Module 3 Corrosion PDF

Corrosion and
its control
Prof. Dr. F. Nawaz Khan, VIT

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Module:3 Corrosion 6 hours SLO: 2
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 4 hours SLO: 2
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 6 hours SLO: 1,14
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. Prof. Dr. F. Nawaz Khan, VIT
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Significance of Corrosion on Infrastructure

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Corrosion
“Gradual eating away (or) disintegration (or) deterioration of a
metal by chemical or electrochemical reaction with the
environment”
 Reasons for corrosion:
o metals compounds are more stable thermodynamically.
o Metal will always have a strong tendency to convert itself

into more stable compound state.
o Hence, metals will try to go to lower energy states through
formation of compounds and thus attain stability.

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Loss of metal
Loss of time
Reduction of value of
goods
Effects of Corrosion
Contamination of fluids
due to chemical reaction
Changes in surface
properties
Mechanical damage
ADI/2018
Detrimental Effects of Corrosion
o Due to formation of corrosion product over the
machinery, the efficiency of the machine gets failure
leads to plant shut down.
o The products contamination or loss of products due to
corrosion.
o The corroded equipment must be replaced
o Preventive maintenance like metallic coating or organic
coating is required.
o Corrosion releases the toxic products.
o Health (eg., from pollution due to a corrosion product or
due to the escaping chemical from a corroded
equipment).
o IN RCC the iron rods, if corroded, can cause serious
damage through collapse of pillars or bridges etc.
ADI/2018
Corrosion effect on steel in concrete constructionADI/2018
Collapsed bridge after steel in concrete got corroded
Corrosion effect on machinery ADI/2018
Pitting
corrosion ADI/2018
Corrosion of monuments and art forms
Atmospheric gases and pollution effect on statues & Art Forms
Acid Rain
effect on
Taj Mahal
ADI/2018
Types of corrosion
a) Chemical corrosion (dry corrosion)
b) Electrochemical corrosion (wet corrosion)
a) Dry corrosion (chemical):
o Classified depending on the corroding agent

i) oxidation corrosion
o Oxygen present in the atmosphere attacks the metal forming
oxide layer on the surface of the metal.
M M2+ + 2 e-
½ O2 + 2e- O2-
M + ½ O2 M2+ + O2- metal + O2
o Oxidation corrosion will lead to an oxide film which may be porous

or non-porous.
o Depends on chemical affinity, temperature, corrosion products
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Types of corrosion
Pilling-Bedworth Rule:
o “If the volume of metal oxide is equal to or greater than the volume
of the metal getting corroded, then the oxide film is non-porous and
protects the metal from further corrosion;
o 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”.
o Cu, Al, Ni, Cr form non-porous oxide layers while Li, Na, K, Mg form
porous oxide layers.
o Types of oxide layers:
i) Stable 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, Sn, Cu forms such impervious layers which prevents oxygen
from diffusing through the metal and hence further attack is stopped.
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Pilling Bedworth Rule - Oxidation Corrosion
o Oxide is the more stable than the metal (for most metals)
o Oxidation rate becomes significant usually only at high temperatures
o The nature of the oxide determines the rate of oxidation
o For good oxidation resistance the oxide should be adherent to the surface
o Adherence of the oxide
f = the volume of the oxide formed : the volume of metal consumed in the
oxidation
where f is Pilling-Bedworth ratio
o PB < 1 tensile stresses in oxide film - brittle oxide cracks
o PB > 1 compressive stresses in oxide film - uniformly cover metal surface and is
protective
o PB >> 1 too much compressive stresses in oxide film - oxide cracks
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Types of corrosion
ii) Unstable oxide layer:
o These are produced on noble metal surfaces and these oxide
layers decompose back to the metal.
Metallic oxide Metal + Oxygen

o Pt, Ag etc. form such oxide films.
Unstable
Exposed surface metal oxide
+ O2 Metal oxide
metal Of air metal metal + O2
decomposes
Unstable oxide layer

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Types of corrosion
iii) Porous oxide layer:
o These oxide layers have minute pores and are not impervious
layers.
o Oxygen will diffuse through the pores and promote further
corrosion.
o Fe is a good example of this type of corrosion.
Exposed Porous
surface metal oxide
Further Attack
metal + O2 through pores &
Of air metal
cracks continues
Porous oxide layer

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Types of corrosion
iv) Volatile oxide layer:
o These are oxide layers which evaporate as soon as they are

formed and hence further corrosion is facilitated.
o After some time the metal itself will disappear.
o Molybdenum is an example of volatile oxide layer corrosion.
Exposed
Volatile Fresh surface
surface
metal oxide Exposed for
Further attack
+ O2 Metal
metal oxide
Of air metal volatalizes metal
Volatile metal oxide

