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This survey of the role of chemistry in the varied processes of friction, lubrica-
tion and wear is written for professional and student chemists. It is hoped that
it may arouse an interest in this branch of their subject; and particularly that
it may indicate the considerable contribution still to be made by chemists in
tribology, especially by exploring the details and exploiting the potentialities
of surface chemical action, which appears so frequently in tribology. A
deliberate attempt has been made to indicate the areas in which the author
believes that fruitful research can be performed.
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responsibility for the presentation. He hopes that the text will be easily
read and may prove stimulating to those having little acquaintance with
tribology. To simplify the presentation, the usual practice of giving detailed
references has been abandoned, but the author wishes to express his obvious
debt to all fellow workers in tribology and particularly to thank D r E. R.
Braithwaite, D r J. P. G. Farr, Mr I. S. Morton and Mr T. G. Rowe who read
the script and made helpful comments. Some books which are recommended
for further reading are cited in the bibliography. These provide comprehensive
lists of research papers.
INTRODUCTORY SURVEY
The word tribology is new, but the subject has been important throughout
recorded history. It covers the whole field of science and technology associated
with sliding, and there is evidence of the solution of tribological problems in
the ancient civilizations of Egypt and the East. Tribochemistry and tribo-
physics are considered as subdivisions of the subject, dealing explicitly with
chemical and physical phenomena associated with sliding surfaces. It is
however important to recognize that most of the characteristics of friction,
lubrication and wear are complex, and their understanding requires some
discussion of chemistry, physics, metallurgy and mechanical engineering. We
shall be concerned here primarily with the role of chemistry in tribology but
the subject cannot satisfactorily be divided into independent academic
compartments.
Let us for example consider one of the simplest and most perfect tribological
devices, a journal bearing operating at its designed speed and load. Such a
bearing consists of a solid cylindrical journal, which may be of any size from a
few thousandths of an inch up to several feet in diameter, rotating within a
hollow cylindrical bearing of slightly larger internal diameter. When the
journal is at rest its centre will be vertically in line with, but slightly below, the
centre of the bearing. The space between the two is filled with lubricating oil of
medium viscosity. As the journal is rotated this oil will be subjected to viscous
drag and forces will develop which create a pressure in the narrow wedge of oil
beneath the journal. Eventually, when full speed is reached, this pressure will
be sufficient to support the journal and the weight of the shaft and other loads
which it may carry. The two surfaces will then be completely separated by a
film of lubricant and the bearing is said to be operating under hydrodynamic
conditions. There will be no wear of the moving parts and the friction will be
determined solely by the viscous properties of the lubricant under these
conditions. The coefficient of friction (frictional resistance divided by load) is
usually very low, of the order of p = 0.002, and may be lower still in aero-
dynamic bearings where the lubricating fluid is air. Engineers consequently
strive to maintain this ideal state of hydrodynamic lubrication wherever
possible.
Considerable success has been achieved in recent years in designing such
bearings, making use of hydrodynamic theory. Chemistry plays no part in
these calculations, except in so far as the molecular structure of the lubricant
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temperature. Data sheets now exist with which mechanical engineers can
design journal bearings to operate under specified load, speed and temperature
conditions with lubricants of known viscosity characteristics.
Bearings cannot always operate under the conditions prescribed in the
design. We have already mentioned that the lubricant film is not established
until the journal attains sufficient speed. At low speed the film of lubricant will
be very thin indeed, and may be completely excluded from some local areas of
the contacting surfaces. This is especially important with aerodynamic bear-
ings, but the problem occurs in all bearings during starting and stopping, and
also when the bearing is subjected to pulsating or shock load. In the regions of
intimate contact the molecular fields of force become very important. As we
shall see later (pp. 139 and 141), if two uncontaminated metal surfaces
are brought into contact the adhesive forces between them will produce
high friction and may lead to transfer of fragments of one surface to the
other during sliding. In some machines the forces developed may be sufficient
to bring the machine to a violent stop. Even if such seizure is avoided, the
transfer of metal eventually results in serious damage to the surfaces, and
loss of the accurate dimensions required for hydrodynamic operation. It is
therefore imperative to reduce the surface forces, which immediately brings
the problem into the realm of surface chemistry and physics. Suitable polar
additives are incorporated in the lubricant to adsorb on, and preferably react
with, the metal surfaces. The most effective materials for this purpose are fatty
acids which, as we shall see, can greatly reduce friction and wear even when
present as only a single molecular layer on each of the metal surfaces.
This regime, known as boundary lubrication, is consequently of very great
importance in bearings. In recent years the development of a new theory
dealing with elastohydrodynamics has shown that hydrodynamic lubrication
can be retained at much lower speeds than had previously been supposed,
because the sliding members themselves deform elastically and thereby
encourage the formation of an oil film between the surfaces. This can be very
valuable, especially when non-polar lubricants are used, but the load-carrying
capacity is considerably improved even in this regime when polar additives
are used. In many applications it is not possible to establish elastohydro-
dynamic lubrication, for example in a door hinge where the components are at
rest for a long period followed by a slow-speed movement of short duration,
which then changes direction. All these conditions tend to prevent the forma-
tion of a film by viscous action. For this and many other familiar purposes,
reliance is placed entirely upon boundary lubricants. As we shall see, the
action of typical boundary lubricants such as the fatty acids depends essentially
upon the formation of a solid film of reaction product, usually a metallic soap.
Cupric laurate, (CllH&O&Cu, is a good example.
The formation of such compounds, by reaction with metals via their atmo-
spheric oxides, is believed to be fairly well understood. In some circumstances,
for example in wire drawing and other metalworking operations, fresh metal
surface is generated continuously and must be lubricated within the time of
passage through the drawing die. At a speed of 3000ft/min this may be
appreciably less than a millisecond. Little attention has been given to lubricant
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continues, this may become a fruitful field for study. The problem is still more
severe in metal cutting and very little is known about the detailed action of
lubricants in metal cutting.
Although metallic soaps are known to be very effective lubricants, their use
is restricted to conditions in which the interfacial temperature is unlikely to
rise above about 150 "C.It is found that breakdown of lubrication occurs at
temperatures approximately corresponding to the softening temperature of the
compound. Copper laurate softens at about 100 "C and sodium stearate, one
of the most stable boundary lubricants, at about 250 "C. Such temperatures
can be generated under apparently moderate frictional conditions because
considerable energy is involved in the plastic deformation of small regions at
the interface. The heat flow and temperature gradients can be calculated by the
principles of physics, and spectacular improvements in performance of, for
example, the mechanical seals used in chemical engineering can be obtained
by suitable design for good heat transfer.
To provide lubrication at temperatures in excess of 150 "C, it is common to
use oil additives known as extreme-pressure (e.p.) compounds. These are
usually organic compounds containing chlorine or sulphur, which are stable
at room temperature but decompose when the temperature rises. The chlorine
or sulphur then reacts with the substrate metal to form a solid chloride or
sulphide film. The chloride shows lower friction on steels, but breaks down at
lower temperatures. In the absence of oxygen, ferric chloride will lubricate up
to about 350 "Cand iron sulphide up to about 700 "C. Frequently oxygen does
not have ready access to the local areas of contact between the sliders, but
these are likely to be exposed on emergence from the interfacial zone. It has
been suggested that the organic chlorides can react through the formation of
HCl, and indeed dilute HCl is an effective lubricant for steel at elevated
temperatures. It is however corrosive and the chloride film formed with HC1
on steel is readily hydrolysed and leads to rusting. Extreme-pressure Zubrication
is thus an application of controlled corrosion and great care must be exercised
to obtain the chemical attack only at the points where it is essential. One
important situation in which accelerated corrosion is desirable arises in the
running-in of an automobile engine. The surfaces as prepared by machining
and grinding are not perfectly smooth and the mating surfaces do not exactly
conform. A lubricant of relatively high reactivity is therefore used and the
engine is run gently. The high spots on the surfaces will be subject to most
heating and so will react most strongly with the lubricant. The inorganic films
formed will be weaker than the metal, and will be relatively quickly worn
away, exposing more metal for chemical attack. In this way the mechanical
and chemical actions will combine to wear down the protruding regions of the
surface and to improve the conformity and smoothness of the interface. It is
clearly undesirable to continue the corrosive action too long, so the lubricant
is replaced by a less reactive one after a short while. Nevertheless, mechano-
chemical interaction is important in all lubrication and wear.
Finally, when all has been done to improve the performance of a bearing by
attention to mechanical design, physical properties, and chemistry of the
metal-lubricant combination, there remains the possibility of metallic contact
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occurring at local areas, either because the temperature is too high for the
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recognize that in this survey we are dealing with only a portion of the whole
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FUNDAMENTALS OF SURFACES
AH = TAS
gas. In chemisorption there is usually some electron transfer between the solid
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and the adsorbate, and the adsorbed molecules are often dissociated into
independent atoms. Chemisorbed material can be removed only if energy is
supplied, usually by heating to high temperature. The heats of adsorption are
respectively of the order of 0.1 eV (-J 1.60 x 10-19 .?) per molecule and
1-10 eV per molecule for physical and chemical adsorption.
Direct friction experiments with metals in a vacuum chamber show that
because of their high surface energy, there is strong attraction between de-
nuded surfaces. The frictional stress developed in sliding one over another can
reach a very high value, comparable to the bulk shear strength of the metal.
Such conditions are however difficult to achieve, and prolonged cleaning is
necessary in the highest available vacuum. Two methods have been used
effectively. One is to heat the metals for about an hour at a temperature just
below that at which evaporation becomes rapid. The other is bombardment
with energetic argon ions, followed by annealing with electron bombardment
to remove the surface strains produced. Low pressures of gas, such as oxygen
at torr (- 0.133 N m-2), can cause a large reduction in the friction
between such denuded surfaces. If the chamber is re-evacuated without heating
the specimens, it is found that there is usually a reversible component attri-
butable to physical adsorption but the major reduction in friction is due to
chemisorption. Experiments of this type performed with copper and low-
pressure oxygen show that the chemisorbed oxygen may survive until the
temperature of the metal is raised to over 900 "C in a high vacuum.
Even without deliberate admission of gases, it is very difficult to maintain
metallic surfaces in a clean state after they have been denuded. The rate of
adsorption of residual gas from the vacuum chamber depends initially only on
the collision rate, which can be calculated by kinetic theory. For example, we
may expect 1 0 2 3 molecular impacts on each square centimetre every second at
atmospheric pressure. There are about 1015 adsorption sites on each square
centimetre of a metallic surface, so if we assume that each molecule or atom
reaching the surface is captured, a monolayer of adsorbate may be expected to
form in one second at a pressure of 10-8 atmospheres (10-5 torr). To maintain
a surface with less than one tenth of a monolayer for several minutes the
pressure should be less than 10-8 torr.
Although this simple type of calculation is reasonably valid when there is
little adsorption, immediately after the exposure of the surface, the situation
soon develops more complexity. As the surface becomes covered, the number
of available sites is reduced so that there is a continuous reduction in the
accommodation coefficient, which is the proportion of the total number of
atoms, colliding with a surface, that remains adsorbed. The adsorbed atoms
are usually highly mobile on the surface, though they cannot easily escape. In
some circumstances there are preferred sites giving a greater reduction in free
energy, so that the adsorbate tends to be localized. In these areas there is a
tendency for a second molecular layer to build up, and this may also happen
elsewhere on the surface when the monolayer is nearing completion, especially
if there is restricted mobility.
