A REVIEW ARTICLE ON

“CHEMISTRY, ROLE AND FUNCTIONS OF ADDITIVES IN PETROLEUM

PRODUCTS i.e. LUBRICATING OILS AND GREASES”

By Shri A K Kanaujia, JAG (NFSG)/Controller and Dr O P Singh, PScO/ Dy.

Controller, DGQA, CQA (PP) Kanpur- 208004, UP

Abstract: The base oils are the main constituents of all lubricating oils but only the use
of different additives makes different grades of lubricating oil having different
performance level. The additives are substance or prepared mixture, added to base
oil, in concentrations typically ranging from 0.05 to 30 % by weight, to impart or
enhance the chemical and physical properties for usage in a combustion engine. The
important additives used in lubricating oils are Friction Modifiers, Anti-wear agents
(A.W.), extreme-pressure (E.P.) additives, Antioxidant additives, Anti-foam (A.F.)
agents, Rust and corrosion inhibitors, Viscosity index improvers, Pour point
depressants and Multifunctional nature of additives.
Like lubricating oils the greases are also unique due to their composition. The most
important components used in greases are base stock and thickener. In similar fashion
to other lubricants a wide range of additives are available to boost the performance of
specific grease. The additives performing in the bulk of greases are Antioxidants and
Scavengers where as the Additives Performing at a Surface are Antiwear Agents, Rust
and Corrosion Inhibitors, Extreme Pressure (EP) Agents, Friction Modifiers, Metal
Deactivators, and Seal Swell Agents etc.

The aim of this article is to review the chemistry, role and functions of lubricant
additives, as well as their role/ benefits towards engine operation.

1. INTRODUCTION:

1.1 Lubrication: The principle of supporting a sliding load on a friction reducing film is
known as lubrication. The substance of which the film is composed is a lubricant, and to
apply it is to lubricate. The basic principle is the prevention of metal-to-metal contact by
means of an intervening layer of fluid or fluid-like material.

1.2 Lubricants: Modern equipment must be lubricated in order to prolong its lifetime. A
lubricant performs a number of critical functions. These include lubrication, cooling,
cleaning, suspending, and protecting metal surfaces against corrosive damage.
Lubricant comprises a base fluid and an additive package. The primary function of the
base fluid is to lubricate and act as a carrier of additives. An important function of the
lubricant is also to prevent these contaminants from doing any damage to the engine.
The contaminants may be wear debris, sludges, soot particles, acids, or peroxides.
1.3 Tribological System (Lubricant Designing Parameters):Designing a lubricant
requires the tribology chemist to start with a performance specification sheet outlining

OPS-additives | 1
parameters and conditions the lubricant must meet and exceed in its finished
commercial form. Typical design parameters include:
(i) Lubricant type (gear oil, hydraulic oil, etc.)
(ii) Application requirements i.e. load, speed, bearing surface motion [sliding,
rolling, combination], delivery method.
(iii) Lubricant quality (viscosity index, lubricant life expectancy, selling point)
(iv) Operating environment (moisture, chemicals, ambient temperatures, etc.)
(v) Operating temperature range
(vi) Biodegradability

These typical design parameters are technically known as the “Tribological System”
within which the lubricant must perform. Lubricant type, application, quality and
operating temperature range are primarily used to determine an appropriate base stock
and additives to strengthen or modify the product’s characteristics to meet the finished
design specification. Even lesser-quality base stocks can be significantly modified to
meet specifications with additive packages.

What’s a Lubricant expected to do:

 Reduce Friction
• Minimize Wear
• Cool Parts
 Prevent Corrosion
• Disperse Contaminants
• Act as a Sealant
• Transmit Power

1.4 Base oils: The lube oil base stock is the building block in which appropriate
additives are selected and properly blended to achieve a delicate balance in
performance characteristics of the finished lubricant. The key achievement for highest
levels of performance in finished lubricants is the understanding of the interactions of
base stocks and additives and matching those to requirements of machinery and
operating conditions to which they can be subjected.
A wide range of base stock/ base oils are available and classified into 5 Groups (Table-
1) based on saturates level, sulfur content and viscosity index (VI).

