UNIT-1:: ENGINEERING MATERIALS

REFRACTORIES:
Definition: Refractory is any material which can with standing high temperatures, with out softening or
suffering from deformation in shape.
The main objective of a refractory is to confine heat (i.e. to resist the loss of heat) and at the same time
to resist the abrasive and corrosive action of molten metals, slags and gases at high operating temperatures, with
out undergoing softening or distortion in shape. Refractories are mostly used for the construction of the linings
of the furnaces, tanks, converters, kilns, crucibles, ladles, etc, employed for the manufacture of metals (ferrous
as well as non ferrous), cement, glass, ceramics, paper, steel, etc.
Characteristics of good refractory:
A good refractory possesses the following characteristics. It should
 Be infusible at the temperature to which it is liable to be exposed.
 Be chemically inert towards corrosive action of gases, metallic liquids and slags, produced in its
immediate contact in furnaces.
 Resist the abrading action of flue gases, flames, etc
 Be able to with stand the overlying load of structure, at operating temperatures
 Not crack and suffer loss in size, at the operating temperatures
 Expand and contract uniformly with temperature raise and fall respectively.
Classification of Refractories:
Refractories are classified in to three main types, on basis of the chemical properties of their constituent
substances.
1. Acidic refractories: Are those, which consist of acidic materials like alumina (Al2O3), silica (SiO2) and fire
clay. They are not attacked by acidic materials, but easily attacked by basic materials. Important members of
this group are alumina, silica, and fire clay
2. Basic Refractories: are those, which consist of basic materials like CaO, MgO, etc. These are not attacked
by basic materials, but easily attacked by acidic materials. Important members of this group are magnesite,
dolomite.
3. Neutral refractories: are made from weakly acid/basic materials like, chromite (Feo.CrO2), Zirconia (ZrO2),
Graphite.
PROPERTIES OF REFRACTORIES:
1. Refractoriness: is the ability of material to with stand the heat, with out deformation or softening under
particular service conditions. it can be expressed in terms of softening temperature.
Measurement: (By Pyrometric cone test or seger cone test). The refractoriness is expressed in terms of
Pyrometric cone equivalents (PCE). These cones are small pyramid shaped, 38 mm height and have a triangular
base, with 19 mm long sides. They melt or fuse at definite temperatures, when heated under standard condition
of 100C per minute called standard cones. The sample refractory material is taken in sample cone and heated
along with the standard cones The PCE value of the given refractory is taken as the number of the standard
cone, which fuses or melts along with the sample cone.

