the polyglycidylmethacrylate (PGMA) in a surfactant free
ungrafted (homopolymerised) polymer. A series of work emulsion.16 The emulsion polymerisation loci have
has been carried out in this field of growing interest for proven to be located on the surface of SiC nanoparticles
purposes of improving the dispersibility of the nano- owing to the higher number of nanoparticles and their
particles in solvents and their compatibility in polymers. hydrophobic surface feature. This reaction mechanism is
Mostly, the graft polymerisation is conducted via two particularly important to ensure effective encapsulation
routes: and graft of PGMA surrounding the nanoparticles.
(i) monomers are polymerised from active com- Surface initiated polymerisation can be achieved by
pounds (initiators or comonomers) covalently different mechanisms such as free radical, cationic,17
attached to the inorganic surface (called ‘grafting ring opening metathesis polymerisation (ROMP),18
from’) atom transfer radical polymerisation (ATRP)19,20 and
(ii) ready made polymers with reactive end groups anionic polymerisation.21,22 Tsubokawa and co-work-
react with the functional groups on the particles ers23–28 systematically investigated the grafting of
(called ‘grafting to’). various polymers onto ultrafine silica and carbon black
The latter benefits the control of the molecular weight of by polymerisation starting from the initiating groups
the grafting polymer. But generally, the former previously introduced onto the surfaces. They have
approach has advantage over the latter one because it conducted anionic, cationic and radical graft polymer-
is more difficult for polymers to penetrate into the isation of various monomers initiated by potassium
particulate agglomeration than monomers. Besides, the carboxylate, acylium or benzylium perchlorate, and
‘grafting to’ technique would lead to a polymer coating peroxyester or azo groups already introduced onto
on the particles, which might hinder the attachments of ultrafine silica respectively. For example, surface
other polymers. anchored peroxide initiator was attached to the surface
With respect to ‘grafting from’ technique, there are by treatment of silica particles with thionylchloride to
two routes initiating polymerisation from the particles. obtain surface Si–Cl groups, which were then reacted
One is surface modification with polymerisable groups, with tert-butylhydroperoxide or diisopropylbenzene
for instance, by means of silane treatment (Fig. 1). The hydroperoxide to form the initiating groups. The azo
other is surface modification with initiating groups groups are usually introduced onto untrafine particle
(Fig. 2). Comparatively, the former is easier while the surface by two ways. One is the reaction of 4,49-
latter favours higher grafting percentage and grafting azobis(4-cyanopentanoic acid) (ACPA) with surface
efficiency. Espiard and Guyot12 firstly treated silica epoxide groups, which are introduced by the treatment
nanoparticle surface with silane coupling agent contain- of the particle with c-glycidoxypropyltrimethoxysilane
ing a double bond, i.e. methacryloxypropyltrimethox- (GPS).24 The other is the reaction of ACPA with surface
ysilane (MPTMS). Then, the modified silica was grafted isocyanate groups, which are introduced by the treat-
with polyethylacrylate in emulsion solution. Oosterling ment of the particle with toluene di-isocyanate (TDI).25
et al.13 grafted polystyrene (PS) and poly(styrene- In addition, by means of an amide bond formed between
block-isoprene) onto nanosilica (,12 nm) by initiating ACPA and an amine containing silane coupling agent
immobilised double bonds on the silica surface with on the silica, azo initiator can also be immobilised onto
t-butylithium and then adding the monomers into the silica substrates.26
reaction suspension. Rong et al.14,15 grafted the nano- Besides chemical grafting, graft polymerisation onto
sized alumina and silicon carbide with PS and poly- nanoparticles can also be realised by c irradiation, which
acrylamide (PAAm) using a similar route in solution. is superior to chemical graft process in improving graft

