Case Study on Lubricants & Nano Particle Oil Additives

INTRODUCTION
It is known since ages that oils and greases reduce the friction between sliding surfaces, by
filling the surface cavities and making the surfaces smoother. Action of liquids/greases
known as lubrication. In other words, lubrication is a process by which the friction and wear
rates in a moving contact are reduced by using suitable lubricant. Lubricant is a substance
introduced between relatively moving parts to reduce friction ( = 0.1 to 0.0001) and wear
rate. The progress in scientific research indicated that reduction in friction occurs due to
decrease in adhesion component of friction compared to abrasion component of friction.
Almost every relatively moving component in an assembly requires lubricant.
Sometimes the choice of lubricant type depends on the properties of system. For example, in
watches or instruments, any lubricant type could meet the load and speed requirements, but
because of need for low friction it is normal to use very low viscosity oil. However, for open
gears, wire ropes, or chains the major problem is to prevent the lubricant from being thrown
off the moving parts, and it is necessary to use thick bituminous oil or grease having special
adhesive properties.

LUBRICANTS
Lubricants are often classified as "Newtonian and "Non-Newtonian" fluids. This
classification is on basis of relation between shear stress and shear strain rate. (Figure 1) For
Newtonian fluid, shear

stress is given by equation

In this relation, is known as dynamic viscosity, which is one of the important lubrication
parameters. Method of replenishing lubricant decides overall performance of the system.

Figure 1: Newtonian and Non Newtonian fluid

Advantages of lubrication in addition to reducing friction and wear rate are :

o Reducing instant failures.
o Reducing fatigue failure (Lubricant reduces the force required in tangential
direction so reduces the Fatigue Failure)
o Reducing surface failures.
o Reducing stress concentration.

Applications of Lubricant :
o Engine & Transmission parts.
o Bearings.
o Cams and followers.
o Journals.
o Seal faces & any situation involving metal to metal contact.

Required lubricant properties are specific to applications. We expect some requirements from
the lubricant which can be explained by consider few examples.
 Lubricant between cylinder liner and rings (Figure 2)

Figure 2: Lubricant between cylinder liner and rings

Requirements are:

Lubricant must form a film to separate the surfaces and reduce the friction between
metal to metal contacts in order to improve the efficiency of the system.

Needs to adhere to the surfaces (attachment of thin lubricant layer on the surfaces).

Must neutralize the corrosive products of combustion.

Withstand high temperature inside the cylinder.

 Lubrication in journal bearings (Figure 3)

Requirements are:

Lubricant should support heavy shaft and loads.

Lubricant should avoid contact stresses.

Lubricant should have ability to dampen vibrations.

Figure 3: Radial journal bearing hydrodynamic pressure profile.

TYPES & PROPERTIES OF LUBRICANTS:

Wear coefficients K for different lubrication mechanisms are provided in Table below. Here
non lubricated wear mean, no intentional lubricant at the interface. If we compare nonlubricated and solid lubricated cases, we find wear rate in the presence of solid lubricants will
be lesser than 1% of wear rate observed under non-lubricated case. These data (Table 1)
motivate us to use lubricants.

Table 1: Wear coefficient for lubricated sliding.

Lubricant Classification:
Lubricant is substance that reduces friction and wear at the interface of two materials. The
lubricant at interface reduces the adhesive friction by lower the shear strength of interface.
Based on the shear strength of lubricant or molecular state, lubricants are classified in four
categories.

Solid lubricants

Semi-solid lubricants

Liquid lubricants

Gaseous lubricants

Solid Lubricants
A solid lubricant is basically any solid material which can be placed between two bearing
surfaces and which will shear more easily under a given load than the bearing materials
themselves. The coefficient of friction in dry lubrication is related to the shearing force
and the bearing load. Two primary property requirements are:
 Material must be able to support applied load without significant distortion,
deformation or loss in strength.
 Coefficient of friction and the rate of wear must be acceptably low.
Examples: Poly Tetra Fluoro Ethylene, Nylon, Synthetic Polymers, Molybdenum Disulphide,
Carbon & Graphite, Ceramic & Cerment.

