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Boundary lubrication by an adsorption layer

Article  in  Journal of Friction and Wear · February 2010

DOI: 10.3103/S1068366610010046

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ISSN 10683666, Journal of Friction and Wear, 2010, Vol. 31, No. 1, pp. 33–47. © Allerton Press, Inc., 2010.
Original Russian Text © I.A. Buyanovskii, 2010, published in Trenie i Iznos, 2010, Vol. 31, No. 1, pp. 48–67.

Boundary Lubrication by an Adsorption Layer

I. A. Buyanovskii
A. A. Blagonravov Institute of Machine Science, Russian Academy of Sciences,
4 Mal. Khariton’evskii per., Moscow, 101919, Russia
email: buyan37@mail.ru
Received September 22, 2009

Abstract—Some key directions of study of the friction and wear of solids under conditions of boundary lubri
cation by an adsorption layer are analyzed. The ideas and methods of the studies are considered in sequence
starting from works of the founder of the boundary lubrication concept W. Hardy and proceeding to the results
of the outstanding scientists of the following generations—F.P. Bowden, D. Tabor, B.V. Deryagin, A.S. Akh
matov, G.I. Fuks, R.M. Matveevskii, and others—and then to those of contemporary researchers. Tribo
chemical aspects of lubrication by an adsorption layer are discussed. Special attention is paid to attempts to
develop physical and mathematical models of the boundary lubrication process.

Key words: boundary layer, boundary lubrication, oriented layer of adsorbed molecules, critical temperature,
tribochemistry, mathematical model.
DOI: 10.3103/S1068366610010046

INTRODUCTION The lubricating effect of boundary layers is

Almost all heavyloaded friction units of modern
machinery lubricated by oils or greases operate in the
boundary lubrication (BL) mode at some point in
time—during starting/stopping, at dead points of
reciprocal mechanisms, etc.—or permanently—in
joints operating at low movement velocities and ele
vated temperatures and under heavy pressures, or
where the geometry hampers fluid lubrication. In this
mode, the friction surfaces are not totally separated by
a lubricating layer and direct contact of the friction
members is prevented, or at least minimized, by the
formation of boundary layers on the direct contact
sites due to the reactions of the friction surface with
the active components of the lubricant [1, 2]. Direct
contact of the friction surfaces leads to a sharp rise of
energy loss from friction, intensive wear of the rubbing
solids, decrease in the parametric reliability of the
unit, and, finally, irreversible damage to the working
surfaces and the total failure of the unit. Boundary
lubrication is the most severe friction mode; it is
accompanied by wear of the contacting solids and
energy loss which is higher than that under fluid lubri
cation. However, the provision of effective BL remains
an important problem—its implementation reduces
the friction coefficient and wear rate several times and
diminishes the friction transfer of metals by several
orders. It is especially topical at present, given the cur
rent trend towards more severe operating conditions of
lubricated friction units—this is caused, in particular,
by their miniaturization down to the creation of
MEMS and NEMS; to provide fluid lubrication of
such units is a difficult task.
explained by the following causes:
—boundary layers separate the rubbing surfaces by
distances which exceed the radius of action of adhe
sion forces, or, at a minimum, promote significant
weakening of adhesion interaction between the sur
faces;
—boundary layers possess significant anisotropy of
mechanical properties—the thinnest boundary layers
are capable of withstanding heavy normal loads with
out breakage. At the same time, when relatively low
tangential forces are applied, shear over the best slip
planes occurs in them. This leads to low energy loss
and high carrying capacity of the layers;
—the active components of the lubricant react
with the friction surfaces, thus causing their adsorp
tion softening (the Rehbinder effect); this reduces the
shear strength in the tribocontact.
Owing to these phenomena, shear deformations at
BL are localized in the boundary layer or in the thin
nest surface layers of the contacting solids, protecting
the base metal against wear.
The existence of boundary lubricating layers and
the process of friction at BL was found by English sci
entist W. Hardy in 1922; however, engineering meth
ods for computing the parameters of friction units
operating at BL have not yet been developed. This is
explained by the exceptional complexity of the BL
process, for which reason its mechanism has not been
fully revealed. It is obvious, though, that BL is a com
plex process involving a number of subprocesses,
which occur both in the surface layers of the rubbing
bodies and in the lubricant and boundary layers pro

