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 INTRODUCTION CAUSES OF
 CORROSION THEORIES OF
 CORROSION CORROSION

 REACTIONS

 FACTORS EFFECTING THE CORROSION TYPES OF

 CORROSION CORROSION CONTROL METHODS

➢ Destruction of a metal by chemical or electrochemical reaction
with its environment.
➢ Physical or mechanical wearing away of a metal is not called
corrosion but is called erosion
➢ If corrosion and erosion take place together the destruction of
the metal takes place very much faster
➢
Corrosion is an unintentional attack on a material by reaction
with a surrounding medium
The corrosion problem should be very seriously considered in
➢
all those cases where the structure or the equipment is meant
to last many years say 20 years…
Corrosion is the deterioration of materials by chemical
interaction with their environment. The term corrosion is
sometimes also applied to the degradation of plastics,
concrete and wood, but generally refers to metals.
➢ The chemical combined state of the metal is known as “ore”

➢ The ore has low energy in its thermodynamical state.

➢ The extracted metal has high energy ,thermodynamically

unstable .

➢ Metal converts itself into stable state by reacting with the

environment and undergoes corrosion.

➢ The corroded metal is thermodynamically stable.

➢ The valuable metallic properties like conductivity,malleability,
ductility etc are lost due to corrosion.

➢ Life span of the metallic parts of the machineries is reduced.

➢ The process of corrosion is very harmful and is responsible for

the enormous wastage of metal in the form of its compound.

➢ The failure of the machinery takes place due to lose of useful

properties of metals.

➢ The approximate estimate of loss of metal due to corrosion is

2 to 2.5 billion dollars per annum all over the world.
Different types of electrochemical corrosions are

➢ Galvanic corrosion

➢ Pitting corrosion

➢ Intergrannular corrosion

➢ Water line corrosion

 This corrosion occurs when different metals are in contact and
exposed to corrosive atmosphere.

 The metal which has higher electrode potential value will form
anode and undergoes corrosion. Example: Zn-Cu galvanic
cell zinc behaves as anode and corrosion occurs, copper
behaves as cathode and protected.
➢ When corrosion starts on a metal surface

at certain spots they become less open to

oxygen with the result that corrosion

➢
proceeds faster at those very spots making
➢ deeper and deeper cavities.

Pitting corrosion can be explained on the

➢
basis of differential aeration.
The pit created becomes deeper, its
bottom becomes less open to oxygen
which makes it more anodic.
The part which has higher oxygen
concentration is cathodic.
➢ The concentration of oxygen dissolved in
water is greater at the surface than deeper
down. This causes formation of a
concentration cell.

➢ Anode is the lower portion .

➢ Cathode is at the water level.

➢ Due to the poor conductivity of water the

ions just below the water level are
available for reaction, the metal corrodes
just below the water level.
➢ In atmospheric corrosion the metals tend to revert to the states in
which they occur in nature.

➢ Several theories of corrosion have been proposed from time to

time..
The three theories are
➢

i) ACIDTHEORY
ii) CHEMICAL CORROSION ( DRY CORROSION)
iii) ELECTROCHEMICAL CORROSION ( WET
CORROSION )
Acid theory of corrosion considers acid to be the main cause.

Rusting takes place faster in acid solutions than in neutral or basic

solutions.

Oxygen and water are necessary for rusting of iron.

This is not true for all the metals like Zn etc..

Rate of corrosion in absence of Carbon di oxide is also seen.

➢ The direct chemical reaction of environment/atmospheric
gases or inorganic liquids with metal surfaces .
➢ There are three types of chemical corrosion
i) Oxidation corrosion

ii) Corrosion by other gases

iii) Liquid metal corrosion

(1.) Oxidation Corrosion:
This is carried out by the direct action temperatures on metals in absence of
oxygen low or high moi st ur e. Alkali metals and Alkaline earth metals are
rapidly oxidized at low temperatures. At high temperature all metals are
oxidized (except Ag, Au, Pt).

