ISSN 10683666, Journal of Friction and Wear, 2010, Vol. 31, No. 1, pp. 68–80. © Allerton Press, Inc.

, 2010.
Original Russian Text © A.P. Krasnov, V.N. Aderikha, O.V. Afonicheva, V. A. Mit’, N.N. Tikhonov, A.Yu. Vasil’kov, E.E. SaidGaliev, A.V. Naumkin, A.Yu. Nikolaev, 2010,
published in Trenie i Iznos, 2010, Vol. 31, No. 1, pp. 93–108.

Categorization System of Nanofillers to Polymer Composites

A. P. Krasnova, *, V. N. Aderikhab, O. V. Afonichevaa, V. A. Mit’a, N. N. Tikhonovc,
A. Yu. Vasil’kova, E. E. SaidGalieva, A. V. Naumkina, and A. Yu. Nikolaeva
a
N.A. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
ul. Vavilova 28, Moscow, 117813 Russia
*email: krasnov@ineos.ac.ru
b
V.A. Belyi MetalPolymer Research Institute, National Academy of Sciences of Belarus,
ul. Kirova 32a, Gomel, 246050 Belarus
cD.I. Mendeleev Russian University of Chemical Technology, Miusskaya pl. 9, Moscow, 125047 Russia

Received October 14, 2009

Abstract—The paper deals with a systematic categorization of nanofillers in terms of their effect arising upon
introduction into polymer composites of tribological applications. The authors study the nature of this effect
and the tribological behavior of different types of nanofillers acting in composites and exhibiting either a tri
bochemical effect or a discrete surface one. Nanofillers having an indirect influence on friction and interca
lation compounds are also studied.

Key words: friction, wear, polymer, nanofiller, discrete contact, intercalator.

DOI: 10.3103/S1068366610010071

INTRODUCTION of the new systematization, the authors draw on both

The science of nanotribological materials deals
with specific problems by disclosing and promoting
new directions connected with the potential of the
fundamental features of nanofillers. There is no lack of
experimental data or published material in this area;
indeed, difficulties arise more due to the overabun
dance of experimental evidence and lack of summa
rizing research works relating the functional properties
of nanofillers to their effect on the tribological behav
ior of composites. According to the Great Soviet
Encyclopedia (Blauber et al., “Systematic Approach,”
Bol’shaya sovetskaya entsiklopediya, 1976, vol. 23,
pp. 476–477), a systematic approach is not a strict
methodological concept, but rather assists in the iden
tification of new objects of study by specifying their
structural and topological characteristics.
In this connection, the authors’ aim is not to
present a detailed, comprehensive list of works on each
topic to be touched upon, even though some reviews
have appeared recently in this field, specifically on
nanosize fillers [1–4], and more and more are being
produced each year.
The authors, who are engaged in developing and
studying the behavior of polymers and composites
during friction against steel counterbodies [5], have
taken on the task of producing a systematic classifica
tion of nanofillers based on their impact on the tribo
logical behavior of polymers and filled polymeric sys
tems. Naturally, in substantiating the appropriateness
published data and their own unreleased data.
The need for the proposed classification system is
quite evident, since works on the development of tribo
chemically stable and wearresistant nanocomposites
are conducted mainly without any preliminary analysis
of the reciprocal effect of the polymer and nanofiller
structures, or of their eventual behavior during friction.
Understanding the mechanism of the frictionzone for
mation upon the introduction of nanofillers of various
characteristics in different amounts may promote fur
ther progress in this sphere of tribology.
In fact, all recent publications of tribologists con
tain information on significant successes in the cre
ation of new polymer nanocomposites [6, 7]. This
activity of researchers is understandable since tribolo
gists traditionally deal with problems of this kind when
studying the effect of ultradispersed nanofillers in
polymers and lubricants and the effect of extremely
small products of degradation down to molecular size
(e.g., gas separation products in tribochemical pro
cesses) [8].
The majority of published papers and reviews show
the advantage of using nanofillers by comparing the
composite to the initial polymer. The performed tests
indicate, and it is undoubtedly very important, that
nanofillers may be used to improve the tribological
characteristics of polymers. It should be noted that
wearresistant composites have already been elabo
rated from most polymers with numerous dispersed
fillers. To elucidate the advantages of nanocomposites

