Corrosion

Corrosion is a process in which a metal reacts with its environment. They normally occur
by two means:
a) Corrosion in the form of direct chemical attack is without the presence of an
electrolyte. It can occur form reaction with certain chemicals such as chlorine or
sulphur. It such cases avoidance of corrosion involves the elimination of
corroding element or the selection of material with a inherent resistance to the
corroding element. High temperature or dry corrosion is the reaction between
metals and gases usually at elevated temperatures such as sulphur or vanadium.
Many HT corrosion are electrolytic with molten fused salts as the electrolyte. The
solution is to reduce the corrosion-causing constituents, lowering the temperature,
selecting a more resistant material.
b) Electrolytic or wet corrosion is the reaction between metals and their
environments usually at temperatures nearer to ambient in which the reaction is
basically electrochemical and is dependent on the presence of an electrolyte such
as sea water. Sea water is high active and conductive as compared to fresh water.
Corrosion by sea water is especially important because of the wide variety of
environmental and material variables and forms in which this occurs.
Sea water corrosion of a metal depends on the composition, heat treatment variations.
Of equal importance re environmental variations such as aeration, extent of SW
exposure (continuous immersion, tidal immersion, splash/spray exposure or marine
atmospheric exposure), fouling, dissimilar-mental couples, velocity, turbulence,
cavitations, temperature and crevices.

Types of corrosion

General Corrosion (Uniform attack):It is a uniform corrosion and can be restricted

by applying paint, metallic coatings, sacrificial anodes, ICCP or use of more
corrosion resistant material.
Galvanic Corrosion: It occurs when two dissimilar metals are electrically coupled in
the presence of an electrolyte such as sea water. Current will flow through the
electrolyte form the anodic material to the cathodic material. Usually the corrosion of
the anode is accelerated and that of the cathode is decelerated.
A galvanic series is a useful method of ascertaining galvanic corrosion tendencies
between two dissimilar metals. It is listing of open circuit potentials of metals or
alloys in an electrolyte as measured against a reference electrode (Saturated calomel
electrode). The listing is not exact as it is affected by water velocity, temperature and
metal passivity.
In general further apart two metals are in the galvanic series greater is the tendency to
corrode. Other factors that affect galvanic corrosion are polarization behavior,
anode/cathode area ratio, distance land geometry.
Pitting Corrosion: It is a form of localized attack that occurs due to the breakdown
of passivity of the metal surface. The area which has broken becomes anodic the rest
of the passive area and results in a severe corrosion. It is further affected by water
velocity, vibrations, oxygen content, pH value etc.
Crevice Corrosion: Crevices are formed by geometry of the components (such as
weld defect, threaded part of nut, deposits). The crevice so formed causes an
electrolytic cell to be formed because of the entrapped electrolyte, salts, iron etc. Such
crevice may also be formed on closely fitted components. The crevice can be either
an anode or a cathode depending on the conditions of oxygen content or ions. Area
with lack of oxygen becomes anode and the other with excess oxygen becomes a
cathode. When the ions concentration in the crevice increases it becomes a cathode.
Erosion Corrosion: it is the increased of deterioration due to abrasion such as those
caused by water movement. Impingement and cavitation are two forms of such
corrosion. As the sea water velocity increase above 1m/s the fouling on the metal
surface diminishes and the pitting of the metals will stop. But above this velocity,
erosion of the material can begin. Copper alloys have a resistance to about 2.5m/s.
titanium alloys 30m/s. Some of the plastics have a higher erosion resistance than gun
metal.
Erosion effect is increased by poorly fitted gaskets, valves, elbows, clogged filters
etc. streamlining throughout the system is seldom possible. So only alternative is
choosing the right material.
Intergranular Corrosion Or Selective Phase Corrosion:
Graphitic Corrosion: It is common to gray cast iron. The iron corrodes away and
leaves a residue of graphite. This has poor mechanical strength.
Dezincification:It is common to brasses having more than 15% Zinc. The commonly
accepted theory is that brass gets dissolved in the electrolyte. This is followed by Zinc
remaining in the solution and copper redepositing. Phosphorous, Antimony and
Arsenic are added to inhibit the process.
Dealuminification: It is common to aluminium bronze alloys containing more than
8% AL. It is inhibited by adding Nickel in excess of 3.5%.
Stress Corrosion: They occur only in the presence of tensile stresses. These may
applied, residual, thermal or welding stresses. It causes a local deterioration form the
combined action of stress and corrosion. It starts with the breakdown of the
passive ,protective layer. The corrosion initiates here and leads to the formation of a
corrosion pit. This is turn leads to stress corrosion cracking finally leading to failure
due to the same stress. A stress corrosion may propagate either around the grains
(Intergranular) or across the grains (transgranular).
Fretting Corrosion: This occurs due to the out of phase vibration of two components
under a mechanical load.
Protection against corrosion:
Painting
Mechanism of protection: Paint consists of pigment in a liquid which, when spread
out thinly allows the pigment to form an adherent film.
a) A barrier coating which prevents ingress of water and oxygen. To provide
an effective protection the paint must be adequate thickness so that it can
provide an impervious layer above the prepared surface, free from flaws
and firmly aherent throughout its life.
b) An inhibitor carrier in which appropriate corrosion inhibitors such as Zinc
Chromate are incorporated in the paint.
 c) By cathodic protection provided by incorporating a high concentration of
metal powders such as zinc in the paint composition. This type of coating
can be effective in the gaps or scratches in the paint film.
d) Anti-fouling pain provides protection against vegetable and animal growth
which can lead to increased resistance.
Most paints contain an organic medium, which after spreading as a thin film,
dries up. Drying up process may occur due to one or combination of the
following.
a) Lacquers which dry by solvent evaporation.
b) Air drying finishes which initially lose solvent and the medium is
then oxidized by air.
c) Chemically cured coatings in which two or more components are
mixed together just prior to application and the chemical reaction
convert the medium into a solid film.
d) Stoving finishes where oxidation or chemical reactions carried out
elevated temperatures.

Surface preparation and application:

a) Removal of rust and dirt form the surface.
b) Removal of grease and salts form the surface.
c) Surface should be dry. Cold and humid conditions promote condensation.
d) Application of suitable primers to be carried out.

Cathodic Protection:
When iron or steel is corroding in sea water atoms of iron leave the metal surface as
ferrous ion as Fe++ ions. The electrons remain in the metal making it negatively
charged with respect to sea water. The metal losing ions is called the anode where the
actual corrosion takes place. The excess electrons left behind in the metal will move
to a place, which is called the cathode. These electrons will move to a place, which is
called the cathode. These electrons will return back to the anode via the sea in order
to complete the circuit. The ions flowing out of the metal surface can be arrested if
we superimpose current on to the anode from an external source thus stopping the
flow local anode current. Thus the metal surface is being protected making cathodic.
This principle is known as cathodic protection.
This may be achieved either by using a metal which has a greater tendency to corrode
than the metal to be protected or by giving low voltage d.c source. Former is known
as galvanic or sacrificial anodes and the latter is known as ICCP.
Cathodic protection greatly reduces the outer bottom and provides a smoother
surface, which results in a reduced fuel consumption. Prevention hull corrosion will
reduce maintenance and repair costs and permit longer intervals between drydocks.
The cathode in the sea water tends to produce an alkali which, attacks the paint.
Hence an alkali resistant paint like coal tar epoxy paints are used.
Sacrificial anodes – Uses Zn, