Journal of Nanoparticle Research 6: 273284, 2004.

2004 Kluwer Academic Publishers. Printed in the Netherlands.

Technology and applications

Synthesis and application of inorganic nanoparticles

as lubricant components a review
V.N. Bakunin, A.Yu. Suslov, G.N. Kuzmina and O.P. Parenago
A.V. Topchiev Institute of Petrochemical Synthesis RAS, Moscow, Russia
Received 17 October 2003; accepted in revised form 17 March 2004

Key words: lubricant additives, tribology, surface-capped nanoparticles, action mechanism, nanoparticle
synthesis, friction, industrial applications

Abstract
Recent achievements in chemistry and technology of nanosized inorganic particles provide possibility of
synthesis in various metal oxides, chalcogenides, and so on. Surface modication of nanoparticles in some
cases provides formation of their stable dispersions in liquid hydrocarbons. State of art in the eld of
inorganic nanoparticles synthesis and their application in tribology is discussed. Special attention is paid to
synthesis of surface-capped and bare molybdenum sulde nanoparticles and to testing thereof as frictionmodifying additives for liquid lubricants. Dierences in action mechanism of MoSx nanoparticles and
molecular molybdenum complexes are discussed. Future trends of inorganic nanoparticles use as lubricant
additives are suggested.

Introduction
Over the last few years, interest in the synthesis
and properties of colloidal inorganic particles has
steadily grown because of the great expectations
for their application in dierent elds of material
science and technology (Henglein, 1989; Klabunde, 1994; Nalwa, 1994). This is due to their unique
properties: catalytic, optical, semiconductive,
magnetic, antifriction and others. Indeed, the
variation of size of metal nanoparticles provides
the regulation of catalytic properties, mainly
changing their activity, while nature of nanoparticle environment can inuence both activity and
selectivity of the catalytic species (Lewis, 1993;
Kung & Kung, 2003). A variety of methods for the
preparation and stabilization of nanoparticles exists in the literature, e.g. including formation of
inorganic nanoparticles in reverse microemulsion
environment (Boutonnet et al., 1982; LopezQuintela, 2003), in polymeric systems (Gubin,
2002; Schmidt, & Malwitz, 2003), by vapor-phase
procedures (Swihart, 2003), by thermal decompo-

sition of organometallic precursors (Dushkin 2000;

Talapin et al., 2002), and so on.
Most of unique and advanced properties are
inherent to bare nanoparticles of metals and
semiconductor compounds. Bare nanoparticles
usually possess excessive surface energy and
should be protected (surface capping or modication) or placed in an inert matrix for use in most
applications (Quaroni & Chumanov, 1999).
Unprotected inorganic nanoparticles in liquid
media are thermodynamically unstable with
respect to growth, and they tend to spontaneously
coalescence and usually the nanoparticle surface is
passivated by suitable capping reagents, i.e. electron donors or acceptors species that bond to the
nanoparticle surface (Mandal et al., 2002; Caponetti et al., 2003). These coatings provide stabilization of nano-sized objects in viscous liquid or
semi-liquid media, such as e.g., polymeric matrixes
(Gubin, 2002).
As for the common low-molecular weight
liquid media such as e.g., water and aqueous
solutions or generally used organic solvents, the