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Types of corrosion
ii) corrosion by other gases:
o CO2, Cl2, SO2, F2 etc. are gases which can attack the metal and corrode
o Extent of corrosion depends on the affinity of the metal to the gas.
o These gases chemically react with the metal forming either porous or non-
porous layers of films.
o Hydrogen corrosion: Hydrogen gas attacks the metal to make them brittle
(Hydrogen embrittlement)
Fe + H2S FeS + 2H (atomic hydrogen)
iii) liquid metal corrosion:
o Flowing liquid metal (Hg) can penetrate through another metal to corrode.
o Gold (Au) can be corroded by mercury (Hg).
o Such corrosion is found in nuclear devices

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Types of corrosion
b) Wet or Electrochemical Corrosion:
o In this type of corrosion, a conducting liquid is in contact with a
metal or two dissimilar metals or alloys
o One part becomes anode and the other part cathode.
o At the anodic part corrosion (oxidation) occurs while reduction
takes place at the cathode.
At the anode: M Mn+ + ne-

o Mn+ either dissolved in solution or forms compounds such as
oxides.
The rate of the electrochemial corrosion will depend on:
a) If the corrosion product is soluble in the medium, rate of

corrosion will be high.
b) If the corrosion product is insoluble in the medium, rate of
corrosion will be very low.
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Types of corrosion
Electrochemical corrosion is present in the following types:
1. Hydrogen evolution type corrosion
2. Oxygen consumption type corrosion
3. Galvanic corrosion
4. Concentration cell corrosion
5. Pitting corrosion
6. Stress corrosion
1. Hydrogen evolution type corrosion

occurs when base metals are in contact with an acidic solution.
Eg. Anode : Fe Fe2+ + 2e- (oxidation)
Cathode : 2H+ + 2e- H2

The overall reaction is:
Fe + 2H+ Fe2+ + H2
o Simultaneously, metal ion will be produced at the anode while hydrogen will evolve at
the cathode
o Displacement of H+ ions All metals above H in the EC series Large anodic areas

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Types of corrosion
2.Oxygen absorption type corrosion:
Occurs when base metals are in contact with neutral solutions like water with
Dissolved oxygen (DO).
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 : ½ O2 + H2O + 2e- 2 OH- (Reduction)
The Fe2+ at the anode and OH- at the cathode diffuse and react to produce
Fe(OH)2: Fe + 2 OH- Fe(OH)2
If sufficient oxygen is present, Fe(OH)2 gets oxidised to ferric hydroxide (rust)
4 Fe(OH)2 + O2 +2H2O 4 Fe(OH)3 or 2(Fe2O3.3 H2O)

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Types of corrosion

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3. Galvanic corrosion:
o Occurs when two dissimilar metals in the electrochemical series are in

contact with each other (Joined by rivetting or welding) and exposed
to corroding environment.
o The metal with more negative potential (higher in EC series ) will

become anode and corrodes.
o Nature of corrosive environment decides cathodic reaction
o This can be avoided or minimized by:
a) coupling metals which are close in the electrochemical series.
b) Making the cathode metal

Prof.smaller
Dr. F. Nawazin area
Khan, VIT than the anodic metal.
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Table of Electrode Potentials
Metal Electrode Potential (V)

Magnesium -2.40 (Anodic – more basic)
Aluminium -1.76 CORRODED END
Zinc -0.76
Chromium -0.65
Iron -0.44
Nickel -0.23
Tin -0.14
Lead -0.12
Hydrogen (REF) 0.00
Copper +0.34
Silver +0.80 PROTECTED END
Gold +1.40 (Cathodic – more noble)
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Galvanic
 Dissimilar metals are physically
joined in the presence of an
electrolyte.
 The more anodic metal corrodes.
Bilge pump -
Magnesium shell cast
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Common Corrosion Problems
Metals in contact Corrosion Rectify
Galvanised tank Zinc corrodes Sacrificial anode