2. Strength or refractoriness-under-load:

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 It is, essential that refractory materials must also possess high mechanical strengths even at operating
temperatures, to bear the maximum possible load, without breaking. Some Refractories, like fire clay and high
alumina bricks, soften gradually over range of temperature, but under appreciable load, they collapse, far below
their true fusion point, as determined by seger cones. On the other hand, other Refractories like silica bricks
soften over a relatively narrow range of temperature and exert good load-bearing characteristics close to their
fusion points.
R.U.L Test: is performed by applying a constant load (of 3.5 or 1.75 kg/cm2) to the refractory specimen (of size
5 cm2 and 75 cm high) and heating in a carbon –resistance furnace at a standard rate (of 100C/minute). The
record of the height of the specimen vs. temperature is made by plot, until the test –piece deforms or collapses
by 10%. The R.U.L is expressed as the temperature at which 10% deformation takes place. Under a load of 3.5
kg/cm2
i A high heat duty brick should not deform a great deal at 13500C,
ii An intermediate heat duty brick at 13,000C and,
iii A low heat duty brick at 11000C .
3. Dimensional Stability:
Dimensional stability of a material is defined as the resistance of that material to any volume changes when it is
exposed to high temperature for a longer period. The dimensional change may be permanent i.e., irreversible or
temporary i.e reversible. The more the dimensional stability of a refractory the better is the refractory.
For example
1) Magnesite brick (amorphous MgO) to periclase (denser brick).
2) Silica bricks to tridymite and cristobolite
4. Chemical inertness: a refractory should be selected that is chemically in active in use and does not easily
form fusible products with slags, fuel ashes, furnace gases, [Link] the environment in most furnaces is
either acidic or basic. It is inadvisable to employ an acid refractory in contact with an alkaline product or vice
versa.
5. Thermal expansion: In a furnace design, allowance has to be made for thermal expansion, since
practically all solids expand, when heated and contract, when cooled. The expansion affects all dimensions (i.e.
length, area, and volume) of a body. So, it is necessary that a refractory material should have least possible
thermal expansion, because
i Expansion of a refractory decreases the capacity of the furnace
ii Repeated expansion and contraction contribute much towards rapid breakdown, and wear and tear of the
refractory material structure.
6. Thermal Conductivity: In industrial operations, refractory materials of both high thermal conductivity
and low thermal conductivity are required, depending upon the type of furnace. In most cases, furnace is lined
with Refractories of low heat conductivities to reduce the heat losses to the outside by radiation; Otherwise
maintenance of high temperatures inside the furnace will become difficult. However a good heat conductivity of
refractory is desirable for effective heat transmission in some furnace construction, as in muffle furnace walls,
coke-oven batteries, in which charge is separated from the flame.
7. Porosity: Porosity is the ratio of its pore’s volume to the bulk volume. Thus, porosity
W D
P X 100
WA
Where W=[Link] saturated specimen
D=[Link] dry specimen
A=[Link] saturated specimen submerged in water
Porosity is an important property of refractory bricks, because it affects many other characteristics, Ex;
Chemical stability, strength, abrasion resistance and thermal conductivity. In a porous refractory, molten charge,
slags, gases [Link] likely to enter more easily to a greater depth and may react and reduce the life of refractory
material. Porosity decreases the strength, resistance to abrasion, resistance to corrosion/penetration by slags,
gases.

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8. Thermal spalling: Is breaking, cracking, peeling off of a refractory brick or block, under high
temperature. So a good refractory must show a good resistance to thermal spalling. Spalling is generally, due to
rapid changes in temperature, which cause uneven expansion and contraction with in the mass of refractory,
there by leading to development of internal stresses and strains. Spalling may also be due to slag penetration in
to the refractory brick, there by causing variation in the coefficient of expansion. It has been found that spalling
can be decreased by
 Using high porosity, low coefficient of expansion and good thermal conductivity refractory bricks, since
all these resist the development of internal stresses.
 Avoiding sudden temperature changes.
 By modifying the furnace design so that stresses are not set up, when the furnace is heated.
Applications of Refractories:
Silica bricks :(SiO2)
Property:
 Stable up to 15000C -16000C under 3.5 kg/cm2 constant load
Applications:
1 Roofs of open hearth furnaces
2 Coke oven batteries
3 Acid converters
Alumina bricks :(Al2O3)
Property:
 Stable up to 17500C under 3.5 kg/cm2of constant load
Applications:
1 Cement rotary kilns
2 Brass melting reverbratories
3 Aluminum furnaces
Magnesite :( MgO)
Property:
 Stable up to 15000C under 3.5 kg/cm2of constant load
 But less dimensional stability at high temperature
Applications:
1 Hot mixer linings, Basic converters
2 Reverbratory furnace
3 Refining of metals
Chromite (FeO.Cr2O3):
Property:
 Stable up to 14300C under 3.5 kg/cm2of constant load
Applications:
Their important use is in separating acidic and basic refractory lining
Ex: Between acid refractory roof and basic refractory walls of furnace
Zirconia (ZrO2):
Property:
 Stable up to 20000C under 3.5 kg/cm2of constant load and very costly
Applications:
1 Used at very high temp
2 High frequency electric furnaces

LUBRICANTS:
“Friction can be defined as the resistance offered by two moving surfaces”.

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 The contact of (between) two rubbing surfaces introduces high-energy weld flat junctions. These welded
flat junctions carry most of the load between the two surfaces

Effects of friction:
1 Friction causes a lot of wear and tear of surfaces of moving parts
2 Large amount of energy are wasted in the form of heat, thereby causing loss in the efficiency of
machine.
3 More over the moving parts get heated up damaged are even sometimes results in seizure (i.e., welding
of the two surfaces due to heat)
4 Life time of machinery will decreases
5 Avoids smooth movement parts
Lubricants: The ill effects of frictional resistance can be minimized by using a suitable Substance, which
forms a thin layer in between the moving parts
Definition: “any substance introduced between two moving/sliding surfaces with a view to reduce the
frictional resistance between them is known as lubricants”
Functions of lubricant: -
1. It reduce surface deformation, wear and tear because the direct contact between the rubbing surfaces is
avoided
2. It reduces the loss of energy in the form of heat. In other words it act as coolants
3. As it reduces waste of energy, efficiency of machine is enhanced
4. It reduces expansion of metal by local frictional heat
5. It avoids seizure of moving parts
6. It avoids or reduces un smooth relative motion of the moving parts
7. It reduces the maintenance and running cost of the machine
8. It also sometimes act as a seal (prevents leakage, deposition of dust in machine parts or holes)
Classification of Lubricants:-
Lubricants can be broadly classified on the basis of their physical state as follows
1. Liquid lubricants or lubricating oils
2. Semi-solid lubricants or greases
3. Solid lubricants
Liquid lubricants:-
I Animal and vegetable oils:-
Animal and vegetable oil play a major role as lubricants before the development and use of petroleum
crude oils as lubricants compared to petroleum crude oils animal and vegetable oils have better oiliness
and adhere to the machine parts even under heavy load. But the animal and vegetable oils undergo
oxidation easily at a high temperature and forms gummy and acidic products. Also these oils get
hydrolyzed easily under moist conditions. Hence animal and vegetable oils are mainly used as blending
agents which can enhance oiliness of lubricants some of the common vegetable oils used as lubricant are
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 palm oil, castor oil, coconut oil that are used for lubricating bearings and light machine parts. Animal
oils such as lard oil made from the fat, intestine, kidney etc of pigs. Tallow oil made from cattle fat is
used for lubricating ordinary machine parts. Whale oil made from sperm whale fat is used as lubricant to
light machineries.
II Mineral or petroleum oils:-
Are obtained by distillation of petroleum. The length of hydrocarbon in petroleum oils varies between
about 12-50 carbon atoms the shorter – chain oils have lower viscosity than the longer chain
hydrocarbons. These are the most widely used lubricants because they are
1 .cheap 2, available in abundance 3 .stability under service conditions.
However they possess poor oiliness as compared to that of animal and vegetable oils. The oiliness of
petroleum oils can be increased by the addition of high molecular weight compounds like oleic acid,
stearic acid etc.
III) Blended oils: Blended oils serve as better lubricants then single lubricating oil. Especially petroleum
oils when mixed with certain additives suit the requirement of modern machineries. The following are some
of the additives(Extreme pressure additives, Oiliness Carriers, Viscosity Index Improvers, Antioxidants)
used as blending agents to enhance the property of lubricants
IV Synthetic lubricating oils:-
Under special conditions of temperature & pressure certain synthetic lubricants are used. These
Synthetic lubricants can be stable under very low temperature (-400C). Some of the synthetic
Lubricants are poly alkene glycols silicone fluids etc.,
Semisolid lubricants:- (greases)
Greases are semi – solid lubricants formed by the dispersion of soap in lubricating oil
The following characters of grease depends on Nature of soap
a) The temp up to which the grease can be used
b) Its consistency
c) Its water and oxidation resistance
Greases are named according to the nature of soap.
Calcium – based greases: Emulsions of petroleum oils with calcium soaps.
Soda – based greases: Are petroleum oils thickened by mixing sodium soaps.
Lithium – Based greases: Are petroleum oils, thickened by mixing Lithium soap
Axle greases:- are very cheap resin greases prepared by adding lime or any heavy metal ‘
hydroxide to resin and fatty oils with constant stirring.
Solid lubricants:-
The important solid lubricants generally used are graphite & MoS2
GRAPHITE:-
Graphite is made of Hexagonal arrangement of ‘C’ atoms present in flat plates with one atom [Link]-
inflammable and not oxidized in air below 3750C. In the absence of air. It can be used up to very much high
temperature.
Molybdenum disulphide:-
Also possesses similar properties as that of graphite. In molybdenum disulphide (has a sand witch like structure)
plate lets of molybdenum atoms and Sulphur atoms slide over one another. It is mainly used in heavy
machineries working under heavy load and high temp.
Properties of Lubricants
I) Viscosity: -
Is the property of a liquid or fluid by virtue of which it offers resistance to its own flow
Viscosity is the most important single property of any lubricating oil, because it is the main determinant
of the operating characteristics of the lubricant

