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LUBE OIL ADDITIVES
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LUBRICANTS• Lubricants were in use before the invention
of wheel.• Building block of 95% of today’s lubricants
is mineral oil.• Straight run MO not satisfactory for
operating under arduous conditions.• Modern Lubricant is highly refined HC
base stock+chemical additives.
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WORLD LUBRICANT USES
4Automotive Transmissions
5Grease
9Process
27Industrial
55Engine
%APPLICATION
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PERFORMANCE-WISE CLASSIFICATION OF ADDITIVES
Modifies crystal growth at low temperature
Pour Point Depressants
Improves viscosity – temp. relationships
Viscosity Index Improvers
Prevent formation of acid, minimize viscosity increase
Antioxidant
Reduce wear, minimize metal to metal contact
Antiwear/EP
Engine Cleanliness, keep sludge in suspension
Detergents Dispersants
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PERFORMANCE-WISE CLASSIFICATION OF ADDITIVES
Control FoamingsDefoamant
Improves Adhesive Properties
Tackiness Agents
Neutralizes Catalytic Effect of Metals
Metal Deactivators
Prevent Corrosion of Ferrous and Non-ferrous surfaces
Corrosion/Rust/ Inhibitors
Reduce Friction between moving parts, improve engine efficiency
Friction Modifiers
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DETERGENT/DISPERSANT ADDITIVE
• Major Use in Crankcase Oil
• Represent 70% of Total Additive Used in Engine Oil
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FUNCTION OF DETERGENT/ DISPERSANT ADDITIVE
•Keep Particulate matter dispersed•Maintain Engine Cleanliness
DIRT IN ENGINE ARISES FROM•Below-by of products from incomplete combustion of fuel•Oil oxidation product•Engine wear
Dirt Leads to Deposit in Engine e.g. On Piston Known as Lacquer or Varnish on English Sump Known as Sludge
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DETERGENTS
• Metal Containing Cleaning Agents
• Capable of dealing deposits/precursor generated under high temperature running conditions
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PARTS OF DETERGENT
• A metal Al, Mg, Zn, Ba, Ca.
• An anionic component e.g.
carboxylate,
Alcoholate,
Phenate,
Sulphonate and
Salicylate.
• Oil Soluble Oleo-philic Component Straight or Branched Alkyl Group.
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TYPES OF DETERGENTS
• Sulphonate
• Phenate• Salicylate• Phosphate• Neutral• Over Base
By-product of white oil
Synthetic From Alkyl Aromatic
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OVER BASE ADDITIVES• Colloidal Disperson Of Metal Carbonate (10-3-1 Micron)• TECHNOLOGY IS COMPLEX TO MAKE STABLE
SUSPENSION• ESTIMATION
As TBN (500)Metal Ratio
• EFFECTIVE IN CONTROLLINGa) Corrosive Acid From Oil Oxidationb) Blow-by Of Combustion Product
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PREPARATION OF OVER BASE ADDITIVE
• Phenate Over Base Are Prepared Similarly
• Phosphates are Phosphoric And Thio Phosphoric Acid Derivatives
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SELECTION DEPENDS ON
• Severity Of Condition
• Anti Rust
• Anti Oxidant
• Load Carrying Properties
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DISPERSANTS
• Non metallic ashless cleaning agents
• Effective in controlling cold-sludge in gasoline engine operating under low-temp. stop-start conditions
• Bipolar molecule having polar head non-polar tail
Head consist of P,O,N atoms
Tail HC moiety
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ADDITIVES TYPES
• Succinimides
• Succinate Esters
• Mannich Type
• Phosphorus Based
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MECHANISM OF ACTION
• Polar Group Absobs on Dirt Oliophillic Group Solubilize Complex in Oil
• React Dirt Precursors e.g. neutralizing acidic matter
• Solubilizing precursors within their micelle structure.
• Absorb on metal surface• Form coating on solid particulate and prevent their
agglomeration to form large particles.
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USES OF DETERGENT / DISPERSANT ADDITIVES
• Essential for most of automotive oils
• Automotive oil for gasoline/diesel
• Rail road engine oil
• Marine Oil
• Two stroke engine
• Tractor Oil
• Automatic Transmission Fluid
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OXIDATION INHIBITOR (AO)
• Lubricants like other natural products deteriorate during use when exposed to oxygen.
• Undergo complicated aging process.• Oxidation alter performance.• 1st oxidation product is hydroperoxides.• Hydroperoxide leads to variety of end products
like alcohol, aldehyde, ketone acid etc.• Eventually depositing as sludge, varnish, liquer.• Leading to equipment failure
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R-H R` + H`
R` + O2 ROO`
Antioxidant perform as radical quenchers
R` + AO RH + AO`
2 AO` INERT PRODUCTS
MECHANISM OF ACTION
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• Engine oil accounts 60-70% of automotive lubricants.