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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 ultimate properties. Recognition of the role of the main
procedure. Under the high energy radiation, the surfaces factors influencing interfacial adhesion and proper
of the nanoparticles outside and inside the agglomerates surface modification would lead to achievements in
are equally activated. Therefore, the low molecular nanocomposites development.
weight monomers are allowed to react with the activated The general idea of nanocomposites is based on the
sites of the nanoparticles throughout the agglomerates.29 concept of creating a very large interface between the
In more recent studies, it was found that various nanosized building blocks and the polymer matrix.
polymers can be successively grafted on the surface of However, very often homogeneous distribution of the
silica nanoparticles by this method under quite mild nanoparticles is problematic, i.e. the expected large
condition (at air atmosphere).30 The key point might be surface cannot always be created. Besides, tuning of
the highly active surface of the nanoparticles. Besides, interfacial interaction or coupling of the components
different silica exhibits different reactivity. The precipi- presents additional problems. In the subsequent para-
tated silica performs better than fumed silica.31 Another graphs, the issues important for further development in
interesting result is that some metal nanoparticles, such this field and the questions to be solved in the future are
as iron, nickel and cobalt, can be grafted with polymers discussed by analysing a few selected references.
under irradiation even though these particles contain
few hydroxyl groups,32 indicating that the reactive site Influence of coupling agent, surfactant and
can be either the hydroxyl group or the surface dispersant
structural defect. Indeed, the double bonds introduced Chan et al.34 added nano-CaCO3 (44 nm) into poly-
to the surface of particles by silane are helpful for the propylene (PP) by melt mixing. The nanoparticles
higher grafting percentage.33 produced an increase in elastic modulus and impact
strength of the PP matrix. The reverse effect was found
Effects of interfacial interaction on for yield stress and tensile strength of the composites.
Both of these quantities were highest for the neat PP and
performance of polymer nanocomposites decreased as the volume fraction of CaCO3 increased. In
Properties of composite materials are determined by a recent report by another group, however, simultaneous
four factors: characteristics of the components, compo- enhancement of yield strength, elongation at break,
sition, structure and interfacial interactions. The effect impact strength, flexural modulus and Vicat softening
of interphase depends on its amount and characteristics. temperature of polyvinyl chloride (PVC) was shown
That is, amount of the material bonded in the interphase by the addition of 0–15 phr nano-CaCO3 particles.35 It
and the interaction strength influence the composites is therefore believed that PP must have very poor

790 Materials Science and Technology 2006 VOL 22 NO 7


Rong et al. Surface modification of nanoscale fillers

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 3 Impact energy of stearic acid treated nano-CaCO3/PP
dispersion in PP. The impact strength of PP had an composites as function of filler content42
increase of ,70% with the addition of 5–6 phr of
coupling agent pretreated nano-CaCO3 while only 50% Young’s modulus and yield stress of the composites
increase was measured for the fatty acid salt treated compared with the uncoated CaCO3 composites while the
nano-CaCO3 composites. impact strength progressively increased.
Home made phosphonate surfactants were also used The aforesaid surface pretreatment of nanoparticles is
to modify nano-CaCO3 particles. Similarly, improve- usually completed by simply mixing the particles with
ment in Charpy impact strength of phosphonate treated coupling agent or dispersant in a higher speed mixer
nano-CaCO3/PP composites was observed.37 In a work except for the wet treatment process (in water).
by Ren and co-workers,38 the effect of a phosphonate However, uniform surface coverage of nanoparticles is
coupling agent was evaluated. The treated nano-CaCO3 hard to be achieved owing to the very low weight ratio
can result in an increase in tensile and impact strength of coupling agent to nanoparticle agglomerates. To
while the untreated ones had nearly no reinforcing solve this problem, an ultrahigh speed mixer has been
effect. From the above discussion, it is possible to designed.42 The mixer has high speed (6000 rev min21),
extract the trend that various coupling agents, includ- special rotors that are designed to deal with nanopar-
ing titanate, phosphate and aluminate,39 favour the ticles and atomiser by which the coupling agent is added.
improvement of nanoparticle dispersion and mechanical It was demonstrated that the mechanical properties of
properties of polymer composites. PP, especially the ductile properties, could be effectively
Usually, silane is not suitable for the surface improved by introducing nano-CaCO3 modified by
modification of CaCO3, but it is widely used in silica stearic acid with the ultrahigh speed mixer (Fig. 3).
treatment. Kruenate et al.40 reported such studies In most cases, nanoparticles were treated by coupling
related to the effects of commercial dispersant (Efka) agents or dispersants before compounding with poly-
and silane coupling agent (thiocyanatopropyl-triethox- mer. Because only the exterior nanoparticles of the
ysilane) pretreatment of nano-silica on tensile properties agglomerates can take part in the reaction, split of the
of PP. The tensile strength and modulus of PP mixed treated nanoparticle agglomerates during the subsequent
with untreated nano-silica increased whereas the elonga- compounding with polymers would lead to an exposure
tion to break decreased. Comparatively, treatment with and reagglomeration of the unreacted interior particles.
silane is more effective in improving the tensile strength Therefore, stabilisation of the split nanoparticles is
and modulus of PP/SiO2 composites (Table 1). important. Wu and Ye43 firstly added HDPE into a two
Actually, all commercial nano-CaCO3 particles have roll mill preheated to 150uC. When the polymer was
been pretreated with stearic acid. Lazzeria et al.41 studied thoroughly melted, both CaCO3 (40 nm) and stearic
the influence of stearic acid treatment on the mechanical acid at a desired composition were incorporated. It was
properties of precipitated CaCO3 (70 nm)/high density expected that the dispersed nanoparticles in the polymer
polyethylene (HDPE) composites prepared by a twin melt can be in situ activated by stearic acid and the
screw mixer–single screw extruder. The addition of formation of larger nanoparticle agglomerates can be
10 vol.-% nano-CaCO3 to HDPE caused a rise in prevented accordingly. Microstructural observation of
Young’s modulus and yield stress of its composites, the fractured surfaces of the composites proved the
accompanied by a sharp drop in impact strength. The feasibility of their idea. That is, nearly no nanoparticle
employment of stearic acid slightly decreased both agglomerates appeared when a proper dosage of the

