CHY1005

INDUSTRIAL CHEMISTRY FOR ENGINEERS

TRIBOLOGY
Tribological system
Elastohydrodynamic lubrication theory
Classification of lubricating oils
Synthetic lubricants:
general purpose, compressor, gear, hydraulic,
high temperature chain, roller chain and
fluorinated oils.
Properties of lubricant oils:
viscosity index, cloud point, pour point
Layer lattice structured solid lubricants:
graphite, MoS2, TiS2 and WS2.
Tribomaterials:
Nanoparticulates, Thin films/layers,
Nanocomposites for lubricant additives,
anti-wear and friction modifier.
 TRIBOLOGY
 Tribology is the study of the science of interacting
surfaces or two moving bodies in relative motion.
 Tribology can be defined as “the branch of science
and engineering which deals with friction, wear and
lubrication”.
 It is related to friction, wear, lubrication, degradation
of metal surfaces, corrosion, engine life, and energy
losses.
 Friction – the resistance to motion of one body
moving against another.
 Wear – the loss of material due to motion.
 Lubrication – the use of a fluid / solid to
minimize friction and wear.
 Lubrication, friction, and wear are related to
tribological performance.
 Lubricity is concerned with the formation of
a protective layer or tribofilm on the contact
surfaces.
 High lubricity reduces direct surface contact,
thereby reducing friction and energy losses.
 When surface asperity contacts each other,
three types of mechanical wear are possible
resulting in the following: adhesion,
abrasion, and fatigue.
Energy Losses in an Automobile
Energy Losses in an Automobile
 LUBRICATION - INTRODUCTION
 Lubricants have been in use for hundreds of centuries and
are essential to our survival.
 Natural lubricants such as saliva and synovial fluid lubricate
the food for easy mastication and reduce wear and tear of
our joints respectively.
 Cooking oils prevent sticking of food onto frying pans and
baking trays at the same time as conducting heat.
 Ancient Egyptians used lubricants to slide large stone
blocks for building the great pyramids while the Romans
used lubricant on the axles of their chariots.
 Ancient lubricants were plant and animal based natural oils.
 With the onset of industrial revolution and our reliance on
metal-based machinery and engines, petroleum-based
lubricants witnessed a growth.
 Lubricants are vital for tribological life of machine
elements.
 Newer, better and environmentally sustainable lubricants
are required for modern machine elements which perform
heavy-duty applications in a wide range of environments.
 Lubricant additives are designed, optimized and blended
to meet the performance requirements of the equipment
or engine.
 The different components can have synergistic or
antagonistic effects due to chemical interactions or
competition at the metal surface or among themselves.
 Therefore, formulation of lubricants requires considerable
expertise and expensive performance testing.
 Green Tribology and Industry 4.0 era will steer the
lubricant development, use and disposal.
 Modern lubricants are more complex and perform various
other functions in addition to lubricating such as cleaning,
cooling, and sealing.
 The primary function of most lubricants is to reduce friction
and this property is known as lubricity.
 A lubricant can be used in solid form, semi-solid, liquid form
or gaseous form.
Solid lubricants: graphite & MoS2, Semi-solid lubricants:
greases, and Liquid lubricants: automobile engine oil.
 Physical state of lubricant chosen is based on application
needs.
 For example, in space environments where liquid lubrication
is not feasible due to vacuum, solid lubricants are chosen.
 Air bearing are preferred in applications in machine tool
applications where precision is of primary importance such
as cutting and finishing of optical lenses.
 Greases are used where a liquid oil would not remain
in position due to its tendency to flow or when a sealing
action is needed to prevent water-ingress in addition to
lubrication.
 Today’s lubricants are designed and packaged to meet
specific requirements for specific applications by
lubricant formulators.
 The lubricant for automobile transmission and drive
train has different requirements to satisfy compared to
lubricant for an internal combustion engine or turbines.
 Further depending upon the type of turbines viz. gas,
steam or hydraulic, the lubricant needs to be designed.
IMPORTANCE OF TRIBOLOGY
 FUNCTIONS OF LUBRICANTS

