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Synthesis and Application of Inorganic

Nanoparticles as Lubricant Components – a
Review

Article in Journal of Nanoparticle Research · January 2004

DOI: 10.1023/B:NANO.0000034720.79452.e3

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Journal of Nanoparticle Research 6: 273–284, 2004.
Ó 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 modification of nanoparticles in some
cases provides formation of their stable dispersions in liquid hydrocarbons. State of art in the field of
inorganic nanoparticles’ synthesis and their application in tribology is discussed. Special attention is paid to
synthesis of surface-capped and bare molybdenum sulfide nanoparticles and to testing thereof as friction-
modifying additives for liquid lubricants. Differences in action mechanism of MoSx nanoparticles and
‘molecular’ molybdenum complexes are discussed. Future trends of inorganic nanoparticles use as lubricant
additives are suggested.

Introduction sition of organometallic precursors (Dushkin 2000;

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 different fields of material
science and technology (Henglein, 1989; Klabun-
de, 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 nanopar-
ticle environment can influence both activity and
selectivity of the catalytic species (Lewis, 1993;
Kung & Kung, 2003). A variety of methods for the
preparation and stabilization of nanoparticles ex-
ists in the literature, e.g. including formation of
inorganic nanoparticles in reverse microemulsion
environment (Boutonnet et al., 1982; López-
Quintela, 2003), in polymeric systems (Gubin,
2002; Schmidt, & Malwitz, 2003), by vapor-phase
procedures (Swihart, 2003), by thermal decompo-
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 modifi-
cation) 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. elec-
tron donors or acceptors species that bond to the
nanoparticle surface (Mandal et al., 2002; Capo-
netti et al., 2003). These coatings provide stabil-
ization 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
274
surface-modified nanoparticles may form rela-
tively 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-modified (or surface-capped) nanoparticles
should be solvated by the bulk solvent used, i.e.
they should be hydrophilic in the case of aqueous-
based 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 ‘solu-
tions’ of inorganic nanoparticles in condensed li-
quid media. The terms ‘solution’ and ‘dispersion’
seem to be not applicable to such systems, appar-
ently 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’ definition 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. Al-
though most of discussed papers describe mostly
tribological applications of inorganic nanoparti-
cles in lubricants, we do not tend to cover the field
of ‘nanotribology’ (Bhushan, 2001; Krim, 2002)
that should be reviewed separately, moreover tri-
bological 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 field of lubrication. An-
other goal is to assist the lubricant chemists in
1
Discussion of the so-called ultrafine inorganic particles
used to improve certain performance characteristics of lubri-
cating oils can be found elsewhere (Liu et al., 2000; Qiu et al.,
1999).
understanding better the place and role of nano-
chemistry in creation of advanced lubricant com-
positions.
2. Nanochemistry of lubricants
Liquid lubricants are used in almost all fields 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 composi-
tions.
Pure petroleum-based hydrocarbon blends or
lubricants based on synthetic hydrocarbon-type
mixtures (polyolefins 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 com-
pounds that provide significant improvement of
base oil properties with regard to either oxidative
degradation or to tribological and other perfor-
mance characteristics. Most of additives comprise
polar functional groups and belong to various
classes of organic or organometallic compounds.
The tribo-active additives generally contain trib-
ologically 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 first step of their action mechanism is usually
physical and/or chemical adsorption on entire
metal surface, and chemical modification 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 trib-
ologically active elements in their molecules, and it
is often necessary to add up to 5 wt% such addi-
tives to prevent from serious metal surface deple-
tion.
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