Table1:Classification of Base oil ( Base Stock)

Group Description Saturates Sulfur Viscosit Trend

level % y index
I Crude oil is distilled, <90% >0.03% 80-120 1. Lower sulfur
refined physically %
with solvents, and
OPS-additives | 2
 may also be 2. Higher VI
hydrofinished, to
leave a base stock
and by-products. 3. Purer higher
saturates
II Crude oil is distilled >90% <0.03% 80-120 level
and chemically
refined by 4. Higher flash
hydrogenation, to point
leave a base stock
with fewer by-
products.

III Cruide oil is distilled >90% <0.03% >120

and refined by
severe cracking and
hydrogenation, to
produce a higher VI
base stock and even
fewer by-products.

IV PAO-polyalphaolfins >>90% <<0.03% >>120

are chemically
synthezised base
stocks with
increased VI
compared to Group
III stocks.

V All base stocks not >>90% <<0.03% >>120

classified in other
groups, including
vegetable oil,
derived base stocks,
esters, diesters,
glycols, etc.

Therefore higher groups of base stock will be viscosity, Flash Point and Saturates level
where as lower will be sulfur contents.

1.5 Additives:

Additives are chemical compounds added to lubricating oils to impart specific properties
to the finished oils. Some additives impart new and useful properties to the lubricant;
some enhance properties already present, while some act to reduce the rate at which
undesirable changes take place in the product during its service life. The function of

OPS-additives | 3
additives is either to enhance an already-existing property of the base fluid or to add a
new property. The examples of already-existing properties include viscosity, viscosity
index, pour point, and oxidation resistance. The examples of new properties include
cleaning and suspending ability, antiwear performance, and corrosion control.

Modern passenger car engines, automatic transmissions, hypoid gears, railroad and
marine diesel engines, high speed gas and steam turbines, industrial processing
machinery, as well as many other types of equipment, runs with the use of various
lubricating oil having different performance level due to addition of additives. Additives
for lubricating oils were used first during the 1920s, and their use has since increased
tremendously. Today, practically all types of lubricating oil contain at least one additive,
and some oils contain additives of several types.
The amount of additive used to formulate lubricants goes upto to 30% or more and
remaining are the base stock. The additives were identified to solved a variety of
engine problems: like corrosion inhibition, ability to keep particles such as soot
dispersed, ability to prohibit acidic combustion, ability to minimize wear by laying down
a chemical film on heavily loaded surfaces. Some additives are multifunctional –certain
viscosity index improvers also function as pour point depressants or dispersants or
antiwear agents or as oxidation inhibitors.
Additive molecules typically have long, oil soluble, hydrocarbon (non-polar) tails and
smaller, hydrophilic (polar) head groups. Since the two parts of the molecule have
different solubility in oil, additives therefore tend to exist colloidally as inverse micelles.

Table 2: Chemistry of Additives used in petroleum lubricants

[Link] Additives Chemical nature

.
1. Viscosity index improver Polymethacrylate
Poly isobutylene
Radial poly isoprene and
Olefins co-polymers
2. Pour point depressant Copolymers of poly alkyl methacrylates
Di(tetra paraffin phenol) phthalate
3. Antioxidants Hindered phenols
Aromatic amine
Alkyl sulfide
Aromatic sulfide
Zinc Dithiophasphate
4. Antifoaming agent Dimethylsilicones
5. Rust and corrosion inhibitors Organic acids , esters
Aminoacid derivatives
Alkaline compounds
6. Antiwear additives Zinc Dithiophasphate(ZnDTP)
Zinc Dialkyldithiophosphate (ZDDP)
Tricresyl phosphate (TCP)
7. Extreme Pressure additives Chlorinated paraffins
OPS-additives | 4
 Sulfurised fat, ester
Zinc Dialkyldithiophosphate (ZDDP)
Molybdenum Disulfide
8. Friction Modifiers Graphite
Molybdenum Disulfide
Molybdenum dithiocarbamate
Boron Nitride
Tungsten disulphide
Polytetrafluoroethylene (PTFE)
9. Detergents Phenolates, Sulphonates and
Phosphates of alkaline elements such as
Ba, Ca, Mg and Na

10. Dispersants Poly Isobutylene Succinimides

11. Seal swell additives Alkylated Sulfone,
Phthalate Esters,
Alicyclic (Naphthenic) components and
other low molecular weight esters.

Table 3: Classification of oil Additives by function

Additives as enhancer Additives for new Additives as suppressant

properties
Anti-foaming Anti-wear Pour point
Anti-oxidant Detergents Viscosity index improvers
demulsifier Dispersants
Rust inhibitors Dye
Extreme pressure
Friction modifier

Table 3. Typical Oil-Type Additive Packages- additives are used in various oil
types

OPS-additives | 5
Table 4: The lubricant properties depends on base oil and additives

Base Oil Dependent Properties of Additive Dependent Properties of

Lubricants Lubricants
Viscosity Metal Corrosion
Pour Point Oxidation Stability
Specific Gravity Antiwear
Flash Point Neutralization Value
Oxdn. Stability Extreme Pressure
Demulsibility
Foaming
Air Release

2. ROLE AND FUNCTION OF VARIOUS ADDITIVES:

2.1 Friction Modifiers:

These are additives that usually reduce friction. The mechanism of their performance is
similar to that of the rust and corrosion inhibitors in that they form durable low
resistance lubricant films via adsorption on surfaces and via association with the oil.
Long-chain polar additives that have an affinity for metal surfaces are added to
crankcase and transmission oils to reduce the surface friction.
They are generally straight chain hydrocarbon with a polar head group. Typical polar
head groups are:
• Amines, amides and their derivatives
• Carboxylic acids or derivatives
• Phosphoric or phosphonic acids and their derivatives
The polar head groups are attracted to the metal surface and form relatively strong
bonds whilst the long hydrocarbon tail (non Polar) is left solubilised in the oil. Therefore
friction modifier contributes to friction reduction.
Molybdenum compounds such as molybdenum dithiocarbamates, molybdenum
dithiophosphates and other more complex molybdenum compounds are extensively
used for friction modification. These compounds react on the metal surface to yield
molybdenum disulfide which has a structure that allows sliding and shearing to take
place. The some friction modifiers are listed in table-2.

OPS-additives | 6
 Molybdenum dithiocarbamate

2.2 Anti wear additives:

The anti wear additives chemically
hemically react to form a film barrier that prevents metal-to-
metal
metal contact and therefore wearing to the metal parts. When loads are high or the
lubricant viscosity is too low, surface asperities on the moving parts come in contact
and lead to metal to metal contact. Under these conditions, reduction in friction is
achieved through the addition
dition of the anti-wear additive to the metal surface and the
formation of a lubricating solid film.
Most anti-wear
wear agents work by forming low shear films on metal surfaces. These anti
wear agents were compounds such as lead salts of long chain carboxylic acids and
used in combination with sulfur
sulfur-containing materials. Oil-soluble
soluble sulfur-phosphorous
sulfur
and chlorinated compounds also worked well as anti wear agents. However, the most
important advance in anti-wear
wear chemistry was made during the 1930s and 1940s 1 with
the discovery of zinc dialkdialkyldithio phosphates (ZDDP)) which is most effective
multifunctional type of anti
anti-wear additives. These compounds were initially used to
prevent bearing corrosion but were later found to have exceptional antioxidant and anti
wear properties.

2.3 Extreme-pressure
pressure (E.P.) additives
Anti-wear
wear (AW) agents have a lower activation temperature than the extreme-pressure
extreme
(EP) agents. The latter are also referred to as anti
anti-seize
seize and anti-scuffing
anti additives.
Extreme pressure additives form extremely durable p
protective
rotective films by thermo-chemical
thermo
reacting with the metal surfaces. This film can withstand extreme temperatures and
mechanical pressures and minimizes direct contact between surfaces, thereby
protecting them from scoring and seizing. Organosulfur and organo-phosphorus
org
compounds, such as organic polysulfides, phosphates, dithiophosphates, and
dithiocarbamates are the most commonly used AW and EP.

Fig 1: Structure of a monomeric zinc dialkyldithio phosphate

OPS-additives | 7
Chlorine, potassium-borate and sulfur-phosphorus extreme pressure (EP) additives are
primarily used for industrial gear lubricants. These additives are temperature-activated
and react with metal asperities to form a sacrificial film. Unfortunately, these types of
EP additives have some limitations

2.4 Antioxidant additives

The engine oils, a mixture of hydrocarbons with (C20 – C70) carbon atoms, are
sensitive to air and get oxidized easily. The Exposure of hydrocarbons to oxygen and
heat will accelerate the oxidation process. The internal combustion engine is an
excellent chemical reactor to catalyzing the process of oxidation. The engine metal
parts such as copper and iron are effective oxidation catalysts. At higher temperature
these hydrocarbons get oxidized to form fatty acids, fatty alcohols, fatty aldehydes and
ketones, fatty esters, fatty peroxides, lacquers and Insoluble asphaltic compounds
which promote corrosion. Oxidation generally increases oil viscosity and formation of
Resins. Blocking the energy source is one path but is effective only for lubricants used
in low-shear and low temperature situations which is not possible practically. The
oxidation process is a chain reaction and propagate further due to formation of free
radical such as
RH → R0+H0

R0 + O2 →ROO0

ROO0 + RH→ROOH+R0

Decomposition of the hydroperoxide molecule caused by called branching reaction

leads to the formation of oxygen bearing compounds. Their oxidation products settle
as deposit causing an increase of oil viscosity.
Thus, addition of antioxidant additives to lubricating oils is important way to reduce
hydrocarbon oxidation and also prevents the formation of all resins, lacquers and acidic
compounds. This can be achieved through the use of radical scavengers, peroxide
decomposers, and metal deactivators.

2.4.1 Primary antioxidants: The radical scavengers are known as primary

antioxidants. They donate hydrogen atoms which react with alkyl radicals and/or alkyl
peroxy radicals and block the radical chain mechanism of the auto-oxidation process.
The primary antioxidant then becomes a stable radical, the alkyl radical becomes a
hydrocarbon, and the alkyl peroxy radical becomes an alkyl hydroperoxide.
Hydrogen donating antioxidants such as sterically hindered phenols and secondary
aromatic amines are excellent free radical scavengers. Hindered phenolics (i.e. BHA
and BHT) and aromatic amines are the two chemical classes of primary antioxidants for
lubricants. The transfer of a hydrogen from the oxygen or nitrogen atom to the radical
forms quinones or quinine imines that prevent oxidation.

OPS-additives | 8
Sterically hindered amines are extremely effective for protection of polyolefins and
other polymeric materials against photodegradation. They are derived from fro 2,2,6,6-
tetramethylpiperidine.. These stabilizers act as light
light-stable
stable antioxidants to protect
polymers from air oxidation in presence of sun light . Antioxidants derived from p- p
phenylenediamine
enylenediamine and diphenylamine are highly effective peroxy radical scavengers.
As a matter of fact, they are more effective than phenolic antioxidants for unsaturated
polymers. They act as an antioxidant as well as antiozonants. Some of the important
commercial
mercial antioxidants based on such aromatic amines are

N
N,N′-Diphenyl-p-phenylenediamine

2.4.2 Secondary Antioxidants: The peroxide decomposers are known as secondary

antioxidants.. Sulfur and/or phosphorus compounds reduce the alkyl hydroperoxides to
alcohols. Zinc dialkyldithiophosphate, phosphites, and thio
thio-ethers
ethers are examples of
different chemical classes of secondary antioxidants.

2.4.3 Metal Deactivator: There are two types o off metal deactivators: chelating agents
and film forming agents.. The chelating agents will form a stable complex with metal
ions to reduce their catalytic activity
activity. Film-forming agents act in two ways. First, they
coat the metal surface and second
second, they minimize
imize corrosive attack of the metal.

OPS-additives | 9
2.4.2 Antioxidant classes: Several effective antioxidants classes have been
developed over the years and being used in engine oils, automatic transmission fluids,
gear oils, turbine oils, compressor oils, greases, hydraulic fluids, and metal-working
metal
fluids. The main classes of oil
oil-soluble organic and organo-metallic
metallic antioxidants are the
following types:

1. Sulfur compounds
2. Phosphorus compounds
3. Sulfur-phosphorus
phosphorus compounds
4. Aromatic amine compounds
5. Hindered phenolic compounds
6. Organo-alkaline
alkaline earth salt compounds
7. Organo-zinc
zinc compounds
8. Organo-copper
copper compounds
9. Organo-molybdenum
molybdenum compounds

