8.
Lubrication and lubricants
8.4.1 Introduction
Lubrication is the operation by which friction and
wear are reduced between contact surfaces of solids
moving in relation to each other by applying a
substance with appropriate characteristics.
As is well known, friction and wear (otherwise
called wear and tear) are clearly different from each
other. Friction is a resisting force resulting from the
total force necessary to break adhesion between
superficial micro-asperities and the deformation force
required to make possible grooves when solid bodies
move or tend to move against each other; it is
associated with the consumption of energy and
production of heat. Wear, on the other hand, is a
process of progressive loss of material caused by the
motion of the surfaces. It can develop due to causes of
a varied nature (for example, adhesion and tearing of
asperities, abrasion, fatigue, corrosion) which in any
case bring about modifications in the surface
morphology, in the dimensions and the mass of the
bodies.
It is not always necessary to reduce friction and
wear together; sometimes reducing wear and not friction
may be desired (for example, in oil-bath clutches), or
friction and not wear (for example, in running-in,
polishing and grinding operations), although generally
speaking the reduction of both is commonly required by
many applications and lubrication, in its various forms,
is the means to obtain it.
It can well be understood that lubrication, because
of the phenomena involved, can have considerable
impact on the dynamic behaviour of machines and
mechanical systems. If carried out correctly, it helps
their proper functioning, improving their general
performance, reducing wasted energy and
deterioration of the components. On the other hand,
unsuitable lubrication, or failure to lubricate, can mean
VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY
that within a brief timespan a machine will be out of
action, or even considerably damaged.
Well-applied lubrication brings significant
economic benefits in the form of energy-saving,
conservation of materials, reduction in maintenance
operations, and also positive effects on environmental
impact. It is estimated that reducing friction lowers the
total energy consumption of industrialized countries
by approximately 4.5%.
Even though some of the elementary practices of
the process have been known since ancient times,
modern lubrication only dates from the second half of
the Nineteenth century, under the impetus of
increasing industrialization, when the first equations
of hydrodynamic lubrication were defined. Since then,
an enormous amount of studies and applications has
led to continuous clarification of the manifold aspects
in which lubrication can be approached. The most
recent studies have revealed various areas still to be
investigated, with promising potential applications,
and show that research in the field of lubrication is
still alive and kicking.
Methods of lubrication
A simple way to reduce friction and wear between
opposed bodies in relative motion is to place a
substance that flows more easily than the underlying
solid between the surfaces. This can be achieved either
by means of a fluid film able to keep the surfaces
completely apart, thereby preventing any contact
between the asperities, or by means of the formation on
the surfaces of a thin runny film with high resistance.
There are three basic methods of lubrication which
can occur in current systems: fluid-film, boundary and
mixed. These three methods of lubrication, marked by
clearly different friction and wear situations, are
generally discriminated on the basis of a guiding
parameter known as the l ratio, defined as the ratio
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TRANSPORT
between the thickness of the film or of the protective
layer, and the average roughness of the surfaces.
Fluid-film lubrication
The main characteristic of this method of
lubrication is that the surfaces are separated by a fluid
considerably thicker than the surface asperities and the
protective films that can be formed on them through
chemical reactions. It is thick enaough to permit the
film to behave like the bulk of the fluid. Separation of
the surfaces is achieved by the pressure of the fluid,
which may be generated internally by contact
(hydrodynamic and variants), or produced
externally (hydrostatic). The friction of the contact
follows the laws of viscous friction.
In hydrodynamic lubrication (aerodynamic in the
case of gas) the pressure generated within the contact
depends on the geometric characteristics, the dynamic
and kinematic conditions of the contact and the
properties of the lubricant. This form of lubrication can
be found in mechanical contacts characterized by
analogous surfaces with decreasing gaps, when
subjected to a sufficient rate of sliding. Prismatic pairs
(e.g. thrust bearings) and rotating pairs (e.g. cylindrical
bearings) are examples of real contacts that reproduce
these conditions. The parameter l can in these cases
take on variable values within an interval ranging from
a minimum of 5 to a maximum of about 100.
In elastohydrodynamic lubrication the internal
pressure reaches locally very high values, enough to
cause elastic deformation of the surfaces. Under such
conditions the fluid film takes on greater stability, and
can thus assure a low friction value even for
thicknesses less than the hydrodynamic film. In this
system the parameter l can take on values of between
1 and 10. Elastohydrodynamic conditions can be
found in mechanical contacts with surfaces having
typically non-analogous geometries and subjected to
movements that include a significant rolling
component. Due to the limited size of the contact area,
which may be simplified as just a point or a line, in
these contacts very high local pressures develop under
the action of even modest loads, and be responsible for
the elastic deformation of the surfaces. Gears, roller
and ball bearings and cams are some examples of real
contacts that can operate in such a system.
Hydrostatic lubrication (aerostatic in the case of
gas) is a form of lubrication with pressure generated
externally to the contact. In this case, the lubricating
fluid is pumped into the connection at a pressure
already high enough to cause the surfaces to separate,
a condition which can then be maintained even
without relative motion. This is a method of
lubrication reserved for particular, often complex and
difficult situations, and is applied, for example, in
752
friction friction in
in mixed hydrodynamic
regime regime
friction coefficient
boundary friction
viscosity.speed/load
Fig. 1. Bearing friction coefficient as a function
of the relevant operational variables (Stribeck curve).
slow, heavy systems, which do not allow
hydrodynamic effects to be exploited or which have to
be safeguarded against undesired stoppages.
Boundary lubrication
This is the opposite condition to the preceding one
as far as the separation of the surfaces is concerned. In
this method of lubrication, friction and wear are
determined by the properties of the solid and of the
surface layers having thicknesses of molecular level or
little more, which are formed by the interaction of the
solid with the lubricant or the surrounding
atmosphere. In many cases, friction follows analogous
laws to those of non-lubricated contacts.
For lubrication purposes the chemical and
chemical-physical characteristics of the lubricant are
important, whereas the physical characteristics
referring to the bulk of the fluid are of little or no
importance. It is a method of lubrication that can be
found in various types of contact which share the
feature of operating in conditions of high load in
relation to the speed of the surfaces.
As the surface layers are thin compared to the
roughness of the surfaces, in this lubrication method
the parameter l assumes values of less than unity.
Mixed lubrication
This includes both of the preceding methods and is
used when in the contact there are areas in which the
surfaces are very close to each other, in which friction
and wear are determined by their interactions and by
boundary lubrication, together with areas in which
ENCYCLOPAEDIA OF HYDROCARBONS
 LUBRICATION AND LUBRICANTS

fluid-film lubrication substantially prevails. The latter is

sometimes favoured by hydrodynamic effects originating
from local irregularities (lubrication of asperities).
The influence of the lubricant is manifest both by
means of its physical bulk properties, and through
chemical interactions with the solids.
This is a very widespread method of lubrication,
used in many machine elements such as gears, roller
and ball bearings, and also in conventional plain
bearings. The conditions under which they operate are
such that the total thickness of the boundary and fluid
films exceeds the surface asperities by a factor that
can vary between 2 and 5 (depending also on the type
of finish of the surfaces).

Action of the lubricant

The same mechanical connection can change the
method of lubrication according to the operating
conditions. The change-over from one system to another
is clearly shown in the Stribeck curve (Fig. 1), in which
the friction coefficient is shown as a function of a
dimensionless parameter given by the product of the
viscosity for the speed divided by the load (force per
unit of length). Varying the method of lubrication offers
different ways of functioning by the lubricant.
In complex mechanical systems, the same
lubricant, in order to carry out its function effectively,
has to perform modalities of action in keeping with the
lubrication system in which it has to operate from time
to time. These actions substantially exploit a number
of its bulk physical properties and also a number of
chemical and chemical-physical properties.
Physical aspects
In the hydrodynamic system the lubricant
contributes towards the internal pressure of the contact
through its viscosity, which also causes friction. A
pressure gradient develops inside these contacts, as a
consequence of the need to maintain a constant flow of
fluid through decreasing sections of the meatus (Figs. 2
p
Fig. 3. Lubricant pressure (p) distribution
in a bearing.
and 3). The action of this gradient is enough to reduce
the speed of the fluid entering the meatus, increase the
outlet speed and at the same time withstand the
crushing together of the surfaces. The theoretical
equations describing this behaviour were defined by
Reynolds towards the end of the Nineteenth century.
Again by means of its viscosity, the lubricant
can contribute towards the pressure of the contact
by another mechanism called squeeze (Fig. 4),
which occurs when the fluid is trapped between
approaching surfaces. In this case, viscosity creates
resistance to the outflow of the lubricant from the
contact, giving rise to a cushioning effect which
withstands the approaching surfaces. This generates
a pressure which is especially important with thin
films and it is given particular attention in the

p
pressure

speed
Fig. 2. Pressure (p) distribution Fig. 4. Squeeze pressure (p)
in a wedge. distribution.

