LUBRICANTS

INTRODUCTION:

The use of lubricants is well known from ancient times. Large-scale consumption of
lubricants started since 1947 in fields such as automotive applications, industrial machinery
and aviation. In all types of machines the surfaces of moving or sliding parts are under
friction. The frictional resistances are produced due to the,

1. Resistance offered by the forces of intermolecular cohesion and

2. Rough and uneven surfaces of the parts.

In practice the surfaces made about 100 % smooth but even though they have very
small projections. During the movement of parts, the projections get interlocked and
frictional resistance is created.

The friction causes lot of wear and tear of machine parts. This requires replacing the
parts periodically. Due to friction large amount of energy dissipates in the form of heat,
which decreases the efficiency of the machine. The parts when gets heated they changes their
shapes on expansion and opposes for the smooth running of the machine. In this case it is
required to cool the parts. In some other machines like internal combustion engines there is
loss in the power generation due to the leakage between piston and cylinder. To avoid all
these difficulties lubricants are introduced in between moving parts.

Lubricant is defined as the substance, which is introduced between moving and

sliding surfaces to reduce the frictional resistance between them. The process of reducing the
frictional resistance’s by introducing lubricants is called as lubrication. The lubricants absorb
the heat produced by frictional resistance and keep the moving parts cool and separate.

FUNCTIONS OF THE LUBRICANTS:

The various functions of lubricants are,

1. It reduces wear and tear, surface deformation by avoiding direct contact of two
moving or rubbing surfaces.
2. It reduces wastage of energy in the form of heat by acting as a coolant or heat
transfer medium.
3. It reduces expansion and destruction of the metal parts by local frictional heat.
4. It increases smooth relative motion of the machine parts.
5. It prevents the entry of moisture, dust and dirt between two moving parts.
6. It increases the efficiency of the machine by reducing the power loss.
7. It reduces the maintenance and running cost of the machine.
8. It acts as a cleaning agent and scavenger to wash off and transport solid particles
produced during wear and tear.
9. In internal combustion engine it acts as a seal between piston and cylinder wall and
prevents the power loss.

TYPES OF LUBRICANTS:

According to their physical states lubricants are classified as,

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 a) Solid lubricants: The solid lubricants are used under the following conditions,

1. When the heavy machinery is working under high load and high speed.
2. When the local temperature is very high and the lubricating oils and greases get
vaporised, catches the fire or decomposes.
3. When entry of dust particles and moisture is unavoidable.
4. When the liquid and semisolid lubricants cannot be maintained.
5. When the parts to be lubricated are not easily assessable.

The solid lubricants are used either in the form of dry powder or as a suspension in
the oil, grease and water. Examples of solid lubricants are graphite, chalk, talc, mica,
molybdenum disulphide, soapstone etc. Aqua dag (graphite suspended in water), oil dag
(graphite suspended in oil) are also useful solid lubricants. These lubricants are used in
railway chains, gears, bearings, lathe machines, foodstuff industry, railway track joints, air
compressors etc. Oil dag is useful in internal combustion engine. Molybdenum disulphide is
stable up to 400 0C and it has very low co-efficient of friction.

b) Semi-solid lubricants: Semi-solid lubricants are neither solids nor liquids at

ordinary temp. They can be used in following conditions,

1. When the machine parts are moving with low speed and heavy load.
2. Where the bearings produces high temperature.
3. Where the oil gives splashes and spoils the whole machine.
4. Where the entry of dust or moisture is undesirable. Dust and moisture spoils the
lubricating action.

The various types of greases, Vaseline’s, waxes, and other compounds of oil and fats
are used as semi-solid lubricants. The greases are the mixtures of petroleum, oil and soaps
which are sodium or potassium salts of higher fatty acids. The greases are prepared by
saponification of fatty acids with alkali like lime, caustic soda etc. Then hot lubricating oil is
added with constant stirring into soap. The consistency of grease depends on quantity of oil
added and its lubricating value depends on properties of oil used.

The properties of greases depends on nature of soap used to prepare them, e.g. the
temperature at which it can be used, its consistency, its water resistance and oxidation
resistance, therefore greases are classified on the basis of their composition and methods of
preparation as,

1. Calcium base greases: These are also known as cup greases or lime greases. These
are the emulsions of petroleum oil and water containing calcium soap as stabiliser. They are
very cheap and most widely used for lubrication. They are insoluble in water, therefore water
resistant. They are useful at low temperature below 80 0C.

2. Soda base greases: These are prepared by mixing sodium soaps with petroleum
oil. They are suitable to use near heat up to 175 0C for different types of gears but as they are
soluble in water, therefore not suitable for bearings exposed to wet conditions.

3. Lithium soap greases: These greases are having combined advantages of both
calcium base and soda base greases. These are prepared by mixing lithium soaps with
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petroleum oils. They are water resistant having good mechanical resistance, low oxidation,
stable in storage and suitable to use at low temperature 15 0C only.

4. Axle greases: They are prepared by adding lime or heavy metal hydroxide and
resins to fatty acids. They are very cheap, water resistant and suitable at high loads and low
speed.

The semisolid lubricants are used in tractor rollers, rail axle boxes, machine bearings
etc.

c) Liquid lubricants: Liquid lubricants are mainly lubricating oils. They reduce the
frictional resistance and wear between two sliding and rubbing surfaces. They can be used in
following conditions,

1. When the machine parts are moving with high speed and low load.
2. When the solid and semisolid lubricants are not useful.
3. Where the working temperature is low.
4. Where the cooling and sealing of the machine parts is required.

They are acting as a cooling medium, sealing agent and anticorrosive agents. These
lubricants are used for delicate machines moving with low load and high speed. The
important properties of the good liquid lubricants to be considered are,

1. High boiling point,

2. Requisite viscosity for working conditions,
3. Low freezing point,
4. High resistance to oxidation,
5. Heat stability and
6. Non-corrosiveness.

Lubricating oils are further classified as,

1. Vegetable oils and animal oils: Before the invention of mineral oils, vegetable and
animal oils were commonly used as lubricants. These oils are having plant and animal origin.
They are more costly and oxidises very easily at high temperature. They are having more
oiliness (i.e. the property by virtue of which the oil sticks to the surface of machine parts,
even under high temperature and heavy loads). These oils are having tendency to hydrolyse
when comes in contact with moist air or aqueous medium. Vegetable and animal oils can be
blended with petroleum oils for lubrication. They are also used to prepare greases and the
emulsions. Examples of these oils are Olive oil, Palm oil, Castor oil, Neat foot oil, hazel nut
oil, Rapeseed oil, Whale oil, Neat foot oil, Lard oil and Tallow oil.

2. Mineral oils: Mineral oils are obtained by the fractional distillation of petroleum
oils at 400 0C. The residue obtained after distillation is further distilled to separate light oil,
heavy oil and asphalt. They are used as lubricants because of their low cost, availability in
bulk and stability under service conditions. However, their oiliness is very poor as compared
with vegetable and animal oils. Their oiliness can be increased by the addition of animal and
vegetable oils or compounds like oleic acid, stearic acid, etc. Examples of mineral oils are
petroleum oil, paraffin’s, etc.

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 3. Blended oils: When the single oils are not serving as a perfect lubricant then the
oils can be blended with the suitable substances called as additives. The mixture of mineral
oil with special additives is called as blended oil. The additives used are the vegetable oils,
animal oils, organic compounds containing chlorine, sulphur and lead phosphates etc. The
additives increases the oiliness, stability at high temperature, corrosion resistance abrasion
resistance etc. The additives are preventing the high temperature oxidation of lubricants.

4. Synthetic oil: Synthetic oils are the special type of lubricants. They are stable at
high temperature (about 250 0C) as well as very low temperature (about -50 0C). They are
very costly and synthesised artificially. They are non-inflammable, having high flash points
and viscosity index. They are useful for lubrication in atomic power plants, rockets and
aircraft’s. Examples of synthetic oils are poly-alkaline glycols, silicon fluids and
fluorocarbons etc.

CHARACTERISTICS /PROPERTIES OF LUBRICANTS:

Lubricants are widely used for various types of machines. Their characteristics are
depending on following properties,

a) Viscosity: Liquid lubricants when applied, spreads easily over a surface. This is
possible only because of viscosity of oil. Viscosity is the property of a liquid by the virtue of
which it offers a resistance to its own flow. When a liquid is flowing over a plain surface then
it is supposed to contain number of parallel layers placed one above the other. The top layer
is moving with high velocity or faster than the next lower layer due to internal friction or the
viscous drag. Thus viscosity is the measure of internal resistance offered by its adjacent
layers.

Consider the two layers of a liquid separated by a distance ‘d’ and moving with a
relative velocity difference of ‘v’. Then the force per unit area ‘F’ required to maintain the
velocity difference is given by,
v
Fη
d

Where,  is the constant of liquid and it is called as co-efficient of viscosity. If v = 1

cm/second and d = 1 cm then F = . From this equation the co-efficient of viscosity is
defined as the force per unit area required to maintain the unit velocity difference of the
layers separated by the unit distance. The CGS unit of viscosity is ‘poise’ and it is the force
of one dyne is required to maintain the velocity 1 cm/second of the liquid layers separated by
the 1 cm distance. The smaller unit of viscosity is ‘centi-poise’ and it is 1/100th of the poise.

Viscosity is the most important property to be considered during lubrication. A good

lubricant should have minimum viscosity, so that it should form a continuous layer in
between the two sliding or moving surfaces. If the viscosity of the oil is too low it will not
form a fluid film and excessive wear will be there. On the other hand, if it is too high it will
resist the smooth relative motion of the machine parts. Therefore, the oils with low viscosity
are useful for high-speed equipments such as turbines, spindles and centrifuges while high
viscosity oils are useful for low speed equipments.

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 Surface Tension

Definition: Surface tension is the tendency of a liquid's surface to resist an external force,
caused by cohesive forces between molecules.

Importance in lubrication:

 Wetting and spreading behavior

 Oil film formation and stability
 Adhesion to surfaces
 Resistance to foaming

Factors affecting surface tension in lubricants:

 Temperature (generally decreases with increasing temperature)

 Chemical composition of the base oil
 Additives (e.g., surfactants can lower surface tension)

.
Applications: Understanding surface tension is crucial in designing lubricants for specific
uses, such as:

 Engine oils
 Metalworking fluids
 Hydraulic fluids
 Greases

Impact on Lubricant Performance:

 Wettability and Spreadability: Lubricants with lower surface tension can spread
more easily over surfaces, ensuring comprehensive coverage and effective friction
reduction. This characteristic is essential in applications like metalworking, where
uniform lubricant distribution is necessary to prevent wear and overheating.
 Film Formation: Adequate surface tension is vital for the formation of a stable
lubricating film between moving parts. A lubricant must possess the right balance of
surface tension to maintain this film under varying pressures and temperatures,
thereby preventing direct metal-to-metal contact and reducing wear.
 Additive Effectiveness: Surfactants and other additives are often included in
lubricants to modify surface tension, enhancing properties like detergency,
dispersancy, and corrosion protection. These additives help the lubricant perform
effectively under diverse operating condition

Considerations in Lubricant Selection:

When selecting a lubricant, it's important to consider its surface tension in relation to
the specific application requirements. For instance, in high-speed machinery, a
lubricant with lower surface tension may be preferred for rapid spreading and heat
dissipation, while in heavy-load applications, a higher surface tension might be
necessary to maintain a robust lubricating film.

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  Understanding and optimizing surface tension in lubricants is essential for ensuring
efficient operation, prolonging equipment life, and reducing maintenance costs.

c) Flash point and fire point: When the lubricants are used at high temperature they
may undergo volatilisation and causes loss in lubricant. A good lubricant should not volatilise
under the conditions of lubrication. If they volatilise, the vapours may catch fire. Hence a
good lubricant should be inflammable at the working temperature.

Flash point of a liquid is the lowest temperature at which the lubricating oil gives off
enough vapours that ignite for a moment when a small flame is brought near it.

Fire point is the lowest temperature at which the lubricating oil gives enough vapours,
which catch the fire and burn continuously for at least 5 seconds, when a small flame is
brought near it.

The most of the lubricating oils are having fire points 5 to 40 0C higher than their
flash points. The flash point and fire points do not have direct effect on the lubricating action
of oils. But they are important when the lubricants are used at higher temperature.

A good lubricant should have flash point at least above the temperature, at which it is
to be used.

The flash and fire points are determined by using Pensky -Marten’s flash point
apparatus.

Distinction between flash point and fire point

Sr. Flash point Sr. Fire point
No. No.
1. It is the lowest temperature at 1. It is the lowest temperature at
which lubricating oil gives enough which the lubricating oil gives
vapours that ignite for a moment enough vapours, which catch the
when a small flame is brought near fire and burn continuously for at
it. least 5 seconds, when a small
flame is brought near it.
2. Flash point should be always 5 – 2. Flash point should be always 5 –
40 0C lower than fire point. 40 0C higher than fire point.

Neutralization value/Acidity:

The acid value (also called neutralization value) is a measure of the free fatty acids (FFA)
present in an oil or fat. It indicates the amount of potassium hydroxide (KOH) in milligrams
needed to neutralize the free fatty acids in 1 gram of the sample.

It is an important parameter in determining the quality, freshness, and potential degradation

of oils and fats, especially in edible oils, as the presence of free fatty acids often results from
the hydrolysis of triglycerides due to rancidity.
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Principle:

The acid value is based on the neutralization reaction between free fatty acids in the oil and a
standard alkali (usually KOH or NaOH). When oils and fats are exposed to moisture, air, or
enzymes (lipase), they tend to break down into free fatty acids and glycerol. A higher acid
value indicates higher levels of free fatty acids, which is usually an indicator of oil
degradation or poor quality.

Process:

1. Weighing the Oil Sample: A known mass of the oil or fat sample is taken.
2. Dissolving in Solvent: The sample is dissolved in a neutral solvent, usually a mixture
of ethanol and diethyl ether (neutral alcohol-ether mixture).
3. Titration: The dissolved oil is titrated with a standard solution of potassium
hydroxide (KOH) or sodium hydroxide (NaOH) using phenolphthalein as an
indicator. The endpoint is reached when the solution turns faintly pink, indicating
neutralization of all the free fatty acids.

Reaction:

RCOOH + KOH ---------- RCCOOK +H2O

Calculation of Acid Value (AV):

AV= V X N X 56.1 / W

Where:

V = Volume of KOH or NaOH used in titration (mL)

 N = Normality of KOH or NaOH

 56.1 = Molecular weight of KOH
 Weight of sample = Weight of oil or fat sample (grams)

Significance of Acid Value:

1. Quality Control: The acid value is a key indicator of the freshness and quality of oils
and fats. Low acid values indicate high-quality, fresh oil, while high acid values
suggest deterioration due to rancidity.

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 2. Shelf Life Assessment: A higher acid value indicates that the oil has undergone
hydrolysis, releasing more free fatty acids. This is commonly used to assess the shelf
life and rancidity level of oils, especially in the food industry.
3. Processing and Refining: During oil processing, the acid value helps determine how
much refining or neutralization the oil needs to make it fit for consumption. Oils with
high acid values may require additional refining to reduce the free fatty acids.
4. Edible and Industrial Uses: In edible oils, the acid value is critical for consumer
safety and taste. In industrial applications, such as in biodiesel production or
lubricants, a high acid value can affect the quality and efficiency of the final product.
5. Health and Safety: In the food industry, higher acid values in cooking oils can lead
to poor taste and potentially harmful byproducts if used for consumption

Saponification value:
Saponification value of oil is defined as the number of milligrams of potassium hydroxide
required for complete saponification of one gram of oil.

When KOH is added to oil, it reacts with oil giving hydrolytic reaction to form soap,
which is potassium salt of higher fatty acid and glycerol is the other product.

The saponification value is a measure of non-fatty impurities present in the oil. Thus,
saponification value is a characteristic of oil. For determination of saponification value a
weighed quantity of oil is heated with excess of KOH solution. The amount of KOH require
for saponification is determined by back titration of KOH with standard acid.

The saponification value can be used to determine the purity of oils and to
differentiate the oils as mineral, animal or vegetable in nature. Animal and vegetable oils
undergoes saponification but mineral oils do not and the saponification value is a
characteristic property of particular oil. A good lubricant should have moderate
saponification value.

Principle:

Saponification refers to the hydrolysis of triglycerides (fats or oils) into glycerol and fatty
acids in the presence of a base like sodium hydroxide (NaOH) or potassium hydroxide
(KOH). The saponification value measures the total amount of alkali required to fully
hydrolyze the ester bonds in 1 gram of fat or oil.

The reaction involves breaking the ester bonds in the triglycerides, releasing the fatty acids
and neutralizing them with a base to form soap (a salt of the fatty acid).

Process:

1. Weighing the Oil Sample: A known mass of oil or fat is dissolved in an alcohol
solution (usually ethanol).
2. Saponification: A measured amount of alcoholic KOH (potassium hydroxide) is
added to the solution. This base reacts with the triglycerides to form glycerol and
potassium salts of fatty acids (soap).
3. Titration: After the reaction, the excess unreacted KOH is titrated with a standard
solution of a strong acid, usually hydrochloric acid (HCl), using phenolphthalein as an
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 indicator. The amount of KOH that was used in the reaction is determined from this
titration.
4. Calculation: The saponification value is calculated by determining the difference
between the amount of KOH added and the amount remaining after the reaction
(determined by titration).

Calculation of Saponification Value (SV):

Saponification value=N(V2-V1)X56
-----------------
W

Where:

 V1= Back Titration Reading

 V2= Blank Titration reading
 N= Normality of KOH
 56.1 = Molecular weight of KOH
 Weight of sample = Weight of oil or fat sample (grams)

Reaction:

Significance of Saponification Value:

1. Chain Length Indicator: Higher saponification values indicate shorter average fatty
acid chains, while lower values suggest longer chains. Short-chain fatty acids require
more KOH to hydrolyze, so oils with short fatty acids (like coconut oil) have higher
SVs.
2. Purity Assessment: SV helps to assess the purity of fats and oils. Deviations from
standard SV values for a particular oil can indicate contamination or adulteration.
3. Industrial Use: In soap making, higher SV oils produce soap that is harder and less
soluble in water, while lower SV oils produce softer soap. The SV is also useful in
industries producing biodiesel or cosmetics.

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4. Identification of Fats and Oils: Each fat or oil has a characteristic SV. This value
can help identify or differentiate between types of oils.

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