Definition

• Corrosion is a process of formation of the compound of pure metal by the chemical

reaction between metallic surface and its environment.
• It is an oxidation process. It causes loss of metal.
• Hence, disintegration of a metal by its surrounding chemicals through a chemical
reaction on the surface of the metal is called corrosion.
• In general, Corrosion is defined as the destruction or deterioration of a material
because of reaction with its environment.
 Examples
 Formation of rust on the surface of iron, formation of green film on the surface of
copper.
 Rusting of iron is the most common example of corrosion. Rust is formed on the
surface of iron in the presence of air and moisture. Rust does not have any
metallic properties, so the rusted iron becomes weak.
 Examples
 Copper exposed to moist air containing CO2 forms a green layer
on its surface.
 This green layer is often found on the statue made of brass
steel deck support
(Cu+Zn alloy). This green layer is composed of CuCO3 + Cu(OH)2 brackets for topside
popularly known as patina. vertical ladder (Naval
ship)

topside rusted steel

Railing of a bridge Cast iron pump impeller pipe hanger (Naval ship) electrical conduit
clamps
 Reasons for corrosion studies
Economic (due to material losses).
Safety (to prevent catastrophic consequences resulting from
operation failure of equipment).
Conservation (to conserve metal resources, which are limited).
Types of Corrosion
There are basically eight types of corrosion

Uniform corrosion
Galvanic corrosion
Crevice corrosion
Pitting corrosion
Transgranular and Intergranular (Intercrystalline ) corrosion
Selective Leaching
Stress corrosion
Erosion corrosion
 Uniform Corrosion
• Most common form of corrosion which is characterized by a chemical or
electrochemical reaction that proceeds uniformly over the entire exposed surface.
• This type of corrosion develops as pits of very small diameter, in the order of a
micrometer, and results in a uniform and continuous decrease in thickness over the
entire surface area of the metal.
• The rate of uniform corrosion can be easily determined by measuring the mass loss,
or the quantity of released hydrogen
Prevention of uniform corrosion

i. Proper material selection

ii. Use of coating or inhibitor
iii. Cathodic or anodic protection
iv. Individual or combination of all the above
Galvanic Corrosion (Two-metal corrosion)
• When two dissimilar metals are in direct contact in a conducting liquid,
experience shows that one of the two may corrode. The less resistant metal
becomes anodic and the more resistant metal cathodic. This is called galvanic
corrosion. The other metal will not corrode; it may even be protected in this way.
• This corrosion is different in its kind and intensity from the one that would occur
if they were placed separately in the same liquid.

Anode (negative terminal): Zinc container

Cathode (positive terminal): Carbon rod surrounded by manganese dioxide

b
 • Environmental Effects: Galvanic corrosion depends on the atmospheric condition.
Largely depends on the type and amount of moisture present.
• Distance Effect: Two-metal corrosion is readily recognized by the localized attack near
the junction.
• Area Effect: An unfavorable area ratio consists of a large cathode and a small anode.

The zinc electrode is purposefully oxidized/corroted in order to

generate electricity.

• Beneficial Application: Galvanic corrosion has some beneficial or desirable

applications such as dry cells, cathodic protection etc.
Prevention of galvanic corrosion:
i. Select combinations of metals as close together as possible in the
galvanic series
ii. Avoid combinations in which the area of the less noble material is
relatively small.
iii. Insulate dissimilar metals if possible.
iv. Apply coating e.g. teflon coating.
v. Use chemical inhibitors which reduces corrosiveness of the
environment.
vi. Avoid threaded joints for materials far apart in the series. Welded
joints using welds of the same alloy are even better.
vii. Install a third metal that is anodic to both metals in the galvanic
contact.
 Crevice Corrosion
• Crevice corrosion is a localized corrosion in crevice/recesses.
• This type of attack is usually associated with small volume of stagnant solution in the
overlapping zones for riveting, bolting or welding, zones under joints and under
various deposits. These zones also called crevices, are very tiny and difficult to
access for the aqueous liquid that is covering the rest of the readily accessible
surfaces.