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surface-modied nanoparticles may form relatively stable dispersions (e.g. see, Steigerwald et al.,
1988), but the entire problem is not investigated
well enough. It is supposed that stability of the
entire liquid system is due to the Brownian
movement of solvent molecules and to extremely
small dimensions of nanoparticles. However, the
general requirement is that the outer shells of
surface-modied (or surface-capped) nanoparticles
should be solvated by the bulk solvent used, i.e.
they should be hydrophilic in the case of aqueousbased solvents or hydrophobic in the case of
low-polar organic media. Up to date only little
information is available about requirements for a
preferable type of core-shell bonding, outer surface
layer nature and architecture that should provide
physically stable and optically transparent solutions of inorganic nanoparticles in condensed liquid media. The terms solution and dispersion
seem to be not applicable to such systems, apparently the liquid nanocomposite system notion
might better describe their physical essence.
In this review, we shall discuss mainly synthesis
and properties of inorganic nano-sized particles
that were tested for use in liquid lubricant systems.
Due to variety of nanoparticle denition with
respect to their dimensions [e.g., Klabunde (1994)
suggests the range of from 1 to 7 nm, while many
authors designate the synthesized particles as
nano-sized objects even when their measured
dimensions lie in the range of tens of nanometers],
we will preferably limit the listing by papers
describing the particles of up to 100 nm1. Although most of discussed papers describe mostly
tribological applications of inorganic nanoparticles in lubricants, we do not tend to cover the eld
of nanotribology (Bhushan, 2001; Krim, 2002)
that should be reviewed separately, moreover tribological properties of the obtained lubricant
compositions comprising nano-sized objects are
usually tested using conventional macrotribology
instruments. Thus the main goal of this review is to
draw attention of researchers to liquid systems
comprising nano-sized inorganic particles that are
widely used in the vast eld of lubrication. Another goal is to assist the lubricant chemists in
1
Discussion of the so-called ultrane inorganic particles
used to improve certain performance characteristics of lubricating oils can be found elsewhere (Liu et al., 2000; Qiu et al.,
1999).

understanding better the place and role of nanochemistry in creation of advanced lubricant compositions.

2. Nanochemistry of lubricants
Liquid lubricants are used in almost all elds of
human technological activity, e.g., lubrication of
various types of vehicles, energy-producing
equipment and metalworking processes involve
thousands of tons of liquid lubricant compositions.
Pure petroleum-based hydrocarbon blends or
lubricants based on synthetic hydrocarbon-type
mixtures (polyolens or esters) do not meet all
requirements provided by OEMs for lubricating
materials used in modern engines or in other
applications. The usual solution is in addition of
relatively small amounts of certain additive compounds that provide signicant improvement of
base oil properties with regard to either oxidative
degradation or to tribological and other performance characteristics. Most of additives comprise
polar functional groups and belong to various
classes of organic or organometallic compounds.
The tribo-active additives generally contain tribologically active elements or combinations thereof
(P, S, Cl, Zn, N, etc.) that are capable of forming
protective tribological inorganic or similar layers
on friction surfaces as a result of reactions with
construction material (iron or its alloys in most
cases). Therefore, the main role of tribo-active
antiwear (AW) or extreme pressure (EP) additives
is to bring these tribologically active elements to
the friction zone at the time when it is required.
The rst step of their action mechanism is usually
physical and/or chemical adsorption on entire
metal surface, and chemical modication process
takes place only in the friction contact zone when
wear process starts. The monomeric AW and EP
additives usually comprise from one to six tribologically active elements in their molecules, and it
is often necessary to add up to 5 wt% such additives to prevent from serious metal surface depletion.
It is well known that lubricant compositions
possess complex colloidal structure, moreover, the
so-called overbased detergent additives comprise a
solid core consisting of alkaline metal carbonate/
hydroxide and in fact represent surface-capped

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nanoparticles. Thus, the inorganic nanoparticles
might be considered as concentrates comprising
the required active chemical elements or compounds at a very high local concentration. So their
use may signicantly improve wear protection of
metal surfaces or other functional properties of
liquid lubricants.
Of course, improvement of tribological properties is not the only purpose for application of
inorganic nanoparticles as concentrates of useful
functional groups. The most illustrative example
represents the action mechanism of overbased
detergent additives in fast neutralization of corrosive NOx or other acidic molecules produced
during fuel combustion.
2.1. Overbased detergents
So, the nanosized or colloidal inorganic particles
are already widely used in the eld of petroleum
chemistry wherein a number of so-called overbased dispersing additives is used since 1950s
(Baker et al., 1954; Marsh, 1987). This class of
substances represents colloidal systems that include dispersions of extremely small particles of
alkaline earth metals hydroxides and/or carbonates in hydrocarbon material such as lubricating
oils (Bray et al., 1975; Glavati, 1989; Shor et al.,
1996; Galsworthy et al., 2000). Their structure and
composition, e.g. in the case of calcium sulfonates,
were often represented by the following general
formula:
R
SO3 2 Cak CaOH2 m CaCO3 n
Modern presentation is more close to images of
inorganic nanoparticles [see Figure 1 (Galsworthy
et al., 2000)]:

Figure 1.

Colloidal structure of overbased detergent

additives was thoroughly investigated using traditional colloidal and physical methods such as solubilization
phenomena
and
viscosity
measurements (Inoue and Nose, 1988; Little and
Singleterry, 1964; Nanni, 2003;), transmission and
conventional electron microscopy (Mansot et al.,
1994), X-ray absorption spectroscopy, extended
X-ray absorption ne structure spectroscopy
(EXAFS), ToF-SIMS (Cizaire et al., 2003; Mansot
et al., 1993), small-angle X-ray scattering (SAXS)
and small-angle neutron scattering (SANS)
(OSullivan et al., 1991), etc., as well as by mathematical modeling (Bandyopadhyaya et al., 2001;
Mansot, 1993; Tobias & Klein, 1996). Interrelations between detergent structure and performance
characteristics were investigated (Chinas-Castillo
& Spikes, 2000). This type of substance possesses
the main properties of liquid nanocomposite systems, especially with respect to the solid core
dimensions. The commercially available products
comprise the solid core with the diameter lying
within the range of 2.53.5 nm and are usually
characterized by narrow size distribution. The size
of particles slightly increases with increase of TBN
(Total Base Number) value that is used for characterization of this type of additive.
In the case of overbased detergent additives, the
role of capping reagent is performed by corresponding alkaline earth metal (Me) salts of alkylated arylsulfonates, phenols, salicylates, etc.
(Marsh, 1987; Galsworthy et al., 2000), i.e. by oilsoluble surfactants (Shor et al., 1996). Basically the
carbonate core of these substances is amorphous,
although nanocrystalline CaCO3 overbased sulfonate is reported to exhibit enhanced stability even
at relatively large core size of 5080 nm (Eckard et
al., 2002).

A number of other lubricant additives are supposed to form reversed colloidal self-organizing
systems in hydrocarbon solvents, moreover,
structural changes take place during lubricant
degradation due to oxidation at high temperatures, and the latter implies quite specic action
(catalytic) mechanism including transport phenomena through surfactant layer (Bakunin et al.,
2001; Shor et al., 1996). The lubricant compositions including complete additive packages thus

276
represent complex colloidal systems that also
should be designated as liquid nanocomposite
systems. These systems are often optically transparent and physically stable for years. General
conclusion is that the surface-capped inorganic
nanosized particles other than above-mentioned
overbased detergent composites might signicantly
improve performance characteristics of modern
and advances lubricant systems. This conclusion
resulted in a number of experimental eorts to
synthesize and to test inorganic nanoparticles as
components of liquid lubricants, basically in the
eld of tribo-active compounds.
2.2. Inorganic nanosized particles as lubricant
additives: state of art
During the last decade, a number of attempts were
made to synthesize various inorganic nanoparticles
as lubricant additives (Liu et al., 2000), mainly as
tribologically active ones. Historically, these syntheses include preparation and tribology testing of
surface-modied MoS2 nanoparticles (Zhang
et al., 1994; Zhang et al., 1997); titanium oxide
(Hu & Dong, 1998a; Xue et al., 1997) and titanium
borate (Hu & Dong, 1998b) nanoparticles;
La(OH)3 nanocluster modied by compound
containing nitrogen (Zhang et al., 1998); dialkyldithiophosphate-coated PbS nanoparticles
(Chen et al., 1998); nanometer zinc borate (Dong
& Hu, 1998) and ferric oxide (Hu et al., 1998);
CeF3 nanoparticles (Qiu et al., 1999) and MoO3
nanocrystals (Wang et al., 1999); ZnS nanoparticles surface-modied with di-n-hexadecyldithiophosphate (Liu and Chen, 2000); nanosized
lanthanum (Hu et al., 2000) and aluminum borate
(Hu et al., 2001) particles; nanometer cobalt
hydroxide (Chen et al., 2001) and Ni nanoparticles
(Qiu et al., 2001); ultrane and amorphous strontium (Chen et al., 2001) and magnesium (Hu et al.,
2002) borate particles; surface-capped molybdenum trisulde nanoparticles (Bakunin et al., 2001;
Parenago et al., 2002; Suslov et al., 2003) and
NiMoO2S2 nanoparticles (Ye et al., 2002). Finally,
nanosized copper nanoparticles were studied as
friction reducing lubricant additives (Zhou et al.,
1999; Tarasov, 2002). However, relatively small
information is available in most cases concerning
solubility of synthesized samples or stability of
their dispersions in hydrocarbons. The authors
often pay main attention to determination of size