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TRANSPORT
design of pulsating load bearings or for
reciprocating machines.
To understand the contribution given by the
lubricant in elastohydrodynamic lubrication (Fig. 5), it
is necessary to consider two specific factors. One is
that, through the effect of the high local pressure, the
lubricant, in its extremely brief time of transit through
the contact, greatly increases its viscosity, reaching an
instantaneous glassy consistency, which greatly
withstands the approach of the surfaces. The other
factor is that the elastic deformation present in this
form of lubrication, by widening the support area,
increases the lubricants capacity not to escape and to
remain in the contact area. The result is that the fluid
film, which takes on a typical quasi-parallel profile,
acquires stability and remains integral down to very
small thicknesses. In such situations the contribution
of the lubricant towards lubrication derives not only
from its viscosity, but also from the dependence of
viscosity on pressure. The theoretical rudiments of
elastohydrodynamic lubrication stated by Ertel and
Grubin in the 1940s were developed in various ways in
the ensuing decades (Ertel 1939; Grubin and
Vinogradova, 1949).
A particular contribution to creating pressure in the
contact, of an extraviscous nature, can be supplied by
fluids with viscoelastic properties. Under the action of
sufficiently great stress, these fluids can give rise to
normal stresses of elastic type which are added to the
viscous effects. The importance that these properties
can take on for lubrication is closely linked to the
working context.
Other mechanisms by which fluids can contribute
towards generating pressure between two surfaces
(density wedge, viscosity wedge, local expansion)
have little impact on lubrication.
Chemical-physical and chemical aspects
In situations where the surfaces are not far apart
and contacts can take place between surface asperities,
Hertzian
pressure
p and load.
in Hertzian region out
Fig. 5. Lubricant pressure (p) distribution
in an elastohydrodynamic contact.
754
the lubricant can also intervene in the process with
thin surface films, possibly contributing to their
formation by way of their chemical or chemical-
physical properties.
This action of the lubricant can take place through
a variety of, at times quite complex mechanisms,
which can be briefly described only with due
simplification.
Surface layers of lubricants can be formed, through
the effect of Van der Waals forces, between the polar
molecules of the lubricant and the solid surfaces. Even
layers are thus formed, consisting of molecules
anchored at one extremity to the surfaces (physical
adsorption), which can easily slide over each other.
This property (sometimes attributed to a property
called greasiness) is possessed in a more or less
accentuated manner by all liquid lubricants, but may
be increased by the use of specific additives. These are
made up of long-chain molecules, provided with a
polar head (for example fatty acids, esters and amides)
through which they are anchored by chemical
adsorption to the metal oxides of the surfaces, keeping
the remaining part of the molecule unchanged. This
gives rise to layers with a high sliding power which
produce little friction (coefficient of friction
0.05-0.10), creating resistance to crushing. The
resistance of these layers is, however, limited to low or
moderate load and temperature values.
Analogous mechanisms of sliding in layers can
also occur with a number of solid lubricants. However,
in these cases the low friction value is linked to the
fact that some planes of the crystal lattice easily tend
to flake (this is the case for example with graphite,
molybdenum sulphide, boron nitride and others) or to
the effect of a smooth molecular profile (e.g. teflon,
high-density polyethylene). These lubricants generally
present difficulties because of their strong adhesion to
the underlying solid.
More resistant thin films are produced by mixing
some commonly-used additives into antiwear
lubricating oils and greases. These are compounds
containing sulphur, phosphorus and metals, of limited
thermal stability, which due to the effect of the
temperature produced by friction, decompose to form
a protective film on the surfaces. This generally
consists of amorphous material which, although with
some degree of shear resistance (coefficient of
friction 0.08-0.12), is in any case able to support
lubrication up to conditions of medium temperatures
Even more resistant surface layers, able to
function under severe conditions, can be formed with
lubricants containing what are known as Extreme
Pressure (EP) additives. The capacity of these
compounds, which contain sulphur, chloride and
ENCYCLOPAEDIA OF HYDROCARBONS

phosphorus, to enable lubrication to be carried out
under extreme conditions, derives from their tendency
to react with the metal of the surfaces, to form
inorganic salts with high melting points (600-700C)
at the high contact temperatures.
Lubricants with a different state of aggregation
The lubricants most used are liquids; however,
situations are not lacking in which the use of
lubricants that exploit properties linked to a different
state of aggregation can be convenient.
Gaseous lubricants
These are the most simple, least viscous lubricants
formed by various types of gas, such as air, nitrogen,
oxygen and helium. The wide temperature range in
which they maintain their state of aggregation and
their high stability unchanged gives these lubricants
certain advantages over liquid lubricants. They can be
applied at very low temperatures (a few Kelvin
degrees) or very high ones (even higher than
400-500C); moreover they present no risks of
contamination, which makes them particularly
interesting for use in the food, pharmaceutical and
electronic industries.
Their low viscosity, appreciably lower than that of
liquids, determines in aerostatic or aerodynamic
lubrication extremely limited friction values. The use
of gases is particularly advantageous in lubricating
bearings when the number of revolutions is very high
(more than 15,000 rpm), where they can operate
without the problems linked to excessive heat
production. Furthermore because, as opposed to
liquids, their viscosity increases with increased
temperature, they do not lose their capacity to support
the load due to overheating.
However, together with the low viscosity of gases
there is a rather low bearing capacity (not more than
0.7 kg/cm2 in aerodynamic bearings). This aspect,
when necessary, is improved at the design stage with
significantly larger bearings than those for liquids. For
this purpose use is sometimes made of hybrid (mixed
aerodynamic/aerostatic) bearings, in which the
capacity to bear the load is generated not only by the
motion of the surfaces, but also by the pressure at
which the gas is supplied.
Liquid lubricants
These are by far the most widely-used lubricants,
which can meet the requirements of very many
applications. This is made possible by the fact that
they possess properties thanks to which, in addition to
their function of lubricating, a series of other desirable
secondary functions can also be carried out. Their use
covers a temperature interval which, considering the
VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY
LUBRICATION AND LUBRICANTS
300
250
paraffinic oil
kinematic viscosity (mm2. s1)
naphthenic oil
200
150
100
50
0
0 20 40 60 80 100 120 140 160
temperature (C)
Fig. 6. Viscosity-temperature diagram
of liquid lubricants.
various classes of products, ranges from about 60 to
around 250C .
They are able to perform their lubricating function
with all the methods of lubrication: fluid-film,
boundary and mixed.
In boundary lubrication, performance is basically
determined by the chemical and chemical-physical
properties naturally possessed by the base liquids or,
as occurs more frequently, conferred through the
addition of specific additives. Under such conditions,
sometimes following complex chemical reactions,
these lubricants form a film on the surfaces, which
creates the last barrier preventing contact between the
solids. The effectiveness and the resistance of this
barrier depend, to a large extent, on the capacity of the
components to develop adequate reactivity in relation
to the severity of the working conditions and at the
same time, to avoid reactions of internal competition.
In fluid-film lubrication, instead, the influence that
the liquid exercises through its rheological properties
appears more simple. A primary role is played, in this
case, by viscosity, which is influenced by the action of
three physical parameters normally present in the
contacts: temperature, pressure and shear stress. The
effect of temperature is particularly important in
lubrication (Fig. 6); an increase in temperature is
matched by a reduction in viscosity, with loss of the
capacity to sustain the load, thereby increasing the risk
of seizure. Pressure, on the other hand, exercises the
opposite effect on viscosity (Fig. 7), with favourable
consequences for lubrication, realized mostly in
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TRANSPORT

1,000,000 The importance of viscosity for liquid lubricants is

solid solid demonstrated by the fact that this property forms the
100,000 basis of important classification systems which make
it possible to identify the viscometric characteristics

C
.8
appropriate for the correct use of lubricants in certain

37
10,000
C important applications (engines, transmissions,
99
0C

industrial machinery).
viscosity (cP)

1,000 Among the secondary functions that liquid

100
10
1 that produced by friction. The forced-lubrication
0.1
0 1 2 3
pressure (GPa)
Fig. 7. Viscosity-pressure diagram
of liquid lubricants.
elastohydrodynamic contacts. As far as shear stress is
concerned, liquid lubricants have a differentiated
response depending on the interactions between the
molecules (Fig. 8). Little combined simple liquids, (e.g.
base oils also containing simple-type additives) have a
viscosity unaffected by shear stress (Newtonian
behaviour), while combined liquids, or those with other
significant molecular interactions (e.g., oils at low
temperatures, oils containing viscosity-modifying
polymers), have a viscosity that decreases with
increasing shear stress, according to a typical sigmoid
trend (pseudoplastic behaviour); this effect, which
determines a reduction in the capacity to support the
load, remains reversible within certain stress limits,
beyond which it can become permanent. The
dependence of viscosity on the above-mentioned
variables is defined by known mathematical relations.
viscosity
lubricants can perform, heat removal, the capacity to
5C remove and to transport fragments of worn material or
218.
solid contaminants, and protection against corrosion
are also important. Their importance is apparent in the
lubrication of thermal machines, in which the heat
generated by thermodynamic processes is greater than
paraffinic oil
naphthenic oil
systems in vehicular internal combustion engines are
well-known examples of applications in this context.
4 5 6 7 8 9 10 Other secondary characteristics based on the
properties of liquid lubricants (e.g. compatibility with
auxiliary antipollution devices, biodegradability,
demulsibility, uninflammability, dielectric rigidity,
resistance to radiations) take on importance mostly in
relation to specific applications.
An essential aspect for the proper functioning of
liquid lubricants concerns the maintaining of
performance for the required time. The capacity of
these lubricants to meet the requirements of duration
adequately in the various applications is mainly
determined by their characteristics of stability, both
chemical (thermic inertia, resistance to oxidation and
to hydrolysis, compatibility with various materials)
and physical (low tendency to evaporate and to form
emulsions and dispersions).
One aspect of fundamental importance for the
technology of liquid lubricants, on which many
application extensions are based, regards the
possibility of their treatment with chemical additives.
Many of the properties of these lubricants can be
improved or imparted by means of additives. Without
additives, the majority of modern lubrication demands
could not be adequately satisfied. The range of
compounds available for this purpose is quite
extensive, although their functions come down to a
relatively limited number. The main ones include the
following: reducing wear, controlling friction,
Newtonian
increasing resistance to oxidation, limiting formation
of deposits on the lubricated parts, minimizing rust

and corrosion, offering variation in viscosity and its

reduction with temperature, improving cold sliding,
non Newtonian pseudoplastic
and lowering the tendency to foam.
The wide variety of properties exhibited by liquid
lubricants is not enough, in many cases, to ensure their
shear stress
proper performance in service. In many applications,
Fig. 8. Liquid lubricant viscosity as a function both for heavy-duty vehicles and for industrial
of shear stress. machinery, performance is guaranteed only by going