nanoparticles. Thus, the inorganic nanoparticles
might be considered as ‘concentrates’ comprising
the required active chemical elements or com-
pounds at a very high local concentration. So their
use may significantly improve wear protection of
metal surfaces or other functional properties of
liquid lubricants.
Of course, improvement of tribological proper-
ties 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 cor-
rosive 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 field of petroleum
chemistry wherein a number of so-called over-
based dispersing additives is used since 1950s
(Baker et al., 1954; Marsh, 1987). This class of
substances represents colloidal systems that in-
clude dispersions of extremely small particles of
alkaline earth metals hydroxides and/or carbon-
ates 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:
½ðR
SO3 Þ2 Cak ½CaðOHÞ2 m ½CaCO3 n
Modern presentation is more close to images of
inorganic nanoparticles [see Figure 1 (Galsworthy
et al., 2000)]:
Figure 1.
275
Colloidal structure of overbased detergent
additives was thoroughly investigated using tradi-
tional colloidal and physical methods such as sol-
ubilization 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 fine 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)
(O’Sullivan et al., 1991), etc., as well as by math-
ematical modeling (Bandyopadhyaya et al., 2001;
Mansot, 1993; Tobias & Klein, 1996). Interrela-
tions between detergent structure and performance
characteristics were investigated (Chinas-Castillo
& Spikes, 2000). This type of substance possesses
the main properties of liquid nanocomposite sys-
tems, especially with respect to the solid core
dimensions. The commercially available products
comprise the solid core with the diameter lying
within the range of 2.5–3.5 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 char-
acterization of this type of additive.
In the case of overbased detergent additives, the
role of capping reagent is performed by corre-
sponding alkaline earth metal (Me) salts of alkyl-
ated arylsulfonates, phenols, salicylates, etc.
(Marsh, 1987; Galsworthy et al., 2000), i.e. by oil-
soluble surfactants (Shor et al., 1996). Basically the
carbonate core of these substances is amorphous,
although nanocrystalline CaCO3 overbased sulfo-
nate is reported to exhibit enhanced stability even
at relatively large core size of 50–80 nm (Eckard et
al., 2002).
A number of other lubricant additives are sup-
posed to form reversed colloidal self-organizing
systems in hydrocarbon solvents, moreover,
structural changes take place during lubricant
degradation due to oxidation at high tempera-
tures, and the latter implies quite specific action
(catalytic) mechanism including transport phe-
nomena through surfactant layer (Bakunin et al.,
2001; Shor et al., 1996). The lubricant composi-
tions including complete additive packages thus
276
represent complex colloidal systems that also
should be designated as liquid nanocomposite
systems. These systems are often optically trans-
parent and physically stable for years. General
conclusion is that the surface-capped inorganic
nanosized particles other than above-mentioned
overbased detergent composites might significantly
improve performance characteristics of modern
and advances lubricant systems. This conclusion
resulted in a number of experimental efforts to
synthesize and to test inorganic nanoparticles as
components of liquid lubricants, basically in the
field 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 syn-
theses include preparation and tribology testing of
surface-modified 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 modified by compound
containing nitrogen (Zhang et al., 1998); dial-
kyldithiophosphate-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 nanoparti-
cles surface-modified with di-n-hexadecyldithio-
phosphate (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); ultrafine and amorphous stron-
tium (Chen et al., 2001) and magnesium (Hu et al.,
2002) borate particles; surface-capped molybde-
num trisulfide 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 ultra-
sonic 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 microemul-
sion-based synthetic procedure and are hardly to
be applied for an industrial-scale production. All
above-mentioned inorganic nanoparticles (surface-
capped or not) were used as tribologically active
additives that are capable to form respective pro-
tective layers on friction surfaces and thus to im-
prove wear resistance of metal species. The choice
of inorganic matter composition was based either
on compounds similar to composition of conven-
tional tribo-protective layers (S, P, Zn, etc.), or on
inorganic substances having graphite- of MoS2-
like crystal lattice parameters. The most attractive
substances in this field seem to be molybdenum
sulfides 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 sulfide nanoparticles
Conventional wear reducing and EP additives
contain phosphorus and sulfur atoms in molecules,
and said elements are responsible for formation of
protective inorganic films on metal surfaces
[e.g. phosphates and sulfides (De Barros et al.,
2003)]. The most efficient compound reducing
friction coefficient is MoS2, although it is not sol-
uble in organic media and can be used only in the
form of fine dispersions (Rastogi and Yadav,
2003), preferably in greases, or in the form of oil-
soluble 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) deriva-
tives:

Additives based on Mo–DDP and Mo–DTC
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 effective anti-
friction additive comprising MoS2 precursors has
encouraged researcher to search for various
molybdenum sulfide-based nanoparticles synthesis
and testing. One more field of nanosized Mo–S
system application is its use as a catalyst in
petroleum desulfurization process (Boakye et al.,
1994).
Synthetic methods for preparation of molyb-
denum sulfide nanoparticles are well described
and involve most of the above-mentioned pro-
cesses. The first methods published in 1994 for
synthesis of molybdenum disulfide nanoparticles
involve different procedures: Zhang et al. (1994)
utilized an ‘ion modification’ (or arrested pre-
cipitation) 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 ap-
proaches 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 specific appli-
cations (Wilcoxon & Samara, 1995), and in fact
are usually protected from coalescence by ad-
sorbed layers of solvents, and/or oxides,and/or
other derivatives.
3.1. Surface-capped oil soluble molybdenum sulfide
nanoparticles
Zhang et al. performed the synthesis of DDP-
capped molybdenum disulfide nanocluster in
aqueous solution by sequential addition of so-
dium molybdate (metal source), hydroxylamine
hydrochloride (reducing agent), pyridinium di-n-
octadecyldithiophosphate (capping layer source),
and Na2S as sulfur source. Final acidity adjust-
ment 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 paraffin also
277
(Zhang et al., 1994; Zhang et al., 1997). The total
chemical route to nanocluster might be described
as follows:
PyDDP Na2 S
MoO2

4 þ NH2 OH ƒ ƒ! ½MoIV  ƒƒƒƒ! ƒƒ!
½MoS2 x fDDPgy
Bakunin et al. have synthesized surface-capped
molybdenum trisulfide nanoparticles using re-
verse 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 appropri-
ate capping agent selected from the group of
aliphatic amines, carboxylic acids, salts of dial-
kyldithiophosphoric acid, alkylated succinimide
derivatives, and substitution of oxygen atoms in
molybdate anion with sulfur by reaction with
hydrogen sulfide. The MoS3 nanoparticles
formed after removal of surfactant excess form
clear solutions in THF, chloroform, benzene and
isooctane or mineral oils, depending on the nat-
ure of capping agent used. Particle size as
determined using small angle X-ray scattering
technique (SAXS) and atomic force microscopy
(AFM) is about 3–6 nm, and capping layer in-
cludes cetyltrimethylammonium fragments
(according to NMR 1H and IR spectroscopy
data). It might be assumed that anion exchange
in microemulsion plays a significant role in
nanoparticle formation providing a shell of
insoluble (R4N)2MoS4 compound around the
molybdenum trisulfide core.
Two more approaches to oil-soluble molybde-
num sulfide nanoparticles suitable for use as
lubricant additives were recently briefly 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 micelle-
forming 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 inor-
ganic nanoparticle synthesis is based on assump-
tion that inner aqueous pool of reverse
microemulsion represents a confined nano-reactor
for production of a desired particle (Boutonnet
et al., 1982; López-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 – hexadecyltrimethylam-
monium bromide, CTAB) (Figure 2a); creation of
reverse microemulsion containing sodium or
ammonium molybdate in aqueous core (Fig-
ure 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 nano-
reactor (Figure 2c).
Figure 2.
The following step of this one-pot synthesis
comprises addition of an appropriate surface-
capping agent, e.g. alkylated succinimide deriva-
tive:
removing surfactant excess (in the case of CTAB,
previous solvent mixture is evaporated and the
residue is extracted with THF), and finally –
removing THF to yield the product in the form of
MoS3 nanosized particles in the matrix of ASI
(Figure 3):
Figure 3.
The obtained product is readily mixed with
hydrocarbon lubricants to form physically stable,
optically transparent brown solutions. The size of
molybdenum sulfide nanoparticles was investi-
gated using SAXS method (Suslov et al., 2003),
and the structure of solid core is considered to be
most consistent with amorphous MoS3 that rep-
resent inorganic polymer constituted of Mo3S9
clusters (Weber et al., 1995),
while the capping layer includes both CTAB and
ASI fragments.
3.3. Bare molybdenum sulfide nanoparticles
Although bare nanoparticles fail to form stable li-
quid nanocomposite systems in hydrocarbon media,
the possible synthetic routes might be used as pri-
mary step for preparation of surface-capped matter.
Boakye et al. (1994) have synthesized bare
molybdenum sulfide nanoparticles by a micro-
emulsionbased route by acidifying (NH4)2MoS4
solution in aqueous compartment of the reverse
microemulsion stabilized with the nonionic sur-
factant polyoxyethylene(5)-nonylphenylether (NP-
5), and the particle size obtained was in the range
of 10–80 nm.
Wilcoxon et al. (1995) utilized another chemical
approach resulting in molybdenum disulfide
nanoclusters (2–15 nm ± 10%):
MoX4 þ 2H2 S
! MoS2 ;
where X is a halogen atom, and performed reac-
tion between two inverse micellar solutions one