• 40-50% of all lubricants sold• Automotive engine oil driving force on AO
market• AV car temperature – 100o
• Hot spot temperature – 300o or more• Chain branching reactions are more prevalent in
high temperature oxidation.
For lube antioxidants is a mixture of peroxide destroyer (TDDP) and radical scavenger.
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ADDITIVE TYPE
• Zn-Di-Thio phosphate
• Phenol
• Aromatic Nitrogen Compounds
• S- and P- Based Antioxidants
• Phenothiazine and Alkyl Derivatives
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USES OF ANTIOXIDANTS
• Antioxidants are used in all type of Lubricant
• Cranckase Oil Mostly Use ZDDP
• Steam Turbine Hindered Phenol
• Jet Air Phenothiazine
Derivatives
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CH2RO OH
NHC8H17C8H17
N
S
R
CNX2
S – M – S X2NC
S S
(XOC – CH2 – CH2)2 S, X – S – X, or X – Se - X
O
X= Alkyl, Aryl, alkylaryl
RO – P – OR
OR
RO – P – H
OR
OHINDERED PHENOL
DIPHENYL AMINE
PHENOTHIAZINE
DITHIOCARBAMATES
ORGANIC SULPHIDE OR SLENIDES
OTHER COMPUNDS GENERALLY USED IN ADDITION TO ZDDP
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VISCOSITY INDEX IMPROVER AND POUR POINT DEPRESSANTS
• These are polymeric additives
• These additives are used to improve rheological properties of oils
• They do it by purely physical means
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VISCOSITY INDEX IMPROVER
• VI is a number showing viscosity temperature characteristic of oil.
• Gear, Transmission, Crankcase oil should have
(a) Low viscosity at low temperature for startup (need low friction drag)
(b) Sufficient viscosity at higher running temperature.
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TYPES OF VI IMPROVERS
• Oil Soluble Org. Polymer
• M wt range 50,000-150,000
(a) Hydrocarbons
(b) Esters
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TYPES OF VI IMPROVERS
HYDROCARBON TYPE• PIB Poly-isobutylene• OCB Olefin Co-polymer
Poly Alkyl Styrene• HSDC Styrene Butadiene Co-polymer
Styrene – Isoprene Co-polymer
ESTER TYPEPMP [Poly Alkyl Acrylate
Styrene Maleic Acid Copolymer]
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USES OF VI IMPROVERS
PMA 21%,
HSDC 17%,
OCP 67%
VI improver made possible the advent of multigrade oils e.g. SAE low 30 or SAE 15w40 for gasoline engine (67%) diesel engine (19%).
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SELECTION DEPEND ON
• Requirement
• Other prop e.g. PPD, Dispersant
• Shear Stability
• Oxidation Thermal Stability
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MECHANISM OF VISCOSITY MODIFICATION IN OIL
Exist as random coil• Swollen by lube oil• Volume determine viscosity increase• At low temp. polymer remain as compact mass• At high temp. coil open up• Compensate fall in viscosity
SolubilityTemperature
LOW
LOW
GOOD
HIGH
Oil associated with polymer
Polymer
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USES OF VI IMPROVERS
• Automotive multi grade oils (engine, gear)
• Gear and transmissions oils
• Hydraulic fluids
• Industrial oils
• Dosage 2-6%
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POUR POINT DEPRESSANTS
• At low temperature wax crystalize out and prevent flow of oil
• Dewaxing can reduce pour point - Reduces yield- Adversely effect VI
• PPD – syn chemical which prevent congelation• PPD offer effective and economical alternative to
dewaxing• PPD improve
- Low temperature fluidity- Low temp performance
• PPD mainly used in paraffinic oils
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TYPES OF PP DEPRESSANTS
•Non Polymeric
•Polymeric
Recent Lit. indicate that majority of products are poly hydrocarbon HC-Ester co-polymer and ester co-polymer
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MECHANISM OF ACTION (POUR POINT DEPPRESANT)
• PPD don’t’ prevent crystallization
• Change crystal habit
• Probably by adsorption
• Smaller crystals form
• Do not interlock
• Permit flow of oil
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USES OF PP DEPRESSANTS
• Mono and multi grade Oil
• Gear & Transmission oil
• Hydraulic Fluid
• Compressor Oil
• Machinery Oil
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LOAD CARRYING ADDITIVES (AW/EP)
• Aw and EP additives are incorporated to extend oil’s load carrying capabilities
• Important but less used
• Inter metallic contact occur at asperities under boundary lubrication resulting heavy wear
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TYPES OF ADDITIVES
• Additive are active compounds of S,Cl and P S-CompoundsDibenzyl disulfide
• Butyl phenol disulfide• Sulfurised vegetable oils• Pb, Sb, Cd and Zn dithiocarbamates
Cl – CompoundsChlorinated wax
• Chlorinated fatty acids
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TYPES OF ADDITIVES
