CORROSION

INTRODUCTION
 Definition:
Corrosion
is the degeneration of
materials by
reaction with
environment.
Examples: Rusting of
automobiles,
buildings and
bridges, Fogging of
silverware, Patina
formation on copper.
UNIVERSALITY OF
CORROSION
 Not only metals, but non-metals like plastics,
rubber, ceramics are also subject to
environmental degradation
 Even living tissues in the human body are prone
to environmental damage by free radicals-
Oxidative stress- leading to degenerative
diseases like cancer, cardio-vascular disease and
diabetes.
CORROSION DAMAGE
 Disfiguration or loss of appearance
 Loss of material
 Maintenance cost
 Extractive metallurgy in reverse- Loss of precious
minerals, power, water and man-power
 Loss in reliability & safety
 Plant shutdown, contamination of product etc
COST OF CORROSION
 Annual loss due to corrosion is estimated
to be 3 to 5 % of GNP, about Rs.700000
crores
 Direct & Indirect losses

 Direct loss: Material cost, maintenance

cost, over-design, use of costly
material
 Indirect losses: Plant shutdown & loss of
production, contamination of products,
loss of valuable products due to leakage
etc, liability in accidents
WHY DO METALS CORRODE?
 Any spontaneous reaction in the universe is
associated with a lowering in the free energy of
the system. i.e. a negative free energy change
 All metals except the noble metals have free
energies greater than their compounds. So they
tend to become their compounds through the
process of corrosion
ELECTROCHEMICAL NATURE
 All metallic corrosion are electrochemical
reactions i.e. metal is converted to its
compound with a transfer of electrons
 The overall reaction may be split into
oxidation (anodic) and reduction (cathodic)
partial reactions
 Next slide shows the electrochemical reactions in
the corrosion of Zn in hydrochloric acid
ELECTROCHEMICAL
REACTIONS IN CORROSION

DISSOLUTION OF ZN METAL IN HYDROCHLORIC ACID,

Zn  2 HCl  ZnCl 2 H2 -------------------- -(1)

Written in ionic form as,
Zn  2H   2Cl   Zn2  2Cl   H ----------------------(2)
2

The net reaction being,

Zn  2H   Zn2  H ------------------------- (3)
2

Equation (3) is the summation of two partial

reactions,
Zn  Zn  2e -----------------------------------------(4) and
2*

2H  2e  H ------------------------------------------(5)

2

Equation (4) is the oxidation / anodic reaction and

Equation (5) is the reduction / cathodic reaction
ELECTROCHEMICAL THEORY
 The anodic &
cathodic reactions
occur simultaneously
at different parts of
the metal.
 The electrode
potentials of the two
reactions converge to
the corrosion
potential by
polarization
PASSIVATION
 Many metals like Cr, Ti,
Al, Ni and Fe exhibit a
reduction in their
corrosion rate above
certain critical potential.
Formation of a
thin oxide
protective,
 film.
Passivation is the
reason for the excellent
corrosion resistance of Al
and S.S.
FORMS OF CORROSION
 Corrosion may be
classified in CORROSION
different ways
WET CORROSION DRY CORROSION
 Wet / Aqueous
corrosion & Dry
Corrosion
 Room
Temperature/ CORROSION

High ROOM TEMPERATURE HIGH TEMPERATURE

Temperature CORROSION CORROSION

Corrosion
WET & DRY CORROSION
 Wet / aqueous corrosion is the major form of
corrosion which occurs at or near room
temperature and in the presence of water
 Dry / gaseous corrosion is significant mainly
at high temperatures
WET / AQUEOUS CORROSION
Based on the appearance of the corroded
metal, wet corrosion may be classified as
 Uniform or General
 Galvanic or Two-metal
 Crevice
 Pitting
 Dealloying
 Intergranular
 Velocity-assisted
 Environment-assisted cracking
UNIFORM CORROSION
 Corrosion over the
entire exposed
surface at a uniform
rate. e.g..
Atmospheric
corrosion.
 Maximum metal loss
by this form.
 Not dangerous, rate
can be measured in
the laboratory.
GALVANIC CORROSION
 When two dissimilar
metals are joined
together and exposed,
the more active of the
two metals corrode faster
and the nobler metal is
protected. This excess
corrosion is due to the
galvanic current
generated at the junction
 Fig. Al sheets covering
underground Cu cables
CREVICE CORROSION
 Intensive localized
corrosion within
crevices & shielded
areas on metal
surfaces
 Small volumes of
stagnant corrosive
caused by holes,
gaskets, surface
deposits, lap joints
PITTING
 A form of extremely
localized attack
causing holes in the
metal
 Most destructive
form
 Autocatalytic
nature
 Difficult to detect and
measure
 Mechanism
DEALLOYING
 Alloys exposed to
corrosives experience
selective leaching
out of the more
active constituent.
e.g. Dezincification
of brass.
 Loss of structural
stability and
mechanical strength
INTERGRANULAR CORROSION
 The grain boundaries in
metals are more active
than the grains because
of segregation of
impurities and depletion
of protective elements.
So preferential attack
along grain boundaries
occurs. e.g. weld decay in
stainless steels
VELOCITY ASSISTED
CORROSION
 Fast moving
corrosives cause
 a) Erosion-
Corrosion,
 b) Impingement
attack , and
 c) Cavitation damage
in metals
CAVITATION DAMAGE
 Cavitation is a special
case of Erosion-corrosion.
 In high velocity systems,
local pressure
reductions create water
vapour bubbles which
get attached to the
metal surface and burst
at increased pressure,
causing metal damage
ENVIRONMENT ASSISTED
CRACKING
 When a metal is subjected to a tensile stress and
a corrosive medium, it may experience
Environment Assisted Cracking. Four types:
 Stress Corrosion Cracking

 Hydrogen Embrittlement

 Liquid Metal Embrittlement

 Corrosion Fatigue
STRESS CORROSION
CRACKING
 Static tensile stress
and specific
environments
produce cracking
 Examples:
 1) Stainless steels in
hot chloride
 2) Ti alloys in
nitrogen tetroxide
 3) Brass in
ammonia
HYDROGEN EMBRITTLEMENT
 High strength
materials stressed in
presence of
hydrogen crack at
reduced stress
levels.
 Hydrogen may be
dissolved in the
metal or present as a
gas outside.
 Only ppm levels of H
needed
LIQUID METAL
EMBRITTLEMENT
 Certain metals like Al
and stainless steels
undergo brittle failure
when stressed in
contact with liquid
metals like Hg, Zn, Sn,
Pb Cd etc.
 Molten metal atoms
penetrate the grain
boundaries and
fracture the metal
 Fig. Shows brittle IG
fracture in Al alloy by
Pb
 CORROSION FATIGUE
S-N DIAGRAM
 Synergisticaction of
corrosion & cyclic

Stress Amplitude
stress. Both crack
nucleation and Air

Corrosion
propagation are
accelerated by log (cycles to failure, Nf)

corrodent and the S-

N diagram is
shifted to the left
CORROSION FATIGUE, CRACK
PROPAGATION

log (Crack Growth Rate, da/dN)

 Crack propagation
rate is increased by
the corrosive
action

Log (Stress Intensity Factor Range, K

PREVENTION OF CORROSION
 The huge annual loss due to corrosion is a
national waste and should be minimized
 Materials already exist which, if properly
used, can eliminate 80 % of corrosion loss
 Proper understanding of the basics of corrosion
and incorporation in the initial design of metallic
structures is essential
METHODS
 Material selection
 Improvements in material

 Design of structures

 Alteration of environment

 Cathodic & Anodic protection

 Coatings
MATERIAL SELECTION
 Most important method – select the
appropriate metal or alloy .
 “Natural” metal-corrosive combinations like
 S. S.- Nitric acid, Ni & Ni alloys- Caustic
 Monel- HF, Hastelloys- Hot HCl
 Pb- Dil. Sulphuric acid, Sn- Distilled water
 Al- Atmosphere, Ti- hot oxidizers
 Ta- Ultimate resistance
IMPROVEMENTS OF
MATERIALS
 Purification of metals- Al , Zr
 Alloying with metals for:

 Making more noble, e.g. Pt in Ti

 Passivating, e.g. Cr in steel

 Inhibiting, e.g. As & Sb in brass

 Scavenging, e.g. Ti & Nb in S.S

 Improving other properties

DESIGN OF STRUCTURES
 Avoid sharp corners
 Complete draining of vessels
 No water retention
 Avoid sudden changes in section
 Avoid contact between dissimilar metals
 Weld rather than rivet
 Easy replacement of vulnerable parts
 Avoid excessive mechanical stress
ALTERATION OF
ENVIRONMENT
 Lower temperature and velocity
 Remove oxygen/oxidizers

 Change concentration

 Add Inhibitors
 Adsorption type, e.g. Organic amines, azoles
 H evolution poisons, e.g. As & Sb
 Scavengers, e.g. Sodium sulfite & hydrazine
 Oxidizers, e.g. Chromates, nitrates, ferric salts
CATHODIC & ANODIC
PROTECTION
 Cathodicprotection: Make the structure
more cathodic by
 Useof sacrificial anodes
 Impressed currents
Used extensively to protect marine
structures, underground pipelines, water
heaters and reinforcement bars in
concrete
 Anodic protection: Make passivating
metal structures more anodic by
impressed potential. e.g. 316 s.s. pipe in
sulfuric acid plants
COATINGS
 Most popular method of corrosion protection
 Coatings are of various types:
 Metallic
 Inorganic like glass, porcelain and concrete
 Organic, paints, varnishes and lacquers
 Many methods of coating:
 Electrodeposition
 Flame spraying
 Cladding
 Hot dipping
 Diffusion
 Vapour deposition
 Ion implantation
 Laser glazing
CONCLUSION
 Corrosion is a natural degenerative process
affecting metals, nonmetals and even biological
systems like the human body
 Corrosion of engineering materials lead to
significant losses
 An understanding of the basic principles of
corrosion and their application in the design and
maintenance of engineering systems result in
reducing losses considerably
Gross and net calorific Value
Gross Calorific Value: It is the total amount of heat
generated when a unit quantity of fuel is completely
burnt in oxygen and the products of combustion
are cooled down to the room temperature.
As the products of combustion are cooled down to
room temperature, the steam gets condensed into
water and latent heat is evolved. Thus in the
determination of gross calorific value, the latent heat
also gets included in the measured heat. Therefore,
gross calorific value is also called the higher
calorific value.
The calorific value which is determined by Bomb
calorimeter gives the higher calorific value (HCV)
Net Calorific Value: It is defined as the net heat
produced when a unit quantity of fuel is completely
burnt and the products of combustion are allowed to
escape.
The water vapour do not condense and escape with
hot combustion gases. Hence, lesser amount than
gross calorific value is available. It is also known as
lower calorific value (LCV).
LCV=HCV-Latent heat of water vapours formed
Since 1 part by weight of hydrogen gives nine parts
by weight of water i.e.
H 2  21 O2  H2O
Therefore,
LCV=HCV-weight of hydrogen x 9 x latent heat of
steam
= HCV-weight of hydrogen x 9 x 587
Determination of Calorific value
1. Determination of calorific value of solid and non
volatile liquid fuels: It is determined by bomb
calorimeter.
Principle: A known amount of the fuel is burnt in
excess of oxygen and heat liberated is transferred to
a known amount of water. The calorific value of the
fuel is then determined by applying the principle of
calorimetery i.e. Heat gained = Heat lost
Bomb Calorimeter
Calculations
Let weight of the fuel sample taken = x g
Weight of water in the calorimeter = W
g
Water equivalent of the Calorimeter, stirrer, bomb,
thermometer = w g
Initial temperature of water = t1oC
Final temperature of water = t2oC
Higher or gross calorific value =
C cal/g
Heat gained by water = W x t x
Heat gained by Calorimeter = w (t2-t1) cal
Heat liberated by the fuel = x C cal
Heat liberated by the fuel = Heat gained by water and
calorimeter
x C = (W+w) (t2-t1) cal
C=(W+W)(t2-t1) cal/g
x
Net Calorific value:
Let percentage of hydrogen in the fuel = H
Weight of water produced from 1 gm of the fuel =
9H/100 gm
Heat liberated during condensation of steam
= 0.09H  587 cal
Net (Lower calorific value) = GCV-Latent heat of
water formed
= C-0.09H  587 cal/gm
Corrections: For accurate results the following
corrections are also incorporated:
(a)Fuse wire correction: As Mg wire is used for
ignition, the heat generated by burning of Mg wire
is also included in the gross calorific value.
Hence this amount of heat has to be subtracted
from the total value.
(b)Acid Correction: During combustion, sulphur and
nitrogen present in the fuel are oxidized to their
corresponding acids under high pressure and
temperature.
S O 
2 2
SO O  2H O  2H SO
2SO H = -144,000 Cal
2 2 2 2 4
2N 5O2  2H2 O  3 H = -57,160 Cal
2
The corrections must be made for the heat liberated
in the bomb by the formation of H2SO4 and HNO3.
The amount of H2SO4 and HNO3 is analyzed by
washings of the calorimeter.
For each ml of 0.1 N H2SO4 formed, 3.6 calories
should be subtracted.
For each ml of 0.01 HNO3 formed, 1.43 calories must
be subtracted.
(C) Cooling correction: As the temperature rises
above the room temperature, the loss of heat does
occur due to radiation, and the highest temperature
recorded will be slightly less than that obtained.
A temperature correction is therefore necessary to get
the correct rise in temperature.
If the time taken for the water in the calorimeter to
cool down from the maximum temperature attained, to
the room temperature is x minutes and the rate of
cooling is dt/min, then the cooling correction = x  dt.
This should be added to the observed rise in
temperature.
Therefore,
Gross calorific value (GCV)
GCV = (W+w)(t2-t1+Cooling correction)-[Acid+ fuse
corrections] / Mass of the fuel.
Theoretical calculation of Calorific value of a
Fuel: The calorific value of a fuel can be calculated if
the percentages of the constituent elements are
known.
Substrate Calorific value

Carbon 8080

Hydrogen 34500

Sulphur 2240
If oxygen is also present, it combines with hydrogen to
form H2O. Thus the hydrogen in the combined form is
not available for combustion and is called fixed
hydrogen.
Amount of hydrogen available for combustion = Total
mass of hydrogen-hydrogen combined with oxygen.

