Corrosion

Cases in Corrosion

Introduction

Corrosion : Deterioration of metal resulting from chemical

attack by its environment.
Temperature and concentration of reactants and products will
affect the Rate of corrosion.
Electrochemical cells exist within the metals with free
electrons.
Metals have tendency to go back to low energy state by
corroding.
Ceramics and polymers suffer corrosion by direct chemical
attack.
A metal (Zn) placed in HCL undergoes corrosion
Zn + 2HCL
ZnCl2 + H2
Zn
Zn2+ + 2e- ( Oxidation half cell reaction)
H2 (Reduction half cell reaction)
2H + + 2eOxidation and reduction takes place at the same rate.

Standard electrode Half-Cell potential of metals.

Zinc
HCl

Oxidation anode

Reduction cathode

Oxidation /reduction half cell potential are compared

with standard hydrogen ion half cell potential
Voltage of metal eg. Zinc is directly measured against hydrogen half cell electrode.

Oxidation Reduction Reactions

A metal (Eg Zn) placed in HCL
undergoes corrosion.
Zn + 2HCL
ZnCl2 + H2
or
Zn + 2H+
Zn2+ + H2
also
Zn
Zn 2+ + 2e(oxidation half cell reaction)
2H+ + 2eH2
(Reduction half cell reaction)
Oxidation reaction: Metals form ions
at local anode.
Reduction reaction: Metal is reduced
in local charge at
Local
cathode.
Oxidation and reduction takes place
at same rate.

Passivation

Passivation is loss chemical reactivity in presence of an

environmental condition.
Formation of surface layer of reaction products that inhibit further
reaction.
Oxide film theory : Passive film is always a diffusion barrier of
reaction products.
Adsorption theory : Passive metals are covered by chemisorbed
films of oxygen.
Example Stainless steel, nickel alloys, titanium and aluminium
alloys.

Macroscopic Galvanic Cells with 1M Electrolyte

Two dissimilar metal electrodes immersed in solution of
their own ions.
Electrode that has more
negative oxidation potential
will be oxidized.
Zn
Zn2+, Cu2+
Cu
Half cell reactions are
Zn
Zn 2+ + 2e- E0 = -0.763 V
Cu
Cu2+ + 2e- E0 = + 0.337 V
Or Cu2+ + 2eCu E0 = -0.337 V (negative sign)
Adding two reactions,
Zn + Cu2+
zn2+ + Cu E0cell = -1.1V

Grain Grain boundary Electrochemical cells

Grain boundaries are more anodic

and hence get corroded by
electrochemical attack.
Grain boundaries are at higher
energy.
Impurities migrate to grain
boundaries.
Solute segregation might cause grain
boundaries to become more cathodic.
Grain
Grain boundary
Boundary (anode)

anode

Grain boundary
(cathode)

Multiple Phase Electrochemical Cells

In multiple alloys, one phase is more anodic

than another.
Corrosion rates are higher in multiphase alloys.
Example: In pearlite gray cast iron, graphite
flake is cathodic than surrounding pearlite
matrix.
Anodic pearlite corrodes
Steel, in martensitic condition
(single phase) after quenching
from austenitic condition, has
better corrosion resistance.
Impurities in metals leads to precipitation of
intermetallic phases and hence forms anodic
and cathodic regions leading to corrosion.

The Galvanic Series.

Many metals do not behave as
galvanic cells due to passive films.
Galvanic series gives the cathodic,
anodic relationship between the
metals.
In flowing seawater, Zinc is more
active than aluminum.
Series is determined experimentally
for every corrosive environment.

Types of Corrosion
Uniform or general attack corrosion:
Reaction proceeds uniformly on the
entire surface.
Controlled by protective
coatings, inhibitors and
cathodic protection.
Galvanic or two metal corrosion:
Electrochemical reaction leads to
corrosion of on metal.
Zinc coatings on steel
protects steel as zinc is
anodic to steel and corrodes.
Large cathode area to small
anode area should be
avoided.

Pitting Corrosion
Pitting: Localized corrosive attacks that produces
holes or pits in a metal.
Results in sudden unexpected failure as pits go
undetected (covered by corrosion products).
Pitting requires an initiation
period and grows in
direction of gravity.
Pits initiate at structural
and compositional
heterogeneities.