Porous surfaces will provide much higher levels of adsorption by capillary
condensation at high vapour pressures. This may be important in lubrication
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experimental evidence from low angle X-ray diffraction and electron scattering
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1’ bP
--
vm
~~
1 + bp
where v is the volume of gas adsorbed at equilibrium pressure
Y, is the volume required to produce a full nionolayer
b is a constant, the adsorption coefficient.
At very low pressures the volume adsorbed is thus proportional to the
pressure, as is frequently observed, but the value of b depends upon the
amount adsorbed:
b = CleEI/R*
where El is the average heat of adsorption
c1 is a term dependent upon the entropy of adsorption
R is the gas constant, and T the absolute temperature.
As the surface becomes covered, both El and c1 will vary. Because surfaces
are usually not uniform, the adsorption will occur first on the high-energy
sites, progressively lowering the heat of adsorption, but this is counterbalanced
to some extent by the attraction between the adsorbed molecules themselves,
which increases the heat of adsorption. This interaction of the adsorbate
molecules is of considerable importance in boundary lubrication and is
believed to contribute largely to the durability of lubricant monolayers. In an
elementary way the adsorbate can be regarded as a two-dimensional ideal
gas, at least at low pressures. The equation of state of this gas can be written
n-A = RT
where n- is the two-dimensional pressure
A is the area covered per mole of adsorbate.
The relationship between n- and the gas pressure p of the superincumbent gas
can be found from thermodynamic considerations. At constant temperature,
Gibbs showed that the relevant equation could be written in the form
Thus r, the number of moles of gas adsorbed on unit surface area is given by
combining these equations
I’ = klp.
As the pressure of gas is increased it is more appropriate to use an equation of
state analogous to the van der Wads equation for a three-dimensional gas.
Thus we may write
Many solid/vapour systems follow this equation when the relative pressure is
low and it has been widely used for determination of specific surface area of
solids. Experiments are commonly performed with nitrogen as the adsorbing
molecule at a temperature of - 183 "C.A linear plot of p/v(ps-p) against p / p s
is obtained. The slope and intercept then give the appropriate values of c and
Vm. The volume of a full monolayer on a known surface is first determined,
and from this, assuming spherical molecules in hexagonal close packing, the
area of a single adsorbed molecule; for example the area of an adsorbed
nitrogen molecule at - 195.8 "C (the boiling point) has been found to be 16.2
square angstroms (0.162 square nm). Consequently the adsorption of nitrogen
can be used to measure an unknown surface area.
The Langmuir equation can thus be considered as a special case of the BET
equation, applying to a single molecular layer adsorption. Other theories have
been proposed and there has been considerable discussion about the nature
and even the existence of long-range forces at a solid surface. As in all surface
studies, the results obtained are critically influenced by small amounts of
impurity. For example, it has been shown by direct weighing with a micro-
balance that, on thoroughly outgassed platinum surfaces, hydrocarbons adsorb
as monolayers. Water vapour adsorbs in only two molecular layers even at
pressures near saturation. When the same surfaces are cleaned in a conven-
tional manner enough water to form as much as 20 molecular layers may be
adsorbed. I t is concluded that even with condensable vapours monolayer
adsorption is observable on uncontaminated surfaces, as would be expected
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Chemisorp tion
We have seen that physical adsorption will occur spontaneously on all
surfaces. Chemisorption may involve an energy barrier, so that activation
energy must be supplied. In such a system only physical adsorption will occur
at low temperatures; but as the temperature is raised chemisorption will occur
at an increasingly rapid rate, until eventually an equilibrium is established
between the rate of arrival of molecules at the surface and the rate of desorp-
tion.
When the adsorbate forms a stable chemical compound with the substrate
it is likely that rapid chemisorption will occur. Most metals react readily with
oxygen, and it is thus to be expected that any metal surface exposed to air will
quickly form a chemisorbed layer of oxygen. The activation energy is so low
that adsorption appears spontaneous at room temperature. As we have seen in
considering the nature of surfaces, this is likely to reduce the surface energy
very considerably, and the oxygen layer will in general be only one molecule
thick because the forces fall off very rapidly with distance (probably l/r6 for
single atoms, but l/r4 for extended surfaces). In chemisorption however this is
a temporary situation. Metal ions will diffuse into the surface layer and react
with the adsorbed ions. At first a non-stoichiometric compound will be formed
but as further diffusion occurs the natural oxide will build up. This will have a
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distorted structure in the first layers, determined by the epitaxial growth, but
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large plastic strain over a highly localized region. It has been shown that there
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Surface topography
Although the topography of a surface is not a chemical feature, it is possibly
related to the surface adsorption characteristics and is certainly of major
importance in lubrication theory and practice. All considerations of friction,
lubrication and wear must take into account the geometric irregularity of
surfaces. Casual inspection affirms that no surface is completely smooth and
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the more detailed the inspection the more obvious it becomes that the surface
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Mechanical preparation
method
Even the most carefully prepared surfaces are thus very rough on a molecular
scale. The c.1.a. is about one quarter of the peak-to-valley height which is thus
about 200 nm even for a polished surface.
Although there has been great emphasis in the past on the height variation
of surfaces, it has also been recognized that in friction and wear the amount of
contact is important. As we shall see later, the highest peaks will deform until
the yield stress of the metal is nowhere exceeded. During the actual sliding
process the surfaces will consist of more or less well-defined plateaux, at
least if one slider is much harder than the other, as is usual in bearings.
The surface topography is consequently sometimes described by an Abbott-
Firestone type of graph which shows the percentage bearing area as a func-
tion of height above some datum. This is produced by taking imaginary
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horizontal cuts at sequential vertical levels and assessing the ratio of solid to
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practice, average measurements of surface area are of little value. The mean
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slope of the surface asperities is seldom greater than a few degrees on a well-
prepared specimen, and the total surface area is consequently unlikely to
exceed the projected area by more than 10 per cent. Nevertheless, these small
asperities are often of paramount importance in friction, lubrication and
wear. The area of intimate contact between two sliding surfaces is frequently
less than one-thousandth of the projected area of the whole contact. Detailed
study of the surface topography is therefore very important and great care
must be exercised in any attempt to correlate theories of solid surface structure
or of physical and chemical adsorption with friction measurements. Yet,
partly for this reason, there is great scope for careful research with this
objective.
PREPARATION AND PROPERTIES OF MINERAL OIL LUBRICANTS
Herodotus, who lived from 484 to 425 BC, described an ancient method of
producing bitumen and a lighter oil from petroleum, but there is evidence of
deliberate use of lubricants from the earliest historical times. The first lubri-
cants (other than water) were probably animal fats, which still play an
important part in lubrication today. They were used widely in situations
requiring retention of the lubricant over long periods. A chariot dating from
the 15th century BC has been found with fat still on the axle. The advantage
of a pad of lubricant in such inaccessible places as the trunnions of church
bells was soon appreciated, but it was realized that for lubrication over short
periods it was convenient to use fluids which could easily be poured onto the
surfaces. Suitable liquids could be obtained from a variety of plants, especially
from seeds. A great many of these vegetable oils and animal fats are still in use
in modern industry though mainly as additives to mineral oils. Palm oil is
considered the best lubricant for cold rolling of thin steel sheet, and tallow is
excellent for drawing large steel bars to reduce their diameter and improve the
surface finish. For many years castor oil was used almost exclusively in air-
craft engines, though this was at least partly due to its resistance to dilution by
petrol.
The first main departure from ancient traditions in lubrication is associated
with the invention of the steam engine during the 18th century. This introduced
rapidly increasing demands for higher speeds, loads and temperatures, which
have continued to rise and to dominate lubricant development ever since.
Steam-engine users first turned to mineral oils, which were known to have
better thermal and oxidation stability than the animal and vegetable oils, but
these properties could not be fully exploited until the refining process had
been sufficiently developed to produce a pure hydrocarbon oil. Mineral oils
are now the most widely used lubricating fluids. The chemical industry has
thus been a keystone in modern lubrication technology. More recently,
especially since the outbreak of the World War 11, the rapid advances in all
branches of technology have created demands for lubricants to operate under
extreme conditions not even considered a few decades ago. To a large extent
these requirements are being met by a revolution in the lubricant industry,
greatly assisted by developments in polymer chemistry, and whole new ranges
of synthetic lubricants are now being produced. These and the wide variety of
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solid lubricants for even more exotic conditions of extraterrestrial space and
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nuclear radiation depend for their existence entirely upon chemical expertise.
These very recent developments are considered later (pp. 168-173). In this
section we are concerned with the production of highly refined mineral oils,
which are still commercially by far the most important group, and the
treatments by which they are converted into general-purpose or specialized
lubricants.
Distillation. The first important stage in a refinery after the crude oil arrives by
tanker, some of which now deliver 100 000 tons at a time, is distillation at
atmospheric pressure. This removes all the more volatile constituents such as
kerosenes and motor fuels, which are condensed and sold separately after
further processing. The remaining oil is generally known as atmospheric
residue. It is not possible to heat this residue beyond about 350 "C because it
would then begin to decompose, or crack. Further distillation is therefore
carried out under vacuum at moderate temperatures. The distillate from this
second process is usually divided into several fractions, according to require-
ments, which can subsequently be blended to produce lubricating oils with the
desired viscosity characteristics. The residual fluid, known as vacuum residue,
can be used as a basis for high-viscosity lubricating oil. Further purification of
both distillate and residue is however necessary in the preparation of lubricants
with satisfactory thermal properties.
Quality control. Different oil companies and different consumers may specify
certain tests which are related to final performance or serve to maintain a
uniform quality. Most of the tests are empirical and some still in current use are
archaic and can even be misleading. Although considerable efforts have been
made to standardize and rationalize test procedures, their relationship to field
performance is often obscure. The Institute of Petroleum annually publishes
Standards for Petroleum and its Products, which are continually revised.
The most important characteristic of a mineral oil for use as a lubricant is
its viscosity, provided that the stability of the oil is satisfactory. Viscosity is
defined as the stress required to shear unit thickness of fluid at unit velocity.
It is usual to quote the kinematic viscosity v in centistokes. It is found from
the ratio of the dynamic viscosity 7 (centipoise) to the density p (g/cm2).
In SI units 7 is expressed in Newton seconds/(metre)2, (1 N s m-2 = 10 poise)
and v in (metre)z/second (1 m2 s-1 = 1 0 6 centistrokes). The viscosity of
mineral oils is therefore carefully measured as a control of quality. A standard-
ized apparatus, usually of the capillary-flow type, is used at specified tempera-
tures. Various other viscometers of empirical design have been widely used to
measure viscosity in Redwood seconds, Engler degrees etc. but it is to be
hoped that these will become obsolete. In addition to the viscosity at a given
temperature it is usually important, for example in an automobile engine, to
know the variation in viscosity of the fluid with temperature. This is very
commonly quoted as the viscosity index (v.i.), which compares the decrease in
viscosity over a given temperature range with that of two oils rated respectively
at 100 and 0. Since it is desirable that viscosity should change as little as
possible, the value 100 represents the reduction in viscosity with increasing
temperature found for the best oil available when the scale was introduced.