Semi Solid Lubricants
In laymans language Grease is: A black or yellow sticky mass used in the bearings for
lubrication purpose. Lubricating greases consist of lubricating oils, often of quite low
viscosity, which have been thickened by means of finely dispersed solids called
thickeners. It consists of base oils (75 to 95%), additives (0 to 5%) and minute thickener
fibers (5 to 20%). Grease advantages are:
 Remains at application point & adhere to surface.
 Less-frequent application needed.
 Good for inclined/vertical shafts.
 Seal out contaminants & less expensive seals needed.
 Water resistant & reduce oil vapor problems.

 Prolong the life of worn parts by filing irregularities as shown in Fig. 4.49.
 Provide better mechanical lubrication cushion for extreme conditions such as
shock loading, reversing operations, low speeds & high loads.
 Reduce noise and vibration.

Liquid Lubricants
There are two systems for oil classification. The SAE (Society of Automotive Engineers)
viscosity grade and the API (American Petroleum Institute) classification that designates
the type of engines for which the oil was designed. The SAE viscosity grade is known as
the W number when classifying winter oils. In general, the lower the first number, the
better the oil performance in extremely cold conditions. Conversely, the higher the second
number the better the oil protection at higher temperatures. The API designation is
typically S designation for gasoline engines and a C designation for diesel engines.
Most of todays oils carry an SH,CF or SJ,CF designation signifying that they are suitable
for use in all gasoline or diesel automotive applications. Examples: Vegetable Oil,
Animal Fats, Minerals oils, Paraffinic oils, Naphthenic Oils, Multigrade oils, synthetic
oils (Polyglycols, esters, Perfluoropolyalkylether, Perfluoropolyethers, silicon).

Gas Lubricants
Gas (i.e., Air, Nitrogen, and Helium) lubrication is used for ultra-thin film thickness
(separation) between tribo-pairs. Its advantageous in Temperature range (-2000C) to
(20000C). No vaporization, cavitation, solidification, decomposition. Also very low
viscosity (1000 times less viscous than even the thinnest mineral oil), therefore ultra-low
friction. Possible high speed, Cleanliness & No seal requirement for lubrication.

LUBRICANT ADDITIVES
In applications where hydrodynamic lubrication films are formed there is no need of
additives, but to counteract high speed, high temperature, high load, etc. additives are
required. Additives are incorporated into either a liquid base (mineral oil, synthetic fluid, etc.)
or grease need to be soluble or uniformly dispersed throughout the carrier media. In practice,
a formulated lubricant comprises a base fluid and a performance additive package.
Practically, all lubricants contain additives to enhance existing properties, or to impart new
properties.
Gears are subjected to very high contact pressure and experience metal to metal contact at
gear teeth. Lubricants with extreme pressure (EP) additives are required. I.C. Engine parts are
subjected to high temperatures. Lubricants need to be oxidation resistant. Detergent and
dispersant additives to remove combustion and breakdown products of the oil from the
surfaces. Corrosion inhibitors to prevent corrosion caused by combustion and oxidation
products. Refrigeration system lubricants encounter the low temperatures the oils need to
have low pour points.
Types of Additive
1. Detergent additives: Detergents, like dispersants, are blended into lubricants to
remove and neutralize harmful products. Detergents form a protective layer on the
metal surfaces to prevent deposition of sludge and varnish. The metallic basis for
detergents includes barium, calcium, magnesium and sodium. In engines, this can
reduce the amount of acidic materials produced. Protective ability of detergent is
measured by its total base number or its reserve alkalinity. Detergent additives are
soaps of high molecular weight; soluble in oil (functional) group attracts particulate
contaminants in the lubricant.
2. Dispersants additives: Purpose of dispersant additives is to suspend or disperse
harmful products (i.e. dirt, water, fuel, process material, and lube degradation
products such as sludge, varnish, oxidation products) within the lubricant. These
compounds have a large hydrocarbon tail and a polar group head. Tail section
serves as a solubilize in the base oil, while polar (functional) group attracts particulate
contaminants in the lubricant. Detergents, like dispersants, are blended into lubricants
to remove and neutralize harmful products. In addition, detergents form a protective
layer on the metal surfaces.

