Surface Engineering &

Tribology
(MME 322)
Dr. Muhammad Umar Manzoor
 Material
Properties

Surface Bulk

Nature Shape Metallurgical Mechanical

Tensile
Cleanliness Contamination Roughness Waviness Bond Energy Crystallinity Shear Strength
Strength

Work
Composition Grain Size Elongation Yield Strength
Hardening

Interaction with
Others Hardness Toughness
Environment

Cohessive
Reconstruction Segregation Surface Energy Elastic Modulus
Energy

Point
Physisorption Chemisorption
Imperfection
Dislocation Thermal & others

Compound Grain
Corrosion Oxidation Conductivity
formation Boundries

Volumetric
Specific Heat
 Adsorption vs Absorbance
• Adsorption implies adhesion
• Absorption implies diffusion.
• Adsorption is a process that occurs when a gas or liquid solute accumulates
on the surface of a solid or, forming a molecular or atomic films (the
adsorbate).
• In absorption, a substance diffuses into a liquid or solid to form a solution.
• Absorption is a bulk phenomenon in which the particles of gas or liquid get
uniformly distributed throughout the body of the solid
• Adsorption is the phenomenon of higher particle concentration of gas or
liquid on the surface so that surface film formation occurs.
• Absorption is a bulk phenomenon
• Adsorption is a surface phenomenon
 Interaction between the solid surface and
the environment
• The mechanism of lubrication partly depends on the nature of interactions
between the lubricant and the solid surface.
• A surface is usually not completely clean, even in a high vacuum.
Some of the events that can take place at surfaces include
reconstruction, segregation, chemisorption, physisorption and chemical
compound formation are shown below.
 Surface Reconstruction
• Reconstruction takes place when the outermost layers of atoms
undergo a change in crystal structure.
• Examples include evaporation of silicon from a SiC surface upon
heating above 800C, Si-C bond secission, leaving behind a layer of
carbon, and conversion of diamond surface layers to graphite or
carbon during rubbing.
• Reconstruction may result in substantial changes in friction coefficient,
from app. 0.8 to 0.2, but the fact that reconstruction has taken place
may be evident only after careful characterization of the surface layers.
• The segregated surface changes the properties of the surface compared to
the non segregated surfaces.
 Segregation
• Segregation takes place in solid containing more than a single element; atoms from the bulk can
diffuse to the surface and segregate there.
• The Segregation of alloy species to grain boundaries in alloys and its effect on mechanical properties
have been known.
• The same segregation occurs at a solid surface and segregation has been observed to exert
considerable influence on adhesion, friction and wear.
• One hypothesis
• Solute segregates the surface
• It reduces surface energy
• Second hypothesis
• Solid produces strain in crystal lattice of solvent
• Unusual lattice state ejects the solute atoms
• The segregation of alloying elements towards the grain boundaries influence the surface energy of an
interface, which has a direct effect on the energy of adhesion.
• This process was found to be irreversible.
• When the alloying elements aggregate to the surface, they remain there for some alloys, e.g., a C-to-
Fe surface, a S-to-Fe surface, Al to the surfaces of both Fe and Cu, and In and Sn to a Cu surface.
 Segregation
• Segregation of alloy species to grain boundaries is a well-known phenomenon that may profoundly
affect mechanical properties.
• Segregation to the surface may also take place
• This generally occurs for small, mobile alloy or impurity atoms, such as interstitial carbon and nitrogen in
iron, during processing or heat treatment.
• In some cases, the segregation of as little as 1 at.% of alloy element to the surface can completely
dominate adhesion between contact surfaces.
• Significant changes in friction properties have been observed for ferrous surfaces with segregation of
carbon, sulfur, aluminum, and boron, and for copper surfaces with segregation of aluminum, indium,
and tin.
• If certain metallic glasses containing boron are tested at increasing temperature, μ increases first with
temperature, from about 1.0-1.5 at room temperature to 1.8-2.5 at 350°C (660°F).
• Above 500°C (930°F), μ drops drastically (to about 0.25), a change that has been associated with the
formation of boron nitride on the surface.
 Chemisorption