Lubricant functions:
Lubrication (A): For surfaces operating in contact with each other, lubricants such as
grease and oil can be used to reduce friction and prevent wear and tear.
Energy efficiency (B): The use of proper lubricants reduces friction, minimizes wear and
tear, and maximizes performance. Thus, it is possible to reduce energy consumption
and minimize resource usage.
Seal against contaminants (C): Lubricants create a thin film in the material surface,
which creates a barrier between the internal component of the material and the
external environment. In addition, any contaminants are transported to the tank or
filter with the help of lubricants where they can be removed.
Heat reduction/control (D): The lubricant reduces the friction between parts, thus also
reducing the heat generation. However, in the case where heat is generated, the
lubricant can absorb and transfer it along with the help of flowing lubricants.
Corrosion prevention (E): The surface coating provided by the lubricants prevents the
possibility of oxidation or corrosion in the metal.
 Uses of lubricating greases and oils
Lubricating Oils Lubricating Greases
Moving machine parts Bearings
Cars Gears
Factory machinery Heavy-duty machinery
Hydraulics
Advantages of lubricating oil:
While grease and oil have similarities and can be interchangeable, they
have their own use cases and there are times when lubricating oil is
preferable over grease.
 When heat transfer from the lubricant to the outside of the system is
needed.
 When the machinery requires a central oil supply that can lubricate
multiple parts of the machine at once.
 To lubricate machinery that requires frequent, constant lubrication.
 To lubricate components that move at high speeds.
 To lubricate machine parts that are easily accessible.
 Uses of lubricating greases and oils
Advantages of lubricating grease:
 To ensure machines/components that are not in use all the time will be
lubricated when they are needed.
 To lubricate inaccessible parts as well as parts that are sealed for life,
such as in gearboxes and other complex moving parts.
 To lubricate machinery that moves at low speed.
 To lubricate machine parts that require operating at extreme conditions,
such as high pressure, high temperature, under high load etc.
 To protect worn components and extend the life of parts previously
lubricated by oil.
When to use oil or grease for lubricating?
 Special Types of Lubricants
Marine lubricants – Optimised for use in the marine sector, so they offer high
water resistance and high salt resistance.
Industrial lubricants – These mechanical lubricants and mechanical greases are
designed to reduce friction between metal parts.
Metalworking fluids – maximise sump life, reduce costs, extend tool life while
also improving the surface finish of goods.
Automotive lubricants – ranging from transmission oil to crankcase lubricants,
these lubrication oils enhance performance, reliability and durability by reducing
the amount of friction and wear in the engine at both the cold start and during
normal operating temperatures.
Agricultural lubricants – agricultural machinery leads a demanding life and these
greases and lubricants are optimised for farm equipment need.
Food grade lubricants – food processing requires greases and lubricants that are
non-toxic and food-safe products and these lubricants meet standards.
Commercial lubricants – Aimed at businesses, this range of lubricants is
designed to help commercial enterprise run smoothly.
Hydraulic oil – Oils used in hydraulic systems are also lubricants.
 LUBRICANT COMPOSITION
Lubricant additives
Pour point depressants
Viscosity index improvers
Anti-wear agent
Antioxidants
Defoamants
Demulsifier
Film strengtheners
Friction modifiers
Detergents
Dispersants
Corrosion and rust inhibitor
Extreme pressure (EP) additives
 Mechanism of Viscosity Index Improvers (VII)

Mechanism of Friction Modifiers -

Adsorption of polar headgroups onto metallic surface
 Lubricant Additives
 Additives are chemical compounds added to
lubricating oils to impart specific properties to the
finished oils.
 Additives impart new and useful properties to the
lubricant.
 Enhance existing properties already present, act to
reduce the rate at which undesirable changes take
place in the product during its service life.
 Additives improving the performance characteristics
of lubricating oils.
 Aided significantly in the development of improved
prime movers and industrial machinery.
 Lubricant Additives
 Improving the wear and friction characteristics
by provision for adsorption and extreme
pressure (E.P.) lubrication.
 Improving the oxidation resistance.
 Control of corrosion.
 Control of contamination by reaction products,
wear particles and other debris.
 Reducing excessive decrease of lubricant
viscosity at high temperatures.
 Enhancing lubricant characteristics by reducing
the pour point and inhibiting the generation of
foam.
 Friction Modifiers (FM) Additives
 These are additives that usually reduce friction.
 The mechanism of their performance is similar to
that of the rust and corrosion inhibitors.
 They form durable low resistance lubricant films
via adsorption on surfaces and via association
with the oil.
 Common materials used: long-chain fatty acids,
their derivatives, molybdenum compounds.
 The friction modifiers also reduce wear, especially
at low temperatures where the anti-wear agents
are inactive, and they improve fuel efficiency.
 Anti-wear agents (A.W.) and
extreme-pressure (E.P.) Additives
 Anti-wear (AW) agents have a lower activation
temperature than the extreme-pressure (EP) agents.
 The latter are also referred to as anti-seize and anti-
scuffing additives.
 Organosulfur and organo-phosphorus compounds,
such as organic polysulfides, phosphates,
dithiophosphates, and dithiocarbamates are the most
commonly used.