Pitting of stainless steel

Growth of Pit
Growth of pit involves dissolution of
metal in pit maintaining high acidity at
the bottom.
Anodic reaction at the
bottom and cathodic
reaction at the metal
surface.
At bottom, metal chloride + water
Metal hydroxide + free acid.

Localized electrochemical corrosion

in crevices and under shielded
surfaces where stagnant solutions
can exist.
Occurs under valve gaskets, rivets
and bolts in alloy systems like steel,
titanium and copper alloys.
Anode: M M+ + eCathode:O2 + 2H2O + 4e4OHAs the solution is
stagnant, oxygen is used up
and not replaced.
Chloride ions migrate to
crevice to balance positive charge
and form metal hydroxide and free
acid that causes corrosion.

Intergranular Corrosion
Localized corrosion at and/or adjacent to highly reactive grain
boundaries resulting in disintegration.
When stainless steels are heated to or cooled through sensitizing
temperature range (500-800 0 C) chromium carbide precipitate along
grain boundaries.
When exposed to corrosive environment, the region next to grain
boundaries become anodic and corrode.

Stress Corrosion
Stress corrosion cracking (SCC): Cracking caused by combined
effect of tensile stress and corrosive environment.
Stress might be residual and applied.
Only certain combination of alloy and environment causes SCC
Crack initiates at pit orother discontinuity.
Crack propagates perpendicular to stress
Crack growth stops if either stress or corrosive environment is
removed.

Erosion Corrosion and Cavitation Damage

Erosion corrosion: Acceleration in
rate of corrosion due to relative
motion between corrosive fluid and
surface.
Pits, grooves, valleys appear on
surface in direction of flow.
Corrosion is due to abrasive action
and removal of protective film.
Cavitation damage: Caused by
collapse of air bubbles or vapor filled
cavities in a liquid near metal surface.
Rapidly collapsing air bubbles
produce very high pressure (60,000
PSI) and damage the surface.
Occurs at metal surface when high
velocity flow and pressure are
present.

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Oxidation- Protective Oxide Films

Oxides form on metals due to
reaction with air.
Degree to which oxide films form
depends on following factors.
Volume ratio of oxide to metal
consumed after oxidation should be
close to 1.
Good adherence.
High melting point of the film.
Low oxide pressure.
Coefficient of expansion equal to that
of metal.
High temperature plasticity.
Low conductivity and diffusion
coefficients of metal ions and oxygen.

Corrosion Control Material Selection

Metallic Metals:
Use proper metal for
particular environment.
For reducing conditions, use
nickel and copper alloys.
For oxidizing conditions, use
chromium based alloys.
Nonmetallic Metals:
Limit use of polymers in
presence of strong inorganic
acids.
Ceramics have better
corrosion resistance but are
brittle.

Coatings
Metallic Coatings: Used to protect
metal by separating from corrosive
environment and serving as anode.
Coating applied through
electroplating or roll bonding.
might have several layers.
Inorganic coatings: Coating with
steel and glass.
Steel is coated with porcelain
and lined with glass.
Organic coatings: Organic polymers
(paints and varnishes) are used for
coatings.
Serve as barrier but should
be applied carefully.

Design
General design rules:
Provide allowance for corrosion
in thickness.
Weld rather than rivet to avoid
crevice corrosion.
Avoid dissimilar metals that can
cause galvanic corrosion.
Avoid excessive stress and stress
concentration.
Avoid sharp bends in pipes to
prevent erosion corrosion.
Design tanks and containers for
early draining.
design so that parts can be easily
replaced.
Design heating systems so that
hot spots do not occur.

Alteration Environment
Lower the temperature
rate.

Reduces reaction

Decrease velocity of fluids

corrosion.

Reduces erosion

Removing oxygen from liquids

corrosion.
Reducing ion concentration
corrosion rate.

reduces
decreases

Adding inhibitors
inhibitors are retarding
catalysts and hence reduce corrosion.

Cathodic Protection
Electrons are supplied to the metal
structure to be protected.
Example: Fe in acid
Fe
Fe2+ + 2e2H+ + 2eH2
Corrosion of Fe will be
prevented if electrons
are supplied to steel
structure.
Electrons can be supplied by external
DC supply or galvanic coupling with
more anodic metal.

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Anodic Protection
Externally impressed anodic currents
form protective passive films on
metal and alloy surfaces.
Anodic currents are applied by
potentiostat to protect metals that
passivate.
Current makes them more passive
and decreases the corrosion rate.

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