Unit 2 (B) Corrosion

ADITYA COLLEGE OF ENGINEERING &
TECHNOLOGY
UNIT –iI: electrochemical cells &

corrosion
By
N.V.V.D.PRASAD, M.Sc.,
Assistant Professor
Dept of Humanities and basic sciences
Aditya College of Engineering
Surampalem.
Aditya College of Engineering & Technology
Unit-II(b): CORROSION
Syllabus
Corrosion:-Definition-theories of corrosion (chemical and
electrochemical)-galvanic corrosion, differential aeration
corrosion, stress corrosion, waterline corrosion-passivity of
metals-galvanic series-factors influencing rate of corrosion-
corrosion control (proper designing, cathodic protection)-
Protective coatings: Surface preparation, cathodic and anodic
coatings, electroplating, electroless plating (nickel). Paints
(constituents, functions, special paints).
Electro Chemistry
INTRODUCTION
• Most metals (except noble metals such as Au, Pt, etc) exist in nature in
combined forms as their oxides, carbonates, hydroxyl carbonates,
sulphides, chlorides and silicates.
Iron (Haematite or Magnatite)
Copper (Copper pyrites)
Mercury (galena)
• These are reduced to their metallic states from their ores, during their
extraction processes.
• During extraction of metals, considerable amounts of energy is
required.
Electro Chemistry
• Hence, when metals are put into use, in various forms, they are
exposed to environment (such as dry gases, moisture, liquids, etc), the
exposed metal surfaces begin to decay (i.e. conversion to more stable
metal compounds) more or less rapidly, when they come in contact
with surroundings.
• In other words destruction or deterioration of the metal starts at the

surface. This type of metallic destruction may be due to direct
chemical attack (by the environment) or electrochemical attack (i.e,
similar to reactions in a Daniel cell).
Electro Chemistry
Definition
“Any process of deterioration or destruction of a metal or alloy, through
an unwanted chemical or electrochemical attack by its environment,
starting at its surface, is called corrosion”. Thus, corrosion is a
process of “reverse of extraction of metals”.
Rusting of iron: A layer of reddish brown scales on the surface of iron
metal. 4 Fe + 3 O2+H20---> 2 Fe2O3.3H2O
Tarnishing of silver: Formation of black layer on the surface of silver

metal. 2Ag+S----->Ag2S
Electro Chemistry
Cause of Corrosion:
• Consequently, isolated pure metals can be regarded as in excited state (higher energy
state) than their corresponding ores, and they have a natural tendency to revert back to
combined state (lower energy state).
• Any spontaneous reaction in the universe is associated with a lowering in the free
energy of the system. i.e. a negative free energy change. All metals except the noble
metals have free energies greater than their compounds. So they tend to become their
compounds through the process of corrosion
Minerals ----------energy---------> Pure metal

(Thermodynamically stable) (Thermodynamically unstable)
Electro Chemistry
CORROSION DAMAGE
Disfiguration or loss of appearance
Loss of material
Maintenance cost
Extractive metallurgy in reverse
Loss of precious minerals, power, water and
man-power
Loss in reliability & safety
Plant shutdown, contamination of product etc
Electro Chemistry
COST OF CORROSION
• Annual loss due to corrosion is estimated to be 3 to 5 % of GNP,
about Rs.700000 crores
Direct & Indirect losses
• Direct loss: Material cost, maintenance cost, over-design, use of costly
material
• Indirect losses: Plant shutdown & loss of production, contamination of
products, loss of valuable products due to leakage etc, liability in
accidents
Corrosion
CONSEQUENCES OF CORROSION:
• Corrosion leads to unpredictable machinery failure which may leads to loss of
machinery life.
• It leads to decrease in efficiency of machine and frequent replacement of
corroded equipment, which is an expensive process.
• Corrosion causes leakage of gases and toxic products from the pipelines.
• It causes contamination of potable water.
• It has been estimated that 25% of annual world production of iron wasted due to
corrosion.
Corrosion
THEORIES OF CORROSION:
• Based on the corroding environment and the mechanism of corrosion, corrosion

is classified into 2 types.
Corrosion
Dry Corrosion
• Dry corrosion, sometimes also called chemical corrosion, is a type of
corrosion that occurs without moisture or water, which are the main
drivers of the conventional types of corrosion.
In dry corrosion, metal oxidizes with only the atmosphere, in a process
sensitive to temperature.
Dry corrosion, therefore, refers to an oxidation process sustained by
oxygen in the air without a liquid solution.
(i) Silver materials undergo chemical corrosion by Atmospheric H2S
gas .
(ii) Iron metal undergo chemical corrosion by HCl gas.
Corrosion
Types of dry or chemical corrosion:

 Corrosion by Oxygen or Oxidation corrosion
 Corrosion by Hydrogen
 Liquid Metal Corrosion
CORROSION BY OXYGEN or OXIDATION CORROSION:

Oxidation Corrosion is brought about by the direct attack of oxygen at
low or high temperature on metal surfaces in the absence of moisture.
Alkali metals (Li, Na, K etc.,) and alkaline earth metals (Mg, Ca, Sn,
etc.,) are rapidly oxidized at low temperature. At high temperature, almost
all metals (except Ag, Au and Pt) are oxidized.
Corrosion
Mechanism:
Oxidation takes place at the surface of the metal forming metal ions
M → Mn+ + ne-
Oxygen is converted to oxide ion (O2- ) due to the transfer of electrons from metal.
n/2 O2 + 2n e- → n O2-
The overall reaction is of oxide ion reacts with the metal ions to form metal oxide
film.
2 M + n/2 O2 → M2O2n
The Nature of the Oxide formed plays an important part in oxidation corrosion
process.
Metal + Oxygen → Metal oxide (corrosion product)
Corrosion
• When oxidation starts, a thin layer of oxide is formed on the metal

surface and the nature of this film decides the further action
(i) Stable layer: A Stable layer is fine grained in structure and can get
adhered tightly to the parent metal surface. Hence, such layer can be of
impervious nature Such a film behaves as protective coating in nature,
thereby shielding the metal surface. The oxide films on Al, Sn, Pb, Cu,
Pt, etc., are stable, tightly adhering and impervious in nature.
(ii) Unstable oxide layer: This is formed on the surface of noble metals
such as Ag, Au, Pt. As the metallic state is more stable than oxide, it
decomposes back into the metal and oxygen. Hence, oxidation
corrosion is not possible with noble metals.
Corrosion
(iii) Volatile oxide layer: The oxide layer film volatilizes as soon as it is
formed. Hence, always a fresh metal surface is available for further
attack.
This causes continuous corrosion. MoO3 is volatile in nature.
(iv) Porous layer: The layer having pores or cracks. In such a case, the
atmospheric oxygen have access to the underlying surface of metal,
through the pores or cracks of the layer, thereby the corrosion
continues unobstructed, till the entire metal is completely converted
into its oxide.
Corrosion
Pilling-Bedworth rule:
• According to it “an oxide is protective or non-porous, if the volume of
the oxide is at-least as great as the volume of the metal from which it
is formed”.
• On the other hand, “if the volume of the oxide is less than the volume
of metal, the oxide layer is porous (or non-continuous) and hence,
non-protective, because it cannot prevent the access of oxygen to the
fresh metal surface below”.
• Thus, alkali and alkaline earth metals (like Li, K, Na, Mg) form oxides
of volume less than the volume of metals.
Corrosion
• Consequently, the oxide layer faces stress and strains, thereby

developing cracks and pores in its structure.
• Porous oxide scale permits free access of oxygen to the underlying
metal surface (through cracks and pores) for fresh action and thus,
corrosion continues non-stop. Metals like Aluminium forms oxide,
whose volume is greater than the volume of metal.
• Consequently, an extremely tightly-adhering non-porous layer is
formed. Due to the absence of any pores or cracks in the oxide film,
the rate of oxidation rapidly decreases to zero.
Corrosion
ii) CORROSION BY OTHER GASES:
Metal reacts with Cl2, H2S, CO2, SO2 etc to form metallic compounds as a layer
on the surface of the metal and it may be either protective or non protective.
2Ag + Cl2 --------> 2AgCl {protective layer}
Sn + 2Cl2 ----------> Sncl4 {non-protective layer}
Protective layer stops further corrosion and non-protective layer do not stop
further corrosion.
Electro Chemistry
iii) LIQUID METALS CORROSION:

When liquid metal is allowed to flow on solid metal at higher
temperature, due to weakening or dissolution or penetration of solid
into liquid, corrosion results.
• Ex: Liquid sodium, used as coolant in nuclear reactors cause the

corrosion of cadmium rods.
Electro Chemistry
WET OR ELECTROCHEMICAL CORROSION

When the metal is in contact with moist environment, a series of
electrochemical cell containing anode and cathode will be formed on
the metal surface.
Electrochemical corrosion involves:
i) The formation of anodic and cathodic areas or parts in contact with
each other
ii) Presence of a conducting medium
iii) Corrosion of anodic areas only and
iv) Formation of corrosion product somewhere between anodic and
cathodic areas. This involves flow of electron-current between the
anodic and cathodic areas.
Electro Chemistry
• At anodic area oxidation reaction takes place (liberation of free electron),

so anodic metal is destroyed by either dissolving or assuming combined
state (such as oxide, etc.). Hence corrosion always occurs at anodic areas.
M (metal) → M n+ + n e-
Mn+ (metal ion) → Dissolves in solution → forms compounds such as oxide
• At cathodic area, reduction reaction takes place (gain of electrons), usually
cathode reactions do not affect the cathode, since most metals cannot be
further reduced. So at cathodic part, dissolved constituents in the
conducting medium accepts the electrons to form some ions like OH and
O2-. Cathodic reaction consumes electrons with either by
(a) evolution of hydrogen or
(b) absorption of oxygen, depending on the nature of the corrosive
environment
Electro Chemistry
ELECTROCHEMICAL THEORY OF CORROSION:
Electrolyte: Atmospheric elements dissolved in water.
At anode: Metal under goes oxidation to form metal ion and electron
Fe ------> Fe+2 + 2e-
Fe+2 moves towards cathode through electrolytic medium electron also moves
towards cathode to carryout reduction.
At cathode:
Reduction reactions takes place at cathode, which can be of two types depending
upon the nature of corrosive environment.
Electro Chemistry
(i)Evolution of Hydrogen:
In absence of oxygen and in acidic environment, evolution of hydrogen takes

place. The H+ ions of the acidic solution pick up the electron and are eliminated
as hydrogen gas.
2H+ +2e- ------> H2 {reduction}
All the metals above hydrogen in the electro chemical series can show this type
of corrosion in evolution of hydrogen type corrosion; anodic area is large as
compared to its cathodic area.
In neutral medium at the cathode formation of OH- takes place along with the
liberation of hydrogen 2 H2O+2e- ------->2H2 +2 OH-
Electro Chemistry
Absorption of oxygen
This type of corrosion takes place in neutral or alkaline medium in presence of

oxygen.
• Fe+2 ions produced at anode migrate towards the cathodic layer through moisture and
react with OH- to form ferrous hydroxide. The ferrous hydroxide which undergoes
further oxidation to ferric hydroxide which converts into hydrated form
Fe +2 + OH- ------------------>Fe(OH)2
4 Fe(OH)2+O2+2H2O--------->4 Fe(OH)3 ------->2 Fe2O3.3H2O.
• The corrosion product ultimately formed gets deposited. Cathode and anode suffers
metal loss due to dissolution of metal.
Electro Chemistry
At Anode: Metal dissolves as ferrous ions with liberation of electrons.