Antioxidant additives (AO)

 One of the most important aspects of lubricating oils
is that the oxidation stability be maximized.
 GREASES
 Greases do not flow like a fluid but bleed (release oil) when
squeezed between contacting surfaces with a gel like
consistency.
 Used in vertical or overhead applications because they can
have good drip resistance due to their Non-Newtonian
rheological properties.
 Useful in applications that are sealed for life; for example
bearings and remote gearboxes.
 Functionality of greases include sealing out contamination
and water ingress, prevent corrosion, compatible with
polymers and elastomers, provide antiwear and extreme
pressure load protection while reducing friction.
 Greases have three main components: fluid, thickener
and additives
 Additives for Greases
Antiwear additives
Antioxidants
Extreme Pressure additives
Friction Modifier
Rust and corrosion inhibitor
Tackifiers (adhesive agents)
Odorants (perfumes)
Dyes
 SOLID LUBRICANTS
Solid lubricants are solid materials, which reduce coefficient
of friction and wear of rubbing parts preventing direct contact
between their surfaces even under high loads.
Forms of solid lubricants
 Solid lubricants may be present in the friction area in forms
of either dispersed particles or surface films.
 Coating of a solid lubricant applied on the part surface.
 Composite coating consisting of particles of a solid lubricant
dispersed throughout a matrix.
 Particles of a solid lubricant dispersed throughout the bulk
of the part material (composite material).
 Powder of a solid lubricant delivered to the rubbing area
(dry lubrication).
 Additives in lubricating oils or greases.
 SOLID LUBRICANTS
Requirements to solid lubricant properties
 Low shear strength in the sliding direction provides low
coefficient of friction due to easy shear movement of the
lubricant material.
 High compression strength in the direction of the load
(perpendicular to the sliding direction). A solid lubricant
possessing high compression strength is capable to
withstand high loads without sufficient direct contact
between the rubbing surfaces.
 Good adhesion of the solid lubricant to the substrate
surface. This property provides a presence of the solid
lubricant on the part surface even at high shear stresses.
 The best combination of the first two properties possess
anisotropic materials like graphite, molybdenum
disulphide or boron nitride having lamellar crystal structure.
 SOLID LUBRICANTS
Advantages of solid lubricants:
 Ability to work under high loads.
 High thermal stability.
 Diversity of the application forms
Disadvantages of solid lubricants:
 Higher coefficient of friction and wear as compared to
hydrodynamic regime.
 Low stability of the lubrication film.
 Less convenient system of the lubricant delivery to the
friction surfaces.
 In contrast to solid lubricants fluid lubricants are
continuously supplied, filtered and cooled.
 Classification of solid lubricants
Inorganic lubricants with lamellar structure
The crystal lattice of these materials has a layered structure consisting
of hexagonal rings forming thin parallel planes.
Within the plane each atom is strongly bonded (covalent bonding to
other atoms. The planes are bonded to each other by weak Van der
Waals forces.
The layered structure allows sliding movement of the parallel planes.
Weak bonding between the planes determines low shear strength and
lubricating properties of the materials.
The most commonly used inorganic solid lubricants with lamellar
structure are graphite, molybdenum disulphide (MoS2) and boron
nitride (BN).
Other examples of such materials are sulphides, selenides and
tellurides (chalcogenides) of molybdenum, tungsten, niobium,
tantalum, titanium (eg. WS2, WS2, MoSe2, TaSe2, TiTe2),
monochalcenides (GaS, GaSe, SnSe), chlorides of cadmium, cobalt,
lead, cerium, zirconium (eg. CdCl2, CoCl2, PbCl2, CeF3, PbI2) and also
some borates (eg. Na2B4O7) and sulfates (Ag2SO4).
 Classification of solid lubricants
Oxides
Examples: B2O3, MoO2, ZnO, Re2O7, TiO2, CuO-MoO2, NiO-Mo2,
PbO-B2O3, CuO-Re2O7.
Soft metals
Due to their low shear strength and high plasticity some soft metals
possess lubrication properties: lead (Pb), tin (Sn), bismuth (Bi), indium