and size distribution for the synthesized particles

and perform primary tribology testing results
along with measurements of tribo-active elements
content at the wear surfaces. The obtained
nanoparticulate matter is usually introduced into
hydrocarbon-based lubricating oils using ultrasonic irradiation, little is known about the physical
stability of thus prepared composites and about
the aggregation state of nanoparticles in solutions.
Most of synthetic methods involve microemulsion-based synthetic procedure and are hardly to
be applied for an industrial-scale production. All
above-mentioned inorganic nanoparticles (surfacecapped or not) were used as tribologically active
additives that are capable to form respective protective layers on friction surfaces and thus to improve wear resistance of metal species. The choice
of inorganic matter composition was based either
on compounds similar to composition of conventional tribo-protective layers (S, P, Zn, etc.), or on
inorganic substances having graphite- of MoS2like crystal lattice parameters. The most attractive
substances in this eld seem to be molybdenum
suldes or MoS2 precursors, such as e.g. MoS3 and
generally Mo(VI) complexes since this type of
compounds is known to reduce friction losses and
decrease fuel consumption up to 5%.
3. Molybdenum sulde nanoparticles
Conventional wear reducing and EP additives
contain phosphorus and sulfur atoms in molecules,
and said elements are responsible for formation of
protective inorganic lms on metal surfaces
[e.g. phosphates and suldes (De Barros et al.,
2003)]. The most ecient compound reducing
friction coecient is MoS2, although it is not soluble in organic media and can be used only in the
form of ne dispersions (Rastogi and Yadav,
2003), preferably in greases, or in the form of oilsoluble
molybdenum-containing
complexes
(Mitchell, 1984; Yamamoto et al., 1986; Graham
et al., 2001; Topolevec Miklozic et al., 2001), such
as e.g. molybdenum (VI) dialkyldithiophosphate
(DDP) or dialkyldithiocarbamate (DTC) derivatives:

277
Additives based on MoDDP and MoDTC
are relatively expensive, their synthesis is complex
and involves most hazardous compounds such as
P2S5 and CS2. These factors strongly limit their
use in conventional lubricant composition. So, the
demand for relatively cheep and eective antifriction additive comprising MoS2 precursors has
encouraged researcher to search for various
molybdenum sulde-based nanoparticles synthesis
and testing. One more eld of nanosized MoS
system application is its use as a catalyst in
petroleum desulfurization process (Boakye et al.,
1994).
Synthetic methods for preparation of molybdenum sulde nanoparticles are well described
and involve most of the above-mentioned processes. The rst methods published in 1994 for
synthesis of molybdenum disulde nanoparticles
involve dierent procedures: Zhang et al. (1994)
utilized an ion modication (or arrested precipitation) method to obtain MoS2 nanocluster
capped by DDP fragments, while Boakye et al.
(1994) and Wilcoxon and Samara (1995) used a
reverse microemulsion-mediated synthesis to
prepare non-capped MoS2 nanoparticles for use
as a catalyst in coal liquifaction. In this review
we will classify the description of synthetic approaches by the nature of end product: whether
it is surface-capped using special reagents or not.
The socalled bare nanoparticles are usually
synthesized for catalytic or other specic applications (Wilcoxon & Samara, 1995), and in fact
are usually protected from coalescence by adsorbed layers of solvents, and/or oxides,and/or
other derivatives.

