Professional Documents
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Microtribology and
Microrheology of
Molecularly Thin
Liquid Films
16.1 Introduction
16.2 Solvation and Structural Forces: Forces Due to
Liquid and Surface Structure
Effects of Surface Structure • Effect of Surface Curvature and
Geometry
16.3 Adhesion and Capillary Forces
Adhesion Mechanics
16.4 Nonequilibrium Interactions: Adhesion Hysteresis
16.5 Rheology of Molecularly Thin Films:
Nanorheology
Different Modes of Friction: Limits of Continuum Models •
Viscous Forces and Friction of Thick Films: Continuum
Regime • Friction of Intermediate Thickness Films
16.6 Interfacial and Boundary Friction: Molecular
Tribology
General Interfacial Friction • Boundary Friction of Surfactant
Monolayer Coated Surfaces • Boundary Lubrication of
Molecularly Thin Liquid Films • Transition from Interfacial
to Normal Friction (with Wear)
16.7 Theories of Interfacial Friction
Theoretical Modeling of Interfacial Friction: Molecular
Tribology • Adhesion Force Contribution to Interfacial
Friction • Relation Between Boundary Friction and Adhesion
Energy Hysteresis • External Load Contribution to Interfacial
Friction • Simple Molecular Model of Energy Dissipation ε
16.8 Friction and Lubrication of Thin Liquid Films
Smooth and Stick-Slip Sliding • Role of Molecular Shape
Alan D. Berman and Liquid Structure
Seagate Removable Storage 16.9 Stick-Slip Friction
Solutions Rough Surfaces Model • Distance-Dependent Model •
Velocity-Dependent Friction Model • Phase Transitions
Jacob N. Israelachvili Model • Critical Velocity for Stick-Slip • Dynamic Phase
University of California Diagram Representation of Tribological Parameters
In a first approximation, the oscillatory force laws may be described by an exponentially decaying
cosine function of the form
( )
E ≈ Eo cos 2πD σ e − D σ (16.1)
where both theory and experiments show that the oscillatory period and the characteristic decay length
of the envelope are close to σ (Tarazona and Vicente, 1985).
It is important to note that once the solvation zones of two surfaces overlap, the mean liquid density
in the gap is no longer the same as that of the bulk liquid. And since the van der Waals interaction
depends on the optical properties of the liquid, which in turn depend on the density, one can see why
the van der Waals and oscillatory solvation forces are not strictly additive. Indeed, it is more correct to
think of the solvation force as the van der Waals force at small separations, with the molecular properties
and density variations of the medium taken into account.
It is also important to appreciate that solvation forces do not arise simply because liquid molecules
tend to structure into semi-ordered layers at surfaces. They arise because of the disruption or change of
this ordering during the approach of a second surface. If there were no change, there would be no solvation
force. The two effects are of course related: the greater the tendency toward structuring at an isolated
surface, the greater the solvation force between two such surfaces, but there is a real distinction between
the two phenomena that should always be borne in mind.
or maxima, may also depend on orientation. This could be even more important than the effects on the
minima. A high barrier could prevent two surfaces from coming closer together into a much deeper
adhesive well. Thus, the maxima can effectively contribute to determining not only the final separation
of two surfaces, but also their final adhesion. Such considerations should be particularly important for
determining the thickness and strength of intergranular spaces in ceramics, the adhesion forces between
colloidal particles in concentrated electrolyte solutions, and the forces between two surfaces in a crack
containing capillary condensed water.
The intervening medium profoundly influences how one surface interacts with the other. As experi-
mental results show (McGuiggan and Israelachvili, 1990), when two surfaces are separated by as little as
0.4 nm of an amorphous material, such as adsorbed organics from air, then the surface granularity can
be completely masked and there is no mismatch effect on the adhesion. However, with another medium,
such as pure water which is presumably well ordered when confined between two mica lattices, the atomic
granularity is apparent and alters the adhesion forces and whole interaction potential out to D > 1 nm.
Thus, it is not only the surface structure but also the liquid structure, or that of the intervening film
material, that together determine the short-range interaction and adhesion.
On the other hand, for surfaces that are randomly rough, the oscillatory force becomes smoothed out
and disappears altogether, to be replaced by a purely monotonic solvation force. This occurs even if the
liquid molecules themselves are perfectly capable of ordering into layers. The situation of symmetric
liquid molecules confined between rough surfaces is therefore not unlike that of asymmetric molecules
between smooth surfaces (see Figure 16.1).
To summarize some of the above points, for there to be an oscillatory solvation force, the liquid
molecules must be able to be correlated over a reasonably long range. This requires that both the liquid
molecules and the surfaces have a high degree of order or symmetry. If either is missing, so will be the
oscillations. A roughness of only a few Ångstroms is often sufficient to eliminate any oscillatory compo-
nent of a force law.
FS = 4 πRγ SV (16.2)
(
FS = 4 πR γ LV cos θ + γ SL ) (16.3)
where the first term is due to the Laplace pressure of the meniscus and the second is due to the direct
adhesion of the two contacting solids within the liquid. Note that the above equation does not contain
the radius of curvature, r, of the liquid meniscus (Figure 16.3). This is because for smaller r the Laplace
pressure γ LV/r increases, but the area over which it acts decreases by the same amount, so the two effects
cancel out. A natural question arises as to the smallest value of r for which Equation 16.3 will apply.
Experiments with inert liquids, such as hydrocarbons, condensing between two mica surfaces indicate
that Equation 16.3 is valid for values of r as small as 1 to 2 nm, corresponding to vapor pressures as low
as 40% of saturation (Fisher and Israelachvili, 1981; Christenson, 1988b). With water condensing from
vapor or from oil it appears that the bulk value of γ LV is also applicable for meniscus radii as small as 2 nm.
The capillary condensation of liquids, especially water, from vapor can have additional effects on the
whole physical state of the contact zone. For example, if the surfaces contain ions, these will diffuse and
build up within the liquid bridge, thereby changing the chemical composition of the contact zone as well
as influencing the adhesion. More dramatic effects can occur with amphiphilic surfaces, i.e., those
containing surfactant or polymer molecules. In dry air, such surfaces are usually nonpolar — exposing
hydrophobic groups such as hydrocarbon chains. On exposure to humid air, the molecules can overturn
so that the surface nonpolar groups become replaced by polar groups, which renders the surfaces
hydrophilic. When two such surfaces come into contact, water will condense around the contact zone
and the adhesion force will also be affected — generally increasing well above the value expected for
inert hydrophobic surfaces.
