Department of Chemistry

School of Advanced Sciences

Vellore Institute of Technology
Vellore, 632014
SJT: 504B
Module 1 Water Technology
Characteristics of hard water - hardness, DO, TDS in water and their determination – numerical problems in hardness
determination by EDTA; Modern techniques of water analysis for industrial use - Disadvantages of hard water in industries

Module 2 Water Treatment

Water softening methods: - Lime-soda, Zeolite and ion exchange processes and their applications. Specifications of water for
domestic use (ICMR and WHO); Unit processes involved in water treatment for municipal supply - Sedimentation with coagulant-
Sand Filtration - chlorination; Domestic water purification – Candle filtration- activated carbon filtration; Disinfection methods-
Ultrafiltration, UV treatment, Ozonolysis, Reverse Osmosis; Electro dialysis
Module 3 Corrosion
Dry and wet corrosion - detrimental effects to buildings, machines, devices & decorative art forms, emphasizing Differential
aeration, Pitting, Galvanic and Stress corrosion cracking; Factors that enhance corrosion and choice of parameters to mitigate
corrosion
 What is Corrosion?
• Gradual eating away (or) disintegration (or) deterioration of a
metal by chemical or electrochemical reaction with the
environment
• Chemical or electrochemical attack from the environment on a
solid metal resulting in its deterioration (destruction or
disintegration) starting at the surface of the metal is called
corrosion. Thus corrosion is a “reverse extraction of metals”
 Naturally occurring compounds of metals are in thermodynamically
stable state (least energy state), while the extracted metals from these
ores have high-energy state because of the taking up of large amount of
energy during its metallurgy. The metals, thus obtained when exposed to
natural environment will have a tendency to go to their stable lower
energy state whenever an opportunity arises.
 Today, unprotected environment due to rapid industrialization has led to
increased pollution of atmosphere and water. Such a created situation
has marked effect on metals and alloys, and obviously has offered a
challenge to Materials Engineers to plan and design materials to protect
them from corrosion. In view of the above , the understanding of the
concepts of corrosion process of metals is, therefore, highly desirable.
 Loss of efficiency
 Contamination of product
 Damage of metallic equipment
 Inability to use metallic materials
 Loss of valuable materials such as blockage of pipes,
mechanical damage of underground water pipes
 Accidents due to mechanical lose of metallic bridges, cars,
aircrafts etc
 Causes pollution due to escaping products from corrosion
 Depletion of natural resource ( Metals)
 Corrosion has many serious economic, health, safety, technological, and cultural
consequences to our society
 Economic effects:
 Studies in a number of countries have attempted to determine the national cost of corrosion. The most
extensive of these studies was the one carried out in the United States in 1976 which found that the
overall annual cost of metallic corrosion to the U.S. economy was $70 billion, or 4.2% of the gross
national product. To get a feeling for the seriousness of this loss, we may compare it to another
economic impact everyone is worried about –the importation of foreign crude oil, which cost $45 billion
in 1977
 Health effects:
 Recent years have seen an increasing use of metal prosthetic devices in the body, such as pins, plates,
hip joints, pacemakers, and other implants. New alloys and better techniques of implantation have been
developed, but corrosion continues to create problems. Examples include failures through broken
connections in pacemakers, inflammation caused by corrosion products in the tissue around implants,
and fracture of weight-bearing prosthetic devices. An example of the latter is the use of metallic hip
joints, which can alleviate some of the problems of arthritic hips. The situation has improved in recent
years, so that hip joints which were was at first limited to persons over 60 are now being used in
younger persons, because they will last longer
 Safety effects:
An even more significant problem is corrosion of structures, which can result in severe injuries or even loss
of life. Safety is compromised by corrosion contributing to failures of bridges, aircraft, automobiles, gas
pipelines etc., the whole complex of metal structures and devices that make up the modern world
 Technological effects:
The economic consequences of corrosion affect technology. A
great deal of the development of new technology is held back by
corrosion problems because materials are required to withstand,
in many cases simultaneously, higher temperatures, higher
pressures, and more highly corrosive environments. Corrosion
problems that are less difficult to solve affect solar energy
systems, which require alloys to withstand hot circulating heat
transfer fluids for long periods of time, and geothermal systems,
which require materials to withstand highly concentrated
solutions of corrosive salts at high temperatures and pressures.
Another example, the drilling for oil in the sea and on land,
involves overcoming such corrosion problems as sulfide stress
corrosion, microbiological corrosion, and the vast array of
difficulties involved in working in the highly corrosive marine
environment. In many of these instances, corrosion is a limiting
factor preventing the development of economically or even
technologically workable systems
 Cultural effects:
International concern was aroused by the disclosure of the serious deterioration of the artistically and
culturally significant gilded bronze statues in Venice, Italy. Corrosive processes will accelerate the
deterioration of precious artifacts such as those in Venice by the highly polluted environments that now are
prevalent in most of the countries of the world. Likewise, inside the world's museums conservators and
restorers labor to protect cultural treasures against the ravages of corrosion or to remove its traces from
artistically or culturally important artifacts.
 The consequences of corrosion are many and varied and the effects of these on the
safe, reliable and efficient operation of equipment or structures are often more serious
than the simple loss of a mass of metal
 Failures of various kinds and the need for expensive replacements may occur even
though the amount of metal destroyed is quite small. Some of the major harmful
effects of corrosion can be summarized as follows:
o Reduction of metal thickness leading to loss of mechanical strength and structural
failure or breakdown. When the metal is lost in localized zones so as to give a crack
like structure, very considerable weakening may result from quite a small amount of
metal loss.
o Hazards or injuries to people arising from structural failure or breakdown (e.g. bridges,
cars, aircraft).
o Loss of time in availability of profile-making industrial equipment.
o Reduced value of goods due to deterioration of appearance.
o Contamination of fluids in vessels and pipes (e.g. beer goes cloudy when small
quantities of heavy metals are released by corrosion)
o Perforation of vessels and pipes allowing escape of their contents and possible
harm to the surroundings. For example a leaky domestic radiator can cause
expensive damage to carpets and decorations, while corrosive sea water may
enter the boilers of a power station if the condenser tubes perforate
o Loss of technically important surface properties of a metallic component. These
could include frictional and bearing properties, ease of fluid flow over a pipe
surface, electrical conductivity of contacts, surface reflectivity or heat transfer
across a surface
o Mechanical damage to valves, pumps, etc, or blockage of pipes by solid
corrosion products
o Added complexity and expense of equipment which needs to be designed to
withstand a certain amount of corrosion, and to allow corroded components to
be conveniently replaced
 Justification to study at this level
 The main global challenges are energy, water and air i.e., sufficient energy to
ensure a reasonable standard of living, clean water to drink and clean air to
breathe
 The ability to manage corrosion is a central part of using materials effectively
and efficiently to meet these challenges
 For example, oil and natural gas are transmitted across continents using high-
pressure steel pipelines that must operate for decades without failure, so that
neither the groundwater nor the air is unnecessarily polluted
 Loss of metal by corrosion is a waste not only of the metal, but also the
energy, the water and the human effort that was used to produce and
fabricate the metal structures
 Hence, the chemistry of materials is always important for society and
education programs
 In nature, most metals (except Au, Pt, etc) prefer exist in nature in combined forms
(as their oxides, carbonates, chlorides, silicates, etc).
 These metallic compounds are thermodynamically more stable
 But, during the extraction process at high temperature, the metallic compounds are
reduced to their pure metallic state Cu2+→Cu0 which is thermodynamically unstable
state
 Hence, the extracted/reduced pure metal will always have a strong tendency to
convert itself into the more stable metallic compound oxidized state through corrosion
 Hence, metals will try to go to lower energy states through formation of compounds
and thus attain stability
 The Gibbs free energy changes of forming oxide and sulphides are negative, so
oxidation reaction is usually spontaneous
Corrosion
Metal Metallic compound + energy
Extraction of
metals
 The most familiar example of corrosion is rusting of iron, when exposed to
atmospheric conditions.
 The corrosion product formed is Fe3O4 or Fe2O3.FeO which is a complex oxide (a
crystalline solid containing more than one cation, red colored scale).
 In this case Fe exists as both the 2+ and 3+ cation. There are two 3+ ions and one 2+
ion for every four O2‒ ions.
 The charge balance is: 2×3+ + 1×2++ 4×2‒ = 0
 CORROSION CORROSION

DRY WET ROOM HIGH

CORROSION TEMPERATURE TEMPERATURE
CORROSION
CORROSION CORROSION
 Types of Dry and Wet Corrosion

CORROSION

DRY WET Evolution of

CORROSION CORROSION H2 type
corrosion
Absorption
Oxidation Corrosion of O2 type
corrosion Galvanic
By other gases corrosion
water line
Liquid metal Corrosion
corrosion
 Dry or Chemical Corrosion
o This type of corrosion occurs mainly through the direct chemical action of
environment/atmospheric gases such as oxygen, halogen, hydrogen
sulphide, sulphur dioxide, nitrogen or anhydrous inorganic liquid with
metal surfaces in immediate proximity
o This type of corrosion produces two important effects on the metal
• Metal is consumed
• The properties of the metal are changed
o The extent of dry corrosion depends upon the following factors:
 Chemical affinity between the corrosive environment and solid
metals
 Ability of reaction product on metal surface to form protective films
 Wet corrosion or Electrochemical corrosion
• This type of corrosion is also known as immersed corrosion and
generally takes place when a conducting liquid is in contact with the
metals or when two different metals or alloys are partially or wholly
dipped or immersed in a solution. This corrosion occurs, due to the
existence of separate anodic and cathodic areas, between which current
flows. This corrosion occurs, due to the existence of separate anode,
oxidation reaction takes place so, anodic metal is destroyed. Whereas in
cathodic areas, reduction reaction takes place.
(i) Evolution of hydrogen-type corrosion
(ii) Absorption of oxygen-type corrosion
(iii) Galvanic or bimetallic corrosion
(iv) Concentration cell corrosion (or water line corrosion)
 Oxidation Corrosion
 Mechanism:
When O2 present in the atmosphere attacks the metal at low or high
temperatures (usually in the absence of moisture), thereby forming an oxide
layer on the surface of the metal (M) like iron.\
M → Mn+ + ne‒ (Oxidation)
n/4 O2 + ne‒ → n/2 O2‒ (Reduction)
M + n/4 O2 → Mn+ + n/2 O2‒ (Total reaction)

o Oxidation corrosion will lead to an oxide film which may be stable,

unstable, porous or non-porous.
o Once the oxide film develops, the nature of film determines the further
action
 Oxidation Corrosion: Example
• Example: Iron
Fe →Fe2++ 2 e‒ (oxidation)
½ O2+ 2e‒ → O2‒ (reduction)
Fe + ½ O2 → Fe2+ + O2‒ or FeO (Total reaction)
Corrosion product is formed at the interface at initial stages and grows outwards due to
the faster diffusion of Fe2+ ions and slower diffusion of O2‒ ions

 Mechanism Oxidation corrosion • Outward diffusion of metal ions through the

results in the formation Fe2+ scale (faster, due to small size of Fe2+)
of an metal-oxide (MO) Fe→Fe2+ + 2e‒ (oxidation)
film: FeO Metal (M)
Atmospheric oxygen
(air) O2
2e‒
• Inward diffusion of oxide ions through the
½ O2+ 2e- → O2‒ (reduction) O2‒ scale (slower, due to larger size of O2‒)
Pilling-Bed worth Rule:
 Δ Rule: “If the volume of metal oxide is equal to or greater than the volume of the
metal from which it is formed, then the oxide film is non-porous and protects the metal
from further corrosion; If the volume of the metal oxide is less than the volume of the
metal getting corroded, it will promote further corrosion of the metal”

 Alkali and Alkaline-earth metals form oxides of volume less than the volume of metals.
Consequently, the oxide layer faces stress and strains, thereby developing cracks
pores in its structure.

 On the other hand, metal like Al forms oxide, whose volume is greater than the volume
of metal. Consequently, an extremely tightly-adhering non-porous layer ifs formed.
 The P–B ratio is defined as:
 PBR = Voxide/Vmetal = Moxide.ρmetal /n. Mmetal.ρoxide
 Where:
• RPB is the Pilling–Bedworth ratio
• M – the atomic or molecular mass
• n – number of atoms of metal per one molecule of the oxide
• ρ – density and
• V – volume
 Usually for oxides:
 PBR < 1: oxide coating layer is too thin, likely broken and provides no protective effect
(Mg)
 RPB > 2: oxide coating chips off and provides no protective effect (Fe)
 1 > RPB < 2: oxide coating is passivating and provides a protecting effect against
further surface oxidation (Al, Ti, Cr-containing steels)
 Types of oxide layers:
I. Stable oxide layer (or stable protective oxide layer):
o It is a fine grain of oxide layer which is non-porous and adheres
strongly to the metal
o Oxides of Al, Pb, Cu, Ni and Cr which form stable, non-porous
and tightly adhering impervious metal-oxide films (<300 Å or 30
nm thick) to the pure metallic surface. Such layers which
prevents oxygen from diffusing through the metal and further
attack is stopped. Further oxidation corrosion is stopped
II. Unstable oxide layer:
Oxide layers produced on noble metal surfaces (Pt, Ag, etc) immediately
decompose back into the metal and oxygen, thereby preventing oxidation
corrosion
Metallic oxide Metal + Oxygen

Exposed Unstable
Metal surface metal oxide

Metal oxide
Decomposes
+ O2 of air immediately
Metal Metal + O2
Metal

Unstable
oxide layer
III. Porous oxide layer:
 These oxide layers have minute pores and are not impervious layers
 Oxygen will diffuse through the pores and promote further corrosion
 Fe is a good example of this type of corrosion

Exposed Porous
Metal surface metal oxide

+ O2 of air Further Attack

Metal through pores &
Metal cracks continues
Porous
oxide layer
IV. Volatile oxide layer
 These are oxide layers which volatilize (evaporate) as soon as they are formed
and hence further corrosion is facilitated.
 The underlying metal surface is exposed for further corrosion. After sometime
the metal itself will disappear.
 Molybdenum (Mo) is an example of volatile oxide layer corrosion. MoO3 is
volatile (MoO2 is non-volatile)
Exposed Volatile
Metal surface metal oxide
Fresh surface
Exposed for
Metal oxide Further attack
+ O2 of air volatilizes
Metal Metal + O2
Metal

