+ MODEL

ARTICLE IN PRESS

Advances in Colloid and Interface Science xx (2006) xxx – xxx

www.elsevier.com/locate/cis

Nanotechnology in action: Overbased nanodetergents

as lubricant oil additives
L.K. Hudson a , J. Eastoe a,⁎, P.J. Dowding b
a
School of Chemistry, University of Bristol, Bristol, BS8 1TS, United Kingdom
b
Infineum UK Ltd, Milton Hill Business and Technology Centre, Abingdon, Oxon, OX13 6BB, United Kingdom

Abstract

The synthesis and study of oil-soluble metal carbonate colloids are of interest in the area of lubricant additives. These surfactant-stabilised
nanoparticles are important components in marine and automotive engine oils. Recently introduced, environmentally driven legislation has focused on
lowering of gaseous emissions by placing limits on the levels of phosphorous sulphur and ash allowed in engine oil systems. These chemical limits,
coupled with improved engine performance and extended oil drainage intervals, have lead to renewed interest in the production of stable, efficient
nanodetergent systems. To date, this has resulted in modification of existing surfactant structures and development of new generations of surfactants.
This review covers the current state of research in the area of nanodetergents.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Lubricant additives; Lubricants; Overbased; Detergents; Nanoparticles; Non-aqueous colloids

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
2. Nanoparticle preparation from microemulsions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
3. The detergent core . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
4. Surfactants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
5. Solvent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
6. Characterisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
6.1. SANS and SAXS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
6.2. Langmuir trough measurement and molecular dynamics simulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
6.3. Acid neutralisation mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
7. Conclusions and future outlook. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0

1. Introduction additives in lubricant oils since the 1940's. A major challenge

This review describes recent advances in a commercial ap-
plication of nanoparticles, which have been routinely used as
⁎ Corresponding author. Tel.: +44 117 9289180; fax: +44 117 9250612.
E-mail address: julian.eastoe@bristol.ac.uk (J. Eastoe).
0001-8686/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.cis.2006.05.003
currently facing potential industrial applications of new nano-
technologies is the ability to generate well-defined, functionalised
particles on a mega-tonne scale. Lubricant detergents represent an
important case study for commercialisation of nanotechnology.
Ever since the invention of the internal combustion engine
lubricant oils have been an essential component. Over the last

CIS-00807; No of Pages 7
 ARTICLE IN PRESS
2 L.K. Hudson et al. / Advances in Colloid and Interface Science xx (2006) xxx–xxx
Fig. 1. Schematic picture of an overbased sulphonate detergent particle.
Reproduced by permission of Elsevier.
century, an increasing range of additives have been incorporated
into lubricating oils to confer chemical stability, improved per-
formance and beneficial physiochemical properties [1]. An
important class are the so-called overbased additives (detergents),
which are colloidal nanoparticles of calcium carbonate (and cal-
cium hydroxide) stabilised by a surfactant layer. These nanode-
tergents essentially consist of an inorganic core (15–40 mass %)
stabilised by oil-soluble surfactants (20–45 mass %) incorporated
into a lubricating base oil, as depicted schematically in Fig. 1 [2].
Fuel combustion yields many by-products, including inorganic
and organic acids formed by oxidation of sulphurous and nitro-
Fig. 2. XANES spectra obtained on overbased sulphonate detergent particles (in grey) and on pure calcite powder (in black). Reproduced by permission of Elsevier.
genous impurities in the fuel, and oxidative degradation of the
lubricant to form organo-acids. If allowed to build up, these acids
would cause severe corrosion, especially under engine start-up
conditions. These nanoparticles are relatively insensitive to tem-
perature, explaining their effectiveness at high temperatures as
slow-release acid neutralisers [3]. The principal functions per-
formed by detergents in engine oil formulations are: (1) acid
neutralisation, (2) high temperature detergency, (3) oxidation inhi-
bition, and (4) rust prevention. These functions promote engine
cleanliness, fuel efficiency and extended trouble-free operation.
Various surfactants are used to stabilise the CaCO3 particles,
typically long chain carboxylic acids, glycols, alcohols, phenates,
sulphonates, salicylates or phosphonates. Recently calixarene/
stearate surfactants have been developed [4]; these novel systems
address environmental concerns about existing detergents (by
containing no sulphur or phosphorous). The term “overbased”
refers to the fact that the quantity of base incorporated in the
particle cores is greater than that needed to neutralise the acid
surfactant. The neutralising strength of an overbased detergent
is measured by its ‘total base number’ (TBN). Where TBN is
defined as the quantity of acid, expressed in terms of the
equivalent number of milligrams of potassium hydroxide that
is required to neutralise all basic constituents present in 1 g of
overbased detergent.
2. Nanoparticle preparation from microemulsions
The commercial synthesis of colloidally stable metal carbo-
nates is known as the “oxide/hydroxide” process; the mechanism
of formation is thought to proceed through a microemulsion route
[5]. The reaction system consists of an excess of metal hydroxide,
appropriate surfactant and a mixture of hydrocarbon and polar
solvents. The polar solvents are usually methanol and water:
water, surfactant and methanol form swollen reverse micelles,
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L.K. Hudson et al. / Advances in Colloid and Interface Science xx (2006) xxx–xxx 3

Fig. 3. Positive ion TOF-SIMS spectrum of overbased sulphonate detergent particles showing the presence of calcium and calcium hydroxide ions. Reproduced by
permission of Elsevier.

which contain dispersed Ca(OH)2. The surfactants are made ‘in
situ’ by the reaction of the corresponding organic acid with the
metal base. Diffusion of gaseous CO2, which is bubbled through
the system, generates CaCO3 in the reverse micellar cores, which
then nucleate at supersaturation [5]. The micellar cores grow
through coalescence. Literature suggests that a stable system
requires a certain amount of residual calcium hydroxide, which
ensures that the inorganic core is amorphous, [5]. If carbonation is
driven to completion, the cores transform into crystalline calcite,
which agglomerates to form larger particles and these eventually
sediment during the reaction [6]. The products are then filtered
under high pressure and temperature to remove unreacted
inorganic material and agglomerated particles. The initial water-
in-oil microemulsion reaction system results in the formation of
nanometre-sized particles, with a narrow particle size distribution.
Although the mechanisms involved in these reactions are not yet
fully understood, [5,7,8], Jacquet and co-workers [6] have studied
the oxide/hydroxide reaction and have drawn some general
conclusions on the behaviour of promoters and determination of
factors controlling the overbasing reaction.
3. The detergent core
The detergent core is typically 1–10 nm in diameter as de-
monstrated by small-angle neutron scattering (SANS) experi-
ments. Many metals have been incorporated into detergents but
currently, based on cost/performance, the three most commonly
used are calcium, magnesium and sodium. The detergent CaCO3
core naturally occurs in many forms, in the bulk as calcite and
aragonite, and also as a variety of unusual forms produced prin-
cipally by living organisms, [9]. Calcite has a rhombohedral
crystal structure, whereas aragonite an orthorhombic crystal struc-
ture. Heyes and co-workers [10] have modelled CaCO3 nano-
particles, and their simulations suggest an essentially amorphous
microstructure. They suggest that there is no thermodynamic bene-
fit from forming local crystalline order in the cores due to the large
surface to volume ratio. Using complimentary techniques such as,
X-ray photoelectron spectroscopy (XPS), X-ray adsorption near
edge structure (XANES) and time-of-flight secondary ion mass
spectroscopy (ToF-SIMS) with examples shown in Figs. 2 and 3,
the authors [11] have been able to prove the existence of Ca(OH)2
in the reversed micelle core and suggest that it is preferentially
located as an outer shell in the micelle core. This can be explained
by residual calcium hydroxide that is not fully carbonated, but still
is present in the core thus creating an amorphous structure. Further,
simulations [2,10] have shown that once nanoparticles of CaCO3
are formed, the stabilising surfactant molecules are essentially
“locked” in place on the surface, perhaps by strong coulombic
forces originating from the inorganic core material.
In 1996 new inorganic colloidal dispersions of calcium, so-
dium and potassium thiophosphate were produced and sub-
sequently characterised [12,13]. These systems have beneficial
anti-wear properties.
4. Surfactants
As mentioned above, a range of surfactants can be used to
stabilise CaCO3 nanoparticles. The chain lengths of these

Table 1
Comparison of detergent properties
Property Phenates Sulphonates Salicylates Phosphonates
Total base number 0–300 0–500 0–300 0–80
(TBN) range
Hydrolytic stability Good Moderate Good Moderate
Oxidation stability Very good Poor Very good Moderate
Thermal stability Excellent Excellent Excellent Moderate
Detergency Good Good Excellent Good
Fig. 4. Molecular structures of surfactants commonly employed in overbased
Rust inhibition Low Good Low Good
detergent systems a) alkyl suphonate, b) sulphurised alkyl phenol (SAP) and c)
Antioxidant effect Very good None Very good Good
alkyl salicylate where R1 is a long chain alkyl tail group.
 ARTICLE IN PRESS
4 L.K. Hudson et al. / Advances in Colloid and Interface Science xx (2006) xxx–xxx

properties [14]. There are four major classes: sulphonates,

phenates, salicylates and phosphonates shown schematically
in Fig. 4 [10]. Table 1 summarises the detergent properties of
the different surfactants commonly employed in stabilising
CaCO3 nanodetergents, [15]. Sulphonates are the most widely
used detergent additives followed by phenates, salicylates and
phosphonates.
Environmental concerns, primarily the problems of sulphur
emissions and sulphur/phosphorous poisoning of automobile
catalytic converters, have led to the demand for sulphur-free
overbased detergents such as salicylates and alkyl bridged
phenates (of which calixarenes are an example, generic
structures of these are shown in Fig. 5) and combination of
such structures (e.g. salixarenes) [16].

5. Solvent

The solvent system employed in preparing these overbased

Fig. 5. Schematics of generic calixarene structures.
surfactants are generally between C9 and C60. On neutralising,
the surfactant prevents both the formation of “varnish” on pistons,
bears polishing of the cylinder and also confers antifriction
detergents is very important. Small changes in the composition of
the solvent mixtures result in very different final products. Jacquet
and co-workers [17] have methodically explored the effects of
varying the solvent level in the preparation of overbased calcium
sulphonate. It was shown that: (1) a minimum amount of water is
required, (2) a minimum amount of methanol is required to give a
significant TBN; however, an excess of water has a detrimental
effect on the rheology, and may even result in an organogel, and
(3) increasing the amount of xylene increases the rate of

Fig. 6. Measured small-angle neutron scattering curves and analysed core shell form factors for surfactant-stabilised nanodetergent particles in mixtures of d8-toluene
and h8-toluene. a) and b) are for 6.2 nm particles with an 1.8 nm shell, a) in 100% h8-toluene, b) in 23% d8-toluene, 77% h8-toluene, c) and d) are for 10.5 nm particles
with a 2.6 nm shell, c) in 60% d8-toluene, d) in d8-toluene. Reproduced by permission of Springer.
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L.K. Hudson et al. / Advances in Colloid and Interface Science xx (2006) xxx–xxx 5

6.2. Langmuir trough measurement and molecular dynamics

simulations

Various molecular simulations have been performed on de-

Fig. 7. Space filling (calcium ions) and stick (all other molecules) representa-
tions of overbased sulphonate detergent nanoparticles using repulsive alkyl tails.
Reproduced by permission of the Royal Society of Chemistry.
tergent systems. Heyes and co-workers [4,23] have shown, by
combined Langmuir trough measurements and molecular dynam-
ics simulations, that different geometries in the detergent particle
are observed when the surfactant chemistry is varied. It was shown
that sulphonate and salicylate stabilised particles were approxi-
mately spherical in shape (Fig. 7 shows an example of modelled
overbased sulphonate detergent); however, phenates and calixa-
rates generated oblates and prolates, respectively (Fig. 8 depicts a
modelled overbased phenate detergent). The addition of a stearate
cosurfactant gave more spherical particles by breaking the natural
regular packing tendency of the surfactants.
The simulations have shown that the internal structure and
arrangement of the ions in the core are sensitive to the surfactant
type, and produce quite specific core shape and internal ionic
structures. Strong coulombic forces between the ions provide
the driving mechanism for the Ca2+, CO32−, and surfactant
moieties to arrange into a reverse micellar structure, with the

carbonation without changing the final TBN. It is known that the

methanol also acts as a promoter at 70 °C for the preparation of
CaCO3 nanoparticles [18].

6. Characterisation

Detergents have been characterised by many different methods

over the years including acid neutralisation, SANS and Trans-
mission electron microscopy [11,19–22,25,26].

6.1. SANS and SAXS

Both small-angle neutron scattering (SANS) and small-angle

X-ray scattering (SAXS) are ideal methods to study nanodeter-
gents [19–22]. Markovic and Ottewill [19,20,21] prepared cal-
cium carbonate particles, stabilised by alkylbenzene sulphonate
surfactants in toluene and dodecane. They used SANS to char-
acterise the system and the Guinier approximation and full model
fitting to analyse the data. Using these approaches, they could
independently determine the metal carbonate core diameter and
the thickness of the surfactant layer. The data and analysis in
Fig. 6 provide a firm evidence for the core shell structure proposed
by others. More detail can be found in relevant papers [20,21].
Further work by Ottewill and co-workers [22] investigated mag-
nesium carbonate systems. During the synthesis of these systems,
conversion of magnesium oxide stopped naturally when the
basic salt 3MgCO3·Mg(OH)2·3H2O was formed. The stabilising
surfactant used was alkylbenzene sulphonate, and the solvents
were iso-octane and toluene. When using dilute systems, it was
found that a single shell model could be used for iso-octane, but a
double shell model had to be employed to accurately account for
the scattering data with toluene solvent systems. This was at-
Fig. 8. a) Front and b) side projections for space filling (calcium ions) and stick
tributed to a partial solvation of the steric stabilising layer by the (all other molecules) representations of overbased phenate detergent nanopar-
toluene. These detailed analyses were broadly consistent with a ticles using repulsive alkyl tails. Reproduced by permission of the Royal Society
core dimension of 1–10 nm and a steric stabilising layer of 1–5 nm. of Chemistry.
 ARTICLE IN PRESS
6 L.K. Hudson et al. / Advances in Colloid and Interface Science xx (2006) xxx–xxx
calcium carbonate in the core and surfactant anions forming an
external stabilising shell [3]. The level of penetration of the core
is greatest for phenate systems and least for sulphonates [23].
Simulations performed by Tobias and Klein [24] modelled
sulphonate stabilised nanodetergents, suggesting that the
structure was roughly spherical. They also hypothesized that
due to large dipole moments, it was conceivable that long-range
electrostatic effects could drive strong attractions between free
polar acid molecules dispersed on the bulk non-polar solvent
and the polar micelle core. This suggests a possible mechanism
for the enhanced stabilisation in the oil medium.
6.3. Acid neutralisation mechanism
The main purpose of nanodetergent oil additives is to neutralise
acids generated by combustion of petrochemical fuels. Various
studies have been made to attempt to elucidate the mechanism of
neutralisation [7,25]. Robinson et al. [26] have studied the reaction
of organic and inorganic acids with overbased detergent additives,
in organic media, using Fourier transform infra-red spectroscopy
(FTIR) and stopped flow UV/Vis spectroscopy; an example of a
typical profile generated by a stopped flow experiment is shown in
Fig. 9. The systems they studied were amorphous calcium car-
bonate and magnesium carbonate cores stabilised alkylbenzene
sulphonate surfactant with TBN of 300.
For hydrochloric acid, it was noted the acid was neutralised on
a timescale of milliseconds to seconds, with the reaction being
both temperature and solvent dependent. Results showed that for a
‘matched set’ of calcium and magnesium overbased sulphonate
detergents magnesium detergents neutralised inorganic acid more
rapidly than their calcium analogues. The molecular weight and
structure of the sulphonate surfactant appeared to have a less
marked influence on neutralisation rate. However, detergents
containing higher levels of surfactant were seen to neutralise acid
Fig. 9. Typical stopped flow trace for the reaction between overbased detergent particles and acid containing water-in-oil microemulsion droplets using methyl range as
the pH indicator. The time (t1/2) taken for the absorbance to decrease by half of the total change (ΔA / 2) is used as a measure of the neutralisation rate. Reproduced by
permission of Elsevier.
more rapidly. The greater neutralising ability of magnesium
detergents was attributed to the fact that neutralisation of inorganic
acid could occur within the aqueous phase, and that magnesium
carbonate had greater aqueous solubility than calcium carbonate.
For organic acids (propanoic, cyclohexanoic, heptanoic, nona-
noic and decanoic acids), it was found that neutralisation occurred
over a longer timescale (up to minutes) than observed for inor-
ganic acid neutralisation, and never appeared to reach 100%
completion. This was explained by the possibility that neutralised
metal carboxylate salt could remain attached to the particle surface
rather than penetrate the inner core. Over time, formation of such a
layer on the periphery of the nanodetergent core would be ex-
pected to hinder any further reaction between the basic core and
acid molecules. The relative rates of neutralisation between mag-
nesium and calcium carbonate nanodetergents were reversed for
organic acids as compared to inorganic acids, and this is thought to
be linked to the relative basicity of the inorganic species, i.e.
CaCO3 > MgCO3 (and Ca(OH)2 > Mg(OH)2). No significant
effects of structure or molecular weight of the sulphonate sur-
factant were reported with regard to rate of acid neutralisation:
again, higher surfactant levels gave rise to faster rates of acid
neutralisation. Studies of neutralisation kinetics as a function of
acid molecular weight showed that the rate of neutralisation de-
creased with increased acid molecular weight. This was explained
by the bulkier acids being more effective at screening the ino-
rganic core, by forming a thicker surface layer, and hence hin-
dering neutralisation. In addition, the relative solubilities of the
carboxylic acids in the solvent (heptane) will also affect neutral-
isation rate: those with relatively low solubilities (such as pro-
panoic acid) effectively ‘driving’ the acid towards neutralisation.
Organic acid neutralisation has also been investigated by Papke
[27] using FTIR and overbased calcium sulphonate nanodeter-
gents. In addition, Robinson and co-workers [26] measured –
COOH absorption at 1705 cm− 1 to follow the percentage of acid
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L.K. Hudson et al. / Advances in Colloid and Interface Science xx (2006) xxx–xxx
neutralised as a function of time. Papke used the sulphonate band
at 1065 cm− 1 as a reference, due to the fact that no sulphonate was
lost in the precipitate (carboxylate salt). This enabled a direct
determination of the relative amount of solubilized carbonate
(865 cm− 1) by comparison to the sulphonate level. The measure-
ments were performed with hexanoic acid; a plateau region was
observed initially during neutralisation, where the amount of
carbonate did not change, followed by a linear region corre-
sponding to reaction of carbonate with acid. The author concluded
that a non-carbonate base was selectively neutralised, which is
residual hydroxide in the core of the nanodetergent. Furthermore,
it must also be accessible and, therefore, is probably located near
the surface of the inorganic core, consistent with the simulations of
Heyes and co-workers [2,10] suggesting an outer hydroxide shell.
7. Conclusions and future outlook
Overbased detergents have been an integral element of lu-
bricant additive packages for over 50 years. Indeed detergents are
examples of nanoparticles, which can be reproducibly produced
on an industrial scale. Production of uniform nanoparticles with
tailored properties on a large scale is a focus of current research
interest. The surfactants used to stabilise detergents are generally
aromatic in nature, often based on structures commercially avail-
able in petrochemical plants. The need for optimised nanoparticle
detergents is increasing, driven by:
• Improvements in engine design for better fuel economy and
longer oil drain intervals
• Environmental legislation aimed at providing reduced gaseous
emissions (by imposing chemical limits on the fuel and
lubricant)
• With the use of more refined base oils (which are more aliphatic
in nature), the necessity for development of stable detergents
with optimised performance is increasing.
This has manifested in the development of novel surfactant
structures. However, a significant amount of research is still re-
quired to characterise and optimise these new systems before they
become commercially viable.
In addition, other issues should be addressed with regard to
environmental acceptability, in particular the synthesis routes.
Current synthesis methods rely on using mega-tonne quantities
of solvents (xylene, methanol, etc.), here work could seek to
7
reduce the levels or replace petrochemical solvents with green
alternatives.
Acknowledgments
LH thanks Impact Faraday (EPSRC) and Infineum UK Ltd for
the provision of a Ph.D. Scholarship.
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