It is clear that the adhesion of two surfaces in vapor or a solvent can often be largely determined by
capillary forces arising from the condensation of liquid that may be present only in very small quantities,
e.g., 10 to 20% of saturation in the vapor, or 20 ppm in the solvent.
R
( )
2
r3 = F + 6 πRγ + 12πRγF + 6 πRγ (16.4)
K
FS = −3πRγ S (16.5)
where, by definition, the surface energy γS, is related to the reversible work of adhesion W, by W = 2γS.
Note that according to the JKR theory a finite elastic modulus, K, while having an effect on the load-
area curve, has no effect on the adhesion force — an interesting and unexpected result that has never-
theless been verified experimentally (Johnson et al., 1971; Israelachvili, 1991).
Equations 16.4 and 16.5 are the basic equations of the JKR theory and provide the framework for
analyzing the results of adhesion measurements of contacting solids, known as “contact mechanics”
(Pollock et al., 1978; Barquins and Maugis, 1982), and for studying the effects of surface conditions and
time on adhesion energy hysteresis (see next section).
W R > WA
Receding Advancing
or
(
∆W = WR − WA > 0 ) (16.6)
where WR and WA are the adhesion or surface energies for receding (separating) and advancing (approach-
ing) two solid surfaces, respectively. Figure 16.5 shows the results of a typical experiment that measures
the adhesion hysteresis between two surfaces (Chaudhury and Whitesides, 1991; Chen et al., 1991). In
this case, two identical surfactant-coated mica surfaces were used in a Surface Forces Apparatus. By
measuring the contact radius as a function of applied load both for increasing and decreasing loads, two
different curves are obtained. These can be fitted to the JKR equation, Equation 16.4, to obtain the
advancing (loading) and receding (unloading) surface energies.
Hysteresis effects are also commonly observed in wetting/dewetting phenomena (Miller and Neogi,
1985). For example, when a liquid spreads and then retracts from a surface, the advancing contact angle
θA is generally larger than the receding angle θR. Since the contact angle, θ, is related to the liquid–vapor
surface tension, γ, and the solid–liquid adhesion energy, W, by the Dupré equation:
we see that wetting hysteresis or contact angle hysteresis (θA > θR) actually implies adhesion hysteresis,
WR > WA , as given by Equation 16.6.
Energy dissipating processes such as adhesion and contact angle hysteresis arise because of practical
constraints of the finite time of measurements and the finite elasticity of materials which prevent many
loading–unloading or approach–separation cycles from being thermodynamically reversible, even though
if these were carried out infinitely slowly they would be reversible. By thermodynamic irreversibility one
simply means that one cannot go through the approach–separation cycle via a continuous series of
equilibrium states because some of these are connected via spontaneous — and therefore thermodynam-
ically irreversible — instabilities or transitions (Figure 16.4C) where energy is liberated and therefore
“lost” via heat or phonon release (Israelachvili and Berman, 1995). This is an area of much current
interest and activity, especially regarding the fundamental molecular origins of adhesion and friction,
and the relationships between them.
Bulk • Thick films (>10σ, Rg), Bulk, continuum properties: Bulk, continuum properties:
• Low or zero loads • Bulk liquid density • Newtonian viscosity
• High shear rates • No long-range order • Fast relaxation times
• No glass temperature
• No yield point
• EHD lubrication
Mixed or • Intermediately thick films Modified fluid properties include: Modified rheological properties
Intermediate (4–10 molecular • Modified positional and include:
diameters, ~Rg for orientational orderb • Non-Newtonian flow
polymers) • Medium to long-range molecular • Glassy states
• Low loads correlations • Long relaxation times
• Highly entangled states • Mixed lubrication
Boundary • Molecularly thin films Onset of non-fluidlike properties: Onset of tribological properties:
(<4 molecular • Liquid-like to solid-like phase • No flow until yield point or
diameters), transitions critical shear stress reached
• High loads • Appearance of new liquid- • Solid-like film behavior
• Low shear rates crystalline states characterized by defect
• Smooth surfaces or • Epitaxially induced long-range diffusion, dislocation motion,
asperities ordering shear melting
• Boundary lubrication
a Based on work by Granick (1991), Hu and Granick (1992), and others (Gee et al., 1990; Hirz et al., 1992; Yoshizawa et al.,
1993) on the dynamic properties of short-chain molecules such as alkanes and polymer melts confined between surfaces.
b Confinement can lead to an increased or decreased order in a film, depending both on the surface lattice structure and
distribution function, the potential of mean force, and various positional and orientational order parameters.
d By dynamic properties are included viscosity, viscoelastic constants, and tribological yield points such as the friction
Experiments have shown that as a liquid film becomes progressively thinner, its physical properties
change, at first quantitatively then qualitatively (Van Alsten and Granick, 1990a,b; Peachey et al., 1991;
Granick, 1991; Hu et al., 1991; Hu and Granick, 1992; Luengo et al., 1997a). The quantitative changes are
manifested by an increased viscosity, non-Newtonian flow behavior, and the replacement of normal melting
by a glass transition, but the film remains recognizable as a liquid. In tribology, this regime is commonly
known as the “mixed lubrication” regime, where the rheological properties of a film are intermediate between
the bulk and boundary properties. One may also refer to it as the “intermediate” regime (Table 16.1).
For even thinner films, the changes in behavior are more dramatic, resulting in a qualitative change
in properties. Thus, first-order phase transitions can now occur to solid or liquid-crystalline phases (Gee
et al., 1990; Israelachvili et al., 1990a,b; Thompson and Robbins, 1990; Yoshizawa et al., 1993; Klein and
Kumacheva, 1995), whose properties can no longer be characterized — even qualitatively — in terms of
bulk or continuum liquid properties such as viscosity. These films now exhibit yield points (characteristic
of fracture in solids) and their molecular diffusion and relaxation times can be 10 orders of magnitude
longer than in the bulk liquid or even in films that are just slightly thicker. The three friction regimes
are summarized in Table 16.1.
can be described by bulk, continuum properties, the friction forces are essentially the hydrodynamic or
viscous drag forces. For example, for two plane parallel surfaces of area A separated by a distance D and
moving laterally relative to each other with velocity v, if the intervening liquid is Newtonian, i.e., if its
viscosity η is independent of the shear rate, the frictional force experienced by the surfaces is given by
ηAv
F= (16.8)
D
v
γ̇ = (16.9)
D
ηeff ∝ γ˙ n (16.10)
where n = 0 (i.e., ηeff = constant) for Newtonian fluids, n > 0 for shear thickening (dilatent) fluids, and
n < 0 for shear thinning (pseudoplastic) fluids (the latter become less viscous, i.e., flow more easily, with
increasing shear rate, e.g., Figure 16.7B). An additional effect on η can arise from the higher local stresses
FIGURE 16.7 Typical rheological behavior of liquid film in the mixed lubrication regime. (A) Increase in effective
viscosity of dodecane film between two mica surfaces with decreasing film thickness (Granick, 1991). Beyond 40 to
50 Å, the effective viscosity ηeff approaches the bulk value ηbulk. (B) Non-Newtonian variation of ηeff with shear rate
of a 27 Å thick dodecane film (data from Luengo et al., 1996). The effective viscosity decays as a power law, as in
Equation 16.10. In this example, n = 0 at the lowest γ,· then transitions to n = –1 at higher γ.· For bulk thick films,
dodecane is a low-viscosity Newtonian fluid (n = 0). (From Berman, A. and Israelachvili, J.N. (1999), Surface forces
and microrheology of molecularly thin liquid films, in Handbook of Micro/Nanotribology, 2nd ed., Bhushan, B. (Ed.),
CRC Press, Boca Raton, FL. With permission.)
FIGURE 16.8 Proposed generalized friction map of effective viscosity plotted against effective shear rate on a log-
log scale (data from Luengo et al., 1996). Three main classes of behavior emerge: (1) Thick films; elastohydrodynamic
sliding. At zero load (L = 0), approximating bulk conditions, ηeff is independent of shear rate except when shear-
thinning may occur at sufficiently large γ.· (2) Boundary layer films, intermediate regime. A Newtonian regime is
again observed (ηeff = constant, n = 0 in Equation 16.10) at low loads and low shear rates, but ηeff is much higher
than the bulk value. As the shear rate γ· increases beyond γ·min, the effective viscosity starts to drop with a power-law
dependence on the shear rate (see Figure 16.7B), with n in the range of –1/2 to –1 most commonly observed. As the
shear rate γ· increases still more, beyond γ·max, a second Newtonian plateau is again encountered. (3) Boundary layer
films, high load. The ηeff continues to grow with load and to be Newtonian provided that the shear rate is sufficiently
low. Transition to sliding at high velocity is discontinuous (n < –1) and usually of the stick-slip variety. (From
Berman, A. and Israelachvili, J.N. (1999), Surface forces and microrheology of molecularly thin liquid films, in
Handbook of Micro/Nanotribology, 2nd ed., Bhushan, B. (Ed.), CRC Press, Boca Raton, FL. With permission.)
of results from experimental, theoretical, and computer simulation work have shown values of n from
–1/2 to –1 for this transition regime for a variety of systems and assumptions (Hu and Granick, 1991;
Granick, 1991; Thompson et al., 1992; Thompson et al., 1995; Urbakh et al., 1995; Rabin and Hersht,
1993).
The intermediate regime appears to extend over a narrow range of film thickness, from about 4 to 10
molecular diameters or polymer radii of gyration. Thinner films begin to adopt “boundary” or “inter-
facial” friction properties (described below; see also Table 16.1). Note that the intermediate regime is
actually a very narrow one when defined in terms of film thickness, for example, varying from about
D = 20 to 40 Å for hexadecane films (Granick, 1991).
A fluid’s effective viscosity ηeff in the intermediate regime is usually higher than in the bulk, but ηeff
usually decreases with increasing sliding velocity, v (known as shear thinning). When two surfaces slide
in the intermediate regime, the motion tends to thicken the film (dilatency). This sends the system into
the bulk EHL regime where, as indicated by Equation 16.8, the friction force now increases with velocity.
This initial decrease, followed by an increase, in the frictional forces of many lubricant systems is the
basis for the empirical Stribeck Curve of Figure 16.6A. In the transition from bulk to boundary behavior
there is first a quantitative change in the material properties (viscosity and elasticity) which can be
continuous, then discontinuous qualitative changes which result in yield stresses and non-liquid-like
behavior.
The rest of this chapter is devoted to friction in the interfacial and boundary regimes. The former
(interfacial friction) may be thought of as applying to the sliding of two dry, unlubricated surfaces in
true molecular contact. The latter (boundary friction) may be thought of as applying to the case where
a lubricant film is present, but where this film is of molecular dimensions — a few molecular layers or less.
F = Fk = Sc A + µL (16.11)
where Sc is the “critical shear stress” (assumed to be constant), A = πr2 is the contact area of radius r
given by Equation 16.4, and µ is the coefficient of friction. For low loads we have:
2 3
R 2
2
K
( )
F = Sc A = Sc πr = Sc π L + 6 πRγ + 12πRγL + 6 πRγ
(16.12)
F = µL (16.13)
Depending on whether the friction force, F, in Equation 16.11 is dominated by the first or second
terms, one may refer to the friction as “adhesion-controlled” or “load-controlled,” respectively.
Figure 16.10 shows a plot of contact area, A, and friction force, F, both plotted against the applied
load, L, in an experiment where two molecularly smooth surfaces of mica in adhesive contact were slid
past each other in an atmosphere of dry nitrogen gas. This is an example of the low load, adhesion-
controlled limit, which is excellently described by Equation 16.12. In a number of different experiments,
Sc was measured to be 2.5 × 107 N/m2, and to be independent of the sliding velocity. Note that there is a
friction force even at negative loads, where the surfaces are still sliding in adhesive contact.
FIGURE 16.11 Sliding of mica surfaces each coated with a 25 Å thick monolayer of calcium stearate surfactant in
the absence of damage (obeying JKR type boundary friction) and in the presence of damage (obeying Amontons’
type “normal” friction) (data from Homola et al., 1989, 1990). At much higher applied loads the undamaged surfaces
also follow Amontons’ type sliding, but for different reasons. Lower line: interfacial sliding with a monolayer of water
between the mica surfaces, shown for comparison. Note that in both cases, after damage occurs, the friction force
obeys Amontons’ law with the same coefficient of friction of µ ≈ 0.3. (From Berman, A. and Israelachvili, J.N. (1999),
Surface forces and microrheology of molecularly thin liquid films, in Handbook of Micro/Nanotribology, 2nd ed.,
Bhushan, B. (Ed.), CRC Press, Boca Raton, FL. With permission.)
therefore be due to some effect other than a low adhesion, for example, the softness of PTFE which allows
material to flow at the interface, behaving like a fluid lubricant. On a related issue, Luengo et al. (1997b)
found that C60 surfaces also exhibited low adhesion but high friction. In both cases the high friction
appears to arise from the bulky surface groups — fluorocarbon compared to hydrocarbon groups in the
former, large fullerene spheres in the latter. Apparently, the fact that C60 molecules rotate in their lattice
does not make them a good lubricant: the molecules of the opposing surface must still climb over them
in order to move, and this requires energy which is independent of whether the surface molecules are
fixed or freely rotating. Larger particles, such as ~25 nm sized nanoparticles (also known as “inorganic
fullerenes”) do appear to produce low friction by behaving like molecular ball bearings, but the potential
of this promising new class of solid lubricant has still to be explored (Rapoport et al., 1997).
16.13, and sliding now proceeds smoothly with the surfaces separated by a 100 to 1000 Å forest of wear
debris (mica or alumina flakes in this case). The wear particles keep the surfaces apart over an area that
is much greater than their size, so that even one submicroscopic particle or asperity can cause a significant
reduction in the area of contact and therefore in the friction (Homola et al., 1990). For this type of
frictional sliding, one can no longer talk of the molecular contact area of the two surfaces, although the
macroscopic or “apparent” area is still a useful parameter. A further discussion on the impact of normal
load and contact area is found in Section 16.7.4.
One remarkable feature of the transition from interfacial to normal friction of brittle surfaces is that
while the strength of interfacial friction, as reflected in the values of Sc, is very dependent on the type of
surface and on the liquid film between the surfaces, this is not the case once the transition to normal
friction has occurred. At the onset of damage, it is the material properties of the underlying substrates
that control the friction. In Figures 16.10 to 16.12 the friction for the damaged surfaces is that of any
damaged mica–mica system, while in Figure 16.13 the damaged surfaces friction is that of general
alumina–alumina sliding (with a friction coefficient that agrees with literature values for the bulk mate-
rials), independent of the initial surface coatings or liquid films between the surfaces.
In order to practically modify the frictional behavior of such brittle materials, it is important to use
coatings that will both alter the interfacial tribological character and remain intact and protect the surfaces
from damage during sliding (Berman et al., 1998b). An example of the friction behavior of a strongly
bound octadecyl phosphonic acid monolayer on alumina surfaces is shown in Figure 16.13. In this case,
the friction is higher than untreated, undamaged α-alumina surfaces, but the bare surfaces easily damage
upon sliding, resulting in an ultimately higher friction system with greater wear rates than the more
robust monolayer-coated surfaces.
This energy may be equated with the change in interfacial or surface energy associated with separating
the surfaces by ∆D, i.e., from the equilibrium separation D = D0 to D = (D0 + ∆D). Since γ ∝ D–2, the
surface energy cost may be approximated by
where γ is the surface energy, A the contact area, and where D0 is the surface separation at equilibrium.
During steady-state sliding (kinetic friction), not all of this energy will be “lost” or absorbed by the lattice
every time the surface molecules move by one lattice spacing: some fraction will be reflected during each
impact of the “cart wheel” molecules (McClelland, 1989). Assuming that a fraction ε of the above surface
energy is lost every time the surfaces move across the characteristic length ∆d (Figure 16.14), we obtain,
after equating the above two equations,
F 4 γε ⋅ ∆D
Sc = = (16.16)
A D0 ⋅ ∆d
For a typical hydrocarbon or a van der Waals surface, γ ≈ 25 × 10–3 J/m2. Other typical values would be:
∆D ≈ 0.5 Å, D0 ≈ 2 Å, ∆d ≈ 1 Å, and ε ≈ 0.1 to 0.5. Using the above parameters, Equation 16.16 predicts
( )
Sc ≈ 2.5 − 12.5 × 107 N m2 for van der Waals surfaces
This range of values compares very well with typical experimental values of 2 × 107 N/m2 for hydrocarbon
or mica surfaces sliding in air or separated by one molecular layer of cyclohexane (Homola et al., 1989).
The above model suggests that all interfaces, whether dry or lubricated, dilate just before they shear
or slip. This is a small but important effect: the dilation provides the crucial extra space needed for the
molecules to slide across each other or flow. This dilation has been measured by Granick et al. (1999)
and computed by Robbins and Thompson (1991).
This model may be extended, at least semiquantitatively, to lubricated sliding, where a thin liquid film
is present between the surfaces. With an increase in the number of liquid layers between the surfaces, D0
FIGURE 16.15 Top: Friction traces (data from Chen et al., 1991) for two fluid-like monolayer-coated surfaces at
25°C showing that the friction force is much higher between dry monolayers (A) than between monolayers whose
fluidity has been enhanced by hydrocarbon penetration from vapor (B). Bottom: Contact radius vs. load (r 3 – L)
curves measured for the same two surfaces as above and fitted to the JKR Equation 16.4 — shown by the solid lines.
For dry monolayers (C) the adhesion energy on unloading (γR = 40 mJ/m2) is greater than that on loading (γA =
28 mJ/m2), indicative of an adhesion energy hysteresis of ∆γ = γR – γA = 12 mJ/m2. For monolayers exposed to saturated
decane vapor (D) their adhesion hysteresis is zero (γA = γR), and both the loading and unloading curves are well-
fitted by the thermodynamic value of the surface energy of fluid hydrocarbon chains, γ ≈ 24 mJ/m2. (From Berman,
A. and Israelachvili, J.N. (1999), Surface forces and microrheology of molecularly thin liquid films, in Handbook of
Micro/Nanotribology, 2nd ed., Bhushan, B. (Ed.), CRC Press, Boca Raton, FL. With permission.)