M → M 2++2e -(Oxidation)
O2+2e - → 2O2(Reduction)
-
2 →
M+O M2+2O(Metaloxide)
+ 2-
M echanism:-
1. When temp increases the metal undergoes oxidation and losses e-

2M →2M+n +2ne-
Metal Ion
2. Electron are gained by the oxygen molecules forms oxide ions

nO2+4ne- →2nO 2-
Oxide Ion
3.Scaleofmetaloxideformed2M+nO 2→2M+2nO 2
Metal Oxide
2.) Corrosion due to other gases: This type of corrosion is due
2 2 2 2 2
to gases like SO , CO , Cl , H S, F etc. In this corrosion, the
extent of corrosive effect depends mainly on the chemical
affinity
between the metal and the gas involved. The degree of attack
depends on the formation of protective or non protective films
on the metal surface which is explained on the basis of Pilling
Bedworth rule.
(i) If the volume of the corrosion film formed is more than the
underlying metal, it is strongly adherent, non-porous does not
allow the penetration of corrosive gases.
Ag + Cl2 → 2AgCl (protective film)
(ii) If the volume of the corrosion film formed is less than the
underlying metal, it forms pores/cracks and allow the
penetration of corrosive gases leading to corrosion of the
underlying metal.
Ex. In petroleum industry, H2S gas at high temperature reacts
with
steel forming a FeS scale. Fe (steel) + H2S FeS (porous)
3.) This corrosion is due to chemical Liquid metal corrosion:
action of flowing liquid metal at high temperatures on solid metal
or alloy. The corrosion reaction involves either dissolution of a
solid metal by a liquid metal or internal penetration of the liquid
metal into the solid metal.
Eg. Coolant (sodium metal) leads to corrosion of cadmium in
nuclear reactors.
➢ The electrochemical corrosion occurs when
i) a conducting liquid is in contact with a metal.

ii) when two dissimilar metals or alloys are immersed

partially in the solution.

➢ Corrosion occurs due to the presence of anodic and

cathodic areas.

➢ At anode oxidation reactions takes place

➢ At cathode reduction reactions takes place
➢ Occurs when aqueous solution or liq uid electrolytes are
present
➢ Wet corrosion takes place in environments where the relative

humidity exceeds 60 %.

➢ Wet corrosion is most efficient in waters containing salts,

such as NaCl (e.g. marine conditions), due to the high
conductivity of the solution.
Mechanism Of Electrochemical Corrosion
Anodic Reaction:
Dissolution of metal takes place.
As result metal ions are formed with the liberation of free
electrons.
M ↔ M+n + e-
Metal Ion
 Cathodic Reaction
(i) Hydrogen Evolution :- Occurs usually in acidic medium
2H++ 2e -↔ H2 (g)

(ii) Oxygen Absorption :- occurs when solution is aerated

sufficiently.
O+4H++4e-
2 ↔2H2O(Inacidicmedium)
O+4H++4e-↔
2 4OH(Inbasicmedium)
-
➢ Hydrogen gas evolution

➢ Oxygen gas absorption

This type of corrosion occurs in acidic medium. E.g.
Considering the metal Fe, anodic reaction is dissolution of
electrons. ferrous ions with liberation of iron as
Anode:Fe---- →Fe2+2e(Oxidation)
+ -

➢ The electrons released flow through the metal from anode to

cathode, whereas H+ ions of acidic solution are eliminated as
hydrogen gas.
+ - →
Cathode:2H +2e ---- H2 (Reduction)
→ 2Fe ++H2
➢ The overall reaction is: Fe + 2H+ -----

➢ All metals above hydrogen in electrochemical series have a

tendency to get dissolved in acidic solution with simultaneous
evolution of H2 gas.
Absorption of oxygen: For example, rusting of
iron in neutral aqueous solution of
electrolytes in presence of atmospheric
oxygen.
➢ Usually the surface of iron is coated with a
thin film of iron oxide.
➢ If the film develops cracks, anodic areas are
created on the surface.
➢ While the metal parts act as cathodes. It
shows that anodes are small areas, while the
.
rest metallic part forms large cathodes
The released electrons flow from anode to
cathode through iron metal.
At anode: Fe ----→Fe++ 2e -(Oxidation)
2
Atcathode:½O+H O+2e---→2OH(Reduction)
- -
2 2
+ - →
Overall reaction: Fe + 2OH ----- Fe(OH)
2 2

The product called yellow rust corresponds to

FeO.
2 33HO2
❑ The factors that effect corrosion are

i) Nature of the metal

ii) Nature of the environment

❑ The rate and the extent of corrosion depends on the
following factors

A ) Purity of a metal
B ) Position in galvanic series
C ) Over voltage
D ) Nature of oxide film
E ) Nature of corrosion product
 1. Purity of the metal:
Heterogeneity of the metal is due to the
presence of impurities which form tiny electrochemical
cells at the exposed parts. The anodic parts get
corroded.
2.Electrode potentials:
metals with higher reduction potentials do not corrode
easily. They are noble metals like gold, platinum and
silver. Whereas the metals with lower reduction potentials
readily undergo corrosion (e.g.. Zn, Mg, Al etc.).