1
H2  O
1g 8g
9g
Fixed Hydrogen = Mass of oxygen in the fuel
Therefore, mass of hydrogen available for combustion
= Total mass of hydrogen-1/8 mass of oxygen in fuel
Dulong’s formula for calculating the calorific value
is given as:
Gross calorific Value (HCV)
1
 [8080C  34,500(H  O ) 
2,240S ]kcal / kg
100 8

Net Calorific value (LCV)

9H
 [HCV 100  587]kcal /
kg
 [HCV  0.09H  587]kcal /
kg
FACTORS AFFECTING CORROSION
FACTORS AFFECTING CORROSION

The rate and extent of corrosion

depends mainly upon two factors–
1. Nature of the metal
2. Nature of the environment
NATURE OF THE METAL OR METALLIC
CONDITIONS

A.Position in Galvanic Series

Metal higher in the galvanic series
are more likely to undergo
a.
corrosion
B. Relative anodic and cathodic areas
Corrosion is more rapid if the anodic area
is small because there is more demand for
electrons by the larger cathodic area.
C.Purity of the metal
Impurities in a metal form minute
electrochemical cells and the anodic part gets
corroded.
D. Physical state of metal
 The rate of corrosion is influenced by the
physical state of the metal such as size,
orientation of crystals, stress etc. The
smaller the size of metal greater will be the
corrosion and the stressed port of the metal
also undergo more corrosion.
E. Nature of corrosion product
 Metals like Fe, Mg etc form a non
protective porous oxide film which
causes maximum corrosion while
metals like Al, Cr, Ni etc form a protective
coating which minimizes corrosion.
F. Solubility of corrosion product
 In electrochemical corrosion, if the corrosion
product is soluble in the medium, then the
corrosion proceeds at a faster rate.
G. Volatility of corrosion product
 If the corrosion product is volatile rapid
and continuous corrosion occurs.
NATURE OF THE ENVIRONMENT

 a. Temperature
Rise of temperature increases the rate of
corrosion.
 b. Humidity
Humidity air is directly related to the rate of
corrosion. In humid condition atmospheric gases
easily form electrochemical cell by which
corrosion occurs to a great extent.
C. Effect of PH
Generally acidic media is PH<7 is more
corrosive than alkaline and neutral media.
D.Formation of O2 concentration cell
 If there is a difference in O2 concn around
the metal, then the less oxygenated metal
part becomes anode and the more
oxygenated part becomes cathode and an
O2 concentration cell is set up resulting
corrosion.
E.Nature of ions
 Presence of anions like silicate ions in the
medium leads to the formation of insoluble
reaction products which inhibit further
corrosion. On the other hand Cl- ions ions etc
destroy the protective surface film thereby
exposing fresh metal surface for corrosion.
Rapid corrosion of Al in sea water is an
example.
 F.Presence of suspended particulars
or compounds
Particulars like NaCl, (NH4)2 SO4 etc along with
moisture act as powerful electrolyte and promote
corrosion.
 G.Conductance of the corroding medium
 In the case of underground and submerged
structures, the conductance of the medium
influences the rate of corrosion. Conductance of dry
sandy soil is lower than that of clayey and
mineralized soil. Hence the corrosion rate of
metallic structures in lower in dry sandy soil than in
clayey and mineralized soil.

Battery :-
 A battery is a storage device used for the storage of chemical
energy and for the transformation of chemical energy into
electrical energy
 Battery consists of group of two or more electric cells connected
together electrically in series.
Battery acts as a portable source of electrical energy.
Energy produced by an electrochemical cell is not suitable for
commercial purposes since they use salt bridge which produce
internal resistance which results in drop in the voltage. The drop in
voltage is negligible only for a small interval of time during which it is
being used. Batteries are of 3 types. Namely
• Primary Batteries (or) Primary Cells
• Secondary Batteries (or) Secondary Cells
• Reserve Batteries
• Fuel Cells (or) Flow Batteries
Primary (Disposable) Batteries

 Leclanché Cells (zinc carbon or dry cell)

 Alkaline Cells
 Mercury Oxide Cells
 Zinc/MnO2 Cells
 Aluminum / Air Cells
 Lithium Cells
 Liquid cathode lithium cells
 Solid cathode lithium cells
 Solid electrolyte lithium cells
Secondary (Rechargeable) Batteries

 Lead–acid Cells
 Nickel/Cadmium Cells
 Nickel/Metal Hydride (NiMH) Cells
 Lithium Ion Cells
Lead-acid battery
Electrolyte – 20 % H2SO4

H2SO4 Concentration decreases

with discharging and regained on
charging

This can tested by specific gravity

measurement of H2SO4

Cell voltage 1.88 – 2.15 V

discharging
PbO2 + Pb + H2SO4 2PbSO4 + 2H2O
charging
Basics-Cell Chemistry
• At the positive plate: D
PbO2 + 4H+ + SO42- + 2e- PbSO4 + 2H2O
C
• At the negative plate: Pb + D PbSO4 + 2e-
SO42- C

• Total Cell Reaction: PbO2 + Pb +2H2SO4 D 2PbSO4

+2H2O C
Note: Active materials include lead
dioxide, lead and sulfuric
acid.
There are four stages in the
discharging−charging
cycle:
• Fully Charged
• Discharging
• Fully Discharged
• Charging
 Positive plate covered with lead oxide
(PbO2)

 Negative plate covered with

a sponge lead (Pb)

 Electrolyte contains water (H2O)

and a sulfuric acid (H2SO4)

FULLY CHARGED
  Current flows in the cell from the negative
to the positive plates.

 Electrolyte separates into hydrogen (H2)

and sulfate (SO4).

 The free sulfate combines with the lead

(both lead oxide and sponge lead)
and becomes lead sulfate (PbSO4).

 The free hydrogen and oxygen

combine to form more water,
diluting the electrolyte.

DISCHARGING
  Both plates are fully sulfated.

 Electrolyte is diluted
to mostly water.

DISCHARGED
 Reverses the chemical reaction
that took place during discharging.

Sulfate (SO4) leaves the positive

and negative plates and combines
with hydrogen (H2) to become
sulfuric acid (H2SO4).

 Hydrogen bubbles form at the

negative plates; oxygen appears
at the positive plates.

 Free oxygen (O2) combines

with
lead (Pb) at the positive plate to
become
lead oxide (PbO2).
CHARGING
Liquid crystals are substances that exhibit a
phase of matter that has properties between
those of a conventional liquid, and those of a
solid crystal.
Note:
Mesogen
: It is the fundamental unit of a liquid
crystal that induces structural order in the
crystals.
 LIQUID CRYSTALS

II. LYOTROPIC LC
I. THERMOTROPIC LC

i. NEMATIC LC ii. CHOLESTRIC LC iii. SMECTIC LC

 I. THERMOTROPIC LIQUID CRYSTALS

Liquid crystals are said to be thermotropic if

there liquid crystalline properties depend
on the temperature.
 i. NEMATIC LIQUID CRYSTALS

One of the most common LC phases is the

nematic, where the molecules (mesogens) have no
positional order, but they have long-range
orientational order. (Most nematics are uniaxial: they have
one axis that is longer and preferred, with the other two being
equivalent (can be approximated as cylinders)
In Greek ‘nematic’ means thread. And hence the thread
like structure of the nematic crystals.

Nematics have fluidity similar to that of

ordinary (isotropic) liquids but they can be easily
aligned by an external magnetic or electric field. An
aligned nematic has the optical properties of a
uniaxial crystal and this makes them extremely
useful in liquid crystal displays (LCD).
 ii. SMECTIC LIQUID CRYSTALS

In the case of
Smectic type LC,
the mesogens
have both
positional order
and orientational
order. The smectic
phases, which are found
at lower temperatures
than the nematic, form
well-defined layers that
can slide over one
another like soap.

Smectic A Smectic C
iii. CHOLESTRIC LIQUID CRYSTALS

The cholestric phase can be

defined as a special type of
nematic LC in which the thin
layers of the parallel mesogens
have their longitudinal axes
rotated in adjacent layers at
certain angle.
 II. Lyotropic LIQUID CRYSTALS
Hydrophobic end
of the mesogen

Liquid crystals which are

prepared by mixing two or more
Hydrophilic end
of the substances, of which one is a
mesogen polar molecule, are known
as lyotropic liquid crystals.

Eg. Soap in water.

Discontinuous cubic phase (micellar cubic phase)
Hexagonal phase (hexagonal columnar phase) (middle phase)
Bicontinuous cubic phase
Lamellar phase
Bicontinuous cubic phase
Reverse hexagonal
columnar phase
Inverse cubic phase
(Inverse micellar phase)
 Used in display devices (LCDs) such
1. Liquid Crystal Displays:
as Laptops, watches, calculators, clocks, etc.
Chiral nematic (cholesteric) liquid
2. Liquid Crystal Thermometers:
crystals reflect light and the color reflected also is
dependent upon temperature.

3. Optical Imaging: An
application of liquid crystals that is only
now being explored is optical imaging and recording.

3. Some of the liquid crystals are used in hydraulic break/clutch

system due to their high viscosity values.
Applications of Liquid Crystals
Liquid crystal technology has had a major effect many areas of science and engineering, as well as device technology. Applications
for this special kind of material are still being discovered and continue to provide effective solutions to many different problems.
Liquid Crystal Displays
The most common application of liquid crystal technology is liquid crystal displays (LCDs.) This field has grown into a multi-billion
dollar industry, and many significant scientific and engineering discoveries have been made. Please refer to the LCD chapter for
more detail.
Liquid Crystal Thermometers
As demonstrated earlier, chiral nematic (cholesteric) liquid crystals reflect light with a wavelength equal to the pitch. Because the
pitch is dependent upon temperature, the color reflected also is dependent upon temperature. Liquid crystals make it possible to
accurately gauge temperature just by looking at the color of the thermometer. By mixing different compounds, a device for
practically any temperature range can be built.
The "mood ring", a popular novelty a few years ago, took advantage of the unique ability of the chiral nematic liquid crystal. More
important and practical applications have been developed in such diverse areas as medicine and electronics. Special liquid crystal
devices can be attached to the skin to show a "map" of temperatures. This is useful because often physical problems, such as
tumors, have a different temperature than the surrounding tissue. Liquid crystal temperature sensors can also be used to find bad
connections on a circuit board by detecting the characteristic higher temperature. [Collings, 140-142]
Optical Imaging
An application of liquid crystals that is only now being explored is optical imaging and recording. In this technology, a liquid crystal
cell is placed between two layers of photoconductor. Light is applied to the photoconductor, which increases the material's
conductivity. This causes an electric field to develop in the liquid crystal corresponding to the intensity of the light. The electric
pattern can be transmitted by an electrode, which enables the image to be recorded. This technology is still being developed and is
one of the most promising areas of liquid crystal research.
Other Liquid Crystal Applications
Liquid crystals have a multitude of other uses. They are used for nondestructive mechanical testing of materials under stress. This
technique is also used for the visualization of RF (radio frequency) waves in waveguides. They are used in medical applications
where, for example, transient pressure transmitted by a walking foot on the ground is measured. Low molar mass (LMM) liquid
crystals have applications including erasable optical disks, full color "electronic slides" for computer-aided drawing (CAD), and light
modulators for color electronic imaging.
As new properties and types of liquid crystals are investigated and researched, these materials are sure to gain increasing
importance in industrial and scientific applications.
POLYMER COMPOSITE
 What is Composites?
A broad definition of composite is: Two or more chemically distinct
materials which when combined have improved properties over the
individual materials. Composites could be natural or synthetic.
Composites are combinations of two materials in which one of the
material is called the reinforcing phase, is in the form of fibers,
sheets, or particles, and is embedded in the other material called the
matrix phase.

 Combination of 2 or more materials

 Each of the materials must exist more than 5%
 Presence of interphase
 The properties shown by the composite materials are differed from
the initial materials
 Can be produced by various processing techniques
 Constituents of composite
materials
1. Matrix phase
Continuous phase, the primary phase.
It holds the dispersed phase and shares a load with it.

2. Dispersed (reinforcing) phase

The second phase (or phases) is imbedded in the matrix in a
continuous/discontinuous form.
Dispersed phase is usually stronger than the matrix, therefore it is sometimes
called reinforcing phase.

3. Interface
Zone across which matrix and reinforcing phases interact (chemical, physical,
mechanical)
Matrix: Function

however the distribution of loads depends on the interfacial bondings

Reinforcement: Function
Reinforcement can be in the form
of:
 Continuous fiber
 Organic fiber- i.e. Kevlar, polyethylene
 Inorganic fiber- i.e. glass, alumina, carbon
 Natural fiber- i.e. asbestos, jute, silk
 Short fiber
 whiskers
 Particle
 Wire
Interface: Function
 To transfer the stress from matrix to
reinforcement

Sometimes surface treatment is carried out

to achieve the required bonding to the
matrix
 Characteristics of dispersed phase that might
influence the properties of composites

a) Concentration (b) size (c) shape (d) distribution (e)

orientation
Classification of composites
Examples of composites

a) Particulate & random

b) Discontinuous fibers & unidirectional
c) Discontinuous fibers & random
d) Continuous fibers & unidirectional
Classification based on Matrices
Composite
materials

Matrices

Polymer Matrix Metal Matrix Ceramic Matrix

Composites (PMC) Composites MMC) Composites (CMC)

Thermoset Thermoplastic Rubber

 Widely used- ease of processing & lightweight
Composites – Ceramic Matrix
Ceramic matrix composites (CMC) are used in applications where
resistance to high temperature and corrosive environment is
desired. CMCs are strong and stiff but they lack toughness
(ductility)
Matrix materials are usually silicon carbide, silicon nitride and
aluminum oxide, and mullite (compound of aluminum, silicon and
oxygen). They retain their strength up to 3000 oF.
Fiber materials used commonly are carbon and aluminum
oxide.

Applications are in jet and automobile engines, deep-see

mining, cutting tools, dies and pressure vessels.
 Mechanica
15 Ken Youssefi l Engineering
Dept.
Composites – Metal Matrix
The metal matrix composites offer higher modulus of elasticity, ductility,
and resistance to elevated temperature than polymer matrix composites.
But, they are heavier and more difficult to process.

16
Properties of composites depend
on
 Amount of phase
- Amount/proportion (can be expressed in
weight fraction (Wf) or volume
fraction (Vf))of phases strongly
influence the properties of composite
materials.
Xc = Xf Vf + Xm (1 - Vf ) - Rule of Mixture
Xc = Properties of composites
Xf = Properties of fiber
Xm= Properties of matrix
Voids
 Free volume
 Gas emission leads to voids in the
final product
 In composites- Voids exist in the
matrix, interface and in between fiber
& fiber
 Voids create stress concentration
points- influence the properties of the
composites
 Geometry of dispersed phase
(particle size, distribution,
orientation)
 Shape of dispersed phase (particle-
spherical or
irregular, flaky, whiskers, etc)
 Particle/fiber size ( fiber- short, long,
continuous); particle (nano or micron
size)
 Orientation of fiber/particle (unidirection, bi-
directions, many directions)- influence isotropic
dan an-isotropic properties
 Dictribution of dispersed phase
(homogenus/uniform, inhomogenus)
Glass Fiber
The types of glass used are as follows:
 E-Glass – the most popular and inexpensive glass fibers. The
designation letter “E” means “electrical” (E-Glass is excellent
insulator). The composition of E-glass ranges from 52-56%
SiO2, 12-16% A1203, 16-25% CaO, and 8-13% B203
 S-Glass – stronger than E-Glass fibers (the letter “S” means
strength). High-strength glass is generally known as S-type
glass in the United States, R-glass in Europe and T-glass in
Japan. S-Glass is used in military applications and in
aerospace. S-Glass consists of silica (SiO2), magnesia (MgO),
alumina (Al2O3).
 C-Glass – corrosion and chemical resistant glass fibers. To
protect against water erosion, a moisture-resistant coating such
as a silane compound is coated onto the fibers during
manufacturing. Adding resin during composite formation
provides additional protection. C-Glass fibers are used for
manufacturing storage tanks, pipes and other chemical
resistant equipment.
Glass Fiber
 Fiberglasses (Glass fibers reinforced polymer matrix
composites) are characterized by the following
properties:
 High strength-to-weight ratio;
 High modulus of elasticity-to-weight ratio;
 Good corrosion resistance;
 Good insulating properties;
 Low thermal resistance (as compared to metals and
ceramics).
 Fiberglass materials are used for manufacturing:
boat hulls and marine structures, automobile and
truck body panels, pressure vessels, aircraft wings
and fuselage sections, housings for radar
systems, swimming pools, welding helmets, roofs,
pipes.
Carbon Fiber
 The types of carbon fibers are as
follows:
 UHM (ultra high modulus). Modulus of
elasticity > 65400 ksi (450GPa).
 HM (high modulus). Modulus of
elasticity is in the range 51000-65400
ksi (350-450GPa).
 IM (intermediate modulus). Modulus of
elasticity is in the range 29000-51000
ksi (200-350GPa).
 HT (high tensile, low modulus). Tensil e
strength > 436 ksi (3 GPa), modulus of
elasticity < 14500 ksi (100 GPa).
 SHT (super high tensile). Tensile
strength > 650 ksi (4.5GPa).
Carbon Fiber
 Carbon Fiber Reinforced Polymers (CFRP) are characterized
by the following properties:
 Light weight;
 High strength-to-weight ratio;
 Very High modulus elasticity-to-weight ratio;
 High Fatigue strength;
 Good corrosion resistance;
 Very low coefficient of thermal expansion;
 Low impact resistance;
 High electric conductivity;
 High cost.
 Carbon Fiber Reinforced Polymers (CFRP) are used for
manufacturing: automotive marine and aerospace parts, sport
goods (golf clubs, skis, tennis racquets, fishing rods), bicycle
frames.
Kevlar Fiber
 Kevlar is the trade name (registered by DuPont Co.)
of aramid (poly-para-phenylene terephthalamide)
fibers.
 Kevlar fibers were originally developed as a
replacement of steel in automotive tires.
 Kevlar filaments are produced by extrusion of the
precursor through a spinnert. Extrusion imparts
anisotropy (increased strength in the lengthwise
direction) to the filaments.
 Kevlar may protect carbon fibers and improve their
properties: hybrid fabric (Kevlar + Carbon fibers)
combines very high tensile strength with high impact
and abrasion resistance.
Kevlar Fiber
 Kevlar fibers possess the following properties:
 High tensile strength (five times stronger per
weight unite than steel);
 High modulus of elasticity;
 Very low elongation up to breaking point;
 Low weight;
 High chemical inertness;
 Very low coefficient of thermal expansion;
 High Fracture Toughness (impact
resistance);
 High cut resistance;
 Textile processibility;
 Flame resistance.
 The disadvantages of Kevlar are: ability to absorb
moisture, difficulties in cutting, low compressive
strength.
Kevlar Fiber
 There are several modifications of Kevlar,
developed for various applications:
 Kevlar 29 – high strength (520000 psi/3600 MPa),
low density (90 lb/ft³/1440 kg/m³) fibers used for
manufacturing bullet-proof vests, composite armor
reinforcement, helmets, ropes, cables, asbestos
replacing parts.
 Kevlar 49 – high modulus (19000 ksi/131 GPa),
high strength (550000 psi/3800 MPa), low density
(90 lb/ft³/1440 kg/m³) fibers used in aerospace,
automotive and marine applications.
 Kevlar 149 – ultra high modulus (27000 ksi/186
GPa), high strength (490000 psi/3400 MPa), low
density (92 lb/ft³/1470 kg/m³) highly crystalline
fibers used as reinforcing dispersed phase for
composite aircraft components.
 Zeolite process
Zeolites are hydrated sodium alumino silicates capable of
exchanging its sodium ions with hardness producing
cations in water.
Na2O Al2O3.xSiO2.yH2O ,
where x=2 to 10 and y= 2 to 6
There are two types of Zeolites:-
(i) Natural Zeolites:- Are amorphous and non
porous in nature.They are derived from green
sand,by
washing,heating and treating with NaOH.
e.g. Natrolite- Na2O Al2O3.4SiO2.2H2O
(ii) Synthetic zeolites are porous and are prepared by
heating together solutions of sodium silicate,sodium
aluminate and aluminium sulphate.
Principle:
Zeolites can be represented as Na2Z,from which Na can
easily be replaced by Ca and Mg ions present in hard
water.
Ca(HCO3) 2+ Na 2 Z CaZ + 2NaHCO3
Mg(HCO3) 2 + Na 2 Z MgZ +2NaHCO3
CaCl2+ Na2Z CaZ + 2NaCl
MgCl2+Na2Z MgZ + 2NaCl
CaSO4 +Na2Z CaZ + Na2SO4
MgSO4 +Na2Z MgZ + Na2SO4
Regeneration
After sometime, sodium Zeolites are completely
:-
converted into Calcium and Magnesium Zeolites i.e.
get exhausted.The process by which exhausted
Zeolite is converted into sodium Zeolite again by t
reating with 10% brine solution is known as
Regeneration
CaZ + 2 NaCl Na2Z + CaCl2
MgZ + 2 NaCl Na2Z + MgCl2
Process:-
Hard water is percolated through Zeolite bed in a
cylindrical tank.Sodium ions are replaced by Ca2+ and
Mg2+ ions to form CaZ and MgZ.After sometimes the bed
gets exhausted.At this stage supply of water is stopped
and regeneration is carried out,by passing 10% brine
solution.
Advantages of Zeolite process:-
1. Water of about 15 ppm hardness is obtained
2. The equipment is compact and occupies less space.
3. It requires less time for softening.
4. There is no danger of sludge formation because
impurities are not precipitated.
Disadvantages of zeolite process:-
5. Only cations are removed and not anions.
6. If water is turbid it clogs the pores of zeolite bed and
makes it inactive.So the suspended impurities must be
removed from hard water by coagulation and filtration
first, before the water is fed to the zeolite bed
3. Mineral acids destroy the zeolite bed, so they must be
neutralised befor hand.
4. Acid radicals which are not removed during softening
cause caustic embrittlement and boiler corrosion.
NaHCO3 NaOH + CO2
CO2 + H2O H2CO3
5. If large quantities of Fe2+ and Mn2+ are present in water
,the zeolite is converted into iron and manganese zeolite
which can not be regenerated.
Limitations:
•If the supply of water is turbid in will clog
the pores of zeolite led
•Water contains large quantities of colored ions
such as Mn+2 and Fe+2 they may be removed
first because these ions produce Mn and Fe
Zeolites
,which can’t be easily regenerated
•Mineral acids destroy the zeolite bed
Biodegradable Polymers: Introduction &
Applications
Definition
A “biodegradable” product has the ability to break down,
safely, reliably, and relatively quickly, by biological
means, into raw materials of nature and disappear into
nature.

