Corrosion

 The disintegration of an engineered

material into its constituent atoms due
to chemical action with its
surroundings.
 For e.g -formation of green layer on
copper surface.


• Rusting: Formation of an oxide of iron

due to oxidation of the iron atoms in
solid solution
• Corrosion can also refer to other
materials than metals, such as
ceramics or polymers-degradation.

 FACTS ABOUT CORROSION
– Corrosion is natural process.
– Corrosion electrochemical process.
– It cannot be eliminated.
– Reverse of extraction: weeping of
metal
–
 Why CORROSION occurs


 Metal Metal salt

 (high energy) (low energy)





 Theories of corrosion:
 1. Direct Chemical attack ,
Chemical Corrosion, Dry Corrosion.
 2. Wet or electrochemical
corrosion
 3. The acid theory
•
1.

Direct Chemical attack ,
Chemical Corrosion, Dry
Corrosion- O2 , S, Halogen, H2 S
– Insoluable: further corrosion is checked
 Cl2 , I2+ Ag AgCl , AgI
– Soluable/liquid: further corrosion e.g
detinningof metal cans using
dry Cl2

i). Oxidation Corrosion: alkali and
alkaline (low temp)
 2M 2Mn+ + 2ne-
(oxidation)
 n/2O2 + 2ne- nO2-
(reduction)
• MO layer: thickness is upto 300 A-
film
• Scale > 300 A
Case I: When metal ion diffuses
faster outward. oxide layer is
formed at the metal oxide – gas or
scale – gas interface.
•



Case II: When oxygen diffuses
inward:
 oxide layer is formed at the metal-
scale interface or metal When
oxygen diffuses inward
•
Nature of metal oxide layer


a) Stable film –An impervious layer is formed,

which checks further oxidation corrosion.
 e.g. oxide films on Al, Sn, Pb, Cu etc.

b) Unstable film-

 Metal oxide Metal + O2

 e.g. in Au and Ag
•
c) Volatile film- oxide layer volatilizes leaving


the underlying metal surface for further attack.

E.g. molybdenum oxide (MoO3)
is volatile.


d) Porous film- atmospheric O2have access to



the underlying surface of metal.

 Pilling Bedworth rule:


 Volume of MO > Volume of metal ___non

porous or protective. eg . AlO
 Volume of MO< Volume of metal-
_____ porous. e.g Alkali & alkaline earth
metal oxides


ii)

Corrosion by other gases:
 CO2, SO2, Cl2, H2S
• Ag + Cl2 AgCl
• Sn + Cl SnCl4
• Extent of corrosion depends upon the chemical
affinity between metal and the gas involved and
the nature of the film formed on the surface
iii) Liquid metal corrosion- occurs due to the


chemical action of flowing liquid metal at high T on solid

metal or alloy.
 Dissolution of a solid metal by a liquid metal.
 Internal penetration of the liquid metal into the solid
metal


2. WET OR ELECTROCHEMICAL CORROSION/
IMMERSED CORROSION:
 All metal have tendency to pass into the solution
 i) When a conducting liquid is in contact with metals
 ii) When two dissimilar metal or alloy are dipped partially in a
solution.
Mechanism:


Anodic reaction
M M n+ + ne - (oxidation)
(s) (aq)
Fe(s)
 Fe2+ (aq) + 2e- (oxidation)
Fe2+ (aq) + 2OH-(aq)
 Fe(OH)2


•
Cathodic reaction:
a)Electroplating

 Cu2+ (aq) + 2e- Cu(s)

b) In acidic solution in the absence of O
2
 2H+ + 2e- H2
c) In acidic solution in the presence of O
2
 O2 + 4H+ + 4e- 2H2O
d) In neutral or alkaline medium in the absence of

O2
 2H2O + 2e- H2 + 2OH-
•
(e) In neutral or alkaline medium in


the presence of O2
 O2 + 2H2O + 4e-
4OH-
 (such type of corrosion involving
O2 is called oxygen type corrosion)
•  

 Rusting of iron:
At anode: Fe Fe2+ + 2e-
At Cathode: ½ O
2 + H2O + 2e-
2OH-
Net reaction

Fe+1/2O2 +H2O Fe2+ +

2OH- or Fe(OH)2
Excess of O
2 : , ferrous hydroxide is
easily oxidized to ferric hydroxide.
 2Fe(OH)2 + H2O + 1/2O2
2Fe(OH)3

 Limited supply of O2:
black magnetite Fe3O4 or ferroferric
oxide is formed.
 Fe(OH)2
Fe2O3.FeO.6H2O
 Black




Wet corrosion Dry corrosion
•
• It takes place in presence of water It takes place in absence of
liquid or
• or an electrolyte. electrolyte. Gases and vapours are
• the corrodants.


• It is an electrochemical attack. It is a chemical attack.

•
• It generally takes place at low It takes place at high
temperature.
• temperature.


• It is also known as low It is also known as

high
• temperature corrosion. temperature
corrosion.