• Chemical adsorption occurs when the lubricant molecules
are held to the surface by chemical bonds as shown in Fig.
• Electron exchange between the molecules of the adsorbate
and the adsorbent takes place.
• The film might be only a monolayer thick, and the
formation is characterized by irreversibility and strong
bonding energies.
• Lubricant films formed by polar molecules of, e.g., fatty
acids, soaps and esters lubricate effectively up to their
melting point.
• At temperatures typically in the range of about 120 to 180C
these lubricants fail as a result of reorientation, softening
and melting.
• Films formed by chemical adsorption provide good
lubrication at moderate loads, temperatures and sliding
velocities.
 Chemisorption
• Chemisorption is a much stronger form of bonding than that associated
with physisorption, with the bond strengths a function of the chemical
activity of the solid surface, i.e.
• surface energy,
• degree of surface coverage of the adsorbate,
• reactivity of the adsorbing species and its structure.
• The higher the surface energy of the solid surface, the stronger the
tendency of chemisorb.
• It was observed that oxygen will chemisorb relatively stronger to copper,
weakly to silver and not at all to gold.
• The reactivity of the adsorbent is also very important, for instance,
fluorine will more strongly adsorb than chlorine.
• However, not all the adsorbates are sufficiently reactive to initiate
Chemisorption.
• A long chain alcohol did not show any retention, even with base metals,
while steric acid showed permanent retention with base metal such as
zinc and cadmium, but not on the noble metals such as gold.
• The strength of the chemical bonding between the adsorbate and the
substrate, which affects the friction transition temperature, depends on
the reactivity of the substrate material.
 Chemisorption
• Chemisorption readily occurs on clean surfaces.
• Adsorbed species include water molecules from atmospheric moisture
and carbon and carbon compounds also derived from the atmosphere or
from lubricants used during operation or manufacture.
• The adsorbed species may also be components of various salts
originating from the environment or from human handling of the
component. H/C Adhesion
• The amount of adsorbed species, the degree of surface coverage, and the Chemisorb Force
nature of the adsorbed molecule can substantially affect the adhesion to Iron (dyne)
between two surfaces, thereby directly or indirectly influencing
friction behavior. Clean Fe >400
• Minor modification in H/C structure can produce considerable difference Ethane 280
in adhesion forces.
• For example, when a monolayer of ethane is introduced on a clean Ethylene 170
iron surface, the adhesive force drops from a value of greater than Acetylene 80
400 dynes to 280 dynes.
• If the monolayer is acetylene, and force drops to 80 dynes. Vinyl 30
• For a vinyl chloride monolayer, the force drops to 30 dynes--that Chloride
is, to only 7 to 8% of the value for the clean surface.
Ethylene <10
Oxide
 Chemisorption
• Chemisorption is often found to occur at temperatures far above the critical
temperature of the adsorbate.
• Chemisorption is usually associated with an activation energy, which means
that adsorbate molecules attracted to a surface must go through an energy
barrier before they become strongly bonded to the surface.
• Because chemisorption involves a chemical bond between adsorbate and
adsorbent, unlike physisorption, only a single layer of chemisorbed species
can be realized on localized active sites.
• However, further physical adsorption on top of the chemisorbed layer and
diffusion of the chemisorbed species into the bulk solid can obscure the fact
that chemisorbed material can be only one layer in depth.
 Physisorption
• Physical adsorption occurs when the molecules of the lubricant are held to
the surface only by bonds such as van der Waal’s forces as shown in Fig.
• No exchange of electrons takes place between the molecules of the adsorbate
and the adsorbent.
• The molecules are weakly bound, the boundary lubricant film has a mono-
or multilayer structure and its formation process is reversible.
• The films can be of either monomolecular (typically<3 nm) or poly-
molecular thickness.
• Many molecules pack in as closely as possible and strengthen the film with
lateral cohesive forces.
• The film is temperature sensitive and provides lubrication only at low loads
and low sliding velocities