Nature’s way: every resource made by nature returns to

nature. Nature has perfected the system we just need
to figure out how
What is Polymer Degradation?

polymers were synthesized

from glycolic acid in 1920s

At that time, polymer

degradation was viewed
negatively as a process
where properties and
performance deteriorated
with time.
Biodegradable Polymers
 Natural polymers
 Fibrin
 Collagen
 Chitosan
 Gelatin
 Hyaluronan ...
 Synthetic polymers
 PLA, PGA, PLGA, PCL, Polyorthoesters
…
 Poly(dioxanone)
 Poly(anhydrides)
 Poly(trimethylene carbonate)
 Polyphosphazenes ...
Degradation Mechanisms
 Enzymatic degradation
 Hydrolysis
(depend on main chain structure: anhydride > ester >
carbonate)

 Homogenous degradation
 Heterogenous degradation
Polyesters

PGA: It is used in fishing industry, controlled release

of pestisides, egg cartons,Razor handles, toys and in
the medical field.
Poly(lactide-co-glycolide)
PCL (Poly caprolactone)
It is a thermoplastic biodegradable polyester synthesized by chemical
Conversion of crude oil, followed by ring opening polymerisation.
PCL has good water, oil, solvent and chlorine resistance. It is
manufactured under trade name “Tone Polymer”.
Polylactic acid

The skeletal formula of poly(lactic acid)

Poly(lactic acid) or polylactide (PLA) is a
thermoplastic aliphatic polyester derived from
renewable resources, such as corn starch (in
the
United States), tapioca products (roots, chips or
starch mostly in Asia) or sugarcanes (in the rest of
world). It c
Polyhydroxyalkanoates

BIOPOL

O
O O
O
+
H O +H O
HO
O HOH HO OH
O H

Bacteri Microbially
Bacteria Catalyzed
a Catalyzed
Microbially
Polymerizati Depolymerizati
Catalyzed Catalyzed
on
on
Polymerization
Depolymerization
O O

O O
n O m

Polyhydroxy buterate
O

valerate (PHBV)
O O
n

m
Medical Applications of Biodegradable Polymers
 Wound management  Dental applications
 Sutures  Guided tissue
 Staples regeneration Membrane
 Clips  Void filler following
 Adhesives tooth extraction
 Surgical meshes  Cardiovascular
 Orthopedic devices applications
 Pins  Stents
 Rods  Intestinal applications
 Screws  Anastomosis rings
 Tacks  Drug delivery system
 Ligaments  Tissue engineering
CONDUCTING
POLYMERS
Discovery of conducting polymers
Discovered in the late seventies (1977) by
Alan Heegar , Dr. Hideki Shirakawa and Alan
Macdiarmid
Before that polymers were used as
insulators in the electronic industry
Advantages over conductors

Chemical - ion transport possible , redox

behavior , catalytic properties,
electrochemical effects, Photoactivity,
Junction effects
Mechanical - light weight , flexible ,
non metallic surface properties
 n
Polyacetylen
e N n
1977 n
H
Polypyrrole Polyphenylene
1979 1979

n
N
Poly(phenylene S n n
H
vinylene) PPV Polythiophene
1979 1982
Polyaniline
1985
Conductivity
 Polymers become conducting upon doping
 Polymer becomes electronically charged
 Polymer chains generate charge carriers
 Concentration of dopant causes certain electrons
to become unpaired
 Formation of polarons and bipolarons
 They have extended p-orbital system
Band structures for semiconductors and insulators
 Semiconductors and Insulators have totally full valence bands and empty
conduction bands with a bandgap between them. Ef exists in the
bandgap.
 The distinction between semiconducting and insulating materials
is arbitrarily set to a bandgap of < or > 4 eV, respectively.
Empty 4p
Energy (conduction)
Empty
Band gap (conduction)

Empty
Band gap
partially (conduction)

Ef,
filled 4s Band gap
E
(conduction) E Filled
Fer f Filled
f
(valence)
mi (valence)
Band gap
Band gap
Band gap Filled
filled
Filled (deep valence)
3p, 2p, 2s, 1p,
level 1s (valence)
(deep valence)
Insulator
Metal Semiconductor (Al2O3)
S (-1 cm-1
Copper n NH
105 Iron n
Doped
Graphite Polyacetylene Doped Polyaniline
Doped Polypyrrole Doped Polythiophene

100 Doped germanium Doped Polyphenylene

silicon
10-5 Non-Doped Polyacetylene

Non-Doped Polythiophene

S n
10-10 Silica
Non-Doped Polyphenylene
Nylon 6
10-15 Polyethylene
Polystyrene

PTFE
Electron-conducting polymers
Polyacetylene
First conducting polymer to be synthesized
Best defined system
Reaction conditions allow to control the
morphology of the polymer to be obtained as
gel, powder, spongy mass or a film
Doped with iodine
Inherent insolubility and infusibility
impose barriers to the processing of the
polymer
 Synthesized by
Dehydrohalogenations of vinyl chlorides:
Polymers prepared by this route have short
conjugation length, structural defects
and crosslinks
Precursor routes: Durham route
Polymers prepared by this route are continuous solid
films, have controlled morphology range and can
be stretched prior to conversion
Conduction mechanism
R and L forms are interconverted through a
charge carrier soliton
Soliton is a mobile, charged or a neutral defect or
a kink in the polymer chain
It propagates down the polymer chain
For short chains Kivelson mechanism is involved
Travel of a soliton by bipolaron
mechanism
Contrast between isomers of
polyacetylene
isomer Conductivity Obtainable structure
(siemens/cm) temperature

cis 10^-13 -77`C

trans 10^-7 170`C

Reasons of trans’ stability

Two fold degeneracy

SOLITON formation due to symmetry

An unpaired electron at each end of an inverted
sequence of double bonds
Stability(contd.)

SOLITONS - Responsible for higher conductivity

Double bond next to a SOLITON may switch over to give
rise a moving SOLITON which leads to conduction
In presence of many SOLITONS , their sphere of
influence overlaps leading to conduction like metals
Doping in polyacetylene
• Amount of dopant used is significantly higher
• Doped polyacetylene is always in tans form
•Neutral polyacetylene can be doped in two ways
p type doping : oxidation with anions eg : ClO4(-)

-e
+ ClO4(-) + ClO4(-)
n type doping : reduction with cations eg :
Na(+)
(-)
++Na(+)
e Na(+)
Method of doping

•Chemical oxidants : iodine , nitronium species ,

transition metal salts
•Chemical reducing agents : sodium
naphthamide
•Electrochemical methods : used dopants
ClO4(-)
, BF4(-) and other complex species
Doping with Iodine
Effect of dopant
•Conductivity - increases upto a certain doping
level
•Stability - decreases
•Morphology : due to presence of charges shape
will not be retained - reason why doped
polyacetylene is always trans
 Various
Applications
 Coatings

• Prevents buildup of static charge in insulators

• Absorbs the harmful radiation from electrical
appliances which are harmful to the nearby
appliances
• Polymerization of conducting plastics used in
circuit boards
Sensors(to gases and solns.)

• Polypyrroles can detect NO2 and NH3 gases by

changing its conductivity
• Biosensor : polymerization of polyacetylene in
presence of enzyme glucose oxidase and
suitable redox mediator like triiodide will give
rise to a polymer which acts as glucose sensor
 Polymeric Ferroelectric
RAM(PFRAM)

• Uses polymer ferroelectric material

• Dipole is used to store data
• Provides low cost per bit with high chip
capacity
• Low power consumption
• No power required in stand by mode
• Isn’t a fast access memory
Biocompatible Polymers

• Artificial nerves
• Brain cells
 Batteries
• Light weight
• Rechargeable
• Example - Polypyrrole - Li & Polyaniline - Li
 Displays

• Flat panels
• Related problems : low life time & long switching
time
 Conductive Adhesive

• Monomers are placed between two conducting plates

and it allows it to polymerize
• Conducting objects can be stuck together yet allowing
electric current to pass through the bonds
 1. Proper selection and designing
 2.Cathodic and anodic protection
 3.Protective coating

 (a ) Metal Coating
 (b) Inorganic coating

 (c) Organic coating

 4. Corrosion Inhibitors
 Design an equipment by avoiding contact
between two dissimilar metals.

 Maintaining a larger anodic area of the

metal.

 Metals should be close in the galvanic

series.
2. Cathodic Protection
In this method, the corroding metal is forced to
behave like a cathode. There are two types of
cathodic protection
In this method, the metallic structure which is to
be protected from corrosion is connected to a
more anodic metal by a wire so that the entire
corrosion is concentrated on this more active
metal.
The more active metal loses and get
corroded and this metal is called
sacrificial anode. Metals commonly
employed as sacrificial anode are Mg, Zn, Al and
their alloys.
 Applications
 Important applications of sacrificial anodic method
include protection of buried pipe lines, underground
cables, marine structures etc.
In this method, an impressed current is applied in the
opposite direction to nullify corrosion current so as to
convert the corroding metal from anode to cathode.
Impressed current can be derived from a direct
current source like battery. An inert or insoluble
electrode like graphite or silica act as anode to
complete the circuit. The surroundings of anode
should be filled with salts and carbon to increased the
conductivity.
 This type of cathodic protection has been applied
to water coolers, water tanks, buried oil and water
pipes, transmission towers etc. This type of
protection is employed when
1. Long term protection is needed
2. Large structures are to be protected
3. There is a cheap source of electrical power.
3. Protective coatings
An important method for protecting a metal from corrosion is to
apply a protective coating. The protective coatings may be of
metal, inorganic or organic. The coated surface isolates the metal
from the corroding medium. The coating applied must be
chemically inert towards the environment.
 Metallic coatings are mostly
applied on Iron and steel because
these are cheap and commonly
used construction materials.
There are two types of metallic
coatings.
 The base metal which is to be protected is coated with
a more anodic metal for eg. Coatings of Zn on steel is
anodic because their electrode potentials are lower than
that of the base metal ie. Fe.
 It is obtained by coating a more inert metal having
higher electrode potential. Than the base metal. Eg.
Coating of Sn, Cr, Ni on Fe surface. The coating
should be continuous
and free from pores and cracks. These
coating metals usually have higher
corrosion resistance than the base metal.
 It is used for producing a coating of low melting
metal such as Zn, Sn, Ph, Al etc on relatively
higher melting metals such as iron, steel, copper
etc. This is done by immersing the base metal
covered by a layer of molten flux. The flux is
used to keep the base metal surface clean and
also to prevent oxidation of the molten metal.
Most widely used hot dipping methods are : (i)
galvanization and (ii) tinning
 It is the process of coating Zn over iron or steel
sheet by immersing it in molten Zn. The
procedure involves the following stages.
 The iron or steel article is Ist cleaned by pickling
with dil H2So4 for 15 – 20 min. at 60 – 900C in an
acid bath. This treatment also removes any oxide
layer present on the surface of the metal. The
article is then washed with water in a washing
bath & dried in a drying chamber.
 It is then dipped in a bath of molten Zn kept at 425
– 4350C. The Surface of the bath is covered with
NH4Cl flux to prevent oxide formation.
 The article gets coated with a thin layer of Zn. It is
then passed through a pair of hot rollers to remove
excess of Zn and to get uniform thickness for
coating. Then it is annealed at about 6500C &
cooled slowly. In the case of Zn coating even if the
protecting layer has cracks on it, iron being
cathodic does not get corroded.
Applications

This method is widely used for protection of Fe from

atmospheric corrosion in the form of
articles like roofing sheets, wires, pipes, nails,
screws, tubes etc. It is to galvanized be noted that not
utensils should contact with acids. come in
 It is an eg. For cathodic coatings. It is the process of coating
Sn over Fe or steel articles by immersing it in molten Sn. The
process consists in Ist treating the iron sheet with dil H2So4 to
remove any oxide film. After this it is passed through a bath
of ZnCl2 flux which helps the molten Sn to adhere to the
metal sheet. Next the sheet passes through palm oil which
prevents through a pair of hot rollers to remove excess of Sn
& produce uniform thickness for Sn coating.
 Tinning is widely used for coating steel, Cu and brass
sheets which are used for making containers for
storing food studs, oils, kerosene & packing food
materials. Tinned Cu sheets are used for making
cooking utensils & refrigeration equipments.
In this process, a thick homogeneous layer of coating metal
is bonded firmly & permanently to the base metal on one
or both the sides. This method cnhanceds corrosion
resistance. The choice of cladding material depends on the
corrosion resistance required for any particular
environment. Nearly all existing corrosion resisting metals
like Ni, Cu, Al, Ag, Pt and alloys like stainless steel, Ni
alloys, Cu alloys can be used as cladding materials.
Cladding can be done by different means.

a. Fusing cladding material over the base metal

b.
c. Welding
Rolling sheets of cladding material over base
metal
 In this process, the coating metal in the molten
state is sprayed on the previously cleaned base
metal with the help of a sprayer. The sprayer
coatings are continuous but somewhat porous a
sealer – oil is applied on such a coating to provide
a smooth surface. However, adhesion strength of
metallic spraying is usually lesser that obtained by
hot dipping or electroplating. It is therefore
essential to have a cleaned metal surface. Spraying
can be applied by the following two techniques.
 In this method, the coating metal in the form of thin
wire is melted by an oxy – acetylene flame and
vaporized by a blast of compressed air. The coating
metal adheres to the base metal. Al is coated on
aircraft steel parts using this techniques.
 In this method, the coating metal is supplied in the form of
fine powder which is converted in to a cloud of molten
globules by a blower and are adsorbed on the base metal
surface.
 it is probably the most important and most
frequently applied industrial method of producing
metallic coatings. Electroplating is carried out by a
process called electrolysis. Thus in this process,
the coating metal is deposited on the base metal by
passing direct current through an electrolyte
containing the soluble salt of the coating metal.
The base metal to be electroplated is made the
cathode of the electrolytic cell whereas the anode
is either made of the coating metal itself or an
inert material of good electrical conductivity like
graphic.
 Electroplating