Table 1 Mechanical properties of PP composites with treated and untreated nanosilica40

Material Elongation to break, % Tensile strength, MPa Modulus, MPa

PP 21.12¡2.43 36.96¡0.40 1178.29¡42.18


PP/2%SiO2 13.19¡1.11 40.21¡2.16 1376.46¡63.79
PP/2%SiO2/Efka 9.14¡2.38 38.19¡1.44 1414.67¡10.40
PP/10%SiO2/Efka 10.12¡1.05 33.60¡0.48 1603.31¡58.43
PP/2%SiO2/silane 11.80¡1.31 43.54¡1.85 1524.20¡45.57

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Rong et al. Surface modification of nanoscale fillers

4 Izod impact strength of nano-CaCO3/PP composites as 5 Tensile strength of nano-CaCO3/LDPE composites as


function of filler content44 function of filler content39

dispersing agent was applied. For the composites particles).47 The resultant PMMA shell covered on
containing 20 wt-% of nano-CaCO3 prepared in this nano-Sb2O3 particles strengthens the interaction
way, both impact strength and elongation to break of between the nanoparticles and the PVC matrix, leading
HDPE were increased by .100%. to breakdown of the nanoparticle agglomerates and
improved dispersion of the nanoparticles in PVC. As
Influence of macromolecules encapsulation and a result, the treated nano-Sb2O3 particles stiffen,
compatibiliser strengthen and toughen PVC matrix with the maximum
In comparison with coupling agent, surfactant and effect at a loading of 2.5 wt-%. For PVC/CaCO3
dispersant that belong to small molecules, encapsulation nanocomposites, Wu et al.48 employed chlorinated
with the high molecules, such as hyperdispersant, should polyethylene (CPE) as an interfacial modifier when
provide stronger interaction with polymer matrix for preparing CPE/nano-CaCO3 (40 nm, titanate pre-
nanoparticles owing to the enhanced interfacial entan- treated) masterbatch. Morphology investigation indi-
glement. Li and Chen44 found that the hyperdispersant cated that the nano-CaCO3 particles in PVC matrix were
CH-1A is more effective to improve impact strength of encapsulated with a CPE layer. Notched Izod impact
PP/nano-CaCO3 composites than the conventional strength of the nanocomposites achieved a significant
dispersant and stearic acid (Fig. 4). Similar results were improvement owing to the incorporation of CPE and
presented in Ref. 39 for nano-CaCO3 reinforced low obtained the high value of 745 J m21.
density polyethylene (LDPE) composites. Both tensile Besides surface treatment of nanoparticles, incorpora-
strength and elongation at break of LDPE composite tion of compatibiliser, such as PP grafted with maleic
film filled by nano-CaCO3 treated with macromolecular anhydride (PP-g-MAH), was also demonstrated to be
interfacial agent performed much better than the capable of improving mechanical properties of nano-
composite containing nano-CaCO3 treated with alumi- composites. Zhang et al.49 studied the effect of PP-
nate (Fig. 5). Zhang et al.45 also reported similar g-MAH as interfacial modifier in PP/nano-CaCO3
behaviour for macromolecular dispersant pretreated composites. PP-g-MAH was synthesised by means of
TiO2 (20 nm)/high impact polystyrene (HIPS) nano- solid phase graft copolymerisation. The addition of PP-
composites. When nano-TiO2 content is ,5 wt-%, not g-MAH improved notched impact strength (Fig. 6),
only Young’s modulus, tensile strength and impact flexural strength and tensile strength of PP/nano-CaCO3
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 6 Effect of PP-g-MAH on notched impact strength of
methylmethacrylate (10 wt-% based on nano-Sb2O3 nano-CaCO3/PP composites49