3. Anti-wear additives: Prevent metal to metal contact. Useful under lighter to

moderate loads (bearings). Anti-wear additives typically contain zinc and phosphorus
compounds. With increase in load anti-wear additive may be ineffective and EP
additives are required in heavy load applications such as gearboxes. Chemical active
is a coat protective layer on the metal surface by chemical decomposition and
absorption. Zinc dithiophosphate (ZDP) is probably the most widely used in
formulated engine oils, also acts as a corrosion inhibitor and antioxidant.
Molybdenum disulfide and graphite additives are a special form of anti-wear additives
known as anti-seize agents, Depletion, Zinc compounds, Stearic acid is also used as
antiwear additive.
4. Anti-foaming agents (Foam Inhibitors): Lubricant foams due to agitation and
aeration that occurs during operation. Foaming interfere with flow rate and heat
transfer and increase oxidation. Detergent and dispersant additives tends to promote
foam formation. The additives (usually long chain silicon polymers are used in small
quantities of about 0.05% to 0.5% by weight) lower the surface tension between the
air and liquid to the point where bubbles collapse.
5. Anti-oxidant additives (Oxidation Inhibitors): Oxidation due to high temp. &
pressure in lubrication oil occurs. Products of oxidation gummy, deposits on surface,
corroded cadmium, copper & lead alloys form. Power loss due to increased viscous
drag & difficulty in pumping increases & it is recommended to replace oil, if tan > 3.
a. Corrosion inhibitors: Used for non-ferrous metals (copper, aluminum, tin,
cadmium, etc. used in bearings, seals), protect surfaces against any corrosive
agents (sulphur, phosphorus, chlorine, and oxidation products) present in oil.
b. Rust inhibitors: Needed for ferrous metals particularly to trap oxygen
dissolved in oil & water. These additives of polar type adsorbed strongly upon
metal surface and neutralize acids. Sulphonate, phenate and amines are few
examples of rust inhibitors additives. Rust inhibitors neutralize acids formed
by oxidation. Chemically react with the metal surfaces to form a protective
film.
6. Pour point depressants: Pour point depressants reduce the pour point and are
therefore required when operating at lower temperatures. Pour point is the lowest
temperature at which the lubricant will flow. Waxy crystals are formed at lower
temperature, therefore additives methacrylate polymers, polyalkylphenol esters.
Encapsulate crystal so that it cannot grow.

CASE STUDY:
Here we are discussing about three cases with different nanoparticle additives & their
performance in respective applications. During the last few years, nanotechnology has
attracted great attention in various research fields because of their special physical and
chemical properties. In tribology, some nanomaterials were added into lubricating oil to
improve extreme pressure, anti-wear and friction reduction properties. Cu nanoparticle as
additives can effectively improve the lubricating properties of 50CC oil. Local high
temperature and high pressure due to direct contact of two surfaces initiate melting of Cu
nanoparticles and forming a copper protective film with low nano hardness and elastic
modulus on the surface. CuO and ZnO suspensions showed better results at 0.5% and 2.0 wt.
% of nanoparticles. Also for obtaining a low coefficient of friction (COF) with hexagonal
boron nitride (hBN) and alumina (Al2O3) nano particles are used in dispersed in
conventional diesel engine oil (SAE 15W40). Bio lubricant used in this experimental was
derived from palm oil-based TMP (trimethylolpropane) ester.
CASE I: (CuO Nanoparticle as an additive)
The main constituents of the nanoparticles used in the experiment are listed in Table 2. CuO
nanoparticles of 50nm are separately dispersed in the lubricant (liquid paraffin) in
concentration of 0.2, 0.25, 2 and 3% wt. using an ultrasonic bath for 5 minutes. Surface
particle modification also taken placed with Oleic Acid separately dispersed for 30 min.

Table 2: The Constituents of Nanoparticle as Lubricant additive CuO.

The test conducted, called anti wear test, the components were cleaned with toluene alcohol
used in the experiment for 3 min and dried with hot air before and after test. CuO
nanoparticle was dispersed primarily using ultrasonic bath for 5 min with the mixture of
certain concentration and glycol. The bottle that contained the nanoparticles was held static
for 3 days; some nanocopper sediment formed in the bottle; the upper solution was then
extracted into another bottle. Adding oleic acid exact volume of upper solution that taken out