756 ENCYCLOPAEDIA OF HYDROCARBONS


through specific test programmes correlated with
actual service. These programmes, which often involve
a fairly large number of tests, are defined within the
framework of the general performance classification
systems or specifications of individual producers of
mechanical hardware. The programmes of engine tests
for the qualification of lubricants for motor vehicle
engines are particularly severe in their complexity,
duration and cost.
As far as the origin of liquid lubricants is
concerned, the majority of them consist of oils
containing mixes of hydrocarbons derived from
petroleum, generally with suitable additives. The
overall prevalence of these products is justified by
their satisfactory general performance, their relatively
low cost and their widespread availability. For special
or particularly demanding uses, when service
requirements justify higher costs, oils of synthetic
origin are sometimes preferred.
Lastly, it is worth remarking upon the flexibility of
application of liquid lubricants. The fact that these
products can stand up to various types of treatment
(pumping, filtering, cooling, nebulization, etc.), makes
them suitable for use in various lubrication systems,
including, as well as the already mentioned forced
lubrication systems, oil-bath systems (e.g. low-speed
cogwheels), oil mist systems (e.g. high-speed gears)
and flap systems (e.g. slow and medium running
engines).
Semisolid lubricants (lubricating greases)
These are solid or semisolid products consisting of
a liquid phase, generally a lubricating oil, and of a
dispersed solid phase, with a thickening function.
The thickening agent serves to confer the
necessary firmness, a property thanks to which the
grease can remain by itself in the parts to be lubricated
without requiring auxiliary devices, preventing, if
necessary, the entry of harmful substances such as dust
and humidity from the surrounding atmosphere.
Lithium, sodium, calcium and aluminium
soaps are generally used as thickening agents. Their
use is limited by the phase changes (fusions)
that take place at various temperatures. For
applications at high temperatures thickeners with
high melting points (complex soaps, polyurea,
bentone) are used.
Rheological properties are of particular importance
for lubrication. From this point of view, greases are
characterized by their plastic type behaviour, with a
viscosity that diminishes as the shear stress increases,
once the minimum stress threshold has been passed.
They may respond not only to the intensity of the
stress, but also to its duration, showing effects
depending on time (thixotropy).
VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY
LUBRICATION AND LUBRICANTS
The oily component makes a substantial
contribution to the lubricating function. In most cases
this consists of products of petroleum origin; for uses
extending into the field of low and high temperatures
and for particular applications, synthetic oils are also
used.
As liquid lubricants, greases can also contain
additives able to give the product special properties
(for example wear prevention, rust prevention,
antioxidant additives).
The main use of lubricating greases is for
lubricating machine elements such as bearings, gears
and joints, found in industrial machinery, engines,
machine tools and so on.
Solid lubricants
These normally have a structure in which the
surface layer consists of laminated aggregates able to
slide easily over each other (e.g. graphite, molybdenum
disulphide, boron azide, cadmium iodide, borax, talc),
or by smooth molecular conformations (teflon, high
density polyethylene). They are mostly used in
conditions in which it is not possible to employ
lubricating oils or greases, like for example in a
vacuum or in the presence of intense radiations. Their
efficiency can be conditioned by the difficulty of
maintaining a sufficient layer for lubrication.
Protection against wear can sometimes be limited as a
consequence of the fact that after breaking the film, it
is not self-regenerating, which instead is the case with
liquid lubricants. From the standpoint of applications
they can be used in various ways, none of which is
wholly devoid of problems. Thus, for instance, they can
be used in suspension (stability problems), in pastes
(difficulty of penetrating restricted spaces), or with
pretreatment of the materials in a high-temperature
furnace (the lubricating layer, when worn down, cannot
be reformed).
8.4.2 Functions and performance
of lubricants for heavy-duty
vehicles
Engine lubricants
Functions for four-stroke engines
These engines are lubricated using oils with
specific characteristics, known as engine oils (or
motor oils). Gears and transmissions generally have
separate lubrication. Important elements of the
lubrication circuit of a four-stroke engine are: the
delivery pump which guarantees a suitable oil flow, a
regulation valve which limits the maximum pressure
of the circuit, the filter which removes both the wear
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TRANSPORT
particles and part of the deposits formed due to
combustion from the oil. In special cases there might
also be a radiator for cooling the oil. In engines
subject to strong centrifugal stresses, as in the case of
engines for competitions or aircraft engines, the oil is
kept in special tanks to which it returns after having
lubricated the various parts, by means of a number of
pumps located in the sump (dry sump engines).
To limit oil consumption as far as possible, engines
are generally fitted with various devices such as: piston
scraper rings, lip seals on the driving shaft, checks on
the valve stem, and blow-by systems for separating the
oil from the combustion gases passing through the
piston scraper rings and entering the crankcase.
Various important functions are carried out by the
engine oils, in particular:
Ensuring an adequate lubricating film on the
various mechanical connections in relative motion
under all operating conditions, so as to limit
friction resistance and wear on the surfaces.
Ensuring that the engine is clean, preventing the
formation of deposits and their accumulation in
critical parts.
Dispersing any deposits formed and particles
resulting from wear, conveying them to the filter.
Protecting the parts of the engine against the
formation of rust and chemical attack by acid
products stemming from combustion.
Favouring the seal between the piston rings and the
cylinder liner in order to guarantee that the correct
compression ratio is maintained and to prevent
combustion products from reaching the oil in the
sump, leading to its early deterioration.
Integrating the engine cooling system so as to keep
the temperature within the limits corresponding to
proper running.
Avoiding the formation of bubbles and foam in the
lubrication plant which could lead to irregular oil
supply to the parts to be lubricated.
Guaranteeing the properties described above for an
adequate running period.
The required characteristics are obtained both
through the use of adequate base lubricants, and by
using appropriate additives.
Functions for two-stroke engines
The typology of two-stroke engines, thus defined
because they work with a cycle consisting of a useful
phase and a load replacement phase, is very different
according to the fields of use. The difference is, in
fact, between the small engines for scooters, chainsaws
and portable generators, and the imposing diesel
marine engines in supertankers and container ships.
In the case of small two-stroke engines, the
lubricant (not recycled) is mixed with the fuel and has
758
to carry out the following tasks: to guarantee the
cleaning of the engine to prevent the formation of
deposits (on the spark plug so as to prevent ignition
failures; on the piston to guarantee the correct seal; on
the inlet or outlet spaces to prevent power losses due to
their blockage); and to guarantee the lubrication of the
various connections and in particular those of the
piston-cylinder and the main and big-end bearings.
For large two-stroke diesel engines for marine use,
two different lubricants are needed: one for the gear
mechanisms, i.e. the mechanisms enabling alternating
motion to be converted into the rotary motion of the
engine crankshaft, and the other one for lubricating the
cylinders (without recycling the oil). While for the
first type of lubricant no special properties are
required, in the case of the second one, the main
property must be the capacity to neutralize the acid
products of combustion, as these engines generally run
on fuels with a high sulphur content.
Viscometric classification and service specifications
Viscosity has a direct influence on certain aspects
of the performance of engine oils. The SAE (Society
of Automotive Engineers) has devised a classification
system for engine oils (SAE J 300) according to
categories based on viscosity measurements at low and
high temperatures (Table 1).
Measurements at low temperatures identify
viscometric ratings consisting of a number with the
suffix W (Winter). These ratings classify the oils that
enable engines in a sound condition to reach the
minimum cranking speed for start-up within a certain
temperature range. The lower the W value, the lower
the start-up temperature. The viscosity correlated with
the cranking speed is measured with a special
viscometer called a Cold Cranking Simulator (CCS).
A lubricant with the right viscosity for starting
up the engine might not be sufficiently pumpable,
being unable to lubricate the various parts of the
engine in the required time and quantity, with the
risk of wear. Sufficient pumpability of the oil is
assured by measurements carried out using a
special instrument known as a Mini-Rotary
Viscometer (MRV).
High-temperature ratings are correlated with
engine lubrication under conditions of normal
operation and are defined on the basis of
measurements of kinematic viscosity at 100C and of
dynamic viscosity at high shear gradients at 150C.
When a lubricant, because of its kinematic
viscosity characteristics at 100C and its CCS viscosity
characteristics, falls within the SAE X and the SAE Y
W grades, it can be classed as YW-X (e.g 15W-40 if it
has a viscosity at 100C between 12.5 and 16.3 mm2
s1, a viscosity at 20C of less than 7,000 mPas,
ENCYCLOPAEDIA OF HYDROCARBONS
 LUBRICATION AND LUBRICANTS

Table 1. Viscometric classification of engine oils (SAE J 300)

Start-up Pumpability Viscosity at high temperature

Viscosity at 150C
Max Max Viscosity at 100C
SAE Grades and 106s1
Viscosity Temperature Viscosity Temperature (mm2s1)
CCS (C) MRV (C) (mPas)
(cP) (cP) min max min

0W 6,200 35 60,000 40 3.8

5W 6,600 30 60,000 35 3.8

10W 7,000 25 60,000 30 4.1

15W 7,000 20 60,000 25 5.6

20W 9,500 15 60,000 20 5.6

25W 13,000 10 60,000 15 9.3

20 5.6 9.3 2.6

30 9.3 12.5 2.9

2.9 (0W-40,
40 12.5 16.3
5W-40, 10W-40)

3.7 (15W-40,
40 12.5 16.3
20W-40, 25W-40)

50 16.3 21.9 3.7

60 21.9 26.1 3.7

number of bodies: ASTM (American Society for

pumpability at 25C and a viscosity at a high
temperature and high shear greater than 3.7 mPas).
Lubricants that possess these characteristics are called
multigrade and guarantee satisfactory viscometric
service (cold start-up and protection at high
temperature) in a very wide temperature range.
In addition to the viscometric classification, engine
oils have to measure up to appropriate service
specifications. These specifications are set out by
manufacturers in their technical publications (manuals,
handbooks of use and maintenance, etc.) and by
lubricant producers on their containers and in their
technical documentation. This enables the end-user to
make the appropriate choice of lubricant according to
the requirements of his machinery and the supply on
offer from lubricant producers.
Each service specification for engine oils typically
envisages more than one series of assessments, the
basic nucleus of which consists of vehicle engineering
tests which simulate actual operation.
United States classification system
In the United States the service classification of
lubricants is the result of the common activity of a
Testing and Materials), which deals with testing
methods and procedures; SAE (Society of Automotive
Engineers) and EMA (Engine Manufacturers
Association), which defines the requirements of the
new specifications; API (American Petroleum
Institute) which publishes the classification system;
and ACC (American Chemistry Council), the
professional organ of additive producers. API also has
the important task of the administration and issue of
trade mark licences.
The Engine Oil Licensing and Certification
System (EOLCS) describes the rules to be followed to
qualify engine lubricants and is responsible for issuing
the symbols to be affixed on the containers: the API
Service Symbol Donut and the Certification Mark
Starburst.
API publishes a list of lubricants which have been
issued a licence to affix the donut and/or the starburst
symbol on its own Internet site.
The API Service Categories are subdivided into
those for gasoline engines and those for diesel
engines, bearing the letter S (for Service) and C (for
Commercial) respectively, as traditionally in the
United States diesel engines are used only in

