HANDOUT 13

MAE 3406 + MEC 3459

Corrosion and its Broad Types
LEARNING OBJECTIVES
• Corrosion and its Significance
• Dry and Aqueous Corrosion
• Corrosion by Gases at High Temperatures
Background to the Contents on ‘Materials’

Essential Properties for Materials used for

Engineering Applications
• Resistance to Deformation due to Stresses:
Mechanical Properties (Strength,
Hardness)
• Resistance of Degradation due to Chemical
Reaction with Environment:
Corrosion Resistance
 Recommended Book

Principles and
Prevention of
Corrosion,
Prentice Hall,
Denny A. Jones
LEARNING OBJECTIVES: ‘Materials’
Arrangement of elemental atoms:
– Structure / microstructure of materials
– Role of microstructure in mechanical properties
– Evaluation of different mechanical properties for
engineering design
– Manipulation of microstructure for achieving
desired mechanical properties
Corrosion Resistance of the materials
– Types
– Combined effect of stress and corrosion
– Ways to avoid corrosion problems (Mitigation)
 What is Corrosion?
Destruction or deterioration of a material
because of reaction with environment

Extractive metallurgy in reverse

 What is Corrosion?
Electroplating in reverse

Power supply (battery)

provides electrons to
the cathode where the
plating occurs.
However, the ultimate
source of the electrons
is the metal at the
anode, which
undergoes corrosion
 Corrosion
• A destructive electrochemical attack of a material

Al Capone's ship, Sapona, off the coast of Bimini

 Corrosion Costs Heavily
Annual cost of corrosion in USA is U$ 276 billion
http://www.corrosioncost.com/
~ 5% of Gross
Annual Income of
any Developed
Country is lost due
to Corrosion and its
Mitigation
Annual cost of loss
due to corrosion
and its mitigation in
Australia : A$8billion
 If we had NO Corrosion !!
• No coatings required for automobiles, ships,
pipelines, household appliances
• Stainless steel industry will disappear, copper will
have very limited use etc.
Economy will be drastically changed

Corrosion is inevitable !
BUT
Its cost can be considerably reduced
by suitable corrosion engineering
 Types of Corrosion
Corrosion is often perceived to be associated only
with Aqueous Environment
However, Corrosion can be caused by
Dry Gases at High Temperatures (Dry Corrosion)
e.g., Power plant steam generators, Gas turbines,
steel processing, Furnaces, Fuel cell components

Aqueous Corrosion (Wet Corrosion)

e.g., Marine structures, Alumina Processing, Pulp and
paper, Aerospace structures, Mg-alloys, Processing
Industry, Electronic components, Automotive parts ….
 High Temperature Corrosion
(Oxidation and Scaling)
Loss of metals due to reaction with
corrosive gaseous environment at
high temperature to form metal
oxides (or compounds, e.g., sulphide)

M + O  MO
 High Temperature Corrosion
How does the scale continue to grow?

Counter diffusion of
oxidizing gas and
metal to the
interfaces:
Out ward diffusion
of metal ions and
electrons and
inward diffusion of
gas ions
 Growth of Oxide Scale
Oxide scale continues to grow due to counter
diffusion of oxidizing gas and metal (but at a
much lower rate than the bare metal),
• So, mechanical stability of oxide scale is
very important (for scale growth at lower
rate),
• One of the ways to decrease oxide scale
growth could be to suitably change the
composition of oxide scale (e.g., stainless
steels)
Mechanical Stability of Oxide Scale
Buckling of Scale
Poor thermal expansion coefficients match, plastic
scale
Mechanical Stability of Oxide Scale
Cracking of the Scale
• Mismatch of thermal expansion coefficients
of metal and oxide
• Adherence and cracking of the scale
depends on the volume difference of the
oxide and the metal from which it is formed
 Mechanical Stability of Oxide Scale
Pilling – Bedworth Ratio
volume of oxide produced AO  M
P - B ratio  
volume of metal consumed AM O
AO – molecular weight of the oxide
AM – atomic weight of the metal
O and M are oxide and metal densities
P-B ratio < 1 – Non Protective oxide layer (porous)
P-B ratio ~ 1 – Protective oxide layer
P-B ratio > 2-3 – Non Protective oxide layer (crack and flake off)
Mechanical
Stability of
Oxide Scale
Cracking Caused / Facilitated by Scale
Jacking of Crack by Scale

Metal Oxide

O2 environment
 Multilayer Scale Formation

Two-layered scale
formed on cobalt
exposed to oxygen
for 10h at 750˚C
 Multilayer Scale Formation on Steel

Oxide scale
developed on Iron
(or Steel) at 1000oC
in Oxygen:
• Inner layer:
Wustite (FeO)
• Intermediate layer:
Magnetite (Fe3O4)
• Outer layer:
Hematite (Fe2O3)
Multilayer Scale Formation on Steel
 Protective Scale Formation
• Role of Cr, Al and Si as alloying additions:
• These elements form oxides that are least
defective of all oxides
• Hence, provide best oxidation resistance
• Si and Al form superior oxide for resistance
(Yet, Fe-Cr alloys are more common as
corrosion resistance alloys, Why?)

• Oxidation of High Cr alloys and stainless

steels
 Protective Scale Formation

Note: Cr-depleted zone in the sub-scale

(area just beneath oxide scale)
 Diffusion Barrier Coatings
• Oxides of Si and Al provide superior
resistance to diffusion
• Si- and Al-oxides provide superior
resistance to scaling
• However, simple Fe-Si or Fe-Al alloys (with
sufficient Si or Al) would have unacceptably
poor mechanical ductility
• Solution: Coating of Si and/or Al containing
material (thus mechanical properties of the
bulk material is retained)
Effects of High Temperature Corrosion on
Mechanical Properties
• Crack initiation due to grain boundary oxidation
• Crack blunting and arrest due to excessive
oxidation at grain boundary crack tip
• Grain boundary strengthening due to preferential
oxide precipitation
• Selective leaching of alloying elements from the
areas adjacent to grain boundaries, and vacancy
and void formation which can assist crack
propagation