Volatile metal
oxide
 Corrosion by other gases:
 In dry atmosphere, CO2, Cl2, SO2, F2, NOx etc. are gases which can attack the
metal and corrode
 Extent of corrosion depends on the affinity of the metal to the gas.
These gases chemically react with the metal forming either porous or non-
porous layers of films
 When the film formed is protective or non-porous (2Ag + Cl2→ 2 AgCl), the
metal is prevented from further attack
 When the film formed is non-protective or porous (Sn + 2Cl2→ SnCl4, volatile),
thereby exposing the underlying fresh metal surface for further attack
o Hydrogen corrosion: H2S gas attacks steel at high temperature and make them
brittle by forming FeS as porous scales
o Hydrogen gas attacks the metal to make them brittle (Hydrogen embrittlement).
 Corrosion by other gases (by hydrogen):
 Hydrogen Embrittlement: It leads to loss in ductility of a material in the presence of
hydrogen.
o 1) When metals are in contact with H2S , at ordinary temperature causes evolution of
atomic hydrogen.
Fe + H2S →FeS + 2H▪
o 2) This atomic hydrogen diffuses readily into the metal and collects in the voids, where
it recombines to form molecular hydrogen
H▪ + H▪ → H2↑
o 3) Collection of these hydrogen gases in the voids develops very high pressure, which
causes cracks and blisters on metal. Thus, the process of formation of cracks and
blisters on the metal surface, due to high pressure of hydrogen gas is called hydrogen
embrittlement.
 Decarburization:
 At higher temperature , atomic hydrogen is formed by the thermal dissociation of
molecular hydrogen.
H2 → 2H▪ (In presence of Heat)
When steel is exposed to this environment, the atomic hydrogen readily combines with
carbon of steel and produces methane gas. Thus the formation of methane gas reduces
the strength of steel and this process is known as decarburization.
C + 4H → CH4
 Corrosion by liquid metals :
• This type of corrosion is experienced in pipe lines used in oil and refineries. In metallic
pipelines , the fast flow of corrosive liquid or aggressive fluid completely removes the
underlying layer of metal in the pipeline due to mechanical abrasion ( like Friction).This is
known as Liquid-metal corrosion or Erosion- corrosion
 Liquid metal (Hg, Zn, Sn, Pb, Cd etc) flowing at high temperature over the solid metal or alloy
can result in either the:
o Dissolution of the solid metal by the liquid metal (Gold can be corroded by mercury) or
Internal penetration of the liquid metal into the solid metal. Molten metal atoms penetrate the
grain boundaries and fracture the metal.
 Such corrosion is found in devices used in nuclear power plants. It causes brittle failure of
metal structure
• Examples
 Certain metals like Al and stainless steels undergo brittle failure when stressed in contact
with liquid metals like Hg, Zn, Sn, Pb, Cd etc
 Liquid metal mercury dissolves most metals by forming amalgams, thereby corroding them
 Wet, Aqueous or Electrochemical Corrosion:
 In this type of corrosion, a conducting liquid (electrolyte) is in contact with a metal,
or two dissimilar metals or alloys either immersed fully or partially in an electrolyte.
 One part becomes anode and the other part cathode. Corrosion occurs due to the
formation of Anode and Cathode areas. Electrons flows between the electrodes
while ions flow through the electrolyte
 At the anodic part corrosion (oxidation) occurs while reduction takes place at the
cathode
 At the anode: M → Mn+ + ne‒
 Mn+ either dissolved in solution or forms compounds such as oxides
 The rate of the electrochemical corrosion will depend on:
o If the corrosion product is soluble in the medium, rate of corrosion will be high
o If the corrosion product is insoluble in the medium, rate of corrosion will be very
low
Its mechanism is based on Nernst theory
 According to which all metals have a tendency to pass into solution
 If a metal having higher electrode potential comes into contact with
another metal having a lower electrode potential, a galvanic cell is set
up and the metal having the higher electrode potential becomes anodic
and goes into solution to a measurable extent. The other becomes
cathodic and does not enter solution
 The extent of galvanic corrosion depends upon the difference in the
electrode potential of the two electrodes and their respective areas
 The greater the difference in the potentials of the cathode and anode, the
greater will be the corrosion
 Also the smaller the area of the anode as compared to the cathode, the
more will be the attack
 Wet, Aqueous or Electrochemical Corrosion
 Electrochemical corrosion takes place in following ways:
o Uniform or General corrosion
o Hydrogen evolution type corrosion
o Oxygen consumption type corrosion
o Galvanic corrosion
o Concentration cell corrosion
o Pitting corrosion
o Stress corrosion
Hydrogen evolution type corrosion:
 It occurs when base metals are in contact with an acidic solution.
 Example:
Anode : Fe →Fe2+ + 2e‒ (oxidation)
Cathode : 2H+ + 2e‒ → H2↑
 The overall reaction is:
Fe + 2H+ → Fe2+ + H2↑
 Simultaneously, metal ion will be produced at the anode while
hydrogen will evolve at the cathode.
 Displacement of H+ ions:
 Metal ions produced at the anode dissolves in the electrolyte while
hydrogen evolves at the cathode. Hence, this type of corrosion
causes “displacement of hydrogen ions from the acidic solution by
metal ions”.
 EC series:
 Li > K > Sr> Ca > Na > Mg > Al > Mn> Zn > Cr(+3) > Fe > Cd> Co
> Ni > Sn> Pb> H >Cu > Hg > Ag > Pd > Ir> Pt > Au
 Oxygen absorption type corrosion:
 It occurs when base metals are in contact with neutral solutions like water with
Dissolved oxygen (DO) or in basic medium
 Rusting of iron is an example of this.
• Anode: Fe → Fe2+ +2e‒ (oxidation)
 These electrons move from anode to cathode and react with the electrolyte and
oxygen giving:
• Cathode: ½O2 + H2O + 2e‒ →2OH‒ (Reduction)
 The Fe2+ at the anode and OH‒ at the cathode diffuse and react to produce
Fe(OH)2: Fe2+ + 2OH‒→ Fe(OH)2 (green)
 If sufficient oxygen is present, Fe(OH)2 gets oxidized to ferric hydroxide (rust):
4Fe(OH)2 + O2 + 2H2O → 4Fe(OH)3 or 2(Fe2O3.3H2O) (reddish yellow rust)
 Galvanic corrosion (differential metal corrosion,
bimetallic corrosion):
 Occurs when two dissimilar metals in the electro chemical
series are in contact with each other (joined by riveting or
welding) and exposed to corroding environment
 The metal with more negative potential (higher in the galvanic
series) will become anode and corrodes. The more anodic
metal corrodes. The electron flows from anode to cathode
 Nature of corrosive environment decides cathodic reaction.
 This can be avoided or minimized by:
o Coupling metals which are close in the electro chemical
series
o Using insulators between two different metals
o Making the cathode metal smaller in area than the anodic
metal
 Differential Metal Corrosion (Galvanic Corrosion)
 When two dissimilar metals are in contact in corrosive environment,
metal with lesser standard reduction potential will act as anode and will
undergo oxidation (corrosion). Metal with higher standard reduction
potential will act as cathode and it will provide surface for reduction of
oxygen

Iron Copper Iron Zinc

Bimetallic couple of Bimetallic couple of

Iron and Copper Iron and Zinc
Steel Copper

Bimetallic couple of
Steel and Copper
 Other examples of differential metal corrosion (galvanic corrosion)
include

 Buried iron pipeline connected to zinc bar

 Steel pipe connected to copper plumbing
 Steel propeller shaft in bronze bearing
 Zinc coating on mild steel
 Lead–tin solder around copper wires
 Table of Electrode Potentials
(Anodic – more basic)
Metal Electrode Potential (V)
ACTIVE: Will corrode
Magnesium -2.40 - act as anode. These
Aluminium -1.76 elements most likely
to be give up CORRODED
Zinc -0.76 electrons END
Chromium -0.65
Iron -0.44
PASSIVE: will not
Nickel -0.23 corrode – act as
Tin -0.14 cathode. These
elements are least PROTECTED
Lead -0.12
likely to give up END
Hydrogen (REF) 0.00 electrons!
Copper +0.34
Silver +0.80 (Cathodic – more noble)
Gold +1.40
 Nature of the metal:
 Position in the galvanic series:
o Advantages of galvanic series over the electrochemical series
(ECS):
 In ECS, since Al forms protective and strongly adhering oxide
layer on its surface, it does not behave as an anode compared
to Fe in the ECS.
 Hence, electrochemical series does not account for the
corrosion of all metals and alloys. Galvanic series depends on
practical environments. Therefore, galvanic series is more
practical and useful in relation with corrosion behavior
 Concentration cell corrosion (Differential aeration corrosion):
 Water-line corrosion:
 Water-line corrosion is observed commonly in steel water tanks and ships floating in seawater for long
periods of time.
 The anodic area moves slowly upwards and gradually the entire tank corrodes with the most intense
corrosion occurring at the water line.
 The metal just below the water line is more anodic (less oxygenated).
 The creep (meniscus) is the one immediately above the water-line which is more oxygenated, acts as
the cathode and is unaffected.
 Amount of creep of the water determines the rate of corrosion.
 Greater the creep the more cathodic the water-line area and more is the rate of corrosion just below the
water line.
 Pitting corrosion:
 Definition: Pitting corrosion is a localized accelerated attack, resulting in the formation of
cavities around which the metal is relatively un attacked.
 The protective oxide layer on the metal surface gets damaged at specific points due to
chemical attack, scratches or cut edges, thereby giving rise to the formation of small anodic
and large cathodic parts.
 Due to rapid penetration of oxygen through some cracks in the oxide film or pin holes on
metallic surfaces, pitting takes place leading to corrosion.
 Pitting start at the oxygen poor region at the bottom of the pit is
 Anodic. Pit tends to deepen leading to premature failure due to fatigue or brittle fracture.
 Examples: Al, Ti and stainless steel undergo pitting corrosion in acidic environment
 The localized form of corrosion is
characterized by the formation of irregularly
shaped cavities on the surface of the metal.
Their diameter and depth depend on several
parameters related to the metal, the medium
and service conditions
 The form of corrosion is often difficult to
detect due to the fact that it is usually
relatively small and may be covered and
hidden by corrosion produced compounds
 Pitting is a localized form of corrosive attack.
Pitting corrosion is typified by the formation
of holes or pits on the metal surface. Pitting
can cause failure, yet the total corrosion, as
measured by weight loss, may be minimal
 Stress corrosion or stress corrosion cracking (SCC):
 Caused by the combined effect of local corrosion(corrosive
environment) and tensile strength(static tensile stresses) on a
metal
 Static tensile stress and specific environments produce
cracking, i.e. a structure that has SCC sensitivity, if subjected to
stresses and then exposed to a corrosive environment, may
initiate cracks and crack grow well below the yield strength of
the metal
 Stresses present in the metal during metallurgical operation
such as poor design, riveting, cold working quenching, welding,
thermal treatment or due to applied load
 Stress corrosion or stress corrosion cracking (SCC):
 In stressed zones the active energy associated with the
metal atoms is very high and very much prone to corrosive
environment. It results in the formation of a crack, which
grows and propagates in the direction perpendicular to the
operating tensile stress until failure occurs or it may stop
after progressing a finite distance.
 In a corrosive environment, the stressed portion atoms are
somewhat displaced creating an anodic zone of anodic
potential
o Examples: Brass in the presence of ammonia
 Stainless steel in the presence of NaOH or chloride
solution at high temperature.
 Ti alloys in nitrogen tetroxide
 Consequently, no corrosion products are visible, making it
difficult to detect or prevent. Fine cracks can penetrate
deeply into the part. (Severe trouble!!! Dangerous!!!)
Dry corrosion Wet corrosion
It occurs in dry condition (absence of moisture). It occurs in wet condition (presence of conducting
medium)
If the corrosion takes place due to direct chemical If the corrosion takes place due to electrochemical
attack (in the absence of moisture), corrosion is attack in presence of moisture or a conducting
known as dry corrosion medium ,corrosion is known as wet corrosion. It
involves formation of electrochemical cell
Explained by absorption mechanism Explained by electrochemical mechanism
It occurs on both heterogeneous and It occurs only on heterogeneous metal surfaces
homogeneous surfaces
The process of corrosion is uniform Corrosion is not uniform. It depends on the size of
anodic part of metal
It is a slow process It is a fast process
Corrosion products accumulate at the place where Corrosion take place at anode but products (rust)
corrosion occurs accumulate (deposit) near or at the cathode
The rate and extent of corrosion depends on the following factors

