Forms of Corrosion

Examples
Examples
 What is Corrosion?
Corrosion is defined as the chemical or
electrochemical reaction between a material,
usually a metal and its environment that produces a
deterioration of the material and its properties.

• Wet Corrosion
• Dry Corrosion
 Anodic reaction: Fe → Fe2+ + 2e–

Cathodic reaction:
2H+ + 2e– → H2 (in acid solution)

O2 +4H+ + 4e– → 2H2O (in acid solution)

O2 + 2H2O + 4e– → 4OH– (in neutral and alkaline solutions)

Fe+3 + e– → Fe+2 (metal ion reduction in ferric salt solutions)

Cu+2 + 2e– → Cu (metal deposition)

SO4-2 + 8H+ + 8e → 4S– + 4H2O (Bacteria-SRB)

Driving Force
An appreciation of equilibrium thermodynamics is essential both to
understand corrosion and to determine whether corrosion can occur in a
particular circumstance.

If a corrosion reaction is to be spontaneous, the Gibbs free energy

associated with the cell reaction must be negative (ΔGcell < 0). These free
energy changes maybe related to the relevant equilibrium potentials:


Gcell  nFEcell 0

i.e.: E cell 0 and: E ecathode  E eanode  0

The cathode process must have a more positive equilibrium potential than
that of the anode process for corrosion to occur.
Electrochemical Series
Electrode reaction (red = ox + ne-) / V(SHE)
Au3+ + 3e– → Au +1.50
O2 + 4H+ + 4e– → 2H2O +1.23
Pt2+ + 2e– → Pt +1.20 More cathodic (noble)
Ag+ + e– → Ag +0.80
Less tendency to corrode
Fe3+ + e– → Fe2+ +0.77
O2 + 2H2O + 4e– → 4OH- +0.40
Cu2+ + 2e– → Cu +0.34
Sn4+ + 4e– → Sn2+ +0.15
2H+ + 2e– → H2 +0.00
Pb2+ + 2e– → Pb -0.13
Sn2+ + 2e– → Sn -0.14
Ni2+ + 2e– → Ni -0.23
Co2+ + 2e- → Co -0.28
Cd2+ + 2e– → Cd -0.40
Fe2+ + 2e– → Fe -0.44
Cr3+ + 3e– → Cr -0.74
Zn2+ + 2e– → Zn -0.76
Ti2+ + 2e– → Ti -1.63
Al3+ + 3e– → Al -1.67
More anodic (active)
Mg2+ + 2e– → Mg -2.36
Greater tendency to corrode
Na+ + e– → Na -2.71
K+ + e– → K -2.92
Copper Corrosion - Feasible or Not ?
Eeο /V
Cathode: 2H+ + 2e– → H2 -0.00
Anode Cu2+ + 2e– ← Cu -0.34

Cell Cu + 2H+ → Cu2+ + H2 -0.34

ΔGcell = +66 kJ mol–1 Cu

Iron Corrosion -Feasible or Not ?

Eeο / V
Cathode: 2H+ + 2e– → H2 -0.00
Anode Fe2+ + 2e– ← Fe -0.44

Cell Fe + 2H+ → Fe2+ + H2 +0.44

ΔGcell = -85 kJ mol–1 Fe

Galvanic Series
Galvanic series for a number of metals
and alloys in flowing seawater (conditions:
2.5 to 4.0 m s–1 and 10 to 25 C).

The galvanic series helps in the choice

of metals for protection. The series show
a galvanic series of pure metals and
alloys based on practical observations in
a specific environment such as seawater.
Forms of Corrosion
Syllabus
• Uniform
• Stress Corrosion
• Galvanic
Cracking
• Dealloying
• Corrosion Fatigue
• Crevice
• Hydrogen Damage
• Pitting
• Concentration
• Intergranular
 Uniform corrosion
• Characterised by corrosion occurring uniformly over
the surface.
• Uniform corrosion is usually manifested in the
progressive thinning of a metal component until it
virtually dissolves away or becomes a delicate lace-like
structure