(Zhang et al., 1994; Zhang et al., 1997). The total

chemical route to nanocluster might be described
as follows:
PyDDP Na2 S

MoO2

! MoIV  ! !
4 NH2 OH
MoS2 x fDDPgy
Bakunin et al. have synthesized surface-capped
molybdenum trisulde nanoparticles using reverse microemulsion procedure in water-in-oil
microemulsions stabilized with cationic surfactant
cetyltrimethylammonium bromide (Bakunin et
al., 2001; Parenago et al., 2002; Suslov et al.,
2003). This method includes the formation of a
microemulsion containing molybdate salt in
aqueous compartment, addition of an appropriate capping agent selected from the group of
aliphatic amines, carboxylic acids, salts of dialkyldithiophosphoric acid, alkylated succinimide
derivatives, and substitution of oxygen atoms in
molybdate anion with sulfur by reaction with
hydrogen sulde. The MoS3 nanoparticles
formed after removal of surfactant excess form
clear solutions in THF, chloroform, benzene and
isooctane or mineral oils, depending on the nature of capping agent used. Particle size as
determined using small angle X-ray scattering
technique (SAXS) and atomic force microscopy
(AFM) is about 36 nm, and capping layer includes
cetyltrimethylammonium
fragments
(according to NMR 1H and IR spectroscopy
data). It might be assumed that anion exchange
in microemulsion plays a signicant role in
nanoparticle formation providing a shell of
insoluble (R4N)2MoS4 compound around the
molybdenum trisulde core.

3.1. Surface-capped oil soluble molybdenum sulde

nanoparticles
Zhang et al. performed the synthesis of DDPcapped molybdenum disulde nanocluster in
aqueous solution by sequential addition of sodium molybdate (metal source), hydroxylamine
hydrochloride (reducing agent), pyridinium di-noctadecyldithiophosphate (capping layer source),
and Na2S as sulfur source. Final acidity adjustment by HCl resulted in brown sediment that
could be dissolved in tetrahydrofuran (THF),
dimethylformamide (DMF) and acetone, and it
could be stably dispersed in liquid paran also

Two more approaches to oil-soluble molybdenum sulde nanoparticles suitable for use as
lubricant additives were recently briey reported
(Bakunin et al., 2003), one including thermal
decomposition of tetrathiomolybdate salts in a
matrix containing surface-capping agent, and
another involving interaction of Mo(CO)6 with
either double bonds or phenyl rings in a micelleforming block copolymer. Subsequent treatment
of the system with H2S leads to MoSx nanoparticle

278
formation either in the polymeric micelle corona
or in the micelle core.
3.2. Microemulsion-mediated synthesis
of surface-capped MoS3 nanoparticles
Reverse microemulsion-based procedure for inorganic nanoparticle synthesis is based on assumption that inner aqueous pool of reverse
microemulsion represents a conned nano-reactor
for production of a desired particle (Boutonnet
et al., 1982; Lopez-Quintela, 2003; Pileni, 2003).
As reported earlier (Bakunin et al., 2001; Parenago
et al., 2002; Suslov et al., 2003), this procedure
includes the following steps: formation of a reverse
micellar solution (solvent mixture isooctane
chloroform, surfactant hexadecyltrimethylammonium bromide, CTAB) (Figure 2a); creation of
reverse microemulsion containing sodium or
ammonium molybdate in aqueous core (Figure 2b); reaction of molybdate salt with H2S to
form tetrathiomolybdate salt with subsequent pH
adjustment to convert molybdenum compound
into MoS3 sediment within the aqueous nanoreactor (Figure 2c).