3.Position of metal in Galvanic series:

Metals which possess low reduction potentials and
occupy higher end of galvanic
series undergo corrosion easily.
 When two metals are in electrical contact in presence of an
electrolyte, then the metal which is more active undergoes
corrosion.
The rate of corrosion depends on the difference in their
position in Galvanic series. Greater the difference more will be
the extent of corrosion at anode.

4.Relative areas of anodic and cathodic cells : When two

dissimilar metals or alloys are in contact, the corrosion of the
anodic part is directly proportional to the areas of the cathodic
and anodic parts. i.e, the relative areas o of corrosion is
influenced by cathodic to anodic cells.

5. Physical state of metal: Metals with small grain size have

more tendencies to undergo corrosion. Metal with more
stress/strain also undergoes corrosion easily.
6. Hydrogen over voltage: when a cathode reaction is hydrogen
evolution type, the metal with lower hydrogen over voltage
on its surface is more susceptible for corrosion, since the
liberation
of hydrogen gas is easy at this condition. Hence the cathodic
reaction is very fast which in turn makes anodic reaction fast.
Hence the rate of corrosion increases. Higher the over
voltage, lesser is the corrosion.
7. Nature of surface film
: If the corrosion product formed is more stable, insoluble
and non porous, it acts as protective layer and prevents
further corrosion (E.g.. Ti, Al and Cr). If the corrosion product
is porous, volatile and soluble, it further enhances the
corrosion (Fe, Zn and Mg).
 1. Temperature:
the rate of corrosion reactions increases with increase in temperature.

2. Humidity in air: the moisture or humidity present in atmosphere furnishes water to the

electrolyte which is essential for setting up of an electrochemical cell. The oxide film formed has

the tendency to absorb moisture which creates another electrochemical cell.

3. Presence of impurities: Atmosphere is contaminated with

gases
like CO2 , SO2, H2S; fumes of H2SO4 , HCl etc. and other
suspended particles in the vicinity of industrial areas. They are
responsible for electrical conductivity, thereby incr ea si ng
corrosion.
4. pH value: pH value of the medium has the greater effect on
corrosion. Acidic pH increases the rate of corrosion.

5. Amount of oxygen in atmosphere: As the percentage of

oxygen in atmosphere increases, the rate of corrosion also
increases due to the formation of oxygen concentration cell.
The decay of metal occurs at the anodic part and the
cathodic
part of the metal is protected.
6.Velocity of ions which flow in the medium: As the velocity
of the diffusion of the ions in the medium increases, the rate
of corrosion increases .
CORROSION CONTROL METHODS
The various measures taken for corrosion protection are

I) CATHODIC PROTECTION

II) SURFACE COATINGS

➢ The method of protecting metals and alloys from corrosion
making them completely cathode.
To achieve this auxilary anode is provided in the corroding
➢ medium which is connected to the structure.
Cathodic protection is of two types

i) Sacrificial anodic method

ii) Impressed current cathodic method

 Force the metal to be protected to behave like cathode.
(i) Sacrificialanodicprotection:
➢ Metal to be protected from corrosion connected to more
anodic metal
Commonly used metals Mg, Zn, Al and their alloys
➢

Eg. A ship-hull which is made up of steel is connected to

sacrificial anode (Zn-blocks) which undergoes corrosion leaving
the base metal protected.

Eg. The underground water pipelines and water tanks are also
protected by sacrificial anode method. By referring to the
electrochemical series, the metal with low reduction potential
is
connected to the base metal which acts as anode.
➢ Direct current is applied in opposite direction to nullify the
corrosion current
➢ Converts the corroding metal from anode to cathode.
 The metal surface is covered with a coating to protect it from
corrosion.

 These may be
i) Metallic

ii) Organic
The metals used for coatings may be placed under two
categories
i) metals which are anodic to the metal i.e., metals above it in
galvanic series.

ii) metals which are cathodic to the metal i.e., metals below it in
galvanic series.
➢ Hot dipping: This technique is most widely used to
control corrosion. Hot dipping is used for producing a
coating for low melting metals such as Zn, Sn, pb ,Al.
➢ on Iron, steel, copper which are having high melting point
usually underwent into corrosion due to their oxidising
property.
➢ The process in general consisting of immersed a metal in a
bath of its molten coating& covered by a molten layer.
➢ The flux cleans the base metal& prevent oxidation of metal
coating with molten solution.
➢ Hot dipping is widely applied either by
(1)GALVANIZING (2)TINNING
➢It is the process in which iron or steel is protected from
corrosion by coating with a thin layer of zinc.
➢ Iron or steel is first cleaned by pickling with dil. H2SO4

solution for 15-20 mts at 600-900c. The steel is then washed

well and dried .
➢ Then the metal sheet is dipped in bath of molten Zinc

maintained at 4250-4300c.
The surface of bath is kept covered with a Zncl2flux to
prevent oxide formation.
➢ Then the metal sheet is passed through a pair of hot rollers

which removes excess of Zinc and maintain uniform

thickness of Zinc on metal sheet.
➢Thesheetissubje ctedtoannealingprocessat650 cand
cooled slowly.