©2010 John Wiley & Sons, Inc. M P

Groover, Fundamentals of Modern
Manufacturing 4/e
 For electroplating of Ni, NiSO4 and NiCl2 are used as
the electrolyte. For electroplating of Cr, chromic acid is
used as the electrolyte. For Au plating, AuCl3 solution
is taken as the electrolyte. For Cu plating CuSO4
solution is used as the electrolyte. In silver plating,
AgNO3 solution is used as the electrolyte.
Metallic plating process driven entirely by chemical
reactions - no electric current is supplied
 Deposition onto a part surface occurs in an
aqueous solution containing ions of the desired
plating metal
◦ Workpart surface acts as a catalyst for the reaction in the
presence of reducing agent
 Metals that can be plated: nickel, copper, and
gold
 Notable application: copper for plating
through-holes of printed circuit boards
Inorganic coatings
The coated surface isolates the metal from the
corroding medium. The coating applied must be
chemically inert towards the environment. Inorganic coatings are
further classified in to chemical conversion coatings and vitreous
coatings.
These coatings are produced on the surface of a metal or
alloy by chemical or electrochemical reaction. The metal
is immersed in a solution of suitable chemical which
reacts with the metal surface producing and adherent
coating. These coatings protect the base metal from
corrosion. Moreover many of these coatings are
particularly useful to serve as excellent bases for the
application of paints, enamels and other protective
coatings. The most commonly used

surface conversion coatings are chromate and

coatings, phosphate coatings chemical
oxide coatings.
 There are produced by the immersion of the article in
a bath of acidic potassium chromate followed by
immersion in a bath of neutral chromate solution.
The surface film consisting of a mixture of trivals
and hexavalent Cr is formed. Chromate coatings
possess more corrosion resistance and can also be
used as a base for paints. These are applied on Zu,
Cd, Mg and Al
 These are produced by the chemical reaction of base metal
with aqueous solution of phosphoric acid and a phosphate of
Fe, Mn or Zn. The reaction results in the formation of a
surface film consisting
of phosphate of a surface film consisting of
phosphates of the metal. These coatings are
usually applied by immersing or spraying or
brushing. These coating do not give complete
corrosion resistance but can serve as base
painting. These are applied for
on metals like Fe, Zn, Cd, Al and
Sn.
These types of coatings are formed on the surface of
metals like Fe, Al, Mg etc by treating the base metal with
alkaline oxidizing agents like potassium permanganate.
This treatment increases the thickness of the original
oxide film on the metal, there by increasing the corrosion
resistance. Oxide coatings form a good base for paints.
These oxide coatings have got only poor corrosion
resistance. However, for better protection the thickness of
the oxide film can be increased 100 to 1000 times by
electrolytic oxidation or anodisation.
 Ceramic protective coatings can be broadly divided
into vitreous enamel coatings and pure ceramic
coatings. These coatings have the following
advantages.
1.They posses high refractoriness and inertness
2. They are wear resistant & easily be cleaned
3. They are glossy in appearance
4.They are good thermal & electrical insulators
Vitreous enamels are defined as glossy
inorganic composition that can adhere to
metals by fusion and protect them from
corrosion, abrasion, oxidation and
temperature. high
Vitreous enamel coatings consists
ceramic mixture of refractories and oflargea
proportion of fluxes. These coatings are
usually applied on steel and cast iron equipments. The
raw materials used for the vitreous coatings are the
following.
 Vitreous coatings
1. Refractories like quartz (SiO2), clay etc.
2. Fluxes like borax (Sodium tetra borate Na2B4O7),
cryolite (Na3AlF6) (Sodium alumino fluoride),
Soda ash (anhydrous sodium carbonate Na2CO3)
etc.
3. Opacifiers like TiO2, SnO2, Al2O3 etc
4. Pigments like metallic oxides
organic dyes etc
5. Floating agents like plastic, clay, gum etc
6. Electrolytes like MgSO4, MgCO3,
Na2Co3 etc.
Polymers and resins (natural or synthetic)
usually formulated to be applied as liquids
that dry or harden as thin surface films
on substrate materials
 Advantages:
◦ Wide variety of colors and textures available
◦ Capacity to protect the substrate surface
◦ Low cost
◦ Ease with which they can be applied

©2010 John Wiley & Sons, Inc. M P

Groover, Fundamentals of Modern
Manufacturing 4/e
1. Binders - give the coating its properties
2. Dyes or pigments - provide color to the
coating
3. Solvents - dissolve the polymers and resins
and add proper fluidity to the liquid
4. Additives

©2010 John Wiley & Sons, Inc. M P

Groover, Fundamentals of Modern
Manufacturing 4/e
Chemicals which are added in small
quantities to the corroding medium in
order to reduce the corrosion rate are
called corrosion inhibitors. They reduce
corrosion by forming a protective film
either at the cathode or anode. Thus there are two
types of corrosion inhibitors – anodic inhibitors
and cathodic inhibitors
Anodic inhibitors
Chromates (CrO42-), phosphate (PO43-) and Tungstates
(WO42-) of transition metals are used as anodic
inhibitors. They react with the newly produced metal
ions at the anode forming a protective film or barrier
there by preventing further corrosion.
Cathodic inhibitors

Cathodic reaction takes place with either

evolution of H2 or absorption of O2
depending on the nature of the corroding
medium.
1. Evolution of H2 in acid medium
2H+ + 2e- → H2 (g)
Evolution of H2 can be prevented by slowing down the
diffusion of H+ ions to the cathode or by increasing H2
over voltage. Diffusion of
H+
ions can be prevented by adding organic
inhibitors such as amines, urea, thiourea etc. These are
adsorbed at the surface as a film. Arsenic oxide or
antimony oxide is added to increase the H2 over
voltage. These oxides form adherent film of metallic
arsenic or antimony at the cathodic areas.
II. Absorption of O2 in metal or alkaline
medium
H2O + ½ O2 + 2e- → 2
The formation of OH- ions
OHcan
- be prevented either by removing
O2 from the medium or by decreasing the diffusion of O2 in to
the cathode. O2 is removed either by adding reducing agents
like Na2SO3, N2H4 etc or by mechanical dearation.
2 Na2SO3 + O2 → 2 Na2SO4
N2H4 + O2 → N2 + 2H2O
Salts of Zn, Mg or Ni are added to the corroding medium to
reduce the diffusion of O2 towards cathode. These salts react
with OH- ions at the cathode forming insoluble hydroxides
which are adsorbed at the cathode.
II. Absorption of O2 in metal or alkaline
medium
H2O + ½ O2 + 2e- → 2
The formation of OH- ions
OHcan
- be prevented either by removing
O2 from the medium or by decreasing the diffusion of O2 in to
the cathode. O2 is removed either by adding reducing agents
like Na2SO3, N2H4 etc or by mechanical dearation.
2 Na2SO3 + O2 → 2 Na2SO4
N2H4 + O2 → N2 + 2H2O
Salts of Zn, Mg or Ni are added to the corroding medium to
reduce the diffusion of O2 towards cathode. These salts react
with OH- ions at the cathode forming insoluble hydroxides
which are adsorbed at the cathode.