& copper pipes or plastic tank
Copper ball-cock Solder corrodes Plastic ball

Soldered to brass in damp atmospheres
Copper flashing Steel corrodes Copper nails

secured by steel nails
Steel radiators with Steel corrodes Corrosion

inhibitors
copper pipes

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4. Concentration cell corrosion: (Differential aeration corrosion)
o When a metal is exposed to different concentration of oxygen or any

other electrolyte, a concentration cell is formed.
o The part of the metal exposed to lower concentration of oxygen (or)
electrolyte becomes anode and the one exposed to higher
concentration becomes cathode.
o Corrosion starts at the anode (dissolves).
o This type of corrosion occurs when metals are partly dipped in
solutions, partly covered with dust, oil marks, sand etc.
o Eg. Zinc rod dipped in brackish water solution, water line corrosion.
Waterline Corrosion
Waterline corrosion: (a) Water storage tank and (b) ocean going ship
5. Pitting corrosion:
o 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
o Eg. Al, Ti and stainless steel undergo pitting corrosion in acidic

environment.
METAL Cathodic
Oxygen poor at
base of crack
Anodic
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Pitting
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.
5th Century sword

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37
6. Stress Corrosion Cracking, SCC
 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.
 Consequently, no corrosion products are visible,
making it difficult to detect or prevent; fine cracks
can penetrate deeply into the part.
 Eg.
 Brass in the presence of ammonia ,
 Stainless steel in the presence of
NaOH or chloride solution at high
temperature
 Ti alloys in nitrogen tetroxide
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ADI/2018
Cause Anode Examples Rectify
Grain structure Grain boundary Steel/damp Isolate steel
Concentration Low Soil types Protective coatings

variations in concentration
electrolyte areas
Differential Oxygen remote Underground Protective coatings

aeration areas steel pipes
Stressed areas Most heavily Steel rivets Protect from

stressed area or nails dampness

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Images of Crevice Corrosion
ADI/2018
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Nature of the metal
Electrode potential difference
Primary Factors Surface state of the metal
Hydrogen overvoltage
Formation of protective films
Factors Influencing by metals
Rate of Corrosion
pH
Temperature
Anodic and cathodic area

effect
Secondary Factors
Conductance of the medium
Humidity
ADI/2018
Factors affecting corrosion
From metal:
o Nature of metal
o Position in galvanic series
o Overvoltage
o Relative area of anodic, cathodic parts
o Purity of metal
o Surface film
o Passive character
o Solubility & volatility of corrosion
products
From Environment
o Temperature
o Humidity
o Impurities
o Suspended particles
o pH
o Nature of ions
o Formation of concentration cells
o Polarisation of electrodes
Factors influencing corrosion
Factors influencing corrosion depend on:
a) Nature of the metal
b) Nature of the corroding environment
 Nature of the metal:
i) Position in the galvanic series:
o When two dissimilar metals are in contact, the more anodic
metal (Higher up in the series) will corrode.
o The extent of corrosion depends on how far apart are the two
metals in the galvanic series.
ii) Over voltage:
o When a metal (eg. Zn) is dipped in 1 N sulphuric acid, the initial

rate of corrosion is quite slow since hydrogen evolution takes
place on Zn at 0.7V.
o If a few drops of CuSO4 are added, the hydrogen over voltage
comes down to 0.33V and corrosion rate increases.
o Reduction in hydrogen over voltage increases the rate of
corrosion. Prof. Dr. F. Nawaz Khan, VIT
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iii) Relative areas of cathode and anode:
o When two dissimilar metals are in contact, the rate of corrosion is
directly proportional to the ratio of cathodic part to anodic part.
o If anodic area is small, the corrosion is rapid.
iv) Purity of the metal:

o Purer the metal, lesser is the rate of corrosion.
o Due to impurities, local galvanic cells are formed and anode gets
corroded.
v) Physical state of the metal:

o The rate of corrosion will depend on the physical state of the metal
such as grain size, orientation of crystals, stress etc.
vi) Nature of surface film: (Pilling-Bedworth rule):
o 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.
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vii) Passive character of the metal:
o Some metals eg. Tl, Al, Cr, Mg, Ni and Co are passive and show
resistance to corrosion.
o They form highly protective oxide layers on their surfaces which

gives the metal passive character and protects it from further
corrosion.
viii) Solubility of corrosion product:

o If the corrosion product is soluble in the environment in which the
metal is working, then the corrosion will proceed faster.
o 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.
viii) Volatility of the corrosion product:

o 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.
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b) Nature of the corroding environment:
i) Temperature:
o As temp. increases, the rate of corrosion also increases.
ii) 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.
iii) Presence of impurities in the atmosphere:

o Gases like CO2, SO2, H2S and fumes of HCl, H2SO4 which are
present in the industrial areas provide conductive environment for
enhancing the electrochemical corrosion.
o In marine environment, the Cl- is responsible for enhanced rate of
corrosion.
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iv) Presence of suspended solids in the environment:
o Particles like NaCl, (NH)4SO4 together with moisture act as conductive
electrolyte and enhance the rate of electrochemical corrosion.
v) Effect of pH: (Pourboux-Evans diagram may be explained)
Acid medium facilitates corrosion than neutral and basic media as a
general rule.
o 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.
o At pH 4.0, the corrosion rate of Fe is very high since Fe2+ gets oxidised
to Fe3+.
o Zinc corrodes rapidly in acidic solutions but the rate of corrosion is low
in alkaline medium (pH 11.0).
o Aluminium corrodes less at pH 5.5 but the rate of corrosion is very
high in pH 8.5.
vi) Nature of ions present:
o Anions like silicates form insoluble salts in the medium and inhibit
further corrosion.
o But, Cl- present in the atmosphere destroy the protective oxide film
and enhance rate of corrosion.
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vii) Conductance of the corroding environment:
o In corrosion of underground and submerged structures, the
conductance of the medium plays a critical role in corrosion.
o Conductance due to stray currents through the soil will promote
the corrosion.
viii) Formation of oxygen concentration cell:
o 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.
o This is called oxygen concentration cell which promotes
corrosion by anodic oxidation/dissolution.
2 H2O + O2 + 4e- 4 OH- (Cathodic reaction-higher O2)
o This OH- will move to the cathode where Fe2+ reacts to form
Fe(OH)2 which later converts into rust (Fe2O3.3H2O).
o Buried pipelines, cables etc., experience this kind of
electrochemical corrosion.
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Corrosion and

Prof. Dr. F. Nawaz Khan, VIT

Alloying for corrosion protection – Basic concepts of Eutectic composition and

Prof. Dr. F. Nawaz Khan, VIT

o Metal will always have a strong tendency to convert itself

Prof. Dr. F. Nawaz Khan, VIT

Atmospheric gases and pollution effect on statues & Art Forms

o Classified depending on the corroding agent

M + ½ O2 M2+ + O2- metal + O2

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

o Types of oxide layers:

i) Stable oxide layer:

Metallic oxide Metal + Oxygen

Unstable oxide layer

Porous oxide layer

o These are oxide layers which evaporate as soon as they are

o After some time the metal itself will disappear.

o Molybdenum is an example of volatile oxide layer corrosion.

Volatile metal oxide

Fe + H2S FeS + 2H (atomic hydrogen)

iii) liquid metal corrosion:

Prof. Dr. F. Nawaz Khan, VIT

At the anode: M Mn+ + ne-

The rate of the electrochemial corrosion will depend on:

a) If the corrosion product is soluble in the medium, rate of

1. Hydrogen evolution type corrosion

Cathode : 2H+ + 2e- H2

Prof. Dr. F. Nawaz Khan, VIT

Anode : Fe Fe2+ + 2e- (oxidation)

Cathode : ½ O2 + H2O + 2e- 2 OH- (Reduction)

If sufficient oxygen is present, Fe(OH)2 gets oxidised to ferric hydroxide (rust)

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

Prof. Dr. F. Nawaz Khan, VIT

Prof. Dr. F. Nawaz Khan, VIT

o Occurs when two dissimilar metals in the electrochemical series are in

o The metal with more negative potential (higher in EC series ) will

o This can be avoided or minimized by:

a) coupling metals which are close in the electrochemical series.

b) Making the cathode metal

Metal Electrode Potential (V)

Galvanised tank Zinc corrodes Sacrificial anode

Copper ball-cock Solder corrodes Plastic ball

Copper flashing Steel corrodes Copper nails

Steel radiators with Steel corrodes Corrosion

Prof. Dr. F. Nawaz Khan, VIT

o When a metal is exposed to different concentration of oxygen or any

o Due to rapid penetration of oxygen through some cracks in the

o Eg. Al, Ti and stainless steel undergo pitting corrosion in acidic

5th Century sword

Grain structure Grain boundary Steel/damp Isolate steel

Concentration Low Soil types Protective coatings

Differential Oxygen remote Underground Protective coatings

Stressed areas Most heavily Steel rivets Protect from

Prof. Dr. F. Nawaz Khan, VIT

Electrode potential difference

Primary Factors Surface state of the metal

Anodic and cathodic area

ii) Over voltage:

o When a metal (eg. Zn) is dipped in 1 N sulphuric acid, the initial

o If anodic area is small, the corrosion is rapid.

iv) Purity of the metal:

v) Physical state of the metal:

vi) Nature of surface film: (Pilling-Bedworth rule):