Thus higher v.i. indicates relatively smaller change in viscosity. It should be
noted that no oils exhibit constant viscosity, but many modern oils with
additives, and especially some synthetic oils, show much less variation than
the original 100 oil. A supplementary scale (v.i. extended) has been introduced
for these oils, but the system has little to recommend it. Not only is it more
precise to state the kinematic viscosity at selected temperatures; there is
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Service tests. Apart from the tests described above, which are mainly used for
routine quality control, it may be desirable to conduct tests more directly
related to the operating conditions. The distinction is not clear, since both
viscosity and pour point can be regarded as service parameters.
Flash-point and $re-point tests are used to indicate possible hazards. The
flash point is the temperature at which sufficient vapour is formed to burn if
ignited in air in a specified apparatus. At the fire point the liquid itself can be
ignited. Both these temperatures are lower than the spontaneous ignition
temperature and are therefore of greater practical significance. It is neverthe-
less unwise to rely entirely on these data, since the flash point may be seriously
lowered if the oil becomes contaminated with volatile compounds.
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addition, oils may become contaminated, particularly when used for internal-
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combustion engines, and it may be necessary to keep the engine and oil-ways
clean by using suitable detergent and dispersant compounds.
All these additives are essentially chemical products and may depend on
surface chemical properties. The additives are discussed individually, but in
practice it is very important to ensure that mixed additives are compatible,
with no mutually deleterious effects.
Viscosity index improvers. All mineral oils show a large decrease in viscosity
with temperature. Even a light paraffinic oil of v.i. 100 can change in viscosity
by a factor of five between 45 and 100 "C, and the variation is greater for more
viscous oils. The cheaper naphthanic oils have much lower v.i. For example a
naphthanic bright stock of kinematic viscosity 4000 CSat 45 "C has a viscosity
less than 100 CSat 100 "C. Slight improvements can be obtained by additional
refining, but this is prohibitively expensive. Additions of up to 10 per cent of
v.i. improvers are now quite widely used. These are polymers of high molecular
weight (10 000 Staudinger units or more), usually polyisobutylenes or poly-
methacrylates such as the copolymer lauryl methacrylate :
Some nitrogenous copolymers have a dual role as v.i. improvers and dis-
persants. These additives may be soluble in the mineral oil, but are more
likely to be present as a colloidal dispersion. Because of their large molecular
size, such polymers increase the apparent viscosity of the oil at room tempera-
ture; but the effect of temperature on the additive is small, so there is a much
greater proportionate increase in apparent viscosity at high temperatures. The
v.i., measured on the extended scale, may be increased to 130 or more.
A characteristic of lubricating oils with polymer additives is that they are
thixotropic and do not exhibit Newtonian flow ;the apparent viscosity depends
upon the rate of shear. When speed is increased the apparent viscosity falls,
but this is a temporary effect which is immediately reversed when the rate of
shear is subsequently reduced. It can be advantageous since the high rates of
shear are generated at high speeds for which, as we have seen, the load-bearing
capacity in a hydrodynamic bearing is improved and consequently high
viscosity merely increases the frictional resistance. At higher rates of shear the
long polymer molecules may be degraded into shorter components with a
consequent irreversible reduction in both viscosity and viscosity index of the
oil.
Oxidation inhibitors. All mineral oils will react with oxygen when exposed to
air at temperatures above about 100 "C. In automobile engines such tempera-
tures can frequently be reached and the oxidation is also accelerated by the
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vigorous agitation of the oil and by catalytic action of the copper and iron
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present. Lead from the fuel may also appear in significant quantities in the
sump. Oxidation inhibitors, also known as antioxidants, are therefore widely
used, especially in engine oils, even though the oils may be quite stable to
oxidation under simple conditions. The concentration of the inhibitor may be
between 0.5 and 5 per cent.
The initial oxidation products of paraffinic oils are high molecular weight
compounds which are soluble in the oil but will cause a significant increase in
its viscosity. Aromatic hydrocarbons, and particularly any animal or vegetable
oil additives present in the final blend, are likely to polymerize to form a gum
or a harder compound usually described as a varnish. This can cause the valves
of the engine to stick, and may contribute to the formation of an insoluble
sludge. Oxidation of the mineral oil can produce corrosive organic acids,
which can attack the metallic engine parts, especially copper-lead bearings.
It is considered probable that oxidation inhibitors function in two ways.
Some adsorb onto metallic surfaces, thereby reducing the catalytic activity.
Others decompose the organic peroxides which are formed as intermediate
oxidation products. The former are of course also useful as corrosion inhibi-
tors. Many of the commoii oxidation inhibitors contain sulphur or phos-
phorus. Sulphurized alkenes, formed by direct attachment of elemental sulphur
at an unsaturated bond, have been extensively used. The reaction product o f
sulphur with sperm oil, a stable fatty ester, was one of the earliest lubricant
additives and is still used. Sulphur compounds with terpenes, for example
sulphurized dipentene, are found to be effective:
Various other complex organic compounds are also used. These are capable
of decomposing on a metal surface at elevated temperatures to produce
metallic sulphides, and can therefore also show extreme-pressure lubricating
properties. The more reactive e.p. additives, including elemental sulphur
dissolved in oil, are too corrosive for use as adsorbed oxidation inhibitors.
Phosphorus is also too reactive if simply dissolved in the oil, and causes
serious corrosion of non-ferrous metals. Oil-soluble organic phosphorus
compounds such as tributyl phosphite are however effective antioxidants :
CH3-(CH2)3-0
R-O/ \SH
] + H2S
R-0 S S 0-R
\pH \,p/
+ H2O
/ \
R-0’ ‘SH R-0 S-Zn-S’ \O-R
I
0
I
6a Barium petroliurn sulphonate
I
0
I
0-Ba-0
I
study of compounds suitable for these purposes. Their detailed action will be
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considered more fully later (pp. 189,192). The most effective boundary lubri-
cants are fatty acids, which react with metallic surfaces to form solid soaps
having good lateral cohesion but relatively low shear strength. A 1 per cent
solution of stearic acid [CH~(CHZ)~&OZH] in a mineral oil can be considered
typical, but many other compounds are used. These all fail to lubricate
satisfactorily at temperatures exceeding about 150-200 "C.The e.p. compounds
are then used. These are mainly organochloride or organosulphur compounds
which decompose on a metal at high temperatures to form metallic chlorides
and sulphides. Suitable long-chain chlorinated compounds can be formed by
direct chlorination of paraffinic oils. Some commercial fluids contain 30-40
per cent by weight of chlorine and are considerably diluted in a base mineral
oil for use. The maximum temperature at which the chloride film formed is
stable on steels is about 350 "C. To withstand higher local temperatures a
sulphur compound is used. Sulphurized fatty acids have proved effectivefor a
range of applications. It is possible to use elemental sulphur dissolved in oil,
for example in a cutting operation where corrosion is not a major factor, but
for most purposes the e.p. active element should be compounded in a molecule
which is then stable until the high temperature is reached. Considerable care is
necessary in the choice of additive, particularly when used to lubricate non-
ferrous alloy materials, since the effectiveness depends essentially upon con-
trolled corrosion. Typical additives are :
/'
CH3 CH3 HC CH
I I I I
(cH2)16 (cH2)14
I
C
I
H-C-H
(CH2)7
I
C
(7H2)7
C
I / \o
'0 'OH CI ' 0 'OH OH
Stearic acid Cetyl chloride Sulphurized oleic acid
Boundary additive Extreme-pressure additives
point depressants which, like many other additives, are surface-active materials.
Very small quantities, often less than 0.2 per cent, are needed. It is believed
that the additive, which may be a polyalkyl methacrylate, alkylated naphtha-
lene, or alkylated phenol, does not prevent the formation of wax crystallites
but adsorbs onto their surfaces, preventing agglomeration and gel formation,
and thus maintaining relatively low viscosity.
It should not be thought that gel formation is always to be avoided in
lubricants. It can be valuable in metalworking lubrication and is an essential
characteristic of greases, which are considered in the next section. High
molecular weight polymers may be incorporated as stringiness additives, for
example to reduce splashing.
Some lubricants contain additives which bear no relationship to the actual
lubrication. It may, for example, be necessary to add compounds which have
germicidal or bactericidal action, particularly for metal-cutting fluids, which
are exposed and may come intocontact with the hands and clothes of operators.
Some oils are even slightly perfumed so that they are more pleasant to handle.
There are still some properties which are important in lubrication but for
which no additives have yet been found. In straight mineral oils these include
thermal stability, demulsibility and air bubble release.
tive stability and fairly high viscosity-indices. They are often also chemically
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inert and fire resistant. Many are resistant to nuclear radiation. For ordinary
applications these advantages may not be important, and most of the synthetic
lubricants are very expensive.
Solid lubricants too have been extensively developed for exotic applications.
Their range of use is much greater than that of the synthetic fluids. Appropriate
solid lubricants are used at bright red heat, in equipment cooled with liquid
nitrogen, in pressure vessels developing 1000 atmospheres, and in space
vacua. Some are used in highly corrosive liquids, including concentrated
HzS04 at 40 "C, and in pumps for high pressure water at over 250 "C.
Graphite is still the most common solid lubricant, though the low friction of
natural graphite has been known and valued for centuries. The development
of synthetic electric-furnace graphites around 1900 and the subsequent dis-
covery of a method of maintaining fine graphite in dispersion provided a new
family of colloidal lubricants. These and many other forms of solid lubricant
have also been extensively developed with the impetus of aviation and space
programmes. Unlike the synthetic fluids, which have so far found an industrial
market mainly in the restricted field where fire resistance is paramount, solid
lubricants of the layer-lattice and polymeric types have considerable commer-
cial application.
Preparation of greases
Processing. The plant for manufacturing greases usually occupies a four-storey
building. Large storage tanks for oil and molten fat are located on the top
floor. The process is started by releasing a weighed quantity of fat, or fatty
acid, into an autoclave on the floor below. An aqueous alkaline solution or
suspension and a proportion of oil are added and the mixture is then saponified
for about half an hour under pressure. For the newer lithium-based soaps the
temperature may be as high as 200 "C. The freshly-formed molten soap is then
allowed to flow down to a mixing kettle on the first floor where it is mixed with
the required proportion of oil from the storage tank, and is slowly cooled.
Special additives can be incorporated at this stage, and any free acid or alkali
is neutralized in accordance with the titrations made using test samples taken
at intervals during cooling. Finally the grease is pumped through filters, while
still at about 70 "C, directly into storage containers where it is left undisturbed
for 24 hours before testing.
Some greases receive special treatment. For example the lithium hydroxy-
stearate greases are held at an equilibrium temperature and stirred vigorously
for a long period to produce soap crystals which have grown to an optimum
1ength:diameter ratio. Gelling agents other than soaps may need to be
dispersed in a colloid mill or homogenizer, and a dispersing agent may have to
be added. Clays, for example, are dispersed with a volatile agent such as
methanol. Some manufacturers of greases omit the saponification stage and
merely dissolve a commercial soap in heated oil. Continuous grease production
methods have been developed, but they have found little application.
Quality control. Many empirical tests have been produced for greases, some
of which have been standardized by the Institute of Petroleum and other
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bodies. It is now recognized that many of the older tests are not reliable since
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they may measure properties which have little influence on the quality of the
grease. Even the best test procedures, which are suitable for quality control,
may give results which are irrelevant or even misleading when applied to
service performance. As for oil technology, a better knowledge of the detailed
chemical and physical action of lubricants in actual use would assist in
formulation of more satisfactory tests. The problem is perhaps more difficult
with greases than with oils, because the greases do not even exhibit Newtonian
viscosity.