(In), cadmium (Cd), silver (Ag).
Soft metals are used in pure form or as alloys, in form of coatings (Lead
based engine bearing overlays, Tin based engine bearing overlays) or the
second phase in Metal Matrix Composites (Copper based bearing
materials, Aluminum based bearing materials).
Coatings from soft metal lubricants are produced by the methods of
Electroplating, Vapor deposition and Thermal spraying.
Composites containing soft metal lubricants are prepared by casting or
sintering methods.
Soft metal are widely used as solid lubricants in engine bearing materials.
 Classification of solid lubricants
Organic lubricants - chain structured polymeric molecules
Polytetrafluoroethylene (PTFE) and polychlorofluoro-
ethylene are the typical examples of such materials.
The molecular structure of the materials consist of long-
chain molecules parallel to each other.
The bonding strength between the molecules is weak and
may slide past one other at low shear stresses.
The strength of the molecules along the chains is high due
to strong bonding between the atoms within a molecule.
Such anisotropy of mechanical properties provides good
lubrication properties of the materials.
Chain structure lubricants are used in form of coatings
(films) applied on the substrates surfaces (Polymer based
engine bearing overlays)
 Solid Lubricants - Uses
 Solid lubricants are used in space missions, satellites
release and deployment mechanisms.
 Thin film solid lubricant is used instead of liquid lubricant
for space missions due to vacuum and microgravity.
 Solid lubricants can be used at low & high temperatures
where the liquid lubricant may solidify or vaporize.
 At extreme pressures where liquid lubricant will be
squeezed out, solid lubricants are used.
 A wide variety of low friction coatings are used in
various engineering applications that require high
electrical and thermal conductivities, low wear rates and
high lubricity at all operating temperatures.
 Solid Lubricants – Uses (continued)
 Newer engineered coatings have increased complexity
and made the multi component structures to
nanostructured and functional gradient structures.
 Solid lubricants on their own are vital to niche
applications such as space missions, satellites release
and deployment mechanisms.
 Vacuum and microgravity of space eliminates the use of
liquid lubricants. The thin film solid lubricant is used for
smooth release with precision of a deployment
mechanism of space missions.
 Solid lubricants can be used at low temperatures as well
as at high temperatures where the liquid lubricant may
solidify or vaporize respectively.
 Solid Lubricants – Uses (continued)
 Even at extreme pressures where liquid lubricant will
be squeezed out, solid lubricants are used.
 A wide variety of low friction coatings are used in
various engineering applications that require high
electrical and thermal conductivities, low wear rates
and high lubricity at all operating temperatures.
 Newer engineered coatings have increased complexity
and have transitioned from single or multi component
structures to nanostructured and functional gradient
structures.
 LUBRICANT OILS
Types of Lubricant Oils:
 Engine Oil
 General Purpose Oil
 Transmission Oil
 Hydraulic Oil
 Gear Oil
 Compressor Oil
 Roller Chain Oil
 High Temperature chain Oil
 Fluorinated Oil
 LUBRICANTS - FUTURE TRENDS
 Current automotive lubricants are optimized for internal
combustion engines and drive trains.
 Electric vehicles (EVs) which use electric motors possess
new challenges of lubrication such as high-power density of
the small gear box which require efficient cooling.
 Hydro lubricants and synthetic gear oils are excellent
candidates for such application but may pose sealing
issues which requires innovative solutions.
 Lubricants are also required in the rolling element bearings
of EVs that must stop electro-erosion caused by high
frequency high energy discharges by being conductive.
 Ionic liquids are having shown good performance in
preventing built up of potential.
 LUBRICANTS - FUTURE TRENDS
 The future for lubricants formulation, manufacturing and
end-use is oriented towards efficiency in terms of cost and