comprising molybdenum (IV) halide and another –
a sulfidizing agent (e.g. metal sulfide or hydrogen
sulfide). The reaction conditions involve catalytic
water and oxygen removal (below 1 ppm) to pre-
vent degradation of Mo(IV) salt.
Marchand et al. (2003) made a choice of anionic
surfactant AOT, or sodium bis(2-ethylhexyl)-sul-
fosuccinate, which favors the formation of spher-
ical water-in-oil droplets at low water content. In
this case MoSx nanoparticles were prepared by
addition of ammonium tetrathiomolybdate solu-
tion to microemulsion stabilized by AOT and
acidified with sulfuric acid, according to the fol-
lowing reaction (Marchand et al., 2003):
þ
MoS2

4 þ 2ð4
xÞH
! MoSx þ ð4
xÞH2 S
The mean size of molybdenum sulfide nanoparti-
cles was from 4 to 8 nm depending on the process
conditions.
Two other synthetic approaches to molybde-
num 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 120°C, or thermal
decomposition of (NH4)2MoS4 in methanol at
100°C under reducing atmosphere of H2/CO; and
sonification (ultrasonic irradiation) of ammonium
tetrathiomolybdate solution in methanol under a
stream of H2. The first method provides prepa-
ration of MoO2L2 species, where L is tert-amyl
alcohol ligand, with the average size of approx-
imately 1.5 nm. Almost no sulfur is detected in
these particles by XPS analysis. Thermal and
sonochemical decomposition of ammonium tet-
rathiomolybdate results in formation of very
small molybdenum- and sulfur-containing colloi-
dal particles (from 2.5 to 4.7 nm) which com-
position is the most consistent with MoS2
formula (Moreno et al., 1998).
Another sonochemical method for synthesis of
a high-surface-area nanophase of molybdenum
sulfide 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 high-
intensity ultrasound (20 kHz) under Ar at 80°C.
The substance obtained represent MoS2 and is
more active in thiophene hydrodesulfurization
than samples obtained by ammonium tetrathio-
molybdate decomposition. Similar procedure is
279
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 diffrac-
tion of samples shows that amorphous product
after annealing at 330°C 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; Rapo-
port et al., 2003; Xiong et al., 2003). These sub-
stances 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 coefficient. In
addition, it is reported that 1 wt% of added IF-
MoS2 (IF designates inorganic fullerene) to poly-
a-olefin (PAO) oil significantly reduces friction
coefficient (Cizaire et al., 2003).
Some other methods used for preparation of
molybdenum sulfide 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 140°C (Duphil
et al., 2002), preparation of molybdenum polysul-
fide hollow microtubules by reaction of
(NH4)2MoS4 and (NH2OH)2ÆH2SO4 under hydro-
thermal conditions (Afanasiev et al., 2000), by sur-
factant-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 vari-
ous types of friction machines – tribometers.
Standard equipment is represented by four (or
five) 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 coefficient measurements
under different conditions, and load-carrying
ability of a liquid lubricant film. All these
parameters strongly depend on activity of tribo-
active 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 pro-
vide measurement of friction characteristics at
the atomic level. At present tribological mea-
surements for lubricant compositions were per-
formed using conventional tribometers in
comparison with either base oils or similar
‘molecular’ additive analogues. Figure 4.
The tribological properties of surface-capped
molybdenum sulfide nanoparticles dispersed or
dissolved in hydrocarbon lubricants were tested by
viscosity decrease e.g. due to increasing tempera-
Zhang et al. (1997) using a four-ball testing
ture (Figure 4b). In the case of MoSx nanoparti-
machine, and by Bakunin et al. using SRV trib-
cles stabilized by a block-copolymer matrix
ometer and Cameron–Plint TE77 High Frequency
(Bakunin et al., 2003), location of molybdenum-