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If the viscosity of the oil is too low, a liquid oil film can not be maintained between two moving surface and
consequently, excessive wear will take place
On the other if the viscosity is too high, excessive friction will result.
Determination of viscosity of lubricating oil: -
Is made with the help of an apparatus called the viscometer
Red wood viscometer: -
It is of two types. “Red wood viscometer No.1” is commonly used for determining viscosities of thin
lubricating oil and has a jet of bore diameter 1.62mm and length 10mm on the other hand “Red wood
viscometer No.2” is used for measuring viscosities of highly viscous oils like fuel oil. It has a jet diameter
3.8mm and length 15mm.
Working:- The leveled oil cup is cleaned and ball of valve rod is placed on the agate jet to close it. Oil under
test free from any suspension is filled in the cup up to the pointer level. An empty Kohlrausch flask is kept just
below the jet water is filled in the bath and side tube is heated slowly with constant stirring of the bath when the
oil is at the desired temperature heating is stopped and the ball valve is lifted and suspended from thermometer
bracket. The time taken for 50ml of the oil to collect in the flask is noted and then the valve immediately closed
to prevent any over flow of the oil. The result is expressed in Red wood No.1 second at the particular
temperature

Viscosity index: - The rate at which the viscosity of lubricating oil changes with rise in temperature is
measured by a scale known as viscosity index. If the increase in temperature makes notable decrease in the
viscosity of the lubricating oil then the oil has a low viscosity index. But if the viscosity of the oil is affected
slowly on rising temperature then the V.I of the oil is high.
Determination of viscosity index:- For this purpose, two series of standard oils are used paraffinic-base
Pennsylvanian oils (With VI-100) and Naphthanic – base gulf oils (With VI-0) against each of these is marked
their viscosities at 1000F & 2100F. The former are known as H- Oils and the latter as L – Oils
Step I:- The viscosities of the oil under test at 1000F and also a 2100F are first found out. Let these values ‘U’ &
‘V’ respectively. The difference between the two values should below, then the oil is good and if it is high the
oil is poor.
Step II:- Now from the list of H-oils (With VI=100). The oil which has the same viscosity at 2100F as the oil
under test is selected, and its corresponding viscosity at 1000F is read off. Let it be ‘H’
Step III:- The from the list of L-oils (With VI=0), the oil which has same viscosity at 2100F as the oil under test
is selected and its corresponding viscosity at 1000Fis read off. Let it be ‘L’
L-U
Then VI  X 100
L-H
II) Flash and Fire points:-

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Flash point:- is the temperature up to which the oil lubricant is heated to produce vapors that ignite for a
moment or produce a flash when a test flame is brought near it.
Fire point:- Is the temperature up to which the oil lubricant is heated to produce sufficient vapors that burn
continuously at least for 5 seconds when test flame is brought near it,. Generally fire point is 5 to 400C higher
than the flash point
A good lubricant should have high fire and flash point so that it can with stand higher working
temperature
The flash and fire point are determined experimentally by using pensky – marten’s apparatus. The apparatus
consists of a small cup with 5cm diameter and 5.5cm height which is closed at the top except in few places
where gaps are provide for inserting the thermometer, stirrer and introducing flame. A shutter which can be
moved on the top of the container is filled up to the standard mark with the lubricating oil. The container is
gradually heated using burner. For every 20 rise the test flame is introduced by opening the lid with the removal
of shutter the temperature at which the introduced test flame produces flash is noted as the flash point.

