UES012 – Engineering Materials

Corrosion process: Corrosion, Cause of corrosion, Types of

corrosion, Protection against corrosion.

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 Corrosion
Corrosion is the deterioration and loss of metal, or material by chemical or
electrochemical reactions with its environments.

 It is a very natural process.

 Most of metallic elements (except noble metals) present in the most stable state
having low energy, normally oxides (as metallic ores)

Reason for corrosion

The tendency to decrease the energy of the system as a result of the corrosion
reactions.

 Metals get oxidized

 Polymers react with oxygen and degrade
 Ceramic refractories may dissolved in contact with molten materials

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 Corrosion
Example: Formation of rust on the surface of iron, formation of green film on
the surface of copper

The responsible factors for the corrosion of a metal are the metal itself, the
environmental chemicals, temperature and the design.

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 Corrosion
All corrosion is electro-chemical in nature.

Broad can be classified in three categories:

 Direct-chemical corrosion: in this corrosion, metal dissolves in a corrosive liquid

medium. The metal continues to dissolve in the liquid until either the metal consumed
or liquid is saturated.
e.g. Zn + 2NaOH – Na2ZnO2 + H2 (gas)

 Oxidation: It is type of corrosion involving the reaction between a metal and air or
oxygen at high temperature in the absence of water or an aqueous phase. It is also
called dry-corrosion. At normal temperatures, the oxides of metals (except gold) are
more stable than the metals.

 Electro-Chemical Corrosion: it is the most common mechanism by which corrosion

occurs at or near room temperature, as result of reaction of metals with water, or
aqueous solutions of salts, acids, or bases. It is named as electro-chemical corrosion
as chemical reaction accompanied with the passage of electric-current takes place.

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 Electro-Chemical Corrosion
Electrochemical reaction: a chemical reaction in which there is transfer of electrons
from one chemical species to another.
Metal atoms characteristically lose or give up electrons in what is called an oxidation
reaction.
M → Mn+ + ne-
Fe → Fe2+ + 2e-
Al → Al3+ + 3e-
The electrons generated from each metal atom that is oxidized are transferred to and become a
part of another chemical species. This is a reduction reaction.

Reduction of hydrogen ions in an acid solution

Reduction reaction in an acid solution

containing dissolved oxygen

Reduction reaction in a neutral or basic

solution containing dissolved oxygen

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 Principle: Electro-Chemical Corrosion
Electrode potential
Not all metallic materials oxidize to form ions with same degree of ease.
If the iron and copper electrodes are connected electrically, reduction will occur for
copper at the expense of the oxidation of iron.

Cu2+ + Fe → Cu + Fe2+
In terms of half-cell reactions: Cu ions will deposit
(electrodeposit) as metallic copper on the copper
electrode, while iron dissolves (corrodes) on the other
side of the cell and goes into solution as Fe2+ ions.
Standard half-cell
Fe → Fe2+ + 2e-
Cu2+ + 2e- → Cu

Cu2+ + Fe → Cu + Fe2+

Cu2+ ions will deposit (electrodeposit) as metallic copper on the copper

electrode, while iron dissolves (corrodes) on the other side of the cell and
goes into solution as Fe2+ ions.
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Principle: Electro-Chemical Corrosion

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Standard electrode potential of metals
Standard potential at 25oC

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 Galvanic Cell
Galvanic cell: This type of corrosion occurs when two dissimilar metals are immersed or
dipped partly in a solution. Formation of a galvanic cell on the surface of metals. Some parts of
the metal surface act as anode and rest act as cathode.

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 Galvanic Cell
Galvanic series: This represents the relative reactivity of a number of metals and
commercial alloys in seawater

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 Corrosion rate
The corrosion rate, or the rate of material removal as a consequence of the chemical
action, is an important corrosion parameter.

Corrosion penetration rate (CPR), or the thickness loss of material per unit of time.

where W = weight loss after exposure time t; ρ = density, and A = exposed specimen
area, K is a constant.

There is an electric current associated with electrochemical corrosion reactions.

Corrosion rate r can be written as

r = i/nF

where
i = current density (the current per unit surface area of material corroding)
n = number of electrons associated with the ionization of each metal atom
F = 96,500 C/mol.

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 Galvanic Cell : Corrosion rate
Two different phases in the same metal may form a galvanic couple at the
microstructural level.