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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
7 Tensile strength of nano-SiO2–GPTS/PP and nano-
nanoparticles, improve the interfacial interactions
SiO2–GPTS–H20–C19/PP composites as function of
between the particles and the matrix and especially
filler content53
enhance the agglomerates strength. The coverage of
grafting polymer around SiO2 helps to increase tensile
strength of the nanocomposites, but nearly has no effect
composites. Fourier transform infrared (FTIR) proved
on elastic modulus. The strain to failure was lower in the
that PP-g-MAH had reacted with CaCO3, resulting in
untreated systems than that of neat PP. In the treated
reactive compatibilisation. In Ref. 50, a more compli-
system, however, the parameter increased with content
cated manufacturing procedure to produce PP/nano-
of the nanoparticles up to 2 vol.-%. At the same filler
CaCO3 composites was reported. Silane coupling agent
loading, PP composites with grafted nano-SiO2 has an
KH-570 treated nano-CaCO3 was encapsulated by
impact strength 3–4 times higher than that of neat PP.
polymerised organic monomers in emulsion; meanwhile,
PP-g-MAH was prepared by a similar process. Through The above concept of strengthening nanoparticle
melt mixing PP, PP-g-MAH and encapsulated CaCO3, agglomerates by grafting polymer also works in making
PP based nanocomposites were prepared. It was found antiwearing nanocomposites. A systematic research
that Izod impact strength of the composites increased carried out by Shi et al.55 evaluated the sliding wear
two times over that of neat PP. By cross-experiments for behaviour of epoxy containing nano-Al2O3 particles
the effects of the filler/encapsulating polymer ratio and with different pretreatments. In this work, nano-Al2O3
the contents of PP-g-MAH and filler, the optimum was grafted with acrylamide, styrene and ethylacrylate
composition was determined as filler/encapsulating poly- by irradiation polymerisation respectively. It has been
mer 10 : 1, PP-g-MAH 10 wt-% and CaCO3 5 wt-%. proven that the amide groups of polyacrylamide take
Huang et al.51 carried out in situ graft polymerisation of part in the curing of epoxy resin, greatly enhancing the
acrylic acid when preparing PP/nano-CaCO3 master- interface interaction.56 Encapsulation of nano-Al2O3
batch, which was then diluted with PP by an extruder with polystyrene or polyethylacrylate is believed to be
and injected into nano-CaCO3/PP composite specimens. able to significantly increase the hydrophobicity of the
It is shown that tensile strength and modulus of the particles and therefore the compatibility with the
nanocomposites can be remarkably improved by this polymer matrix. As shown in Fig. 8, the high wear rate
measure while impact strength varies in reverse trend. of unfilled epoxy owing to the three-dimensional cross-
Epoxy has been used as a processing aid and a linking network is greatly reduced by adding nano-
dispersing agent for fumed nanosilica in producing melt Al2O3 particles, especially when treated nano-Al2O3 is
mixed polyethersulphone (PES) composites.52 Having incorporated.57 Besides, the nanoparticles also reduce
dispersed in matrix polymer, epoxy component was frictional coefficient of epoxy and the composites with
polymerised to recover its mechanical properties. It was treated nanoparticles have lower frictional coefficients.
found that strong interaction between the polar groups For example, the frictional coefficient of Al2O3-c-
of epoxy and the silanol groups on nanosilica helped to PAAM/epoxy is 0.35 that amounts to 61% of the value
disperse the particles into PES. Improvement in barrier of unfilled epoxy and 69% of the value of untreated
resistance to diffusion of solvents such as methylene nano-Al2O3/epoxy.
chloride, heat deflection temperature and impact Recently, Friedrich et al.58 combined chemical graft
strength over neat PES was observed. approach of nanoparticles and reactive compatibilisa-
tion for nanocomposites preparation. That is, reactive
Influence of graft polymerisation and reactive groups (epoxide or amine groups) were firstly introduced
compatibilisation onto nanoparticles by chemical graft polymerisation,
Very interesting results were obtained by Xu et al.,53 which was then melt blended with PP at different
who prepared a series of PP/silica grafted hyperbranched compositions. Meanwhile, differently functionalised PP,
polyester nanocomposites. The silane 3-glycidoxy pro- such as maleic anhydride grafted polypropylene (PP-
pyltrimethoxysilane (GPTS) pretreated silica (30 nm) MAH), amine functionalised PP (PP-NH2) and epoxide
was grafted by hyperbranched polyester (Boltorn H20), functionalised PP (PP-GMA), was added respectively so
which was then terminated by octadecylisocyanate (C19) as to build up chemical bonding at the filler/matrix
groups after the graft reaction. The incorporation of interface during the composites manufacturing. It was
silica grafted modified Boltorn H20 (3–5 wt-%SiO2) shown that the reactive compatibilisation is capable
greatly enhanced notched impact strength (Fig. 7) as of providing better dispersion of the nanoparticles,

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Rong et al. Surface modification of nanoscale fillers

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
8 Specific wear rate (testing configuration: block on temperatures owing to the gradual change of the
ring) ẇs of neat epoxy and its composites filled with polymer dynamics approaching the nanoparticle sur-
nano-Al2O3 before and after surface modification:57 face. That is, the changes in surface dynamics give rise to
Al2O3-c-PAAM denotes that Al2O3 nanoparticles are the expectation that attractive interactions will increase
grafted by PAAM without removing homopolymers Tg while very weak interactions can suppress Tg. If the
generated during graft polymerisation while Al2O3-g- bound polymer region is thin (very few layers), Tg will
PAAM represents that Al2O3 nanoparticles are accom- probably increase with attractive monomer–particle
panied only with unextractable grafting polymers attractions. For a larger thickness of bound polymers
(many layers), where outer layers of monomer relax far
stronger interfacial adhesion and improved mechanical more quickly than that of inner monomers, Tg will
properties. Such reactive compatibilisation has also been probably decrease.
successfully applied in SiC/epoxy nanocomposites for
obtaining higher wear resistance.59 In this work, PGMA Conclusions
was chemically grafted onto silane pretreated nano-SiC
particles by means of soapless emulsion polymerisation. In an attempt to understand how nanosized inclusions
Compared with untreated nano-SiC particles, the affecting properties of polymer nanocomposites, a
grafted versions exhibited improved dispersibility. selection of representative and recent literature was
Besides, they are able to form chemical bonding between reviewed to highlight the key issues related to surface
the fillers and the epoxy matrix through reaction modification of nanoparticles and their influence on the
between the epoxide groups and the curing agent. mechanical behaviour of nanocomposites.
Owing to these advantages, the epoxy composites filled As discussed above, some trends are observed but no
with PGMA grafted nano-SiC particles possess rather universal patterns can be deduced for the moment.
high sliding wear resistance and low frictional coefficient Table 2 summarises the polymer nanocomposites dis-
at low filler loading, which cannot be observed in cussed in the present paper in terms of component
species, filler treatment and ultimate properties of the
untreated SiC nanoparticles/epoxy system.
composites. It is seen that coupling agent (including
surfactant and dispersant) effectively operates in most
Micromechanical models cases to enhance the mechanical performance of
In contrast to the experimental studies in the area of polymer nanocomposites, but can scarcely bring about
nanocomposites, only a few micromechanical models remarkable improvement in overall properties. This is
have been developed which are in agreement with the reasonable because uniform coverage of coupling agent
behaviour of nanocomposites. Chaberta et al.60 pre- around nanoparticles is hard to attain. Comparatively,
dicted the elastic response of polymer nanocomposites macromolecules encapsulating nanoparticles have super-
based on a mean field approach or a discrete simulation. ior effects than the small molecules owing to the
Two micromechanical models were proposed to account stronger interface entanglements.
for the short range interactions between filler particles: a To intensify the fragile nanoparticle agglomerates,
self-consistent scheme introducing a third rigidifying chemically induced graft polymerisation from nanopar-
phase of matrix immobilised on the surface of filler ticles surface proves to be a favourable way. Especially,
particles and a discrete model of sphere assembly taking when reactive groups are introduced into the grafting
into account the local contacts between filler/filler and chains, reactive compatibilisation between the grafted
matrix/filler. The physical bases are the same in the two nanoparticle and the matrix polymer would further
models, but they were differently treated: in homo- benefit interfacial adhesion.
genisation scheme, the thickness of interphase (or In general, even though various treatments and
effective volume of filler) is the key parameter whereas modification techniques are applied, agglomeration of
in the discrete simulation, the surface of contact (or nanoparticles can be rarely avoided when preparing
interaction forces) between filler particles rules the nanocomposites with traditional compounding facilities
mechanical behaviour. Therefore, it is necessary to and techniques. For the moment, every effort has to be
increase considerably the effective fraction of filler in made to decrease in its amount to the greatest extent.
the self-consistent model to account for the observed It is worth noting that mechanical performance of
reinforcement whereas in discrete simulation, a slight polymer nanocomposites is dependent not only on

794 Materials Science and Technology 2006 VOL 22 NO 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.

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