Module 3: LUBRICANTS

Pre requisite: Definition of Lubricants and Lubrication

Functions of lubricants, Mechanism of lubrication Thick Film, Thin Film and
Extreme Pressure
Classification of lubricants, solid lubricants (graphite and molybdenum
disulphide), semi- solid: lubricants (Greases), liquid lubricant (animal/vegetable
oil, Blended oils)
Lubricants for special applications,
Properties of lubricants, definition and significance, viscosity, viscosity index,
flash and fire point, cloud and pour point, acid value and problems, saponification
values and problems.

In all types of machines, when the surfaces of moving or sliding or

their
rolling parts rub against each other, a frictional resistance is offered to
movemnent and this causes a lot of wear and tear tô the surfaces of moving parts
effects of
and alarge amount of energy is dissipated in the fom of heat. The il
frictional resistance can be minimized by using a suitable substance, which
forms a thin layer between the moving paris.
Any substance pla zed hetwien two moving or sliding surfaces with a
view to reduce the frictional resistance between them thereby reducing the wear
and tear, is known as lubricant.
The process of reducing friction between two metallic sliding surfaces
by the introduetion of lubYicants is called lubrication.

Functions of a lubricant (Purpose of lubrication)

the
t reduce[ friction, wear and tear because direct contact between
rubbing surfaces is avoided.
2. It reduces the frictional heat, or it act as a coolant.
of
3. It increases the efficiency of machine by minimizing the loss
mechanical, electrical or chemical energy.
moisture.
4. It acts as a sealant preventing the entry of dust, dirt and
5. It reduces the maintenance cost and running cost of machines.
7. It makes the relative motion of sliding parts noise free.

Dept. of Applied Sciences (Chemistry)

 down conditions, i
8. I avoids corrosion of metallic surfaces during shut
which the ubricant film avoids the direct contact of atmospheric gases
with metal surfaces.

Mechanisms of Lubrication
The phenomenon of lubrication can be explained with the help of three
types of mechanisms:

Hydrodynamic or fluid fim or thick film lubrication

ln this type of lubrication, the ubricant is forming a thick film having
about 1000 A° thickness betwcen the moving surfaces so that the direct surface
to-surface contact and welding of junction rarely ocçurs, The lubricant covers
the irregularities of the sliding surfaces and forms athick layer in between. The
coefficient of friction is very low ie. 0.00l o 0.03 under hydrodynamic
lubrication.
When oil is introduced between the moving surfaces, some of the oil
molecules are held up tightly at the surface due to adsorption. The remaining oil
molecules are loosely arranged away from metal surfaces. The frictional
resistance is only due to the internal reiSalce between the particles of
lubricants moving over. each cthèr. So the lubricant chosen should have the
minimum viscosity and should remain inplace and separate the surfaces.

Thick film lubrication

For hydrodynamic lubrication to occur, two essential conditions are to be
satisfied: (i) liquid must be viscous and (ii) the shape of the surface should be
2
 case of a shaft running
such that awedge shaped film should be formed. In the
bearing with low load, a wedge
at a high speed as well as in well-lubricated
shaped ilm is formed between the surfaces.
Journal bearings - consist of a shaft or journal that rotates
Example:
metal sleeve or shell with lubricating oil in the interface
freely in asupporting rotates at sufficient speed to
During normal operation the shaft
between them. the shaft and the shell
the oil between the confornming curved surfaces. of
force allows these
thus creating the oil wedge and hydrodynamic film. This film
understaDd that the
heavy loads. It is important to
bearings to supportextremely shellduring normal operations.
bearing
rotating shaft is not centered in the

satisfactory for fluid film lubrication. In order to maintain

Hydrocarbonoils are polymers may also be added.
seasons, Jong chain
proper viscosity in different guns etc. requires hydrodynamic
laus,
Watches, clocks, sewing machine,
lubrication.
lubrication
Boundary layer or Thin film the film thickness between two
Boundarý lybrication occurs when
that the formation hydrodynamic oil
so thin, so
surfaces in relative motion is metal-metal contact. Such a situation
in direct
film is not possible and result
may arise when
I, The load is very high
2. A shaft starts from rest
insufficient supply of oil
3. Low speed resulting in
4. Viscosity of the oil is too low

Dept. of Applied Sciences (Chemistry)

 High load

Adsorbed layer

surfaces is
In boundary lubrication, the space between the metal
lubricated with oil lubricants, a thin layer of which is adsorbed chemically or
physically and avoid direct metal to metal contact.The thin film will have
thickness around 10A° and consists of one or/two molecular layers. The
coefficient of friction is about 0.05 to 0.15. The load is carried by the layers of
the adsorbed lubricant on both metal surfaces. The extent with which the
lubricant gets adhered to the metal surfáce depends on oiliness of lubricant.
Mineral oils blended with vegetable and animal oils, graphite,
molybdenum disulphide etc are use:lirboundary lubrication.
Gears, railway track joints, tractors, rollers etc are provided with this
type of lubrication.
For boundary lubrication to be effective, the lubricant molecules should
bave:
1. Longhydrocarbon chains
2. Polar groups to promote spreading and orientation over the metallic
SUtfaces at high pressure
3. Lateral attraction between the chains
with the metals
4. Active groups or atoms that can form chemical linkages
ór other surfaces.

Extreme pressure Lubrication

Under heavy load and high speed operating conditions, large amount of
frictional heat is generated. This will lead to the evaporation or decomposition
4
of the lubricant. To withstand such extreme conditions, special
added to the lubricating oil. Additives are generally organic additives are
compounds hav1ng
active radicals or groups such as chlorine, sulphur, phosphorus etc. They react
with the metal surfaces at high temperature and form durable films of metallic
chlorides, sulphides and phosphides. These compounds posses high melting
pomt and good thermal stability and hence, serve as good lubricant. However,
they are noteffective on chemically inert metal surfaces of Ag, Ti, and Cu.
This type of lubrication is used for cutting tools, in wire drawing, ock
crushing machines etc.

Classification of lubricants
Lubricants are broadly classified on the basis of their physical state as
1. Solid lubricants
2. Semi-solid lubricants or greases
3. Liquid lubricants (lubricating oils)
Solid Lubricants
They are used when the operating conditions are such that a lubricating film
cannot be formed or maintainea.

1. Contamination of liquid orsemi-solid lubricant, with dust or dirt is not

desirable; eg: open gears.
2. Combustible Aubricants must be avoided due to the high operating
temperaturé and pressure.
3. Heavy machinery working on a crude job at very high loads and slow speed.
4. Wherethe parts to be lubricated are not easily accessible.
Solid tobricaDts are thermally stable, and are used either in powder form or
mixed with water or oil. The solid covers up the irregularities in the surfaces of
moving parts and form solid films, which have low frictional resistance. The
usual cóefficient of friction bet ween solid lubricants is between 0.005 and 0.01.
Graphite, Molybdenum disulphide, Talc, Soap stone etc are examples.
Graphite
Graphite is the most widely used of all solid lubricants. It consists of a layered
lattice structure. A layer of hexagonally arranged sp² hybridized carbon atoms in
Dept. of Applied Sciences (Chemistry)
 neighboring parallel
the planar graphite molecules bonded covalently. The two
Waals forces.
layers are 3.7 A° apart and are held together by weak vander

Van ccr
ntoracin

e
/aal%

Layered structure of graphite

Graphite is the most widely used of all solid lubricants. It consists of a

layered lattice structure. A layer of hexagonally arranged sp hybridized carbon
atoms in the planar graphite molecules bonded covalently. The two neighboring
parallel layers are 3.7 A° apart and afe, held together by weak vander Waals
forces. Therefore the force requwred to shear layers is very low and the
molecules can slide over eahother casily by mechanical force. Hence, graphite
powder is very soapy to touch o very soft and can act as lubricant. It is not
inflammable and not oxidizedin air below 375°C. In the absence of air, it can be
used up to very high temperature. Usually some organic substances are mixed
with solid iubricants so that they may stick firmiy to the netai surface. Graphite
is used eitherin powdeYed form or as suspension in water (called "Aqua dag")
or oil (called "Oildag"). Oil dag is useful in IC Engines,. Aqua dag is useful in
air compressors,general machine shop work, lathes and for machinery used in
food industry.
Molybdenum disulphide (MoS>)
It has a layered lattice structure (sandwich type) in which Mo layer lies between
S layers. Poor interlaminar attraction is responsible for si.car strength in a
direction parallel to the layers. Hence it is smooth and has very low coefficient
of friction.

6
 Mo

Mo

Layered structure of Molybdenum disulphide

It is stable in air up to 400°C. It is sprinkled as finë powder on the

surface sliding at very high velocities and fills up valleys on metal surfaces and
forms a film. Itis used also along with solventS and greases. It is used for high
temperature high velocity situation.
Semi Solid lubricants (Greases)
Greases, Vaseline and waxes are exâmples. Lubricating grease is a semisolid
consisting of thicken.ng "e such a_ metallic soaps, dispersed throughout
liquid lubricating oil. The liquid ubYicant may be petroleum oil or even
synthetic oil and it may contain anyof the additives for specific requirements.
Soap is obtained by the reaction of a vegetable oil with an alkali.
Vegetable oil+ Alkli Soap Glycerine
(Metal carboxylate)

Alkali may be NaOH, KOH, Li(OH), Ba (OH)2 etc.

Soap (Gelling agent) +Synthetic or Petroleum oil ’ Grease

Greases are prepared by the saponification of fat such as talow or fatty
acid with alkali like lime, caustic soda etc, followed by udding hot lubricating
oil, while under agitatioi. The total amount of mineral oil added determines the
consistency of the finished grease. Consistency may vary from a heavy viscous
liquid to a stiff solid mass.

Dept. of Applied Sciences (Chemistry)

 thickening
To improve the heat resistance of greases, inorganic solid
agents like finely divided clay, bentonite, colloidal silica, carbon black etc
added.

Greases are used under the following conditions.

1. In situations whcre the oil cannot remain in placc duc to high Joad, low
speed, intermittent operation, sudden jerks etc.
2. Insituations where bearing has to be protected against entry of dirt, dust,
moisture etc because greases are less liable to contamination by thése.
3. In situations where dripping or spurting of oil is undesirable because
unlike oils, grease i! used do not splash or drip över articles being
prepared by the nachines e.g: machines used in paper,, food, textile ard
dying industry.
4. When the machine is worked at high
The main function of soap is as
ternperature and high pressure.
thickening agent, so that grease sticks
firmly to the metal surfaces. However, the nature of
svap
consistency, (2) its water and oxidation resístance and (3) the decides (1) its
which grease can be used. So greases are classified on the temperature up to
basis of soaps used.
Calciun based greases (cup greases)
These are gels of calcium soap and petroleum oils.
adding requisite amount of Ca(OH)2 to hot oil while under They are prepared by
greases are cheapest, and most commonly used. They can be agitation. These
range of consistency. They can prepared in a wide
be used up to 80'C.
Soda based greases'
They arà petroleum oils thickened by mixing
resistant to water. They can be used up to 175"Candsodiumare
soaps. They are not
bearings, where the lubricants get heated due to friction. suitable for use in ball
Lithium based greases
These are petroleum oils thickened by
water and heat resistant, and are mixing lithium soaps. These are
suitable for use at lower temperature. They can
be used at higher temperature after adding certain additives. They have high
mechanical and oxidation stability. They have high mciting point ( about 150°C)
Axle greases
Ihey are very cheap resin greases prepared by adding lime, resin and
fatty oil. The mixture is thoroughly mixed and allowed to stand, when the
grease tloats as stiff mass. Fillers like talc, mica etc. may be added."hey are
water resistant and suitable for les delicate equipments working underhigh
loads and slow speeds.
Liquid lubricants (Lubricating oils)
Lubricating oils reduce friction and wear betweentwo moving / sliding
metallic surfaces by providing a continuous fluid film in between them. They
also act as cooling medium, sealing agent ¥nd prevent corrosion. A good
Jubricant should possess
1. low freezing point
2. high oxidation resistance
3. high thermal stability
4. higl. flash and fire point
5. high viscosity index
Animal or vegetable oils
The oils are glyceryl esterS of higher fatty acids. The oils are extracted by hot
pressing of oil bearing seeds or animal fats.
1. They possess góodoiliness.
2, Undergo oxidation easily, forming acidic products.
3. High cloud and pour points
4. Low flash and fire points
5. Low Viscosity Index
6. Easily emulsified with water.

Dept. of Applied Sciences

(Chenmistry)
Mineral Oils
petroleum. The length of carbon atoms
These are obtained by the distillation of
chain increases, the viscosity
will vary from 20 to 35. As the length of carbon
They are cheap, have
also increases. They are most widely used as lubricants.
used after
good thermal stability, but possess poor oiliness. The mineral oils are
purification.
Blended oils

No single oil serves as most satisfactory lubricant for many Of the modern
machineries. Properties of petroleum based lubricating oils are improved by
incorporating speciric additives. These so called blended oils give desired
lubricating properties required for particular machinery:
Name of additive Functions Example
1 Oiliness carriers Improves the strength of Animal and vegetable
the oil film oils
2 Extreme pressure To maintain ilm àt high | Chlorinated esters,
additives pressure and termperature sulphurised oils etc
conditions
3 Thickeners ToimprOve the viscosity Polystyrene, Polyesters
4 Viscosity IndexTo reduce the rate of Polymers and
improvers change of viscosity copolymers of olefins,
Styrenes etc

Antifoaming
agentsg
Prevents persistant foam
formation
Glycols, Glycerol

6 Antioxidants Reduce Oxidative Aromatic amines.

decomposition phenolic compounds
Antiwear additives Reduces wear and iear and Organic phosphates,
prevent seizure sulfurized fats
Pour point Helps the flow of lubricants Phenolic polymers,

10
 depressants at low temperatures
alkylated naphthalenes
Emulsifiers Keeps the contaminants Polymeric alkyl thio
dispersed phosphonates
10 Corrosion Prevents rusting of metal Fatty acids and amines
inhibitors parts

Synthetic oils
Synthetic lubricants have developed which can be used under drastic and severe
conditions. Important classes of synthetic lubricants are:
1. Polyalkylene glycols and their derivatives. Hàve high V.I, low
viscosity at sub zero temperature and low treezing points. They
decompOse at high temperature to volatile pårts and hence considered as
residue free high temperature lubricants.
2. Silicones: -Possess high V.I, can be used upto 200oC, above which it
gets decomposed
3. Dibasic acid esters: 2- ethyl hexyl sebacate. Has excellent thermal
stability, low volai nOn coiosive, excellent V.I
4. Organophosphate esters :- good fire resistant properties, stable upto
1500C

5. Halogenated hydrocarbons greater stability, non inflammability,

thermal and chemical resistance, high V.I
Properties of lubricants
Viscosity and Viscosity index
Viscosity is the property of a liquid by virtue of which it offers
resistance to its own flow. If the viscosity of the oil is too low, the oil film
cannot be maintained between the moving surfaces and as a result, wear and tear
will take place. If the viscosity is too high, then there is excessive friction.
Viscosity of liquid decreases with rise in temperature and the
Iubricating oil become thinner as the operating temperature increases and hence
the tendency t0 remain in place becomes less. Hence the viscosity of good
Dept. of Applied Sciences (Chemistry)
 change in temperalure, SO that it
change much with
lubricating oil should not
used under varying conditions of temperature. using Redwood
can be can be measured by
Viscosity of lubricating oil
Viscometer.
oil changes with tenmperature, is
of an
The rate at which the viscosity Index (V.I). If the viscosity of
scale called Viscosity
measured by an arbitrary oil is said to have hgh V.I.
raising the temperature, the
oil is slightly affected on
other hand, if the viscosity of an oil falls rapidly as the temperatuYe is
On the
raised, it has a low V. I.
lubricating oil should possess moderate viscosity so that it can remain in
Good
have high viscosity index.
place under the working conditions and should

Flash point and Fire point

tenipeYature at which the lubricant
Flash point is defined as the lowest
off enough vapours to cause a momentary flash when a standard test flame
gives
is brought near it.
vapours catch fire
Fire point is the lowest temperature at which the oil
for at least 5 seconds, on being, lighted by a test flame.
point. A good
In most cases, the fire point is 5 -40°C above the flash
temperature. This
lubricant should have flash puint u least above the working
acts as a guide
ensures safety against the risk of fire hazards. Thus flash point
machines.
for thesafe storage, transportation and use in
and Abel's
Flash and fre points can be deterninedby Pensky - Mariens
flash point apparatus.
Goodlubricating oil should have high flash and fire point.

Cloud and pour point

When oil is cooled slowly, the temperature at which it becomes cloudy
or hazy in appearance is called its cloud point.
After cooling oil, the temperature at which it ceases to flow is called its
pour point.
Cloud and pour point indicates the suitability of the lubricating oil in
cold conditions. Lubricant used in a machine working at low temperatures
12
slhould peOSsCSs low pour point. Otherwise solidification of the lubricant will
cuse the jumming of the machine. I1 has been found that presence of waxes in
the oil raises the pour point.
Good ubricating oilshould h¡re lon cloud and pour point.

Acid value (Neutralization number)

Acid value is defined as the number of milligrams of KOH required to
neutralize tree acidpresent in Igram of lubricating oil.
period, the
When petroleum oil is used at high temperature for a long
get oxidized by air which results in the formation of carboxylic acids
molecuies
and increase the acid value.
R-CH;-CH)-R - RCOOH + RCOOH

Normality of KOHx56
Acid Value = Volume of KOH x
Weight of oil taken

lubricating oil
Generally ne aeids are not present in the lubricants. Good
.0uld have acid value less th£n 0.2

Saponification valve
required
Saponification value is definedas the no of milligrams of KOH
oil.
losponilyone gran ofvegetable or animal saponified
and get
Animal and vegetable oils are esters of fatty acids
saponification value.
with alkali and they posses their own characteristic
KOH x 56
Saponification Value = Volume of KOH x Normality of
Weight of oil in grams

helps to ascertain the presence of

The determination of saponification value
animal and vegetable oils in a lubricant.

Dept. of Applied Sciences (Chemistry)