The most important physical test for a grease is the consistency orpenetrution
test. A cone of standard dimensions is allowed to descend under its own weight
into the grease at a specified temperature. The depth reached after five seconds
is measured on a dial depth-indicator reading in 0.1 mm intervals. Since the
result depends upon the amount of shearing which has been sustained by the
grease before the test, it is usual to pre-work the test specimen in the penetro-
meter vessel by forcing a perforated plate through it 60 times. This also serves
to mix heterogeneous samples. The National Lubricating Grease Institute of
the USA has classified greases according to this test in a scale which is accepted
throughout the world but is not always used in quoting consistency. A
variation of this test is one which determines the mechanical stability of the
grease by measuring the penetration after prolonged working, usually 1000
strokes of the perforated plate. Unworked grease penetration results are
unreliable because some shearing is inevitable in filling the test vessel.
Although the penetration test is widely used, it has been criticized. Mechani-
cal stability can be determined under conditions more closely relating to
service by the roll stabiEity test. In the standard form laid down by the Ameri-
can Society for Testing Materials a 5 kg roller rotates inside a cylinder
revolving at 160 rev/min. The consistency is measured in a penetrometer after
two or four hours working at ambient temperature. A good grease should not
have softened considerably. A test of this type can also be used at elevated
temperatures, and under other conditions for research purposes. A further
characteristic of greases which may be important in ball bearings is known as
cleurubility. Various greases having approximately the same consistency, as
measured by the penetration test, but different physical appearance can be
prepared from the same soap and oil by altering the processing technique.
Some are smooth and shiny while others are rough and look dry. Detailed
study with polarized-light microscopy reveals that the latter contain tangled
fibres which are partly crystalline, and are probably aggregates of smaller
fibres. These clear from the bearing quite rapidly and the grease exudes past
the seals, a phenomenon known as ‘winding out’. This depletion of the
reservoir of lubricant leads to early wear and failure. Smooth greases are less
aggregated and are so resistant to winding out that the packed grease remains
under pressure in the bearing, which consequently tends to run hot. Inter-
mediate textures are therefore chosen for most practical purposes.
For very soft greases the penetration value depends on both the yield stress
and the apparent viscosity because the cone descends at an appreciable speed.
It may be preferable to measure the cone resistance value (c.r.v.) by recording
the equilibrium depth to which a standard cone will sink under a specified
164 RIC Reviews
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Types of greases
Common greases. We have already noted that the commonest greases are lime-
based. The cheapest, known as Sett grease, is made from lime and rosin oil or
heavy fuel oil. This has long been used for rough service conditions. The more
modern calcium-based greases are usually made from a medium viscosity
petroleum oil with suitable fats and hydrated lime. To stabilize this type of
grease it is found to be necessary to include a small proportion of water. The
action of this water is not fully understood but electron micrographs have
Rowe 165
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twist in the soap fibres, which is thought to increase their mechanical stability;
though there has been a contrary suggestion that the similar twist seen in
lithium hydroxystearate fibres is attributable to the method of production for
electron microscopic examination. I t may be that the water assists crystalliza-
tion which, as we saw above, affects texture and durability. If calcium greases
are used at temperatures above about 60 "C, water will slowly be lost and the
grease will become unstable. Excess water can be tolerated because the
calcium soaps are insoluble and a water-in-grease emulsion may be formed.
This will not greatly affect the consistency, so the grease may be considered
water-resistant, in contrast to the greases containing water-soluble sodium or
potassium soaps which form thin grease-in-water emulsions and are liable to
leak away. Calcium greases are thus more suitable for example in rolling mills
which are cooled by water sprays. Sodium soaps are to be preferred when only
small quantities of water are present since the grease-in-water emulsion is less
corrosive than water droplets which may be expressed from moist calcium
greases. The sodium soaps are also stable to higher temperatures, even up to
100 "C. The upper limit is set by phase transformations to less ordered condi-
tions which occur well before the grease finally becomes a soap solution.
Several such transformations with appreciable latent heats can be detected in
some greases by differential thermal analysis (often referred to as DTA). This
alone casts doubt upon the validity of such crude measurements as the drop
point.
The sodium soaps are now tending to be superseded by lithium soaps,
particularly in the USA. These were introduced primarily for aircraft uses
because they combine a high upper service-temperature, up to 145 "C,with
good low-temperature performance when blended with low pour-point
synthetic oils such as the diesters discussed later (pp. 169-170). Lithium soaps
can also be compounded with silicone fluids. In addition to good thermal
stability the lithium-based petroleum-oil greases are mechanically stable,
particularly if lithium hydroxystearate is used, and their water resistance is
almost as good as that of the calcium greases. There are many industrial
applications, particularly as multipurpose greases, and it seems likely that
lithium greases will be used widely in future. It should nevertheless be recog-
nized that the general classification covers a very wide range of products, as
with calcium greases, and not every lithium grease necessarily has the desired
properties and range of utility. There is a tendency to emphasize the solid
phase in a grease, but the liquid phase can also have a strong influence on the
performance. In the USA the NLGI (National Lubricating Grease Institute)
survey reveals that the sales of lithium greases now equals those of calcium
greases. Aluminium-, bismuth- and strontium-based greases have been
rendered virtually obsolete; at best they found only a small market in the
USA. There may continue to be some demand for lead-based greases for
special applications because the lead soaps are surfactants conferring some
anti-corrosion and e.p. properties.
interest in other possible materials. The main demand has come from aircraft
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production and space research but there are possible commercial applications,
especially for clay-thickened greases. In all the new high-temperature greases
the gelling agent is insoluble in the liquid at all temperatures. Most interest has
centred on the silicone fluids as the liquid phase. Carbon black, or silica
powder obtained in the micron size range from sodium silicate can be used in
these fluids at temperatures up to 200 "C. The silica is, however, hygroscopic,
so if other fluids are used it is necessary to add a surface-active hydrophobic
compound such as butyl alcohol to 'waterproof' the dispersion and prevent it
breaking down. Greases composed of silica in silicone oil are resistant to
nuclear radiation as well as being temperature stable, and are good electrical
insulators. They also have low vapour pressure, but are very expensive.
Silicone greases containing boron nitride, a lamellar compound somewhat
resembling graphite except in colour, have been found effective for high
temperature applications.
Gelling agents of greater commercial interest are derived from mont-
morillonite clays such as bentonite. These are hydrated magnesium aluminium
silicates, which are easily obtainable and inexpensive but are stable over a
wide temperature range. The natural clays are hydrophilic, like silica, but they
can be reacted with a surface-active ammonium salt or an amide to produce
an affinity for oils. It seems likely that clay-based petroleum greases will
compete with the lithium-based greases for the multipurpose commercial
market. Clays can also be dispersed in silicone fluids for high-temperature
applications. They can, however, be rendered unstable by strong surface-active
agents, such as the conventional e.p. additives.
There will undoubtedly be considerable activity in the field of high tempera-
ture greases for some time to come. There may also be scope for improving
specific properties. Thus, for example, it is claimed that sodium octadecyl
terephthalamate, formed by reacting NaOH with the methyl ester of n-octa-
decyl terephthalamic acid, makes greases which are much more water resistant
than those using sodium stearate; while at the same time the sensitivity of
clay-based greases to additives is avoided.
during long periods of storage. More active agents such as phenothiazine may
be necessary for protection under more severe conditions of agitation and
higher temperatures. In the presence of copper alloys a further surface-active
compound, often disalicylidene ethylene diamine, is used to form an adsorbed
layer on the metal and so prevent catalysis.
Corrosion is less likely to be troublesome with greases than with oils. Most
greases are either naturally hydrophobic or can readily be converted, and they
usually form a relatively impermeable coating on the bearing. To allow for
condensation or the presence of moisture, corrosion inhibitors are however
sometimes required. Oil-soluble lead soaps can be incorporated. To protect
steel surfaces, micron-sized sodium nitrite crystals may be dispersed in the
grease. These dissolve in water to form a passivating solution. Some greases
used under severe conditions require fortifying by the addition of e.p. com-
pounds. Mild e.p. action can be provided by lead soaps but chlorinated or
sulphurized organic compounds may be used to provide greater protection
from frictional damage to the surfaces. As with oils, sulphurized fatty acids
are among the most effective e.p. additives.
tional oils the upper temperature limit is set by the stability of the carbon-
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Such fluids are several times as expensive as petroleum oils, but are used in
atomic energy and spacecraft work. They have found some uses in chemical
engineering because of their general inertness.
Esters. The ester linkage C-0-R is much more stable to heat than the C-C
bond, and forms the basis of the most important group of synthetic lubricants
at the present time. Castor oil, the original aircraft engine lubricant, is a
natural ester but it has poor thermal stability. It consists mainly of the
triglyceride of ricinoleic acid and can be represented by:
CH2.O.CO-R
I R=CH3*(CH2)5*CHOH*CH2.
CH
CO * R
CH * 0. II
I CH.(CH2)7*CO2H
CH2.O.CO.R
CH3
Monobasic acids are also reacted with dihydric alcohols, and more complex
esters formed from polyhydric alcohols - including neopentyl polyol esters
Rowe 169
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R'
I
0
I
R-0-Si-0-R"
0
I
R"
The substituent groups can be alkyl or aryl, derived from alcohols reacted with
silicic acid. These compounds are relatively easily hydrolysed to silica.
Tetraethyl orthosilicate is actually used to preserve masonry. The long-chain
alkyl derivatives are more resistant to hydrolysis and are consequently
preferred as lubricants. These also show the highest viscosity index, but their
main application is in hydraulic transmission rather than in lubrication. They
are non-corrosive, but do not exclude water, so rust-preventatives are usually
added. Organosilicon fluoroesters, stable in air at 200 "C and in the absence of
oxygen at 350" C, can be used as lubricants, sometimes with alkali-metal salts
as antioxidants.
Phosphate esters of the type:
OH
I
0.R
I
R.O-P=O with, e g . R =
0.R
have been used for many years as antiwear additives, the best known being
tricresyl phosphate shown above. Some, such as alkyl polyethyleneoxyphos-
phate esters have been reported to show good load-carrying capacity in a four-
ball testing machine. They are now available in a wide range of viscosity and
other properties but the main interest is in their good fire-resistant properties.
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When used as lubricants, they dissolve many seal and gasket materials and
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fairly easily hydrolyse to corrosive acids. At temperatures below about 100 "C
they have good performance in both hydrodynamic and boundary conditions.
Ethers. Various ethers have been suggested for aerospace uses. Polyphenyl
ethers may be stable oxidatively to 260 "C and thermally to 400 "C. Metal
chelates and other organometallic compounds can inhibit oxidation in these
ethers though conventional antioxidants such as amines and phenols are
ineffective. Some alkylated aromatic ethers are thermally stable to 450 "C and
can withstand high radiation levels. They are used in atomic reactors and in
gas turbines. Some inhibited aromatic ethers are effective as lubricants from
-35 "C to 250 "C but are less resistant to radiation.
Elaborate formulations have been proposed, for example 65 per cent
+
bis-(m-phenoxybenzene) 30 per cent bis(m,p-diphenoxybenzene) +
5 per
cent bis(p-phenoxybenzene). This is recommended to be used with 1 per cent
by weight of CC13C02H or with Zn, Bi or other salts of trichloropropionic
acid, presumably to confer boundary lubricating properties since these are
usually poorer in the absence of carboxylic compounds.