For example,
 cementite in steel is more noble (cathodic) with respect to ferrite.
 Under corrosive conditions, ferrite will form the anode and corrode away.

The finer is the distribution of ferrite and

cementite in a steel, the more are the number of
galvanic cells that can form and the faster will be
the corrosion rate.

Corrosion rate of a quenched and tempered steel

as a function of the tempering temperature.
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 Galvanic Cell : Corrosion rate

 Initially, the quenched steel has only one phase, martensite.

 On tempering the martensite, cementite precipitates in a fine form, resulting

in the formation of a number of galvanic cells, with cementite and ferrite as
the two ‘electrodes’.

 The corrosion rate increases initially with increasing tempering temperature.

When the tempering temperature is above 400°C, the corrosion rate
decreases.

 Here, during tempering, the cementite particles coalesce or coarsen into

larger particles resulting in a decrease of the number of galvanic cells, as
compared to that at a lower tempering temperature. Hence, a decrease in
the corrosion rate is observed.

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 Galvanic Cell : concentration cell
 A galvanic cell set up due to such differences in metal ion
concentration is known as a concentration cell.

 If, in a region of the electrolyte, the metal ions are deficient, the
metal near that region will be anodic with respect to the metal
near a different region where the electrolyte has excess metal
ions.

 Concentration cell can also arise due to differences in oxygen

concentration.

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 Galvanic Cell : Stress cell

 A galvanic cell can form due to different residual stresses in

the same metal.

 The stressed region is more active and is anodic with respect

to a stress-free region.

 Such stress cells can form between regions of different

dislocation density in a cold-worked metal or in a
polycrystalline metal, where the grain boundaries are anodic to
the interior of the grains.

 A bent wire is likely to corrode at the bend, where it has been

plastically deformed.

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 Galvanic Cell : Polarization
 When a galvanic cell is short circuited, a corrosion current flows through the
cell. This current would set up differences in concentration of the metal ions
near the electrodes.

 In the zinc–copper cell, due to continued dissolution of zinc at the anode, the
zinc ion concentration near the anode builds up. The potential of the zinc
electrode will shift towards the noble end, that is, towards that of copper.

 Similarly, at the cathode, the cupric ions are being used up in the cathode
reaction, resulting in a deficiency of these ions near the cathode.

 This shifts the cathode potential towards the active side, that is, towards that
of zinc.

 The electrodes are said to be polarized, as the current flows (as shown in
figure in next slide).

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 Galvanic Cell : Polarization
A steady state current is established, when the potential difference between the cathode
and the anode becomes equal to the IR drop through the electrolyte.

The variations in the cathode and the anode potentials with increasing current density.

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 Galvanic Cell : Passivation

 Some normally active metals and alloys, under particular

environmental conditions, lose their chemical reactivity and
become extremely inert. E.g., chromium, iron, nickel, titanium,
and many of their alloys.

 This passive behaviour results from the formation of a highly

adherent and very thin oxide film on the metal surface, which
serves as a protective barrier to further corrosion.

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 Types of Corrosion

1. Uniform/general attack Corrosion

2. Galvanic or two-metal Corrosion
3. Pitting Corrosion
4. Crevice Corrosion
5. Intergranular Corrosion
6. Stress Corrosion
7. Erosion Corrosion
8. Cavitation Damage
9. Fretting Corrosion
10. Selective Leaching
11. Hydrogen Damage

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 Uniform/general attack Corrosion
The chemical reaction proceeds uniformly on the entire metal surface exposed to the
corrosive environment. It often leaves behind a scale or deposit.

E.g., general rusting of steel and iron and the tarnishing of silverware

Represent greatest destruction of metals!

The most common form of corrosion. It is also the least objectionable because it can be
predicted and designed for with relative ease.

Prevention:
1. Protective Coating
2. Inhibitors
3. Cathodic Protection

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 Galvanic or two-metal Corrosion
Galvanic corrosion occurs when two metals or alloys having different compositions are
electrically coupled while exposed to an electrolyte.

The less noble or more reactive metal in the particular environment will experience
corrosion; the more inert metal, the cathode, will be protected from corrosion.
For example,

 steel screws corrode when in contact with brass in a marine environment.

 copper and steel tubing are joined in a domestic water heater, the steel will corrode
in the vicinity of the junction.