for particle surface modification; reduced formed nanocopper sediment formed in the bottle.
The content of nanocopper was 0.2, 0.25, 2 and 3% CuO with other modified samples. Three
test were conducted for each suspensions at a sliding speed 1200rpm, 400N applied via
cantilever and 60-65 degree Celsius adjusted thermocouple in four-ball tribomachine. Wear
surface on ball bearing were characterized using optical microscope (OM) to detect the wear
scar diameter of each suspension.
Results Shows that The 3% CuO of paraffin oil has the highest viscosity among the other
nanoparticle contents concentrations and hence, should shows the lowest friction coefficient
among the modified nanoparticle surface suspension but high wear scar diameter makes it
among highest friction coefficient. Even though for commercial oil (SAE15W-40) showing
highest viscosity (at 40 and 100 degree Celsius) with small wear scar diameter but still 3%
with modification has the lowest friction coefficient. All nanoparticle concentrations in liquid
paraffin diminished the friction coefficient compared to pure liquid paraffin. The lowest
friction coefficient was 0.185 obtained for a nanoparticle content of 0.2% CuO and the
highest was for a 3% CuO concentration at 0.247 for liquid Paraffin + CuO suspensions. In
contrast after modification, the lowest friction coefficient was obtained at 3% CuO modified
at 0.123 and the highest at 0.2% of CuO modified at 0.158 for liquid paraffin + Modified
CuO suspensions. The lowest friction coefficient (and therefore maximum friction reduction)
of all tested suspensions was found for a content of 3% of CuO modified. The highest friction
coefficient and lowest friction reduction was provided by the Paraffin + 0.2%CuO
suspension.
Figure 4: Sample of microstructure of wear surface for the suspension with high anti wear behavior; (a)

Figure 4: Sample of microstructure of wear surface for the suspension with high
anti wear behavior; (a) pure liquid paraffin; (b) CuO2% + liquid paraffin.
The anti-wear mechanism of Nano particulate additive can be explained as when the lubricant
film between tribopairs becomes thinner and mixed lubrication or boundary lubrication occur,
the nanoparticles may carry a proportion of load and separate the two surfaces to prevent
adhesion, thus benefit the anti-wear properties. CuO is sphere-like with average sizes of
about 50-60mm that may results in rolling effect between the rubbing surfaces when the
boundary lubrication occurs. Wear scar diameter is lesser than that of pure paraffin oils
shown in figure 4.

Verdict suggest that Nanoparticle copper as additives in liquid paraffin can effectively
improve the lubricating properties of suspensions in paraffin. The formation of copper film
separates two friction surfaces and avoids their direct contacts. Furthermore, the low hardness
of the film results in the reduction of friction, while the low elastic modulus increase the
elastic deformation of the contact surface and reduces wear. Suspension of 3% CuO
nanoparticle content with modified exhibited the best friction coefficient at 0.13 and
nanoparticle content of 0.2 % CuO modified showed the better result for wear scar diameter
results at 590 mm. The results indicate that the higher concentrate of CuO, the better the
tribological properties and surface modification inferred that a protective film with lower
elastic modulus and hardness is formed on the particle surface.
CASE II: (Hexagonal boron nitride (HBN) & alumina (Al2O3) Nanoparticle as an
additive)
Nanoparticles can be considered as modern lubricant additives. They present several major
advantages over organic molecules that are currently used as lubricant additives. Good
lubrication and thermal conductivity properties, which can simultaneously improve
tribological performance and boost heat transfer in engines, were the key factors in using
hBN and Al2O3. Furthermore, both types of nanoparticles are environmentally friendly.

Table 3: HBN/Al2O3 contents and experimental condition: three parameters and three
levels.
In order to observe the degree of significant of the design parameters in vol. % contributions,
three factors (each at three levels), were taken into account given in table 3. The nano-oil
samples were prepared by dispersing several concentrations of 70nm sized hBN and Al2O3
in two different brands of conventional diesel engine oil (SAE 15W40).The samples could be
stabilized with only the addition of an appropriate amount of surfactant (oleic acid). The
mixture of solid particles in diesel engine oil was homogenized for 20 minutes using an
ultrasonic homogenizer with 50% amplitude and 0.5 active time interval.

Figure 5: SEM micrograph of worn surfaces on the ball under lubricated conditions of
(a) Conventional diesel engine oil, (b) with 0.5 vol. % of hBN additive, and (c) with 0.5 vol.
% of Al2O3 additive.
Results shows COF and wear scar diameter have been reduced significantly by dispersing
several concentrations of hBN nanoparticle in conventional diesel engine oil. This was
because of the hBN nanoparticle made both ball bearing effect and polishing effect, by
changed the sliding friction into rolling friction between the friction pair and consequently
smoothing the rough friction contact surfaces. Moreover, the negative effect of friction
reduction and wear was observed in conventional diesel engine oil containing Al2O3
nanoparticle due the ploughing effect of harder Al2O3 nanoparticle. It was found that a
contribution of 0.5 vol.% of hBN and 0.3 vol.% of oleic acid as a surfactant can be used as an
optimal additive composition in conventional diesel engine oil, to obtain a lower COF. The
predicted value of COF by utilizing the levels of the optimal design parameters (0.5 vol. %
hBN, 0.3 vol. % surfactant), as made by the Taguchi optimization method, was consistent
with the confirmation test (average value of COF = 0.07215), which fell within a 95% CI.