Silicones. Silicone fluids are used for many applications. They are very inert
and have very poor boundary lubricating properties unless halogenated. All
the common additives reduce the stability of the silicones, but these fluids
show very little change in viscosity with temperature and are thus good
lubricants under hydrodynamic conditions. Most of the silicone lubricating
fluids are semi-organic polymers with repeating Si-0 bonds along the chain :
R
The side groups are usually methyl or mixed methyl and phenyl. Chlorine may
be substituted into the phenyl groups, producing greatly improved results in
wear tests. The long molecules are flexible, without branching or cross-linking
which would increase the dependence of viscosity on both temperature and
pressure, and the viscosity varies less than that of any other synthetic lubricant.
They remain liquid even with high molecular weights. For hydraulic systems
this is advantageous, but a viscosity increase, and even solidification under
pressure, can often be valuable in elastohydrodynamics and lubrication in
metalforming. At high temperatures, 360 "C in the absence of air, thermal
degradation reduces the molecular weight and the viscosity. In air the silicones
can be used at 200 "C, where a slow oxidation increases the viscosity. Organo-
selenium compounds, for example 5-methyl-benzo[2.1.3]selenadiazole,have
been used as antioxidants conferring fair stability at temperatures up to 300 "C.
At 150 "C they are stable indefinitely. They have a very low vapour pressure
and are widely used as vacuum diffusion pump fluids. The flash points are
generally high (280 "C), but the spontaneous ignition temperature may be
below that of the phosphate esters. For low temperature use their exception-
ally low pour point (-70 "C) may be significant. It has also been suggested
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improve the wear preventive properties, equalling those of a good mineral oil,
but with greater oxidation resistance.
A minor use of the silicones in lubrication has already been mentioned. A
few parts per million, when finely dispersed, will effectively collapse foam.
the vehicle has passed outside the filtering influence of the atmosphere, and
high electron and proton intensity in the van Allen band. Solar flares increase
all the radiations and also produce heavier ions. All these sources provide
energy for chemical reactions that can degrade or decompose lubricants.
For external lubrication, the vapour pressure requirement may be dominant.
Vapour-diffusion pump oils have been used; for example, phenyl methyl
silicone fluids and sebacates such as di-2-ethylhexyl sebacate. Diesters and
polyphenyl esters can also be used. Somewhat surprisingly it has been found
possible to use certain mineral oils of low volatility, though these may have
vapour pressures of about 10-8 torr. The loss of fluid by evaporation can be
substantially reduced by using labyrinth seals, or the fluid can be replaced by
wicks or other devices. In this context it should be remembered that bearings
usually become warm. At least one satellite camera failure has been attributed
to condensation of volatilized bearing oil onto the lens. Eventually this re-
evaporated and the lens became clear again.
The advantage of the mineral oils is their better boundary lubricating ability,
though this may be impaired by lack of oxygen. Boundary lubricating proper-
ties can be imparted to the inert fluids by halogenation; thus trifluoropropyl
methyl polysiloxane appears to be useful. A chlorinated methyl phenyl silicone
is reported to give good rolling contact fatigue life at 180 "C.
cal hysteresis of rubbers. Rubbers with high hysteresis can be used on the tread
of pneumatic tyres to provide increased resistance due to rolling when the
sliding component is diminished by a lubricant, thus affording protection from
skidding on wet roads.
The sliding friction between dry surfaces is obviously useful in transmitting
tractive forces, but most of the thought associated with dry sliding has been
directed towards reducing the friction force, and especially the wear which
usually accompanies high friction. This problem too was recognized by the
technologists of ancient civilizations, who realized that some combinations of
materials had desirable tribological properties. For example, a mural painting
from Egypt clearly shows a stone bearing-cup being used with a bow drill.
This principle is still very important and there is currently considerable
interest in jewel and ceramic bearings for mechanisms operating in space
environment. We have already seen how some of the widely-used modern
lubricants and additives, such as the fatty oils, were also anticipated some
thousands of years ago. Nevertheless, the processes of friction and the detailed
actions of lubricants have been studied systematically for only a few decades.
The majority of the research in this field has been related to metals and
metallic alloys. These are, of course, the most widely used materials in
machinery of all types.
(p. 142). Any displacement of one atom relative to another by less than the
effective radius of the potential well (ignoring small probabilities of escape)
will raise the energy of the appropriate atoms, but the position is unstable and
on release of the displacing force the atoms will revert to their equilibrium
spacing. I t is in fact possible to calculate the elastic modulus (stress/strain) on
this basis. If however a tensile displacement is given which separates one atom
from another beyond the position of the subsidiary energy maximum or hump,
the atom cannot return. In principle it would be expected that this position
would be unstable with respect to further separation and consequently fracture
would occur. Under special circumstances, such as may occur in metallic and
non-metallic whiskers, this can be observed. These whiskers have been of
great interest in the past decade because of their very high strength. Usually, in
bulk materials, the atoms will separate into new equilibrium positions relative
to different atoms, at much lower stress levels. This is known to be essentially
a shear process, analogous to moving one row of close-packed spheres over
another. Each sphere in the row moves from one low-energy position to the
adjacent one, without losing contact. Such a process requires little energy if for
example one atom in a row is missing, and the atoms move along one at a time
to fill in the holes. Obviously this process can be regarded as the vacancy
moving one space at a time in the opposite direction. As shown in modern
textbooks of metallurgy and solid-state physics, all common materials contain
a high density of vacancies and dislocations in the crystallographic structure.
Dislocations can be considered as extended vacancies, in which for example
a whole row or plane is missing. They move with relatively low activation
energy and cause plastic deformation to occur at a stress (energy) level much
lower than that required in theory for elastic fracture. Because plastic flow is
essentially a shear process it can be initiated whenever the appropriate shear
conditions are established, whether the applied forces are tensile or com-
pressive.
The final size of the indentation made in our experiment with butter is thus a
measure of the amount of plastic flow produced, and the extent of the recovery
from the deformed state is a measure of its elastic properties. This type of test
is very valuable, and is widely used in metallurgy to determine hardness. The
hardness number, which is really a yield pressure expressed in kgmm-2, is
calculated by dividing the applied load W by the projected area A of the
indentation or, in a more common form of the test, by the curved surface area.
Elastic recovery is usually ignored for metals. It will be clear that soft materials
will deform more under a specified load and the area of contact between the
sphere and the test block will be greater.
We can now return to the friction experiment with solid krypton. Because
the interatomic forces are relatively weak, and the resistance to plastic
deformation is much lower still as a result of the crystallographic imperfec-
tions, the hardness of krypton is low. Direct measurement has shown it to be
of the order of 0.25 kg mm-2 at the temperature of liquid hydrogen, compared
with crystalline NaCl, for example, which has a hardness of about 20 kg mm-2
at room temperature. Two krypton specimens placed in contact under load
will deform plastically until the area of contact between them is large enough to
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support the load W a t their mutual yield pressurep, which depends to some
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extent on the geometry but is roughly equal to the hardness. If for example the
load is 25 g as in a typical friction experiment, the contact area will be
25 x 10-3/0.25, about 10-1mm-2, compared with about 10-3mm-2 in a
comparable experiment with rock salt. As we saw earlier (p. 140), the surface
free energy of a solid is considerable, and so when two surfaces are brought
into intimate contact by the processes of plastic flow it is energetically ravour-
able for the solids to coalesce and so to eliminate the interface. The force
required to deform such a region subsequently in shear will be comparable
with that required to shear a similar area of polycrystalline material. The shear
stress, found by dividing the force F by the area of contact A , is usually
denoted by s. Thus we may suppose that if the resistance to sliding arises from
the necessity to shear the junction between the two surfaces, the frictional
force F will be given by
F = A.s = (W/p)S
Because the shear strength and yield pressure are inherent properties and their
ratio remains nearly constant, the frictional force is proportional to the normal
load for many materials. This is one of the two classical laws of friction. The
equation also shows that F is directly proportional to the area of intimate
contact. Because all practical surfaces are rough (p. 139), this is usually very
much less than the apparent geometrical area so the friction force is found to
be independent of the latter. This is the other important law of friction. The
coefficient of friction p is found by dividing the friction force by the load :
It is known from the general theory of plasticity that the stress required to
cause yielding in pure shear is approximately 0.6 times the stress to cause
yielding by simple compression. For reasonably flat sliders the coefficient of
friction would thus be expected to be about 0.6. The coefficient of friction for
solid krypton approximates to this value, but as we shall see later this agree-
ment is fortuitous, resulting from the interaction of two opposing effects.
Nevertheless, the simple theory is sufficient to show why the coefficient of
friction is practically unaffected by the change in plastic yield properties,
which differ by a factor of 100 between a van der Waals solid, krypton, and an
ionic solid, NaCl. The coefficient of friction depends upon the ratio of two
mechanical properties but both of these depend upon the same basic atomic
displacement process of shear within the material, so the ratio remains
constant.
In general, perfect cohesion between two solids in contact will not be
experienced. Two important factors are the topographical mismatching and
chemical contamination. A perfect match can be obtained only in special
circumstances. If a mica sheet is partially cleaved and the two leaves are
released they may fit together perfectly. A strength equal to that of the original
sample can then be measured if the experiment is performed rapidly. It has
already been shown that clean surfaces in air become contaminated spon-
taneously and at a high rate. Therefore, if the mica surfaces are left exposed to
air for a short time the surface energy will be greatly reduced by adsorption
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and the adsorbate will not be eliminated when the leaves come into contact
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again. The measured junction strength is then greatly reduced even for
perfectly matching surfaces.
In the krypton experiment the contact between the sliders is intimate be-
cause the plastic deformation allows the surface topography to adjust to
conformity, at least partially. At the low temperature of liquid hydrogen the
rate of contamination will be low. This system is consequently suitable for
analysis, though it is experimentally more difficult than common frictional
studies.
The frictional behaviour of krypton is also interesting at higher tempera-
tures. As the temperature is raised the hardness diminishes but since the shear
strength also diminishes, the coefficient of friction remains unchanged between
20 K and 70 K. If however the experiment is interrupted and the specimens
are allowed to stand under load at an elevated temperature, the area of
contact will slowly increase. This is the same phenomenon that is observed in
creep of metals. If a weight is hung on a metal wire at a high temperature
(above about half the melting point 8, measured in degrees absolute) the wire
will slowly extend plastically. The process is attributable to self-diffusion and
an activation energy can be calculated from the results. For solid krypton this
amounts to about 0.25-0.5 kJ mol-1, as determined from the creep in hardness
tests. Incidentally, a tensile creep-test on a metallic wire can be used to
determine the surface tension of a single crystal. The creep rate is measured as
a function of load at a given temperature near the melting point. A linear
relationship is obtained, from a balance between the tendency of the wire to
contract under surface tension and to extend under load. The load correspond-
ing to zero creep-rate exactly balances the surface tension, and the results are
in fair accordance with the theoretical predictions discussed earlier.
In the interrupted type of friction experiment the area of contact becomes
larger, but when sliding is resumed the shear yield stress remains the same as
before the pause, so the frictional force is initially greater than before. After a
short distance of sliding the conditions revert to normal. This behaviour can
also be observed in metals at high temperatures and in some solid polymers at
room temperature.