Nature of metal Nature of Environment

a) Physical state of metal a) pH
b) Purity of metal b) Temperature
c) Electrode potential c) Conductance of medium
d) Nature of surface film d) Humidity
e) Relative areas of the e) Presence of impurities
anodic and cathodic parts
f) Over voltage
 Nature of the metal:
 Position in the galvanic series:
 To account for complete corrosion behavior of metal and its alloy system a
separate chemical series is required called galvanic series.
 When two dissimilar metals are in contact, the more anodic metal (Higher up in
the series) will corrode.
 The extent of corrosion depends on how far apart are the two metals in the
galvanic series
o Example: Galvanic series of some selected metal/alloy systems in sea water.
Cathodic end: Platinum < gold < graphite < titanium < silver < 18-8 Mo stain
less steel (passive) < nickel (passive) < silver solder < monel < bronze <
copper < brasses < tin < lead < 18-8 Mo stain less steel (active) < chromium
stain less steel < cast iron < cadmium < zinc < magnesium : Anodic end
 Electrode potential:
 The electrode potential (E0) value is the main factor which determines
the rate of corrosion
 When two different metals contact are exposed to the atmosphere, it
forms galvanic cells and larger the difference in Eo values greater will be
the corrosion rate
 For example: The potential difference between iron and copper is 0.78 V
which is more than that between iron and tin (0.3 V)
Therefore, iron corrodes faster when it is contact with copper compare to
tin
 Over voltage (over potential):
 In electro chemistry, over potential is the potential difference (voltage)
between a half-reaction's thermodynamically determined reduction
potential and the potential at which the redox event is experimentally
observed. The term is directly related to a cell's voltage efficiency. In an
electrolytic cell the existence of over potential implies the cell requires
more energy than thermodynamically expected to drive a reaction.
 When a metal (eg. Zn) is dipped in 1N sulphuric acid, the initial rate of
corrosion is quite slow since hydrogen evolution takes place on Zn at
0.7V.
 If a few drops of CuSO4 are added, the hydrogen over voltage comes
down to 0.33 V and corrosion rate increases.
 Reduction in hydrogen over voltage increases the rate of corrosion
 Relative areas of cathode and anode:
 When two dissimilar metals are in contact, the rate of corrosion is directly
proportional to the ratio of cathodic part to anodic part.
 If anodic area is small, the corrosion is rapid. If the anodic area is small,
corrosion is more rapid and severe, and localized because the current density
at a smaller anodic area is much greater, and the demand for electrons (by
larger cathodic areas) can be met by smaller anodic areas only by under going
corrosion is more rapid.
 Purity of the metal:
 Purer the metal, lesser is the rate of corrosion.
 Due to impurities, local galvanic cells are formed and anode gets corroded.
 Pure metal is some what resistant to corrosion and impure metal cause
heterogeneity to system and forms small minute galvanic cells and hence
heterogeneity favors corrosion
 Physical state of the metal:
 The rate of corrosion will depend on the physical state of the
metal such as grain size, orientation of crystals, stress etc.
 The smaller the grains in size, the greater will be its solubility
and hence greater will be its corrosion. Different faces of a
metal have different corrosion rate
 Nature of surface film: (Pilling-Bed worth rule):
 Corrosion depends on the nature of surface film i.e. the oxide
film is stable or unstable or volatile or porous or non-porous will
decide the rate of corrosion of the metal
 Passive character of the metal (passivity)
 It is the phenomenon in which a metal or an alloy exhibits a much higher corrosion-
resistance than expected from its position in the electrochemical series.
 Reason: Passivity is due to the formation of a highly protective thin layer on the
surface of that metal. It is a very thin (~30 nm thick) and quite invisible film on the
surface of the metal or an alloy, which makes it more noble.
 Characteristics: This film is non-porous, insoluble and resistant to corrosive
atmosphere. It is self-healing in nature. After it is broken, it will repair it self on re-
exposure in the presence of oxygen
 Passivity is not a constant state, but exists only in certain environment conditions
which tend to maintain thin protective oxide films on their surface.
 Some metals eg. Ti, Ni, Cu, Al, Cr, Co and stainless steel containing Cr are passive
and show resistance to corrosion
They form highly protective oxide layers on their surfaces which gives the metal passive
character and protects it from further corrosion
 Solubility of corrosion product:
 If the corrosion product is soluble in the environment in which the metal
is working, then the corrosion will proceed faster.
 If the product is insoluble in the environment, then the corrosion is very
slow since the corrosion product becomes a protective layer on the
metallic surface .Eg. PbSO4

 Volatility of the corrosion product:

 If the corrosion product is volatile, it evaporates as soon as it is formed
exposing fresh metal for corrosion and hence the corrosion becomes
very rapid and the metal will disappear over a period of time.
 Nature of the corroding environment:
Corrosion can occur at any time during the year depending upon the extent of
following factors.
 Temperature:
o As temperature increases, the rate of all chemical reactions also increases. This
includes corrosion. Increase in temperature results in an increase in the conductance
of the aqueous medium as result conductance of the medium increases.
 Humidity in environment:
o “Critical humidity” is the humidity above which the metallic corrosion rate increases
sharply.
o Critical humidity depends on the nature of the metal as well as the corrosion product.
o When the humidity is higher, the gases eg. CO2, O2 dissolved in the moisture and
provide the conducting medium for electrochemical couple to get formed and anode
corrodes.
 Presence of impurities in the atmosphere:
 Gases like CO2, SO2, H2S and fumes of HCl, H2SO4 which are present in
the industrial are as provide conductive environment for enhancing the
electrochemical corrosion.
 In marine environment, the Cl‒ is responsible for enhanced rate of
corrosion
 Conductance of the corroding environment:
 Corrosion involves electrochemical reactions, and an increase in the electrical
conductivity of the electrolyte will therefore increase the corrosion rate.
 In corrosion of under ground and submerged structures, the conductance of the
medium plays a critical role in corrosion. (humidity!)
 In sea water the chloride content causes rapidly increased conductivity.
 Conductance due to stray currents through the soil will promote the corrosion.
o (Stray currents pertaining to under ground pipelines are direct currents flowing through
the earth from a source
not related to the pipe line being affected. When these stray direct currents
accumulate on a metallic pipeline or structure, they can induce electrolytic corrosion of
the metal or alloy. Sources of stray current include cathodic protection systems, direct
current power trains or street cars, arc-welding equipment, direct current transmission
systems, and electrical grounding systems.)
Formation of oxygen concentration cell:
 If one part of the metal is exposed to higher levels of oxygen, it becomes
cathode and the other part which is exposed to lesser levels of oxygen
will become anode
 This is called oxygen concentration cell which promotes corrosion by
anodic oxidation/dissolution
2H2O + O2 + 4e- → 4OH- (Cathodic reaction-higher O2)
 This OH- will move to the cathode where Fe2+ reacts to form Fe(OH)2
which later converts into rust (Fe2O3.3H2O)
 Buried pipelines, cables etc., experience this kind of electrochemical
corrosion
 Presence of suspended solids in the environment:
 Particles like NaCl, (NH)4SO4 together with moisture act as conductive electrolyte and
enhance the rate of electrochemical corrosion
 Effect of pH: (Pourboux-Evans diagram may be explained)
 Acid medium facilitates more corrosion than neutral and basic media as a general
rule. Generally, acidic medium favors corrosion rate while basic medium corrosion is
normal and highly alkaline medium ceases due to formation protective coating of
hydroxide of metal
 The corrosion rate of Fe in oxygen free water is very slow up to pH 5.0 but in the
presence of oxygen, the corrosion at pH 5.0 enhances greatly
 At pH 4.0, the corrosion rate of Fe is very high since Fe2+ gets oxidized to Fe3+
 Zinc corrodes rapidly in acidic solutions but the rate of corrosion is low in alkaline
medium (pH11.0)
 Aluminium corrodes less at pH5.5 but the rate of corrosion is very high in pH 8.5
 Nature of ions (dissolved salts) present:
 Anions like silicates form insoluble salts in the medium and inhibit further corrosion.
 But, Cl-present in the atmosphere destroy the protective oxide film and enhance
rate of corrosion
 NaCl: the rate of corrosion of steel increases with increasing NaCl concentration
up to a certain point and then decreases with further increase in salt concentration
 The initial increase in the rate of steel corrosion is attributed to the increase in
solution conductivity with increasing NaCl concentration
 The decrease in the rate of corrosion at high NaCl concentration is attributed to the
decrease in the amount of dissolved oxygen [NaCl salt out O2, the phenomena is
known as salting out]
 Acidic salts such as NiSO4, AlCl3, NH4Cl, FeCl2, MnCl2, etc these salts produce
acidic solutions because of hydrolysis. Steel dissolves in these solutions with H2
evolution especially in concentrated solutions
 Alkaline salts such as Na2SiO3, Na3PO4, Na2CO3 and Na2B4O7 (Borax), these salts
produce alkaline solutions because of hydrolysis. Under this condition these salts
form an insoluble iron salt on steel surface which acts as a diffusion barrier and inhibit
corrosion. Alkalinity also favors the formation of a protective oxide film on steel
 Oxidizing salts such as FeCl3, CuCl2, HgCl2 and NaOCl and oxidizing salts such as
Na2Cr2O7, NaNO2 and KMnO4
 The first group of salts is highly corrosive (contain chloride ions) while the second
groups oxidizes the steel surface and inhibit its corrosion
 Effect of solution stirring:
 If the cathodic reaction of the corrosion cell is oxygen reduction (pH 4-10) the rate of
corrosion increases in general with increasing the degree of stirring owing to the
increase in the rate of transfer of dissolved O2 from the solution bulk to the steel
surface.
 If the cathodic reaction is H2 evolution (pH<4) stirring has no effect on the rate of
corrosion because there action is chemically controlled (i.e not diffusion controlled as
in the case of O2 reduction).
 Effect of metallurgical factors:
 As mentioned before in the pH range 4-10 the cathodic reaction of corrosion cells is
O2 reduction, the rate of this reaction depends on the rate of transfer of dissolved O2
from the solution bulk to the surface of the corroding metal. Accordingly in the pH
range 4-10 the rate of corrosion does not depend on the composition of the steel or its
heat treatment
 In acid solution (pH < 4), the cathodic reaction of the corrosion cell is H2 evolution, this
reaction is chemically controlled i.e its rate depends on nature of the metallic surface
and its composition.
 Pure iron dissolves slowly in acids while impure iron containing impurities such as P,
N, S and C dissolves rapidly because these impurities form nobler phase with iron on
which H2 evolution is fast. On the other hand addition of Ni and Cr to iron decreases
its rate of dissolution in acids.
 Water:
 Water can be divided into soft and hard water.
Hard water which contains cations such as Mg2+, Ca2+ is less corrosive
than soft water because Mg2+, Ca2+ combine with the cathodically
formed OH‒ to form an insoluble film of Ca(OH)2 or Mg(OH)2 which
blocks the cathodic sites of corrosion cells and inhibit corrosion
 Department of Chemistry
School of Advanced Sciences
Vellore Institute of Technology
Vellore, 632014
SJT: 504B
Module 3 Corrosion
Dry and wet corrosion - detrimental effects to buildings, machines, devices & decorative art forms, emphasizing Differential
aeration, Pitting, Galvanic and Stress corrosion cracking; Factors that enhance corrosion and choice of parameters to mitigate
corrosion
Module 4 Corrosion Control
Corrosion protection: cathodic protection –sacrificial anodic and impressed current protection methods. Advanced protective
coatings: electroplating and electroless plating, PVD and CVD. Alloying for corrosion protection –Basic concepts of Eutectic
composition and Eutectic mixtures -Selected examples –Ferrous and non-ferrous alloys
Module 5 Electrochemical Energy Systems
Brief introduction to conventional primary and secondary batteries; High energy electrochemical energy systems: Lithium
batteries – Primary and secondary, its Chemistry, advantages and applications. Fuel cells – Polymer membrane fuel cells, Solid-
oxide fuel cells- working principles, advantages, applications. Solar cells – Types – Importance of silicon single crystal,
polycrystalline and amorphous silicon solar cells, dye sensitized solar cells - working principles, characteristics and applications.
 Corrosion can be controlled by preventing formation of galvanic cells. By retarding
either the anodic or cathodic reactions the rate of corrosion can be reduced
 This can be achieved in several ways. The commonly available methods for
controlling corrosion are:
o Changing the environment
o Design and selection of suitable materials
o Protective coatings:
• Metal coatings: anodic and cathodic
• Surface conversion coatings: anodizing, phosphating and chromating
• Paints and enamels
• Vacuum coatings process (physical vapor deposition (PVD), metal spray
and chemical vapor deposition (CVD))
o Cathodic protection
o Anodic protection
o Corrosion inhibitors
 What is Cathodic Protection?
 The principle involved in this method is to force the metal to be
protected to behave like a cathode thereby corrosion doesn’t occur
 Cathodic protection is an electrochemical technique in which a cathodic
potential is applied to a metal structure in order to prevent corrosion from
taking place
 The material to be protected is supplied with an external cathodic current
 The electrochemical potential of the protected material is moved in a negative
direction to the immunity area
 The material is completely protected when it reaches the Protection Potential
 Cathodic protection is a method of corrosion control that can be applied to
buried and submerged metallic structures
 Cathodic protection can be applied in two ways:
 Sacrificial anode or galvanic protection
 Impressed current cathodic protection

Cathodic Protection

Sacrificial Anode

Impressed Current
 Sacrificial anode/galvanic protection:
 In this method the metallic structure to be protected is connected by a wire to a more anodic
metal, so that all the corrosion is concentrated at this more active metal implies the more
active metal sacrifices itself and gets corroded slowly. While the parent structure which is
cathodic is protected .The more active metal so employed is called “sacrificial anode”
 Whenever the sacrificial anode is consumed completely, it is replaced by a fresh one. Metal
commonly employed as sacrificial anodes are Mg, Zn, Al and their alloys. Sacrificial anodes
are used for the protection of buried pipe lines underground cables, marine structures, ship
hulls, water tanks etc
 The method involves the use of sacrificial anode in contact with metal structure being
protected usually made of Fe, Cu or brass
 In this method, the metal structure is protected by connecting it with a piece of more anodic
metal (active metal) from the galvanic series
 The active metal behaving as anode gets corroded thereby sacrificing itself
 Metals like Mg, Zn, Al are more active or more anodic and provide electrons to the metal being
protected thereby converting the anodic sites on the metal structure to cathodic sites
 Sacrificial anode or galvanic protection

Bentonite is an absorbent aluminium phyllosilicate clay consisting mostly of

montmorillonite (Na,Ca)0.33(Al,Mg)2(Si4O10)(OH)2·nH2O)
 Advantages:
 No external power is required
 Easy to install
 Minimum of cathodic interference problems
 Anodes can be readily added
 Minimum of maintenance required
 Uniform distribution of current
 Disadvantages:
 More than one anode is required some times
 It does not work properly in high corrosive environment
 Sacrificial anode must be replaced periodically as and when it is
consumed
 The metal structure being protected is connected to an insoluble metal anode (lower in
the galvanic series: stainless steel, Pt or even graphite). Early anodes were made
from scrap steel but most modern ICCP systems use lead silver alloy, titanium or
niobium.
 When an impressed current from a DC current source (like battery or rectifier) is
applied in the direction opposite to the corrosion current, the metal structure being
protected now behaves as cathode and hence protected. The insoluble metal behaves
as anode.
 Exposed surface area or length of the anode determines how many square feet of
cathode like steel it can protect.
 A buried pipeline is connected to the negative terminal of a rectifier or battery (power
supply) and the anode to the positive terminal.
 Both terminals must be well insulated; otherwise, current leakage (stray-current)
occurs and the structure may not be protected adequately
 The significance of the cathodic protection setups
shown in the following figure is that the current flows
from the rectifier to the inert anode (graphite or
platinum coated titanium) through the soil (electrolyte)
to the cathode.
 When this method is used in soil, the anode is usually
in a “back-fill” (coke or gypsum) or conducting
grounding bed so as to increase the electrical contact
with the protected cathode through the surrounding
soil.
 For structures immersed in seawater, the anodes may
be platinum-coated titanium or high-silicon cast iron.
 The purpose of the rectifier is to convert alternating
current (ac) to uniform direct current (dc).
 Applications: protection of ship-hulls, river dam gate,
steel bridge, large buried oil or water pipes,
transmission towers, etc.
 The surface of the base metal coated with another metal (coating metal) is
called metallic coatings. Metallic coatings are broadly classified into anodic
and cathodic coatings
 Anodic coatings:
 The metal used for the surface coating will be more anodic than the base metal
which is to be protected
o For example, coating of Al, Cd and Zn on steel surface are anodic, because
their electrode potentials are lower than that of the base metal iron. Therefore,
anodic coatings protect the underlying base metal sacrificially
 The formation of pores and cracks over the metallic coating exposes the base
metal and a galvanic cell is formed between the base metal and coating metal.
The coating metal dissolves anodically and the base metal is protected
 Cathodic Coatings:
 Cathodic coatings are obtained by coating the base metal with more noble metal (i.e.
metals having higher electrode potential like Sn, Au, Ag, Pt etc.) than the base metal.
They protect the base metal as it now behaves as cathode having higher corrosion
resistance than the base metal due to cathodic nature.
 Cathodic coating protects the base metal only when the coating is uniform and free
from pores.
 The formation of pores over the cathodic coating exposes the base metal (anode) to
environment and a galvanic cell is set up. This causes more damage to the base
metal.
 The most important step before protective coatings are applied to metals is surface
preparation
 Surface preparation is a process to remove rust, oxide scales, oil, grease, dust etc
 If these materials are not removed, the protective coating will not be smooth, uniform,
cohesive and will not adhere to the metallic surface
 Hence, mechanical and electrical methods are used to prepare the surface of the
metallic article to be coated clean and free of these impurities
 Mechanical cleaning, sandblasting, solvent cleaning, alkali cleaning, acid pickling and
etching are normal processes followed for surface preparation of the article to be
coated
a) Mechanical cleaning:
 Useful for removing loose scales and rust
 Hammering, wire brushing, grinding, pneumatic blasting, polishing are the methods
commonly used
b) Sand blasting:
 Fine sand or abrasive material along with air stream at a
pressure of 25-100 atm is impinged on the metal surface
 This will produce enough roughness for good adherence of the
protective coating
 Though the method is expensive, it is quite fast and useful
c) Solvent cleaning:
 Solvent cleaning is mainly used to remove oil, grease and rust
from the base metal
 Alcohols, xylene, toluene, chlorinated hydrocarbons are used
 Hot water cleaning is followed after solvent cleaning is done
d) Alkali cleaning:
o Cleaning of the base metal with sodium hydroxide, trisodium phosphate
(Na3PO4), sodium silicate, soda ash (Na2CO3) etc., is carried out to
remove old paint coatings soluble in alkaline medium
o After alkali cleaning, washing is done with 1% chromic acid solution
e) Acid pickling and etching:
o Base metal is dipped inside the acid solution at higher temperature for
long periods of time
o This treatment ensures cleaning of the base metal surface free from all
kinds of impurities including oils, greases, rust etc.
o H2SO4, HCl, HF, H3PO4, HNO3 are the acids commonly used for pickling
and etching
Methods of application of metallic coatings:
Hot Dipping
 Hot dipping process is applicable to the metals (Base metal) having
higher melting point than the coating metal
 It is carried out by immersing a well cleaned base metal in a bath
containing molten coating metal and a flux layer
 The flux cleans the surface of the base metal and prevents the oxidation
of the molten coating metal. Eg: Coating of Zn, Pb, Al on iron and steel
surfaces
The most widely used hot dipping processes are
• (a) Galvanizing
• (b) Tinning
 Galvanizing
• Galvanizing is a process in which the iron article is protected from corrosion by coating
it with a thin layer of zinc
• It is the anodic protection offered by the zinc
• In this process, at first iron or steel is cleaned by pickling with dil. H2SO4 solution for
15- 20 minutes at 60-90 ⁰C. In pickling any scale, dirt, oil, grease or rust and any other
impurities are removed from the metal surface
• The article is washed well and then dried
• It is then dipped in bath of molten zinc maintained at 425-430 oC.
• The surface of bath is kept covered with ammonium chloride – flux to prevent oxide
formation. The article is covered with a thin layer of zinc when it is taken out of bath.
• It is then passed through a pair of hot rollers, which removes any excess of zinc and
produces a thin film of uniform thickness
• Then it is annealed and finally cooled slowly
 Applications:
• Galvanizing is widely used for protecting iron exposed to the atmosphere (roofs, wire
fences, pipes etc.) Galvanized Iron [GI] sheets are not used for keeping eatables
because of the solubility of zinc is higher in acidic pH’s
 Galvanization of Steel
 Dip steel sheet in molten zinc. Get a pretty thin coating
 Zinc will be anode. Steel exposed by crack is the cathode. Since we
have a huge anode having to be served by a small cathode, corrosion
rate will be slow
Tinning
• The process of coating tin metal over the iron or steel articles to protect them from undergoing
corrosion is known as tinning.
• Tin is a noble metal and therefore it possess more resistance to chemical attack. In this
process, iron sheet is treated in dilute sulphuric acid (pickling) to remove any oxide film, if
present.
• A cleaned iron sheet is passed through a bath of ZnCl2 molten flux followed by molten tin and
finally through a suitable vegetable oil. The ZnCl2 flux helps the molten metal to adhere to the
base metallic surface. A cathodic protection on iron sheets are offered by the tin coatings.
• Palm oil protects the tin coated surface against oxidation.
• Finally the sheet is passed through rollers to remove excess of tin and produce thin layer of tin
coatings with uniform thickness
 Applications:
• Tin metal possess good resistance against atmospheric corrosion. Tin is non-toxic and widely
used for coating steel, copper and brass sheets
• The containers coated with tin are used for storing food stuffs, ghee, oil etc and packing food
materials.
• Tinned copper sheets are used for making cooking utensils and refrigeration equipment
 Electroplating:
 Electro plating is a process that passes DC electric
current through an electrolytic solution contain
soluble salt of the coating metal to reduce
dissolved coating metal cations so that they form a
thin metal or alloy layer coating over another metal
(as cathode)
 The term is also used for electrical oxidation of
anions onto a solid substrate, as in the formation
silver chloride on silver wire to make silver/silver-
chloride electrodes
 The process used in electroplating is called
electrode position. It is analogous to a galvanic cell
acting in reverse. The part to be plated is the
cathode of the circuit
 Both ferrous and non-ferrous metals can be plated
with Ni, Cr, Cu, Zn, Pb, Al, Ag, Au, Sn etc
 Electroplating DC power supply
 Theory:
 If the anode is made of coating metal itself in the electrolytic cell, during
electrolysis, the concentration of electrolytic bath remains unaltered
 Since the metal ions deposited from the bath on cathode (Base metal)
are replenished continuously by the reaction of free anions with the
anode
 If the anode is made of an inert material like graphite, electrolyte should
be added continuously to maintain the concentration of the coating metal
ions in the bath
 Process:
Let us consider the electroplating of Copper.
a. Base metal (object) is treated with dil. HCl or dil. H2SO4 to remove oxide layers
b. Object to be coated acts as cathode. Copper foil is taken as the anode. Copper
sulphate is used as an electrolyte
c. When a direct current is passed from an external source, the copper ions migrate
towards cathode and get deposited over the surface of base metal (object) in the form of
a thin layer
Anode: Cu(s) →Cu2+(aq) + 2e-
Cathode: Cu2+(aq) + 2e- →Cu(s)
d. Low temperature, medium current density, low metal ion concentration are maintained
for better electro-plating.
Temperature: 20-40 ºC (low temp for brighter and smooth surface)
Current density: 20-30 mA/cm2
Copper sulphate : 0.44 Molar solution
 Objectives of electroplating
 Electro plating can be done on (a) metals and (b) non-metals. Electroplating is
primarily used to change the surface properties of an object (e.g. abrasion and
wear resistance, corrosion protection, lubricity, aesthetic qualities, etc.) but may
also be used to build up thickness on under sized parts or to form objects by
electro forming
o A decorative appearance
o An improved corrosion resistance
o An improved heat resistance
o An improved surface hardness.
o To provide good electrical and thermal conducing surface.
o To provide chemical resistance.
o To increase thermal resistance.
o To increases good optical reflectivity.
o In the manufacturing of electrical and electronic component
 Objectives of electroplating------
 Electroplating is mainly used in automobile, aircraft, refrigerator, chemical and
electrical appliances etc
 On Metals:
 To increase the corrosion/chemical/wear/heat resistance of the electro plated metal
 To improve surface properties (surface hardness, electrical conductivity, thermal
conductivity, optical reflectivity)
 To increase the decorative value of the metal
 On Non-Metals (plastics, wood, glass, etc.):
 To decorate the surfaces.
 To make the surface conductive (by depositing a metal film).
 To improve optical performance.
 To increase strength
 Electroplating setup:
 Electroplating bath solution:
o It contains a suitable salt solution of the metal being plated. It also contains other
additives.
 Solution of MxXm (salt) in water.
o Anode: It is positive electrode in the electrolysis, where metal ions are created. It
should be electrically conducting. It may be an inert electrode.
M(s) → Mm+(aqueous) + m e-
or other oxidation reaction.
o Cathode: It is negative electrode in the electrolysis, where metal ions gets deposited
and it is an article to be plated.
Mm+(aqueous) + m e-→ M(s) (reduction reaction)
o DC-power supply: The +v terminal of the power supply is connected to the anode
and the –v terminal is connected to the cathode. The electricity passes from the anode
to the cathode.
 Cleaning of the article is essential for strong adherence of the electroplating:
- Scraping, grinding, sand blasting, wire brushing, solvent cleaning and acid pickling are used for
surface cleaning.
- A well cleaned and properly pre treated surface of any material to be electroplated is necessary
for obtaining the coating of long life.
 Concentration of the electrolyte is another important factor:
- Low concentration of metal ions will give uniform coherent deposition.
- To maintain low conc. of metal ions, complexing agents are added to the electrolyte.
 Thickness of the deposition should be optimised to get a strong and adherent
deposition:
- For corrosion protection multiple coatings are given to get impervious coating without any
discontinuity.
- For decorative purpose, thin coating is given.
 Current density
- Current density is the current per unit area of the article being plated (amps cm-2).
- The C.D should be maintained at optimal level to get uniform and adherent deposition.
 Additives to electrolytic bath
- Additives to electrolyte are added in small quantities to get strong adherent
deposition
- Commonly used additives are gelatin, glue, glycine, boric acid etc. and brighteners
for bright plating.
 pH of the bath
- For a good electro deposit, the pH of the bath must be properly maintained. For
most plating baths, pH ranges from 4 to 8
 Method of Electroplating
- Method depends upon the type of metal to be electroplated, the size and type of
article to be electroplated.
- Its main objectives and economics are also considered.
 Composition of the electrolytic bath:
 Organic additives: Certain organic compounds added to the plating baths to
have a remarkable influence on the nature of electro-deposit.
 They modify the structure, morphology and properties of the electro-deposit.
These include brighteners levellers, structural modifiers and wetting agents.
 Brighteners: To produce “microscopic fine deposits” which reflect the light on
the surface. Brighteners plate over the metallic surface by encouraging the
plating parallel to the surface and simultaneously inhibiting the plating
perpendicular to the surface. Examples: aromatic sulphonates or sulphones,
molecules containing C≡N, N=C=S (or) C=O groups Coumarin, thiourea.
 Levelers: To produce a level deposit by getting itself adsorbed at regions
where rapid diffusion of ions may occur. For Ni plating, sodium allyl sulphate is
used as a leveler.
Choice of the electrolyte:
 It should be a good conductor and highly soluble. It should not under go
hydrolysis, oxidation, reduction or any other chemical changes. It should
possess sufficient covering power.
 Some times single electrolyte can not satisfies all the above requirement.
Usually a mixture of electrolytes are used. Example: In copper plating,
CuSO4 is used along with dilute H2SO4.
 Method of Electroplating:
 Method depends upon the type of metal to be electroplated, the size and
type of article to be electroplated.
 Its main objectives and economics are also considered
 Electroless plating
a. The method of deposition of a metal from its salt solution on a catalytically active
surface by a suitable reducing agent without using electrical energy is called electroless
plating.
b. This process is also called autocatalytic plating, since it takes place on catalytic
surface.
c. The metallic ions (M+) are reduced to the metal with the help of reducing agents(R-).
When the metal(M) is formed, it gets plated over a catalytic surface.
 Advantages :
1. Electrical energy is not required.
2. Even intricate parts (of irregular shapes) can be plated uniformly.
3. There is flexibility in plating volume and thickness.
4. The process can plate recesses and blind holes with stable thickness.
5. Chemical replenishment can be monitored automatically.
6. Plating on articles made of insulators (like plastics) and semiconductors can easily be
carried out.
7. It is a pore free coatings with very high hardness , corrosion resistance and wear
resistance values
 Electroless plating, also known as chemical or auto-catalytic plating, is a non-
galvanic plating method that involves several simultaneous reactions in an aqueous
solution, which occur without the use of external electrical power.
 The process is a chemical reaction and is autocatalytic.
 It is mainly different from electroplating by not using external electrical power.
 The deposition rate is normally 12.5 – 25 um (.0005 – .001 in).
 The plating thickness tends to be uniform compared to electroplating due to the
absence of electric fields and the associated problems in making them uniform.
 Typically nickel and copper are used in electroless platings.
 In the case of nickel, the deposits are dense, relatively hard and brittle.
 Electroless Nickel is not as bright as electroplated, easy to solder and braze, but
difficult to weld.
 Autocatalytic platings are widely used for machine frames, base plates, fixtures, some
machine parts where metal-to-metal wear applications are needed and the
conventional oils and greases can not be used.
Physical vapour deposition (PVD)
and
Chemical vapour deposition (CVD)
 Industrial coating processes can be broadly classified into three
groups:
 Physical vapour deposition (PVD)
 Chemical vapour deposition (CVD)
 Metal spray
 What is PVD?
 It is a thin-film coating process which produces coatings of pure metals, metallic
alloys and ceramics with a thickness usually in the range 1 to 10 μm
 Physical vapor deposition, as its name implies, involves physically depositing
atoms, ions or molecules of a coating species on to a substrate
 The surface of substrate and target should have accessibility [line of sight] to
receive coatings
 PVD is a process of depositing some material atom-by-atom, molecule-by-
molecule or ion-by-ion on a solid substrate under vacuum conditions
 The physical vapour deposition technique is based on the formation of vapour of
the material to be deposited as a thin film
 The process of thin film coating by means of PVD is to apply electric current and
voltage or bombardment of inert gas to ionize the desired material. Once the
material is ionized into vapour form it is the deposited on the desired substrate
PVD is of three main types:
 Thermal evaporation (vacuum thermal evaporation)
 Sputtering
 Ion plating
o All these three processes are performed under vacuum. Vacuum
evaporation is also known as vacuum deposition and this is the process
where the material used for coating is thermally vaporized and then
proceeds by potential differences to the substrate with little or no
collisions with gas molecules. Normal vacuum levels are in the medium
to high vacuum range of 10-5 to10-9 Torr.
 How does PVD process work?
 PVD processes involved five steps:
1. Evaporation, 2. Transportation, 3. Reaction, 4. Deposition, 5. Rotary evaporation
1. Evaporation: A target is melted or bombarded by a high energy source such as a beam of
electrons or ions. The atoms are dislodged from the surface of the target, and get ‘vaporized’
2. Transportation: Movement of ‘vaporized’ atoms from the target to the substrate
3. Reaction: In order to coat metal oxides, nitrides, carbides, etc, the atoms from the target
will react with an appropriate gas (reactive gases such as oxygen, nitrogen and methane)
during the transportation stage to form the metal oxides, nitrides, etc
In cases where the coating on the substrate should be only the pure metal, then this step
would not be applicable
4. Deposition: This is the process of coating build-up on the substrate surface. More the
time, higher the coating thickness
5. Rotary evaporation: A common step used to ensure uniform coating is to rotate and tilt
the sample during evaporation. This technique is sometimes called rotary evaporation
 PVD-1: Thermal evaporation:
 Thermal Evaporation method involves the
deposition of a thin film on a substrate
according to the following sequence of steps:
 The target material to be deposited is
converted into vapor by physical means.
 The vapor is transported across a region of
low pressure to the substrate.
 The vapor undergoes condensation on the
substrate to form the thin film.
 Thermal evaporation is a low cost process,
but all these processes are normally batch
processes because of vacuum chamber
requirements
 PVD-2: Sputtering:
 What is Sputtering?
 Sputter deposition are methods of depositing thin films by sputtering.
They involve ejecting material from a “target” that is a source onto a
“substrate” such as a metal or a silicon wafer
 Sputtering is done by bombarding a target material with a charged gas
(typically argon) which releases atoms from the target and these atoms
condense over the nearby substrate to make a thin film. It takes place
inside a magnetron vacuum chamber under low pressure.
 If the surface of a target (containing coating materials) is bombarded by atomic
particles of sufficiently high energy, individual atoms of the target materials may
acquire enough power due to the collision that they are ejected from the
target’s surface by transfer of momentum. This is the process of dislodging
atoms from the target material is known as sputtering.
 The most convenient form of high energy particle is an ionized gas, such as
argon, energized means of an electric field to form a plasma
 The dislodged atoms will have substantial kinetic energies, and some will fly to
the substrate to be coated and stick there.
 As a PVD process, sputtering involves bombardment of the cathodic coating
material with argon ions (Ar+), causing surface atoms to escape and then be
deposited onto a substrate, forming a thin film on the substrate surface. The
ionized form of inert gas (Ar+) is known as plasma
• Example : TaSi2 – x coatings for electro-
magnetic applications. [x = 0.01 - 0.1]
• The simple set-up of sputtering is given
below:
• The target atoms hit the substrate coming
from all directions.
• Disadvantages:
• The coatings are having very poor
crystallinity.
• Formation of holes inside the coating matrix
due to very energetic hitting of target atoms.
 Mechanism of sputtering :
 The sputtering methods are characterized by a non thermal mechanism for the transfer of the
solid target material into the vapor phase. In the sputtering method, the ejection of atoms from
the cathode surface by impinging the energetic positive ions of noble gases such as helium,
argon, neon, krypton, at a reduced gas pressure under high voltage gives rise to the
sputtering.
 This process involves a momentum-transfer between the impinging positive ions and the
cathode surface atoms as a result of which a physical removal of atoms takes place. The
sputtering yield is defined as ratio between the mean number of emitted atoms to the number
of incident ions on the target surface.
 Sputtered atoms ejected from the target have a wide energy distribution, typically up to tens of
eV. The sputtered atoms and ions (typically only a small fraction, ~1% of the ejected particles
are ionized) can ballistically fly from the target in straight lines and impact energetically on the
substrates. The sputtering gas is often an inert gas such as argon. For efficient momentum
transfer, the atomic weight of the sputtering gas should be close to the atomic weight of the
target, so for sputtering light elements neon is preferable, while for heavy elements krypton or
xenon are used. The compound can be formed on the target surface, in-flight or on the
substrate depending on the process parameters.
 Sputtering is a process whereby particles are
ejected from a solid target material due to
bombardment of the target by energetic particles.
 Sputtering is done either using DC voltage (DC
sputtering) for metals or using AC voltage (RF
sputtering) for dielectric materials and polymers.
 The gas atoms are ionized and they bombard the
material to be coated.
 The energy of imposing ions cause atoms of the
target material to be sputtered off and they are
transported through the plasma to form a coating.
 Direct current sputtering is used when the target
is electrically conductive. Radio-frequency
sputtering, which uses a RF power supply is used
when the target is a non conductor such as
polymer
 Sputtering offers the following advantages over other PVD methods used in VLSI
fabrication:
1) Sputtering can be achieved from large-size targets, simplifying the deposition of thins with
uniform thickness over large wafers;
2) Film thickness is easily controlled by fixing the operating parameters and simply adjusting the
deposition time;
3) Control of the alloy composition, as well as other film properties such as step coverage and
grain structure, is more easily accomplished than by deposition through evaporation;
4) Sputter-cleaning of the substrate in vacuum prior to film deposition can be done;
5) Device damage from X-rays generated by electron beam evaporation is avoided
 However, has the following disadvantages too:
1) High capital expenses are required;
2) The rates of deposition of some materials (such as SiO2) are relatively low;
3) Some materials such as organic solids are easily degraded by ionic bombardment;
4) Sputtering has a greater tendency to introduce impurities in the substrate than deposition by
evaporation because the former operates under a lesser vacuum range than the latter.
 PVD-3: Ion plating:
 Ion plating is the combination of thermal evaporation and
sputtering methods. sometimes called ion assisted
deposition (IAD) or ion vapor deposition (IVD)
 Metal is evaporated thermally and plasma is established to
ionize the evaporated species
 Evaporated metal ions bombard the substrate with energy.
 They physically implant into the substrate to produce an
extremely strong coating bond
 Sputter and ion plated coatings are used in design for very thin
films for electrical, optical and wear-resistant applications
 The wear properties of tools are greatly enhanced by hard thin
film coatings
 Sputtered coating processes produce microscopic modules of
diameter of several micrometers and they are called macros.
These macros are undesirable for metal to metal sliding
systems. On the other hand they are usually beneficial to
cutting tools
 Advantages of PVD-Sputtering over other PVD methods:
 Able to deposit a wide variety of metals, insulators, alloys and
composites. Sufficient target material for many depositions
 Replication of target composition in the deposited films
 Can use large area targets for uniform thickness over large substrates.
 Better film quality and step coverage than evaporation
 Film thickness is easily controlled by adjusting the deposition time
 Control of the alloy composition and grain structure is more easily
accomplished than by thermal evaporation method
 Capable of in-situ cleaning (Sputter-cleaning of the substrate) prior to film
deposition by reversing the potential on the electrodes
 Device damage from X-rays generated by electron beam evaporation is
avoided
 Disadvantages of PVD-Sputtering over other PVD methods:
 Substrate damage due to ion bombardment or UV generated by plasma. Some
materials such as organic solids are easily degraded by ionic bombardment
 Higher pressures 1 –100 m torr (<10-5 torr in evaporation), more contaminations
unless using ultra clean gasses and ultra clean targets. Sputtering has a
greater tendency to introduce impurities in the substrate than deposition by
evaporation
 High capital expenses are required
 The rates of deposition of some materials (such as SiO2) are relatively low
 Most of the energy incident on the target becomes heat, which must be
removed.
 Difficult to deposit uniformly on complex shapes such as turbine blades.
 High performance thick coatings are hard to produce due to high internal
residual stress levels.
 Applications of PVD coatings:
 Medical implants:
 Physical vapor deposition (PVD) has become widely used to
deposit wear-resistant thin-film coatings on a variety of medical
devices, including orthopedic implants, pacemakers, surgical
instruments, orthodontic appliances and dental instruments. The
value of PVD technology rests in its ability to modify the surface
properties of a device without changing the underlying material
properties and biomechanical functionality.
 TiN, ZrN, CrN, TiAlN, are acceptable for external and internal
medical devices that contact bone, skin tissue or blood. PVD
coatings on medical devices must also be compatible with the
sterilization process. Both TiN and CrN resist corrosion that can
be caused by steam and chemical autoclaving.
 TiN has been in clinical use on orthopedic implants for more than
9 years in north America and Europe. The most common
applications involve total joint replacement with Co-Cr-Mo or Ti-
6-4 alloy implants. TiNis used for hip, knee, shoulder and ankle
implants.
 Chemical vapor deposition or CVD is a generic name for a group of processes that
involve depositing a non-volatile solid film on a substrate by the reaction of vapor
phase chemicals (reactants) that contain the required constituents from a gaseous
phase and is similar in some respects to physical vapor deposition (PVD).
 The reactant gases are introduced into a reaction chamber and are decomposed and
reacted at a heated surface to form the thin film.
 A number of forms of CVD are in wide use. These processes differ in the means by
which chemical reactions are initiated (e.g., activation process) and process
conditions.
WF6(g) + 3H2→W(s)+ 6HF(g)
B2H6(g) → 2 B(s) + 3H2(g)
Ni(CO)4(g) → Ni(s) + 4CO(g)
Si(CH3)Cl3(g) → SiC(s) +3HCl(g)
TiCl4(g) + CH4 → TiC(s) + 4HCl(g)
TiCl4(g) + 1/2N2 + 2H2 → TiN(s) + 4HCl(g)
Al2Cl6 + 3CO2 + 3H2 → Al2O3(s) + 3CO + 6HCl(g)
 In CVD, precursor gases (often diluted in carrier gases) are delivered into the reaction
chamber at approximately ambient temperatures. As they pass over or come into
contact with a heated substrate, they react or decompose to form a solid phase which
are deposited onto the substrate. The substrate temperature is critical and can
influence what reactions will take place. Example: Ni(CO)4 for the deposition of Ni.
 PVD differs in that the precursors are solid. The material to be deposited being
vaporized from the solid target. The vaporized solid is deposited onto the substrate.
 CVD Apparatus
 A CVD apparatus will consist of several basic components:
o Gas delivery system – For the supply of precursors to the reactor chamber
o Reactor chamber – Chamber within which deposition takes place Substrate loading
mechanism – A system for introducing and removing substrates, mandrels etc
o Energy source – Provide the energy/heat that is required to get the precursors to
react/decompose.
o Vacuum system – A system for removal of all other gaseous species other than those
required for the reaction/deposition.
o Exhaust system – System for removal of volatile by-products from the reaction chamber.
o Exhaust treatment systems – In some instances, exhaust gases may not be suitable for
release into the atmosphere and may require treatment or conversion to safe/harmless
compounds.
o Process control equipment – Gauges, controls etc to monitor process parameters such as
pressure, temperature and time. Alarms and safety devices would also be included in this
category
 Many materials may be deposited using CVD and related techniques. Metals, oxides, sulfides,
nitrides, phosphides, arsenides, carbides, borides, silicides…
o Example: Preparation of TiB2, melting point 3325°C. May be deposited by CVD at 1000°C:
TiCl4+ 2BCl3+ 5H2→ TiB2+ 10 HCl
 CVD can be used to produce synthetic diamond by creating the circumstances necessary for
carbon atoms in a gas to settle on a substrate in crystalline form.
 CVD of diamond has received a great deal of attention in the materials sciences because it
allows many new applications of diamond that had previously been considered too difficult to
make economical. CVD diamond growth typically occurs under low pressure (7.5-203 Torr)
and involves feeding varying amounts of gases into a chamber, energizing them and providing
conditions for diamond growth on the substrate. The gases always include a carbon source,
and typically include hydrogen as well, though the amounts used vary greatly depending on
the type of diamond being grown. The energy source (hot filament) is intended to generate a
plasma in which the gases are broken down and more complex chemistries occur. The actual
chemical process for diamond growth is still under study and is complicated by the very wide
variety of diamond growth processes used.
 Colorless gem cut from diamond grown by chemical vapor
deposition
 Principle:
 Fundamental principle is that a chemical reaction takes place between
the source gases.
 The product of that is a solid material that condenses on all surfaces
inside the reactor.
 Precursor gases (often diluted in carrier gases) are delivered into the
reaction chamber at approximately ambient temperatures
 Advantages of CVD over PVD:
 One of the primary advantages is that CVD films are generally quite
conformal, i.e., that the film thickness on the sidewalls of features is
comparable to the thickness on the top. In, contrast, physical vapor
deposition (PVD) techniques, such as sputtering or evaporation, generally
require a line-of-sight between the surface to be coated and the source
 Another advantage of CVD is that, in addition to the wide variety of
materials that can be deposited, they can be deposited with very high purity.
 This results from the relative ease with which impurities are removed from
gaseous precursors using distillation techniques.
 Other advantages include relatively high deposition rates, and the fact that
CVD often doesn’t require as high a vacuum as PVD processes
 CVD Applications:
 A newer process known as plasma assisted
chemical vapors deposition. This process is
used to apply diamond and diamond like
carbon coatings.
 Silicon carbide barrier coatings are applied on
plastic films and semiconductors.
 CVD is used to produce bulk shapes of high
purity silicon carbide. Reactants are deposited
on a chamber wall to a thickness in terms of
milli meters.
 Thin-film coatings are key to the manufacture
of many electronic devices. They involve the
application of dopant, sealant and other
microelectronic paste.
 Alloying for corrosion protection

 Basic concepts of Eutectic composition and Eutectic mixtures

 Selected examples – Ferrous and non-ferrous alloys

 Alloy is a homogeneous substance formed by mixing two or more elements, at least one of
them being a metal
 Alloys are of three types:
a) Alloys which are formed by two or more metals; eg. Cu-Zn (Brass)
b) Alloys which are formed between a metal and a non-metal; eg. WC
c) Alloys which are formed between mercury and another metal; eg. Zinc amalgam
 Characteristics of alloys:
a) Hardness and tensile strength of the alloy is higher then its constituents
- Tensile strength of iron is increased by 10 fold by alloying with 1% Carbon
b) Melting points of alloys is generally lower than the melting points of the constituents
- Solder melts at 183 ⁰C while its constituents Pb melts at 327 ⁰C and Sn melts at 232 ⁰C
c) Alloys are less conductive than pure metals
- Small quantity of impurities in copper will reduce its conductivity
d) Colour of alloy gets modified as compared to the individual metals
- Red coloured copper and Silver white Zinc will get modified to Yellowish brown in brass
e) Chemical Properties are modified i.e. either enhanced or depressed
- Dissolution of alloy in HCl is lower compared to its constituent metals
 Characteristics of alloys:
f) Corrosion:
o The most useful property of alloying is its ability to resist
corrosion.
o Generally alloys are more resistant to corrosion than pure metals.
Eg. Stainless steel (an alloy of Fe, C, Ni and Cr) is not corroded by
atmospheric conditions though pure Fe corrodes heavily in moist
environment.
g) Solidification character of an alloy is more suitable for making a
casting