Uses of Galvanization: It is used to protect Iron used for

roofing sheets, wires, pipes, nails, bolts, screws, buckets,
and tubes.
Defects :Galvanised utensils are not used for cooking
because of solubility of Zn.
 TINNING
➢Tinning is the process of coating of tin over the Iron sheet or
steel articles
➢
A cleaned iron sheet is passed through a bath of molten flux,
then passes through a tank of molten tin and finally through a
layer of palm oil which protect hot tin coated surface against
oxidation.
Uses: (1)It is widely used for coating of steel, copper, brass &
bronze etc . It is used to store food stuff, ghee oils, kerosene&
pickels and used for refrigerators equipment.
 ELECTROPLATING
➢ Deposition of coating metal on the base metal by passing
direct current through an electrolytic solution which
contain the soluble salts of the coating material.
➢ Pure metal is made as cathode and base metal as anode.
➢ Electrochemically coat metal is deposited on base metal.
➢ This metal gives smooth, fine and uniform coating
➢ It depends on
(i) Temperature

(ii) Current density

(iii) ElectrolyteConcentration

(iv) Nature of base metal (v) Time

➢ It is most important & frequently usedtechnique in industries
to produce metallic coating

➢ Both metals & non metals can be electroplated.

➢ In metals the electroplating increases resistance to

corrosion, chemical attack, hardness, wear resistance and
surface properties.

➢ In non metals electroplating increases strength and decorates

the surface of non metal like plastics, wood, glass.
❑ Pre treatment of surface:

❑ (1) CO, Ni, steel and Al can be directly plated.

❑ (2)Pb, Cd and Sn are first electroplated with Ni prior to

electroless plating.

❑ (3)Non conductors are a ctivated in Sncl 2 &HCl

followed by dipping in Pdcl2,Hcl.on drying thin pd layer
is formed.
❑ Organic coatings protect the surface as they act as
physical barriers between the metal to be protected and
the corroding environment and are decorative.

❑ The extent of protection given by the organic coatings

depends on
A) Impermeability to gases ,salts and water
B) Chemical inertness to the corrosive environment
C) Good surface adhesion
 Paints form a protective layer over the surface of the metal to
prevent corrosion.
The main constituents of the paints are
 Pigment
 Vehicle
 Thinner
 Driers
 Fillers
 Plasticizers
 Anti skinning agents
➢ It is a solid constituent that obscures the surface and provides
a decorative color.
A liquid binds the pigment to the surface and protects it from
➢
decay.

It usually comprises of 60 to 80% of the weight of the paint

➢

film.
➢
Increases the life of paint film since it prevents the entry of
ultra violet rays.
➢ E.g.; lead oxide, red lead, lead chromate etc.,
➢ Film forming constituent of the paint. They hold the
➢ pigment on the metal surface.
They give metal adhesion to the metal surface. They
➢

impart durability and toughness to the film. They

➢

isomerize , polymerize and condense to form

➢
characteristic tough, elastic ,coherent, highly cross linked
structured macromolecular film.

➢ E.g.: mustard and sunflower oil etc.,

❑
Viscosity is reduced by the addition of thinners.
❑ It is a volatile solvent helps to adjust the consistency of the paint.
❑
Thinner being volatile evaporates.

❑
They remain permanently in paints and varnishes.

❑ They improve elasticity of the film.

❑ They suspend the pigments in the paints.

E.g. Turpentine, mineral spirits, xylol, kerosene.
❑ They are inert materials.
❑ They are used to improve the properties of the paints.
They reduce the cost of paints.
❑
They serve to fill the voids in the film.
❑
Increases the random arrangement of pigment particles.
❑
Improves the durability of the film.
❑
E.g.: talc, chalk, silica etc.,
❑
 Drying of the oil film is accelerated or catalyzed by
driers.

 To reduce the drying time a drier is added.

 They are oxygen carrier catalyst.

 To improve the drying quality of oil film.

 This is done by condensation , oxidation and

polymerization.
E.g. linoleates , borates, resinates etc.,
 They remain permanently in paints and varnishes.

 They improve elasticity of the film.

 To prevent cracking of the film.

 Anti skinning agents prevent the gelling and skinning of

the paint film.

E.g.: tricresyl phosphate, tri phenyl phosphate,

di butyl tartarate etc.,