Additives in lubricant:

Types and chemical composition of

lubricant additives

Semira Hajrlahovic Mehic, M.Sc.

Inspector Counsellor
Chemicals Office of the Republic of
Slovenia

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 Content
• Lubricant function
• Formulation of lubricants
• Types of additives
• Main reasons to add additives
• Typical additives

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 Lubricant function
• Modern equipment must be lubricated in
order to prolong its lifetime
• A lubricant performs a number of critical
functions:
– lubrication, cooling, cleaning, suspending,
– protecting metal surfaces against corrosive
damage….

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 Formulation of lubricants
• Lubricant comprises a base and an additive package
• The primary function of the base fluid:
– to lubricate and act as a carrier of additives
• The function of additives:
– to enhance an already existing property of the base fluid
• viscosity, viscosity index, pour point, oxidation
resistance
– to add a new property
• cleaning/suspending ability, antiwear performance,
corrosion control
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 Formulation of lubricants
• Typically lubricants contain 90% base oil and
less than 10% additives
• Base :
– most often petroleum fractions (called mineral oils)
– vegetable oils or synthetic liquids such as
hydrogenated polyolefins, esters, silicones,
fluorocarbons are sometimes used as base oils

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 Formulation of lubricants
• Non-liquid lubricants include grease, powders
(dry graphite, molybdenum disulfide, tungsten
disulfide)
• Dry lubricants such as graphite, molybdenum
disulfide and tungsten disulfide offer
lubrication at temperatures (up to 350 °C)
• The amount of additive used varies from a few
hundredths of a percent to 30% or more

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 Lube oil base and additives logic
• The lube oil base is the building block
– which appropriate additives are selected and
properly blended
– to achieve a balance in performance
characteristics of the finished lubricant
• To achieve the highest levels of performance in
finished lubricants:
– understanding of the interactions of base oil and additives
– matching those to requirements of machinery and
operating conditions
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 Types of additives
• Some additives impart new and useful
properties to the lubricant
• Some enhance properties already present
• Some act to reduce the rate at which
undesirable changes take place in the product
during its service life

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 Main reasons to add additives
• To impart desirable characteristics
• Improvements in lubricating oil over the last
decades
• Are organic compounds like:
– chlorine (as in chlorinated esters),
– sulphur (as in sulphurized oils)
– phosphorus (as in tricresyl phosphate)

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 Main reasons to add additives
• To protect the lubricant in service by limiting
the chemical change and deterioration
• To protect the mechanism from
– harmful combustion products
– malfunctioning combustion products and
– malfunctioning lubricating oil
• To improve existing physical properties and to
create new beneficial characteristics

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 Typical additives
• Increase oil and machinery life
– effect many oil and surface characteristics
• Decrease sludge on surface (metal), varnish
the metal parts, clean the surface
• Some are multifunctional:
– certain viscosity index improvers also have
function as pour point depressants
– dispersants or anti-wear agents have also function
as oxidation inhibitors

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 Typical additives
• Friction modifiers
• Anti-wear agents
• Extreme-pressure additives
• Anti-oxidation additives
• Rust and corrosion inhibitors
• Foam inhibitors
• Oiliness agents
• Detergents and dispersants
• Alkaline agents
• Pour point depressants (PPD)
• Viscosity index improvers 12
 Friction modifiers
• Added to lubricants to reduce the surface friction
of the lubricated parts
• Mechanism similar to rust and corrosion
inhibitors
– form durable low resistance lubricant films via
adsorption on surfaces and via association with the oil
• Polar chemical compounds with high affinity for
metal surfaces and possessing long alkyl chains
– long-chain fatty acids, their derivatives, and the
molybdenum compounds

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 Anti-wear agents
• Protect rubbing surfaces operating with film
boundary lubrication
– Organo-sulfur and organo-phosphorus
compounds:
• organic polysulfides
• phosphates, dithiophosphates
• dithiophosphates (ZDDP)
–Also antioxidant

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 Extreme-pressure additives
• Form extremely durable protective films by
thermo-chemically reacting with the metal
surfaces
• The film can withstand extreme temperatures
and mechanical pressures and minimizes
direct contact between surfaces
• Anti-wear agents have a lower activation
temperature than the extreme-pressure

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 Extreme-pressure additives
• Chlorinated paraffins
– 2,3,4,5,6,8-hexachlorodecane (short-chained
chlorinated paraffin)

• Sulphurized fats
• Zinc dialkyldithiophosphate (ZDDP)
• Molybdenum disulfide (MoS2)
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 Anti-oxidation additives
• One of the most important aspects of lubricating oils
• Engine's metal parts (copper and iron) act as effective
oxidation catalysts
– engine oils are probably more susceptible to oxidation
• High temperature, high pressure, high friction, and high
metal concentration in motors, lead to oxidation of
lubricating oil
• Oxidation generally increase oil viscosity and results in
formation of resins, lacquers and acidic compounds

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 Anti-oxidation additives
• Protect by forming the oxidation of metal
component
– Sulfur compounds
– Phosphorus compounds
– Sulfur-phosphorus compounds
– Aromatic amine compounds
– Hindered phenolic compounds
– Organo-zinc compounds (Zn- dithiophosphate ZDDP)
– Organo-copper compounds
– Organo-molybdenum compounds

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 Rust and corrosion inhibitors
• Rust inhibitors: compounds with high polar
attraction toward metal surfaces
• By physical or chemical interaction at the
metal surface, they form a continuous film
that prevents water from reaching the metal
surface
• Amino salts and salts of sulphonic acids
(functional group R-SO3−)

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 Rust and corrosion inhibitors
• Form a protective film on the bearing surfaces
– prevents the corrosive materials from reaching or
attacking the metal
• The film may be adsorbed on the metal or
chemically bonded to it
• Inclusion of highly alkaline materials in the oil
help to neutralize strong acids, greatly
reducing this corrosion

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 Rust and corrosion inhibitors
• Alkaline compounds
• Organic acids
• Esters
• Amino-acid derivatives

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 Foam inhibitors
• Foaming of lubricants is a very undesirable
effect
– can cause enhanced oxidation by the intensive
mixture with air
• Dimethylsilicones (dimethylsiloxanes)

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 Oiliness agents
• Reduce friction seizure point and wear rates
• Glycerin monooleate (GMO)
•

• Pentaerythritol Monooleate
(PMO)

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 Detergents
• Tend to neutralize the deposits
• before formation under high temperature and
pressure conditions, or
• as a result of using a fuel with high sulphur
content
• The organic portion of the detergent (“soap”), has the
ability to
– associate with the salts to keep them suspended in the
bulk lubricant
– to suspend nonacidic oxygenated products, such as
alcohols, aldehydes, and resinous oxygenates
• To keep surfaces clean

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Detergents

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 Detergents in lubricants
• Phenolates, sulphonates and phosphonates of
alkaline and alkaline-earth elements
– calcium (Ca), magnesium (Mg), sodium (Na) or Ba
(barium) salts
• Sodium dodecylbenzenesulfonate

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 Dispersants
• Used to disperse or suspend the deposits
forming contaminants
• More effective than detergents due to higher
molecular weight
• Molecules have a polar charge at one end
which attracts and holds the deposits
• Polyesters and benzlamides

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 Dispersants
• Long chain hydrocarbons succinimides (such
as polyisobutylene succinimides)

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 Detergents and dispersants
• Together make about 45–50%, of the total
volume of the lubricant additives manufactured
• Differences:
– Dispersants are metal-free, detergents contain metals
(magnesium, calcium)
– Dispersants have little or no acid-neutralizing ability,
but detergents do
– Dispersants are much higher in molecular weight,
(approx. 4–15 times higher) than the organic portion
(soap) of the detergent

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 Alkaline agents
• Alkaline level (total base number=TBN) must m
atch the acidity of the lubricant
• Neutralize acids of the oil and include additives
such as dispersants and detergents
• Acid neutralizing alkalis are present in the
detergents
– failure to keep an oil alkaline can lead to damage to
bearings due to acidic attack as well as increased
liner wear
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 Pour point depressants (PPD)
• Pour point:
• The lowest temperature at which the oil is
fluid
• Improve low temperature viscosity
– Polymethacrylate (PMA)
– Styrene Esters
• Oils used under low-temperature conditions
must have low pour points

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 Pour point depressants (PPD)
• Two general types:
– Alkylaromatic polymers adsorb on the wax
crystals as they form, preventing them from
growing and adhering to each other
– Polymethacrylates co-crystallize with wax to
prevent crystal growth
• The additives do not entirely prevent wax
crystal growth, but rather lower the
temperature at which a rigid structure is
formed
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 Viscosity index improvers
• Probably the most important single property of a
lubricating oil
• Viscosity varies with temperature → it is
necessary to consider the actual operating
temperature of the oil in the machine
• Different oils have different rates of change of
viscosity with temperature
– a distillate oil from a naphthenic base crude shows a
greater rate of change of viscosity than a distillate oil
from a paraffin crude

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 Viscosity index improvers
• Can be blended into oils to increase V.I.
– But not always stable in lubricating environments
exposed to shear or thermal stressing
• Methacrylate polymers and copolymers

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 Viscosity index improvers
• Acrylate polymers
• Olefin polymers and copolymers
• Styrene butadiene copolymers

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General capabilities expected from an
engine lubricant
• Dispersivity or capacity to keep the cold parts
of an engine clean
• Detergency or capacity to keep hot parts of an
engine clean
• Thermal strength or capacity to withstand
temperature changes
• Anti-oxidant or capacity to resist the action of
oxygen

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General capabilities expected from an
engine lubricant
• Anti-wear or capacity to contain wear
• Anti-scuffing or capacity to preserve oil film
even in the presence of high pressures
• Alkalinity reserve/capacity to neutralize acids
formed during combustion
• Deemulsibility or capacity to separate
contaminants

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General capabilities expected from an
engine lubricant
• Resistance to hydrolysis or capacity to
withstand the action of water which can affect
additives
• Centrifuge ability and filterability or capacity
to separate insoluble elements
• Anti-rust, anti-corrosive and anti-foam
– just some of the other properties which protect
the metalic object from wear down

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 Thank you!

semira.hajrlahovic-mehic @gov.si

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