Friction Machine (Bakunin et al., 2001; Parenago
containing species in corona of polymeric micelle
et al., 2002; Suslov et al., 2003). The Chinese group
provides good contact and subsequent adsorption
compared friction coefficient reduction and anti-
of metal sulfide on metal surface (Figure 4c).
wear properties of synthesized MoS cluster in a
Thus it seems that tribo-active properties of the
paraffin oil with Zn dialkyldithiophosphate
tested molybdenum sulfide nanoparticles strongly
(ZnDTP)-type additive, and demonstrated that
depends on the first (adsorption) step of their
both antifriction and antiwear properties are sig-
action mechanism and are related mainly to the
nificantly improved in the case of nanoparticle-
nature of surface-capping layers and to the entire
based substance (Zhang et al., 1997).
structure of inorganic nanoparticle core and its
The Russian group reported (Bakunin et al.,
organic shell. Unfortunately, this field of nano-
2001; Parenago et al., 2002; Suslov et al., 2003)
chemistry is one of the most unclear and specula-
that surface-capped MoS3 nanoparticle additive
tive and it should be discussed separately.
is more efficient than Mo–DTC in friction coef-
However, it might represent one of the possible
ficient reduction when tested at SRV tribometer
building blocks in making a bridge to fill the gap
under load-increasing conditions, and is similar
between the macro- and nanotribology. At pres-
to Mo–DTC under temperature-increasing con-
ent, serious attempts are made in the field of
ditions (Cameron–Plint). It is also reported that
understanding the chemistry and physics of cova-
the best friction coefficient-reducing properties
lent bonding of organic functionalized molecules
are demonstrated by compositions comprising
to infinite inorganic surfaces at molecular and
molybdenum sulfide nanoparticles at extremely
atomic level (Bent, 2002).
high testing temperatures of 150–160°C (Bakunin
Respectively, such knowledge would be the most
et al., 2003).
useful in understanding the nature of core-to-shell
On the basis of these results it is suggested that
bonding in surface-capped inorganic nanoparticles
action mechanism of surface-capped MoSx nano-
and in properties of self-assembled organic shell
particles is strongly determined by the properties
layer.
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 tem-
peratures, when ‘molecular’ molybdenum-con- 4. Conclusions
taining friction modifier is easily adsorbed on
metal surface, the surface-capped MoSx nanopar- Thus, two main tendencies characterize utilization
ticles come in contact with metal preferably by the of inorganic nanoparticles as components of liquid
outer non-polar and viscous shell of modifying lubricants: (a) more than 50 years successful
substance (see Figure 4a). Formation of friction- experience in application of overbased detergent
reducing MoS-containing layer may be achieved additive demonstrate that this nanoparticle-based
after destruction of surface-capping shell or its substances play an important role in modern and

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 modification 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 nano-
composite systems and possibility of their practical
application.
Main attention of researchers is paid to inves-
tigation 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 prom-
ising type of nanosized additives is represented as
surface-capped molybdenum sulfide 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 efforts are necessary in the
fundamental problem of capping layer structure,
nature of its interaction with the inorganic core
substance. This research field is important also
for the field of nanotribology and might assist in
bridging the gap between conventional macro-
tribology 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
281
(CRDF) and Award #1577 of the International
Science and Technology Center (ISTC).
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