III) Cloud and Pour points:

Cloud Point:- The temperature at which the lubricating oil becomes cloudy or hazy on cooling is known as the
cloud point
Pour point: - The temperature at which the lubricating oil ceases to flow on cooling is known as the pour point.
Machines working at low temperature lubricants with low cloud and pour points are preferred for the
determination of cloud and pour point. The apparatus used is shown below
The apparatus consist of flat bottom glass tube containing the lubricating oil at standard height. This is placed in
side an air jacket flat-bottomed bigger glass tube. In the center of the main glass tube a thermometer is
introduced for noting the temperature of the lubricating oil. The test tube along with the outer air jacket test tube
are placed in side a beaker containing ice and salt (CaCl2). The middle test tube containing lubricating oil is
with drawn from the ice mixture and outer jacket for every 10C fall of temperature and noted .For any change in
state. The temperature at which cloudiness is noted is recorded as the cloud point, similarly after sometime the
temperature at which the lubricating oil solidifies and resists flowing is recorded as the pour point

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IV) Neutralization number:-
Neutralization number is defined as the number of mgs of KOH required to neutralize the free acids in 1 g of
the oil. It is other wise referred as “Acid number” generally free acids should not be present in the lubricating
oils. A good lubricating oil should possess acid less than 0.1
V) Mechanical stability:- The suitability of a lubricant under certain specific conditions are studied with the
help of different mechanical test one of the important such test is four – balls extreme pressure lubrication test.
In this test the sample lubricant is poured in a machine containing four balls. The lower three balls are stationary
and the upper ball is rotated load is gradually increased and the three stationary balls are pressed up wards
against the fourth ball by a lever carrying an adjustable load. The coefficient of friction is continuously
measured. In this test, the highest load that a ball can stand for 1 min with out squeezing can be taken as a
measure of lubricants quality.

Applications of lubricants
 Automotive
 Engine oils
 Petrol (Gasoline) engine oils
 Diesel engine oils
 Automatic transmission fluid
 Gearbox fluids
 Brake fluids
 Hydraulic fluids

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  Tractor (one lubricant for all systems)
 Universal Tractor Transmission Oil – UTTO
 Super Tractor Oil Universal – STOU – includes engine
 Industrial
 Hydraulic oils
 Air compressor oils
 Gas Compressor oils
 Gear oils
 Bearing and circulating system oils
 Refrigerator compressor oils
 Steam and gas turbine oils
 Aircrafts
 Gas turbine engine oils
 Piston engine oils
 Marine
 Crosshead cylinder oils
 Crosshead Crankcase oils
 Trunk piston engine oils
 Stern tube lubricants
 Greases
Are used in
 Motorcycle wheels bearing
 Bicycle wheel bearing
 All other bearings
 Brakes and clutches
 Solid lubricants
Are used in
 Aero space applications
 High-temperature lubricants,
 Brushes for electrical motors,
 battery and fuel cells

Abrasives:
Abrasives are very hard materials that can be used to wear off and disintegrate other object and help in
polishing shaping grinding, drilling and cutting operations.
Hard ness of abrasive is most important quality and is measured roughly on Moh’s Scale. According to
this scale the hardness of talc (weak abrasive) taken 1 and diamond (strongest abrasive) is taken as [Link]
hard ness of all abrasives measured with in this limit.
Properties:
The efficiency of good abrasive mainly depends on the following characters.
1) Hardness: It is the ability of the abrasive to scratch (or) grinds other materials. The harder the abrasive
quicker will be its abrading action.
2) Tough ness: Abrasive are generally hard and brittle, which is other wise known as toughness. Toughness
must be high for the abrasive
3) Refractoriness:
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4) It is the capacity to with stand high temperature by the abrasives.