As the temperature is still further raised, beyond about 8 = 0.9 Om, a large
drop in friction is observed, attributable to surface melting. If a liquid film
forms between the surfaces the interfacial shear strength is greatly reduced,
though the area of contact is still determined by the substrate strength and
remains unaffected by the melting, so the coefficient of friction falls. Values
well below p = 0.1 have been recorded with krypton. Similar low coefficients
of friction have been measured with ice near 0 "C. Surface melting has been
shown to account for the low friction of skates and skis on ice and snow at
moderately low temperatures. When the temperature is well below zero as in
the polar regions of the world the frictional resistance of sledges is known to be
greatly increased. It is possible to observe the same effect of surface melting
on metals when the speed is high enough. Bowden has suggested that if speeds
of 2000 mile h-1 could be maintained it would be possible to ski on a copper
mountain. Practical use of this phenomenon is made in the copper driving
bands of artillery projectives.
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p = - = - = -As A Cc w-113
w w w
It is found that the friction is little influenced by lubricants and there is a
widespread but fallacious belief that the friction of diamond is inherently low.
This is commonly associated in a general way with the extreme hardness of
diamond, about 2000 kg mm-2, but as we have seen it is the ratio of shear
strength to hardness which determines p, not the absolute value of hardness.
We shall find that there are some highly anisotropic solids, such as molyb-
denum disulphide, which exhibit a low ratio of s t o p , but for most materials s
and p are closely related, and diamond shows high values for both. Actually
diamond is slightly anisotropic and directional dependence of p can be
detected. The low coefficient of friction usually measured results from the
reduction of surface fields by adsorption from the atmosphere. Then, of course,
if the interfacial shear strength is no longer a property of the slider material
but has a much lower value associated with the adsorbate, the friction will be
low and a high hardness value will reduce p still further. It is possible to
demonstrate this experimentally by outgassing the diamond surfaces, that is,
heating the diamonds to a high temperature in a good vacuum to remove as
much as possible of the chemisorbed material, and subsequently cooling to
room temperature while maintaining the vacuum. The coefficient of friction
between two such diamonds will be increased about 10-fold. The shear
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strength deduced from the frictional force and the measured contact under
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pairs or in contact with a metal. This is somewhat lower than the friction of
rock salt, for example, but higher than that of diamond which has not been
specially cleaned in vacuum. A notable exception is polytetrafluoroethylene,
to which we shall refer in detail later because it possesses unique low-friction
properties.
J.
[-NH(CHz)lo* CO. NH(CH2)lo.CO-1, + 2nH20
Many other polymers have similar frictional properties.
Experiments have been carried out over a very wide range of loads with
nylons and other polymers. It is found that the influence of load on frictional
force can be represented by:
F = aW + bWn or more simply by F = kWn
For a simple spherical slider with normal load the area of contact varies with
the $ power of the load, as for elastic sliders such as diamond. As the com-
plexity of the surface increases, the index n tends towards unity, also as men-
tioned before. The friction force does not bear exactly the same relationship to
load because the shear strength increases slightly with pressure. The results are
also speed dependent because the viscoelastic deformation resembles creep, in
that the area of contact under load increases with time of loading and con-
versely decreases with increasing speed. Heating of the surface at higher
speeds tends to soften the load-bearing region and so to produce larger areas
of contact. It may also help to desorb surface contaminants and thus promote
welding. Both these effects will increase the frictional resistance, but if the
speed is very high it may be possible to produce surface melting, which, as
with krypton, ice and other materials, gives very low coefficients of friction.
At moderate speeds it is believed that the flexibility of the long molecules in
the polymer chains is the dominant feature. Rigid cross-linked polymers show
relatively small dependence of friction upon speed or temperature.
mills, where it is often essential to use bearings which will perform well in the
presence of water. Such bearings give very low friction, with coefficients of
about p = 0.006. They can also be used to replace lignum vitae in the stern-
tube bearings of ships. Formerly this dense wax-filled natural wood was
widely used for this and similar purposes, but more recently it has become
common to use oil-lubricated white-metal bearings with a seal to prevent
ingress of sea-water and thus to reduce corrosion in the bearing. An attractive
feature of the reinforced resin bearings is that they are much more resistant to
nuclear radiation than the thermoplastic materials and so can be used in
nuclear power plant, needing no attention. Reinforced resins are also quite
widely used in gears and numerous small sliding components.
A second group of thermosetting resins used in bearings is based on
epoxides. These are in general more expensive, but give good performance
especially when filled with graphite or molybdenum disulphide. They may
conveniently be sprayed onto metal backing strips.
porous metal matrix, usually made from sintered bronze powder. The viscosity
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of PTFE is very high above its transition point (327 "C) (despite the postulated
low interaction forces of the molecules) so injection moulding is unsatisfactory.
Bearings are usually made by pressing powdered PTFE into the surface of the
porous metal and sintering at a temperature above the transition. Other forms
of bearing are coated with PTFE but difficulty arises from the marked lack of
adhesion between PTFE and other materials. Various techniques can be used,
such as weaving PTFE fibres together with cotton or glass fibres, so that the
polymer appears on one side and the cotton cloth can easily be attached by
resin or other adhesive to a steel backing. Another method which has been
used in the USA involves chemical attack by sodium dissolved in liquid
ammonia. Surfaces so treated can form adhesive bonds, and it is interesting to
notice that they also show high friction. It is also possible t o heat a PTFE
surface to about 400 "C, which is believed to liberate free radicals that can
then be copolymerized with some more reactive monomer.
brush in an evacuated bell jar. As the gas pressure is reduced the sliding mode
will change suddenly, and the brush will wear out rapidly in a cloud of dust.
After the experiment it will be found that the debris even contains small
metallic turnings. Small traces of water vapour or other contaminants will
prevent this catastrophic wear and maintain the friction at a low level. Clearly
the lubricating characteristics of graphite are associated with adsorption. In
contrast, molybdenum disulphide shows low friction over a wide temperature
range in high vacuum, but is readily hydrolysed in moist air to Moo3 with
production of H2S and SOz. When this occurs, the low-friction property is
lost.
Any theory of the lubricating action of lamellar solids must consider these
marked differences between graphite and molybdenum disulphide, which are
also found in various degrees with other lamellar solids. There have been
several hypotheses for specific materials, but the most comprehensive interpre-
tations fall into two groups. Both emphasize adsorption but one considers
adsorption on the basal planes to be dominant while the other attributes the
action of vapours mainly to adsorption and interaction at the edges of crystal-
lites. To follow the arguments, which are still the subject of controversy, it is
necessary to consider the structures in some detail.
The characteristic spacing of the C-atoms in graphite is 140pm in contiguous
hexagonal rings, forming the lamellae. The bond energy is about 20 kJ mol-1.
The rings lie in parallel planes separated by 340pm. The interlayer bond
energy is difficult to specify with precision but has been assessed at values from
2.4 to 4.8 kJ mol-1, depending on the material studied. It is considerably
greater than the typical van der Waals bond energy of about 1.2 kJ mol-1 and
the reason for this is apparent from the electronic structure of graphite. All
C-atoms have two s- and two p-electrons in the second shell, and in graphite
one 2s-orbital is hybridized with the two 2p-orbitals to form three equivalent
orbitals spaced mutually at 120 O in one plane. These overlap with the orbitals
of adjacent C-atoms to form covalent a-bonds. The remaining 2s-electron
from each C-atom forms part of a n-electron cloud between the layers that is
believed to increase the interlayer bonding. This cloud is also responsible for
the electrical conductivity of graphite. Molybdenum disulphide has a similar
crystallographic structure, but it is a very poor electrical conductor. Each
layer consists of a plane of Mo-atoms between two planes of S-atoms. The
separation of the Mo-atoms, which are hexagonally disposed, averages 320
pm but the distance between one Mo-layer and the next is 620 pm.
One hypothesis for the action of adsorbates on the friction of graphite is
that the n-bonding is weakened, thereby reducing the shear strength, at least
between the layers near the surface. MoS2, having naturally weak van der
Waals bonding between the S-layers, shows low friction in the absence of
adsorbates. In support of this theory it is shown that graphite can form inter-
calation products, for example with bromine, which increase the interlayer
spacing and seriously reduce the mechanical strength, even causing the
material to crumble into powder. Direct measurements of the strength of
graphite show a marked increase, by 50 per cent or more, after thorough out-
gassing. Bend tests show strong anisotropy; the effect of vapours is most
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purposes. It is likely that some of these will be useful, and may also find
applicationin high-temperature terrestrial devices,though they are all at present
expensive. MoS2 provides low friction in vacuum at temperatures up to
900°C. Both graphite and boron nitride show inherently low friction in
vacuum at temperatures in excess of about 1500 "C.The strength of graphite
is also lower at these temperatures, despite reports to the contrary. It has been
suggested that graphite is unique in showing a marked increase in strength
with increasing temperature, up to 2000 "C. It seems likely however that the
increase is due to removal of adsorbed material. If the graphite is outgassed
for a long period at a temperature of about 2000 "C it shows a relatively high
shear strength of about 1.5 kg mm-2 at least 50 per cent greater than under
ordinary conditions. This is maintained at room temperature if contamination
is prevented. A short exposure to air immediately reduces the strength.
Usually it is not feasible to form these lamellar compounds directly on the
surfaces to be used, and they are often applied as powders. An important
feature is then the ability to form a coherent film on the substrate. It has been
suggested that the dominant characteristic for this purpose is the ability of the
lamellae to penetrate into the metal or other surface during sliding, so that
they form barriers behind which the powder may accumulate. An appreciable
resistance to deformation and fracture of the individual lamellae is con-
sequently required. Talc, for example, is a relatively soft hydrated magnesium
silicate corresponding to Mgs(OH)zSi4Olo and is unable to penetrate a steel
surface. Talc, although inherently a low-friction material, will not lubricate
steel but will lubricate gold, whose penetration hardness is about 30 kg mm-2
compared with 150 kg mm-2 for steel. Mica has a structure somewhat similar
to that of talc, but usually has strong potassium bonding between the layers,
with a representative composition K(OH)2A12(Si3Al)Olo. The shear strength
of mica has been measured directly and is found to be 10 kg mm-2. The fric-
tion of mica is normally high, but the potassium atoms can be progressively
leached out, weakening the structure. Carefully controlled experiments of this
type might be very useful in elucidating the general problem of the low-friction
properties of lamellar solids.
prevent undue formation of Moo3 from MoS2. The smallest particles used
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Friction of metals
Historically, metals have been studied much more extensively than the solids
we have so far considered, but chemically and physically they are more com-
plex and they exhibit simultaneously many of the features discussed separately
above, especially when contaminated by the atmosphere or by lubricants.
At ordinary temperatures metals behave as elastic and plastic solids, but if
the temperature exceeds about half the melting point, in degrees absolute, the
elastic contribution can usually be ignored. The metal is then relatively soft
and deforms plastically with appreciable creep. Thus lead (m.p. 600 K)
exhibits 'high-temperature' behaviour at room temperature (20 "C, 293 K).