A ∆γ πr 2
Friction force: F =
σ
=
σ R
(
γ −γA ) (16.17)
or
which is the desired expression and which has been found to give order of magnitude agreement between
measured friction forces and adhesion energy hysteresis (Chen et al., 1989). If we equate Equation 16.18
with Equation 16.16, since 4∆D/D0∆d ≈ σ, we obtain the intuitive relation
∆γ
ε≈ (16.19)
γ
Figure 16.15 illustrates the relationship between adhesion hysteresis and friction for surfactant-coated
surfaces under different conditions. This effect, however, is much more general, and has been shown to
hold for other surfaces as well (Vigil et al., 1994; Israelachvili et al., 1994, 1995). Direct comparisons
between absolute adhesion energies and friction forces show little correlation. In some cases higher
adhesion energies for the same system under different conditions correspond with lower friction forces.
For example, for hydrophilic silica surfaces it was found that with increasing relative humidity the
adhesion energy increases, but the adhesion energy hysteresis measured in a loading–unloading cycle
decreases, as does the friction force (Vigil et al., 1994). For hydrophobic silica surfaces under dry condi-
tions, the friction at load L = 5.5 mN was F = 75 mN. For the same sample, the adhesion energy hysteresis
was ∆γ = 10 mJ/m2, with a contact area of A ≈ 10–8 m2 at the same load. Assuming a value for the
characteristic distance σ on the order of one lattice spacing, σ ≈ 1 nm. Inserting these values into
Equation 16.17, the friction force is predicted to be F ≈ 100 mN for the kinetic friction force, which is
close to the measured value of 75 mN. Alternatively, we may conclude that the dissipation factor is ε =
0.75, i.e., that almost all the energy is dissipated as heat at each molecular collision.
F 4 γε ⋅ ∆D Pext ε ⋅ ∆D
Sc = = + (16.20)
A D0 ⋅ ∆d ∆d
Sc = F A = C1 + C 2Pext (16.21)
where Pext = L/A, and where C1 and C2 are constants characteristic of the surfaces and sliding conditions.
The constant C1 = (4γε·∆D/D0 ·∆d) depends on the mutual adhesion of the two surfaces, while both C1
and C2 = ε·∆D/∆d depend on the topography or atomic bumpiness of the surface groups (Figure 16.14) —
the smoother the surface groups, the smaller the ratio ∆D/∆d and hence the lower the value of C2. In
addition, both C1 and C2 depend on ε — the fraction of energy dissipated per collision which depends
on the relative masses of the shearing molecules, the sliding velocity, the temperature, and the charac-
teristic molecular relaxation processes of the surfaces. This is by far the most difficult parameter to
compute, and yet it is the most important since it represents the energy transfer mechanism in any
friction process, and since ε can vary between 0 and 1, it determines whether a particular friction force
will be large or close to zero. Molecular simulations offer the best way to understand and predict the
magnitude of ε, but the complex multibody nature of the problem makes simple conclusions difficult to
draw. Some of the basic physics of the energy transfer and dissipation of the molecular collisions can be
drawn from simplified models (Urbakh et al., 1995; Rozman et al., 1996, 1997) such as a one-dimensional
three-body system (Israelachvili and Berman, 1995). This system, described in more detail in
Section 16.7.5, offers insight into the mechanisms of energy transfer and relates them back to the familiar
parameter De, the Deborah number.
Finally, the above equation may also be expressed in terms of the friction force F:
F = Sc A = C1A + C 2L (16.22)
Equations similar to Equations 16.21 and 16.22 were previously derived by Derjaguin (1988, 1934)
and by Briscoe and Evans (1982), where the constants C1 and C2 were interpreted somewhat differently
than in this model.
In the absence of any attractive interfacial force, we have C1 ≈ 0, and the second term in Equations 16.21
and 16.22 should dominate. Such situations typically arise when surfaces repel each other across the
lubricating liquid film, for example, when two mica surfaces slide across a thin film of water
(Figure 16.11). In such cases the total frictional force should be low, and it should increase linearly with
the external load according to
F = C 2L (16.23)
An example of such lubricated sliding occurs when two mica surfaces slide in water or in salt solution,
where the short-range “hydration” forces between the surfaces are repulsive. Thus, for sliding in 0.5 M
KCl it was found that C2 = 0.015 (Berman et al., 1998a). Another case where repulsive surfaces eliminate
the adhesive contribution to friction is for tethered polymer chains attached to surfaces at one end and
swollen by a good solvent (Klein et al., 1994). For this class of systems C2 < 0.001 for a finite range of
polymer layer compressions (normal loads, L). The low friction between the surfaces in this regime is
attributed to the entropic repulsion between the opposing brush layers with a minimum of entanglement
between the two layers. However, with higher normal loads, the brush layers become compressed and
begin to entangle, resulting in higher friction.
F = µL (16.24)
where µ is the coefficient of friction. When damage occurs, there is a rapid transition to “normal” sliding
in the presence of wear debris. As previously described, the mechanisms of interfacial friction and normal
friction are vastly different on the submicroscopic and molecular levels. However, under certain circum-
stances both may appear to follow a similar equation (see Equations 16.23 and 16.24) even though the
friction coefficients C2 and µ are determined by quite different material properties in each case.