 Purpose of alloying is to get

a) Increased mechanical strength
b) Reduced chemical reactivity
c) Increased/Reduced electrical conductivity
d) Increased corrosion protection
 Significance of Alloying
 The alloy coatings bring quality, reliability and durability for process
vessel linings and pipe linings along with the surface protection of
components and equipment against extreme conditions such as high
temperature, higher abrasion or high acidity surroundings.
 Examples
 Lead-Tin alloys are used for soldering purpose
 Nickel alloys are known for resistance to extreme corrosion and high
temperature requirements.
 Copper-nickel alloys are used for anti-fouling resistance.
 Iron-nickel alloys show low thermal expansion.
 Nickel-titanium alloys exhibit shape memory.
 Phase The homogeneous, physically distinct and mechanically separable
portion of a system which is separated from other parts of the system by
definite boundary surface
 Examples:
o (1) Completely miscible gases (N2+O2) and liquids (H2O+alcohol): Single
phase (P = 1)
o (2) Pair of immiscible liquids (water+kerosene): Two phases
o At specified condition all three phases of water coexists (P=3)
o A heterogeneous system of equilibrium, such as CaCO3 ↔ CaO + CO2
There are two solid phases and one gaseous phase (P = 3)
 The three fundamental phases of matter are solid, liquid, and gas (vapour),
but others are considered to exist, including crystalline, colloid, glassy,
amorphous, and plasma phases.
Gibbs' Phase Rule
 When an equilibrium between any number of phases is influenced only by temperature,
pressure and concentration, but not influenced by gravity, or electrical or magnetic
forces or by surface tension, then the number of degree of freedom of the system is related
to the number of components and of phases by the phase rule equation:

P + F = C + 2
P = Number of phases in the system
F = Number of degrees of freedom in the system
(also referred to as the variance of the system)
C = Minimum number of components
 It provides the theoretical foundation for characterizing the chemical state of a system and
predicting the equilibrium relations of the phases present as a function of pressure and
temperature
Phase Rule
In a heterogeneous system in equilibrium, the number of degrees of freedom plus the
number of phases equal the number of components plus 2
F+P=C+2
In those cases, where the pressure variations are small and negligible as in many
physico chemical investigations carried out under atmospheric pressure, the equation
is reduced to
F=C–P+1
In those cases when the extent of surface affects the equilibrium, the number of
degrees of freedom increases by unity
F=C–P+3
The number of phases
 A phase is a form of matter that is uniform throughout in chemical composition and
physical state
 Single phase (P = 1)
• A gas, or a gaseous mixture, crystal of a substance, two fully miscible liquids form a
single phase, solution of sodium chloride in water, ice is a single phase.
 Two-phase system (P = 2)
• A slurry of ice and water, pair of immiscible liquids, such as water and hexane
 Three-phase system (P = 3)
• At some specific condition all three phases of water coexist (ice-water-vapour)
 A system in which calcium carbonate undergoes the thermal decomposition of CaCO3(s)
→ CaO(s) + CO2(g) consists of two solid phases (CaCO3 and CaO) and one gaseous phase
(CO2)
Number of degrees of freedom
 The state of a state in equilibrium can be defined in terms of
thermodynamic variables such as Pressure (P), Temperature (T),
Composition (C) etc
 Number of degrees of freedom (or, variance) (F): It is defined as the
number of independently variable, such as pressure, temperature and
composition which must be specified in order to define the state of system
 In a single-component, single-phase system (C = 1, P = 1)
• F = 2 >> pressure and temperature may be changed independently without
changing the number of phases
 Ice-water-vapour system:
• In this system P = 3 and C = 1 >>> F = 0
 Water-vapour system:
• In this system P = 2 and C = 1 >>> F = 1
 The number of components

 A component is a chemically independent constituent of a system.

 The number of components (C) in a system is the minimum number of types
of independent species (ions or molecules) necessary to define the
composition of all the phases present in the system
 C = N – E (C = No of component, N = No of constituent, Relation between them)
So, C = 3-2 = 1 Because No of constituents = 3 and no of relation is E = 2
o H2O (l) H2O (g) H2O (g)
 Water system: can be defined in terms of H2O >>> C = 1
 Homogeneous mixture of Pb and Ag >>> C = 2
 Constituent of a system we mean a chemical species that is present. Thus, a
mixture of ethanol and water has two constituents.
 For the system CaCO3(s) ↔ CaO(s) + CO2(g)
• Calculate the no of component

C = N – E (C = No of component, N = No of constituent, E = Relation between

them)
C=3–1=2
Phase diagram

 A phase diagram is a type of chart used to show conditions (pressure,

temperature, volume) at which thermodynamically distinct phases (such as
solid, liquid or gaseous states) occur and coexist at equilibrium
 Generally the phases at equilibrium are studied under the conditions
considering following variables
• Temperature and Pressure
• Temperature and Composition
 Phase diagram is one of the most succinct ways of presenting the physical
changes of state that a substance can undergo.
Phase diagram of one component water system

 For a one-component system, such as pure water, F = 3 − P

 For one phase, F = 2
• Both pressure and temperature can be varied independently without changing the
number of phases.
• In other words, a single phase is represented by an area on a phase diagram.
 For two phases, F = 1
• Pressure is not freely variable if the temperature is set
• At a given temperature, a liquid has a characteristic vapour pressure.
• It follows that the equilibrium of two phases is represented by a line in the phase
diagram.
 When three phases are in equilibrium, F = 0 and the system is invariant. This special
condition can be established only at a definite temperature and pressure
 L
S