Indium (m.p. 429 K) shows still less elasticity. Experiments with lead and
indium show that their frictional behaviour is somewhat similar to that of
krypton. As long ago as 1724 an experiment was performed which demon-
strated appreciable adhesion, with a tensile strength of 150-300 kg mm-2,
between two cleaned lead balls which had been placed in contact under a load,
with a slight twisting motion. After the introduction of the asperity-welding
theory, two centuries later, it was believed that this type of adhesive junction
or weld was primarily responsible for the frictional resistance between two
metallic sliders. The coefficient of friction would then be given, as already
discussed in connexion with the van der Waals solids, by
p =F/W= AslAp
because the contact area A is determined at any given load W by the yield
pressure p of the metal, and the shear strength s of the weld is presumed to be
equal to that of the solid metal. Since this theory ignores elastic deformation,
it would be expected to apply most accurately to lead and to indium. Numeri-
cally the yield pressure p is known to be related to the shear strength s of a
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where Sm is the yield stress of the metal in the absence of normal stress. If it is
assumed that siis some finite fraction p of Sm, the coefficient of friction can be
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written :
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The frictional resistance is thus due entirely to the average, low shear strength
of the interface, which need not contain any contribution from metallic junc-
tions. In fact, radiotracer experiments show that under lubricated conditions
the amount of metallic contact makes a negligible contribution to the friction,
though it is clearly important in wear.
It is curious that the experiments performed to examine the deficiency of the
adhesion theory confirmed on the one hand the possibility of strong adhesion
and led to a more complex formulation which eventually reduced to the simple
formula for lubricated conditions, but on the other hand showed that in this
form the friction was not dependent upon metallic adhesion. The determining
mechanical parameters for most practical purposes are the yield pressure or
elastic properties of the metal substrate and the shear strength of the lubricant
layer. I t is therefore important to consider these layers in some detail.
much higher in a region within about 100 nm of the surface. It is not yet
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the superior lubricating properties of the fatty acids. The durability of all such
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degassed lubricant which excludes the air. The friction is then much higher
than usual.
The lubricant layer formed by reaction of copper, oxygen and a fatty acid is
likely to be a copper soap. If a preformed copper laurate, for example, is
smeared onto a copper surface the friction is the same as that of copper
lubricated with lauric acid in air. Moreover, the low friction persists for both
as the temperature is raised to 100 "C, as mentioned before, well above the
melting point of lauric acid. Electron diffraction studies confirm this con-
clusion. It is necessary to use low-energy electrons in order to obtain clear
diffraction patterns from the surface layers, without the confusion from the
substrate which would arise if more penetrating ,%radiation or X-rays were
used. Layers of a solid paraffin show a characteristic rhombic pattern with the
carbon chains perpendicular to the surface. Fatty acids show an interesting
structural transition. The outer layers form into monoclinic crystals but the
first molecular layer at the metal surface shows a different pattern, indicating
adsorption of the polar groups at the interface with the long hydrocarbon
chains normal to the surface. The outer layers become distorted by rubbing,
but the monolayer is remarkably stable. It is found that the greatest degree of
orientation of the monolayer is produced in films formed by reaction between
the metal or oxide and the fatty acid.
When the temperature of the substrate is raised, the electron diffraction
pattern shows disorientation as the melting point of the fatty acid or of the
reaction product is approached. The diffraction pattern of the metal does not
however become clear until a considerably higher temperature is reached,
showing that soap films remain adsorbed well above their melting points.
muir trough on carefully cleaved mica which was molecularly flat. The back
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surfaces of the mica had previously been partially silvered so that the area of
contact between the two cleaved faces could be examined with multiple-
beam interferometry. The interface between the two strips of mica, with the
deposited soap film, was then subjected to normal and tangential forces. The
tangential stress sufficient to cause macroscopic motion was recorded as the
shear strength of the monolayer. This was found to be about 250 g mm-2 for
calcium stearate. A similar value has been deduced from sliding experiments
with a pointed crystal of sodium stearate on a clean platinum surface. The
coefficient of friction in the latter experiment was about p = 0.3. If the same
fatty acid is used as a lubricant film between two platinum sliders the friction
is lower, p = 0.1, but far from being as low as the simple theory of friction
would suggest. The yield stress p of platinum is about 40 kg mm-2, so if
p P s / p we should expect 0.25/40 2 0.006. The difference from p fl 0.1 has
been explained in a general way by supposing that the shear strength is greatly
increased by the pressure. This is at least plausible, by analogy with the known
strong dependence of viscosity of organic liquids on pressure, but little detailed
work has been done on this. It seems likely that even at this low shear-stress
level some junction growth occurs.
An attempt has been made by Cameron to evaluate the shear strength of an
adsorbed hydrocarbon layer theoretically. The long-chain molecules are
assumed to be orientated perpendicular to the opposing surfaces. It is then
possible, as shown by Miiller, to calculate the van der Waals attraction be-
tween respective -CHz- groups and to sum these over the molecules. The
repulsive forces can be calculated from the adjacent hydrogen atoms, the
difference between these two values giving the equilibrium energy, which can
be considered as existing at a potential well, as for single atoms (p. 142). This
provides an upper limit to the force required to move each hydrocarbon
chain from one equilibrium position to an adjacent one. A typical value of the
shear strength derived on this basis is about lo4 N cm-2 or 10 kg mm-2, which
is considerably higher than the measured value for calcium stearate and dem-
onstrates the possibility of the frictional resistance being entirely attributable
to molecular interaction in the lubricant.
about 300 "C. In the open laboratory a film of FeC13 deposited on a steel
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specimen will also provide low friction up to this temperature. Similar results
are obtained if the surfaces are lubricated with stearyl chloride, even if it is used
as only a 0.5 per cent solution in a paraffin. It can thus be concluded that the
action of an e.p. compound is to produce a surface film, of iron chloride for
example, which will withstand higher temperatures than the organic materials.
The process is essentially one of controlled corrosion. Hydrochloric acid will
form a satisfactory lubricating layer on steels, but is too corrosive. The
compound used should remain stable in the temperature range over which
boundary lubricants are effective, but it should decompose to liberate the
inorganic ion when the temperature rises above this. Extreme-pressure
additives are, therefore, commonly used in conjunction with boundary
additives. Various compounds of chlorine can be used. Even inorganic com-
pounds such as SeClz can provide e.p. lubrication, but the most widely used
chlorine additive is commercial chlorinated paraffin. This is mainly composed
of long-chain paraffins such as CH3.(CH&s wCH2C1, but the commercial
material contains an excess of dissolved chlorine which is thought to be labile.
It is important to recognize that moisture may adversely affect these lubricants.
HCl may be formed in the bulk lubricant if it is exposed to water vapour or
water, with consequent risk of corrosion. The chloride films themselves are
easily hydrolysed and may lead to rusting, as well as losing their lubricating
effectiveness.
Sulphide films are less sensitive to moisture and are stable at higher
temperatures. The reaction film of sulphide formed on iron exposed to HzS
at an elevated temperature will continue to lubricate in the absence of air at
temperatures up to about 750 "C, but the friction is considerably higher than
that of the chloride film, probably because FeS does not have a lamellar
structure. Sulphide films can be formed with ammonium polysulphide, or with
flowers of sulphur dissolved in a paraffinic oil. Sulphurized oleic acid is a
commonly used additive combining e.p. and boundary properties. Sulphur
compounds are used in lubricating oils when local high temperatures are
anticipated and where the general operating conditions are too severe for
chlorinated oils. For the former purpose they are usually compounded with
chlorinated and boundary additives to provide low friction over the lower
temperature range. It is also believed that the chlorine assists in the reaction
between the metal and the sulphur.
The same compounds are used on other metals, for example the copper
alloys. There are, however, complications ;long-chain paraffinic sulphides and
some other compounds such as dithiocyanates will provide e.p. action on steel
but not on copper. Mercaptans will react with copper and provide good
lubrication over a wide temperature range, but are unsuitable for general use.
Staining, which may be inevitable if reaction is to occur, can be undesirable in
many applications where the appearance of copper or aluminium alloys is
important. For aluminium even the fatty acid reaction in boundary lubrication
may spoil the surface.
It seems likely that a new family of e.p. compounds based on iodine will
become available. Vacuum-chamber experiments showed some years ago that
an effective lubricating film of Ti12 could be formed by heating titanium in
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MoS2 and shows low friction at temperatures up to 250 "C.Because of its inert
surface oxide, which will not react with common boundary lubricant additives,
titanium is otherwise very difficult to lubricate. Fatty acids and chlorinated oils
have little more effect than paraffins. Recently it has been found that iodine
dissolved in organic fluids can provide e.p. lubrication for titanium. Butyl-
benzene is reported to be a particularly effective solvent because it is hydro-
phobic and prevents hydrolysis of the Ti12 which is otherwise easily decom-
posed. I t is reported that simple solutions of iodine in paraffinic oil can also
lubricate titanium, stainless steel and even glass. There may be a fruitful field
for development of these fluids if health hazards can be avoided.
cutting, grinding or other fabrication process are worn away and the surfaces
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come into better local and general conformity. The rate of removal of material
decreases progressively during this period and eventually reaches a low steady
value when the machine is fully run-in. In the absence of adventitious circum-
stances this low rate will persist with little alteration for a very long time, in
fact for the useful life of the machine. The wear rate will finally increase again,
for a variety of possible reasons. Steady wear may have increased the mechani-
cal clearance between the sliding members to such a value that a bearing, for
example, is loose and allows percussive loading or vibration. The wear debris,
which is usually strain-hardened or oxidized and consequently abrasive, may
also have accumulated in sufficient quantities to aggravate the wear. Often
local corrosion leads to pitting and to stress concentrations which initiate the
catastrophic stage of wear. Even in the absence of these causes, long repetition
of cyclic stressing may produce surface or subsurface fatigue failures, so that
small fragments of the surface break away. This is particularly likely to occur
in gear teeth and in ball bearings where high local loading occurs for short
periods at frequent intervals. Any of these conditions, once established, will
tend to become rapidly worse. The machine will then need to be renovated or
replaced.
Earlier we mentioned the co-operative chemical and mechanical actions of
formation and removal of surface films with e.p. additives, which are beneficial
in the running-in stage. The steady state of wear is discussed later in this
section. To prolong the life of a machine it is clearly desirable to delay
the onset of the final stage. This is mainly the province of the mechanical
designer, who endeavours to avoid high stress levels, vibration, and shock
loading ; to exclude abrasive materials and to provide adequate lubrication.
Proper attention to the chemistry of the overall system can however be very
important. All the materials must be chosen to avoid corrosion due to direct
chemical or electrochemical attack, and the lubricants must have no deleterious
effects even if they decompose or oxidize in use. Particular care must be taken
if, because of relatively high temperatures, it is necessary to use chlorinated or
sulphurized lubricants, which might lead to stress-corrosion failure as well as
direct acidic attack of the metals. The chemical nature of the lubricant has, of
course, a major positive influence in reducing the tangential stress at a sliding
surface and in preventing metallic transfer which can otherwise easily become
cumulative and lead to early failure.
It has been shown in this way that metal transfer can be a very important
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same path obscure the detail because the first fragments act as an abrasive lap.
The wear rate is increased in a second traversal, and loose debris is produced.
Abrasive particles of silicon carbide or alumina embedded during metallo-
graphic preparation of the copper similarly increase the wear. It has however
been shown using radioactive 28A1, despite its short half-life of 2-3 min, that
normal metallographic preparation technique removes the residual grit from
each grinding paper at about the time that the visible scratches are removed by
the next in the sequence. Careful preparation, finishing with 4/0 grade S i c
paper, if performed under a flood of methanol or benzene, will produce a
copper surface which is free from damaging debris or scratches. On such a
copper plate the transference from the radioactive WC/Co slider can be
detected by exposing an X-ray film for a period of up to 2 4 h and then
developing the image. Within the detection limit imposed by the grain size of
the film, which must be rather coarse (about 10 pm) to achieve adequate film
speed, the deposit of tungsten carbide will be found to be uniform over areas
of more than 1 cm2. The wear rate will however vary from one part of the plate
to another, and this variation can be associated with the drying pattern of the
benzene or other solvent. To obtain uniform and reproducible results it is
necessary to produce a chemically uniform surface on the copper, as well as
removing the mechanical scratches.
A preparation technique has been developed which has given reliable
results over a number of years. A metal plate is first abraded unidirectionally
under light pressure with grade 0 emery paper under a flood of methanol.
When the surface is uniformly scratched, the plate is thoroughly washed with
methanol and then abraded on grade 2/0 at right angles to the original direc-
tion until none of the first set of scratches remain. This procedure is repeated
with 3/0 and finally 4/0 emery papers. After the final washing the plate is
leached with a continuous flood of 1 : 1 solution of concentrated HCl in
distilled deionized water, gradually changing without exposure of the
plate to a flood of purified water alone. It is then dried rapidly in clean
warm air.
The method has been proved by the following experiment. Immediately
after the final abrasion and methanol wash, one third only of the plate was
leached with 1 : 1 HCI and another third with 1 : 3 NH40H, both separately
followed with purified water and dried. The hydrochloric acid dissolved any
copper oxide on the surface and detached the organic residue left by the sol-
vent, without attacking the copper itself, whereas the ammonium hydroxide
reacted with the metal. The central zone was untreated, so that there were
three distinct zones on a single plate, separated by boundary regions. In one
of these boundaries there was a residue of CuClz, which is a soft solid of
lamellar structure, and in the other a residue of Cu(OH)2, which is a mild
abrasive. A polished radioactive tungsten carbide slider traversed over this
plate in a spiral showed increased wear in the hydroxide boundary and de-
creased wear in the chloride boundary, but the wear rate in the leached and
water-washed zones was uniform and practically identical whether HCl or
NH40H had been used. The surface film in each of these zones was thus
attributable to the action of water and air only. It is probable that it was a
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chemisorbed hydroxyl which was rapidly converted by the air to a thin film of
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copper oxide. A remarkably sharp change in the wear rate occurred at each
boundary region, reaching full intensity on each side within a distance of 0.2
mm, though the time taken to traverse this distance was only about 3 ms. This
illustrates the extreme sensitivity of wear to the local environment, and the
care necessary to obtain reproducibility. In comparison with this standardized
treatment, the film formed by exposure to benzene, possibly a copper phenate,
shows a reduction in wear by a factor of about 10. Care must therefore be
exercised in interpreting friction and wear data obtained with conventionally
degreased surfaces. Even electrolytic degreasing may leave a chloride or similar
residue.
For carbon and alloy steels a solution of 2 per cent nitric acid in alcohol
(commonly used by metallurgists for etching, and known as Nital) may be
used instead of ammonia. This may be preferable to the use of HC1 since any
inadvertent residue will increase the wear locally and may be more readily
detected.
‘severe’ and ‘mild’ wear even in open air, as we have seen earlier in this
chapter. A tenacious oxide skin is thus advantageous. Some oxides are
sufficiently soft at high temperatures to provide a positive lubricating action.
CuO, for example, is softer than copper at temperatures above about 600 “C
and can be used to lubricate copper in extrusion processes. Most oxides are
however harder than the metals from which they are formed, and if broken
during the sliding process will provide abrasive particles that increase the wear.
More subtle distinctions can be drawn on the basis of mechanical properties;
it has for example been shown that a-Fe304 is a better lubricant than Fez03.
PbO has been found to be a good lubricant for use at high temperatures in a
space environment.
A striking example of the influence of oxygen in a more industrial sliding
process can be seen in metal cutting. If the atmospheric oxygen is removed
from an enclosure surrounding the cutting tool and workpiece, the cutting
forces are approximately doubled for mild steel (0.1 per cent C), and there is
considerable tearing of the surface. Even at a pressure of 0.2 torr, normal
cutting performance can be restored at speeds up to 160 ftlmin, with almost
complete prevention of build-up of metal at the tool face. In contrast, it
requires less energy to cut a magnesium alloy in a vacuum than in air, and a
good surface is produced in both conditions. The tentative explanation given
is that an oxide film is formed on the free metal surface, away from the cutting
tool, and acts as a barrier impeding the emergence of the dislocations associa-
ted with the plastic flow of the metal. These consequently pile up beneath the
surface, and plastic deformation becomes increasingly difficult. The film thus
strengthens the material in the critical region of shearing.
Recent studies of metal flow show that there is an analogy between some
cutting processes and the ‘ploughing’ action of a simple slider heavily loaded
on soft metal. It is consequently suggested that the balance between these
competing effects of oxygen may be relevant to some wear problems. Very
little work has been done in this area, though there is evidence in cutting that
chemically active lubricants such as chlorine compounds can influence the
performance by attack both at the tool face and on the free surface. We refer
to this again when discussing corrosive wear.
We have already seen that oxygen can be important in boundary lubrication
by assisting in the formation of metallic soap films. There is evidence that some
lubricants become more effective when they contain dissolved oxygen. Both
the friction and the wear are reduced, but it must be recognized that oxidation
of the lubricant itself is almost always undesirable.
Water vapour is almost as effective as oxygen in reducing the friction of
clean sliders in a vacuum chamber. It may however promote corrosive attack
and thus increase wear considerably. The formation of acids in condensation
products of automobile engines, for example, can be a serious cause of wear.
From some recent laboratory sliding tests it appears that the rate of loss of
material from a slider increases as the relative humidity of the surrounding
atmosphere is increased, up to about 85 per cent, but above this level the wear
either remains sensibly constant or decreases. The decrease may be associated
with the formation of relatively thick, liquid, films. As we saw earlier
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ate films.
would otherwise form on a metal. When the chloride is removed from a surface
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during sliding, nascent metal is exposed and the high surface energy promotes
rapid chemisorption of further chlorine. The surface layer is then removed as
sliding proceeds and a continuous cycle is established. The rate of chemical
attack may thus be much greater than it would be under static coizditions with
the reaction rate controlled by diffusion through the layer of reaction product.
Direct experiments with radioactive WC/Co, as described above, showed
that the rate of formation of a chloride film from a highly chlorinated lubricant
was increased from 100 x 10-lo g in two minutes to 100 000 x 10-10 g in two
minutes, by sliding under moderately severe conditions. The ratio of Co to W
in the product was approximately 4 : 1 over this time. Eventually, of course,
the relative wear rates must adjust to the composition ratio 6 : 94. The high
initial rate of removal is due to chemical attack of the cobalt which is present
as a continuous matrix phase, containing some dissolved WC, between the
relatively massive grains of tungsten carbide (1 pm diagonal platelets).
Detailed studies suggest that the attack proceeds most rapidly in the interface
between the grains and the matrix. The grains are thereby loosened and can
fairly easily be detached mechanically before they are themselves fully con-
verted to chloride. The overall rate of removal of both phases is thus rapid. If
however the grains are closely packed, as they will be in a well-prepared
commercial material, the reaction between the cobalt phase and the lubricant
will be retarded by the narrow channels becoming packed with reaction
product. The observed wear rate will then be dominated either by abrasive
removal of material or by chemical action on the carbide grains. It is generally
recognized that the best wear resistance of these composite bonded carbides is
obtained with low Co content and fine WC grains.
Many examples of corrosive wear can be found in practice, in addition to
the obvious problems arising in marine and other hostile environments.
Automobile engines are particularly susceptible to corrosion and corrosive
wear of piston rings and cylinder liners. Formerly this could become serious in
private cars as a result of condensation and solution of acidic combustion
products on the cylinder walls, but the more rapid attainment of working
temperature in modern cars has reduced this problem. Nevertheless, striking
improvements have been claimed when a sodium-potassium eutectic has been
used to dry the circulated oil. Steam and gas turbines present special corrosion
problems and numerous seals must operate with low friction and wear under
highly corrosive conditions. Many difficulties of this type arise in chemical
engineering where rotating seals must be provided for pumps handling sul-
phuric acid, superheated water and a host of other materials. The usual
solution is to provide accurately flat graphite, ceramic or polymer/glass sealing
faces and to allow an infinitesimal leakage of the fluid itself to act as a lubri-
cant. Provided that the leakage is no more than can be dispersed by volatiliza-
tion at the outer edge of the seal this system proves highly satisfactory over
periods of years. The seals will of course wear but this can be allowed for
in the design by using annular faces transverse to the axis of rotation and
maintaining a positive pressure between them by a spring.
We have already seen that corrosive wear involving the production of
abrasive oxides can be very damaging. A special example of this process that
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site where the shear zone reaches the surface. It is suggested that by reacting to
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form a chloride instead of the stronger oxide normally formed, the barrier to
emergence of dislocations is reduced. The effective shear strength of the metal
is thus reduced and less force is required to cut the metal, even though the
lubricant is not applied between the rubbing surfaces. In some processes, where
the fluid cannot gain access to the interface, this may be a significant function
of a reactive lubricant.
A more extensive study has been made of stress corrosion, which occurs
during elastic deformation, at much lower stress levels. Many metals, and
particularly alloys, are prone to this type of damage, in static structures as
well as in sliding components. It is thought that stress corrosion usually starts
by slight selective attack by the fluid, which may otherwise have negligible
corrosive properties. The local areas of heterogeneity are often grain bound-
aries subjected to stress. As the corrosion proceeds, the stress concentration
will increase and a crack may develop. This exposes more metal to attack so
that the action can continue. The damage is enhanced if a brittle phase is
present. Intercrystalline stress-corrosion of this type is found in brasses
exposed to moist ammoniacal atmospheres, and in many other instances, but
steels are relatively immune under normal service conditions. In some materials
such as Mg alloys the crack may propagate along certain crystallographic
planes across the grains. Even the residual stresses produced by cold working
can cause stress-corrosion of a-brass (70 Cu : 30 Zn) in moist ammonia. This
season cracking is not usually a direct tribological problem but is sufficiently
common in drawn brass to be the subject of routine testing. In tribology, stress
corrosion is probably most important in enhancing wear by surface fatigue.
Repeated stress cycles, for example in rolling-element bearings and in gears,
are likely to initiate fatigue cracks at or just below the surface, especially in
case-hardened materials. In the presence of a mildly corrosive agent, such as
a n e.p. compound, the crack, once formed, will propagate more rapidly.
Surface fatigue is believed to be a common cause of wear damage under
conditions which are sufficiently well-controlled to make abrasive wear
negligible.
The study of chemical attack during metal cutting has led to development of
a novel reaction technique. During cutting, large areas of nascent metal are
exposed. These can be used for catalytic reactions and also for continuous
production of organometallic compounds. For example, synthesis of phenyl-
magnesium bromide is rather dangerous when carried out as a conventional
Grignard reaction and it can be performed only with small batches. I t has
been shown that by cutting solid magnesium chips under the surface of a
mixture of ethyl ether and phenyl bromide continuous production is possible.
The nascent metal reacts spontaneously with the phenyl bromide and the
product dissolves in the ether. It is desirable to conduct the process under
nitrogen to avoid the presence of oxygen but no other precautions are
necessary. Such mechanochemical activation processes appear to be potenti-
ally useful for a variety of purposes.
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BIBLIOGRAPHY
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