At the molecular level, a thermodynamic analog of the Coulomb or cobblestone models (see
Section 16.7.1) based on the contact value theorem (Berman et al., 1998a; Berman and Israelachvili, 1997;
Israelachvili, 1991) can explain why F ∝ L also holds at the microscopic or molecular level. In this analysis
we consider the surface molecular groups as being momentarily compressed and decompressed as the
surfaces move along. Under irreversible conditions, which always occur when a cycle is completed in a
finite amount of time, the energy lost in the compression/decompression cycle is dissipated as heat. For
two nonadhering surfaces, the stabilizing pressure Pi acting locally between any two elemental contact
points i of the surfaces may be expressed by the contact value theorem (Israelachvili, 1991):
Pi = ρi k B T = k B T Vi (16.25)
where ρi = 1/Vi is the local number density (per unit volume) or activity of the interacting entities, be
they molecules, atoms, ions, or the electron clouds of atoms. This equation is essentially the osmotic or
entropic pressure of a gas of confined molecules. As one surface moves across the other, as local regions
become compressed and decompressed by a volume ∆Vi, the work done per cycle can be written as ε Pi
∆Vi where ε (ε ≤ 1) is the fraction of energy per cycle lost as heat, as defined earlier. The energy balance
shows that for each compression/decompression cycle, the dissipated energy is related to the friction
force by
Fi x i = ε Pi ∆Vi (16.26)
where xi is the lateral distance moved per cycle, which can be the distance between asperities or the
distance between surface lattice sites. The pressure at each contact junction can be expressed in terms of
the local normal load Li and local area of contact Ai as Pi = Li /Ai . The volume change over a cycle can
thus be expressed as ∆Vi = Aizi, where zi is the vertical distance of confinement. Plugging these back into
Equation 16.26, we get
(
Fi = ε Li z i x i ) (16.27)
which is independent of the local contact area Ai . The total friction force is thus
( ) ( )
F = Σ Fi = Σ ε Li z i x i = ε z i x i Σ Li = µ L (16.28)
where it is assumed that on average, the local values of Li and Pi are independent of the local “slope”
zi /xi . Therefore, the friction coefficient µ is a function only of the average surface topography and the
sliding velocity, but is independent of the local (real) or macroscopic (apparent) contact areas.
While this analysis explains nonadhering surfaces, there is still an additional explicit contact area
contribution for the case of adhering surfaces, as in Equation 16.22. The distinction between the two
cases arises because the initial assumption of the contact value theorem, Equation 16.25, is incomplete
for adhering systems. A more appropriate starting equation would reflect the full intermolecular inter-
action potential, including the attractive interactions in addition to the purely repulsive contributions of
Equation 16.25, much as the van der Waals equation of state modifies the ideal gas law.
Thus, it is found that m1 loses most of its energy to the m2–m3 couple when the collision time is close
to the characteristic vibration time of the m2–m3 harmonic system, which corresponds to De = 1. When
the collision time is much larger or smaller than the system characteristic time, mass m1 is found to
retain most of its original kinetic energy (Figure 16.16c). In this simple example the interaction times
are functions only of the three masses, the intermolecular potential between m1 and m2, and the potential
or spring constant of the m2–m3 couple. In more complex systems with more realistic interaction
potentials (i.e., attractive interactions between m1 and m2), the velocity v0 becomes an important factor
as well, and also affects the Deborah number.
It is important to note that in this simple one-dimensional analysis, additional energy modes and
degrees of freedom of the molecules have not been considered. These modes, when present, will also be
involved in the interaction, affecting the energy transferred from m1 and sharing in the final distribution
of the energy transferred. In addition, different types of energy modes (e.g., rotational modes) will
generally have different relaxation times, so that their energy peaks will occur at different measuring
times. Such real systems may be considered to have more than one Deborah number.
The three-body system sheds some light on the molecular mechanisms of energy dissipation and the
impact of the Deborah number on the dissipation parameter ε, but because of its simplicity, does not
offer predictive capabilities for real systems. More sophisticated models have been presented by Urbakh
et al. (1995) and Rozman et al. (1996, 1997).
FIGURE 16.17 Measured change in friction during interlayer transitions of the silicone liquid octamethylcyclotet-
rasiloxane (OMCTS, an inert liquid whose quasispherical molecules have a diameter of 8 Å) (Gee et al., 1990). In
this system, the shear stress Sc = F/A, was found to be constant so long as the number of layers n remained constant.
Qualitatively similar results have been obtained with other quasispherical molecules such as cyclohexane (Israelachvili
et al., 1988). The shear stresses are only weakly dependent on the sliding velocity v. However, for sliding velocities
above some critical value vc, the stick-slip disappears and sliding proceeds smoothly in the purely kinetic value. (From
Berman, A. and Israelachvili, J.N. (1999), Surface forces and microrheology of molecularly thin liquid films, in
Handbook of Micro/Nanotribology, 2nd ed., Bhushan, B. (Ed.), CRC Press, Boca Raton, FL. With permission.)
schematically in Figure 16.18 for the case of spherical liquid molecules between two solid crystalline
surfaces. The following regimes may be identified:
Surfaces at rest — Figure 16.18a: Even with no externally applied load, solvent–surface epitaxial inter-
actions can induce the liquid molecules in the film to solidify. Thus at rest the surfaces are stuck
to each other through the film.
Sticking regime (frozen, solid-like film) — Figure 16.18b: A progressively increasing lateral shear stress
is applied. The film, being solid, responds elastically with a small lateral displacement and a small
increase or “dilatency” in film thickness (less than a lattice spacing or molecular dimension, σ).
In this regime the film retains its frozen, solid–like state — all the strains are elastic and reversible,
and the surfaces remain effectively stuck to each other. However, slow creep may occur over long
time periods.
Slipping and sliding regimes (molten, liquid-like film) — Figure 16.18c, c′, c″: When the applied shear
stress or force has reached a certain critical value Fs, the static friction force, the film suddenly
melts (known as “shear melting”) or rearranges to allow for wall-slip or film-slip to occur, at which
point the two surfaces begin to slip rapidly past each other. If the applied stress is kept at a high
value, the upper surface will continue to slide indefinitely.
Refreezing regime (resolidification of film) — Figure 16.18d: In many practical cases, the rapid slip of
the upper surface relieves some of the applied force, which eventually falls below another critical
value Fk, the kinetic friction force, at which point the film resolidifies and the whole stick-slip cycle
is repeated. On the other hand, if the slip rate is smaller than the rate at which the external stress
is applied, the surfaces will continue to slide smoothly in the kinetic state and there will be no
more stick-slip. The critical velocity at which stick-slip disappears is discussed in more detail in
Section 16.9.