G
 Isomorphous phase diagrams:
 Example: Cu-Ni Alloys follow Hume-Rothery rules
Hume-Rothery rules for solid solutions
1.The atomic radius of the solute and solvent atoms
must differ by no more than 15%.
2.The crystal structures of solute and solvent must be
similar
3.Complete solubility occurs when the solvent and
solute have the same valency. (A metal of higher
valency is more likely to dissolve in a metal with lower
valency).
4.The solute and solvent should have similar
electronegativity (If the electronegativity difference is
too great, the metals tend to form intermetallic
compounds instead of solid solutions).
 The “Eutectic” is a state of
two components in a
homogeneous solid of
definite composition which
melts at the lowest
temperature at point C C
 Phase: In the physical sciences, a phase is a region of space (a thermodynamic system),
throughout which all physical properties of a material are essentially uniform. Examples of
physical properties include density, index of refraction, magnetization and chemical
composition. A simple description is that a phase is a region of material that is chemically
uniform, physically distinct, and (often) mechanically separable. In a system consisting of ice
and water in a glass jar, the ice cubes are one phase, the water is a second phase, and the
humid air is a third phase over the ice and water. The glass of the jar is another separate
phase.
 Eutectic system: A eutectic system is a homogeneous solid mixture of two or more types of
atoms or chemicals that form a super-lattice. The phrase most commonly refers to a mixture
of alloys. A eutectic system only forms when there is a specific ratio between the components.
The word comes from the Greek words "eu" meaning "good" or "well" and "tecsis" meaning
"melting".
 Solidus: In chemistry, materials science, and physics, the solidus is the locus of temperatures
(a curve on a phase diagram) below which a given substance is completely solid(crystallized).
The solidus is applied, among other materials, tometalalloys,ceramics, and natural rocks and
minerals.
 Liquidus: Above the liquidus temperature the material is homogeneous and liquid at
equilibrium. Below the liquidus temperature, more and more crystals will form in the
melt if one waits a sufficiently long time, depending on the material. Alternately,
homogeneous glasses can be obtained through sufficiently fast cooling, i.e., through
kinetic inhibition of the crystallization process.
o The liquidus temperature, TL or Tliq specifies the temperature above which a material
is completely liquid, and the maximum temperature at which crystals can co-exist with
the melt in thermodynamic equilibrium. It is mostly used for impure substances
(mixtures) such as glasses, alloys and rocks.
 Eutectoid: It describes the transformations of one solid into two different solids. When
the solution above the transformation point is solid, rather than liquid, an analogous
eutectoid transformation can occur. For instance, in the iron-carbon system, the
austenite phase can undergo a eutectoid transformation to produce ferrite and
cementite, often in lamellar structures such as pearlite and bainite. This eutectoid
point occurs at 727 °C (1,341 °F) and about 0.76% carbon
 Eutectic systems form when alloying additions cause a lowering of the liquidus lines
from both melting points of the pure elements. At a specific composition, there is a
minimum melting point, where the mixed solid-liquid phase regions (L + α and L + β)
vanish. This is the eutectic point, e, which defines an alloy composition that has the
lowest melting point of the A-B system.
 The eutectic composition also solidifies completely at a single temperature that is
referred to as an invariant point.
 In a eutectic reaction, a liquid freezes to form two solid solutions:
Liquid L → Solid α + Solid β
 The maximum solid solubility of element B is defined by point a on the A-rich side of
the diagram, and the maximum solid solubility of element A in the lattice of element B
is defined by point b. The methods of determining the equilibrium temperature ranges
for solidification, fractions of phases, and compositions of phases are all similar to
those illustrated for the isomorphous systems.
 Eutectic Percentage Ratio: This is defined as the relative composition of
components of a eutectic mixture. The composition, particularly for binary mixtures, is
often shown on a phase diagram.
 Eutectic reaction:
The three-phase reaction that takes place at the invariant point, where a liquid phase
freezes into a mixture of two solid phases, is called a eutectic reaction (from the Greek
word for “easily melted”). The alloy that corresponds to the eutectic composition is
called a eutectic alloy.
Liquid L → Solid α + Solid β
 Hypoeutectic and Hypereutectic: These terms apply to compositions which could form
a eutectoid, but do not have the appropriate ratio of components. A hypoeutectic
system has a smaller percentage of β and a greater percentage of α than the eutectic
composition, which a hypereutectic system has a greater percentage of α and a lower
percentage of β than the eutectic composition. An alloy having a composition to the
left of the eutectic point is called a hypoeutectic alloy (from the Greek word for “less
than”)
 Ferrous Metals mostly contain Iron.
• They have small amounts of other metals or elements added, to give the
required properties.
• Ferrous Metals are magnetic and give little resistance to corrosion.
Some examples of the ferrous metals are:
Vehicle scrap metal, Demolition site scrap metal, metal offcuts from
manufacturing industries, etc.
 Iron is a pure element (Fe).
 Iron-carbon alloy contain very small amount (about 0.03%) to about 2% carbon (and 0.25-1%
Mn, Si, P, S) is known as plain carbon steel.
 The iron carbon diagram contains the following solid phases;
 α- iorn or ferrite:
• A solid solution of C in BCC Fe
• Stable form of Iron at room temperature
• Maximum solubility of C is 0.022 wt percent at 723 ⁰C
• Transforms to FCC γ-austenite at 912 ⁰C
• α- ferrite is magnetic below 768 ⁰C
 γ-iron or Austenite:
 Austenite, also known as gamma-phase iron (γ-Fe)
 This is FCC crystal structure with high solubility of carbon
 The solubility reaches a maximum of 2.08 percent at 1148 ⁰C
 Transforms to BCC δ-ferrite at 1395 ⁰C
 Not stable below eutectic temperature
 It is nonmagnetic
 Cementite (Fe3C): An intermetallic compound with 6.67% C and 93.3% Fe. It is a
hard and brittle compound.
o Cementite (or iron carbide) is a compound of iron and carbon, more precisely an
intermediate transition metal carbide with the formula Fe3C. By weight, it is 6.67%
carbon and 93.3% iron. It has an orthorhombic crystal structure. each unit has 12 Fe
and 4 C atoms
 δ ferrite:
 The interstitial solid solution of carbon in BCC crystal structure.
 Maximum solubility is 0.09% at 1493 °C
 Same structure as α-ferrite
 Stable only at high temperature above 1493 °C
In metallurgy, a non-ferrous metal is a metal, including alloys, that does not contain iron (ferrite)
in appreciable amounts.
●Generally more costly than ferrous metals are used because of desirable properties such as
low weight (e.g. aluminium), higher conductivity (e.g. copper), non-magnetic property or
resistance to corrosion (e.g. zinc).
●Some non-ferrous materials are also used in the iron and steel industries. For example, bauxite
(a sedimentary rock with a relatively high aluminium content) is used as flux for blast furnaces,
while others such as wolframite, pyrolusite and chromite are used in making ferrous alloys.
●Important non-ferrous metals include aluminium, copper, lead, nickel, tin, titanium and zinc, and
alloys such as brass. Precious metals such as gold, silver and platinum and exotic or rare metals
such as cobalt, mercury, tungsten, beryllium, bismuth, cerium, cadmium, niobium, indium,
gallium, germanium, lithium, selenium, tantalum, tellurium, vanadium, and zirconium are also
non-ferrous. They are usually obtained through minerals such as sulfides, carbonates, and
silicates. Non-ferrous metals are usually refined through electrolysis.
Some examples of Non-ferrous metals are: Lead-Tin alloy for solder, Aluminium, Copper,
Magnesium, Beryllium, Nickel, Cobalt and Titanium Alloys
 Non-Ferrous Alloys
• Some examples of Non-
Ferrous Metals are:
• Lead-Tin alloy for solder
• Aluminium Alloys
• Copper Alloys
• Magnesium Alloys
• Beryllium Alloys Eutectic point (183 ⁰C, 38% Pb)
• Nickel and Cobalt Alloys
• Titanium Alloys
• Refractory and Precious Metals
Lead-Tin alloy Phase diagram
 Although lead-tin alloys are too weak for use as structural materials, they
are widely used as solders for everything from joining copper plumbing to
soldering electrical circuits.
o However, there is an international effort to develop lead-free solders
because of the health concerns associated with lead. Nevertheless, lead-
tin solders are still widely used.
 At 183 °C (361 °F), which is the eutectic temperature, all of the liquid
solidifies by the eutectic reaction and forms a eutectic mixture of solid
solutions of α (19.2% Sn) and β (97.5% Sn) according to the reaction:
Liquid (61.9% Sn) →α (19.2% Sn) + β (97.5% Sn)
 Applications of Ferrous alloys
 Ferrous steel is produced as sheet for automobiles, appliances, and
containers
 As plates for ships, boilers and bridges, as a structural member (such as
I- beams)
 Bar products for leaf springs, gears axles, crank shaft and railroad rails
 As stock for tools and dies
 As music wire and as fasteners such as bolts, rivets and nuts.
 Ferrous materials comprise 70% to 85% by weight of virtually all
structural members and mechanical components.
 Carbon steels are least expensive.
 Copper Alloys:
 One of the largest used of Cu is probably in coins.
 The various Euro coins are made of Cu-Ni, Cu-Zn-Ni or Cu-Al-Zn-Sn alloys.
 Brasses and Bronzes are most commonly used alloys of Cu.
 Brass is an alloy with Zn. Bronzes contain tin, aluminum, silicon or beryllium.
 Other copper alloy families include copper-nickels and nickel silvers
 More than 400 copper-base alloys are recognized.
 Magnesium Alloys:
 Aerospace industry,
 High speed machinery
 Transportation and materials handling equipments
 Nickel Alloys:
 Corrosion resistant parts: Valves, pumps, vanes Heat exchangers, shafts, impellers
 Heat treatment equipments, Gas turbines, Chemical reactor components
 Aluminum-silicon alloys are a family of industrially important casting alloys
 At 580 °C, or 1075 °F, the liquid phase reaches the eutectic composition of 12 wt% Si.
On cooling through the eutectic temperature, the liquid solidifies at a constant
temperature to form the eutectic structure consisting of an intimate mixture of α and β
phases.
 The primary reason for their widespread use is that silicon greatly increases the
fluidity, or lowers the viscosity, of aluminum during casting, allowing for better mold
filling and fewer casting defects.
 Department of Chemistry
School of Advanced Sciences
Vellore Institute of Technology
Vellore, 632014
Module 3 Corrosion
Dry and wet corrosion - detrimental effects to buildings, machines, devices & decorative art forms, emphasizing Differential
aeration, Pitting, Galvanic and Stress corrosion cracking; Factors that enhance corrosion and choice of parameters to mitigate
corrosion
Module 4 Corrosion Control
Corrosion protection: cathodic protection –sacrificial anodic and impressed current protection methods. Advanced protective
coatings: electroplating and electroless plating, PVD and CVD. Alloying for corrosion protection –Basic concepts of Eutectic
composition and Eutectic mixtures -Selected examples –Ferrous and non-ferrous alloys
Module 5 Electrochemical Energy Systems
Brief introduction to conventional primary and secondary batteries; High energy electrochemical energy systems: Lithium
batteries – Primary and secondary, its Chemistry, advantages and applications. Fuel cells – Polymer membrane fuel cells, Solid-
oxide fuel cells- working principles, advantages, applications. Solar cells – Types – Importance of silicon single crystal,
polycrystalline and amorphous silicon solar cells, dye sensitized solar cells - working principles, characteristics and applications.
 The cathode is the source of electrons for the reduction
 The anode is the sink of electrons for the oxidation
 The solution in contact with the electrode is called the electrolyte of each half-reaction or
half-cell. The electrolytes conduct electrical current within the electrochemical cell
 The anode and cathode electrolytes are often different in electrochemical cells. The
electrolytes then are brought into contact either directly through a porous separator or
indirectly using a salt bridge, which is a solution of a non-redox active strong electrolyte
such as KNO3
 Wires attached to the electrodes conduct the electrons between the cathode and anode
through a voltmeter or current source(DC power supply)
 Galvanic cell: An electrochemical cell that is spontaneous is called a galvanic cell.
Batteries are examples of galvanic cells. Galvanic cells are sources of energy, for example
for running cell phones. The cell voltage of a galvanic cell is measured with a voltmeter
 Electrolytic cell: A non-spontaneous electrochemical cell is called an electrolytic cell.
Electrolytic cells require an external source of energy
Anode Oxidation Cathode Reduction Anode Oxidation Cathode Reduction
e-sink e-source e-sink e-source
o Cathode half reaction: o Cathode half reaction:
 Cu2+ (aqueous) + 2 e–→Cu (s) reduction  Ni2+ (aqueous) + 2 e– → Ni(s) reduction
o Anode half reaction: o Anode half reaction:
 Zn (s) → Zn2+ (aqueous) + 2 e–oxidation  Cu(s) → Cu2+ (aqueous) + 2 e–oxidation
o Cell reaction: o Cell reaction:
 Zn(s) + Cu2+ (aqueous) → Zn2+ (aqueous) + Cu (s)  Cu(s) + Ni2+ (aqueous) → Cu2+ (aqueous) + Ni(s)
Galvanic cells, such as batteries, produce energy. Electrolytic cells require an external source of energy.
Reduction always occurs at the cathode. The reduction of Ni at the cathode is not spontaneous so
that an external energy source is required.
 An electrochemical cell is a device in which
a reduction-oxidation(redox) reaction is
utilized to get electrical energy. Chemical
energy produced in this redox reaction is
converted into electrical energy (during
discharging). It is commonly referred to as
voltaic cell or galvanic cell.
• Or a device in which the electrical energy is
converted to chemical energy thereby
resulting in a chemical reaction (during
charging).
 The electrode where oxidation occurs is
called anode while the electrode where
reduction occurs
 A shorthand description of Voltaic cell:
electrode | electrolyte || electrolyte | electrode
 Oxidation half-cell (anode) on the left:
Electrode(metal or solid phase)|Electrolyte(molecule or ion)
Example: Zn|ZnSO4(1M) .
 Reduction half-cell (cathode) on the right
Electrolyte(molecule or ion) |Electrode(metal or solid phase).
Example: CuSO4(1M)| Cu .
 A single vertical line “|” is a phase barrier.
 Multiple electrolytes that are in the same phase are separated by a comma.
 Two vertical lines “||”denote a salt bridge to separate two half cells.
Example: Zn|ZnSO4(1M) || CuSO4(1M)| Cu
or Zn|ZnSO4(aq) || CuSO4(aq)| Cu
 ECell⁰ is the electromotive force (emf, voltage) of the cell at standard condition
 The difference between the two electrode potentials equals the cell voltage
Ecell =Ecathode − Eanode = ERight−Eleft
At standard condition: ECell˚ = ECathode˚ − EAnode˚= ERight˚ −ELeft˚
 Electrochemical cell (Galvanic Cell) Electrolytic cell
A Galvanic cell converts chemical energy into electrical An electrolytic cell converts electrical energy into chemical
energy energy
The redox reaction is spontaneous and is responsible for the The redox reaction is not spontaneous and electrical energy
production of electrical energy. has to be supplied to initiate the reaction.
The two half-cells are set up in different containers, being Both the electrodes are placed in a same container in the
connected through the salt bridge or porous partition. solution of molten electrolyte
The anode is negative and cathode is the positive electrode. The anode is positive and cathode is the negative electrode.
The reaction at the anode is oxidation and that at the The reaction at the anode is oxidation and that at the cathode
cathode is reduction is reduction.
The electrons are supplied by the species getting oxidized. The external battery supplies the electrons. They enter through
They move from anode to the cathode in the external circuit. the cathode and come out through the anod
 Cell:
 A cell is the basic electrochemical unit providing a source of electrical
energy by direct conversion of chemical energy.
 A cell uses a chemical reaction to do work on charge and produce a
voltage between its output terminals.
 The cell consists of an assembly of electrodes, separators, electrolyte,
container and terminal
Battery:
 Battery is a device that consists of one or more electrochemical cells
connected in series or parallel or both and converts the chemical energy by
means of an electrochemical oxidation-reduction reaction depending on their
desired output voltage and capacity
 The cell consists of three major components:
• The anode or negative electrode: It is the reducing electrode which gives up
electrons to the external circuit and is oxidized during the electrochemical
reaction.
• The cathode or positive electrode: It is the oxidizing electrode which
accepts electrons from the external circuit and is reduced during the
electrochemical reaction
• The electrolyte: It is the ionic conductor which provides the medium for
transfer of charge, as ions, inside the cell between the anode and cathode
 Primary battery (Primary cells, non-rechargeable batteries): In this kind of battery
the cell reaction is not reversible. When all the reactants have been converted to
products, no more electricity is produced and the battery is dead. It cannot be
recharged or it is not rechargeable. Then it should be disposed
 Example: Lechlanche Cell (Dry Cell), Alkaline Cell and Lithium batteries
Secondary battery (secondary cells, rechargeable batteries): In this kind of
battery the cell reactions can be reversed by passing electric current in the opposite
direction. It can be recharged or it is rechargeable. Thus it can be used for a large
number of cycles
 Example: Lead acid batteries, Ni-Cd batteries, Ni-Metal Hydride batteries,
Lithium ion batteries
Fuel cell: in which materials (reactants, products, electrolytes) pass through the
battery, which is simply an electrochemical cell that converts chemical to electrical
energy
 Example: Hydrogen-oxygen fuel cell (HOFC), Alkaline fuel cell (AFC), Solid oxide
fuel cell(SOFC), etc.
Primary batteries:
Leclanche cell (wet cell).
Dry battery.
 Zinc-carbon battery.
 Alkaline battery.
 Lithium Primary cells/batteries

Secondary batteries:
Lead acid battery (wet cell).
Nickel‐Cadmium (NiCd) battery(dry cell)

Fuel cells:
Hydrogen-oxygen fuel cell (HOFC).
Alkaline fuel cell (AFC).
Solid oxide fuel cell (SOFC).
Primary battery Secondary battery
Electrochemical cell reaction is irreversible Electrochemical cell reaction is reversible
The reactants cannot be regenerated The reactants can be regenerated by passing
DC current in the opposite direction to the
discharging direction
Disposable after complete discharge. Usable Reusable after complete or partial discharge
for only once
Cheaper in cost More expensive than primary batteries.
Higher charge density. Less charge density
Examples: carbon-zinc (dry cell), alkaline Examples: Lead-acid, Ni-Cd, Ni-MH, Lithium-
and Lithium cells ion rechargeable cells
 Lithium cells are primary cells in which lithium acts as anode and the
cathode may differ.
Lithium metal is used as anode because of
• Most electropositive metal in the electrochemical series
• It has very low density
• Largest amount of electrical energy per unit weight
Li cannot be used with the traditional aqueous electrolytes
• Very vigorous corrosive reaction between Li and water
• Flammable hydrogen as the product.
As the reactivity of lithium in aqueous solution is more, lithium cells use
non-aqueous solvents as electrolyte.
 Lithium batteries are classified into several categories, based on
the type of electrolyte (or solvent) and cathode material used
 They are:
Lithium cells with liquid cathode
Lithium cells with solid cathode
Solid electrolyte cells
 Lithium cells with liquid cathode
Lithium/sulphur dioxide (SO2) cell is an example of liquid
cathode. The co-solvents used are acrylonitrile or propylene
carbonate (or) mixture of the two with SO2 in 50% by volume.
Cell reaction:
o At anode: 2Li ⟶ 2Li+ + 2e-
o At cathode: 2e-+ 2SO2⟶ S2O42- (dithionite)
o Net reaction: 2Li + 2SO2⟶ Li2S2O4
 Lithium/thionyl chloride (SOCl2) cell is
another example of liquid cathode. It consists
of high surface area carbon cathode, a non –
woven glass separator. Thionyl chloride acts
as an electrolyte and as a cathode.
Sometimes it is mixed with LiGaCl4 to avoid
its decomposition
Cell reaction:
o At anode: Li ⟶ Li+ + e-
o At cathode: 4e- + 2SOCl2⟶ 4Cl- + SO2 + S
o Net reaction: 4Li + 2SOCl2⟶ 4LiCl + SO2 + S
 Lithium/sulfuryl chloride (SO2Cl2) cell is another example of liquid
cathode. A lithium anode, a carbon and the electrolyte/depolarizer of
LiAlCl4 in SO2Cl2 are used to construct lithium sulf5uryl cell.
Cell reaction:
o At anode: 2Li ⟶ 2Li+ + 2e-
o At cathode: 2e- + SO2Cl2⟶ 2Cl- + SO2
o Net reaction: 2Li + SO2Cl2⟶ 2LiCl + SO2
Uses
1. They are used for military and space applications.
2. In medicinal devices such as neuro-stimulators, drug delivery system,
lithium batteries are widely used.
3. They are also used in electric circuit boards for supplying fixed voltage for
memory protection and standby functions.
Advantages:
High energy density.
These provide very high current.
Long shelf-life of around 10 years.
Though costly, Li cells require low maintenance.
Lithium cells can produce voltages more than twice the voltage of an ordinary
zinc-carbon battery or alkaline cell. The higher voltage reduces the number of
cells in a battery pack by a factor of at least 2.
Less self-discharge rate compared to Ni-Cd batteries.
Does not generate gas even under short circuit.
Operation over a wide temperature range (-40 to 70 ⁰C).
Flat discharge characteristics.
It needs less maintenance.
It can provide high current.
 Lithium cells with solid cathode:
Lithium-manganese dioxide (Li-MnO2) cell
The electrolyte in this system is a solid electrolyte. The most widely used cell is lithium –
manganese dioxide cell (3V). MnO2 should be heated to over 300 ⁰C to remove water before
keeping it in the cathode, thereby increasing the efficiency of the cell.
Anode: Lithium Metal
Cathode: MnO2 as an active material.
Electrolyte: LiBF4 salt in a solution of propylene
carbonate and dimethoxy ethane.
Reactions:
At anode: Li⟶ Li+ + e-
At cathode: e- + MnO2 ⟶ MnO2‒
Net reaction: Li + MnO2⟶ LiMnO2
 Applications:
1. The coin type cells are used in watches and
calculators.
2. Cylindrical cells are used in fully automatic
cameras
 Lithium-vanadium pentoxide (Li-V2O5) cell
It consists of lithium anode and cathode that is composed of 90% V2O5 and
10% graphite on weight basis. The electrolyte solution is 2M LiAsF6 + 0.4M
LiBF4 in methyl formate.
Anode: Lithium Metal
Cathode: 90% V2O5 and 10% graphite
Electrolyte: 2M LiAsF6 + 0.4M LiBF4 in methyl formate
Reactions:
At anode: Li ⟶ Li+ + e-
At cathode: Li+ + e- + V2O5 ⟶ Li V2-x5+Vx4+O5