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 Galvanic or two-metal Corrosion
Area Effect: The rate of galvanic attack depends on the cathode–anode area ratio; that
is, for a given cathode area, a smaller anode will corrode more rapidly than a
larger one.
Reason: corrosion rate depends on current density, the current per unit area of
corroding surface, and not simply the current. Thus, a high current density results for the
anode when its area is small relative to that of the cathode.

A number of measures may be taken to significantly reduce the effects of galvanic

corrosion. These include the following:

1. If coupling of dissimilar metals is necessary, choose two that are close together in
the galvanic series.

2. Avoid an unfavourable anode-to-cathode surface area ratio; use an anode area as

large as possible.

3. Electrically insulate dissimilar metals from each other.

4. Electrically connect a third, anodic metal to the other two; this is a form of
cathodic protection.

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 Pitting Corrosion
 Localized corrosive attack which produces holes or pits in a metal. Very destructive!
leads to perforation of the metal.

 Difficult to detect: May be covered by corrosion products Depth and no of pits vary
Until Failure!!

 Generally requires an initiation period. Once started the pits grow at an ever
increasing rate. Grow in the direction of gravity and on lower surfaces of the
equipment.

 Pits are initiated at places where local increase in corrosion rates occurs. Local
structural and/or compositional heterogeneities.

• Use materials with non-pitting

tendency.
• Best resistance (2% molybdenum
Steels) Always do corrosion test
before final selection.

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 Crevice Corrosion
Crevice corrosion is a localized corrosion in recesses especially in overlapping zones
for riveting, bolting or welding.

 These zones also called crevices and are very tiny and difficult to access for the
aqueous liquid that is covering the rest of the readily accessible surfaces.
 This type of corrosion is also known as deposit attack.

In many aqueous environments, the solution within the crevice has

been found to develop high concentrations of H+ and Cl- ions, which
are especially corrosive. (Stainless steel, Ti, Al and Cu alloys)

Many alloys that passivate are susceptible to crevice corrosion

because protective films are often destroyed by the H+ and Cl- ions.

Prevention
 using welded instead of riveted or bolted joints,
 using non-absorbing gaskets (like Teflon) when possible,
 removing accumulated deposits frequently, and
 designing containment vessels to avoid stagnant areas and ensure
complete drainage.
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 Intergranular Corrosion
 It occurs preferentially along grain boundaries for some alloys and in specific
environments. The net result is that a macroscopic specimen disintegrates along its
grain boundaries.
 This type of corrosion is especially prevalent in some stainless steels. When heated
to temperatures between 500oC and 800oC for sufficiently long time periods, these
alloys become sensitized to intergranular attack. Temperature range is called as
sensitizing temperature range.

• This heat treatment permits the formation of small precipitate particles of chromium carbide
(Cr23C6) by reaction between the chromium and carbon in the stainless steel. These particles
form along the grain boundaries
• Both the chromium and the carbon must diffuse to the grain boundaries to form the
precipitates, which leaves a chromium-depleted zone adjacent to the grain boundary.
Consequently, this grain boundary region is now highly susceptible to corrosion.
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 Intergranular Corrosion
Intergranular corrosion is an especially severe problem in the welding of stainless steels, when it
is often termed weld decay.

Stainless steels may be protected from intergranular corrosion by the following measures:
 subjecting the sensitized material to a high-temperature heat treatment (heating followed by
water quenching) in which all the chromium carbide particles are re-dissolved.

 lowering the carbon content below 0.03 wt.% C so that carbide formation is minimal.

 Alloying the stainless steel with another metal such as niobium or titanium, which has a
greater tendency to form carbides than does chromium so that the Cr remains in solid
solution.

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 Stress Corrosion
 It is also known as stress corrosion
cracking (SCC).

 It results from the combined action of

an applied tensile stress and a
corrosive environment.

 Some materials that are virtually inert

in a particular corrosive medium
become susceptible to this form of
corrosion when a stress is applied.

 Small cracks form and then

propagate in a direction
perpendicular to the stress
resulting in failure.

 Failure behaviour is characteristic of

that for a brittle material, even though
the metal alloy is intrinsically ductile.
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 Stress Corrosion
 The cracks may form at relatively low stress levels, significantly below the tensile
strength.

 Most alloys are susceptible to stress corrosion in specific environments, especially

at moderate stress levels.

 For example, most stainless steels stress corrode in solutions containing chloride
ions, whereas brasses are especially vulnerable when exposed to ammonia.

The stress that produces stress corrosion cracking need not be externally applied;
it may be:
 a residual one that results from rapid temperature changes and uneven
contraction,
 for two-phase alloys in which each phase has a different coefficient of
expansion
 gaseous and solid corrosion products that are entrapped internally can give rise
to internal stresses.

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 Stress Corrosion
Probably the best measure to take in reducing or
totally eliminating stress corrosion is to lower the
magnitude of the stress:

 This may be accomplished by reducing the

external load
 Increasing the cross-sectional area perpendicular
to the applied stress.
 Furthermore, an appropriate heat treatment may
be used to anneal out any residual thermal
stresses.
 Eliminate the corrosive environment.
 Change the alloy.

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 Erosion-Corrosion
It arises from the combined action of chemical attack and mechanical abrasion or wear as a
consequence of fluid motion

 All metal alloys are susceptible to erosion–corrosion.

 It is especially harmful to alloys that passivate by forming a protective surface film; the
abrasive action may erode away the film, leaving exposed a bare metal surface. If the
coating is not capable of continuously and rapidly reforming as a protective barrier,
corrosion may be severe.

Usually it can be identified

by surface grooves and
waves having contours
that are characteristic of
the flow of the fluid.

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 Erosion-Corrosion
Erosion–corrosion is commonly found in piping, especially at bends, elbows, and abrupt
changes in pipe diameter—positions where the fluid changes direction or flow
suddenly becomes turbulent. Propellers, turbine blades, valves, and pumps are also
susceptible to this form of corrosion.

 One of the best ways to reduce erosion–

corrosion is to change the design to eliminate
fluid turbulence and impingement effects.

 Use materials that inherently resist erosion.

 Removal of particulates and bubbles from the

solution will lessen its ability to erode.

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 Cavitation Damage
 It is caused by the formation and collapse of air bubbles /
vapour filled cavities in a liquid near a metal surface.

 The rapidly collapsing vapour bubbles can produce localized

pressures as high as 60, 000 psi.

 It is sufficient to remove surface films, tear metal particles from

the surface resulting in increased corrosion rates and surface
wear.

 It occurs where high velocity liquid flow and pressure changes

exist. Pump impellers and ship propellers.

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 Fretting Corrosion
 It is caused at the interface of materials under load subjected
to vibration and slip.

 The metal between the rubbing surfaces is oxidized. The

oxidized film is torn. And the oxide particles so formed act as
abrasive.

 Appears as grooves / pits surrounded by corrosion product.

 Tight-fitting surfaces: between shafts and bearings or sleeves.

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 Selective Leaching
 It is the preferential removal of one element of the solid alloy by the corrosion
process.

E.g. : Dezincification of Brass leaving spongy weak matrix of Cu.

Method: dissolution followed by re-plating of Cu while Zn remains in the solution.

Protection:
1. Lower zinc content.
2. Change the alloy
3. Change the environment
4. Cathodic protection

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 Hydrogen Damage
Load carrying capability of metallic component is reduced due to interaction with atomic
or molecular hydrogen usually in conjunction with residual or externally applied tensile
stresses

Hydrogen Embrittlement: Hydrogen damages directly related to loss of ductility

 Hydrogen environment embrittlement: occurs during plastic deformation of metals such as
steels, stainless steels and titanium alloys.
 Hydrogen stress cracking: brittle fracture in a ductile material such as carbon and low alloy
steels.
 Loss in tensile ductility: significant reduction in elongation capability and reduction area in
steel and aluminium alloys.

Hydrogen attack: High temperature mode of attack in which hydrogen enters metals such
as steels and reacts with carbon to produce methane gas resulting in formation of cracks
or decarburization.
Blistering: atomic hydrogen diffuses into internal defects and precipitates as molecular
hydrogen which produces high internal pressure resulting in local plastic deformation and
blistering.
Prevention
1. Change the material susceptible.
2. Reverse hydrogen contamination: Bake out.
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 Prevention of Corrosion

 Metallic coating such as tin, zinc, aluminium on steel

 Use Inhibitors (substances that, when added in relatively low

concentrations to the environment, decrease its
corrosiveness

 Cathodic Protection

 Non-metallic coating such as oil, paint, tar

 Avoid physical contact between dissimilar metals

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Prevention of Corrosion

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