• A typical example of physisorption is inert gas adsorption on metal surfaces
at low temperatures
 Physisorption
• Physisorption or physical adsorption is the classical form of adsorption of
species on a solid surface.
• The physical adsorption process is a relatively weak process.
• Molecules of the adsorbate may be attached from a surface without any
irreversible changes to the surfaces or adsorbate.
• A very small amount of energy is required to remove the physisorbed atoms.
• in Physisorption, van der walls or dispersion forces provide the bonding
between the substrate and adsorbate.
• It is observed that, if the interaction involves less than 10 cal/mol, the
process is one of the Physisorption.
• A useful byproduct of Physisorption is the so-called Rehbinder effect.
• Rehbinder effect is the reduction of the modulus and yield stress of metals
and nonmetals in the presence of an adsorbed film.
• Physisorption is effective in reducing friction during the running in of a
bearing surface provided that temperatures do not rise much above the
ambient temperature.
• When the critical temperature (ambient temperature) is exceeded, the
adsorbed film disorders and ceases to function as a lubricating layer.
 Chemical Compound Formation
• Compound formation on solid surfaces plays an important role in tribological systems.
• Physisorbed and chemisorbed films are very effective in reducing friction and mild wear during a
friction process.
• They fail fairly easily under severe rubbing conditions and therefore are not very effective in
preventing wear.
• The naturally occurring oxides present on metals prevent their destruction during rubbing, but
when they are removed the reoxidation of the surface may be too slow to be effective.
• With metals in contact, and with metals and nonmetals, compound formation by chemical reaction
has been observed to occur on the solid surface like (phosphorous on Iron).
• The compound formation produces strong interfacial bonds at the contacting surfaces and influence
the adhesion behaviour.
• Similarly, more active chemicals can be added to the lubricants to react with the rubbing surfaces
and produce protective films.
• Suitable films include sulfides, phosphides and phosphates, that will react with the rubbing
surfaces to produce such a substance will be effective in producing protective films.
 Chemical Compound Formation
• Chemical compound formation may take place when surface comes into
contact with a different solid, a gas, or a chemisorbed species.
• Without any tribological contacts, a surface will readily acquire a layer of oxide or
hydroxide due to reactions with ambient moisture and oxygen.
• When two surfaces rub against each other, they may adhere at local spots
that can reach elevated temperatures by frictional heating; inter-diffusion may then
take place, resulting in local compound formation in the surface layers.
• This can strongly affect friction.
• It is well known, for example, that friction between two metals that can
form alloy solutions or alloy compounds with each other generally is
greater than if the two are mutually insoluble. This fact has been used to
develop a generalized "map" showing which metals can safely slide against one
another and which metal couples should be avoided.
 Polar Non-polar Molecules
• Molecules can be grouped as polar or non-polar molecules.
• Some are also in between.
• The arrangement or geometry of the atoms in some molecules is such that
one end of the molecule has a positive electrical charge and the other side
has a negative charge.
• If this is the case, the molecule is called a polar molecule, meaning that it
has electrical poles. Otherwise, it is called a non-polar molecule.
• Whether molecules are polar or non-polar determines if they will mix to
form a solution or that they don't mix well together.
• Also, polar molecules are water soluble, while non-polar molecules are fat
soluble.
 Polar Molecules
• Water is a polar molecule because
of the way the atoms bind in the
molecule such that there are excess
electrons on the Oxygen side and a
lack or excess of positive charges
on the Hydrogen side of the
molecule.
• Ammonia (NH3)
• Sulfur Dioxide (SO2)
• Hydrogen Sulfide (H2S).
Non-polar Molecules
• A non-polar molecule is one that
the electrons are distributed more
symmetrically and thus does not
have an abundance of charges at
the opposite sides. The charges
all cancel out each other.