TABLE 16.2 Effect of Molecular Shape and Short-Range Forces on Tribological Propertiesa
Short-Range Type of Friction Bulk Liquid
Liquid (dry) Force Friction Coefficient Viscosity (cP)
Organic
Cyclohexane Oscillatory Quantized stick-slip 1 0.6
Octane Oscillatory Quantized stick-slip 1.5 0.5
Tetradecane Oscil ↔ smooth Stick-slip ↔ smooth 1.0 2.3
Octadecane (branched) Oscil ↔ smooth Stick-slip ↔ smooth 0.3 5.5
PDMSb (M = 3700, melt) Oscil ↔ smooth Smooth 0.4 50
PBDb (M = 3500, branched) Smooth Smooth 0.03 800
Water
Water (KCl solution) Smooth Smooth 0.01–0.03 1.0
a For molecularly thin liquid films between two shearing mica surfaces at 20°C.
b PDMS: polydimethylsiloxane, PBD: polybutadiene, OMCTS: octamethylcyclotetrasiloxane.
minimum rather than the oscillatory force profile that is characteristic of linear molecules. During sliding,
however, these molecules can be induced to align further, which can result in a transition from smooth
to stick-slip sliding.
Table 16.2 shows the trends observed with some organic and polymeric liquids between smooth mica
surfaces. Also listed are the bulk viscosities of the liquids. From the data of Table 16.2 it appears that
there is a direct correlation between the shapes of molecules and their coefficient of friction or effective-
ness as lubricants (at least at low shear rates). Small spherical or chain molecules have high friction with
stick-slip because they can pack into ordered solid–like layers. In contrast, longer chained and irregularly
shaped molecules remain in an entangled, disordered, fluid-like state even in very thin films, and these
give low friction and smoother sliding. It is probably for this reason that irregularly shaped branched
chain molecules are usually better lubricants. It is interesting to note that the friction coefficient generally
decreases as the bulk viscosity of the liquids increases. This unexpected trend occurs because the factors
that are conducive to low friction are generally conducive to high viscosity. Thus, molecules with side
groups such as branched alkanes and polymer melts usually have higher bulk viscosities than their linear
homologues for obvious reasons. However, in thin films the linear molecules have higher shear stresses
because of their ability to become ordered. The only exception to the above correlations is water, which
has been found to exhibit both low viscosity and low friction (see Figure 16.12). In addition, the presence
of water can drastically lower the friction and eliminate the stick-slip of hydrocarbon liquids when the
sliding surfaces are hydrophilic.
If an “effective” viscosity ηeff were to be calculated for the liquids in Table 16.2, the values would be
many orders of magnitude higher than those of the bulk liquids. This can be demonstrated by the
following simple calculation based on the usual equation for Couette flow (see Equation 16.8):
ηeff = Fk D Av (16.30)
where Fk is the kinetic friction force, D is the film thickness, A the contact area, and v the sliding velocity.
Using typical values for experiments with hexadecane (Yoshizawa and Israelachvili, 1993): Fk = 5 mN,
D = 1 nm, A = 3 × 10–9 m2 and v = 1 µm/sec, yields ηeff ≈ 2000 N m–2 s, or 20,000 Poise, which is ~106
times higher than the bulk viscosity ηbulk of the liquid. It is instructive to consider that this very high
effective viscosity nevertheless still produces a low friction force or friction coefficient µ of about 0.25.
It is interesting to speculate that if a 1 nm film were to exhibit bulk viscous behavior, the friction coefficient
under the same sliding conditions would be as low as 0.000001. While such a low value has never been
reported for any tribological system, one may consider it as a theoretical lower limit that could, conceiv-
ably, be attained under certain experimental conditions.
Various studies (Van Alsten and Granick, 1990a,b, 1991; Granick, 1991; Hu and Granick, 1992) have
shown that confinement and load generally increase the effective viscosity and/or relaxation times of
molecules, suggestive of an increased glassiness or solid-like behavior. This is in marked contrast to
studies of liquids in small confining capillaries, where the opposite effects have been observed (Warnock
et al., 1986; Awschalom and Warnock, 1987). The reason for this is probably that the two modes of
confinement are different. In the former case (confinement of molecules between two structured solid
surfaces), there is generally little opposition to any lateral or vertical displacement of the two surface
lattices relative to each other. This means that the two lattices can shift in the x-y-z space (Figure 16.20A)
to accommodate the trapped molecules in the most crystallographically commensurate or “epitaxial”
way, which would favor an ordered, solid-like state. In contrast, the walls of capillaries are rigid and
cannot easily move or adjust to accommodate the confined molecules (Figure 16.20B), which will there-
fore be forced into a more disordered, liquid-like state (unless the capillary wall geometry and lattice is
exactly commensurate with the liquid molecules, as occurs in certain zeolites).
Experiments have demonstrated the effects of surface lattice mismatch on the friction between surfaces
(Hirano et al., 1991; Berman, 1996). Similar to the effects of lattice mismatch on adhesion (Figure 16.2,
Section 16.2.1), the static friction of a confined liquid film is maximum when the lattices of the confining
surfaces are aligned. For OMCTS confined between mica surfaces (Berman, 1996) the static friction was
found to vary by more than a factor of 4 (Figure 16.21), while for bare mica surfaces the variation was
by a factor of 3.5 (Hirano et al., 1991). In contrast to the sharp variations in adhesion energy over small
twist angles, the variations in friction as a function of twist angle were much more broad — both in
magnitude and angular spread. Similar variations in friction as a function of twist or misfit angles have
also been observed in computer simulations (Gyalog and Thomas, 1997).
Robbins and co-workers (He et al., 1999) computed the friction forces of two clean crystalline surfaces
as a function of the angle between their surface lattices. They found that for all nonzero angles (finite
“twist” angles) the friction forces fell to zero due to incommensurability effects. They further found that
submonolayer amounts of organic or other impurities trapped between two incommensurate surfaces
can generate a finite friction force, and they therefore concluded that any finite friction force measured
between incommensurate surfaces is probably due to such “third-body” effects.
With rough surfaces, i.e., those that have random protrusions rather than being periodically structured,
we expect a smearing out of the correlated intermolecular interactions that are involved in film freezing
and melting (and in phase transitions in general). This should effectively eliminate the highly regular
stick-slip and may also affect the location of the slipping planes. The stick-slip friction of “real” surfaces,
which are generally rough, may therefore be quite different from those of perfectly smooth surfaces
composed of the same material (see next section). We should note, however, that even between rough
surfaces, most of the contacts occur between the tips of microscopic asperities, which may be smooth
over their microscopic contact area.
the mechanical construction of the system, for example, the axle of a car wheel which connects it to the
engine. In Figure 16.22A, this coupling is shown to act via the material supporting the upper surface,
which can be modeled (Figure 16.22B) as an elastic spring of stiffness K and mass M. This is the simplest
type of mechanical coupling and is also the same as in SFA- and AFM-type experiments, illustrated in
Figure 16.23. More complicated real systems can be reduced to a system of springs and dashpots, as
described by Luengo et al. (1997a).