P - CompoundsTri cresyl phosphates ZDDP
• Di-alkyl phosphates etc• P & S-Compounds
Zinc dialkyl dithio phosphatesCl & S - CompoundsChlorinated alkyl sulfide
• Sulfurised chloronaphthalene
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MECHANISM OF ACTION
• Act by physical adsorption, chemisorption or chemical reaction with metal forming protective film
• Film not penetrated by asparities
• Prevent scoring and surface damage
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USES OF AW/EP ADDITIVES
• Engine oil
• Gear and transmission oil
• Shock absorber oil
• Hydraulic oils
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FRICTION MODIFIERS (FM)
• During start-up and shut-down sliding surfaces subjected to high load (mixed friction range)
• FM additives used, to prevent stick-slip oscillation, noise and reduce frictional force
• To save energy, reduce fuel consumption (additives known as FM)
• FM Similar to AW/ EP Additives
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• FM are polar oil soluble materials
Only few gained commercial Acceptance
• Mo-dithiophosphate and carbonate complexes
• Dispersion of MoS2, graphite, PTFE
• Ash less carboxylic acid esters, their oligomers and amines, amides
TYPES OF FRICTION MODIFIERS
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• Mechanism
• By physical adsorption
• Uses
• Engine oil
• Gear and transmission oil
• Industrial oil
• greases, etc.
MECHANISM AND USES
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ANTIFOAMING AGENTS
• Requires where violent churning or agitation of oil occur
Effect of Foams on the Performance of Engine
• Rise oil level,results in loss of oil
• Oil feed pressure drops,
• Insufficient oil supply
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TYPES OF ADDITIVES
• POLYMERICi) Poly organo siloxane
CH3 CH3 CH3
Si O Si O Si O
CH3 CH3 CH3
ii) Poly acrylateIii) poly ethylene oxides
DOSAGE 4-15 ppm
n
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MECHANISM OF ACTION
• Oil insoluble
• Lower interfacial tension between air and oil
• Permitting easy aggregation of air
• Reduce foam stability
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USES ANTIFOAMING AGENTS
• Engine oils (automotive, rail, marine)
• Gear oils
• Automotive transmission fluids
• Industrial oils
• Metal working oils
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RUST AND CORROSION INHIBITORS
• Rust and corrosion of metal parts undesirable
• Leads to wear and break down
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RUST INHIBIOTRS
• RESULT OF CHEMICAL ATTACK OF WATER IN PRESENCE OF OXYGEN
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• A large variety of compounds patented mostly three types:a. Neutral b. Acidic c. Overbased
• Most Popular are• High mil. Wt. Carboxylic acid (Succinic acid) • Sulphonic acid• Phosphoric acid and their salts• Compounds formed by neutralization of these
acids with organic base (e.g. Amines)
TYPES OF RUST INHIBITORS
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MECHANISM OF ACTION
• Physical Means
• Work by forming strongly absorbed hydrophobic film
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CORROSION INHIBITORS• Corrosion occur due to attack of acid• Arising from
A) oil oxidation (org>)B) blow-by of combustion products
(SO2 inorg)• Later sever in diesel engine
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ADDITIVE TYPES
• Metal dialkyl dithio phosphates,
• Phospho sulphurized olefins, terpenes
• Org Phosphites,
• Dithio carbamate• Most popular are basic detergent /
dispersant additive
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MECHANISM OF ACTION
• Forming absorbed protective films
• By neutralizing acid materials
• Also acts as Antioixdants, load-carrying additives
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MISCELLANEOUS LUBE ADDITIVES
• Anti-microbial agents used in cutting oil emulsions
• Emulsifiers to manuf. Water based cutting oils
• Odour masking agents• Dyes for identifications
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MISCELLANEOUS ADDITIVES
• Tackiness agents impart stickiness/ adherence property (PIB, ethylene-propylene co-polymer)
• Seal swalling agent to help swalling of rubber elastomers to required volume (phthalic acid ester, most popular di-octyl phthalate [DOP]
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SOME GENERAL TYPE OF ADDITIVES USED IN A WIDE VARIETY OF LUBRICANTS
Seal Swell
Pour Point
Viscosity Improvers
Antifoam Agents
Extreme Pressure Agents
Friction Modifiers
Corrosion Inhibitors
Rust Inhibitors
Antiwear Agents
Antioxidant
Ashless Dispersant
Metallic Detergent
Metal Working Fluids
Turbine Oils
Gear Oils
Hydraulic Oils
Axle Oils
Automatic Trans. Fluid
Engine Oil
LUBRICANT TYPEADDITIVE