Classification:
Abrasives can be classified in to
a) Natural abrasives
b) Artificial abrasives

Natural Abrasives:
Diamond:
Crystallized carbon.
Properties:
a) It is the hardest known substance on Moh’s scale -[Link] high refractoriness
b) It is chemically in active to acids and alkalis
c) Diamonds, which are faulty of colour or block, colour diamonds arte only usedas abrasives
Applications:
As abrasives in drill points, grinding wheels, rock cutting saw teeth etc
Aluminum Oxide:
It is crystalline alumina other name corundum
Property: Its hardness on moh’s scale is 9
Applications: It is used as abrasive in grinding wheels especially for grinding iron castings
Emery:
It is a mixture of corundum (Al2O3) and ferric oxide (Fe3O4)
Property: Its hardness on moh’s scale is 8
Application: It is used as abrasive in the cutting and drilling tools
Quartz:
It is pure form of silica
Property: its hardness on Moh’s scale is7
Application :It is used as granules in grinding machines
Garnet:
It is a trisilicate alumina, magnesia&ferrous oxide.
Property: the hardness on moh’s scale is 6
Application: It is used in making abrasive paper and abrasive cloth
Artificial Abraisves:
Carborundum (or) Silicon carbide (SiC)
Preparation: It is prepared by treating mixture of silica and carbon at a high temperature (20000 C) with the
help of electric furnace.
SiO2 + 3C SiC+2CO
Properties:
a) It is Very hard synthetic abrasive (Moh’s scale 9.3)
b) Chemically inert
c) Possess high refractoriness.
Application:
a) Used in grinding and cutting wheels
b) Used in polishing machines

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 Alundum:( Al2O3)
Preparation:
It is prepared by heating mixture of calcined bauxite, coke and iron in an electric furnace at 40000 C
Property: Its hardness on moh’s scale is 9
Application: It is used in grinding wheels and in abrasive paper abrasive cloth
Boron carbide:(B4C)
Preparation: It is prepared by heating a mixture of boron oxide (B2O3) and carbon in an electric furnace at
about 27000 C
2 B2O3 +7C B4C+6 CO
Property: The hardness on moh’s scale is nearly 9
Application: It is used in grinding wheels and cutting, shaping of high-speed tools

Ionic liquids as Lubricants

Ionic liquids (ILs) are a class of salts composing of bulky organic cations and organic or inorganic anions.
Some of the typical IL molecular structures are shown in Figure. The large molecular size of the ions and their
possible delocalized charge contribute to the uncommonly low melting points of ILs, which are below 100 °C.
The first IL, ethyl ammonium nitrate [(C2H5NH3)NO3], reported by Walden in 1914 is found to have a melting
point of 12 °C. since the 1970s, the research of ILs has become increasingly popular and now ILs have been
used for various applications such as effective solvent, catalyst, electrolytes in batteries, and carbon and carbon
dioxide capturing.

In material science, IL have shown great potential as advanced lubricants and tailor made lubricating additives
since 2001. ILs have excellent physicochemical properties including low melting point, low flammability,
negligible vapor pressure, and high thermal stability that meet the demands of high-performance lubricants. One
of the most important characteristics of ILs is that their properties can be tailored by varying the species of the
cations and anions, giving rise to numerous families that can be used across different tribological systems.
The superiority of ILs in lubrication can be attributed to their inherent polarity,
a. which can make them form stable ordered layers in the liquid state on metal surfaces to prevent them against
contact; and
b. some elements of ILs can react with the substrate materials to generate a tribofilm to protect the substrate from
further wear.

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ILs can be conventionally categorized into aprotic ionic liquids (AILs) and protic ionic liquids (PILs), based on
the nature of the cation present in the combinations.