The lithium ions in the interstitial sites of the host V2O5 lattice reduce V5+ state to V4+
state. The voltage of the Li-V2O5 cell is 3.2 V
Advantages:
High energy density.
These provide very high current.
Long shelf-life of around 10 years.
Though costly, Li cells require low maintenance.
Lithium cells can produce voltages more than twice the voltage of an ordinary
zinc-carbon battery or alkaline cell. The higher voltage reduces the number of
cells in a battery pack by a factor of at least 2.
Less self-discharge rate compared to Ni-Cd batteries.
Does not generate gas even under short circuit.
Operation over a wide temperature range (-40 to 70 ⁰C).
Flat discharge characteristics.
It needs less maintenance.
It can provide high current.
 Disadvantages:
• Require protection circuit to maintain voltage and current within safer limits.
• Lithium batteries can provide extremely high currents and can discharge very
rapidly which can result in overheating of the battery and even explosion.
Hence, lithium batteries incorporate vents in order to prevent explosion.
• Transportation of lithium batteries by air is restricted.
• Expensive to manufacture; about 40% higher in cost than Ni-Cd battery.
• Lithium metal scrapped from the batteries can be illegally used as a reducing
agent in methamphetamine (used as drugs) labs.
 Lithium-ion battery is a secondary battery.
 It does not contain metallic lithium as anode.
 As the name suggests, the movement of lithium ions are
responsible for charging & discharging.
 Lithium-ion cell has the following three components:
• Cathode: Layers of lithium-metal oxide (LiCoO2, LiNiO2 and
LiMn2O4)
• Anode: Layers of porous carbon (graphite, usually with
composition Li0.5C6
• Electrolyte: Polymer gel, organic liquid, gel, polymer and ceramic-
solid electrolytes
How it works?
Lithium-ion uses a cathode (positive
electrode), an anode (negative
electrode) and electrolyte as
conductor
The cathode is metal oxide and the
anode consists of porous carbon
During discharge, the ions flow from
the anode to the cathode through Cathode: Layers of lithium-metal oxide
(LiCoO2, LiNiO2 and LiMn2O4)
the electrolyte and separator;
charge reverses the direction and Anode: Layers of porous carbon (graphite,
usually with composition Li0.5C6
the ions flow from the cathode to
Electrolyte: Polymer gel, organic liquid,
the anode. gel, polymer and ceramic-solid electrolytes
 Charging Reaction:
 During charging, Li+ ions flow from
the positive electrode (LiCoO2) to
the negative electrode (graphite)
through the electrolyte
 Electrons also flow from the
positive electrode to the negative
electrode. The electrons and Li+
ions combine at the negative
electrode and deposit there as Li.

LiCoO2 + C → Li1-xCoO2 + CLix

 Discharging Reaction:
 Li+ ions flow back through the
electrolyte form negative
electrode to the positive
electrode. Electrons flow from
the negative electrode to the
positive electrode.
 The Li+ ions and electrons
combine at the positive electrode
and deposit there as Li

Li1-xCoO2 + CLix → LiCoO2 + C

 Advantages (or) Characteristics:
 Lithium-ion batteries are high voltage and light weight batteries.
 It is smaller in size.
 It produces three time the voltage of Ni-Cd batteries.
 Uses:
 It is used in cell phone, note PC, portable LCD TV, semiconductor
driven audio, etc.
 Polycarbon monofluoride cells have an output of 2.8 V and moderately high
energy density.
 Commercial Li/CFx battery:
• Cathode: Composite of CFx,
conductive additive and a polymeric
binder,
• Anode: Lithium
• Polypropylene separator and a non-
aqueous electrolyte (such as LiBF4 in
γ-butyrolactone).

 Discharge reaction: CFx + xLi + xS → C(Li+SF-)x

C(Li+SF-)x → C + xLiF + xS
 Exploded laptop
 Li-ion batteries use organic solvents as dispersing medium.
 In situations where the structure of the battery is compromised, that solvent
can ignite and vent from the pressurized battery.
 The result is a dangerous explosion
 The main advantage of Li-poly batteries that has been discussed in the press
recently is their reluctance to explode under duress
 A fuel cell is a device that converts
chemical potential energy (energy
stored in molecular bonds) into
electrical energy
 Electricity is generated without
combustion by combining hydrogen
and oxygen to produce water and heat
 They offer higher electrical efficiency
(≥40%) compared to conventional
power generation systems.
 A fuel cell is a device that uses hydrogen (or hydrogen-rich fuel) and
oxygen to create electricity by an electrochemical process
 Hydrogen and oxygen (air) are supplied to anode and cathode,
respectively.
 When hydrogen is led to the anode, the hydrogen molecules are split into
proton and an electron.
 The protons migrate through the electrolyte to the cathode, where they
react with oxygen to form water.
 At the same time, the electrons are forced to travel around the electrolyte
to the cathode side, because they cannot pass the electrolyte. This
movement of electrons thus creates an electrical current
 Unit cell
 Stacks: Individual cells are modularly combined
 Balance of plant which consists of components that provide feed-stream
conditioning
 There are eight main types of fuel cells, based mainly on the type of electrolyte
• PEMFCs, proton exchange membrane or polymer electrolyte membrane
fuel cells
• AFCs, alkaline fuel cells
• PAFCs, phosphoric acid fuel cells
• MCFCs, molten carbonate fuel cells
• SOFCs, solid oxide fuel cells
• DMFCs, direct methanol fuel cells
• DAFCs, direct ammonia fuel cells
• DCFCs, direct carbon fuel cells
 Apart from DAFCs, DMFCs, and DCFCs other types of fuel cells are fed with
hydrogen
 This cell is a common type of fuel cell. Similar to a galvanic cell, fuel cell
also have two half cells.
 Both half cells have porous graphite electrode with a catalyst (platinum,
silver or a metal oxide).
 The electrodes are placed in the aqueous solution of NaOH or KOH (alkaline
fuel cells-AFC) or H2SO4 (acidic fuel cell) which acts as an electrolyte.
 Hydrogen and oxygen are supplied at anode and cathode respectively at
about 50 atmospheric pressure, the gases diffuse at respective electrodes.
 The overall chemical reaction in a hydrogen fuel electrochemical cell
involves the oxidation of hydrogen by oxygen to produce only water.
2 H2 + O2 → 2 H2O
 Alkaline fuel cells consume hydrogen and pure oxygen producing potable water, heat,
and electricity.
 Structure:
• Anode and cathode: inert and porous graphite electrode impregnated with finely
divided platinum catalyst or alloy of Pd, Ag and Ni serves the purpose if hydrogen is
the fuel.
• Hydrogen (through anode) and oxygen (through cathode) gases are bubbled through
the respective compartments.
• Electrolyte: 25% KOH hot solution (alkaline).
• Hydroxyl ions (OH-) migrate from the cathode to the anode.
• At the anode, hydrogen gas reacts with the OH- ions to produce water and release
electrons.
• Released electrons supply electrical power to an external circuit then return to the
cathode where electrons react with oxygen and water to produce more hydroxyl ions
 H2 gas and pure O2 gas are bubbled through the anode and cathode
respectively, and the fuel cell produces power through a red-ox reaction
between H2 and O2

 At anode:
2 H2 (g) + 4 OH- (aq) → 4 H2O (I) + 4 e-
EAnode˚= -0.83 V
 At cathode:
O2 (g) + 2 H2O (I) + 4 e- → OH- (aq)
ECathode˚= 0.40 V
 Net reaction:
O2 (g) + 2 H2 (g) → 2 H2O (I)
ECell˚= 1.23 V
 Advantages
• The energy conversion is very high (75-82%).
• Fuel cell minimizes expensive transmission lines and transmission losses.
• It has high reliability in electricity generation.
• The by-products are environmentally acceptable.
• Maintenance cost is low for these fuels.
• They save fossil fuels.
• Noise and thermal pollution are very low

 Disadvantages:
• The major disadvantage of the fuel cell is the high cost and the problems
of durability and storage of large amount of hydrogen.
• The accurate life time is also not known.
 Application:
• The most important application of a fuel cell is its use in space
vehicles, submarine or military vehicles.
• The product H2O is valuable source of fresh water for the astronauts.
• Fuel cell batteries for automotive will be a great boon for the future.
 Limitations:
• The life time of fuel cells is not accurately known
• It cannot store electricity
• Electrodes are expensive ad short lived.
• Storage and handling of H2 gas is dangerous because it is inflammable
 Proton exchange membrane fuel cell (PEMFC) or Polymer electrolyte
membrane fuel cells (PEMFC)

 This type of fuel cell utilize water-based,

acidic polymer electrolyte membranes
(PEMs), such as Nafion, to conduct
protons for ion exchange purposes
 PEMFC cells operate at relatively low
temperatures (< 80°C)
 Due to the relatively low temperatures Nafion
and the use of precious metal-based
electrodes, these cells must operate on
pure hydrogen.
Hydrogen fuel is processed at the anode where electrons are separated from
protons on the surface of a platinum-based catalyst
The protons pass through the membrane to the cathode side of the cell while
the electrons travel in an external circuit, generating the electrical output of
the cell
On the cathode side, another Pt electrode combines the protons and
electrons with oxygen to produce water

• At anode: H2 (g) → 2 H+ + 2 e-
• At cathode: O2 (g) + 4 H+ + 4 e- → 2 H2 O
• Net reaction: O2 (g) + 2 H2 (g) → 2 H2O (I)
ECell˚= 1.23 V
PEMFC
Advanced PEMFC:
A variant of the PEMFC which operates at elevated temperatures
is known as the high temperature PEMFC (HT PEMFC).
By changing the electrolyte from being water-based to a mineral
acid-based system, these can operate up to 200 °C.
This overcomes some of the current limitations with regard to fuel
purity
Electrolyte in HT-PEM is phosphoric acid.
Membrane is polybenzimidazole (PBI) or pyridine based
SOFC is a high-temperature FC that utilizes solid ceramic inorganic
oxide as an electrolyte; e.g., zirconium oxide stabilized with yttrium
oxide, instead of a liquid or membrane. Also known as Yttria-stabilized
Zirconia (YSZ)
SOFC is also referred to as ceramic FC.
Both hydrogen and carbon monoxide are used as fuels.
Solid oxide fuel cells work at very high temperatures, the highest of all
the fuel cell types at around 800 °C to 1,000 °C
Efficiency: over 60% when converting fuel to electricity
This cell relatively resistant to small quantities of sulphur in the fuel,
compared to other types of fuel cell, and hence can be used with coal
gas
Anode or fuel electrode:
Nickel mixed with YSZ (yttria stabilized zirconia) or called Nickel-YSZ cermet
(a cermet is a mixture of ceramic and metal).
It is a porous ceramic layer to allow the fuel to flow towards electrolyte
Cathode or air electrode:
The cathode is usually a mixed ion-conducting and electronically conducting
ceramic material.
It is a thin porous ceramic layer coated over the solid electrolyte where
oxygen reduction takes place. One example being, strontium doped
lanthanum manganite (LSM)
Electrolyte:
Oxide ion (O2-) conducting ceramic.
The most popular electrolyte material is a bilayer composite electrolyte (YSZ
layer + gadolinium doped CeO2) (GDC) layer) or a mixture of ZrO and CaO.
 At anode (oxidation):
H2 (g) + CO (g) + 2 O2- → H2O (g) + CO2 (g) + 4e-
 At cathode (reduction):
O2 (g) + 4e- → 2 O2-
 Net reaction:
H2 (g) + CO (g) + O2 (g) → H2O (g) + CO2 (g)
Advantages of SOFC:
SOFCs have a number of advantages due to their solid materials and high
operating temperature.
Since all the components are solid, as a result, there is no need for
electrolyte loss maintenance and also electrode corrosion is eliminated.
Also because of high-temperature operation, the SOFC has a better ability
to tolerate the presence of impurities as a result of life increasing.
High efficiencies: Due to high-quality waste heat for cogeneration
applications and low activation losses, the efficiency for electricity
production is great.
Low emissions. Releasing negligible pollution. It is the cleanest among all
fuel cells.
 Disadvantages:
• High operating temperature (500 to 1,000 °C) which results in longer start up
times and mechanical/chemical compatibility issues.
• The cost and complex fabrication are also significant problems that need to be
solved

Applications:
• SOFCs are being considered for a wide range of applications, such as working
as power systems for trains, ships and vehicles; supplying electrical power for
residential or industrial utility.
• Stationary power generation
• By product gases are channeled to turbines to generate more electricity:
cogeneration of heat and power and improves overall efficiency
• Auxiliary power units in vehicles