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TRANSPORT
commercial vehicles. These letters are followed by a
second letter (for example L, making the combination
SL) which progresses according to the successive
re-editions; for the diesel (C) categories, there might
also be a number, which defines the field of application.
In addition and complementary to the service
categories, API also defines an Energy Conserving
performance level. To be classed in this level,
lubricants must demonstrate their fuel saving
properties in an operating test compared with the
results obtained in the same test by a standard oil
taken as reference. According to what has been
reported by API in the EOLCS, the widespread use of
engine oils satisfying this requisite should lead to an
overall saving of fuel by the vehicles in circulation.
As a complement to the EOLCS, API administrates
a monitoring programme of the effective quality of the
lubricants placed on the market which have warranted
the donut symbol.
European classification system
ACEA (Association des Constructeurs Europens
de lAutomobile) publishes what are known as
lubricant sequences, which set out the reference
service levels for both light and heavy gasoline and
diesel engines,. The first of these sequences were
published in 1996, updating the preceding CCMC
(Comitato Costruttori Mercato Comune) sequences,
which are revised every two years.
As far as the qualification rules are concerned, the
European system, the EELQMS (European Engine
Lubricants Quality Management System) is based on
API EOLCS. Participating in the European system are
such bodies as CEC (Coordinating European Council),
responsible for developing and cataloguing testing
methods, ATIEL (Associazione Tecnica Industria
Europea Lubrificanti) and the ACC (American
Chemistry Council).
ACEA does not issue a symbol of its own nor does
it manage a certification system. The list of operators
who officially adhering to the EELQMS system
undertake to respect its rules is published on ATIELs
Internet site.
Japanese classification system
Japanese manufacturers generally follow American
specifications or European ones, according to the
market in which they operate.
It should however be observed that what are termed
genuine oils, sold by the manufacturers themselves,
are widespread in Japan. Their characteristics are often
defined on the basis of motor engineering tests, always
developed by the manufacturers.
The Japanese Automotive Standardizing
Organization (JASO) is particularly important in the
760
sector of oils for motor vehicles, and envisages service
levels for two-stroke and four-stroke engines
(respectively FB, FC and FD, MA and MB). Its system
offers the possibility of registration, the use of a
symbol marked on the containers and publication in
the list of registered oils on its Internet site.
Manufacturers specifications
Many manufacturers offer the issue of a formal
approval and publish lists of approved oils. Each
manufacturer normally stipulates an articulated series
of performance specifications, depending on the
various traffic control authorities and/or of the
intervals between oil changes.
Trends in engine oils
The evolution of engine oils is in step with that of
engines and therefore it has been conditioned by
improvement in performance and the reduction of
emissions.
Reduction of CO2 (Kyoto Protocol)
With the Kyoto Protocol the industrialized
countries undertake to reduce, in the period 2008-12,
the total amount of gas emissions with greenhouse
effect (CO2, methane, nitrogen oxide,
hydrofluorocarbons, perfluorocarbons, sulphur
hexafluorine; see Chapter 10.2) by at least 5% in the
transport sector compared with 1990 levels. The
European Union has drawn up a strategy to reduce
CO2 emissions by new motor vehicles from 186 g/km
to 120 g/km not later than 2012, in agreement with the
associations of motor vehicle manufacturers in
Europe, Japan and South Korea.
Reduction of emissions of automotive pollutants
(EU legislation)
In recent years there has been growing concern
about problems connected with the particulate matter
emitted by motor vehicles (see Chapter 10.2), mainly
following a series of toxicological studies which
identified a relationship between exposure to
environmental particulate matter and negative effects
on human health.
Another environmental problem concerning
urban and highly industrialized areas which has
recently attracted attention concerns photochemical
smog, a particular type of air pollution produced on
days with stable meteorological conditions and
strong insolation.
Evidence of the effects of motor vehicle emissions
on the environment and on human health has
suggested the introduction of appropriate legislation to
regulate emissions from transport vehicles, depending
on the type of vehicle and on the fuel used.
ENCYCLOPAEDIA OF HYDROCARBONS

All vehicles should, at present, be approved on the
basis of Community regulations which are becoming
increasingly more restrictive for exhaust emissions.
The EURO 4 limits apply as from 2005 to newly
approved vehicles and from 2006 to all newly
registered ones.
Lubricants and emissions
Lubricating oil influences exhaust emissions
first of all through its influence on fuel
consumption (fuel economy) because of its direct
repercussions on the quantities of CO2 discharged.
Other more direct forms of contribution to
emissions are due to the quantity of oil that seeps to
the combustion chamber or directly to the exhaust
(commonly indicated by the term oil consumption),
the possibility and capacity for it to burn in the
combustion chamber itself, the phenomena of
absorption and desorption of the fuel and lastly,
more indirectly, its impact on the exhaust gas
post-treatment systems.
Fuel economy
In an internal combustion engine the energy
supplied by the fuel is distributed according to a
typical scheme: about 15% of the energy resource of
the fuel is actually usable by the vehicle; about 30% is
dissipated in cooling the cylinders; about 30% is lost
with the exhaust gases; and about 25% is absorbed by
the processes of mechanical friction that take place in
the engine contacts.
The friction responsible for these reductions in
efficiency stems from different load, speed and
temperature conditions which determine, in the parts
of the engine concerned, combinations of
hydrodynamic, mixed and boundary lubrication.
The lubricant can exercise a significant role in
limiting these phenomena, contributing effectively
towards what is termed Fuel Economy (FE), which in
the motor vehicle sector is the reference parameter for
assessing energy saving.
Two main options are available for reducing
friction: the first is the use of fluid oils (with low
viscosity) when fluid-film lubrication (typical of
bearings) prevails, with an oil film of considerable
thickness; the second option is the use of chemical
additives called Friction Modifiers (FM), active in
mixed and boundary systems (typical of distribution),
with molecular films.
In the first case, the selection of the lubricating
bases is crucial. The important factors with regard to
friction are the rheological characteristics: the
kinematic viscosity, the viscosity index, the HTHS
(High Temperature High Shear) index, and the
viscosity/pressure index. Furthermore, especially
VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY
LUBRICATION AND LUBRICANTS
during the aging of the oil, other properties of the fluid
are also significant, especially thermo-oxidative
stability and volatility.
In the second case, instead, the adoption of
appropriate Friction Modifiers and the control of the
additive/additive and additive/ base system
interactions are fundamental.
Quantity determinations of FE are of a
comparative nature with respect to standard oils of
average quality and are affected both by the test cycles
and by the type of motorization.
In the United States, lubricants which, throughout
their life cycle, exceed a fuel saving of 2% are
recognized as excellent, while in Europe the
corresponding qualification threshold for new oils is
fixed at 2.5%. Under particular operating conditions
(low-temperature urban cycles), however, fluid
lubricants, compared to more traditional technologies,
can even reach FE levels of 4-5%.
Oil consumption
Oil consumption has always been the subject of
great attention by users, and it is very often considered
to be one of the main parameters for judging the
quality of a product. Latterly, consumption has taken
on even greater importance due to its implications for
exhaust emissions.
Leaving aside any seal losses to the outside, which
have environmental repercussions but do not influence
exhaust emissions, there are mainly three sources of
oil seepage which determine its presence at the
exhaust: the first one is the valve area, the second one
is the piston ring area, and the third one is linked to
the possible presence of auxiliary parts such as the
multistage centrifugal blower, of widespread use above
all in diesel engines.
The lubricant, apart from indirectly influencing oil
consumption as a function of its capacity to keep the
engine in a good state of repair, also has a more direct
action on the phenomenon, linked to its volatility and
its rheological characteristics.
Direct effect on emissions
The lubricant influences all regulated emissions as
it is able to contribute towards the carbonaceous
fraction of the particulate matter (soot), towards the
Volatile Organic Fraction/Soluble Organic Fraction
(VOF/SOF) and to the unburnt or partly burnt
hydrocarbons; through FE, it is also able to influence
NOx and CO2 emissions.
Obviously the lubricant conditions the state of the
engine in the course of time in terms of the formation
of deposits and wear, and its capacity to combat these
phenomena translates into the possibility of
maintaining the original gas and particulate matter
761
TRANSPORT
levels. Even the aging of the lubricating oil can lead to
negative effects on the exhaust emissions. Moreover,
the quantity of sulphates present in the particulate
matter depends to some extent on the lubricant; the
presence of sulphur compounds in lubricants
contributes, in fact, towards the presence of sulphates
in the emissions, as has been confirmed by using gas-
oils virtually without any sulphur.
Various studies have shown that the use of oils
with a lower SAE viscometric grade, compared to
traditional grades, and of synthetic composition, can
bring about the simultaneous reduction of particulate
and NOx emissions. In some cases, it has been
demonstrated experimentally that diesel vehicles with
levels of particulate and NOx emissions at more or less
the maximum limits have easily returned within the set
limits by using synthetic fluid oils.
Reduction of the temperature at the exhaust, due to
a reduction in specific consumption, made possible by
using fluid oils, can nevertheless have a negative
influence on the efficiency of catalytic converters,
especially when activating their delicate light-off
phase. Optimizing the engine according to the
rheological characteristics of the oil is of particular
importance in the light of the need to maintain the
efficiency of catalytic conversion systems.
To conclude this analysis of the effects of the
lubricant on emissions, it must be mentioned that both
the chemical and the physical characteristics of the oil
can influence the solubility and the dispersion of the
fuel in the lubricant. This phenomenon regulates the
capacity of the thickness of the oil film present on the
walls of the cylinder to absorb fuel during
compression and release it during expansion, when it
no longer has any possibility of burning. In diesel
engines the phenomenon can also regulate the capacity
of the particulate matter to become enriched with
unburnt fuel.
Although modern lubricating oils contain very low
concentrations of PolyNuclear Aromatic hydrocarbons
(PNA), in operation they are able to absorb PNA
produced by combustion.
Indirect effect on emissions
Recently the association of European manufacturers
and a number of automobile manufacturers which
issue specifications for lubricants have decided on new
categories of lubricants, fixing the maximum chemical
contents of ash, sulphur, and in some cases of
phosphorus, primarily to take into consideration the
requirements of diesel engines fitted with Diesel
Particulate Filters (DPFs), but also of other current
and future systems.
The presence of organometallic products in the
lubricant is, as already mentioned, responsible for the
762
slow but progressive blocking up of DPF in the course
of time. The limitation on ash places restrictions on
certain types of additives such as detergents and wear
preventers which contain organometallic compounds.
These requisites have led to research being carried out
to obtain ashless products that are equally effective.
The reduction of ash is accompanied by that of
sulphur and phosphorus, also in consideration of the
fact that its limitation leads to automatic repercussions
on organometallic additives containing those elements.
The main argument against sulphur is that it
reduces the effectiveness of NOx traps, necessitating
more frequent regeneration, but in reality it causes
the reversible poisoning of all types of catalysts.
The presence of sulphur in lubricants currently used
derives from the contribution of the base products, if
of mineral type, and of some components of the
package of additives. Mineral oils or oils with a
minimum presence of synthetic bases can have a
sulphur content of up to 7,000-8,000 ppm, while oils
with wholly synthetic or unconventional bases can
have a content of 2,000-4,000 ppm. This shows the
emerging importance of limiting sulphur in
lubricants in post-treatment systems of exhaust gases
which are susceptible to sulphur poisoning. The first
step in this direction is clearly linked to using
sulphur-free base lubricants, which in the near future
will vie against traditional mineral bases to the
advantage of synthetic bases and of mineral bases
that have been subjected to hydrocracking and
isomerization treatment. A further contribution
towards reducing sulphur will however also be
demanded of oil additives, which will mean limiting
the use of a series of additives containing sulphur
with various functions (detergent, antiwear,
antioxidant and anti-friction elements).
The only source of phosphorus is the lubricant, and
particularly the antiwear additives contained in it (zinc
dithiophosphates). Traditional oils generally have a
phosphorus content of about 1,000-1,200 ppm. The
problem of the interference of phosphorus with the
functioning of catalytic systems for treating spent
gases has already been a matter of attention for several
years but the presence of this element is justified by its
important wear-prevention role. The limitation of this
element raises the question of the need for alternative
wear preventers without phosphorus and, if possible,
without sulphur.
Evolution of traditional performance requirements
Reaching compatibility with post-treatment
systems for exhaust gas has to coexist both with
traditional performance requirements and with aspects
emerging from the most recent technological evolution
in engines.
ENCYCLOPAEDIA OF HYDROCARBONS

In the field of gasoline engines, the development of
direct-injection engines has possibly resulted in
greater contamination of the oil by the fuel, because of
the direct contact between the injected fuel and the
thickness of the oil film on the cylinder walls. The
fluidodynamics of the combustion chamber seems,
however, to play an important role in favouring or
impeding contact as well as in determining the correct
preparation of the mix.
Another problem that seems to emerge regarding
this typology of engine concerns increased deposits on
the suction valves, on which the partially scouring
action of fuel injection towards the valves which
takes place in injection engines in the manifold is
lacking. As the lubricating oil that seeps along the
valve remains one of the items that most likely forms
deposits on them, there are increasing demands by
manufacturers for oils with a low contribution to the
deposits on the valves.
In the last few years, in the field of diesel engines
for motor vehicles, there has been an upswing in the
specific power permitted by the new high-pressure
injection plants (common rail and pump-injectors).
The greater specific power implies a greater thermal
load on the piston, which in its turn translates into a
demand for higher antioxidant and detergent
performances from the oil.
The high injection pressures, accompanied by high
supercharging, moreover, have caused an increase in
mechanical stress on the piston, on the compression
rings and on the bearings. Consequently the oil is
required to optimize the real rheological
characteristics (viscosity index, HTHS,
viscosity-pressure coefficient) and to provide better
antiwear properties.
For the purpose of reducing NOx emissions,
widespread use has been made of Exhaust Gas
Recirculation (EGR) in diesel engines and in some
gasoline engines. This technique consists of taking off
a certain quantity of exhaust gas and reintroducing it
into the cylinders together with the air drawn in, whose
volumetric capacity is thereby reduced by a quantity
corresponding to the amount of recirculated gas. The
effect of this recycling is to lower the peak
temperature in the combustion chamber, directly
influencing NOx production. However, the gas
recirculated and sucked in again by the engine
increases the contamination of the lubricating oil by
carbonaceous material, unburnt elements of the fuel,
and acid substances generated in the combustion
chamber. The use of EGR therefore calls for greater
attention as far as the neutralizing and dispersive
properties of the lubricant are concerned.
Attempts to absolutely soundproof the engine space
tends to impede the loss of heat externally with a general
VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY
LUBRICATION AND LUBRICANTS
increase in engine temperature. The aerodynamic design
of vehicles, seeking the best aerodynamic coefficient
of resistance to motion, for the purpose of reducing
the power lost through aerodynamic resistance, does
not improve the negative heat situation of engines.
The antioxidant properties of oils come to the
forefront also in this case because of their fundamental
importance in maintaining the performance of the
lubricant in the course of time.
At the same time, the trend towards extending
vehicle maintenance frequency is also causing
manufacturers to extend the oil-change frequency. To
this end, it is becoming more and more frequent for
many manufacturers to ask for long-life oils, that is,
ones able to last longer than traditional types.
Conferring long-life properties naturally means
upgrading all the performance aspects of the oil, the
effect of which is assessed through standardized
engine tests of greater severity.
Transmission lubricants
Functions of transmission lubricants
The characteristics of oil for transmission systems
are, in part, different from those of engine oil as the
causes of contamination and the high temperatures
found in the application of the latter are not present.
Their functions may be summed up as follows:
forming a lubricating film between the various
surfaces in relative motion and in particular between
the surfaces of gear teeth, even in the most severe
operating conditions; removing the heat produced by
friction; and protecting metal surfaces against
oxidation.
The capacity of the oil to bear loads is
fundamental, in view of the high pressures generated
between meshed gear teeth. These pressures and the
consequent high local temperatures make the solid
film formed with antiwear additives inadequate; in
these cases it is necessary to use special EP additives
which are able to react with the surfaces to form
compounds that act as solid lubricants.
Classifications and performance specifications
Oils for motor vehicle transmissions include oils
for gears and differentials and Automatic Transmission
Fluids (ATF), the latter are very widespread in the
United States but relatively uncommon in Europe,
with the sole exception of modern public transport
vehicles.
Oils for gears and differentials, which deal with the
most extreme cases because of design (hypoid gears)
and the loads and temperature conditions in which
they operate, come under the more general category of
gear-oils.
763
TRANSPORT
As for engine oils, for transmission oils, too, the
SAE has drawn up a viscometric classification system
based on measurements made at low and high
temperature (SAE J 306) which act as a guide to the
choice of lubricant according to environmental
conditions and the expected heat stress in use.
The characteristics of transmission oils are
commonly identified by the series MIL-L-2105, as
defined by a special US military organization, and by
the series GL (Gear Lubricant) and MT (Manual
Transmission), drawn up by API. European
manufacturers follow API specifications integrated in
many cases with their own specifications. These
specifications are targeted at every sector of
application and require different properties from the
lubricant; from this point of view, the main
characteristic is the possession or otherwise of EP
properties.
A good part of the requisites for automatic gears
are met by automatic transmission fluids (ATF).
Modern automatic transmissions require oils able to
carry out a complex series of tasks: in fact they act as
torque converters, hydraulic fluids, gear oils and fluids
for eliminating heat. But the main function remains
that of supplying adequate friction characteristics for
the proper functioning of an oil-bath clutch system.
Such a system normally consists of a series of steel
plates connected to clutches of refractory material,
paper, graphite, bronze, etc.
In 1967, General Motors introduced the trademark
DEXRON; approval of the product was accompanied
by the licence to use the trademark on the container.
Since then the DEXRON specification has
progressively evolved. Ford has followed the same
procedure with the introduction of its own trademark
MERCON.
The specifications for transmission oils issued
by General Motors and by Caterpillar are
particularly important, especially in the sector of
heavy-duty transport vehicles and off-highway
equipment (earthworks and construction equipment,
tractors, etc.).
For the lubrication of agricultural machinery,
because of the presence of particular mechanical parts
(such as brakes in an oil bath) and the need to
standardize the lubrication of said parts as far as
possible, there are specific lubricants: oils for
lubricating both the engine and the auxiliary parts
(STOU, Super Tractor Oil Universal); oils for
lubricating only the auxiliary parts, not the engine
(UTTO, Universal Tractor Transmission Oil).
Generally speaking these are oils which meet the
specifications of the main off-road vehicle
manufacturers (Deutz-Allis, J.I. Case, John Deere,
Massey-Ferguson, etc.) and which anticipate, as well
764
as various rheological requisites, tests for wear,
corrosion and oxidation, for compatibility with
elastomers, for water tolerance, and tests on apparatus
simulating actual operation.
Special fluids
To complete the range of products for heavy-duty
vehicles there are other fluids (which are merely
mentioned here), whose main function may or may not
be that of lubricating the mechanical components.
They include engine oils for running-in and protection,
fluids for braking systems and hydraulic clutches, for
centralized hydraulic systems (CHF, Central Hydraulic
Fluid), and for cooling systems. Lastly, for some
applications (greasing, oils for air-conditioning
systems), for-life products of industrial origin are
used.
8.4.3 Main components
of lubricants
for heavy-duty vehicles
Base oils
Use of base oils in lubricants for heavy-duty
vehicles
Alongside the base mineral oils, obtained by
processing crude, Non Conventional Base Oils
(NCBO) and synthetic oils so called as they do not
derive directly from the processing of crude or because
they are obtained by processes of synthesis are
becoming more and more important.
Base mineral oils and NCBO derived from
processing crude oils are dealt with in Chapters
8.1 and 8.2 in Volume II. The synthetic bases most
commonly used in the sector of lubricants for
motor transport vehicles are: PAO
(polyalphaolefins, hydrocarbon bases from
hydrogenated a-olefins), PIO (poly internal
olefins, hydrocarbon bases from hydrogenated
internal olefins), and esters. Other synthetic bases
of more limited use are: polyglycols, polybutenes
and alkylated aromatics.
Choice of the base or of the mixture of bases is of
fundamental importance because, although many
properties of the lubricant are guaranteed by adequate
additives, the chemical nature of the base can strongly
influence a number of performance characteristics of
the lubricant.
Hence, according to the base used, the effects will
be positive or otherwise both on the chemical-physical
and rheological characteristics and on the performance
characteristics of the finished lubricant.
ENCYCLOPAEDIA OF HYDROCARBONS
 LUBRICATION AND LUBRICANTS