•
3.THE ACID THEORY:
 applicable particularly to rusting of iron
• Occurs in presence of acid.
• Fe + O2, CO2& moisture
soluableferrous bicarbonate
ferric carbonate
 hydrated ferric oxide.
• 2Fe + O2 + 4CO2 + 2H2O
2Fe(HCO3)2
• 2Fe(HCO3)2 + H2O + [O]
2Fe(OH)CO3+2CO2+ 2H2O
• 2Fe(OH)CO3 + 2H2O 2Fe(OH)3 +
 Types of Corrosion
1.Galvanic corrosion/bimettalic
corrosion:
 Occurs when two metals with
different electrode potential is
connected in a corrosive electrolytic
environment.
• More reactive: anode- corrosion
• Less reactive: cathode-protected
 Factors affecting
corrosion:
– Potential difference b/w the two metal
coupled
• E.g. Zinc and copper couple
 More reactive
 Zn Zn2+ + 2e- At anode
(Corrodes)
 Less reactive
 Cu2+ + 2e- Cu At Cathode
(protected)
• e.g.
a) Steel pipe connected to copper

plumbing.
b) Steel screw in brass marine

Electrochemical series
Galvanic series

• The arrangement of metals and non-metals in increasing order The
arrangement of metals and alloys in their standard reduction potential is
known as decreasing order of their corroding electrochemical series
tendency in an unpolluted
sea water is known as galvanic series.

•
•  It contains metals and non-metals It contains metals and alloys.

• It is an ideal series It is a practical series

•
• ECS is based upon the electrode potential which This series is based on
actua is determined by using Nernst equation corrosion rate

•
• Position of metals is fixed in ECS Position of a given metal in
Galvanic
• series may change
 2. Erosion Corrosion: Abrading action of
turbulantflow of gases, vapors, liquids and
due to rubbing action
 minimization: Harder metal, less friction
design, lubrication.
3. Crevice Corrosion: dirt deposit, cracks in
paints , coating etc
 Minimization: selection of proper design,
clean surface
4. Pitting corrosion: Breakdown of the
protective film on the metal specific points-
forming small anodic area, rest of the surface
will act as cathode.
 e.g. Al & stainless steel –pitting corrosion in
chloride environment.

Facts about Pitting Corrosion :
 Pitttingcorrosion is autocatalytic, self
stimulating or self propogating.
 Stagnant condition leads to pitting
corrosion
 It takes place exclusively in chloride
and chloride containing environment.



 Minimization:
– Prevent stagnant conditions
– Add Mo to ordinary steel for better
pitting resistance
– Periodic inspection of the structure
and cleaning the deposit
5. Waterline Corrosion
 6 Micro-Biological Corrosion :
– Due to metabolic activity of various
micro-organisms.
• Produces corrosive environment
• Create electrolytic concentration cell
 7 Stress Corrosion Cracking
– Metal under stress becomes more anodic and
tend to increase the rate of corrosion.
– The stress can be due to non-uniform
deformation by unequal cooling from high
temperature as in welding

Factors affecting chemical corrosion


1. Nature of the metal

1 Position in the Galvanic series
2 Relative areas of anode and cathode
3 Purity of metal
4 Solubility of corrosion products
5 Volatility of corrosion products
6 Passive character of metal
•
  (vii) Nature of surface film :
 Specific volume ratio = Volume of metal oxide
volume of metal
 (viii) Passive character of metal: Tl, Al, Cr, Mg etc
form thin layer of passive metal oxide.
e.g. Cr present in stainless steel


2. Nature of environment
3.
1 Temperature: Rate of chemical reaction and rate of diffusion
increases with temperature
2 Presence of moisture:
 Critical humidity is the relative humidity above which the
atmospheric corrosion rate of metal increases sharply
3 Presence of impurities in atmosphere: due to CO2, H2S,
SO2 etc in the vicinity of industrial area


•
3
4 Effect of pH
5 Nature of ions present: Chloride ions present
in the medium destroy the passive film,
while silicate in the medium leads to the
formation of insoluble film over the metal
surface.
6 Concentration of O2
•
PROTECTION FROM CORROSION
(I) Design and Material Selection
(II) Cathodic Protection:
a) Appropriate galvanic coupling:
Metal will be made to act as cathode
(b) By impressed current
Advantages over sacrificial
cathodic protection
 It is controlled from outside.
 No anode has to be replaced.
(III) Modifying the Environment
a) Deaeration
b) Deactivation : addition of chemicals,
capable of combining rapidly with O2in
aqueous solution
c) Dehumidification: by using alumina or
silica gel
d) Alkaline neutralization
e) Use of inhibitors
i) By forming a layer in between
which acts as a barrier between the
material
and environment.
IV) Metallic coatings
i. Electroplating
ii.Hot dipping
iii.Vaporizing
Zn- Sheradising or dry galvanising
Al- Calorising
i. Metal spraying
ii.Cementation: The base metal articles are packed in
the powdered coating metal and is heated to a
temperature just below the m.p. of more fusible
metal, so that an alloy layer is formed over the
surface.
Types of metallic coating

Sacrificial coating Noble coating

Base metal is coated with a metal which is Base metal is

coated with a more reactive than the base metal. metal
which is more noble than the base metal.

Protects the underlying base metal sacrificially. Protects the

underlying base metal due to its noble character
and higher corrosion resistance.

This is known as anodic coating as the reduction This is known as

cathodic coating aspotential of coating metal is less than that
the reduction potential of coating the base metal. Metal
is more than that of the base metal

 Zn, Cd, Al are generally used as sacrificial coating Ni, Ag, Cr, Pb,
Au etc. are generally used as noble coating

E.g. Galvanised iron i.e. coating of Zn E.g. coating of Sn on

V) Inorganic non-metallic coatings
i) Chemical dip coating or surface conversion
Chromate, phosphate
2 Anodized oxide coating
AlOChromic acid, oxalic acid

VI) Organic coatings: paints, varnishes etc