33
34 BUYANOVSKII
duced by reactions of the active components of the
lubricant with the surface layers. The composition and
structure of the boundary layers depend greatly on the
operating regime of the friction unit. The complex
effect of numerous factors and the simultaneous—
either synergetic or antagonistic—occurrence of pro
cesses whose mechanisms are not quite clear make it
difficult to develop an engineering method for com
puting the parameters of friction units which operate
at BL, and complicate the process of selection of lubri
cants for friction units at the stage of their design.
Of course, the discoverer of the BL phenomenon
W. Hardy, who died in 1936, was able only to scratch
the surface of the issue. For example, he knew nothing
of the influence of surfactants on the surface strength
(the Rehbinder effect), of the wedging effect of thin
surface layers (the Deryagin effect), of the phenome
non of selective transfer (the effect of wearless fric
tion), and so on. However, according to E. Ruther
ford, he discovered “a fundamentally new direction of
studies” for the next generation of tribologists. There
fore, it is worthwhile to analyze both the principles of
the theory of Hardy and the evolution and transforma
tion of his ideas by his numerous followers.
The aim of the current work is to consider and ana
lyze the evolution of some promising studies in the
field of BL by an adsorbed layer (more precisely, lubri
cation by media which initially contain no chemically
active agents), including the investigation of tribo
chemical process in media with no specially intro
duced chemically active agents, during the period
from the 1920s to present.
BOUNDARY LUBRICATION ACCORDING
TO HARDY
As mentioned above, the existence of the boundary
mode of lubrication was discovered by Hardy in 1922.
He wrote: “There exists a mode of lubrication, when
the surfaces of two solids are so close to each other that
they affect directly physical properties of the lubri
cant… Then… friction depends not only on the lubri
cant, but also on the chemical nature of the bound
aries of the solids. Boundary lubrication differs from
perfect lubrication so much that this difference forces
one to suppose a gap to exist between the two states”
[3]. He drew this conclusion based on the results of his
experiments, which were carried out to assess the static
friction of a loaded slider—flat or hemispherical—in
contact with a flat plate. The specimens were made of
glass, steel, and bismuth. Pure chemical com
pounds—homologous series of paraffins, as well as
corresponding alcohols and fatty acids—were used for
lubrication. The friction coefficients were almost the
same for all methods of lubricant deposition, since in
case of flood lubrication the excess lubricant was
squeezed out of the friction zone and the surfaces con
tacted through a thin film of lubricant. This thin layer
is not squeezed by heavy pressures (up to 103 MPa) and
JOURNAL OF FRICTION AND WEAR
plays the main role in the separation of the contacting
surfaces as they move relative to each other. Hardy
called it a boundary layer. The specific state of the
lubricant, in which it stays under the effect of the force
field of the solid phase and which, according to Hardy,
“cannot be called either liquid or solid,” was also be
called the boundary state. In his opinion, this state of
the lubricant expands over a distance of hundreds of
nanometers from the solid surface.
As was shown by Hardy, the friction coefficient is a
linear descending function of the molecular weight of
the lubricant for each homologous series, i.e., of the
length of a carbon chain or the number of methylene
groups in each chain. These dependences—up to the
tenth term of the homologous series of fatty acids,
according to Hardy—are retained in the friction of
specimens made of various materials. Subsequently,
this was confirmed by W.G. Beare and F.P. Bowden
(1935) up to the sixth term of this homologous series,
by W.A. Zisman (1957) up to the fourteenth term, and
by G.N. Uchuvatkin (1969) up to the twentieth term,
depending on the experimental methods applied.
Note also that S. Jahanmir showed (1985) that the
friction coefficient diminishes linearly with increasing
length of the hydrocarbon radical in each homologous
series of surfactants, provided that the concentration
of the surfactants in the inactive solvent is kept con
stant. Thus, the dependence of the friction coefficient
on the length of the chain of surfactants found by
Hardy in 1922 was extended to solutions of these sur
factants. G. I. Fuks discovered a similar dependence as
early as 1964 when studying the mechanical properties
of boundary layers by the method of plane–parallel
discs, i.e., without performing tribological experi
ments.
The highest friction coefficients of all the studied
materials were obtained when they were lubricated
with paraffins, while the lowest ones were found under
lubrication with fatty acids, provided that the molecu
lar weight of the paraffns and fatty acids were the same.
The decrease in the friction coefficient with increasing
length of the hydrocarbon chain of the lubricant mol
ecules is explained by the fact that the molecules are
adsorbed on the friction surfaces by their polar groups
forming oriented layers similar to those observed by
I. Langmuir, who studied adsorption on a liquid sur
face. Such molecules in the condensed adsorbed layer
are oriented almost normally to the surface, forming a
“molecular fluff” (Fig. 1).
Thus, with increasing length of the surfactant mol
ecule, the distance which separates the surfaces
increases, and therefore the interaction of the force
fields of the solids becomes weaker, causing, according
to Hardy, resistance to their relative displacement, i.e.,
reduction in the friction coefficient. If the chain
length is sufficiently great, the force field of the solid
surface is shielded. Hardy confirmed this and showed
that, with the use of ricinoleic acid, in liquid phase at
the test temperature, the friction coefficient was so low
Vol. 31 No. 1 2010
 BOUNDARY LUBRICATION BY AN ADSORPTION LAYER
that almost spontaneous sliding, i.e., the “superlubric
ity effect,” occurred. In 1963, A.S. Akhmatov proved
this effect, though in 1951 he had considered Hardy’s
results as “mere fantasy.”
Another proof of high ordering of a boundary layer
is the effect of a latent period of friction in surfactants,
discovered by Hardy. If the friction pair is kept in this
medium, after a span of time—from a few minutes to
a few hours—the friction coefficient decreases from
the initial, quite high value to a much lower value,
which depends little on the exposure time [4]. Hardy
attributed this effect to the kinetics of the adsorption
and orientation of lubricant molecules in the force
field of the solid. For normal hydrocarbons, whose
molecules are symmetrical and hence possess no sur
face activity, the latent period is not observed. On the
contrary, surfactant molecules are immediately
adsorbed either “rightly”—in case of fatty acids, the
carboxyl group is attached to the metal—or
“wrongly,” when the methyl radical is attached to the
metal. Since in the latter case, the positions of
the molecules are unstable, after a span of time, i.e.,
the latent period, they “flip over” and assume stable
positions.
Finally, Hardy studied the influence of the degree
of filling of friction surfaces with active components of
the lubricant on the friction coefficient. He fed air
with different content of ethyl alcohol vapor into a test
chamber and found the friction coefficient to decrease
as the content of the active component in the mixture
increased. Subsequently, Hardy investigated the prop
erties of some twocomponent systems, i.e., solutions
of various hydrocarbons—carboxylic acids, monohy
dric alcohols, solid paraffins, etc.—in nonpolar oil,
and obtained “static friction isotherms” for the binary
mixtures studied. For such systems, as the content of
the active component in the mixture increases, the
friction coefficient decreases down to a value which
remains constant if the content of the component
increases still more [2]. The shape of the isotherms of
the lubricating effect was further elucidated by
N.I. Kolesnikova (1938), B.V. Deryagin, and
M.M. Samygin (1940), and later by other research
ers. At a later time, works on the tribological behav
ior of mixtures of lubricant components occupied a
prominent place in the development of lubricating
compositions.
STRUCTURE OF A BOUNDARY LAYER
Hardy’s discoveries had a profound impact on fur
ther works in the field of BL; studies of many research
ers concerned the refinement and explanation of the
results of Hardy and contributed to the development
of his principles.
Successive researchers gave much attention to the
analysis of Hardy’s assertion that a boundary layer is
an oriented and highly ordered object. To confirm this
assertion, intensive works on the study of the structure
JOURNAL OF FRICTION AND WEAR Vol. 31 No. 1
35
1
3
2
Fig. 1. Model of contact at boundary lubrication according to
Hardy: 1—specimen; 2—adsorbed molecule (䊊—active
group; |—hydrocarbon radical); 3—shear surface.
of boundary layers formed on a solid substrate were
launched in the first half of the 20th century. The
instrumentation available at that time gave no way of
observing this directly in a tribocontact. Because of
this, researchers restricted themselves to the investiga
tion of the composition and structure of boundary lay
ers formed on single plates made of various materials.
During Hardy’s lifetime, in 1925, W. Bragg applied X
ray methods and found that boundary films had a lay
ered structure. These results enabled him to suppose
that the lubricity of various media was due to their
capacity for acquiring a layered structure in the fric
tion contact. The presence of the orientation of mole
cules of surfactant, e.g., fatty acids, alcohols, esters of
fatty acids, normal hydrocarbons of the paraffin series,
and mineral and castor oils, in a boundary layer was
confirmed by electron diffraction with a reflected
beam (R.G. Brummage, 1944; J.W. Menter, 1951) and
with a transmitted beam (F.P. Bowden and D. Tabor,
1964; J.A. Chapman and D. Tabor, 1957) as well as by
the methods of Xray diffraction (A. Bondy, 1951;
J.J. Trillat, 1928) and Xray adsorption spectroscopy
(D.A. Fisher, Z.S. Hu, and S.V. Ysu, 1997). It is signif
icant that no orientation effect was found for fluori
nated silicones having poor lubricity (W. Menter,
1951).
B.V. Deryagin used the socalled blowoff method
to study the structure of a boundary layer [5]. A flow of
air or another gas directed parallel to a solid surface
produces a tangential force. Under the effect of this
force, layerbylayer flow occurs in an oil film depos
ited on the surface. As a result, the film becomes
shaped as a sloped wedge. The analysis of the shape of
the wedge makes it possible to assess the “wall” viscos
ity of the studied fluid as a function of the distance
from the wall. In transition from the bulk of the oil
including surfactants to the boundary layer—at a dis
tance of 0.1–0.2 μm from the solid surface—the vis
cosity changes sharply (in most cases it increases).
Thus, this layer has a wellmarked interface with the
fluid bulk. This allowed B.V. Deryagin to conclude
that “the boundary layer of a fluid is in a specific aggre
2010
36 BUYANOVSKII
f “immobile layers” on the sample surfaces; they were
0.8
I II III IV
0.4
I II III IV
0 C
Fig. 2. Dependence of friction coefficient on concentra
tion of surfactant in inactive oil and probable character of
orientation of polar molecules on friction surfaces at dif
ferent surfactant concentrations [10].
gate state and has the property of a specific phase,
which differs from the bulk phase” and confirm the
layerbylayer arrangement of centers of adsorbate
molecules in the boundary layer [5, 6]. The specific
structure of the boundary layers “makes natural the
similarity of their properties to those of smectic phases
of liquid crystalline solids.” Marked parallelism is
observed between changes in the viscosity of wall
boundary layers due to their specific structure and the
efficiency of the lubricating effect.
It was especially important to confirm the multilay
ered structure of boundary films and the orientation of
the molecules in them directly during friction. The
orientation of the molecules in a boundary layer was
first elucidated by V. Vieweg and J. Kluge (1933), who
found the rectification of the current passed through a
lubricated bearing. The maximal orientation effect
assessed by the strength of the rectified current corre
sponds to the minimal friction coefficient. As the slid
ing velocity increases, the orientation effect becomes
weaker and finally disappears. The effect becomes
more pronounced if the load increases and unsatur
ated compounds are introduced into the oil.
In more recent studies, J. Israelachvili (1982) used
an apparatus for surface force measurement and
showed that in contact between two molecularly
smooth mica surfaces, simple molecular organic fluids
formed structures a few molecular layers thick. Subse
quently, when studying the shear strength of simple
hydrocarbons, he found that, if the gap between the
mica surfaces was less than three molecular layers, the
viscosity of the fluid began to sharply exceed its bulk
viscosity. However, as the shear rate increased, the vis
cosity dropped sharply again. The shear strength
increased abruptly when the layer thickness varied
from three molecular layers to two layers and from two
layers to one layer. At the same time (1993)
J.M. Georges also used a force balance (a surface
force apparatus) but applied it to the sphere–plane
contact. He found that simple hydrocarbons formed
JOURNAL OF FRICTION AND WEAR
on the order of 1 nm thick and possessed anomalous
viscosity. However, Georges failed to discover the lay
ered structure of the films which was observed by
Israelachvili. In sliding, the thickness of the layers
increased little but the friction force decreased consid
erably. This was attributed to the elimination of the
overlapping of the force fields in the static contact and
to the effect of weak interaction of end methyl groups
of stearic acid molecules adsorbed on the friction sur
faces [7–9].
The complexity of the BL process is due primarily
to the fact that the “relationship between the orienta
tion of adsorbed molecules and the friction coefficient
is mutual and the friction process may vary the orien
tation of surfactant molecules” (Deryagin, 1957).
Note also that Deryagin and his students discovered
the nonmonotonous character of variation in the fric
tion coefficient for very clear steel and glass surfaces
lubricated by pure vaseline oil with small additives of
some surfactants (Fig. 2).
This effect is explained by the different degrees of
filling of the friction surfaces with adsorbed surfactant
molecules and by the changes in the character of their
orientation from planar to mixed planar–homeotro
pic and then to homeotropic closepacked. This pro
motes the “smoothing” of the “molecular roughness”
formed in the case of mixed orientation [10].
The evolution of the views of Deryagin’s school has
lead to the development of the Deryagin–Levchenko
model of the formation of a structurally ordered epi
tropic liquidcrystal (ELC) layer [11]. It is based on
the experimentally discovered fact that a solid surface
induces orientation ordering, which is maximal at the
interface and decreases gradually approaching the
middle of the ELC layer. According to this model, the
friction surfaces are separated by a boundary layer,
which is an ELC layer of oil molecules. The ordering
of adsorbed (transition) layers, which lie between the
solid surfaces and ELC layers, differs from that of the
ELC layers remote from the surface. Surface forces
vary the positions of the centers of mass of the mole
cules in the ELC layers of the lubricant, thus giving
them an orientation homeotropic to the interface and
forming a layer with quasismectic ordering, i.e.,
hyperdense packing, and the parameter of orientation
ordering close to unity. Since the ELC layer lies
between two solid substrates with marked homeotro
pic orientation, the direction of the director is the
same over the whole bulk of the layer. The solid sub
strates induce homeotropic orientation into the bulk
of the ELC layer of the lubricant, thus forming the
uniform ordering of the boundary layer. The latter,
owing to its specific structure, possesses shape elastic
ity and the orientation parameter of order; it produces
conditions for the minimal energy dissipation during
the relative sliding of the solids. For example, the
application of transmission electron microscopy
showed the effect of the orientation of molecules of
Vol. 31 No. 1 2010
 BOUNDARY LUBRICATION BY AN ADSORPTION LAYER
(а)
Fig. 3. Electron diffraction pictures for coating of highly ordered monocrystalline carbon (a) and for thin layer of vaseline oil
deposited on this coating (b).
inactive medicinal vaseline oil on a highly ordered
monocrystal carbon orienting coating (Fig. 3). How
ever, no such effect was observed on an amorphous
carbon coating even for the same oil with a surfactant
additive [12].
The works of A.S. Akhmatov and his disciples had
a profound impact in the refinement of Hardy’s
model. According to [13], boundary layers are formed
from coordination dimers. The dimers disintegrate on
the metal surface, since their bonding energy is less
than the adsorption potential. When boundary layers
are formed from the bulk of twodimensional bound
ary crystals, the selection of linear configurations
occurs. These configurations are involved in crystal
formation and, partially, in “untwisting” of rotational
isomers, which “reflects the adaptation of molecules
in their transition from the bulk to adsorption fixa
tion.” Deformations of the carbon chains of molecules
forming boundary layers, e.g., axial compression, ten
sion, bending, etc., may also occur due to the defor
mation of tetrahedral angles of similar structures. At
sites of heavyloaded tribocontacts, the rubbing solids
are separated by monomolecular or bimolecular
adsorbed layers, so that methylene chains of molecules
forming a mono or bimolecular layer experience
mainly axial and uniform compression. As Akhmatov
assumed, it was the elasticity of the methylene struc
ture that explained the capacity of those layers for
“having an enormous resistance to compression and
crushing.” The multimolecular layer is considered as
an ensemble of parallel macromolecules whose meth
ylene chains are linked by multiple, cross, and addi
tively amplified dispersion forces, as well as by quadru
pole interaction. The tangential shear resistance of
such a layer is proportional to the squared number of
interacting groups or radicals and its normal resistance
to compression is proportional to the cubed number of