Figure 3.

The obtained product is readily mixed with

hydrocarbon lubricants to form physically stable,
optically transparent brown solutions. The size of
molybdenum sulde nanoparticles was investigated using SAXS method (Suslov et al., 2003),
and the structure of solid core is considered to be
most consistent with amorphous MoS3 that represent inorganic polymer constituted of Mo3S9
clusters (Weber et al., 1995),

while the capping layer includes both CTAB and

ASI fragments.
3.3. Bare molybdenum sulde nanoparticles
Figure 2.

The following step of this one-pot synthesis

comprises addition of an appropriate surfacecapping agent, e.g. alkylated succinimide derivative:

removing surfactant excess (in the case of CTAB,

previous solvent mixture is evaporated and the
residue is extracted with THF), and nally
removing THF to yield the product in the form of
MoS3 nanosized particles in the matrix of ASI
(Figure 3):

Although bare nanoparticles fail to form stable liquid nanocomposite systems in hydrocarbon media,
the possible synthetic routes might be used as primary step for preparation of surface-capped matter.
Boakye et al. (1994) have synthesized bare
molybdenum sulde nanoparticles by a microemulsionbased route by acidifying (NH4)2MoS4
solution in aqueous compartment of the reverse
microemulsion stabilized with the nonionic surfactant polyoxyethylene(5)-nonylphenylether (NP5), and the particle size obtained was in the range
of 1080 nm.
Wilcoxon et al. (1995) utilized another chemical
approach resulting in molybdenum disulde
nanoclusters (215 nm 10%):
MoX4 2H2 S
! MoS2 ;
where X is a halogen atom, and performed reaction between two inverse micellar solutions one

279
comprising molybdenum (IV) halide and another
a suldizing agent (e.g. metal sulde or hydrogen
sulde). The reaction conditions involve catalytic
water and oxygen removal (below 1 ppm) to prevent degradation of Mo(IV) salt.
Marchand et al. (2003) made a choice of anionic
surfactant AOT, or sodium bis(2-ethylhexyl)-sulfosuccinate, which favors the formation of spherical water-in-oil droplets at low water content. In
this case MoSx nanoparticles were prepared by
addition of ammonium tetrathiomolybdate solution to microemulsion stabilized by AOT and
acidied with sulfuric acid, according to the following reaction (Marchand et al., 2003):

MoS2

4 24
xH
! MoSx 4
xH2 S

The mean size of molybdenum sulde nanoparticles was from 4 to 8 nm depending on the process
conditions.
Two other synthetic approaches to molybdenum based colloidal particles were described by
Moreno et al. (1998): thermal decomposition of
Mo(CO)6 in tert-amyl alcohol in the presence of
tetrahydrothiophene at 120C, or thermal
decomposition of (NH4)2MoS4 in methanol at
100C under reducing atmosphere of H2/CO; and
sonication (ultrasonic irradiation) of ammonium
tetrathiomolybdate solution in methanol under a
stream of H2. The rst method provides preparation of MoO2L2 species, where L is tert-amyl
alcohol ligand, with the average size of approximately 1.5 nm. Almost no sulfur is detected in
these particles by XPS analysis. Thermal and
sonochemical decomposition of ammonium tetrathiomolybdate results in formation of very
small molybdenum- and sulfur-containing colloidal particles (from 2.5 to 4.7 nm) which composition is the most consistent with MoS2
formula (Moreno et al., 1998).
Another sonochemical method for synthesis of
a high-surface-area nanophase of molybdenum
sulde is described by Mdleleni et al. (1998). A
typical procedure includes irradiation of a slurry
of molybdenum hexacarbonyl and sulfur in
1,2,3,5-tetramethylbenzene (isodurene) with highintensity ultrasound (20 kHz) under Ar at 80C.
The substance obtained represent MoS2 and is
more active in thiophene hydrodesulfurization
than samples obtained by ammonium tetrathiomolybdate decomposition. Similar procedure is

described for preparation of MoSe2 nanoparticles

by sonochemical reaction between Mo(CO)6 and
Se in decalin under nitrogen atmosphere (Kristl
and Drofenik, 2003). The X-ray powder diraction of samples shows that amorphous product
after annealing at 330C yields nanocrystalline
MoSe2.
An interesting example of similar nanosized
objects used as solid lubricants, namely WS2 and
MoS2 fullerene-like nanoparticles is described by
Tenne et al. (Rapoport et al., 1999; Feldman et al.,
2000; Rapoport et al., 2002; Tenne, 2002; Rapoport et al., 2003; Xiong et al., 2003). These substances are prepared by gas-phase synthesis from
e.g. MoO3 and H2S (Rapoport et al., 2002;
Rapoport et al., 2003), and they are insoluble in
hydrocarbons, but can be used as solid lubricant
component providing low friction coecient. In
addition, it is reported that 1 wt% of added IFMoS2 (IF designates inorganic fullerene) to polya-olen (PAO) oil signicantly reduces friction
coecient (Cizaire et al., 2003).
Some other methods used for preparation of
molybdenum sulde nanosized materials involve
gas-phase decomposition of Mo(CO)6 and H2S
(Close et al., 1999; Lee et al., 2003), reaction of
Mo(CO)6 and sulfur in xylene at 140C (Duphil
et al., 2002), preparation of molybdenum polysulde hollow microtubules by reaction of
(NH4)2MoS4 and (NH2OH)2H2SO4 under hydrothermal conditions (Afanasiev et al., 2000), by surfactant-assistant method (Afanasiev et al., 1999), or
using arc discharge in water (Sano et al., 2003).
3.4. Tribological properties and action mechanism
Activity of tribo-active additives in improving
tribological properties in conventional tribology
(macrotribology) is usually evaluated using various types of friction machines tribometers.
Standard equipment is represented by four (or
ve) ball machines (rotation of a steel ball on a
bed formed by three other balls), pin-on-disk
tribometers (linear wear) and tribometers that
utilize reciprocating movement. The main
parameters measured include wear rate at a
constant load, friction coecient measurements
under dierent conditions, and load-carrying
ability of a liquid lubricant lm. All these
parameters strongly depend on activity of triboactive additives used (as well as on properties of

280
base oil, e.g. its viscosity). Nanotribological
approach is based mainly on the use of atomic
force microscopy (AFM) instruments that provide measurement of friction characteristics at
the atomic level. At present tribological measurements for lubricant compositions were performed using conventional tribometers in
comparison with either base oils or similar
molecular additive analogues.
The tribological properties of surface-capped
molybdenum sulde nanoparticles dispersed or
dissolved in hydrocarbon lubricants were tested by
Zhang et al. (1997) using a four-ball testing
machine, and by Bakunin et al. using SRV tribometer and CameronPlint TE77 High Frequency
Friction Machine (Bakunin et al., 2001; Parenago
et al., 2002; Suslov et al., 2003). The Chinese group
compared friction coecient reduction and antiwear properties of synthesized MoS cluster in a
paran oil with Zn dialkyldithiophosphate
(ZnDTP)-type additive, and demonstrated that
both antifriction and antiwear properties are signicantly improved in the case of nanoparticlebased substance (Zhang et al., 1997).
The Russian group reported (Bakunin et al.,
2001; Parenago et al., 2002; Suslov et al., 2003)
that surface-capped MoS3 nanoparticle additive
is more ecient than MoDTC in friction coefcient reduction when tested at SRV tribometer
under load-increasing conditions, and is similar
to MoDTC under temperature-increasing conditions (CameronPlint). It is also reported that
the best friction coecient-reducing properties
are demonstrated by compositions comprising
molybdenum sulde nanoparticles at extremely
high testing temperatures of 150160C (Bakunin
et al., 2003).
On the basis of these results it is suggested that
action mechanism of surface-capped MoSx nanoparticles is strongly determined by the properties
of capping layer that complicates the initial step of
physical and/or chemical adsorption of additive on
metal surface (Bakunin et al., 2003). At low temperatures, when molecular molybdenum-containing friction modier is easily adsorbed on
metal surface, the surface-capped MoSx nanoparticles come in contact with metal preferably by the
outer non-polar and viscous shell of modifying
substance (see Figure 4a). Formation of frictionreducing MoS-containing layer may be achieved
after destruction of surface-capping shell or its