Example: Rusting of steel in air

Mechanism
Fe2+(aq) + 2OH- (aq) = Fe(OH)2(s)
4Fe(OH) 2 + O2 + 2H2O = 4Fe(OH) 3

4Fe(OH) 2 + O2 = 2Fe2O3 • H2O + 2H2O

Environment
• Dry atmosphere
• Damp atmosphere
• Wet atmosphere
• Acids (HCl, HCIO4, H3PO4)
• Atmospheric contaminants.
• Process water containing hydrogen sulfide
• Brines.
• Industrial atmosphere
• Hydrocarbon containing wet hydrogen sulfide
Control
• Slow down or stop the movement of electrons
(a) Coat the surface with a non-conducting medium such as paint,
lacquer or oil
(b) Reduce the conductivity of the solution in contact with the metal an
extreme case being to keep it dry. Wash away conductive pollutants regularly.
(c) Apply a current to the material (see cathodic protection)

• Slow down or stop oxygen from reaching the surface. Difficult to do

completely but coatings can help.

• Prevent the metal from giving up electrons by using a more corrosion

resistant metal higher in the electrochemical series. Use a sacrificial coating
which gives up its electrons more easily than the metal being protected.
Apply cathodic protection. Use inhibitors.
• Select a metal that forms an oxide that is protective and stops the reaction.

Control and consideration of environmental and thermal factors is also essential.

 Galvanic Corrosion
Bimetallic / dissimilar metal or contact corrosion

SS Screw

Heat Exchanger

Cadmium plated Steel washer

Galvanic Series
Galvanic series for a number of metals
and alloys in flowing seawater (conditions:
2.5 to 4.0 m s–1 and 10 to 25 C).

The galvanic series helps in the choice

of metals for protection. The series show
a galvanic series of pure metals and
alloys based on practical observations in
a specific environment such as seawater.
 Condition necessary
• the voltage difference between the two metals on the
galvanic series
• the size of the exposed area of cathodic metal relative to
that of the anodic metal
• the amount of dissolved oxygen available at the cathodic
surface
• cathodic efficiency of the noblest metal
• temperature
• the presence of biofouling.
Pitting corrosion

Pitting cause formation of pits or holes

It is a form of localized corrosion of a

metal surface where small areas corrode
preferentially leading to the formation of
cavities or pits, and the bulk of the surface
remains unattacked.
Environment
• The marine environment is the most conducive environment for pitting.

• Ions, such as Cl-, Br- and I- in appreciable concentrations tend to cause pitting
of steel.

• Aluminum also pits in an environment that cause the pitting of steel. If traces of
Cu2+ are present in water, or Fe+3 ions are in water, copper or iron would be
deposited on aluminum metal surface and pitting would be initiated.

• Breaks in the passive films or other defects, such as a lack of homogeneity in

the film on the metal surface.

• Stagnant conditions in service.

Mechanism

– – Cl–
Cl Cl Cl–
MOH
+
H MOH
MOH
H+
• Pitting initiation H+
H+
• Pitting propagation
• Pitting termination.
Pits Shape
THROUGH PITS SIDEWAY PITS
Stress Corrosion Cracking
SCC is the brittle cracking of a metal due to the result of combined
effects from localized corrosion and a tensile stress.
Stress Corrosion Cracking
Stress Corrosion Cracking
Characteristic
• Most of areas unaffected

• Specific to certain environments

Brass - SCC in solutions with ammonia.
Steel - SCC in caustic (high pH), amine solutions.
Stainless steels and aluminium alloys - SCC in solutions containing chlorides.
Ti-alloys - SCC in nitric acid or methanol.

• Can be Intergranular (Al-Cu, Cu base alloys) transgranular (Mg alloy or

18/8SS) or mixed mode of cracking.

• Residual stresses due to cold working, welding etc.,

• Compressive stress does not cause

• Threshold stress is required

Mechanism
 Factors affecting Corrosion: Metal

1.Position in galvanic series

2.Relative anodic and cathodic area

3.Passivity

4.Purity

5.Nature of corrosion product form

 Environment:
1.Temperature

2.Humidity and moisture content

3.PH

4.Conductance of the medium

 Prevention or remedies to reduce corrosion
Metal:

1. Proper design

2. Cathodic protection

Sacrificial anodic protection

Impressed current cathodic protection

3. By using protective coating

metallic coatings
I. Galvanising
II. Tinning

Inorganic coatings Anodized oxide coatings:

chemical conversion coatings Vitreous or porcelain enamel coating
phosphate coating
chromate coating Organic coatings
chemical oxide coatings Paints: