Lubricants

Lubricant

 A lubricant usually consists of a base fluid, generally of petroleum

origin, combined with additive chemicals that enhance the various
desirable properties of the base fluid.

 Base fluids are essentially obtained from two main sources:

 the refining of petroleum crude oil and
 the synthesis of relatively pure compounds with properties that are
suitable for lubricants.
 TYPES OF LUBRICANTS

(1) Solid lubricants

 Solid lubricants are used for railway tract joints, chains, air compressors, open gears, heavy
machines etc - wax, talc, mica, molybdenum disulphide graphite etc.
(2) Semi solid lubricants
 It is used where the machine parts are subjected to slow speed, heavy load & sudden jerks -
grease & Vaseline.
(3) Liquid lubricants
 Liquid lubricants are used in delicate and light machines which work at high speed but under
low pressure - Mineral oils, vegetable oils & animal oils
(4) Synthetic lubricants
 It can be used, where extreme temperature, chemical reactive atmosphere or some very
particular operating conditions are involved & where all other lubricants fail to work
effectively. e.g. polyglycols, silicones, organic amines, imines & amides.
 CLASSIFICATION OF LUBE OILS

 The two basic categories of lube oil are mineral and synthetic.

 Mineral oils are refined from naturally occurring petroleum, or crude oil.

 Synthetic oils are manufactured polyalphaolefins, which are hydrocarbon-

based polyglycols or ester oils.
 FUNCTION OF LUBRICANTS

 It reduces wear and tear of the surfaces by avoiding direct metal to metal
contact between
 the rubbing surfaces, i.e. by introducing lubricants between the two
surfaces.
 It reduces expansion of metal due to frictional heat and destruction of
material.
 It acts as coolant of metal due to heat transfer media.
 It avoids unsmooth relative motion.
 It reduces maintenance cost.
 It also reduces power loss in internal combustion engines.
ADDITIVES USED IN LUBRICANTS

 Anti-oxidant --- Aromatic amines, phenols, sulphides and phosphates

 Corrosion Inhibitor --- Amino salts and salts of sulphonic acids
 Anti-wear agents --- Tricresyl phosphate
 Foam inhibitors --- Glycerols
 Lubrication/Tribology

 Tribology (a term first introduced in 1966) is the cience that deals with
problems of friction, wear and lubrication.

 The lubrication efficiency and the application of lubricants depends

primarily on consistency and flow properties (viscosity) of lubricants,
which appear in nearly all lubricant specifications.

 Lubrication has always implied the use of lubricating oil, usually

formulated by blending appropriate quality lube base stocks(s) and
additives.
 Lubrication/Tribology

 On an average lubricating oil consists of about 93% base stock(s)

and 7% chemical additives and other components.

 The performance of a finished lubricant depends on the type and

quality of base stocks and additives used.

 Very little un-additized lube base stocks are used as lubricants.

 Petroleum Base Oils

 Petroleum lubricating oils are made from the higher boiling portion of the
crude oil that remains after removal of the lighter fractions.
 The manufacture of lube base stocks from crude oil involves a series of
processes to remove undesirable components.
 Essentially five steps are involved:
a) Vacuum distillation
b) Solvent Extraction
c) Wax Removal
d) Finishing Process
e) Hydrocracking
 Vacuum Distillation

 It separates the atmospheric residue mixture into a series

of fractions representing different molecular weight ranges
or viscosity ranges from the 90-100 neutrals to the 500
neutrals. (The neutral number is the SUS viscosity at 100oF).
 The residue contains the heavier base oils such as the bright
stocks (150 to 250 SUS at 210oF).
 Heavier base oil must be separated from the asphaltenes and
resins prior to introduction into the extraction process.

**Saybolt Universal Seconds (SUS), which is the time in seconds for 60 milliliters of
oil to flow through a standard orifice at a given temperature. 
 Solvent extraction

 It separates aromatic compounds from non-aromatic compounds.

 The process consists of mixing furfural with the feedstock and allowing the
mixture to settle into two phases - the extract and the raffinate.
 The extract phase is rich in aromatics, and the raffinate phase is rich in
paraffinic hydrocarbons.
 The extraction process improves thermal and oxidative stability compared
to the fraction prior to extraction.
 In addition, the viscosity/temperature characteristics improve, as evidenced
by a higher viscosity index.

**raffinate is the liquid stream which remains after solutes from the original liquid are removed through contact
with an immiscible liquid
 Wax Removal

 The next step in lube oil manufacture is the removal of wax to

improve its flow characteristics at low temperature.
 Typically, methyl ethyl ketone (MEK) is mixed with the waxy
oil.
 The mixture is then cooled to a temperature 10 to 20oF (-12 to
-6oC) below the desired pour point.
 The wax crystals that form are then removed from the oil by
filtration.
 Finishing Process

 Some base stocks, particularly premium stocks, require a finishing process

such as hydrofinishing or clay treatment to improve color, oxidation stability,
and thermal stability.
 Hydrofinishing consists of passing heated oil and hydrogen through a catalyst
bed.
 The process removes some color bodies and unstable components, such as
nitrogen and sulfur compounds.
 An alternative process, clay treatment, also removes dark colored and
unstable molecules.
 Several hydrogen processes have been used in addition to hydrofinishing.
 Hydrotreating

 Hydrotreating, a more severe process, is sometimes used prior to solvent

extractions.

 The objective is to improve the yield from the extraction process by

converting some aromatic molecules, which would end up in the extract, into
nonaromatic molecules that will remain in the raffinate.

 This process usually results in a high degree of desulfurization as well as

moderate nitrogen removal.
 Hydrocracking

 A totally different approach to lube oil manufacture involves an even

more severe hydrogen process called hydrocracking.
 This process changes the structure of many of the molecules in the
feedstock.
 Aromatics are converted into naphthenes, many naphthene rings are
broken open, and many paraffinic molecules are rearranged or
fragmented.
 This massive "reforming" of the feedstock produces molecules that have
improved viscosity/temperature characteristics and improved thermal and
oxidative stability.
 This process allows production of high-quality lube stocks.
 Petroleum Base Oils

 To minimize variations and produce products what will

provide consistent performance, the refiner exercises care
in:
a. Selection and segregation of crudes.
b. Separation into similar fractions in the same general boiling
range.
c. Processing to remove undesirable constituents and upgrading
into more desirable materials.
d. Blending to the required physical characteristics and
incorporation of chemical additives that improve performance.
 Lubricant Base Stocks

 Lube base stocks (of petroleum origin) continue to constitute a major part of
today's lubricant.

 These are complex mixtures of paraffinic, aromatics and naphthenic

hydrocarbon, ranging from C14 to C40+.

 Different processing configurations involving replacement of

dearomatisation, dewaxing and hydrofinishing steps have been developed.
 Lubricant Base Stocks

 Hydrocracking / hydroisomerisation enabled the refineries to produce High

Viscosity Index (designated as VHVI or X-HVI) paraffinic base stocks /
oils that are comparable in performance to synthetic base fluids.

 Paraffinic base stocks are preferentially used to formulate automotive and

industrial lubricants, including engine oils, transmission fluids and gear
oils, due to their better oxidation stability, higher viscosity index and lower
volatility relative to comparable viscosity grade naphthenic base oils.
 Lubricant Base Stocks

 Naphthenic base oils have lower pour points and better

solvency characteristics, compared to paraffinic base oils.
 This makes them, particularly useful in formulating low
temperature, hydraulic oils, refrigeration oils, rubber process
oils, metal working oils, as well as cylinder lubricants for
large engines and greases.
 Base stocks differ widely in molecular composition, physical
and chemical properties due to the crude source and
processing steps used in their manufacture.
Lubricant Base Stocks

 The differences in base stock composition, even with similar physical

properties can impact the end use performance of finished lubricants.

 In 1990 the American Petroleum Institute (API) established a base oil

classification system to help marketers to minimize re-testing costs
when blending licensed engine oils with base oils from different
manufacturing sources.

 The system uses physical and chemical parameters to divide all base
stocks (oils) into five groups as listed in Table below :
API- Classification of Base Oils

Group Saturate wt % Sulphur wt % Viscosity Index

I < 90 and/or > 0.03   > 80 to < 120
II  90 and  0.03  80 to  120
III  90  0.03  120
IV All poly alpha olefins (PAOs)
V All base stocks not included in Groups I-IV
 Synthetic Base Oils

• Another source of lubricant base fluids is the synthetic route.

• Definition for such a material is "A product prepared by
chemical reaction of lower molecular weight materials to
produce a fluid of higher molecular weight designed to provide
certain predictable properties."
• This is in contrast to refined petroleum oils, which are composed
of many compounds of varying chemical composition,
depending on the refining method and the crude stock source.
 Synthetic Base Oils

 The synthetic hydrocarbons or syn base fluids were developed simultaneously

in Germany and U.S.

 In Germany low temperature performance and the need to over come the
general shortage of petroleum base stocks was the driving force behind their
development.

 Most of the economically important syn fluids can be synthesized starting

with ethylene - mainly produced in steam crackers.
Synthetic Lubricant

Type Principal Application

Olefin olegomers (PAOs) Automated and Industrial
Dibasic Acid Esters Aircraft and Automative
Polyol Esters Aircraft and Automative
Alkylated Aromatics Automative and Industrial
Polyalkylene Glycols Industrial
Phosphate Esters Industrial
 Synthetic Lubricant

 Except polyglycol fluids, all the above syn fluids have viscosities in the
range of lighter HVI neutral base stocks.
 Their VIs and flash points, however, are higher and their pour points are
considerably lower.
 This makes them valuable blending components when formulating oils for
extreme service at both high and low temperatures.
 Some of these fluids are considered to be environmentally more acceptable
as well.
 The main disadvantage of synthetic base fluids is that they are inherently
more expensive than traditional base stocks, and are available in limited
supply.
 Synthetic Lubricant

• Among the advantages claimed for synthetic lubricants over comparable

petroleum-based fluids are:

 improved thermal and oxidative stability,

 more desirable viscosity/temperature characteristics,
 improved low-temperature properties,
 superior volatility characteristics, and
 preferred frictional properties.
 Commercial synthetic fluids are not confined to a single chemical type.
 Lubricant Properties

Some of the most important properties necessary for satisfactory lubricant

performance are:
a. Low volatility under operating conditions.
• Volatility characteristics are essentially inherent in the choice of base oil for a
particular type of service and cannot be improved by the use of additive
materials.
b. Satisfactory flow characteristics in the temperature range of use.
• Flow characteristics largely depend on the choice of base oil; however, they can
be improved through the use of pour point depressants and viscosity modifiers.
• Pour point depressants improve low-temperature flow properties, while viscosity
modifiers enhance high-temperature viscosity characteristics.
 Lubricant Properties

c. Superior stability or ability to maintain desirable characteristics for a

reasonable period of use.
• They are primarily associated with additive materials, which enhance base fluid
properties in this area.
• Lubricant stability is affected by the environment in which it operates.
• Such factors as temperature, oxidation potential and contamination with water,
unburned fuel fragments, and corrosive acids limit the useful life of a lubricant.
• This is the area where additives have made a major contribution in improving the
performance characteristics and extending the useful life of lubricants.
 Lubricant Properties

d. Compatibility with other materials in the system.

• Compatibility of lubricants with seals, bearings, clutch plates, etc., may also be
partially associated with the base oil.
• However, additive chemistry can have a major influence on such characteristics.
 Additives

• Almost all commercial lubricants contain additives to enhance their

performance.

• Their amount varies from > 1% to 25% or more.

• The function of additives:

 Protect metal surfaces (rings, bearings, gears etc.)
 Extend the range of lubricant applicability
 Extend lubricants' life
 Additives

• Additives consist of a variety of classes.