Fe → Fe2+ + 2e-
At Cathode: The liberated electrons are intercepted by the dissolved oxygen.
½ O2 + H2O + 2e- → 2OH-
The Fe2+ ions and OH- ions diffuse and when they meet, ferrous hydroxide is
precipitated.
Fe2+ + 2OH- → Fe(OH)2
If enough oxygen is present, ferrous hydroxide is easily oxidized to ferric
hydroxide.
4Fe(OH)2 +O2 + 2H2O → 4Fe(OH)3 (Fe2O3 .H2O)
If the supply of oxygen is limited, the corrosion product may be even black
anhydrous magnetite, Fe3O4
Electro Chemistry
Corrosion
Corrosion
DRY CORROSION WET CORROSION

• This corrosion occurs at dry conditions • This corrosion occurs at wet conditions
• Corrosion is uniform • Corrosion is not uniform. If the anodic
• It is a slow process ares is small, pitting is more frequent.
• It involves direct chemical attack of the • It is a rapid process
metals by environment. • It involves the formation of large no. of
• It is explained by absorption coefficient electro-chemical cells.
• It occurs both on homogeneous solutions • It is explained by mechanism of electro-
• Corrosion products are produced at the chemical cells.
place where corrosion takes place • It takes place only on heterogeneous
processes.
• Corrosion occurs at the anode and
corrosion product occurs in between
cathodic and anodic areas.
Electro Chemistry
Different types of Electrochemical corrosion

Galvanic corrosion or bimetallic corrosion:
When two dissimilar metals ( Zinc and Copper) are electrically connected and
exposed to an electrolyte, the metal higher in electrochemical series undergoes
corrosion. This type of corrosion, is called ‘Galvanic Corrosion’.
For example, if Zn and Cu are connected, Zn acts as anode and undergoes

corrosion, where as Cu acts as cathode.
Corrosion
Mechanism: In a Zn-Cu Couple

In acidic solution, the corrosion occurs by evolution of hydrogen
At anode: Zn  Zn2+ + 2e- (Oxidation)
At cathode: 2H+ + 2e- H2 (Reduction)
Zn + 2H+ Zn2+ + H2 
In neutral or slightly alkaline medium, corrosion occurs by absorption of oxygen
At anode: Zn  Zn2+ + 2e-
At cathode: H2O + ½ O2 + 2e- 2OH-
Zn + H2O + ½ O2Zn(OH)2
Corrosion
Corrosion
Examples:
 Steel screw in brass marine hardware
 A steel propeller sharf in bronze bearing
 Lead-antimony solder around copper wise
 Steel pipe connected to copper plumbing.
It is minimized by
 Avoiding galvanic couple
 Avoiding suitable medium for corrosion
 Providing insulator between two metals.
Corrosion
Concentration cell corrosion:

This type of corrosion is due to electrochemical attack on the metal surface,
exposed to an electrolyte of varying concentrations or of varying aeration.
Differential aeration corrosion (the most common type of concentration cell

corrosion) occurs when one part of metal is exposed to a different air concentration
from the other part. This causes a difference in potential between differently aerated
areas and poor oxygenated parts are anodic and highly oxygenated areas become
cathodic.
Corrosion
Waterline corrosion:
If a Zinc meal is partially immersed in a neutral solution (say Nacl) and the solution
is not agitated, the parts above and closely adjacent to the waterline are well aerated
and act as cathode. The parts immersed inside the solution are anodic, as the
concentration of oxygen is low. Thus a potential develops that causes a flow of
current between two areas of the same metal. Zn dissolves at the anodic area
At anode: Zn → Zn2+ + 2e-
At cathode: ½ O2 + H2O + 2e- → 2OH-
Zn + ½ O2 + H2O → Zn(OH)2
The circuit is completed by migration of ions, through the electrolyte, and flow of
electrons through the metal, from anode to cathode.
Corrosion
Corrosion
Pitting Corrosion:
• Pitting is a localized attack, which results in the formation of a hole
around which the metal is relatively unattacked.
• The mechanism of this corrosion involves setting up of differential
aeration or concentration cell.
• Metal area covered by a drop of water, dust, sand, scale etc. is the
aeration or concentration cell.
• Pitting corrosion is explained by considering a drop of water or brine
solution (aqueous solution of NaCl) on a metal surface (especially
iron).
Corrosion
• The area covered by the drop of salt

solution as less oxygen and acts as
anode. This area suffers corrosion, the
uncovered area acts as cathode due to
high oxygen content.
• It has been found that the rate of
corrosion will be more when the area of
cathode is larger and the area of the
anode is smaller. Hence there is more
material around the small anodic area
results in the formation hole or pit.
Corrosion
Corrosion
Stress Corrosion:
Stress corrosion or stress cracking occurs due to combined effect of
tensile stress and when metal is exposed to corrosive environment.
The metals develop internal stress during manufacture process like
fabrication, quenching, bending, heating etc. In all such cases, metal
under stress become more anodic and stress free areas act as cathode.
The anodic area becomes highly reactive and is attacked even by a mild
corrosive environment resulting in the formation of a crack.
Corrosion
For example
a) Mild steel undergoes stress corrosion in the presence of caustic
alkalies and strong nitrate solution.
b) Strain less steel in the presence of acid chloride solution
c) Brass in the presence of ammonia
Corrosion
Intergranular corrosion
• It is also known as intergranular attack (IGA), is a form
of corrosion where the boundaries of crystallites of the material are more
susceptible to corrosion than their inside
• This situation can happen in otherwise corrosion-resistant alloys, when
the grain boundaries are depleted, known as grain boundary depletion, of
the corrosion-inhibiting elements such as chromium by some mechanism.
• In nickel alloys and austenitic stainless steels, where chromium is added
for corrosion resistance, the mechanism involved is precipitation
of chromium carbide at the grain boundaries, resulting in the formation of
chromium-depleted zones adjacent to the grain boundaries
Corrosion
Corrosion
GALVANIC SERIES:
• A metal high up in the electrochemical series is more anodic and undergoes

corrosion faster than the metal below it. However, it is observed in few cases,
electrochemical series does not account for the corrosion of all metal and alloys, as
expected.
Example, when aluminium and Zinc are connected, Zinc metal gets corroded
while aluminium is protected, though Zn in below Al in the electrochemical series.
Corrosion
This reversal of the order in the above series is due to the formation of ‘Passivity’
which results in the production of a thin film of Al2O3 on the surface of Al, which
protects it from corrosion.
A more sensible and informative series known as galvanic series, has been
adopted by observing the corrosion behaviour of metals and alloys in sea water.
An arrangement of metals and alloys in order of their corrosion tendencies in a
corrosive environment is referred to as galvanic series.
Corrosion
Difference between electrochemical series and galvanic series

ELECTROCHEMICAL SERIES GALVANIC SERIES
1. Based on electrode potential value, the 1. Metal may have a different position in galvanic
position of a metal is fixed in electrochemical series depending on the corrosion aspect
series.
2. Galvanic series comprises both metals and

2. Metals and non-metals are included in the alloys
series
3. The relative corrosion tendencies of metals and

3. It predicts relative displacement tendencies alloys can be predicted.
4. No position is given to alloys with their 4. Alloys are given position in galvanic series
potential values based on the corrosion behaviour.
Corrosion
FACTORS INFLUENCING RATE OF CORROSION:
The rate of corrosion and extent of corrosion depends upon the
(i)Nature of the metal (ii)Environment factors
(i)NATURE OF METAL
Physical state:
The rate of corrosion is influenced by physical state of the metal (such as grain size,
orientation of crystals, stress, etc). The smaller the grain size of the metal or alloy, the
greater will be its solubility and hence greater will be its corrosion. Moreover, areas
under stress, even in a pure metal, tend to be anodic and corrosion takes place at these
areas.
Electro Chemistry
Purity of metal:
Impurities in a metal cause heterogeneity and form minute/tiny
electrochemical cells (at the exposed parts), and the anodic parts get
corroded. The cent percent pure metal will not undergo any type of
corrosion.
Over voltage:
The over voltage of a metal in a corrosive environment is inversely
proportional to corrosion rate. For example, the over voltage of
hydrogen is 0.7 V when zinc metal is placed in 1 M sulphuric acid and
the rate of corrosion is low. A small amount of Cu (0.3V) added to it
accelerates the corrosion
Electro Chemistry
Position of the metal in galvanic series:
Position of the metal in the electrochemical series determines the extent

of corrosion. Metals occupying higher positions have high oxidation
potentials and they act as anode. Hence they suffer corrosion.
Metals occupying lower positions have low oxidation potential and they
act as cathode. Hence they are protected. More the metals apart in the
series, greater is the potential difference, higher is the rate of corrosion.
Electro Chemistry
Nature of surface film:

In aerated atmosphere, all metals get covered with a thin surface film
(thickness=a few angstroms) of metal oxide. The ratio of the volumes
of the metal oxide to the metal is known as a specific volume ratio
(PBR). Greater the specific volume ratio, lesser is the oxidation
corrosion rate. The specific volume ratios of Ni, Cr and W are 1.6, 2.0
and 3.6 respectively.
• Consequently the rate of oxidation of tungsten is least, even at
elevated temperatures.
• Stable, Unstable, volatile, Porous oxide
Electro Chemistry
Relative areas of the anodic and cathodic parts:

When two dissimilar metals or alloys are in contact, the corrosion of the anodic
part is directly proportional to the ratio of areas of the cathodic part and the
anodic part.
• Corrosion is more rapid and severe, and highly localized, if the anodic area is
small (eg., a small steel pipe fitted in a large copper tank), because the current
density at a smaller anodic area is much greater and the demand for electrons
Passivity:
When metals form a continuous stable and non-porous layers then they show
the properties of passivity. Eg: Al, Ni, Co
Electro Chemistry
(ii)Corroding Environment
Temperature:
The rate of corrosion is directly proportional to temperature i.e., rise in
temperature increases the rate of corrosion. This is because the rate of
diffusion of ions increases with rise in temperature.
Humidity of air:
The rate of corrosion will be more when the relative humidity of the
environment is high. The moisture acts as a solvent for oxygen, carbon
dioxide, sulphur dioxide etc in the air to produce the electrolyte which
is required for setting up a corrosion cell.
Electro Chemistry
Presence of impurities in atmosphere:

Atmosphere in industrial areas contains corrosive gases like CO2, H2S,
SO2 and fumes of HCl, H2SO4 etc. In presence of these gases, the
acidity of the liquid adjacent to the metal surfaces increases and its
electrical conductivity also increases, thereby the rate of corrosion
increases.
Effect of pH:
Acidic media are more corrosive than Alkaline or neutral media. Since
low pH accelerates corrosion by providing plentiful supply of
hydrogen ions.
Electro Chemistry
Conductance of corroding medium:

Dry sandy soil contains moisture. It conducts more than clay or mineralized
soils. Hence the metallic pars submerged under clay or mineralized soil
undergo faster corrosion.
Presence of suspended particles in atmosphere:
In case of atmospheric corrosion:
(i) if the suspended particles are chemically active in nature (like NaCl,
Ammonium sulphate), they absorb moisture and act as strong electrolytes,
thereby causing enhanced corrosion;
(ii) if the suspended particles are chemically inactive in nature (charcoal), they
absorb both sulphur gases and moisture and slowly enhance corrosion rate.
Electro Chemistry
CORROSION CONTROL (PROTECTION AGAINST CORROSION)

• As the corrosion process is very harmful and losses incurred are tremendous, it
becomes necessary to minimize or control corrosion of metals. Corrosion can be
stopped completely only under ideal conditions. But the attainment of ideal
conditions is not possible.
• However, it is possible only to minimize corrosion considerably. Since the types
of corrosion are so numerous and the conditions under which corrosion occurs
are so different, diverse methods are used to control corrosion.
• As the corrosion is a reaction between the metal or alloy and the environment,
any method of corrosion control must be aimed at either modifying the metal or
the environment.
Electro Chemistry
Protection against corrosion (Corrosion Control)

The various methods by which corrosion can be controlled and
prevented are as follows:
1.Protection by proper designing
2.Material selection
3.Cathodic protection or electrochemical protection
4.Use of protective coating
Corrosion
Proper Designing
Use always simple design and structure
 The design must avoid more complicated shapes having more angles,
edges, corners etc.
Avoid the contact of dissimilar metals as they may lead to galvanic type
corrosion. To overcome this, insulation can be used.
When two dissimilar metals are to be in contact, the anodic area must be as
large as possible and the cathodic area should be as small as possible.
As far as possible, gap or cracks should be avoided between adjacent
parts of a structure.
Electro Chemistry
Bolts and rivets should be replaced by proper welding

Metal washers should be replaced by rubber or plastic washers as they
do not adsorb water. They also act as insulation.
Corrosion in pipelines can be prevented by using smooth bends.
A good design of water storage container is the one from which water
can be drained and cleaned easily. Such a design avoids accumulation
of dirt etc.
Electro Chemistry
Material selection
1. The first choice is to use noble metals such as gold and platinum. They are
most resistant to corrosion. As they are precious, they cannot be used for general
purposes.
2. The next choice is to use purest possible metal. But in many cases, it is not
possible to produce a metal of high chemical purity. Hence, even a trace amount
of impurity leads to corrosion.
3. Thus, the next choice is the use of corrosion resistant alloys. Several corrosion
resistant alloys have been developed for specific purposes and environment.
a) Stainless steel containing chromium produce an exceptionally coherent oxide

film which protects the steel from further attack.
(b) Cupro-nickel (70% Cu + 30%Ni) alloys are now used for condenser tubes
and for bubble trays used in fractionating column in oil refineries.
Electro Chemistry
Cathodic protection:
• The reduction or prevention of corrosion by making metallic structure
as cathode in the electrolytic cell is called cathodic protection. Since
there will not be any anodic area on the metal, corrosion does not
occur. There are two methods of applying cathodic protection to
metallic structures.
a) Sacrificial anodic protection (galvanic protection)
b) Impressed current cathodic protection
Electro Chemistry
Sacrificial anodic protection:

The metallic structure which is to be protected
is connected through a metallic wire to a more
anodic metals. Corrosion will take place only
on the anodic metal. The artificially made
anode gets gradually corroded protecting the
original metallic structure. After sometime, the
anode is corroded completely and is replaced
with a fresh anode. This type of protection is
used in industry to protect buried pipelines,
ship hulls. Zn, Mg, Al and their alloys are used
as anodes under ground cables.
Corrosion
Applications:
1. Protection as buried pipelines, underground cables from soil corrosion.
2. Protection from marine corrosion of cables, ship hulls, piers etc.
3. Insertion of magnesium sheets into the domestic water boilers to prevent the formation of
rust.
4. Calcium metal is employed to minimize engine corrosion.
Advantages:
1. Low installation and operating cost.
2. Capacity to protect complex structures.
3. Applied to wide range of severe corrodents.
Limitations:
1. High starting current is required.
2. Uncoated parts cannot be protected.
3. Limited driving potential, hence, not applicable for large objects
Corrosion
Impressed current cathodic protection:

• In this method, direct current is send in the
opposite direction in order to nullify the
corrosion current, and convert the corroding
metal from anode to cathode usually a battery is
connected to an insoluble anode like graphite,
carbon, stainless steel and is buried in a backfill
like gypsum to increase. Other terminal is
connected to a metallic structure and electrons
flow to metallic object. Hence it acts as between
itself cathode and is protected.
Corrosion
Advantages:
Long Term Protection(For 20yrs), No need to

replace anode
Limitations:
Highly Sensitive Components are used, highly

Expensive method
Applications:
1) Ships are protected against corrosion by
connecting the surface to –Ve terminal or DC
generator.
2) Water tanks, buried oil or water pipelines are
protected by this method.
Corrosion
Corrosion
By using inhibitors:
• Inhibitors are organic or inorganic substances which decrease the rate
of corrosion. Usually the inhibitors are added in small quantities to the
corrosive medium.
Inhibitors are classified into
1) Anodic inhibitors (chemical passivators)
2) Cathodic inhibitors (adsorption inhibitors)
3) Vapour phase inhibitors (volatile corrosion inhibitors)
Corrosion
Anodic Inhibitors:
• Inhibitors which retard the corrosion of metals by forming a sparingly
soluble compound with a newly produced metal cations. This
compound will then adsorb on the corroding metal surface forming a
passive film or barrier.
Anodic inhibitors are used to repair
a) the crack of the oxide film over the metal surface
b) the pitting corrosion
c) the porous oxide film formed on the metal surface.
Examples: Chromate, phosphate, tungstate, nitrate, molybdate etc.
Corrosion
Cathodic Inhibitors:
• Depending on the nature of the cathodic reaction in an electrochemical corrosion,
cathodic inhibitors are classified into
In an acidic solution: the main cathodic reaction is the liberation of hydrogen gas,
the corrosion can be controlled by slowing down the diffusion of H+ ions through
the cathode.
Ex: Amines, Mercaptans, Thiourea etc.
In a neutral solution: in a neutral solution, the cathodic reaction is the adsorption
of oxygen or formation of hydroxyl ions. The corrosion is therefore controlled
either by eliminating oxygen from the corroding medium or by retarding its
diffusion to the cathodic area.
Corrosion
• The dissolved oxygen can be eliminated by adding reducing agents like Na 2SO3.
The diffusion of oxygen can be controlled by adding inhibitors like Mg, Zn or Ni
salts.
Ex: Na2SO3, N2H4, Salts of Mg, Zn or Ni.
Vapour phase inhibitors:

• These are organic inhibitors which are readily vapourised and form a
protective layer on the metal surface. These are conveniently used to
prevent corrosion in closed spaces, storage containers, packing materials,
sophisticated equipments etc.
Ex: Dicyclohexylammonium nitrate, dicyclohexyl ammonium chromate,
benzotriazole, phenylthiourea etc.
Corrosion
Use of protective coatings:

• The metallic structure to be protected is covered with metallic or non
metallic coatings.
• The metallic coatings often used are Zinc, tin, Nickel, Aluminium, Copper etc.
• These coatings separate the base metal from the corrosive environment and
protect it from corrosion. There are two types of coatings.
Anodic coatings: In this method the base metal is coated with a more reactive
metal which is more anodic than the base metal.
Ex: Coating of Zn on Fe (galvanization)
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Cathodic coatings: In this method the base metal is coated with a noble
or less reactive metal. The protective coating is corrosion resistant
and hence protects the base metal.
Ex: Coating of Sn on Fe/SS (Tinning)
Surface preparation: (method of cleaning metal surface)

The common method of protecting a metal from its surrounding is by
applying a protective coating. Before applying a protective coating
metal surface has to be cleaned. Some methods of cleaning are
Corrosion
i) Solvent cleaning: It is used to remove oil, greese and fatty substances. This
involves the application of organic solvents like naphta, CCl4, toluene etc. Then
the metal surface is cleaned with steam and hot water containing wetting reagents
and alkalies.
ii) Flame cleaning: This method involves heating the metal surface with a hot
flame to remove loosely adhering scales followed by wire brushing.
iii)Pickling and etching: It is a method to remove scales. It is done by immersing
the metal (expect Al) in acid pickling solution. Acid pickling of steel is done with
dil. H2SO4 or Cold HCl to which some inhibitors are added.
• Aluminium is pickled in alkaline solution.
Corrosion
Methods of application of metal coating: [protective coating]

Hot dipping: This is a method of coating a low-melting metal on the
surface of a high melting point.
• In this method, the metal to be coated is dipped in molten bath of the
coating metal and then removed out along with the adhering film.
The widely used hot dipping methods are
a)Galvanization
b)Tinning
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a) Galvanization
The process of coating a layer of Zinc on iron is called galvanization.
The base metal iron is cleaned by picking with dil. H2SO4 for 15-20
minutes at 60-900C then this metal is dipped in a molten Zinc bath
maintained at 4300C. The surface of bath is covered with ammonium
chloride flux to prevent oxide formation on the surface of molten zinc.
The coated base metal is then passed through rollers to have uniform
thickness of the film.
Corrosion
Applications: Used to protect iron which is used to roofing sheets,

wires, pipes, nails, bolts, screws, buckets & tubes etc.
Corrosion
Corrosion
Tinning: Coating Tin over iron (or) steel articles