interacting groups—both end groups and groups
forming methylene chains. This explains why the
compression modulus of the boundary layers exceeds
many times their shear modulus [13]. Akhmatov and
L.V. Koshlakova carried out measurements using
JOURNAL OF FRICTION AND WEAR Vol. 31
37
(b)
additive summation or multiplication of deformations
of a pile of thin, extremely smooth, metallic plates.
Each of them was covered with a boundary layer of a
preset thickness, which was the same for all the plates.
The results of the measurement of total deformations
of this “layer pile” showed that the boundary layers
possessed true shape elasticity and that they obeyed
the Hooke’s law. The Poisson ratio for the boundary
layers was close to 0.5; i.e., they were compressed and
stretched almost without variations in their volume.
The boundary layer can be considered as a quasisolid
body, which possesses shape elasticity and a certain
limiting shear stress depending on the layer thickness
and the applied normal pressure.
The studies of G.I. Fuks [14] have shown that poly
molecular (mutimolecular) layers of surfactants and
their solutions are capable of lubricating smooth solid
surfaces at moderate velocities of relative motion and
under pressures no more than 5–6 MPa. Under these
conditions, they remain 0.3–0.4 μm thick and provide
friction coefficients a little lower than at fluid lubrica
tion, i.e., 0.01–0.10 or less. The formation of “thick”
boundary layers is explained by the adhesion of surfac
tant micelles to the metal surfaces and their possible
untwisting, as well as by the appearance of micelles
directly in the adsorption layer. A similar view of the
boundary layer was also expressed by A.V. Bloom in
1961. Surfactant molecules form spherical micelles
covered with an elastic solvate shell. The micelles sep
arate the friction surfaces and make up something like
a ball bearing, thus facilitating the relative motion of
the contacting solids. According to Bloom, cyclic
hydrocarbons like hexane are optimal substances to
produce such micelles; this explains the good lubricity
of naphthene oils. Paraffin hydrocarbons do not pro
duce such micelles; therefore, their lubricity is quite
poor.
The processes which promote aggregation, e.g.,
electric effects, improve the lubricity of oils.
M.M. Snitkovskii and coauthors studied the structure
and electrical properties of surfactant boundary layers
on the surface of heattreated steel (1971). The results
No. 1 2010
38
Speed
Decreasing friction
(a)
Fig. 4. Schematic representation of three possible phase states of boundary monolayers of lubricating fluid that contains mole
cules of nalkanes: a—ordered structure of lubricant in “glassy” state; b—partially amorphized structure in the vicinity of phase
transition; c—fluidlike structure (according to [7, 15]).
showed that the layers had the domain structure; i.e.,
they consisted of single volumes within which dipole
moments were ordered. For example, in the case of a
boundary layer of oleic acid, a domain contained
about 1400 molecules. The domains of the boundary
layer were coherent to the domains of a ferromagnetic
at quite high distances from the surface. The appear
ance of these layers is attributed to the effect of elec
tromagnetic forces rather than dispersion ones.
The study of the dynamic properties of thin lubri
cating layers by experiments and computer simulation
allowed the authors of [7] to find that, at sliding in sur
factants, various types of ordered states may appear on
the friction surfaces depending on the temperature,
load, and sliding velocity (Fig. 4). Dynamic phase
transitions between these states occur during the rela
tive motion of the solids. Most likely, it is the investi
gation of boundary layers directly in the tribocontact
that may answer the question which has agitated tri
bologists over many years: what is the real structure of
the boundary layers and how correct are the ideas on
their structure based on studies performed without
friction.
The authors of paper [16] made an interesting
attempt to simulate a boundary lubricating layer using
new computer methods of molecular dynamics. They
considered the selforganization of lubricant mole
cules under conditions of instability, which resulted
from the force gradient of a solid surface. The solution
of the problem involved both the simulation of volu
metric interaction of lubricant molecules and taking
into account the effect of adsorption forces. It was
shown that variation in the distance between the solid
surfaces simulating a friction pair affects both the
adsorption energy and the structure ordering of the
boundary lubricating layer. For some organic sub
JOURNAL OF FRICTION AND WEAR
BUYANOVSKII
Temperature
Decreasing friction
(b) (c)
stances, the energy of their adsorption on the surface
was determined. This method seems quite promising
but its application to systems with a great number of
particles, higher molecular weight of particles, and
more diverse elementary composition is hampered by
limitations of computational power.
CONCEPT OF SHARE
OF METALLIC CONTACT
Hardy’s model retains its validity to this day,
though data alluding to the necessity of its refinement
were obtained quite a long time ago. For example, in
1924 A. Devauh found experimentally that effective
lubrication at static friction was possible even though
the concentration of the active component was lower
than that required for the appearance of a condensed
monolayer. In addition, Hardy’s model failed to explain
such phenomena discovered in the mid20th century as
friction transfer of a metal to the counterbody under BL
and the transition from smooth sliding to stick–slip
motion when conditions of friction became more
severe, e. g., when the transition temperature is
reached. F.P. Bowden and D. Tabor generalized the
obtained results of the study of BL and the accompa
nying processes, e.g., friction transfer of a metal to the
counterbody through a boundary layer, and confirmed
experimentally their own views on friction under these
conditions. They polemized with Hardy and believed
that his model was simplified and suitable just for
describing light friction regimes. They arrived at the
conclusion that in heavyloaded friction units, direct
metallic contact occurred at the peaks of single
microasperities of the contacting solids; this contact
was localized by adsorbed molecules of the active
component of the lubricant. The force of friction of
Vol. 31 No. 1 2010
 BOUNDARY LUBRICATION BY AN ADSORPTION LAYER
the solids consists of the shear resistance of adhesive
bonds at the area of metallic contact and the tangential
resistance of the lubricating layer on the rest of the
contact area. The second component is many times
weaker than the first one. Then, according to [17], the
friction coefficient is
f = αf m + ( 1 – α )f l , (1)
where α is the share of metallic contact; fm and fl are
the friction coefficients on the area of metallic contact
and on the fully lubricated area of surface, respec
tively; they are determined from independent experi
ments. This model explains well the existence of the
wear of rubbing bodies at BL even up to the breakage
of the boundary layer. It also explains the friction
transfer of metal particles from one surface to the
counterface, which also occurs under BL; however, as
noted above, the boundary layer reduces the friction
coefficient, the wear of the rubbing bodies, and the
friction transfer many times compared to the case
when the layer is broken or altogether absent. Formula
(1) shows no means of determining the parameters it
contains, but it is of great methodical importance.
Subsequent researchers attempted, above all, to esti
mate the magnitude of the “lubricating layer defect”
α, for which purpose the models of the processes of
friction, wear, and seizure under BL were developed.
Kingsbury proposed the most known method for
estimating this characteristic [18]; he treated the latter
as the probability of metallic contact and defined it as
the ratio of the time it takes for a single counterface
asperity to pass the distance between two surfactant
molecules adsorbed on the plate being studied to the
duration of a period when a surfactant molecule stays
in the adsorbed state, according to the formula of
Ya.I. Frenkel. Then we have
α = 1 – exp –  exp ⎛ – 
E⎞
Z
, (2)
vt 0 ⎝ RT⎠
where Z is the distance between the adsorbed mole
cules that is, as a first approximation, the molecule
diameter; v is the velocity of the relative motion of a
single asperity; t0 is the reciprocal of the oscillation
period of a surfactant molecule in the adsorbed state;
E is the adsorption heat, according to Kingsbury; R is
the gas constant; and T is the absolute temperature. By
substituting α from equation (2) into equation (1), one
can calculate the friction coefficient at BL within
broad ranges of the parametersv and T, staying, of
course, within the limits of the BL regime. Since equa
tion (2) is derived under serious assumptions, which
are not necessarily justified, the calculation of the fric
tion coefficient on its basis is quite approximate.
The characteristic α from equation (2) was used in
some calculation models, e.g., in Rowe’s model for
calculating the wear rate of rubbing bodies [19] and in
the Wang’s and Huang’s model for calculating the fric
tion coefficient at BL [20]. In both cases, equation (2)
was applied in modified form. In the first case, it was
JOURNAL OF FRICTION AND WEAR Vol. 31 No. 1
39
simplified and in the second case, followed by Beer
bower (1971) and Akin (1973), the ratio Z/t0 is
replaced, in accordance with the Lindemann formula,
by the ratio M/T, where M is the molecular weight of
the lubricant and T is the critical temperature of the
lubricant. Attempts have been made to determine the
share of metallic contact from isotherms of Henry,
Freindlich (V.L. Lashkhi), Langmuir (Deryagin and
M.N. Slonimskii, A. Cameron), Temkin (Jahanmir),
etc. Dickrell, Sawyer, and Erdemir proposed the equa
tion for estimating the share of the coating covered
with adsorbed gas, as applied to diamondlike coatings
providing superlow friction. It is based on the joint
consideration of the adsorption process, according to
Langmuir, and the breakage of the boundary layer,
according to Blanshe and Sawyer [21]. The adequacy
of the listed models was verified experimentally to
lesser or greater degrees of reliability depending on
researchers’ facilities.
Subsequently, it was found that if the share of
metallic contact exceeded a certain value that was crit
ical for the given friction unit, the friction coefficient
and wear rate rose sharply and, finally, the seizure of
the friction unit occurred. It has become clear that an
estimate of the maximum permissible share of metallic
contact is necessary to develop kinetic models of the
occurrence of transition temperatures during
BL. Bowden and his coworkers found (1939) that,
when lubricating a steel–steel friction pair by such
media as technical white oil, liquid alcohols, and
lower fatty acids, motion ran in a stick–slip manner,
i.e., the friction coefficient varied jumpwise. When
higher fatty acids were used as lubricants, smooth slid
ing without jumps occurred. Subsequently, it was dis
covered—also for the steel–steel pair—that, under
lubrication with higher fatty acids and some commer
cial oils at room temperature, smooth sliding
occurred. When the friction unit and the surrounding
lubricant were heated to a temperature specific for
each lubricant, smooth sliding was replaced by stick
slip motion and the friction coefficient increased to
the values typical for dry friction [22]. Further studies
of Tabor and Frewing (1940–1942) have shown that
for pure hydrocarbons, alcohols, ketones, and amides,
transition temperatures were close to their melting
temperatures, while for higher fatty acids and ethers
they exceeded greatly their melting temperatures. For
fatty acids, transition temperatures increase with
increasing length of the hydrocarbon radical.
In Fig. 5, the typical dependence of the friction
coefficient on the temperature is presented by the por
tion OAB2 of the generalized dependence f(T). The
transition temperature, according to Tabor, is symbol
ized here as Tcr1 (i.e., the first critical temperature).
Tabor assumed that this effect was explained by the
disorientation and desorption of lubricant molecules
in the boundary layer, i.e., by decrease in the share of
the surface area covered with the adsorption layer.
Subsequent works of Huges and Wittingam (1942),
2010
40 BUYANOVSKII
f B2
B ness of his theory based on the adsorption mechanism
E of the formation and breakage of a boundary layer.
O A
B1
C D
Tcr1
Tkhm Tcr2 T
Fig. 5. Generalized temperature dependence of friction
coefficient [23].
R.M. Matveevskii and his students (1956–1972),
Cameron and his students (1966–1973), and other
researchers have shown that the transition tempera
tures of lubricants under friction depend on their com
position and the concentration of active components
in them. M.M. Khrushchov and R.M. Matveevskii dis
covered that the transition temperature estimated by
using a test machine with slow rotation, or the critical
temperature, was equal to the total temperature in the
tribocontact during the seizure of the friction unit, the
rubbing materials and lubricant being the same [24].
KINETIC MODELS OF THE BL PROCESS
Frewing considered the lubricant as a dilute solu
tion of a surfactant in an inactive medium and
assumed that surfactant molecules on the friction sur
face were in dynamic equilibrium with the lubricant
bulk [25]. In other words, two processes run simulta
neously—adsorption and desorption—and the
dependence of the equilibrium constant of this process
on the temperature at which it occurs is presented by
the van’t Hoff isochore. He postulated that the transi
tion temperature corresponded to the temperature at
which the surface concentration of surfactant mole
cules forming the boundary layer decreased to a criti
cal value. In other words, α increases to a value which
remains constant for the given combination of the rub
bing surfaces and lubricant. From these consider
ations, Frewing derived the relation lnC = –U/RTt +
const, where C is the concentration of the surfactant in
the lubricant; U is the adsorption heat, or more specif
ically, the activation energy of desorption; Tt = Tcr1 is
the transition temperature on the absolute scale, or the
first critical temperature. It follows from this relation
that the dependence of lnC on 1/Tcr1 should be linear.
One can use it to calculate the value of U, which char
acterizes the strength of the bond of adsorbed mole
cules with the friction surface and can be estimated as
the tangent of the slope angle of the straight line
approximating this dependence multiplied by R.
Experiments of Frewing with dilute solutions of
various surfactants, first of all, fatty acids, carried out
JOURNAL OF FRICTION AND WEAR
under friction of steel surfaces, proved completely the
linearity of these dependences and hence, the correct
These results were repeatedly confirmed at the labora
tories of R.M. Matveevskii, A. Cameron, and others.
Cameron and his students arrived at the conclusion
that the transition to seizure, i.e., the attainment of the
critical temperature during friction, occurred at a
share of contact through the lubricating layer βcr = 0.5
or at α = 0.5.
Kingsbury analyzed the dependence α(T) and drew
the conclusion that at dα/dT = max or at α ≈ 0.5,
when the marked inflection of the curve approximat
ing this dependence appeared, the temperature Tc was
reached. He called it the characteristic temperature
and identified it with the transition temperature.
According to [26], this temperature can be calculated
from the following equation:
T c =  1 –  exp ⎛ 
E⎞
E Z
. (3)
2R vt 0 ⎝ RT⎠
Thus, the load in the tribocontact is taken into
account in equation (3) only through the temperature
that does not always represent the facts. Akin gives this
equation in a somewhat modified form and introduces
the load into the calculation formula [27]. Here, the
load is introduced through the real contact area. In
addition, Akin postulates that the value of the share of
the metallic contact above which the critical tempera
ture is reached during friction is much lower than that
assumed in [25]; i.e., seizure occurs at α Ⰶ 1, when
d2α/dT2 = max or d3α/dt2 = 0.
Subsequently, it was put forward that the attain
ment of the critical value of α required for Tcr1 to occur
is a necessary but not sufficient condition. This tem
perature is reached when the number of adhesive
bonds between the contacting surfaces acquires the
value which is critical for the given combination of the
lubricant and rubbing materials. In this case, the pro
cess of bond formation is considered as a kinetic pro
cess and is described, as a first approximation, by a
kinetic equation of the first order [28]. Assuming that
the number x of the formed adhesive bonds is propor
tional to the real contact area, one can derive the fol
lowing equation for calculating x at the temperature T
on the contact portion with the broken boundary layer
[2, 29]:
Ex ⎞
x = αa ( p a /H )t k 0 exp ⎛ – 
m i
 , (4)
⎝ RT x⎠
where α is the share of metallic contact; a is the num
ber of active centers on the unit’s real contact area;
i
k 0 is the preexponential factor; pa is the pressure; H is
the Brinell hardness of the softer friction member at
the test temperature; t is the duration of the process
(t = d/v, where v is the velocity of relative motion; d is
the characteristic dimension or the distance between
Vol. 31 No. 1 2010
 BOUNDARY LUBRICATION BY AN ADSORPTION LAYER
the active centers); m is the equation constant; Ex is the
activation energy of the process of the adhesion bond
formation; R is the gas constant; and Tx is the temper
ature of the process.
Assuming that for dilute solutions the share of the
area of contact between two solids covered with
adsorbed lubricant molecules is described by the
Langmuir isotherm, one can derive the following
equation for the “lubricating layer defect”:
Δμ –1
α = b 0 C exp ⎛ ⎞ ,
ν hydrocarbon molecules with –CH3 end groups, which
(5)
⎝ RT a⎠
where b0 is the preexponential factor in the calculation
of the exchange constant, which accounts for the
micro and macrogeometry of the contact with con
sideration of the conversion of the active component
concentration in mole fractions to the weight concen
tration; C is the concentration of the active component
of the lubricant; ν is the exponent which characterizes
the test regime; Δμ is the difference of the chemical
potentials of the surfactant in the boundary layer and
in the lubricant bulk; and Ta is the temperature of the
surface on which surfactant molecules are adsorbed.
We substitute equation (5) into (4) at Tx = Ta and
x = xcr and solve the latter equation for the tempera
ture T, which in this case is equal to Tcr1; then we
obtain
E x + Δμ
T cr1 = 