Properties of ionic liquids

ILs are highly tunable by changing either the cation structures or anion structures or both to satisfy specific
engineering and manufacturing requirements. Their physicochemical properties can be easily influenced by
combining different types of cations and anions or varying their alkyl chain lengths.
Viscosity and thermal stability
The viscosity behavior will affect the load-carrying capacity of ILs, as well as their formation of boundary
lubricating films. In addition, the thermal stability of an IL is also a prerequisite for being used in various
tribological systems. In general, the molecular structure modification of the cation or the anion will affect the
IL’s viscosity and thermal stability. ILs having symmetric cations with long alkyl side chains are found to have
high viscosity, which is attributed to the closer packing and enhanced van der Waals interactions between the
long alkyl chains. Particularly, the branched ILs are reported to possess higher viscosity than the linear ones. In
addition, ILs having high molar mass and ion-interactions such as hydrogen bonds in their molecular structures
will get high viscosity. For instance, an imidazolium-based IL with a hydroxyl group (-OH) grafted into the N-1
position of its cation obtained an increase in viscosity, which is attributed to the increased hydrogen bond
interactions and the resulting higher molar mass. In a study the viscosity of the hydroxylammonium PIL is
highly dominated by the hydrogen bond interactions among its molecules instead of its molar mass.

The thermal stability of an IL is also closely related to its cation and anion. Generally, when pairing with the
same anion, the imidazolium based ILs have a higher thermal stability than the tetraalkylphosphonium based
and the tetraalkylammonium-based ILs. And the imidazolium-based ILs are reported to have a higher thermal
stability when their cations have a smaller alkyl chain. In contrast to cations, the anions have more impact on
the thermal stability of ILs. For example, an alkylammonium PIL derived from a stronger acid tends to have a
higher thermal stability. For e.g. the thermal stability of the alkylimidazolium-based PILs is mainly determined
by the anions nature instead of the cation structure. PILs having the cation with larger size and branched chain
structure would get a higher thermal stability. In several studies, the hydroxylammonium PILs with carboxylate
anions were found to have low thermal stability. The reason underlying this phenomenon is related to the
reversal proton transfer, leading to the presence of free acid and ethanolamine.

Corrosion
The use of neat PILs significantly improved the corrosion resistance of copper and iron sheets. The results from
the electrochemical test demonstrated the excellent corrosion inhibition of PILs additives and their attributes of
anodic corrosion inhibitors. A protective film generated by the adsorption of PIL molecules, particularly the
hydrophilic functional group on steel surface is attributed to anticorrosion performance. 2-
hydroxypropylammonium di-(2-ethylhexyl) phosphate was found to have the best corrosion resistance, and
PIL’s corrosion inhibition efficiency was related to its functional groups.
Recently, a PIL 2-hydroxyethylammonium oleate, was proved to be an effective corrosion inhibitor for
aluminum 1100 in neutral sodium chloride solution. The PIL adsorption layer on the aluminum substrate
surface was pointed out to inhibit the diffusion of chloride anions during the electrochemical measurement,
where it can provide a corrosion protection at high chloride concentration for 72 hours

Biodegradability and toxicity

In terms of the prospective large-scale industrial applications of ILs, it is crucial to examine their
biodegradability and toxicity to control the discharge of IL involved solvents or lubricants, minimizing the
environmental damage. To understand the correlation between the molecular structure and biodegradability and
toxicity of ILs is essential to design green IL lubricants. Nowadays, many experimental studies have been
conducted to evaluate the environmental impact of ILs. In general, cations and anions do have an influence on
the ILs toxicity particularly, cations have a greater impact than anions. ILs having longer alkyl chain length and
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more branched-chain groups on their cations tend to be more toxic. However, some anions containing fluorine
in their structure will cause an increase in toxicity of their corresponding ILs. For example, although the
hydroxylammonium and imidazolium cations were evaluated to be less toxic, the toxicity of their ILs increased
drastically once NTf2 was incorporated as the anion.

