CORROSION

SCHOLAR NAME -

S.GNANASEKARAN

Under the guidance - Dr. G. PADMANABAN

Dr. V. BALASUBRAMANIAN

UNIT IV: CORROSION BEHAVIOUR

Definition and classification of Corrosion, Introduction to
corrosion principles, corrosion rate Expressions, Electro chemical
Aspects: Electro chemical Reactions, polarization, and passivity.
Environmental Effects: Effect of Oxygen and oxidizers, Velocity,
Temperature, Corrosive Concentration, Galvanic Coupling &
Metallurgical aspects (Metallic properties). Forms of Corrosion:
Galvanic, Crevice, Pitting, Inter granular, Selective leaching, Erosion,
Stress corrosion, Hydrogen damage (Definition and mechanisms only).

Definition

The destruction of a material by chemical or

electrochemical reaction to its environment
Typically a transfer of electrons from one metal to
another through an Oxidation-Reduction Reaction.

Losses due to Corrosion

Forms of Corrosion
1.
2.
3.
4.
5.
6.

Galvanic corrosion
Crevice corrosion
Pitting corrosion
Intergranular Corrosion
Erosion-corrosion
Hydrogen damage

GALVANIC CORROSIO

1. Galvanic or Dissimilar metal corrosion

Takes place when two metals are in physical contact with each
other and are immersed in a conducting fluid. (electrically
connected)
Examples:
1. Plate and screw (different electrical potentials).
2. domestic water heater (Copper and steel )
Fundamental Requirements :
1. Dissimilar metals (or other conductors).
2. Electrical contact between the dissimilar conducting materials.
3. Electrolyte (the corrosive medium)
dissimilar conducting materials.

in

contact

with

the

Galvanic corrosion between stainless

steel screw and Aluminium.

Galvanic corrosion between Steel

and Brass.

Environmental
Effects

Anodic- cathodic behavior of steel with zinc and tin outside layers
exposed to the Atmosphere (0.05M NaCl medium).
(a) zinc is anodic to steel and corrodes
(b) steel is anodic to tin and corrodes (the tin layer was perforated
before the corrosion began)

Area Effect

Copper

(Copper
)

(steel)
(a)

(steel)
(Copper
)
(b)

Distance Effect
Accelerated corrosion due to galvanic effects is usually
greater near the junction, with attack decreasing with
increasing distance from that point.
The distance affected depends on the conductivity of the
solution.
Eg. Current flow and the resistance of the circuits

Signs of Galvanic Corrosion

Blistering of paint
1st Warning Sign

Formation of powdery substance

2nd Warning Sign

Pitting of metal
Too late
Severe Galvanic Corrosion

Prevention
1. Select combination of metals as close together as possible in the galvanic
series.
2. Area of Metals
Good applying a less noble metal to a large area
Bad applying a more noble metal to a larger area
Steel screws / bolts on large bronze
Insulate dissimilar metals wherever possible.
3. Indirect Cathodic Protection
Used when direct contact not possible
Zinc bolted to outside of hull
4.

Resistance of Electrical Path

Fresh water is less conductive than salt water
Less galvanic current
Use magnesium sacrificial anodes

CREVICE CORROSION

2. Crevice Corrosion
Intensive Localized corrosion usually associated
stagnant solution on the micro-environmental level.

with

Also known as deposit or gasket corrosion.

Occurs in crevices (shielded areas) such as under gaskets,
washers, insulation material, fastener heads, surface deposits,
disbonded coatings, threads, lap joints and clamps.
Extremely dangerous because it is localized and can lead to component
failure while the overall material loss is minimal.
The initiation and progress of crevice corrosion can be difficult to detect.

Mechanism

Stage 1
The O2 content in
the H2O occupying a
crevice is equal to
the level of soluble
oxygen

Stage 2

The
corrosion
reactions
in
the
crevice (anodic) and
on the open surface
(cathodic).

Stage 3
1. The metal ions hydrolyze giving off protons (acid) and forming
corrosion products.
2. Serious increase in the corrosion rate
3. The accumulation of positive charge in the crevice becomes a
strong attractor to negative ions in the environment.

Environmental factors
Depending on the environment developed in the crevice and the
nature of the metal, the crevice corrosion can take a form :

Pitting (i.e., formation of pits)

Filiform corrosion (this type of crevice corrosion that may occur
on a metallic surface underneath an organic coating)

Intergranular attack

Stress corrosion cracking.

Steel components in open

atmospheric environment.

Underside of Air craft panel

Marine environment

Close-up picture showing the

severity of corrosion

Prevention
Use welded butt joints instead of riveted or bolted joints in new
equipment.
Avoid sharp corners and stagnant areas.
Provide uniform environment.

PITTING CORROSION

3 Pitting
Corrosion

A localized form of corrosive attack that produces holes or small

pits in a metal.
Generally, the bulk surface remains unattacked.
Often found in situations where resistance against general
corrosion is conferred by passive surface films.
Localized pitting attack is found where these passive films have
broken down.
one of the most dangerous forms of corrosion because it is
difficult to anticipate and prevent, relatively difficult to detect,
occurs very rapidly, and penetrates a metal without causing it to
lose a significant amount of weight.

Pitting is initiated by:

by
1. Localized chemical or mechanical damage to the protective oxide
film; low dissolved oxygen concentrations (protective oxide film less
stable) and high concentrations of chloride (as in seawater)
2. Localized damage or poor protective coating.
3. The presence of non-uniformities in the metal structure of the
component, e.g. nonmetallic inclusions.
THROUGH PITS

SIDEWAY PITS

Subsurface

Narrow, deep

Shallow, wide

Undercutting

Elliptical
Horizontal grain attack
Vertical Grain Attack

Corrosion Pit Shapes

Mechanism
Localized corrosion developing on metal in a O2 environment
It is an autocatalytic process.
Metal oxidation results in localized acidity, maintained by the
cathode and anode

Which creates a potential gradient and electromigration of

aggressive anions into the pit.
Polished surfaces display higher resistance to pitting.

A local cathode cell that leads to

the initiation of a pit

Prevention (Crevice and Pitting)

Prefer welding as a replacement of rivets & bolts
Avoid stagnant areas
Provide uniform environments
Use solid non-absorbent gaskets (Teflon)

INTERGRANULAR
CORROSION

4. Intergranular Corrosion
Localized corrosion along grain boundaries or adjacent

to grain boundaries, while the bulk of the grains remain

largely unaffected.
Usually

associated with chemical segregation effects or

specific phases precipitated on the grain boundaries.

Sensitized stainless steels and aluminum alloys represent

example of this form of damage.

Intergranular corrosion of a
failed aircraft component

Severe problem in the welding of

stainless steels (weld decay).

Knife line attack (KLA)

Influences steels stabilized by niobium, such as 347 stainless steel.
Titanium, niobium, and their carbides dissolve in steel at very high temperatures.
At some cooling systems, niobium carbide does not precipitate and the steel then
behaves like unstabilized steel, forming chromium carbide as an alternative.
This affects only a thin zone several millimeters wide, making it difficult to spot and
increasing the corrosion speed.

Sensitization effect
Precipitation of carbides at grain boundaries in a stainless steel or alloy subject to
intergranular corrosion or intergranular stress corrosion cracking.
In a corrosive atmosphere, the grain interfaces of these sensitized alloys become
very reactive to intergranular corrosion.
This is characterized by a localized attack at and adjacent to grain boundaries with
relatively little corrosion of the grains themselves.

Normal microstructure

Sensitized

EROSION CORROSION

5. EROSION-CORROSION
(Flow-Assisted or Flow-Accelerated Corrosion)

An increase in corrosion carried by a high relative velocity between

the corrosive environment and the surface.
Removal of the metal:
As corrosion product which spalls off the surface because of the
high fluid shear and bares the metal beneath;
As metal ions, which are swept away by the fluid flow before they
can deposit as corrosion product.
Difference between erosion-corrosion and erosion:
Erosion is the straight forward wearing away by the mechanical
cut caused by suspended particles . . . e.g., sand-blasting, erosion
of turbine blades by droplets .
Erosion-corrosion also involves a corrosive environment . The
metal undergoes a chemical reaction.

Erosion-corrosion produces a typical surface finish

grooves, waves, holes, etc., all oriented with respect to the fluid flow

Erosion-corrosion of stainless alloy pump

impeller.
Erosion-corrosion of condenser
tube wall.

Mechanis
m
Attack occurs when film cannot form because of erosion caused
by suspended particles, or when rate of film formation is less than
rate of dissolution and transfer to bulk fluid.

Erosion-Corrosion found in: - water contaning solutions;

- gases;
- organic liquids;
- liquid metal.
If fluid contains suspended solids, erosion-corrosion may be
aggravated.
Weak equipment :
- pipes (bends, elbows, tees);
- valves;
- pumps;
- blowers;
- propellers, impellers;
- stirrers;
- stirred vessels;
- HX tubing (heaters,
condensers);

- flow-measuring orifices, venturies;

- turbine blades;
- nozzles;
- baffles;
- metal-working equipment (scrapers, cutters,
grinders, mills);
- spray impingement components;
- etc.

Prevention of Erosion-Corrosion

Design (avoid impingement, high velocity, etc.)

Materials (use Cr-containing steels)

Use hard corrosion-resistant coatings.

HYDROGEN DAMAGE

destroyed

6. Hydrogen damage
Generic name given to a large number of metal destroyed
due to interaction with hydrogen.
Hydrogen Effects
Hydrogen can degrade metals by:

Hydrogen blistering

Hydrogen embrittlement

Decarburization

Hydrogen attack.

Blistering
Hydrogen enters the lattice of a metal, diffuses to voids, creates high
internal stresses blisters . . .
Blistering may occur during exposure to:
Hydrocarbons
Electroplating solutions
Chemical process streams
Pickling solutions
H-containing contaminants during welding
General corrosive environments.

Carbon steel plate showing a large

hydrogen blister. Exposure time: 2
years.

Mechanism of hydrogen blistering

The mechanism of hydrogen uptake by metals must
involve atomic hydrogen.
Molecular hydrogen cannot diffuse through metal lattices.

Mechanism of hydrogen blistering.

Prevention of Blistering
Use coatings
Remove impurities that can promote hydrogen
evolution .
Use different materials (Ni-base alloys have low
diffusion rates for hydrogen).

Embrittlement
Similar to blistering . . . hydrogen enters metal lattice. High-strength
(and more brittle) steels are susceptible.
H-embrittlement different from SCC in nature of cracks . . . stresscorrosion cracks usually propagate anodically.

Prevention of Embrittlement
Reduce corrosion rate (surface treatment, coatings, etc.)
Change electroplating process to minimize H effects
(voltage, current density, bath composition, etc.)
Heating the material to remove H
Minimize residual stresses
Use less susceptible material
Maintain clean conditions during welding.

Hydride-forming metals
Are susceptible to H- embrittlement . . .e.g., Zr-alloy pressure tubes.
These hydrides are themselves brittle, and crack.
The crack can propagate through the material, with more hydride
progressively precipitating at the crack tip.

Pressure tube-Crack
propagation

Hydrogen Attack
High temperature process - C or carbide in steels can
react with gaseous hydrogen . . .
C + 2H2 CH4
May crack the steel from high internal pressure.
May cause loss of strength as C disappears.

Thanking you