CASE III: (Trimethylolpropane ester Nanoparticle as an additive)

The TMP ester is produced from palm oil, which is biodegradable and has high lubricity
properties such as a higher flash point temperature and VI (viscosity index). The friction and
wear experiments were performed using four-ball machine tribotester. Experimental was
carried out for 10 minutes under 40 kg, 80kg, 120kg, and 160kg at 1200rpm. Test
temperatures were set at room temperature. The constituents of TMP shown in table 4.
The COF of TMP ester and TMP ester with added nanoparticle as an additive were
investigated through a series of four-ball friction tests. The four-ball wear tester consists of
three balls held stationary in a ball pot plus a fourth ball held in a rotating spindle. The balls
used in this study were steel balls, AISI 52-100, 12.7 mm in diameter, with 60-64 Rc
hardness. These balls were thoroughly cleaned with toluene before each experiment. The
sample volume required for each test was 10 ml. The test conditions were the load is varied
from 40 kg to 120 kg, operating temperature is at room temperature, rotational speed of 1200
rpm and operation time is 10minutes. The wear produced on the three stationary balls is
measured under a calibrated microscope and reported as the WSD or calculated volume.

Table 4: Density of TMP ester added nanoparticle and pure TMP ester

Results show that as the load increased, COF increased. The higher percentage reduction of
COF as nanoparticle added in TMP ester was at 160kg which around 15%. All COF values in
this experiment were in a mixed lubrication regime which the lubricant thickness around 3 to
25nm. Therefore it is believed that as in the mechanical entrapment theory, which as the
nanoparticle penetrates in the contact area and embedded in the contact area and create
additional protective layer because have similar to lubricant film thickness.

Figure 6: Surface morphology as WSD of the ball using SEM

For all load, TMP ester added with nanoparticle reduced COF up to 15% at high load.
Nanoparticle also improved WSD of the TMP esters especially at low load (40kg) by creating
an additional protective layer. For all load, TMP ester added with nanoparticle reduced COF
up to 15% at high load. Nanoparticle also improved WSD of the TMP esters especially at low
load (40kg) by creating an additional protective layer.

CONCLUSION
Nanoparticle copper as additives in liquid paraffin can effectively improve the lubricating
properties of suspensions in paraffin. The formation of copper film separates two friction
surfaces and avoids their direct contacts. Furthermore, the low hardness of the film results in
the reduction of friction, while the low elastic modulus increase the elastic deformation of the
contact surface and reduces wear.
COF and wear scar diameter have been reduced significantly by dispersing several
concentrations of hBN nanoparticle in conventional diesel engine oil. This was because of the
hBN nanoparticle made both ball bearing effect and polishing effect, by changed the
sliding friction into rolling friction between the friction pair and consequently smoothing the
rough friction contact surfaces. Moreover, the negative effect of friction reduction and wear
was observed in conventional diesel engine oil containing Al2O3 nanoparticle due the
ploughing effect of harder Al2O3 nanoparticle.
TMP Nanoparticle improved WSD of the TMP esters especially at low load (40kg) by
creating an additional protective layer.

REFRENCES:
1. M. Asrul, N.W.M. Zulkifli, H. H. Masjuki, M.A. Kalam, Tribological properties and
lubricant mechanism of Nanoparticle in Engine Oil, Procedia Engineering 68, (2013)
Page No. 320 325.
2. Muhammad Abdullah, Mohd Fadzli Bin Abdollah, Optimization of Tribological
Performance of hBN/AL2O3Nanoparticles as Engine Oil Additives, Procedia
Engineering 68 (2013), Page No. 313 319.
3. N.W.M. Zulkifli, M.A. Kalam, H.H. Masjuki, R. Yunus, Experimental analysis of
tribological properties of bio lubricant with nanoparticle additive., Procedia
Engineering 68, (2013) Page No. 152 157.
4. http://nptel.ac.in/courses/112102015/# (e-learning course Industrial Tribology)