Ionic liquids as lubricants

ILs were used as lubrication since 2001, as neat lubricants for various contact systems such as steel-steel
contact, steel-ceramic contact, and steel-aluminum contact have received considerable attention. Compared to
AILs, the use of PILs as neat lubricants has gained more attention than before, owing to their low cost and facile
synthesis process.
The effect of anion chain length on the friction and wear behavior of ammonium-based PILs was investigated
for steel-aluminum contact. The results revealed that increasing the anion chain length will improve the
lubricating ability of PIL with a low friction coefficient. From another study three oleic-acid derived
ammonium-based PILs were evaluated as lubricants in alumina- aluminum contact. In addition to the low
friction coefficient, the use of PILs yielded an important wear reduction (98%) compared to the dry condition.
Hexanoate-based PILs were also found to greatly reduce the wear of steel with respect to mineral oil as well as
a commercial oil.
In addition to the above-mentioned bulk lubricants, ILs can also be employed in the form of thin layers for
lubricating micro/nano electromechanical systems (MEMS/NEMS). For example, a PIL - di[bis(2-
hydroxyethyl)ammonium] succinate thin layer was created on a steel substrate surface by evaporating water
from the PIL + Water mixture, where the PIL thin layer extremely reduced the wear rate of steel compared to
the bulk neat PIL

Surface interactions
As shown in Figure below, it has been widely accepted that when neat ILs or IL additives are introduced
between the contacting work pairs, the IL molecules tend to adsorb onto the work piece surfaces physically
or/and chemically and form an ordered boundary lubricating film to protect the moving components from direct
contact, leading to low friction. During the sliding frictional process, a protective tribofilm will be subsequently
generated on top of the substrate by means of the tribochemical reactions between ILs or their decomposition
products and the contacting metal surfaces to reduce mechanical wear.

Ionic liquids as lubricant additives

Limited to the high cost of being used as neat lubricants (particularly when AILs are used), ILs as additives
have gained more and more research attention in recent years. Their highly tunable molecular structures and
physicochemical properties make ILs suitable to be added to base lubricants with different nature (polar or
nonpolar), such as ester, polyethylene glycol (PEG), PAO, mineral oils (MO), grease, and water-based
lubricants. Most imidazolium-ILs are insoluble in the non-polar synthetic oils and mineral oils. So they are
always used as lubricant additives in very low concentrations or in oil-IL emulsions.
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Generally, larger cation sizes lead to higher solubility of IL in nonpolar oils. In addition, ILs having symmetric
cations would outperform the ones with asymmetric cations in wear reduction, and the symmetric-cation ILs are
hypothesized to have a better mobility in the base oil to interact with metal surfaces and form protective
boundary lubricating film

Ionic liquids in water-based lubricant

Water or water-based lubricants can effectively reduce the temperature and clean the contaminants from surface
contacts, which leads to a better working conditions and increase the machine lifetime. Since the high volatile
characteristic and high freezing point of water-based lubricants, they are preferable in some specific industrial
applications such as cutting and machining.
A lower friction and wear rate, and excellent extreme- pressure and abrasion resistance were obtained compared
to an oil-based lubricant. The superior tribological property was attributed to the physical adsorption of ILs on
the steel surfaces and the formation of a protective film due to the tribo-chemical reactions between NP and
sliding surfaces.

Ionic liquids and nanoscale additives

Nanomaterials, such as nanoparticles (NPs), graphene, and carbon nanotubes (CNTs), have been regarded as
attractive solid lubricants which can be applied as lubricant additives and components for coatings to achieve
good lubricity or super lubricity. However, the poor dispersion and low solubility of nanomaterials in the base
lubricants limit their long-term practical applications. Therefore, the nanomaterial surface functionalization
becomes necessary to their lubrication performance. The use of an oil-soluble PIL with long-alkyl-chain to
incorporate the copper oxide nanoparticles as additives to a base oil PAO was firstly reported in [84]. In this
study, the PIL was employed to improve the
dispersion of the copper oxide NPs, where the hybrid PIL-NPs additives exhibited an enhanced oil-load
capacity and a better anti-wear performance compared to that just using copper nanoparticles as additives.

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