CORROSION

OXIDATION
CORROSION
PREVENTION AGAINST CORROSION

Attack of Environment on Materials

Metals get oxidized
Polymers react with oxygen and degrade
Ceramic refractories may dissolved in contact with molten materials
Materials may undergo irradiation damage

Oxidation
Oxide is the more stable than the metal (for most metals)
Oxidation rate becomes significant usually only at high temperatures
The nature of the oxide determines the rate of oxidation

Free energy of formation for some metal oxides at 25oC (KJ/mole)

Al2O3

Cr2O3

Ti2O

Fe2O3

MgO

NiO

Cu2O

Ag2O

Au2O3

1576

1045

853

740

568

217

145

13

+163

Progress of oxidation after forming the oxide layer: diffusion controlled

activation energy for oxidation is activation energy for diffusion through
the oxide layer

Oxygen anions

Oxidation occurs
at metal-oxide
interface

Oxide

Metal Cations

Oxidation occurs
at air-oxide
interface

Metal

Diffusivity = f(nature of the oxide layer, defect structure of the oxide)

If PB >> 1 and reaction occurs at the M-O interface expansion cannot
be accommodated

Oxidation resistant materials

As oxidation of most metals cannot be avoided the key is to form a
protective oxide layer on the surface
The oxide layer should offer a high resistance to the diffusion of the species
controlling the oxidation
The electrical conductivity of the oxide is a measure of the diffusivity of the
ions (a stoichiometric oxide will have a low diffusivity)
Alloying the base metal can improve the oxidation resistance
E.g. the oxidation resistance of Fe can be improved by alloying with
Cr, Al, Ni
Al, Ti have a protective oxide film and usually do not need any alloying

Diffusion in Ionic crystals

Schottky and Frenkel defects (defects in thermal equilibrium) assist the
diffusion process
If Frenkel defects dominate the cation interstitial of the Frenkel defect
carries the diffusion flux
If Schottky defects dominate the cation vacancy carries the diffusion
flux
Other defects in ionic crystals impurities and off-stoichiometry
Cd2+ in NaCl crystal generates a cation vacancy s diffusivity
Non-stoichiometric ZnO Excess Zn2+ diffusivity of Zn2+
Non-stoichiometric FeO cation vacancies diffusivity of Fe2+
Electrical conductivity Diffusivity
Frenkel defect
Cation (being smaller get
displaced to interstitial voids
E.g. AgI, CaF2

Schottky defect
Pair of anion and cation vacancies
E.g. Alkali halides

Alloying of Fe with Cr
A protective Cr2O3 layer forms on the surface of Fe
(Cr2O3) = 0.001 (Fe2O3)
Upto 10 % Cr alloyed steel is used in oil refinery components
Cr > 12% stainless steels oxidation resistance upto 1000oC
turbine blades, furnace parts, valves for IC engines
Cr > 17% oxidation resistance above 1000oC
18-8 stainless steel (18%Cr, 8%Ni) excellent corrosion resistance
Kanthal (24% Cr, 5.5%Al, 2%Co) furnace windings (1300oC)
Other oxidation resistant alloys
Nichrome (80%Ni, 20%Cr) excellent oxidation resistance
Inconel (76%Ni, 16%Cr, 7%Fe)

Corrosion
THE ELECTRODE POTENTIAL
When an electrode (e.g. Fe) is immersed in a solvent (e.g. H 2O) some metal ions
leave the electrode and ve charge builds up in the electrode
The solvent becomes +ve and the opposing electrical layers lead to a dynamic
equilibrium wherein there is no further (net) dissolution of the electrode
The potential developed by the electrode in equilibrium is a property of the
metal of electrode the electrode potential
The electrode potential is measured with the electrode in contact with a solution
containing an unit concentration of the ions of the same metal with the standard
hydrogen electrode as the counter electrode (whose potential is taken to be zero)

Metal
-ve ions
+ve

Standard electrode potential of metals

System

Potential in V

Noble end

Au / Au3+

+1.5

Increasing propensity to dissolve

Standard potential at 25oC

Ag / Ag+

+0.80

Cu / Cu2+

+0.34

H2 / H +

0.0

Pb / Pb2+

0.13

Ni / Ni2+

0.25

Fe / Fe2+

0.44

Cr / Cr3+

0.74

Zn / Zn2+

0.76

Al / Al3+

1.66

Li / Li+

3.05

Active end

 Alloys used in service are complex and so are the electrolytes (difficult to
define in terms of M+) (the environment provides the electrolyte
Environment

Corrosion rate of mild steel (mm / year)

Dry

0.001

Marine

0.02

Humid with other agents

0.2

Metals and alloys are arranged in a qualitative scale which gives a measure
of the tendency to corrode The Galvanic Series
Galvanic series
Galvanic series in marine water
Noble end
18-8 SS
Passive

Active end

More reactive
Ni

Cu

Sn

Brass

18-8
SS
Active

MS

Al

Zn

Mg

Galvanic Cell

e flow

Anode
Zn
(0.76)

Zn Zn2+ + 2e
oxidation

Cathode
Cu
(+0.34)

Cu2+ + 2e Cu
Reduction

Zn will corrode at the expense of Cu

or
2H+ + 2e H2
or
O2 + 2H2O + 4e 4OH

Anodic/cathodic electrodes
Anodic/cathodic phases at the
microstructural level

How can galvanic cells form?

Differences in the concentration of the

Metal ion
Differences in the concentration of
oxygen
Difference in the residual stress levels

 Different phases (even of the same metal) can form a galvanic couple at the
microstructural level (In steel Cementite is noble as compared to Ferrite)
Galvanic cell may be set up due to concentration differences of the metal ion in the
electrolyte A concentration cell
Metal ion deficient anodic
Metal ion excess cathodic
A concentration cell can form due to differences in oxygen concentration
Oxygen deficient region anodic
O2 + 2H2O + 4e 4OH
Oxygen rich region
cathodic
A galvanic cell can form due to different residual stresses in the same metal
Stressed region more active anodic
Stress free region
cathodic

Polarization
Anodic and Cathodic reactions lead to concentration differences near the
electrodes
This leads to variation in cathode and anode potentials (towards each other)
Polarization

Potential (V)

Vcathode

IR drop through the electrolyte

Vcathode

Steady state current

Current (I)

Passivation
Iron dissolves in dilute nitric acid, but not in concentrated nitric acid
The concentrated acid oxidizes the surface of iron and produces a thin protective
oxide layer (dilute acid is not able to do so)
potential of a metal electrode in current density (I/A)
On current density reaching a critical value fall in current density
(then remains constant) Passivation

Prevention of Corrosion
Basic goal protect the metal avoid localized corrosion
When possible chose a nobler metal
Avoid electrical / physical contact between metals with very different electrode
potentials (avoid formation of a galvanic couple)
If dissimilar metals are in contact make sure that the anodic metal has a larger
surface area / volume
In case of microstructural level galvanic couple, try to use a course
microstructure (where possible) to reduce number of galvanic cells formed
Modify the base metal by alloying
Protect the surface by various means
Modify the fluid in contact with the metal
Remove a cathodic reactant (e.g. water)
Add inhibitors which from a protective layer
Cathodic protection
Use a sacrificial anode (as a coating or in electrical contact)
Use an external DC source in connection with a inert/expendable electrode

UNIVERSALITY OF CORROSION
Not only metals, but non-metals like
plastics, rubber, ceramics are also
subject to environmental degradation
Even living tissues in the human body
are prone to environmental damage
by free radicals-Oxidative stressleading to degenerative diseases like
cancer, cardio-vascular disease and
diabetes.

CORROSION DAMAGE

Disfiguration or loss of appearance

Loss of material
Maintenance cost
Extractive metallurgy in reverse- Loss
of precious minerals, power, water
and man-power
Loss in reliability & safety
Plant shutdown, contamination of
product etc

COST OF CORROSION
Annual loss due to corrosion is estimated to
be 3 to 5 % of GNP, about Rs.700000 crores
Direct & Indirect losses
Direct loss: Material cost, maintenance
cost, over-design, use of costly material
Indirect losses: Plant shutdown & loss of
production, contamination of products, loss
of valuable products due to leakage etc,
liability in accidents

WHY DO METALS CORRODE?

Any spontaneous reaction in the
universe is associated with a lowering
in the free energy of the system. i.e.
a negative free energy change
All metals except the noble metals
have free energies greater than their
compounds. So they tend to become
their compounds through the process
of corrosion

ELECTROCHEMICAL NATURE
All metallic corrosion are
electrochemical reactions i.e. metal is
converted to its compound with a
transfer of electrons
The overall reaction may be split into
oxidation (anodic) and reduction
(cathodic) partial reactions
Next slide shows the electrochemical
reactions in the corrosion of Zn in
hydrochloric acid

ELECTROCHEMICAL REACTIONS IN
CORROSION
DISSOLUTION OF ZN METAL IN HYDROCHLORIC ACID,

Zn 2 HCl ZnCl

H 2 -------------------- -(1)

Written in ionic form as,

Zn 2 H 2Cl Zn 2 2Cl H 2

----------------------(2)

The net reaction being,

Zn 2 H Zn 2 H 2

------------------------- (3)

Equation (3) is the summation of two partial reactions,

Zn Zn 2* 2e -----------------------------------------(4) and
2 H 2e H 2 ------------------------------------------(5)
Equation (4) is the oxidation / anodic reaction and
Equation (5) is the reduction / cathodic reaction

ELECTROCHEMICAL THEORY
The anodic &
cathodic reactions
occur simultaneously
at different parts of
the metal.
The electrode
potentials of the two
reactions converge to
the corrosion
potential by
polarization

PASSIVATION
Many metals like Cr, Ti,
Al, Ni and Fe exhibit a
reduction
in
their
corrosion rate above
certain
critical
potential. Formation of
a protective, thin oxide
film.

Passivation is the
reason for the excellent
corrosion resistance of
Al and S.S.

FORMS OF CORROSION
Corrosion may
be classified in
different ways
Wet / Aqueous
corrosion & Dry
Corrosion
Room
Temperature/
High
Temperature
Corrosion

CORROSION
WET CORROSION

DRY CORROSION

CORROSION

ROOM TEMPERATURE
CORROSION

HIGH TEMPERATURE
CORROSION

WET & DRY CORROSION

Wet / aqueous corrosion is the
major form of corrosion which occurs
at or near room temperature and in
the presence of water
Dry / gaseous corrosion is
significant mainly at high
temperatures

WET / AQUEOUS CORROSION

Based on the appearance of the corroded
metal, wet corrosion may be classified as
Uniform or General
Galvanic or Two-metal
Crevice
Pitting
Dealloying
Intergranular
Velocity-assisted
Environment-assisted cracking

UNIFORM CORROSION
Corrosion over the
entire exposed
surface at a uniform
rate. e.g..
Atmospheric
corrosion.
Maximum metal
loss by this form.
Not dangerous, rate
can be measured in
the laboratory.

GALVANIC CORROSION
When two dissimilar
metals are joined
together and exposed,
the more active of the
two metals corrode
faster and the nobler
metal is protected.
This excess corrosion
is due to the galvanic
current generated at
the junction
Fig. Al sheets covering
underground Cu cables

CREVICE CORROSION
Intensive localized
corrosion within
crevices & shielded
areas on metal
surfaces
Small volumes of
stagnant corrosive
caused by holes,
gaskets, surface
deposits, lap joints

PITTING
A form of extremely
localized attack
causing holes in the
metal
Most destructive
form
Autocatalytic nature
Difficult to detect
and measure
Mechanism

DEALLOYING
Alloys exposed to
corrosives
experience selective
leaching out of the
more active
constituent. e.g.
Dezincification of
brass.
Loss of structural
stability and
mechanical strength

INTERGRANULAR CORROSION
The grain boundaries in
metals are more active
than the grains
because of segregation
of impurities and
depletion of protective
elements. So
preferential attack
along grain boundaries
occurs. e.g. weld decay
in stainless steels

VELOCITY ASSISTED
CORROSION
Fast moving
corrosives cause
a) ErosionCorrosion,
b) Impingement
attack , and
c) Cavitation
damage in metals

CAVITATION DAMAGE
Cavitation is a special
case of Erosioncorrosion.
In high velocity
systems, local
pressure reductions
create water vapour
bubbles which get
attached to the metal
surface and burst at
increased pressure,
causing metal damage

ENVIRONMENT ASSISTED
CRACKING
When a metal is subjected to a tensile
stress and a corrosive medium, it may
experience Environment Assisted
Cracking. Four types:
Stress Corrosion Cracking
Hydrogen Embrittlement
Liquid Metal Embrittlement
Corrosion Fatigue

STRESS CORROSION CRACKING

Static tensile stress
and specific
environments
produce cracking
Examples:
1) Stainless steels in
hot chloride
2) Ti alloys in
nitrogen tetroxide
3) Brass in ammonia

HYDROGEN EMBRITTLEMENT
High strength
materials stressed in
presence of hydrogen
crack at reduced
stress levels.
Hydrogen may be
dissolved in the
metal or present as a
gas outside.
Only ppm levels of H
needed

LIQUID METAL EMBRITTLEMENT

Certain metals like Al
and stainless steels
undergo brittle
failure when stressed
in contact with liquid
metals like Hg, Zn,
Sn, Pb Cd etc.
Molten metal atoms
penetrate the grain
boundaries and
fracture the metal
Fig. Shows brittle IG
fracture in Al alloy by
Pb

Air
Corrosion

log (cycles to failure, N f)

log (Crack Growth Rate, da/ dN)

Synergistic action
of corrosion &
cyclic stress. Both
crack nucleation
and propagation
are accelerated by
corrodent
Effect on S-N
diagram
Increased crack
propagation

Stress A mplitude

CORROSION FATIGUE

Log (Stress Intensity Factor Range, K

PREVENTION OF CORROSION
The huge annual loss due to corrosion is
a national waste and should be
minimized
Materials already exist which, if
properly used, can eliminate 80 % of
corrosion loss
Proper understanding of the basics of
corrosion and incorporation in the initial
design of metallic structures is essential

METHODS

Material selection
Improvements in material
Design of structures
Alteration of environment
Cathodic & Anodic protection
Coatings

MATERIAL SELECTION
Most important method select the
appropriate metal or alloy .
Natural metal-corrosive combinations
like
S. S.- Nitric acid, Ni & Ni alloys- Caustic
Monel- HF, Hastelloys- Hot HCl
Pb- Dil. Sulphuric acid, Sn- Distilled water
Al- Atmosphere, Ti- hot oxidizers
Ta- Ultimate resistance

IMPROVEMENTS OF MATERIALS

Purification of metals- Al , Zr
Alloying with metals for:
Making more noble, e.g. Pt in Ti
Passivating, e.g. Cr in steel
Inhibiting, e.g. As & Sb in brass
Scavenging, e.g. Ti & Nb in S.S
Improving other properties

DESIGN OF STRUCTURES

Avoid sharp corners

Complete draining of vessels
No water retention
Avoid sudden changes in section
Avoid contact between dissimilar metals
Weld rather than rivet
Easy replacement of vulnerable parts
Avoid excessive mechanical stress

ALTERATION OF ENVIRONMENT

Lower temperature and velocity

Remove oxygen/oxidizers
Change concentration
Add Inhibitors
Adsorption type, e.g. Organic amines, azoles
H evolution poisons, e.g. As & Sb
Scavengers, e.g. Sodium sulfite & hydrazine
Oxidizers, e.g. Chromates, nitrates, ferric salts

CATHODIC & ANODIC

PROTECTION
Cathodic protection: Make the structure
more cathodic by
Use of sacrificial anodes
Impressed currents

Used extensively to protect marine

structures, underground pipelines, water
heaters and reinforcement bars in concrete
Anodic protection: Make passivating metal
structures more anodic by impressed
potential. e.g. 316 s.s. pipe in sulfuric acid
plants

COATINGS
Most popular method of corrosion protection
Coatings are of various types:
Metallic
Inorganic like glass, porcelain and concrete
Organic, paints, varnishes and lacquers

Many methods of coating:

Electrodeposition
Flame spraying
Cladding
Hot dipping
Diffusion
Vapour deposition
Ion implantation
Laser glazing

Surface Treatment
(Coatings)

Organic paints
Chromating and phosphating:

The Process - chromating and phosphating are surface-coating processes that enhance the
corrosion resistance of metals. Both involve soaking the component in a heated bath based on
chromic or phosphoric acids. The acid reacts with the surface, dissolving some of the surface
metal and depositing a thin protective layer of complex chromium or phosphorous compounds

Anodizing (aluminum, titanium)

The Process - Aluminum is a reactive metal, yet in everyday objects it does not corrode or
discolor. That is because of a thin oxide film - Al2O3 - that forms spontaneously on its surface,
and this film, though invisible, is highly protective. The film can be thickened and its structure
controlled by the process of anodizing. The process is electrolytic; the electrolyte, typically, is
dilute (15%) sulfuric acid. Anodizing is most generally applied to aluminum, but magnesium,
titanium, zirconium and zinc can all be treated in this way. The oxide formed by anodizing is
hard, abrasion resistant and resists corrosion well. The film-surface is micro-porous, allowing it
to absorb dyes, giving metallic reflectivity with an attractive gold, viridian, azure or rose-colored
sheen; and it can be patterned. The process is cheap, an imparts both corrosion and wear
resistance to the surface.

Surface Treatment
(Coatings)

Electro-plating

The Process -Metal coating process wherein a thin metallic

coat is deposited on the workpiece by means of an ionized
electrolytic solution. The workpiece (cathode) and the
metalizing source material (anode) are submerged in the
solution where a direct electrical current causes the
metallic ions to migrate from the source material to the
workpiece. The workpiece and source metal are suspended
in the ionized electrolytic solution by insulated rods.
Thorough surface cleaning precedes the plating operation.
Plating is carried out for many reasons: corrosion
resistance, improved appearance, wear resistance, higher
electrical conductivity, better electrical contact, greater
surface smoothness and better light reflectance.

Bluing
Bluing is a passivation process in which
steel is partially protected against rust, and
is named after the blue-black appearance of
the resulting protective finish. True gun
bluing is an electrochemical conversion
coating resulting from an oxidizing chemical
reaction with iron on the surface selectively
forming magnetite (Fe3O4), the black oxide
of iron, which occupies the same volume as
normal iron.
Done for bolts called
blackening

Hot-dip Coating (i.e.

galvanizing)

Hot dipping is a process for coating a metal, mainly ferrous

metals, with low melting point metals usually zinc and its
alloys. The component is first degreased in a caustic bath,
then pickled (to remove rust and scale) in a sulfuric acid bath,
immersed (dipped) in the liquid metal and, after lifting out, it
is cooled in a cold air stream. The molten metal alloys with the
surface of the component, forming a continuous thin coating.
When the coating is zinc and the component is steel, the
process is known as galvanizing.
The process is very versatile and can be applied to
components of any shape, and sizes up to 30 m x 2 m x 4 m.
The cost is comparable with that of painting, but the
protection offered by galvanizing is much greater, because if
the coating is scratched it is the zinc not the underlying steel
that corrodes ("galvanic protection"). Properly galvanized steel
will survive outdoors for 30-40 years without further
treatment.

CONCLUSION
Corrosion is a natural degenerative process
affecting metals, nonmetals and even
biological systems like the human body
Corrosion of engineering materials lead to
significant losses
An understanding of the basic principles of
corrosion and their application in the
design and maintenance of engineering
systems result in reducing losses
considerably