In tinning, the base metal is first picked with dil. H2SO4 and passed
through Molten tin covered with zinc chloride flux. The Tin coated is
passed through a series of rollers immersed in palm oil bath to remove
the excess tin.
Applications:
Tin is non- toxic and hence it is widely used in coating of steel and copper.
Containers coated with tin are used for storing food stuffs, Ghee, oil &
packing food materials.
Corrosion
Corrosion
Corrosion
ELECTROPLATING OR ELECTRODEPOSITION
• Electroplating is a coating technique. It is the most important and most
frequently applied industrial method of producing metallic coating.
• Electroplating is the process by which the coating metal is deposited on
the base metal by passing a direct current through an electrolytic
solution containing the soluble salt of the coating metal.
• The base metal to be plated is made cathode whereas the anode is either
made of the coating metal itself or an inert material of good electrical
conductivity (like graphite).
Corrosion
Objectives:
Electroplating is carried out for
1) Decoration or better appearance
2) Increasing the resistance to corrosion of the coated metal.
3) Improving the hardness of the metal
4) Increasing the resistance to chemical attack
5) Electro refining.
Corrosion
Electro Plating Method:
This method often uses coating copper, Nickel, zinc, Lead, Tin, Gold and Silver.
Process: In this method an electrolytic cell is set up as follows for coating base
metal with protective metal.
• Anode: Coating Metal (Cu)/ Inert metal
• Cathode: Article to be coated/protected(base metal)
• Electrolyte: CuSO4 solution
Corrosion
Electrolyte : CuSO4 -------> Cu+2+ SO4-2
At anode : Cu+SO4-2--------->CuSO4 +2e-
At cathode : Cu+2+2e- ---------> Cu
Gold Electroplating:
Anode: Gold
Cathode: Metal article
Electrolyte: Gold + KCN
Temperature: 60 deg C.
Current density (mA cm-2): 1-10
Corrosion
• Use:
i) This is used for electrical and electronic applications.
ii)It is used for high quality decorations and high oxidation resistant coatings
iii)Usually for ornamental jewellery, a very thin goldcoating (1x10 -4 cm) is given.
To Improve the corrosion resistance of the metal, Chromium & Nickel coated
Components are used in Automobile parts.
1) For the Aesthetic appearance of the metals/reducing the cost of the metals, Gold
covering Ornaments are used.
2) To Increase the thermal conductivity of the metal, Copper bottomed vessels are used.
3) To Increase the Tensile strength of the metal, Alumimum coatings are used.
Corrosion
ELECTROLESS PLATING
• Electroless plating is a newer technique of depositing a noble metal from

its salt solution on a catalytically active surface of the metal to be
protected by using a suitable reducing agent without using electrical
energy.
• The reducing agent reduces the metal ions into metal which gets plated
over the catalytically activated surface giving a uniform and thin coating.
• Metal ions + reducing agents Metal (deposited) + Oxidised product
Corrosion
Process :
Soluble Salt of coating metal : NiSO4
solution
Reducing Reagent : sodium
hypophosphite (Na2H2PO2)
Buffer solution : Sodium Acetate
PH : 4.5-5.0
Temperature : 70 – 720c
Corrosion
Procedure:
During the electroless plating
• At Anode : H2PO2-+H2O--------> H2PO3-+2H++2e-
• At Cathode : Ni+2+2e------------> Ni(deposited on the article)
• A Ni metal forms a thin and uniform layer on the base metal resulting as nickel
electroless coating, providing corrosion resistance to the base metal.
Applications:
1) It is used extensively in electronic appliances.
2) It is used in domestic as well as automotive fields (eg., jewellery, tops of perfume
bottles).
3) Its polymers are used in decorative and functional works.
4) Its plastic cabinets are used in digital as well as electronic instruments.
Corrosion
Paints
Paint is a dispersion of a pigment in medium oil. When paint is applied on a
surface, the medium oil saves the surface from corrosion. The Pigment saves the
medium oil from the UV light given by the sun.
Constituents of paint:
a) Pigment
b) Vehicle or medium or drying oil
c) Thinner
d) Driers
e) Fillers or Extenders
f) Plasticizers
g) Antiskinning agents
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Requisites of a good paint:

A good paint should the following properties, it should
1) have a high hiding power
2) form a good and uniform film on the metal surface
3) the film should not crack on drying
4) give a glossy film
5) the film produced should be washable
6) give a stable and decent colour on the metal surface
7) have good resistance to the atmospheric conditions
8) be fluid enough to spread easily over the surface
9) possess high adhesion capacity to the material over which it is intended to be used
10)dry quickly or in a reasonable duration.
11)the colour of the paint should not fade.
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Constituents of paints & their Functions

Pigment :
A pigment is a solid and colour producing substance in the paint.

Functions :
i) It gives Opacity and colour to the
ii) It protects the film by reflecting the UV rays.
iii) Provide an aesthetical appeal
iv) Give protection to the paint film by reflecting UV light.
v) Increase weather resistance of the film
vi) Provide resistance to paint film against abrasion.
• White pigments - White lead, ZnO, BaSO4, TiO2, ZrO2
• Blue pigments - Prussian blue, ultramarine blue
• Black pigments - Graphite, carbon black, lamp black
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Vehicle or drying oil or medium:

Vehicle is a liquid substance and film forming material. It holds all the
ingredients of a paint in liquid suspension.
Eg., linseed oil, tung oil.
Functions:
i) To hold the pigment on the metal surface
ii) to form the protective film by evaporation or by other means.
iii)to impart water repellency, durability and toughness to the film
iv)to improve the adhesion of the film
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Thinners
Thinners are volatile substances which evaporate easily after application of
the paint. They are added to the paints for reducing the viscosity of the
paints so that they can be easily applied to the metal surface.
Eg., Dipentine, turpentine, toluol, xylol.
Functions:
i) To reduce the viscosity of the paint
ii) To dissolve vehicle and the additives in the vehicle
iii)To suspend the pigments
iv)To increase the penetration power of the vehicle
v)To increase the elasticity of the paint film
vi)To help the drying of the paint film.
Corrosion
Driers:
These are the substances used to accelerate the process of drying. They
are oxygen carrier catalysts.
Ex. Naphthenates, linoleates, borates, resonates and tungstates of heavy
metals (Pb, Zn, Co, Mn).
Functions:
i) To accelerate the drying of the oil film through oxidation,
polymerization and condensation
ii) To improve the drying quality of the oil film.
Corrosion
Extenders or Fillers:
These are the inert materials which improve the properties of the paint.
Ex: Gypsum, chalk, silica, talc, clay, CaCO3, CaSO4.
Functions:
i) To fill the voids (empty space or any curved area) in the film
ii) To act as a carrier for the pigment color.
iii)To reduce the cost of the paint
iv) To increase the durability of the paint
v) To reduce the cracking of dry paint
vi) To increase random arrangement of pigment particles
Corrosion
Plasticisers:
These are added to the paint to provide elasticity to the film and to
minimize its crack.
Ex: Triphenyl phosphate, dibutyl tartarate, tributyl phthalate, tricresyl
phosphate, diamyl phthalate.
Antiskinning agents:
These are sometimes added to some paints to prevent gelling and
skinning of the finished product.
Ex: Polyhydroxy phenols
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Special Paints
They are obtained by mixing paints with specific types of additives for
special effects.
There are several types of special paints
Heat Resistant Paints :
They can withstand temperature even up to red hot condition. They

contain base of metallic powders like Al, Zn,etc. Such paints are used
as finishes of oven, furnaces etc.
Corrosion
Aluminum Paints:
The fine powder of ‘Al’ is mixed either with sprit varnish or an oil
varnish. It is widely used to paint the metal surface to reduce
corrosion.
Distempers (Water Paints):
The ingredients of distempers are whitening or chalk powder, glue,

colouring pigment and water. These are used as finishing coat on
White washed surfaces of interior walls etc.
Corrosion
Anti-Fouling Paints:
These are used in marine construction . They specially contain Anti-

Fouling agents like HgO, Penta Chloro Phenol, etc.
Water Repllant Paints :
These are prepared by hydrolysis & condensation of Organo ethoxy

silane & Organo chloro silane. Water repellant paints are quite
durable & can last for more than 5 years.
Corrosion
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Electro Chemistry

Unit 2 (B) Corrosion

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Unit 2 (B) Corrosion

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ADITYA COLLEGE OF ENGINEERING &

UNIT –iI: electrochemical cells &

• In other words destruction or deterioration of the metal starts at the

Tarnishing of silver: Formation of black layer on the surface of silver

Minerals ----------energy---------> Pure metal

• It causes contamination of potable water.

• Based on the corroding environment and the mechanism of corrosion, corrosion

Types of dry or chemical corrosion:

CORROSION BY OXYGEN or OXIDATION CORROSION:

• When oxidation starts, a thin layer of oxide is formed on the metal

• Consequently, the oxide layer faces stress and strains, thereby

ii) CORROSION BY OTHER GASES:

2Ag + Cl2 --------> 2AgCl {protective layer}

Sn + 2Cl2 ----------> Sncl4 {non-protective layer}

iii) LIQUID METALS CORROSION:

• Ex: Liquid sodium, used as coolant in nuclear reactors cause the

WET OR ELECTROCHEMICAL CORROSION

• At anodic area oxidation reaction takes place (liberation of free electron),

ELECTROCHEMICAL THEORY OF CORROSION:

Electrolyte: Atmospheric elements dissolved in water.

Fe ------> Fe+2 + 2e-

In absence of oxygen and in acidic environment, evolution of hydrogen takes

2H+ +2e- ------> H2 {reduction}

This type of corrosion takes place in neutral or alkaline medium in presence of

4 Fe(OH)2+O2+2H2O--------->4 Fe(OH)3 ------->2 Fe2O3.3H2O.

At Anode: Metal dissolves as ferrous ions with liberation of electrons.

DRY CORROSION WET CORROSION

Different types of Electrochemical corrosion

For example, if Zn and Cu are connected, Zn acts as anode and undergoes

Mechanism: In a Zn-Cu Couple

Concentration cell corrosion:

Differential aeration corrosion (the most common type of concentration cell

• The area covered by the drop of salt

• A metal high up in the electrochemical series is more anodic and undergoes

Difference between electrochemical series and galvanic series

2. Galvanic series comprises both metals and

3. The relative corrosion tendencies of metals and

FACTORS INFLUENCING RATE OF CORROSION:

The rate of corrosion and extent of corrosion depends upon the

(i)Nature of the metal (ii)Environment factors

Position of the metal in galvanic series:

Position of the metal in the electrochemical series determines the extent

Nature of surface film:

Relative areas of the anodic and cathodic parts:

Presence of impurities in atmosphere:

Conductance of corroding medium:

CORROSION CONTROL (PROTECTION AGAINST CORROSION)

Protection against corrosion (Corrosion Control)

Bolts and rivets should be replaced by proper welding

a) Stainless steel containing chromium produce an exceptionally coherent oxide

Sacrificial anodic protection:

Impressed current cathodic protection:

Long Term Protection(For 20yrs), No need to

Highly Sensitive Components are used, highly

Vapour phase inhibitors:

Use of protective coatings:

Surface preparation: (method of cleaning metal surface)

Methods of application of metal coating: [protective coating]

Applications: Used to protect iron which is used to roofing sheets,

Tinning: Coating Tin over iron (or) steel articles

Electro Plating Method:

• Anode: Coating Metal (Cu)/ Inert metal