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 CATEGORIZATION SYSTEM OF NANOFILLERS TO POLYMER COMPOSITES
it seems expedient to compare them to the available
analogues and identify the effect the nanofiller dis
plays in this case as a pronounced amelioration of the
specific functional properties of the materials. This
effect is connected with the activity, specific surface
area, and some other features of the nanoparticles,
exhibited, first of all, in considerable reduction of the
nanofiller concentration.
Nanofillers are widely used at present in significant
and insignificant amounts. This requires the develop
ment of special facilities for their introduction into the
polymer, which should be taken into account when
considering the general problem of nanofilling. The
abovementioned reviews [1, 3] underline the impor
tance of the methods of incorporating nanofillers.
Since this direction generally determines the investi
gation results but is poorly reflected in the literature,
we propose a special brief section devoted to the for
mation of nanocomposites for tribological purposes.
SOME KNOWN AND PROPOSED METHODS
OF SYSTEMATIZATION OF NANOFILLERS
FOR TRIBOLOGICAL COMPOSITES
Of the numerous available works devoted to nano
fillers, we have chosen two reviews that present the
highest interest for the given paper since the authors
propose categorizations of nanofillers based on exten
sive experimental data.
Nanofilling of tribological polymers is one of the
main problems examined by B. Briscoe, et al. in his
work [2] covering the past, present, and future of the
tribology of polymers. The authors subdivide the poly
mer composites analyzed in the paper into two types
according to criteria of nanofiller nature, and further
subcategorize them as ceramic nanofillers and carbon
nanotubes (CNT). Based on literature data, the
authors give a brief overview of the influence of nano
fillers on the tribological properties of 47 nanocom
posites under the optimal nanofiller content, which
varies by a factor of 10 from 0.2 to 30–40 wt %.
The first type of nanofillers contains ceramic nano
particles such as SiO2, SiC, ZnO, TiO2, Al2O3, Si3N4,
and CuO with binders such as epoxy resins, polyether
ether ketone (PEEK), polytetrafuoroethylene
(PTFE), and polyphenylene sulfide (PPS). The opti
mal content of nanoparticles in a given polymer
depends on the composite type. It is quite high for
PTFE systems (up to 30–40 wt %), where the nano
particles ensure mechanical elasticity. In such systems,
the friction coefficient is independent of the nanopar
ticle concentration. The authors’ conclusions are
debatable with respect to the amount of nanoparticles
in PTFE, since other works demonstrate the creation
of commercial materials incorporating 0.2 wt % βsia
lon [3] and 0.13 wt % aluminum oxide [9] that cause
sharp increases in wear resistance. Most likely, these
two works deal with materials having different wear
mechanisms; for composites with minimal filler con
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69
tent, the most important factor is likely to be, not the
mechanical elasticity, but the crystalline structure
recombination under the maximum preserved relative
elongation. The role of nanoparticles in epoxy resins
PEEK and PPS consists in increasing the bearing
capacity of the material and reducing the actual con
tact area.
Another type of nanocomposite is represented by
polymers filled by CNT. The role of CNT in antifric
tional polymers has been studied chiefly on PTFE
composites; the main mechanism in this case is
strengthening of the composite. The use of CNT in
some optimal amount as a filler for superhighmolec
ularweight polyethylene and epoxy resins exerts a
positive effect on their wear resistance as well.
It should be noted that, proceeding from the results
of tribotests, Briscoe sees no need to make any
changes in the general characteristics of the proposed
eight types of wear mechanism of polymers. The
results published in [2] and their interpretation by the
authors represent an attempt to establish the relation
ship between the physicomechanical and tribological
properties of various types of nanofillers that differ in
their chemical origin. The analysis of the first and sec
ond types of fillers presented by the authors [2] proves
that there is no significant difference between them in
their interaction with the polymer or in the tribologi
cal behavior of the latter. The classification of the fill
ers presented in the paper is based on the chemical
structure of the nanoparticles and is provisional in
nature.
A profound and detailed review by S.S. Pesetskii,
et al. [1] devoted to nanocomposites produced by dis
persion of nanofillers in polymer melts also classifies
nanofillers mainly in terms of their chemical nature by
referring them to the following three groups: carbon
nanomaterials, metalcontaining compounds, and
organoclays. The strengths of this review lie in its pre
sentation of manufacturing methods for commercial
materials by highly efficient extrusion methods and in
its presentation of results of study of materials’ tribo
logical properties.
Of special interest for the present authors and those
of review [1] are intercalates of clays used as fillers.
The structure of intercalation compounds of layered
inorganic substance is so complex that they may result,
depending on the modification direction, either in
unpredictable or in targeted variations in the tribolog
ical behavior of nanocomposites. In this connection,
they are discussed in the given review in a separate sec
tion as nanofillers able to exert either direct or indirect
effects on the friction of polymers.
The accumulated experimental data together with
the reviews on the problem under consideration have
made it possible to isolate three groups of nanofillers.
The first group consists of nanofillers affecting the
processes directly in the friction zone due to their
functional features. We have subdivided this group into
two subgroups.
2010