time, customized and optimized for each individual tribo-
system and run reliably for even longer drain interval time.
 New industrial lubricants must meet stringent regulations
and guarantee ecological sustainability, and climate change
actions. Hence, new lubricants will contribute to ‘Green
Tribology’.
 Tribology of lubricants plays a significant role in technology
and economics of industrial development.
 As the fourth industrial revolution ‘Industry 4.0’ (combines
automation with the internet of things, IoT) is in progress,
several concepts can be extended to lubricant and lubricant
additive development and evaluation.
 LUBRICANTS - FUTURE TRENDS
 For example new electronic smart sensors can be used
for lubricant analysis and condition monitoring.
 The information of various performance parameters can be
stored as data and transferred to the stakeholders and
decision-making points using the information and
communication technologies involved in “Industry 4.0” such
as internet and wireless connections to and via several
electronic devices.
 Continuous monitoring can also aid in corrective measures.
In-service lubricant performance testing and evaluation
generates big quantities of data from various equipment
and sensors.
 Therefore, ‘Big Data’ concepts can be applied in several
ways.
 LUBRICANTS - FUTURE TRENDS
 One such example can be combining lubricant data with
machine data, another can be correlation study of
amount of soot produced, change in oil viscosity, friction,
wear of an engine.
 The benefits of Industry 4.0 include shorter lubricant
development time, reduced number of trials, lubricant
performance prediction through chemical and physical
modeling and simulations.
 This will transform product development process from
being empirically driven to using data and simulation
driven approach.
 Exploring new lubricant additives with high tribological
performance especially under extreme conditions will be
the focus of basic researches and applications in future.
 LUBRICANT ANALYSIS
Physical and chemical Performance test
characteristics
Engine test evaluation
evaluation
Oxidation stability and bearing
Color Oxidation Tests
corrosion protection
Density and
Thermal Stability Single cylinder high Temperature tests
API gravity
Carbon Residue Foaming Tests Multi cylinder high temperature tests
Corrosion and Rust
Flash point Multi cylinder low temperature tests
Protection Test
Neutralization
EP and Antiwear Test Rust and corrosion protection tests
Number
Emulsion and
Total Acid Number Oil Consumption rates and volatility
Demulsibility Test
Emission and protection of emission
Total Base Number -----
control systems
Pour Point ----- Fuel Economy
LUBRICANT ANALYSIS
 NANOLUBRICANTS
The use of nanoparticles / nanomaterials as lubricant
additives are known as nanolubricants.
Nanolubricants can be synthesized by TWO methods.
One-step method:
The nanolubricants are directly formulated through a
chemical process.
Two-step method:
First procedure is the nanomaterials are synthesized
in dry powder form by either physical or chemical
methods, and
the second procedure is to disperse them into base
oil by mixing techniques with or without dispersants
or surfactants.
 Synthesis of nanolubricants
The size, concentration, and morphology of
nanoparticles used in nanolubricants are
relevant to the improvement of tribological
characteristics.
 Lubrication Mechanism of Nanoparticles
1. Rolling effect 2. Protective film formation

2. Mending effect 4. Polishing effect

(a) Rolling bearing effect of nano-diamond.
(b) Rolling bearing effect of fullerene-like WS2 nanoparticles.
Synergistic effect model of
Au@GO nanocomposites
 The synergistic effect model of
Mn3O4@Graphene nanocomposites
 Various Types of Nanoparticles as
Lubricant Additives
1. Metals – Bi, Cu, Al, Sn, Fe, Pd
2. Metal oxides – Al2O3, TiO2, CuO, ZnO
3. Metal sulphides – FeS, MoS2, WS2
4. Carbon-based Nanoparticles – graphite, graphene
5. Nanocomposites – TiO2-SiO2, Ag-MoS2, Cu-MoS2
6. Rare earth compounds – CeO2, LaF3, CeVO4
Parameters of Nanoparticle Affecting
the Tribological Properties
1. Concentration of Nanoparticles
2. Size of Nanoparticles
3. Morphology of Nanoparticles
4. Dispersion Stability of Nanoparticles