We now consider four different models of stick-slip friction. These are illustrated in Figures 16.24 to
16.27, where the mechanical couplings are assumed to be of the simple elastic spring type as shown in
Figures 16.22 and 16.23. The first two mechanisms (Figures 16.24 and 16.26) may be considered as the
“traditional” or “classical” mechanisms or models (Rabinowicz, 1965); the third (Figure 16.27) is essen-
tially the same as the freezing–melting phase-transition model described in Section 16.8.
FIGURE 16.24 Figures 16.24 through 16.27 show three different models of friction and the stick-slip friction force vs.
time traces they give rise to. Figure 16.24 shows Rabinowicz’ model (Rabinowicz, 1965) for rough surfaces which produces
irregular stick-slip (inset) when the elastic stiffness of the system (reflected by the slopes of the SLIP lines) is not too high.
(From Berman, A. and Israelachvili, J.N. (1999), Surface forces and microrheology of molecularly thin liquid films,
in Handbook of Micro/Nanotribology, 2nd ed., Bhushan, B. (Ed.), CRC Press, Boca Raton, FL. With permission.)
The friction force therefore remains high during the creep stage of the slip, but once the surfaces have
moved the characteristic distance Dc, the friction rapidly drops to the kinetic value. Any system where
the kinetic friction is less than the static force (or one that has a negative slope over some part of its
F0–V0 curve) will exhibit regular stick-slip sliding motion for certain values of K, m, and driving velocity, V.
This type of friction has been observed in a variety of dry (unlubricated) systems such as paper-on-
paper (Baumberger et al., 1994; Heslot et al., 1994) and steel-on-steel (Rabinowicz, 1958; Sampson et al.,
1943; Heymann et al., 1954). This model is also used extensively in geologic systems to analyze rock-on-
rock sliding (Dieterich, 1978, 1979).
While originally described for adhering macroscopic asperity junctions, the distance-dependent model
may also apply to molecularly smooth surfaces. For example, for polymer lubricant films, the characteristic
length Dc would now be the chain–chain entanglement length, which could be much larger in a confined
geometry than in the bulk.
MX 0 0 ( 0 )
˙˙ = F − F = F − X − X K
0 ( ) (16.31)
or
0 0 ( 0)
˙˙ + X − X K − F = 0
MX (16.32)
where F0 = F0(X0, V0, t) is the intrinsic or “real” friction force at the shearing surfaces which is generally
·
a function of X0, V0 = X0 and t, F is the force on the spring (the externally applied or measured force),
and Fs = (F0 – F) is the force on the stage. To fully solve Equation 16.31, one must also know the initial
(starting) conditions at t = 0, and the driving or steady-state conditions at finite t. For example, in the
present experiments, the driving condition is
X =0 for t < 0,
(16.33)
X = Vt for t > 0, where V = constant
Vc ≈
(F − F )
S k
(16.34)
5Kτo
where το is the characteristic nucleation time or freezing time of the film. For example, inserting the
following typically measured values for a ~10 Å thick hexadecane film between mica: (Fs – Fk) ≈ 5 mN,
spring constant K ≈ 500 N/m, and nucleation time (Yoshizawa and Israelachvili, 1993) τo ≈ 5 sec, we
obtain Vc ≈ 0.4 µm/s, which is close to typically measured values (Figure 16.28). The second equation is
based on computer simulations (Robbins and Thompson, 1991):
∆F ⋅ σ
Vc ≈ 0.1 (16.35)
M
where σ is a molecular dimension and M is the mass of the stage. Again, inserting typical experimental
values into this equation, viz., M ≈ 20 gm, σ ≈ 0.5 nm, and (Fs – Fk) ≈ 5 mN as before, we obtain Vc ≈
0.3 µm/s, which is also close to measured values.
Stick-slip also disappears above some critical temperature Tc, which is not the same as the melting
temperature of the bulk fluid. Certain correlations have been found between Vc and Tc , and between
various other tribological parameters, that appear to be consistent with the principle of “time-temper-
ature superposition,” similar to that occurring in viscoelastic polymer fluids (Ferry, 1980). We end by
considering these correlations.
FIGURE 16.31 Different dynamic phase states of boundary monolayers during adhesive contact and/or frictional
sliding. Low adhesion hysteresis and friction is exhibited by solid-like and liquid-like layers (A and C). High adhesion
hysteresis and friction is exhibited by amorphous layers (B). Increasing the temperature generally shifts a system
from the left to the right. Changing the load, sliding velocity, and other experimental conditions can also change the
“dynamic phase state” of surface layers, as shown in Figure 16.30. (From Berman, A. and Israelachvili, J.N. (1999),
Surface forces and microrheology of molecularly thin liquid films, in Handbook of Micro/Nanotribology, 2nd ed.,
Bhushan, B. (Ed.), CRC Press, Boca Raton, FL. With permission.)
boundary layer sliding is illustrated in Figure 16.31, which shows the three main “dynamic” phase states
of boundary monolayers.
In contrast to the characteristic relaxation time associated with fluid lubricants, for unlubricated (dry,
solid, rough) surfaces it has been established that there is a characteristic “memory distance” which must
be exceeded before that system loses all memory of its initial state (original surface topography). The
underlying mechanism for a characteristic distance was first used to successfully explain rock mechanics
and earthquake faults (Ruina, 1983) and, more recently, the tribological behavior of unlubricated surfaces
of ceramics, paper, and elastomeric polymers (Berthoud et al., 1999; Baumberger et al., 1999). Recent
experiments (Israelachvili et al., 1999) suggest that fluid lubricants composed of complex branched-chain
or polymer molecules may also have “characteristic distances” (in addition to characteristic relaxation
times) associated with their tribological behavior — the “characteristic distance” being total sliding
distance that must be exceeded before the system reaches its steady-state tribological conditions.
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