Mineral bases
Their characteristics depend on the Table 2. API and ATIEL classification of base oils.
hydrocarbon composition of the crude and on the According to the group concerned, the rules
severity of the extraction and paraffin cleanout of interchangeability in the final lubricants vary
(dewaxing) process. It is however possible to
define some general characteristics typical of this Viscosity
Saturation Sulphur
type of base. The presence of aromatic compounds Group
(% wt) (% wt)
Index
determines its good solvent capacity and a fair (IV)
resistance to oxidation thanks to the sulphur 90 and/or 0.03 80-120
I
compounds which act as natural antioxidants. On
the other hand, aromatic compounds can give rise 90 0.03 80-120
II
to polymerization products which in the long run III 90 0.03 120
can lead to deposits.
Mineral bases have cold characteristics decidedly IV PAO
inferior to those of synthetic bases because of their
V all other bases
high n-paraffin content, so that they enable lubricants
to be formulated in not particularly fluid viscometric VI (*) PIO
grades.
Lastly, they possess greater volatility than synthetic (*) only ATIEL
bases and this, together with degradation caused by
oxidative processes, can contribute towards a more Esters are another class of synthetic base,
rapid deterioration of the lubricant. typically used for motor transport vehicles; these are
polar compounds and for this reason are generally
Non-conventional mineral bases used in mixtures with PAOs. Depending on the type
The processes used in producing non-conventional of acid and alcohol used in the synthesis, it is
bases make it possible to achieve a final composition possible to give the base the desired rheological and
of cuts relatively independent of the characteristics of performance characteristics. Thanks to their
the original crude. Hence the quality of these base oils lubricating capacity and, when required, their
is superior to that of the base oils obtained from the pronounced biodegradability, esters are widely used
traditional solvent cycle, compared to which they offer in oils for two-stroke engines.
the following advantages: Other classes of synthetic bases are used in
Lower volatility with the same viscosity (lower particular lubricating sectors.
consumption in operation).
Higher viscosity index (wider temperature range Classification of base oils
in use). (according to API and ATIEL)
Better stability with temperature (longer useful Both API and ATIEL supply a base oil
life). classification criterion in relation to the content of
Low or negligible sulphur content (an element of sulphur and saturated compounds and to the viscosity
ever-increasing importance for engine oils, due to index (Table 2).
the growing demands for compatibility with
exhaust gas treatment devices). Additives

Synthetic bases The additive content in lubricating oils ranges

PAO are the class of synthetic bases most used for
heavy-duty vehicles. They consist of saturated
hydrocarbon chains with a high degree of branching.
Their characteristics in a cold state and their volatility
are far better than those of mineral oils derived from
extraction processes with solvent, hydrocracking or
hydroisomerization.
They are not very polar and consequently have
limited solvency, which can be prejudicial to the
capacity to solubilize the polar additives present in the
lubricating oil and the oxidation products formed in
operation.
from just a few parts per million to several
percentage points and, depending on the function
that these products have to carry out, they may be
classed as:
Substances intended to improve the intrinsic
characteristics of the base oils (viscosity index
modifiers and pour point improvers).
Lubricant protective substances (antioxidants).
Substances giving new properties and protecting
the metal surfaces of engines (detergents,
dispersants, friction modifiers, antiwear-EP
additives, rust and corrosion inhibitors).

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TRANSPORT
Viscosity index modifiers
Viscosity is the main physical property of a
lubricant and is a measure of the intermolecular
interactions of the oil and hence of the resistance
to flow. As temperature increases the viscosity of
the lubricant tends to diminish also causing a
decrease in the thickness of the lubricating film
between parts in relative motion. Viscosity Index
Improvers (VII), or Viscosity Modifiers (VM)
influence the viscosity-temperature trend, slowing
down the diminution in viscosity as temperature
increases thanks to the conformation variations
that their structure undergoes as a result of the
temperature.
VIIs are polymers with a variable molecular weight
belonging to the following main categories:
Hydrogenated ethylene-propylene copolymers
(also called OCP, Olefin Co-Polymers).
Hydrogenated polyisoprenes which may be linear,
partly branched or star-shaped.
Polymetacrylates (PMA) of long-chain alcohols
variable from C12 to C18 , linear and/or partly
branched.
Hydrogenated styrene-isoprene copolymers, which
may be linear, partly branched or star-shaped.
Polyisobutenes (PIB).
At a low temperature, these polymers have
a closely-knit structure which minimizes
interactions with the lubricant base;
as temperature increases, the polymer increases
its interactions with the base, extending its chains
and expanding, countering the decrease in
viscosity of the base.
In the production of VMs, control of the molecular
weight and its distribution represents a critical element
as these parameters regulate two important
characteristics of the polymer, i.e. its thickening power
and its mechanical shear stability.
Pour point improvers
These additives (Pour Point Depressants, PPD)
improve the pour-point characteristics of the lubricant
at a low temperature. The main types of these are
polymethacrylates, ethylene-vinyl acetate copolymers
and polyfumarates.
The effect of PPDs depends largely on the
characteristics of the bases used and on their
concentration. Normally, the action of these additives
is more effective compared to fluid bases (SN 80,
SN 150). Each class of PPD has a limit to its
effectiveness; above a certain percentage the effect on
the pour point ceases (and in certain cases it could
worsen) and the thickening effect starts to make itself
felt. The typical treatment percentages vary between
0.1 and 1%.
766
Antioxidants
Oxidation is the result of the interaction of the
components of the lubricant with oxygen at the
working temperatures of the engine. It is the chief
cause of the degradation of oil and leads to the
formation of acid species which gradually increase in
molecular weight, giving rise to dirt and sludges which
lead to an increase in the viscosity of the lubricant and
form deposits in the cold areas of the engine.
The oxidative degradation of the lubricant occurs
due to a complex series of radical chain reactions,
which can be acted upon by special antioxidant
additives or oxidation inhibitors. These additives on
the one hand interrupt the chemical reactions
responsible for the processes mentioned, and on the
other hand decompose the first degradation products
preventing any further evolution towards more harmful
species.
The main types of this class of substances are:
alkylated aromatic amines, sterically hindered phenols,
zinc dialkyl dithiophosphates, and derivatives of
dialkyl dithiocarbamic acid.
The amines and the hindered phenols act as radical
scavengers, transforming the reactive peroxides into
inactive species. The zinc dithiophosphates, apart from
acting with these mechanisms, decompose the
hydroperoxides (ROOH) heterolithically and
deactivate them.
Detergents and dispersants
These are two of the most important categories of
additives to engine oils and their function is to keep
the engine clean. This aim is pursued by trying to
reduce the formation of deposits and to keep the
insoluble substances produced by them in suspension,
hindering their further aggregation and adhesion to the
hot/cold metal surfaces.
Metallic detergents. These serve to neutralize the
acid products of combustion (organic acids and
sulphur oxides), to reduce sludges and deposits on the
pistons and to prevent problems for the piston rings
under severe temperature conditions. Generally, they
consist of colloidal dispersions in carbonaceous
lubricant bases of alkaline or alkaline-earth metals,
stabilized by an adsorbed layer of surfactant
molecules. The carbonaceous nucleus, typically
amorphous, represents the base reserve necessary to
neutralize the acid compounds, whereas the surfactant
layer consists of oleophilous chain acid salts (soap)
long enough to ensure the stability of the colloid. The
main chemical classes of metal detergents usually
employed are: sulphonates, sulphophenates and
salicylates.
The value of the basicity number (BN) determines
the neutralizing capacities of the additive while the
ENCYCLOPAEDIA OF HYDROCARBONS