Figure 4.

viscosity decrease e.g. due to increasing temperature (Figure 4b). In the case of MoSx nanoparticles stabilized by a block-copolymer matrix
(Bakunin et al., 2003), location of molybdenumcontaining species in corona of polymeric micelle
provides good contact and subsequent adsorption
of metal sulde on metal surface (Figure 4c).
Thus it seems that tribo-active properties of the
tested molybdenum sulde nanoparticles strongly
depends on the rst (adsorption) step of their
action mechanism and are related mainly to the
nature of surface-capping layers and to the entire
structure of inorganic nanoparticle core and its
organic shell. Unfortunately, this eld of nanochemistry is one of the most unclear and speculative and it should be discussed separately.
However, it might represent one of the possible
building blocks in making a bridge to ll the gap
between the macro- and nanotribology. At present, serious attempts are made in the eld of
understanding the chemistry and physics of covalent bonding of organic functionalized molecules
to innite inorganic surfaces at molecular and
atomic level (Bent, 2002).
Respectively, such knowledge would be the most
useful in understanding the nature of core-to-shell
bonding in surface-capped inorganic nanoparticles
and in properties of self-assembled organic shell
layer.

4. Conclusions
Thus, two main tendencies characterize utilization
of inorganic nanoparticles as components of liquid
lubricants: (a) more than 50 years successful
experience in application of overbased detergent
additive demonstrate that this nanoparticle-based
substances play an important role in modern and

281
advanced lubricant compositions; (b) recent
achievements in nanochemistry suggest numerous
new processes for synthesis of novel inorganic
nanosized particles and these substances are under
testing in lubricant chemistry.
State of nanoparticles in liquid organic solvents,
hydrocarbons in particular, is crucial for their use
as lubricant additives. Stabilization of inorganic
nanoparticles in non-polar hydrocarbon medium
can be achieved by their surface modication using
various capping agents comprising polar groups
and long hydrocarbon chains, or using various
soluble polymeric matrixes. Good solvation of
outer shell of such surface-capped nanoparticles
provides physical stability of such liquid nanocomposite systems and possibility of their practical
application.
Main attention of researchers is paid to investigation of inorganic nanoparticles comprising
tribo-active elements such as phosphorous, sulfur,
zinc, molybdenum, etc. Also a lot of compounds
possessing layered structure were tested as
lubricant additives in the nanosized form. The
obtained results clearly indicate that inorganic
nanosized particles play an important role in
lubricant chemistry. Apparently the most promising type of nanosized additives is represented as
surface-capped molybdenum sulde compounds,
although structure-activity interrelations need to
be investigated in more details. It seems that in
this case good stabilization in solution means
worse interaction of inorganic core with metal
surface. This should be accounted at least for
tribo-active or other lubricant additives which
action mechanism involves adsorption on polar
surfaces.
Further research eorts are necessary in the
fundamental problem of capping layer structure,
nature of its interaction with the inorganic core
substance. This research eld is important also
for the eld of nanotribology and might assist in
bridging the gap between conventional macrotribology and advanced nanotribology.

Acknowledgement
This publication was made possible in part by
Award No. RC1-545-MO-02 of the US Civilian
Research & Development Foundation for the
Independent States of the Former Soviet Union

(CRDF) and Award #1577 of the International

Science and Technology Center (ISTC).

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