m ν –1
R ln [ B 1 p a ( Hν C ) ]
i
where B1 = adm k 0 /(xcrb0). In this case, of course, Tx =
Ta = Tcr1.
Equation (6) takes into account the properties of
the contacting solids (H) and the lubricant (C), the
friction regime (v and pa), as well as the interaction of
the lubricant with the friction surfaces (Δμ) and the
interaction of the contacting solids (Ex). Equation (3)
and its derivatives can be considered as particular cases
of equation (6).
Of great interest are the two theories of the BL pro
cess that allow one to calculate its basic characteristics
without performing tribological experiments. Both theo
ries have been under development for a long time and
both have been confirmed experimentally. However,
they have not yet gained recognition. The first theory
is based on the concept of a boundary layer as a highly
ordered ensemble of adsorbed molecules (Hardy’s
concept), while the second one involves the alternative
treatment of lubricant molecules in the boundary layer
as a twodimensional gas. It seems likely that the com
ing years will elucidate which of these concepts reflects
adequately the real structure of boundary layers.
The first theory was proposed by Cameron for
boundary layers of hydrocarbons having strictly regu
lar quasicrystal structure under conditions of heavy
pressures and low velocities of relative motion [30]. It
is supposed that each of the contacting surfaces is cov
JOURNAL OF FRICTION AND WEAR Vol. 31
41
ered with a closepacked monolayer of lubricant
adsorbed molecules. During the relative motion of the
surfaces, the system periodically passes from the posi
tion characterized by the equilibrium energy E1 to the
position characterized by the maximal energy E2. The
distance between these positions is x; the friction force
F and the energy increment during motion (kinetic
friction) is E2 – E1, which characterizes the first com
ponent of the friction force. The second component
results from the forces of attraction acting between the
are adsorbed on the friction surfaces. This induces
forces which attempt to separate the surfaces by the
distance δ. Under the load N the potential energy is
δN. Then the total energy spent for friction is Fx =
(E2 – E1) + δN and the friction coefficient is f = F/N =
(E2 – E1)/Nx + δ/x. Cameron believed that the second
component of the friction force was much greater than
the first one, so that the Amontons’ law was obeyed.
A.S. Akhmatov subjected the first version of the theory
of Cameron to sharp criticism [13] and considered his
assumptions as incorrect. Akhmatov also believed that
the agreement between experimental and calculation
results was random, though he noted that the attempt
to develop a strict theory of BL based on exact laws of
atomic interactions held promise. As early as 1990,
Cameron asserted that the subsequent evolution of his
theory could answer a number of questions in the the
ory of friction at BL, including the issue of the origin
, of the friction force [30].
A more modern theory is proposed by
Yu.N. Vasil’ev [31], based on analysis of the friction of
graphite materials under BL. This analysis has been
successfully applied to conditions of metal friction.
The contact between the rubbing solids is considered
as a slot micropore with a movable wall. The condition
of BL occurrence is the equality of the external pres
sure pc to the pressure in the lubricating layer. Since the
adsorption heat in such a pore is twice as great as the
adsorption heat on the free surface, lubricant mole
cules are adsorbed in the slot gap and separate the fric
tion surfaces. In this case, heat Q is released, which is
equal to the difference between the integral heat of
adsorption in contact qc and the integral heat of
adsorption on the two free surfaces qs before they enter
contact. The plane of the rubbing body is assumed to
be equipotential, so that the molecules adsorbed on it
are in the state of a twodimensional gas (Fig. 6). The
counterbody moves along this plane and slides over the
substrate formed by the adsorbed lubricant molecules;
the motion work of the counterbody is equal to zero.
At the stage of the adiabatic rupture of contact, the
work is equal to the heat of the desorption of lubricant
molecules from the contact zone. The friction coeffi
cient at BL is calculated as the desorption heat (which
in turn is the difference between the adsorption heat in
the slot and twice the adsorption heat on the free sur
face) divided by the product of the average distance
between the defects and the contact pressure. There
No. 1 2010
42
T T
1 2
Fig. 6. Threestage scheme of formation (1), implementation (2), and rupture (3) of friction contact at boundary lubrication
according to Yu. N. Vasiliev: T—vector indicating path of formation and rupture of contact; La—average distance single contact
passes from its formation to rupture, or size of crystallite; Q—adsorption heat liberated at stage of lubricating layer formation;
pr—real contact pressure.
fore, friction forces at BL can be reduced by increasing
either the size of the surfactant molecules or the size of
the blocks on the friction surface.
Closing this section, we return to Fig. 5. As is
known, lubricants for heavyduty friction units con
tain chemically active additives, i.e., compounds with
chemically active elements—sulfur, chlorine, phos
phorus, oxygen, etc.—that react with solid surfaces at
elevated temperatures (temperatures above Tcr1). At
temperatures above the temperature of chemical mod
ification of the surface Tch, the surface becomes cov
ered with a thin layer of products of reactions with the
active elements of the lubricant. It should be noted
that the process of chemical modification of the fric
tion surfaces is substantially governed by the adsorp
tion of lubricant molecules on these surfaces (P. Studt,
1986). At temperatures exceeding Tch, the friction sur
face becomes covered with a modified layer of prod
ucts of reactions between active components of the
additives and the metallic surface, e.g., with a layer of
sulfides. The heat of adsorption on sulfides is much
higher than on iron oxides (S. Hironaka, Y. Yagagi,
and T. Sakurai, 1978). Because of this, the layer of
adsorbed molecules and fragments of molecules on the
sulfide film is efficient within a much broader temper
ature range than the layer formed on steel; the break
age temperature Tcr2 for this layer formed on the sul
fide film is substantially higher than for the layer
formed on steel. Therefore, such an increase in the
level of the adsorption of surfactants on friction sur
faces governs the antifriction and antiscoring charac
teristics of a lubricated friction unit.
TRIBOCHEMISTRY OF FRICTION CONTACT
Transformations of the Lubricant in the Friction
Zone. It has been found that boundary layers result
mainly from a number of interrelated tribochemical
processes. In other words, they are the product of tri
boactivated reactions between the lubricant compo
JOURNAL OF FRICTION AND WEAR
BUYANOVSKII
La
pr T
3
Q
nents and contacting materials. Chemical reactions
and processes of adsorption and desorption running
during friction differ substantially from similar ther
mally activated processes running in a static contact
[32, 33]. Great energy concentrations and anomalous
aggregate states of matter occur in the friction zone;
owing to this, chemical reactions occur which are
characterized by higher activation energies under
static conditions and require much higher tempera
tures. In many cases, such reactions are unlikely to
operate under static conditions; moreover, they are
unfeasible from the viewpoint of thermodynamics.
These reactions are called tribochemical [2, 32, 33].
Mechanical activation, which occurs primarily during
friction, may induce chemical reactions of various
character, i.e., reactions of synthesis, decomposition,
exchange, etc. [32].
Figure 7 illustrates a block diagram of the process
of friction at BL, which explains, particularly, the role
of tribochemical processes. A friction unit is fed by a
lubricant, whose active components react with the
working surfaces of the friction members and are
adsorbed on them. The friction unit operates under
the load N and at the velocity of the relative motion of
the rubbing solids V and the temperature T. During
friction, the surface layers of the contacting solids
undergo elastoplastic deformations, which lead to
phase transformations in the layers, breakage of sur
face films, and the appearance of juvenile areas on the
surfaces. This results in activation of the contacting
surfaces, which stimulates exoelectron emission of
highenergy particles, as well as frictional heating.
These processes affect substantially both the character
of reactions of the active components of the lubricant
with the surface layers of the rubbing solids, and the
rate of the reactions.
The processes which operate during BL can hardly
be described in terms of common chemical (thermo
chemical) reactions. Reactions of the rubbing solids
with the lubricant and with each other, as well as trans
Vol. 31 No. 1 2010
 BOUNDARY LUBRICATION BY AN ADSORPTION LAYER 43

N
V @ @
@ @
T CM

@ @
@ @
@ @ @ @
@ @ @ @
@

@ @
@ @
@ @
@
@
@
@
@

@
@

Fig. 7. Scheme of process of friction at BL: L—lubricant; N—load; V—velocity; T—temperature.

formations occurring in the surface layers of the solids,
are activated by frictional heating. Frictional heating
results in total contact temperature sufficient for the
activation of chemical reactions on the friction sur
faces. The following factors also contribute to this
activation: the catalytic effect of the metal that
becomes juvenile in friction (“tribocatalysis”); the
mechanochemical disruption of lubricant molecules;
electrization by friction that results in a corresponding
force field; deformation processes leading to distor
tions and the partial fracture of the lattice, as well as to
the appearance of defects in the surface layers stimu
lating adsorption and chemical processes; exoelectron
emission and the emission of highenergy electrons
from the friction surfaces; etc. (M. Fink, 1930–1967;
S.W. Chaikin, 1967; Thiessen et al., 1967; I.L. Goldb
latt, 1973). The methylene structure of hydrocarbons
in the boundary layers remains nondipole only until
the stress state of the tribocontact occurs and the
related mechanical deformation develops [33]. The
areas of the metallic friction surface which become
juvenile in friction acquire such high activity that
hydrocarbons may be adsorbed chemically on them
and even react with them, a situation which is not pos
sible at the same temperatures under static conditions
(S.M. Hsu and E.E. Klaus, 1978). The activation
energies of some tribochemical reactions are much
lower than those of common thermochemical reac
tions. The rates of tribochemical reactions exceed
many times those of thermochemical reactions, and
the degradation of the active components of the lubri
cant in friction is more intensive compared with the
case of exposure of the metal in the same lubricant at
the same temperature [2, 32]. Thus, thermochemical
processes operate, rather than thermally activated
chemical reactions. At the same time, these processes
lead to the transformation of lubricant active compo
nents into cokelike products, which do not possess
lubricity (not shown in Fig. 7). Finally, the lubricating
layer loses its carrying capacity because of the gradual
exhaustion of the active components in the lubricant.
Mechanism of Tribochemical Processes. Today,
when accurate instrumentation has been developed
and plenty of experimental data have been obtained, it
is crucial to elucidate the mechanism of tribochemical
reactions and the manner of transfer of frictionally
generated mechanical energy to the reactor repre
sented by the tribocontact. Nowadays, researchers
attribute the activation of the friction contact zone,
which stimulates tribochemical reactions, mainly to
the processes of transfer of electrons and the appear
ance of anions of organic compounds in friction.
According to Kajdas’ concept of the anionradical
mechanism of effect of oils and their components, or
the NIRAM concept, the reactions of lubricants with
friction surfaces are mostly governed by the following
two processes of transfer of the frictional energy to the
reaction zone: frictional heating and the effect of low
energy electrons, or exoelectrons, which are sponta
neously emitted by solid surfaces in friction, as well as
in deformation, machining, and the desorption of
adsorbed lubricant molecules. The exoelectrons ion
ize the lubricant molecules that are in the immediate
vicinity of the exoelectron source; this leads to the
appearance of anions and anion radicals reacting with

JOURNAL OF FRICTION AND WEAR Vol. 31 No. 1 2010

44 BUYANOVSKII
the areas of the metallic surface which acquired a pos
itive charge owing to exoelectron emission [32].
The sequence of the formation of boundary layers
as a result of tribochemical reactions is as follows [35]:
—freshly exposed areas of the metallic friction sur
faces emit exoelectrons and the areas which have lost
electrons become positively charged;
—exoelectrons interact with the lubricant mole
cules adsorbed on the friction surface or with the mol
ecules desorbed just now. This yields negative ions,
ionradicals, and radicals;
—reactions of a positively charged area of the
metallic surface with anions and anion radicals result
in their chemisorption and the formation of adsorp
tion complexes. The radicals formed react with the
surface, which is covered with a chemically adsorbed
layer, and are capable of entering into reactions yield
ing various resins, peroxides, and friction polymers. It
is the consideration of the effect of both the anions and
radicals formed in friction at BL that allows one to call
the above mechanism of lubricity the ionradical
mechanism.
Kajdas emphasized the anionradical concept and
substantiated the mechanism of the lubricity of hydro
carbons, alcohols, and ethers, as well as chemically
active additives. In particular, he explains quite well
the difference in the tribological effect of dibenzyl dis
ulfide and diphenyl disulfide and attributes the better
antiscoring properties of the first additive to the specif
ics of the structure of the dibenzyl disulfide radical and
its transformations during the tribochemical reaction;
the transformations lead to the appearance of acety
lene, which is polymerized in the friction zone. Rely
ing on the generalized NIRAMHSAB concept, Kaj
das also substantiated the mechanism of tribochemical
1
reactions of water with some ceramics, etc. [32, 35].
In the 1950s, two phenomena were discovered,
whose application had a profound impact on the optimi
zation of the BL process. They are selective transfer, or
the effect of wearless friction, and tribopolymerization;
both are classified as tribochemical processes as well.
The phenomenon of selective transfer (ST) was dis
covered by D.N. Garkunov and I.V. Kragel’skii in
1957. It was originally called “the atomic transfer of
copper in friction” [37]. When inspecting the techni
cal state of airplanes, they found the spontaneous for
mation of a pure copper film 1–2 μm thick on the
working surfaces of a steel–bronze joint lubricated
with alcoholglycerol mixture. The film covered both
the steel and bronze surfaces and yielded a sharp drop
of the wear rate of the contacting parts; it also reduced
the friction force by several orders of magnitude. The
first explanation of this effect was presented as early as
1960 and was based on the capacity of the lubricant to
1 The
HSAB concept, or Lewis’s principle of strong and weak
acids and bases, was used by Kajdas when developing the gener
alized NIRAMHSAB concept, which possesses better prognos
tic capabilities than NIRAM alone [36].
JOURNAL OF FRICTION AND WEAR
reduce copper oxide to pure copper, whose dispersed
particles were transferred later to the steel surface. The
thin layer of pure copper formed in this way had a very
low shear strength; it was recovered during wear owing
to the above tribochemical reaction, so that the wear
rate was negligibly low. Subsequently, this gave
grounds to call the phenomenon the effect of wearless
friction. Later on, studies of the mechanism of this
unique phenomenon were carried out (Garkunov,
A.A. Polyakov, Yu.S. Simakov, A.S. Kuzharov, and
others) and intensive work commenced to uncover
engineering applications. For example, when studying
structural changes in the thinnest surface layers of
metals operating under the ST conditions, it was found
that intensive diffusion flow of atoms occurred at a
depth of about one micron and less; the coefficients of
diffusion reached values typical of thermally activated
diffusion at a temperature close to the melting point of
the alloy. This flow is accompanied by the depletion of
the surface layer of the antifriction alloy in alloying
elements owing to their selective solution in the sur
factant medium and by the formation of a pure copper
film on the interface of the rubbing solids. A clear
boundary is seen between the alloy material in the bulk
and the formed servovite film, whose material is in the
state similar to a melt and possesses anomalous ductil
ity. When studying the physicalchemical processes
operating during SF, it was discovered that films
appeared periodically in the process of association of
molecules of complex compounds, which resulted
from reactions of lubricant ligands with the metal
atoms appearing on the surface together with disloca
tions. These films slide over the surface and over each
other, thus providing lubricity during ST (Simakov,
1982). However, it was found that ST can be achieved
for a relatively confined range of combinations of rub
bing materials and lubricants. Nevertheless, it was
possible to widen somewhat the range of action of ST
by varying the composition of the antifriction alloy
and thus eliminating the deformation decomposition
of its structural components during diffusion running
in friction, as well as by changing the lubricant compo
sition (L.I. Kuksenova et al., 1990). It was also found
that the great catalytic activity of the servovite film led
to the formation of polymeric films on it, which con
sisted of free radicals of organic compounds. The rad
icals appear during lubricant destruction. The high
thermal conductivity of the servovite film favors
decrease in the surface temperature owing to heat
removal deep into the material and its good deform
ability provides a lower real contact pressure [38, 39].
Tribopolymerization is also a quite effective pro
cess. In 1958, H.W. Hermance and T.F. Egan found
resinous deposits on relay contacts resulting from
chemical transformations of vapors of organic com
pounds that evolved from insulating materials. The
appearance of the deposits, which were called by the
above researchers “friction polymers,” reduced the
resistance of the rubbing solids to relative motion. The
Vol. 31 No. 1 2010
 BOUNDARY LUBRICATION BY AN ADSORPTION LAYER
IR spectra of the hard amorphous product formed at
friction in lowmolecular unsaturated and aromatic
hydrocarbons—benzol, cyclohexane, etc.—attest
that benzol rings open during a tribochemical reaction
and benzol transforms to a hydrocarbon having ali
phatic structure; subsequently, this hydrocarbon serves
as the parent of a friction polymer (R.S. Fein and
K.L. Kreus, 1965).
The practical application of this effect has been
hampered by the fact that, since mineral oils are com
plex mixtures of hydrocarbons, not every combination
of their components—even within a standard compo
sition—makes this process possible under the speci
fied conditions. Therefore, Yu.S. Zaslavskii and
R.N. Zaslavskii [40] hit upon the idea of using com
pounds which easily produce friction polymers as
additives. They studied the influence of the structure
of unsaturated hydrocarbons—monomers and oligo
mers—on the nature and lubricity of the appearing
films, i.e., on the formation of a protective polymer
film, which continuously regenerates in the process of
wear. Thus, they found model organic compounds that
produced friction polymers in the tribocontact and
developed industrial additives on their base, which
reduced effectively the friction and wear of the tribo
joint members [40]. Subsequently, they continued
studying the mechanism of tribopolymerization and
its practical application in order to improve the lubric
ity of oils. For example, in the case of acetylene and
olefinic additives that produce friction polymers and
improve the antiwear properties of the base oil, the intro
duction of groups –OH, –COOH, –CHO, –COOR,
and some others into a compound molecule signifi
cantly improves their antiwear properties [2, 41].
Chemical compounds which produce metalpolymer
complexes in the friction zone provide better antiwear
effects compared to compounds which do not produce
such complexes. A monomer or oligomer should have
the configuration or conformation that favors the easy
chemisorption of the compound on the metallic surface.
Researchers from abroad also study actively the
effect of tribopolymerization (see, e. g., [36]). Their
works relate largely to the search for compounds suit
able for practical application (as mentioned above,
this problem was successfully solved by specialists
from the USSR and Russia [39, 40]). Here, we note
the studies of the mechanism of tribopolymerization
carried out by Furey and Kajdas [42]. The wide use of
modern analytical instrumentation has allowed them,
with the use of computer software, to calculate the
structure of a molecule of the tribopolymer resulting
from the studied monomers. For this purpose, they
proceeded from the determination of the minimal
energy spent for chemical transformations of the
structure of the original monomer into a tribopolymer
structure if the set of atoms forming the molecule is
known. They hit upon the idea of using media which
produce tribopolymers to lubricate parts made of
chemically inert ceramics.
JOURNAL OF FRICTION AND WEAR Vol. 31 No. 1
45
The study of lubricant degradation in friction is
extremely vital since the level of the degradation of
lubricants governs largely the durability and reliability
of friction units. Lubricants gradually deteriorate and
fail to perform their functions. As a rule, the greater
the sample of the lubricant and the higher its oxidation
resistance, the less intensive is the deterioration pro
cess. Lubricant deterioration involves the following
processes:
—physical and physicalchemical processes of
changes in the lubricant composition because of deep
manystage transformations such as oxidation, poly
merization, cracking;
—the passivation of lubricant active components,
first of all, surfactants, including the deterioration of
the active components, as well as changes in their
composition and structure owing to tribochemical and
mechanochemical transformations;
—the gradual accumulation of contaminants in
the lubricant, coming from outside—dust, water,
etc.—or appearing during operation, as well as soluble
and insoluble products (including wear products,
which passivate the lubricant volume exceeding their
own volume 20 times) that stimulate the processes of
wear, corrosion, and changes in the physicochemical
properties of the lubricant.
These processes are interrelated and intensify each
other, thus accelerating the deterioration of the lubri
cant. For this reason, it is quite difficult to distinguish
the processes of tribochemical degradation in such a
complex phenomenon. Moreover, oils deteriorate var
iously in different units, e.g., internalcombustion
engines, transmission units, sliding and rolling bear
ings, etc. Therefore, it is problematic to present any
systematic description of the problem of lubricant
degradation in a short section of this article. We restrict
ourselves to some typical examples. Thus, according
to the results of tests of microsamples of lubricants, a
quite small amount of insoluble products of oil
destruction appears during the wear of the contacting
balls. However, they form pasty mixtures with the oil
that hamper the penetration of the fresh oil to the fric
tion surfaces, thus leading to the seizure of the friction
unit (H. Li et al., 1999). The products of the degrada
tion of the oil are similar to the products of its oxida
tion at 400°C and higher, while the portion of the oil
that has not penetrated into the contact zone has a
temperature of no more than 150°C. We note that the
portion of the oil spent for the formation of the pasty
products is 4% (for polyalpha olefins) to 35% (for
polyglycol ethers) from the initial volume of the oil.
According to the data of L.N. Sosulina and T.B. Skry
abina (1984), the degree of lubricant deterioration at
which a rolling bearing fails is 45–50%. Of crucial
importance are the works on the development of phys
ical and mathematical models of lubricant degrada
tion, based on which one may describe the kinetics of
changes in the level of lubricant efficiency or at least
propose criteria for the assessment of this level. To
2010
46 BUYANOVSKII
date, a number of such models have been developed
(see, e. g., [43–46]).
CONCLUSIONS
The key principles of the theory of BL originated by
Hardy in 1922 are presented, formulated, and ana
lyzed. They are as follows: the formulation of the con
cept of BL as a mode of lubrication principally differ
ing from fluid lubrication; the presence of an oriented
layer of lubricant molecules, which separates the con
tacting surfaces; the existence of the latent period of
friction; the decrease in the static friction coefficient
with increasing molecular weight for each homologous
series of compounds that are used to lubricate friction
pairs; and the presence of “friction isotherms.” The
most significant works are considered, which have
confirmed almost all of Hardy’s principles on modern
test equipment, and have developed Hardy’s ideas,
including the study of conditions of the breakage of
boundary layers and criteria for the occurrence of this
breakage. The mathematical models of friction at BL
are described that reflect Hardy’s theory or are based
on alternative approaches. The studies of specialists
are analyzed, which, unlike Hardy and some of his
successors believing lubricants to be unchanged in
operation and storage, take into account transforma
tions occurring in them. The presented material can
be used in the development of a generalized theory of
friction at BL.
This work was sponsored by the Russian Founda
tion for Basic Research (Grants 080800804a, 08
0812153ofi, and 080890031Bel_a).
DESIGNATIONS
α—the share of metallic contact; fm and fl—the
friction coefficients on the area of metallic contact
and on the fully lubricated area of the surface, respec
i
tively; b0 and k 0 —the preexponential factors; C—the
concentration of the active component of the lubri
cant; ν—the exponent which characterizes the test
regime; Δμ—the difference in the chemical potentials
of the surfactant in the boundary layer and in the lubri
cant bulk; Ta—the temperature of the surface on
which the surfactant molecules are adsorbed; T—the
vector indicating the path of the formation and rupture
of the contact; La—the average distance a single con
tact passes from its formation to rupture, or the size of
a crystallite; Q—the adsorption heat liberated at the
stage of lubricating layer formation; pr—the real con
tact pressure; F—the friction force; N—the contact
load; x—the distance between the position character
ized by the equilibrium energy E1 and the position
characterized by the maximal energy E2; a—the num
ber of active centers on the unit’s real contact area;
pa—the nominal pressure; t—the duration of the pro
cess; m—the equation constant; Ex—the activation
JOURNAL OF FRICTION AND WEAR
energy of the process of the adhesion bond formation;
R—the gas constant; Tx—the temperature of the pro
cess; H—the Brinell hardness of the softer friction
member at the test temperature; U—the adsorption heat
or the activation energy of desorption; Tt = Tcr1—the
transition temperature on the absolute scale or the first
critical temperature.
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2010