• For the automotive lubricants :

a. Surface protective additives : antiwear and EP agent, detergent, dispersant
and friction modifiers.
b. Performance additives : Pour point depressant, viscosity modifiers and seal
swell agents.
c. Protective additives : antifoament, antioxidant and metal deactivators
 Additives

• Additive - Additive interactions have been widely studied and their

performance attributed to a specific chemistry or functionalities of these
interactive additive pairs.

• Many factors that govern their applications are :

 additive must be capable of being handled in conventional blending equipment,
 stable in storage,
 free of offensive odour
 non-toxic by normal industrial standards.
 Lubricant Additives

Detergents (Metallic Salicylates, Sulfonates, Phenates and Sulfophenates

Dispersants)
Ashless Dispersants N-substituted long-chain alkenyl succinimides
High-molecular-weight esters and polyesters
Amine salts of high-molecular-weight organic acids
Copolymers of methacrylic or acrylic acid derivatives containing polar
groups such as amines, amides, imines, imides, hydroxyl, ether, etc.
Ethylene-propylene copolymers containing polar groups.
Oxidation and Bearing Organic phosphites,
Corrosion Inhibitors metal dithiocarbamates,
Sulfurized olefins and
Zinc dithiophosphates
Antioxidants Phenolic compounds,
Aromatic nitrogen compounds and
Phosphosulfurized terpenes
 Lubricant Additives

Viscosity Modifiers Polymethacrylates

Ethylene-propylene copolymers (OCP)
Styrene-diene copolymers
Styrene-ester copolymers

Antiwear Additives Organic phosphites

Sulfurized olefins
Zinc dithiophosphates
Alkaline compounds as acid neutralizers

Pour Point Wax alkylated naphthalene & Polymethacrylates

Depressants Crosslinked wax alkylated phenols
Vinyl acetate/fumaric-acid-ester copolymers
Vinyl acetate/vinyl-ether copolymers
Styrene-ester copolymers
 Tests of lubricants and their
significanceC
Viscosity- The resistance to flow of liquid is known as viscosity. Viscosity Index :
The rate of change of viscosity with change in temperature is called viscosity index. A good lubricant is
one whose viscosity does not change much with change in temperature.
Oilness -The power of an oil to maintain a continuous film under pressure while it is used as lubricants.
A lubricant which does not squeeze out from the sliding surface & maintain a continuous film is known
as lubricant having high degree of oiliness.
Volatility - Volatility of a lubricant is its tendency to vaporise with the increase of temperature. If the
lubricant is highly volatile, it will vaporise readily even at low temperature. A good lubricant should have
low volatility.
Flash Point - The minimum temperature at which a lubricant gives momentary flash of light when a
flame is applied to it, but it does not continue to burn. Lubricants with higher flash point are preferred.
Fire Point - The temperature at which a lubricant catches fire and burns continuously when the flame is
applied to it. Fire point of oil is always greater than its flash point.
Pour Point - It is the lowest temperature at which the oil ceased to flow when cooled under prescribed
conditions. If oil is used at a temperature below the pour point, the lubrication action will stop.
Cloud Point - The cloud point of lubricating oil is the temperature at which cloudiness develops due to
separation of wax on cooling.
 Test of Lubricant and their
significance

 Neutralization Number or Acid Value - It is defined as “The number of milligrams of KOH required to
neutalise one gram of the oil.”
 Saponification Number - It is defined as the number of milligram of KOH required to saponify one gram of oil
or fats.
 Emulsification - When oil is mixed with water or water is mixed with oil, emulsion is formed. A good lubricant
is one which does not form emulsion and even if it forms, the emulsion should break quickly.
 Copper strip test for Corrosion - for a particular length of time at a specific temperature. Copper strip is taken
out after specified time. If some pitting or furnished spots are observed, it means the lubricating oil contain some
corrosive material. The presence of corrosive material reduces the quality of lubricants.
 Carbon Residue Test - The deposition of carbon by a lubricating oil, when it is subjected to heat under working
conditions is called carbon residue test. Deposition of carbon is harmful.