2.5 Anti-foam
foam (A.F.) agents

Foam
oam is a substance that is formed by trapping pockets of gas in a liquid phase of
lubricant. Several conditions are needed to produce foam that is due to mechanical
work and presence of surface active components (surfactants) that reduce the surface
tension and lead to the formation of foam faster than its breakdown. The foaming of
lubricants is a very undesirable effect that enhanced oxidation by making intensive
mixture with air and cause lack of lubrication. In many applications, there may be
considerable tendency to agitate the oil and cause foaming, while in other cases even
small amounts of foam
oam can be extremely troublesome.
In these cases, the addition of antifoaming agent or defoamant can reduce foaming
troubles. A defoamer or an antianti-foaming agent is a chemical additive that reduces/
hinders the formation of foam in lubricants. It is thought
ht that the defoamant droplets
attach themselves to the air bubbles and form unstable bridges between bubbles so
that surface of the foam layer collapse to release air.
Dimethylsilicones (dimethylsiloxanes)
dimethylsiloxanes) is commonly used as anti-foaming
anti agent in
lubricants. Polysiloxanes and modified polysiloxanes belong to the most widely used
group of defoaming substances. Polysiloxane defoamers have very high spreading
characteristics and are highly effective.. Modified polysiloxanes are synthesized by
forming a Si-O-C C or a Si Si-C
C link between the siloxane block and the organic
modification.

Poly dimethyl silaxane

OPS-additives | 10
2.5.1 How do defoamers work?
Whether defoamers or deaerators are used depends on the type of foam, i.e macro- or
micro-foam. To eliminate macro-foam on the surface defoamers are preferred and in
case of micro foam where finely dispersed air needs to be removed from the system,
deaerators are preferred. Defoamers work by penetrating the foam lamella,
destabilizing it and making it burst.

2.6 Rust and corrosion inhibitors

The corrosive chemicals present in lubricant causes rusting on metal surfaces when
come in contact of lubricants. To protect metal surfaces anti-rust and anticorrosion
additives are added to the lubricants.
A number of corrosion can occur in systems served by lubricating oils. Probably the two
most important types are corrosion by organic acids developed in the oil itself and
corrosion by contaminants that are picked up and carried by the oil. Corrosion by
organic acids can occur in the bearing inserts used in internal combustion engines.
Some of the metals used in these inserts, such as the lead is readily attacked by
organic acids in oil.
The Anti-rust/ corrosion inhibitors form a protective film on the bearing surfaces that
prevents from reaching or attacking the metal. The film may be either adsorbed on the
metal or chemically bonded to it. It has been found that the inclusion of highly alkaline
materials in the oil will help to neutralize these strong acids as they are formed and
protect from corrosion. Rust inhibitors are compounds having a high polar attraction
toward metal surfaces. By physical or chemical interaction at the metal surface, they
form a tenacious, continuous film that prevents water from reaching to the metal
surface. Typical materials used for this purpose are amine succinates and alkaline
earth sulfonates.

2.7 Detergent and dispersant (D / D) additives

Modern equipment must be lubricated in order to prolong its lifetime. One of the most
critical properties of the automotive lubricants i.e. engine oils, is to suspend undesirable
products from thermal and oxidative degradation of the lubricant. Such products form
as byproducts of fuel combustion, such as hydroperoxides and free radicals which are
reactive species, initiate lubricant oxidation. The final products of combustion and
lubricant decomposition include organic and inorganic acids, aldehydes, ketones, and
other oxygenated materials. The acids have the property to attack metal surfaces and
cause corrosive wear.
Oxidation inhibitors, detergents and dispersants make up the general class of additives
called stabilizers and deposit control agents.
Detergents are metal salts of organic acids that contain excess bases, usually in the
form of carbonate and neutralize the acids to form salts. This decreases the corrosive
tendency of the acids. The organic portion of the detergent, commonly called “soap”
associate with the salts to keep them suspended in the bulk lubricant. The detergents
are Phenolates, sulphonates and phosphonates of alkaline and alkaline-earth metals
like calcium (Ca), magnesium (Mg), sodium (Na) or Ba (barium) salts .

OPS-additives | 11
Dispersants are metal-free
free and are of higher molecular weights than detergents. The
two types of additives work in conj
conjunction with each other. The soap in detergents and
the dispersants also have the ability to suspend nonacidic oxygenated products, such
as alcohols, aldehydes, and resinous oxygenates.
Dispersants and detergents together make up the bulk, about 45–50%, 45 of the total
volume of the lubricant additives manufactured. This is a consequence of their major
use in engine oils, transmission fluids and tractor hydraulic fluids, all of which are high-
high
volume lubricants. Therefore, these additives control rust, corrosion
corrosi and resinous
buildup in the engine.
The detergents consisting Calcium and M Magnesium
agnesium find most extensive use as
lubricant additives due to its lower cost preferably. The use of barium-derived
barium
detergents is being curbed due to concerns for barium’s toxicity.
Technically, one can use metal oxides, hydroxides, and carbonates to manufacture
neutral (non-overbased)
overbased) detergents.
Dispersants differ from detergents in three significant ways:
1. Dispersants are metal-free,
free, but detergents contain metals. This means that on
combustion detergents will lead to ash formation and dispersants will not.
2. Dispersants have little or no acidacid-neutralizing
neutralizing ability, but detergents do. This is
because dispersants have either no basicity or low basicity
basicity. The detergents are basic
as contain metal bases like metal hydroxides and metal carbonates.
arbonates. These are strong
bases neutralizes inorganic acids and organic acids derived from combustion or
oxidation of lubricants.
3. Dispersants are much higher in molecular weight, appr approx 4–15 15 times higher than
detergent.
etergent. Because of this, dispersants are more effective in removing undesirable
suspend deposit and cleaning functions than detergents. The dispersants modify soot
particles so as to prevent their aggregation. The aggregation w will
ill lead to oil thickening
which is a typical problem in heavy
heavy-duty diesel engine oils.

Dispersant: long chain hydrocarbon succinimide such as polyisobutylene succinimide

Detergent: Sodium dodecylbenzenesulfonate

2.8 Viscosity index improvers

OPS-additives | 12
Probably the most important single property of lubricating oil is its viscosity. The
viscosity affects heat generation in bearings, cylinders and gears and it governs the
sealing effect of the oil and the rate of consumption or loss and also determines the
ease with which machines may be started under cold conditions. For any piece of
equipment it is essential to use an oil of proper viscosity to meet the operating
conditions. In selecting the proper oil for a given application, viscosity is a primary
consideration. It must be high enough to provide proper lubricating films but not so high
that friction losses in the oil will be excessive.
The kinematic viscosity of a fluid is the quotient of its dynamic viscosity divided by its
density, both measured at the same temperature and in consistent units. The most
common units for reporting kinematic viscosities now are the stokes (St) or centistokes
(cSt; 1 cSt = 0.01 St), or in SI units, square millimeters per second (mm2/s; 1 mm2/s =
1 cSt). The viscosity of any fluid changes with temperature, increasing as the
temperature is decreased, and decreasing as the temperature is increased. Thus, it is
necessary to have some method of determining the viscosities of lubricating oils at
temperatures other than those at which they are measured. This is usually done by
measuring the viscosity at two temperatures i.e. 40ºC and 100ºC, then plotting these
points on special viscosity–temperature charts developed by ASTM.
Different oils have different rates of change of viscosity with temperature. For example,
a distillate oil from a naphthenic base crude would show a greater rate of change of
viscosity with temperature than would a distillate oil from a paraffin crude. The viscosity
index (VI) is a method of applying a numerical value to this rate of change of viscosity.
A high VI indicates a relatively low rate of change of viscosity with temperature while
low VI indicates a relatively high rate of change of viscosity with temperature. The VI of
an oil is calculated from viscosities determined at two temperatures using ASTM Tables
based on viscosities determined at both 40ºC and 100ºC. For finished mineral-based
lubricating oils made by conventional methods, VI ranges from somewhat below 0 to
slightly above 100. Mineral oil base stocks refined through special hydroprocessing
techniques can have VIs well above 100.
Additive VI improvers are long chain, high molecular weight polymers that function by
causing the relative viscosity of an oil to increase more at high temperatures than at low
temperatures. Viscosity index improvers resist the thinning that occurs in a lubricant as
the temperature is increased. It is postulated that in cold oil the molecules of the
polymer adopt a coiled form so that their effect on viscosity is minimized. In hot oil, the
molecules tend to straighten out to produces greater thickening effect (viscosity
maximized). VI improvers can be blended into oils to increase VIs; however, VI
improvers are not always stable in lubricating environments exposed to shear or
thermal stressing. Accordingly, these additives must be used with due care to assure
adequate viscosity over the anticipated service interval. Among the principal VI
improvers are methacrylate polymers and copolymers, acrylate polymers, olefin
polymers and copolymers, and styrene butadiene copolymers. The degree of VI
improvement from these materials is a function of the molecular weight distribution of
the polymer.

Viscosity index improvers are commonly used in multigrade engine oils, gear oils,
automatic transmission fluids, power-steering fluids, greases and some hydraulic fluids.
They allow the fluid to flow more freely at a lower temperature so it can reach the
OPS-additives | 13
bearings quicker. At a higher operating temperature, the fluid will have a higher
viscosity and will provide the required film thickness to protect the bearings and moving
parts within our equipment.

One of the major issues with the viscosity index improver additives is that they are very
susceptible to mechanical shearing. For example, imagine a piece of spaghetti moving
with the oil throughout an engine or in a gearbox. There are areas in the engine or
gearbox that have very tight clearances and will act much like a pair of scissors cutting
the spaghetti noodle (viscosity index improver molecule) into smaller pieces. Over time
this greatly reduces the ability of these molecules to add to the viscosity of the fluid.

When creating a viscosity index improver, a balance between the thickening efficiency
and shear stability of the polymer is important. Higher molecular weight polymers make
better thickeners, but tend to have less resistance to mechanical shear. Lower
molecular weight polymers are more shear resistant, but do not improve viscosity as
effectively at higher temperatures and must be used in larger quantities.

The materials that are generally used for viscosity index improvers include
polymethacrylates (PMA), polyisobutylene (PIB), radial polyisoprene and olefin co-
polymers (OCP)
(a) Polymethacrylates (PMA)- These are polymerised esters of methacrylic acid. They
normally exhibit pour-point depressing activity. Dispersant properties can be
obtained by incorporating polar groups in the molecular structure.

Benzyl Methacrylate
(b) Polyisobutenes (PIB)- These are non-dispersant polymers and they have no
effect on the pour point of formulated lubricants. They have limited use in modern
formulations. A polymer of isobutylene, [—C(CH 3)2—CH2—]n.
(c) Olefin co-polymers (OCP)- These are usually co-polymers of ethylene and
propylene. Dispersant properties can be obtained incorporating polar groups in the
moleculare structure.
(d) Styrene/diene co-polymers- The molecular weight distribution is optimised to give
good shear stability in crankcase applications. Its uniquely effective thickening power in
solution gives an overall thickening efficiency that is superior to other polymers of
equivalent shear stability

2.9 Pour point depressants:

The pour point of lubricating oil is the lowest temperature at which it will pour or flow
when it is chilled without disturbance under prescribed conditions. Most mineral oils
OPS-additives | 14
contain some dissolved wax. When oil is chilled, these waxes begin to separate as
crystal and interlock to form a rigid structure and the oil will no longer flow under the
conditions of the test. Cooling rates also affect wax crystallization and in these oils the
viscosity becomes progressively higher and no flow can be observed. These waxes
composed of saturates, aromatic, polars and asphaltenes, vary in molecular weight and
composition with their temperature of precipitation in a waxy crude. Waxes that
precipitate out of the crude oil solution at temperatures above the pour point are of
higher molecular weight and have a high asphaltene content while that precipitate at
lower temperatures have lower molecular weights and contain mostly saturates.
Asphaltenes appear to play an important role in pour point reduction. They either
symptomize waxes that are susceptible to chemical additives, or else interfere with the
congealing mechanism. The presence of asphaltenes with waxes indicates that the
waxes will be modified by chemical additives.
Two general types of pour point depressant are used as additives:
1. Alkyl aromatic polymers which adsorb on the wax crystals as they form, preventing
them from growing and adhering to each other.
2. Polymethacrylates which crystallize with wax to prevent crystal growth.

The PPD additives do not entirely prevent wax crystal growth but rather lower the
temperature at which a rigid structure is formed.
The removal of the residue waxes from the oil is somewhat expensive, pour point
depressants are an economical alternative to reduce the pour point of lubricants. The
most common pour point depressants are the same additives used for viscosity index
improvement.
The mechanism through which these molecules reduce pour point is still poorly
understood and somewhat controversial. These molecules adsorb into the wax crystals
and redirect their growth, forming smaller and more isotropic crystals that interfere less
with oil flow. Depending on the type of oil, pour point depression of up to 10ºC can be
achieved by these additives.
(i) Polymethacrylates- Methacrylate polymers used in lubricating oils as pour
point depressants and viscosity index improvers.

(ii) Polyacrylates- These are very similar in behavior to the polymethacrylates

OPS-additives | 15
 (iii) Di (tetra paraffin phenol) phthalate-

2.10 Seal Swell Additives:

Seal swell additives help maintain hydraulic pressures, and minimize lubricant
contamination and loss in lubrication systems and also maintain the integrity of certain
elastomeric materials used as seals. This prevents elastomer shrinkage, brittleness and
deterioration during service. Seals are used within lubrication systems to isolate
lubrication environments from harmful elements.
The seal swelling additives were not required prior to 1930 as seals were made from
leather or similar material which are not affected by lubricant. At that time the additive in
lubricants were not required because engines were operated at low pressure and low
cycle rate. The use of additive to improve fluid performance began with the military
fluids. Industrial fluid developed parallel to the military fluid development.
With the enhanced development of military aircraft and reciprocating engines spurred
by second World War starting approximately 1935, advance fighters and bombers
required new, high performance lubricating fluids and seals. The new military fluids
were based largely on petroleum base stocks or mineral oil for hydraulic system.
Various additives were used to develop additive packages for these hydraulic fluid
depending on the aircraft type and intended mission. These development efforts
resulted in certain of a military specification- MIL-H 5606 for these fluids. The
specification allowed for some flexibility in formulation for competitive purposes and
guaranteed a performance band for the fluid and its compatibility with elastomeric
seals. the seal swell additive consist alkylated sulfone, phthalate esters, other low
molecular weight esters and alicyclic (Naphthenic) components.

2.11 Multifunctional nature of additives

A number of additives perform more than one function. Zinc dialkyl dithiophosphates,
known mainly for their antiwear action, are also potent oxidation and corrosion
inhibitors.

OPS-additives | 16
Styrene-ester polymers and functionalized polymethacrylates and can act as viscosity
modifiers, dispersants, and pour point depressants. Basic sulfonates, in addition to
acting as detergents, perform as rust and corrosion inhibitors.

3. Conclusion:
From this article it may be concluded that since 1930s role of additive arises in
petroleum industry. The base oil alone is not effective lubricant now a days for use in
engines / machinery with modern technology. Therefore additives play important role in
lubricant and provide desired lubrication performance to the engines. The use of
additives also protects machines / engines from wearing, corrosion, seal swelling,
dryness of their parts and frictions etc.
In future lubricant additives will continue to grow and required to focus on additives with
ashless, friendly with environment, excellent stability, Enhanced durability,
Sustainability and with unique performance properties. The new market also required to
include biodegradable lubricants, biodiesel, fuel friendly lubricants & advanced suitable
transportation lubricants. The future of technology w.r.t. both the machine and the
lubricant, additional perspectives of the environmental aspects is also important.

Reference:
1. Farzad abdolahi et al. “The mechanism of action of anti-foam” Journal of applied
science 5(6):1122-1129,2005
2. Lubricant Additives: Chemistry and Applications, Third Edition, edited by Leslie
R. Rudnick.
3. Understanding the pour point depression mechanism-II microfiltration analysis of
crude oils By D. S. Schuster and C. A. Irani,Gulf Oil Research & Development
Houston.
4. Tribology - Lubricants and Lubrication, Lubricating Oil Additives by Nehal S.
Ahmed and Amal M. Nassar Egyptian Petroleum Research Institute Egypt,
available at [Link]
5. Lubricant Additives: Use and Benefits, by Technical Committee of Petroleum
Additive Manufacturers in Europe, AUGUST 2016 / ATC DOCUMENT 118

OPS-additives | 17