Fig : Crevice corrosion

• Sand, dirt, corrosion products, different types of gasket form a shield and creates a
stagnant condition for crevice corrosion.
• To function as a corrosion site, a crevice must be wide enough to permit liquid entry
but sufficiently narrow to maintain a stagnant zone.
 Oxidation M→ M++ e
Reduction O2 + 2H2O + 4e → 4OH-
M+Cl- + H2O → MOH + H+Cl-
• Chlorides concentrate inside the crevice (the
anode), worsening the situation.
• Ferrous ions form ferric chloride and attack
the stainless steel rapidly.
• The pH and the oxygen content are lower in
the crevice than in the bulk water solution,
just as they are inside a pit.
• The pH inside the crevice may be as low as 2
in a neutral solution. Once a crevice has
formed.
The major factors influencing crevice corrosion are:
• crevice type: metal-to-metal, metal-to-non-metal
• crevice geometry: gap size, depth, surface roughness
• material: alloy composition (e.g. Cr, Mo), structure
• environment: pH, temperature, halide ions, oxygen

Combating Crevice Corrosion:

i. Use welded joints instead of riveted or bolted joints in new equipment
ii. Close crevices in existing lap joints by continuous welding, caulking
iii. Design vessels for complete drainage; avoid sharp corners and stagnant areas
iv. Inspect equipment and remove deposit frequently
v. Remove wet packing materials during long shutdown
vi. Use solid nonabsorbent gaskets such as Teflon wherever possible
 Pitting Corrosion
• This localized form of corrosion is characterized by the formation of irregularly shaped cavities
on the surface of the metal. Their diameter and depth depend on several parameters related to
the metal, the medium and service conditions.
• Often difficult to detect pits because of their small size and pits are covered with corrosion
products
• Difficult to measure and compare extent of pitting because of varying depths and number of pits

Fig : Pitting Corrosion

 Pitting Corrosion

• Autocatalytic Nature of Pitting:

 Unique type of anodic reaction
 Corrosion processes within a pit produce
conditions which are stimulating and
necessary for continuing activity of the pit
 Rapid dissolution occurs in the pit and oxygen
reduction takes place on adjacent surfaces
 Pits cathodically protect the rest of the metal
• Prevention of Pitting

Lessen the aggressiveness of the environment (e.g. Cl- concentration, temperature,

acidity etc.)
Upgrade materials of construction (e.g. Cr (12%) containing SS, Mo (4-6%)
containing SS etc.)
Modify the design of system (e.g. ensure proper drainage, avoid crevices etc.)
Intergranular (Intercrystalline) Corrosion
• Grain Boundary: Atoms are randomly distributed in the liquid state. When solidifies during
casting they arrange themselves in a crystalline array. However, this ordering usually
begins at many points in the liquid and these blocks of grains meet where is a mismatch at
their boundary.

• Particular crystal lattice is the most stable configuration of a metal and grain boundaries
are high energy areas. These areas are more active chemically and attacked more easily
when exposed to corrosive.
• Solid-solution alloys are usually more corrosion resistant than alloys with two or more
phases, since galvanic coupling effects are not present.
• Localized attack at and adjacent to grain boundaries with little corrosion of the grains is
known as intergranular corrosion.
• Intergranular (Intercrystalline) corrosion follows preferential paths. corrosion propagates at grain
boundaries. Intercrystalline corrosion consumes only a very small amount of metal, which is why
mass loss is not a significant parameter for assessment of this type of corrosion.
• This type of corrosion can be caused by impurities at the grain boundaries, enrichment of one of
the alloying elements or depletion of one of the elements in the boundaries. Depletion of Cr in the
grain boundary results in corrosion of SS.
• At temperature range 950 to 1450 °F, the SS become sensitized and form Cr23C6 when C content
is about 0.02% or higher. Chromium is thus removed from solid solution and the metal with
lowered Cr content adjacent to the grain boundaries is attacked.
• At sensitizing temperature carbon diffuses to the grain boundaries quite readily but Cr is much
less mobile.
Control of intergranular Corrosion:
• Employing high temperature solution heat treatment,
commonly known as quench annealing or solution
quenching
• Adding elements that are strong carbide formers
(stabilizers)
• Lowering the carbon content to below 0.03%
 Selective Leaching
• Selective leaching is the removal of one element from a solid alloy by corrosion process.
• Most common example is the selective removal of zinc in brass alloys (dezincification).
Similar process occur in other alloy systems in which aluminum, iron, cobalt, chromium
etc. are removed.
• The commonly accepted mechanism consist of
3 steps:
• The brass dissolves
• The zinc ion stays in solution and
• The Cu plates back on
Zinc is quite reactive but Cu is more noble. Zinc
can corrode slowly in pure water by the cathodic
ion reduction of H2O into hydrogen gas and
hydroxide ions.
For preventing this type of corrosion 1% tin and small amount of As, Sb or P is added as
inhibitors.
 Stress corrosion
• This type of corrosion results from the combined action of a mechanical stress (bending,
tension) and a corrosive environment.
• This form of corrosion is particularly dangerous because it may not occur under a
particular set of conditions until there is an applied stress. The corrosion is not clearly
visible prior to fracture and can result in catastrophic failure.
 Erosion Corrosion
• Corrosion by erosion occurs in moving media. This type of corrosion is related to the
flow speed of the corrosive fluid.
• It is a degradation of material surface due to mechanical action, often by impinging
liquid, abrasion by a slurry, particles suspended in fast flowing liquid or gas, bubbles
or droplets, cavitation, etc.
• It leads to local thinning of the metal, which results in scratches, gullies, and
undulations, which are always oriented in the same direction, namely the flow
direction.
Factors affecting erosion corrosion:

• Surface film: The ability of the protective film to protect the metal depends on the
speed or ease with which the form when originally exposed to the environment,
their resistance to mechanical damage or wear and their rate of reforming when
destroyed or damaged. A hard, dense, adherent and continuous film would provide
better protection then one that is easily removed by mechanical means or worn off.
• Velocity: High velocity increases attack particularly when the corrosive contains
solids in suspension.
• Turbulence: Turbulence results in greater agitation of the liquid at the metal surface
than in the case for laminar flow. Turbulence results in more intimate contact
between the environment and the metal.
• Impingement: The vertical and horizontal runs of pipe were relatively unaffected
but the metal failed where the water was forced to turn its direction of flow.
DIFFERENT THEORIES OF CORROSION
Dry or chemical theory of corrosion and
Wet or Galvanic or electrochemical theory
Dry corrosion: Corrosion by oxygen
Dry corrosion: Corrosion by oxygen
Dry corrosion: Corrosion by hydrogen
Dry corrosion: Corrosion by hydrogen
Wet corrosion: electrochemical corrosion
Wet corrosion: Oxygen absorption
Wet corrosion: Concentration cell
corrosion
Factors affecting corrosion
 e) Environment: Temperature, Humidity of air, Presence of impurities in atmosphere, Presence of
suspended particles in atmosphere, Influence of pH
 Corrosion control
Choice of metal and alloys
The first choice is to use noble metals such as gold and platinum.
The next choice is to use purest possible metal.
Thus, the next choice is the use of corrosion resistant alloys.
• Stainless steel containing chromium produce an exceptionally coherent oxide film which
protects the steel from further attack.
• Cupro-nickel (70% Cu +30%Ni) alloys are now used for condenser tubes and for bubble
trays used in fractionating column in oil refineries.
• Highly stressed Nimonic alloys (Ni-Cr-Mo alloys) used in gas turbines are very resistant to
hot gases.
Proper designing
Use always simple design and structure
The design must avoid more complicated shapes having more angles, edges, corners etc.
Avoid the contact of dissimilar metals as they may lead to galvanic type corrosion.
As far as possible, crevices (gap or crack) should be avoided
Bolts and rivets should be replaced by proper welding
 Corrosion control: Cathodic protection
Sacrificial anodic protection
Protection as buried pipelines, underground cables from soil corrosion.
Insertion of magnesium sheets into the domestic water boilers to prevent the formation of
rust.
Calcium metal is employed to minimize engine corrosion.
Impressed current
An impressed current is applied in opposite direction to nullify the corrosion current and
convert the corroding metal from anode to cathode.
• Impressed current cathodic protection has been applied to open water box coolers, water
tanks, buried oil or water pipes, condensers, transmission line towers, marine piers, laid up
ships etc.
Modification of environment
• Deaeration: Deaeration involves the removal of dissolved oxygen by increase of
temperature together with mechanical agitation.
• By using inhibitors: 1) Anodic inhibitors (chemical passivators), 2) Cathodic inhibitors
(adsorption inhibitors) & 3) Vapour phase inhibitors (volatile corrosion inhibitors)
Anodic inhibitors
Inhibitors which retard the corrosion of metals by forming a sparingly soluble compound
with a newly produced metal cations. This compound will then adsorb on the corroding
metal surface forming a passive film or barrier. Anodic inhibitors are used to repair
a) the crack of the oxide film over the metal surface
b) the pitting corrosion
c) the porous oxide film formed on the metal surface.
Exemples: Chromate, phosphate, tungstate, nitrate, molybdate etc.
Cathodic inhibitors
In an acidic solution: the main cathodic reaction is the liberation of hydrogen gas, the
corrosion can be controlled by slowing down the diffusion of H+ ions through the cathode.
Examples: amines, mercaptans, thiourea etc.

In neutral solution: In a neutral solution, the cathodic reaction is the adsorption of oxygen or
formation of hydroxyl ions. Eliminating oxygen from the corroding medium or by retarding its
diffusion to the cathodic area.
Example: hydrazine, salts of Mg, Zn or Ni
Vapor phase inhibitors
• These are organic inhibitors which are readily vaporized and form a protective layer on the
metal surface.
• These are conveniently used to prevent corrosion in closed spaces, storage containers,
packing materials, sophisticated equipment's etc.
• Examples are Dicyclohexylammonium nitrate, dicyclohexyl ammonium chromate,
benzotriazole, phenylthiourea etc.
• Protective coatings
These coatings act as a physical barrier between the coated metal surface and the environment.
Classification: Inorganic coatings and organic coatings
Metallic coating: Hot dipping, metal cladding, cementation, electroplating

• Inorganic coating
Vitreous enamel coating
i. Powdered glass applied on metal surface and heated in furnace.
ii. Hard glassy external layer.
iii. Susceptible to mechanical damage or cracking by thermal shock.
Portland cement coating
i. Used to protect cast iron or steel on water or soil or both.
ii. Thickness is 5 to 25 mm.
iii. Low cost coating.
iv. Susceptible to mechanical damage and thermal shock.
Chemical conversion coating
i. Formed in situ by chemical reaction with metal surface.
ii. Anodic oxidation (anodizing) of metal (e.g. Al2O3).
iii. Phosphate coating on steel (Parkerizing); (e.g. ZnH2PO4 plus H3PO4)

• Organic coating

Paint: mixture of insoluble pigments (metal oxides; e.g. TiO2, Pb3O4, Fe2O3, ZnCrO4,
PbCO3, BaSO4, clay etc.) in organic vehicle (natural oil).
Paint is not useful to protect buried structures.
Natural oil based paints not recommended for metal structures totally immersed in
water.
Varnishes: mixture of drying oil, dissolve resin and volatile thinner.
Lacquers: resin dissolved in volatile thinner.
• Metallic coatings
5) Electroplating
6) Electroless plating
Importance of Preventing Corrosion
Increases equipment availability in defense service.
Reduces rehabilitation costs.
Means to incorporate best particles and best value products.
Allows testing of new technologies.
Compliance with environmental laws and regulations.
Decreases intervals in calibration requirements.
Extends life expectancy of equipments