soap content determines its effective detergent action.
Detergents are classified as neutral (BN25) or supra
basic (BN25) according to their neutralizing ability.
For heavy-duty vehicles, detergents having a base of
alkaline-earth metals are used, above all those with a
calcium base.
Dispersants. These additives are fundamental
for purposes of performance as they control the
state of aggregation of sludge and, in diesel
engines, of soot; in the lubricant they account for
more than 50% of the quantity of additives. Among
the most important molecular typologies are
derivatives of succinic anhydrides (succinimides,
succinesters, etc.) of very widespread use, and
whose synthesis has by now been documented by
more than 1,500 patents.
Dispersants, too, consist of amphiphilic molecules
in which the lipophilic portion usually consists of
polyolefinic chains (generally polyisobutene) with a
molecular weight that varies between 700 and 3,000,
while the polar group is, in general, the derivative of a
polyamine or of a polyol. The bond between these two
parts of the final molecule is obtained by means of
different chemical reactions. The most important
classes of dispersants are: succinimides, succinic
esters, alkylphenolamine (Mannich bases), and
polymeric dispersants.
Of them all, the succinimides are probably the
most important class and the one produced in the
largest volumes. They are prepared in two stages: the
first consists of functionalizing the chain of an alkyl
oligomer (polyolefin, preferably polyisobutene) with
maleic anhydride to produce a polyisobutylene
succinanhydride (PIBSA), while in the second stage
the PIBSA is converted into the final polyisobutylene
succinimide (PIBSI) causing it to react with an
N-amino-polyalkylamine (for example hexaethylene
hepta-amine, HEHA; tetraethylene penta-amine,
TEPA, etc.).
The succinic esters used as dispersants for
lubricants for motor transport vehicles are products
formed by esterifying a succinic derivative of a
polyolefin (analogous to those used for succinimides)
with mono- or poly-alcohols (for example
pentaerythritol), so as to produce dispersants having
molecular weights in general of the same order of
magnitude as those of succinimides.
Alkylphenolamines are polyisobutylenic phenols
(or polyalkyl-substitutes) made to react with
polyalkyleneamine by means of formaldehyde,
through the Mannich reaction.
Friction modifiers
These additives are chemical species able to
influence the friction coefficient under boundary
VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY
LUBRICATION AND LUBRICANTS
lubrication conditions. They may consist of very
long amphiphilic organic molecules or of
metal-organic compounds (generally with a
molybdenum base). The reduction of the friction
coefficient of the surfaces takes place by means of
the formation of an extremely smooth film of
molecules over them (e.g. example MoS2 in the case
of Mo dithiocarbamate).
Antiwear/EP additives
These are additives mainly used for reducing wear
under boundary lubrication conditions. Under
conditions of medium-to-high or extreme pressure
(EP), they react with the metal surfaces forming
protective tribo-chemical layers. In engine oils, they
perform essentially antiwear functions. The EP role,
which is marginal, is left to metal detergents.
The main class of antiwear additives consists of
zinc dialkyl dithiophosphates, whose introduction
coincided with the start of the technology of using
additives in lubricants. There are also
wear-prevention additives with a molybdenum base
(dialkyl dithiophosphates, dithiocarbamates),
organic compounds and metal detergents.
Widespread use is made of EP additives in
transmission oils. Among these, the main ones are: with
sulphur (antiwear/EP), sulphur-phosphorus compounds
(antiwear/EP), chlorinated paraffins (EP).
The chemical structure of zinc dithiophosphates is
as follows:
RO S S OR
P Zn P
RO S S OR
The alkoxide part (RO) derives from a short-chain
primary alcohol (C6) or a long-chain one (C6-C8) in
primary dithiophosphates or from a secondary alcohol
(C3-C6) in secondary dithiophosphates, and rarely
from an alkyl phenol (aryl dithiophosphates).
They are polar compounds and for this reason they are
generally used in mixes with PAOs. Thermal stability
increases in the order: secondary, short-chain primary,
long-chain primary, acrylic, while antiwear
effectiveness varies in the reverse order. The antiwear
additive, in fact, acts as such because, by breaking
down at the metal-metal contact temperatures it reacts
with the surfaces and forms layers with a low friction
coefficient. As stated, the zinc dithiophosphates also
carry out a very effective antioxidant function.
Currently, the use of zinc dithiophosphates is
limited because the phosphorus contained in them,
released during the partial combustion of the lubricant,
can interact negatively with the catalytic systems of
treating spent gases.
767
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8.4.4 Lubricants for industry

Table 3. Viscometric classification
of industrial lubricating fluids (ISO 3448) Classification
To guarantee effective lubrication, it is important to
Average Viscosity interval select the correct viscosity so that a lubricating film
ISO symbol viscosity (cSt at 40C) able to separate the two contact surfaces will be
(cSt at 40C) min max formed. In general, it is necessary for the oil to be
highly viscous in a situation of high loads and low
ISO VG 2 2.2 1.98 2.42 speeds, whereas in the case of high speeds, precisely
ISO VG 3 3.2 2.88 3.62 so as to reduce friction, very fluid lubricants are used.
A viscometric classification system has therefore been
ISO VG 5 4.6 4.14 5.06
drawn up for the lubricants used in industry.
ISO VG 7 8.8 6.12 7.48 Numerous methods exist to determine the correct
viscosity of an oil in relation to industrial mechanical
ISO VG 10 10 9.00 11.0
contacts: some of these are standardized, while others
ISO VG 15 16 13.5 16.5 have been developed by manufacturers, as is the case
ISO VG 22 22 19.8 24.2
for example with gears and bearings. Their purpose is
to provide, together with the viscosity index (VI), a
ISO VG 32 32 28.8 36.2 guide to choose the most suitable lubricant for the
ISO VG 46 46 41.4 60.8 particular application.
In the past, the Engler viscosity system was used in
ISO VG 68 68 61.2 74.8 Europe, while the SUS system was used in the United
ISO VG 100 100 90 110 States. Today for industrial oils the ISO (International
Standardization Organization) system has become well
ISO VG 150 150 136 186 established; it makes reference to kinematic viscosity
ISO VG 220 220 198 242 at 40C in mm2/s (or centistoke, cSt). The reference
temperature (40C) was chosen so as to be close to the
ISO VG 320 320 288 362
average working temperatures, and to the reference
ISO VG 480 460 414 508 temperatures of the old lubricant viscosity
classification methods. The standard grades envisaged,
ISO VG 680 680 614 748
defined as ISO VG (ISO Viscosity Grade), enable all
ISO VG 1000 1,000 900 1,100 practical demands of industrial lubrication to be
covered (Table 3).
ISO VG 1500 1,500 1,350 1,850
A very large number of products comes under the
definition of industrial lubricants, having an extremely
Anticorrosives/rust-inhibitors wide range of characteristics in their composition and
These protect the metal surfaces of the engine in their intended use for many different applications.
against corrosion and against the aggressive agents In fact, four basic typologies of products can be
generated during combustion (water, acid products, identified in this category: industrial lubricating fluid
oxidants, etc.) or act as protection during transport and in the strict sense of the word, lubricating grease,
storage. They act by creating a physical barrier on the products for mechanical processes and oils for various
metal surface, which prevents the corrosive agents applications and for process purposes.
from attacking it. ISO has issued a precise and extensive standard
The main types are: etoxylate alcohols, long-chain classification of industrial lubricants (ISO 6743-99)
carboxylic acids, phosphoric esters, amines, identifying 18 families of products, according to their
imidazoline and thioderivatives. application, each of them bearing a letter of the
By their nature they are compounds which can vie alphabet (Table 4). These are all the types of products
against other classes of additives (for example, zinc intended for lubricating industrial machinery, such as
dithiophosphates), with which they often compete for hydraulic oils, oils for turbines, oils for compressors,
treating metal surfaces, or which can negatively oils for bearings and oils for industrial gear systems.
influence other properties of the medium in which The relevant characteristics for purposes of
they operate (for example demulsibility). The presence application are: viscosity/viscosity index, pour point,
of metal surfaces of a varied nature in the engine, demulsibility, antifoam properties, air retention,
moreover, often requires the use of mixes of various compatibility with gaskets, antiwear properties,
anticorrosion additives. rust-prevention properties and stability to oxidation.

768 ENCYCLOPAEDIA OF HYDROCARBONS


Table 4. Classification of industrial lubricants
and of correlated fluids (ISO 6743-99)
Family
Application
(letter symbol)
A Once-only systems
B Pattern-drawing
C Gears
D Compressors
E Internal combustion engines
F Mandrels and spindles
G Guides and slides
H Hydraulic systems
M Metal working
N Dielectric
P Pneumatic tools
Q Diathermic
R Temporary protective
T Turbines
U Heat treatments
X Applications of greases
Y Other applications
Z Steam-driven machines
Apart from these characteristics, there are others that
take into account the specific use for which the
product is intended. These characteristics are
determined with testing methods drawn up by
international regulatory bodies; for the majority of
them the methods concerned are those of ASTM
(American Society for Testing and Materials).
Applications
Turbines
The various typologies of applications often
require specific products, as in the case of turbines.
In fact, for these, particular performance
characteristics are needed in terms of the chemical
stability of the product. In the case of steam
turbines the oil must have an outstanding ability to
separate from any water that might accidentally
contaminate it, while for gas turbines the properties
of resistance to oxidation are all-important. Oils for
VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY
LUBRICATION AND LUBRICANTS
industrial steam and gas turbines generally use
special mineral bases of higher quality than the
standard type, while for gas turbines of
aeronautical-type synthetic oils are used, generally
esters or polyalphaolefins.
Bearings
A vast part of the applications of industrial
lubricants regards the lubrication of roller or sliding
bearings. For these, specially formulated oils are used
which have no problems of compatibility with the
materials, which possess very high thermo-oxidative
stability and which at the same time take into account
the particular operating conditions associated with
their application; suffice it to mention the oils for
rolling mill bearings, characterized by their high
viscosity and outstanding demulsive characteristics,
and oils for paper mills, which may be of mineral type
but at times are of synthetic type (polyalphaolefins or
polyglycols) for operating in the hot parts of the
machines, or even of detergent-dispersant type to
maintain paper fibres in suspension as they could
otherwise accidentally contaminate them.
Hydrostatic plants
The main volumes of industrial lubricants,
consisting essentially of hydraulic fluids for
oil-pressure controls of construction site machinery,
industrial plants, etc., are concentrated in this category.
These products, as well as satisfying given chemical
and physical requisites, also have to pass bench tests
of tribological type, or rig tests simulating real
conditions. In this sector, the specifications are issued
by various organizations (ISO, DIN BS, etc.) or by the
manufacturers of components or machinery (Eaton
Vickers, Bosch Rexroth, Denison, etc.).
Gears
The products for lubricating industrial gears are
formulated by taking into account the type of gear
(design/shape), the presence of a covering or a
crankcase, the specific pressures, the contact area on
the gear mesh, the speed, the relative motion (rolling
or sliding) and the materials. For particularly severe
applications, EP lubricants are used with a
sulphur/phosphorus compound base.
Compressors
The lubrication of compressors is an extensive
sector with products that are extremely diversified in
their formulation in order to take into account both the
type of compressor and the chemical composition of
the gas to be compressed.
In reciprocating air compressors, the air can even
reach temperatures of around 200C, according to the
769
TRANSPORT
Table 5. Consistency and method of application of lubricating grease
NLGI Penetration
Consistency
number worked (dmm)
000 445-475 fluid
00 400-430 fluid
0 355-385 semifluid
1 310-340 very soft
2 265-295 soft
3 220-250 low consistency
4 175-205 low consistency
5 130-160 high consistency
6 85-115 hard
operating modalities, and under such conditions the oil
can leave deposits on the valves and on the upper part
of the cylinders. It is therefore important for the oil to
be able to withstand oxidation and to have a low
tendency to leave deposits. In screw compressors, the
air is compressed by confinement between two screws
encapsulated in a case. In this system, the oil is
introduced in large quantities and finely nebulized in
the air for the dual purpose of providing lubrication
and eliminating heat. The temperatures reached are
lower (100-120C) but as the lubricant is continuously
separated from the air and reused, it needs to have
strong resistance to oxidation.
In general, for the compression of other gases and
of frigorific gases, further problems arise, such as
miscibility or immiscibility, according to the operating
system of the lubricating circuit, as well as problems of
reciprocal chemical stability between gas and lubricant.
In compressors of dynamic type (centrifugal and
axial) the problems of lubrication, except for particular
cases of compatibility with the gas, can be likened to
those of steam turbines.
Guides and slides
These mechanical parts are in widespread use in
practically all industrial machinery. The situation of
machine tools is a particular one; in these, in order to
achieve a high degree of precision in production, the
clearance between slide and guideway has to be
extremely limited and it is necessary to avoid
conditions of hydrodynamic lubrication which would
reduce the regularity and evenness of movement of the
toolslides (or of the worktables). That is, it is
necessary to avoid what is known as stick and slip
770
Method of application
centralized system
centralized system
centralized system
grease guns and centralized systems
grease guns
compression cup
stauffer lubricators
grease in cakes
grease in cakes
which is caused by the tearing of the lubricating film
during motion. At the moment of such tearing, the
metal surfaces come into direct contact and friction
increases. The moment the motive power overcomes
this additional resistance there is an abrupt increase in
speed. The repetition of these irregular slow-downs
and accelerations produces a jerky movement which
has repercussions on the machine tool and hence on
the finish of the item being worked. To avoid the
inconvenience described above, additives with a high
polarity are used which reduce the static friction
coefficient, thereby making the movement smooth.
Lubricating greases
According to the ASTM definition, a lubricating
grease is a product from solid to semi-fluid made up of
a thickening agent in a liquid lubricant in which other
ingredients may be present (solid lubricants and
additives) which give special properties. This definition
establishes a fundamental concept, i.e. grease is not a
highly viscous oil, but a thickened oil, a multiphase
system consisting of two distinct components: the
thickener (or thickening agent) and a fluid oil. On the
basis of this, by varying the percentage of the thickener,
the consistency of the product will vary, this being
codified by numbers established by the United States
NLGI (National Lubricating Grease Institute). The
different consistencies are necessary according to the
type of application and the grease distribution system,
to the position of the item to be lubricated and to the
efficiency of the seal (Table 5). To obtain the desired
consistency, numerous types of thickening agents are
used, the chief categories of these being soaps, complex
soaps, organic thickeners and inorganic thickeners.
ENCYCLOPAEDIA OF HYDROCARBONS
 LUBRICATION AND LUBRICANTS

Soaps are obtained by saponification of a fatty acid
with an alkaline or alkaline-earth metal. Complex
greases are obtained by causing a fatty acid and a
second polar compound, termed complexing agent, to
react simultaneously with a basic component. These
greases were developed as they make it possible to
operate at higher temperatures than are possible with
ordinary soaps.
By organic thickeners are understood those with a
polyurea base, obtained by the reaction of isocyanates
and amines. They have high stability in time and
therefore are used for components with permanent
lubrication.
The most commonly used inorganic thickeners are
those based on bentone obtained from special clays:
bentonite and hectorite. Their feature is not having a
real melting point, for which reason they lend
themselves to being used in wide temperature
intervals. Thickeners with a silica base form another
category. And lastly there are also supra basic calcium
sulphonates. This variety of thickener stems from the
fact that, apart from the strong cost differences
between one typology and another, their performance
characteristics also differ (Table 6).
The base oil used in the formulation of a grease
may be of mineral, vegetable or synthetic type
according to the performance characteristics and the
application desired.
Additives are mixed with greases, as also with
liquid lubricants, to provide them with particular
properties; use is therefore made of antioxidants, wear
preventers, EP agents, rust preventers, corrosion
inhibitors, etcetera.
Greases are used for lubrication and for protecting
mechanical organs in all cases in which lack of space
or problems of seal do not allow liquid lubricants to be
used. In many applications, greases are used on a
recurrent basis (in steelmaking, continuous paper mill
machines, etc.), but in several cases their function is to
keep a component permanently lubricated (roller
bearings or small reduction units).
Products for mechanical processing
This is a very extensive range of products which,
utilizing the intrinsic properties of lubricating and
cooling oils, facilitate mechanical operations, which
may be grouped into two main categories: for plastic
deformation and with the removal of material.
Plastic deformation operations make it possible to
obtain items in their final form by acting on blanks.
These operations may be performed cold or hot
according to the type and the amount of deformation
that the item has to undergo.
Some of these operations regard the working of
metal in the metallurgical process (steelmaking), such
as rolling, extrusion of bars, forming pipes from solid
pieces, down to wiredrawing. Other plastic
deformation operations are aimed at obtaining end
products or components, such as pressing, drawing,
bending, punching.
In plastic deformation operations the main
requisite for the lubricant is that it shall reduce friction
which directly influences the life of the tool, power
consumption and surface finish. However, it is always
necessary to optimize performance; for example in
rolling operations it is sought to achieve a friction

Table 6. Properties of lubricating greases according to type of thickener

(Sscanty; Dmoderate; Bgood; Eexcellent)

Conventional Calcium Complex Complex Complex

Property Sodium Lithium Polyurea Bentonite
calcium anhydride aluminium calcium lithium

Smooth, Smooth, Smooth, Smooth, Smooth, Smooth, Smooth, Smooth, Smooth,

Aspect
fibrous buttery buttery buttery buttery buttery buttery buttery buttery
Drop point
170 100 140 190 260 260 260 240 infusible
(C)
Max
temperature 120 80 120 140 170 170 180 180 180
of use (C)
Resistance
D-S B-E E B B-E B-E B B-E B
to water
Oxidation
D S B-E B-E B-E D B-E B-E B
stability
Pumpability S-D B-E B B B S B-E B-E D

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TRANSPORT
coefficient low enough to guarantee low power
consumption but it is essential to avoid any slipping
which would prevent a grip on the incoming material.
In hot working, the increase in plasticity that occurs in
metals as temperature increases is exploited, but
without reaching melting point.
In processing with the removal of material, a layer
of surface metal is removed from the blank being
worked by one or more tools, and this layer is
transformed into a shaving. These operations are
carried out cold, that is without previously heating the
metal to be worked.
Emulsible products
Products emulsified with water are used in
operations in which it is necessary to increase cooling
capacity. A wide variety of typologies are used, in
consideration of the fact that the materials to be
worked have different mechanical characteristics
which influence their workability and compatibility
(problems of spotting) and there are multiple
processing characteristics.
The emulsions used are normally of oil/water type,
and their formulation is generally as follows:
A mineral oil preferably with a naphthenic or
mixed base.
Emulsifying substances, such as mixtures of
natural or synthetic sulphonates.
Stabilizing substances, such as alcohol compounds,
which help to make the bond between the
emulsifiers and the oil more stable.
Rust preventers.
Bacterially static or bactericidal substances and
those against fungal proliferation.
If necessary, anticorrosion (copper), antiwear and
EP additives.
Antifoam additives.
According to the type of oil and the applications,
the percentages of oil dispersed in water can vary from
1 to 25% in order to obtain the right protection against
corrosion and to allow for the difficulty of processing
and of the material.
By mixing emulsible oil with water, emulsions are
obtained whose aspect differs according to the state of
dispersion of the oil, its concentration and the type of
emulsifier. Generally, for the preparation of emulsible
oils intended for cutting operations ionic-type
emulsifiers are used, as these confer a slightly basic
reaction on the emulsion (pH8-9). These emulsions
are stable in an alkaline environment, but they
progressively lose their stability when they undergo
acid pollution. The stability of emulsions also depends
on the characteristics of the water, in particular its
hardness.
772
Synthetic products
Synthetic products are defined as products
consisting exclusively of aqueous solutions of
anticorrosive, oily, antifoam, bactericide additives.
Said products are used in the preparation of
transparent cooling liquids intended basically for
finishing and super-finishing operations on metal
items, carried out with abrasive tools such as grinding
wheels, abrasive stones.
Cutting oils
Cutting oils are used in cases in which
lubricating properties are more important than heat
removal. This occurs in certain extremely difficult
operations, such as for example deep well drilling.
Cutting oils consist of mineral oil with EP and
antiwear additives. In the past, products with a
chlorine or sulphur-chlorine base were widely used
as EP additives, but today such chlorine-based
products have been abandoned in many countries
for environmental reasons.
Bibliography
Booser E.R. (editor) (1983-1994) CRC handbook of
lubrication: theory and practice of tribology, Boca Raton
(FL), CRC Press, 3v.
Del Ross S. (1977) I lubrificanti. Caratteristiche fisiche,
chimiche e tecnologiche. Raffinazione additivi, Milano,
Etas.
Klamann D. (1984) Lubricants and related products: synthesis,
properties, applications, international standards, Weinheim,
Chemie.
Neale M.T. (1973) Tribology handbook, London, Butterworths.
Nortier R.M., Orszulik S.T. (1997) Chemistry and technology
of lubricants, London, Blackie Academic & Professional.
References
Ertel A.M. (1939) Hydrodynamic lubrication based on new
principles, Akad. Nauk SSSR Prikadnaya Mathematica i
Mekhanika, 3, 41-52.
Grubin A.N., Vinogradova I.E. (1949) Investigation of the
contact of machine components, Central Scientific
Research Institute for Technology and Mechanical
Engineering, 30.
Riccardo Maione
Eni - Divisione Refining & Marketing
Monterotondo, Roma, Italy
Luigi DElia
EniTecnologie
San Donato Milanese, Milano, Italy
ENCYCLOPAEDIA OF HYDROCARBONS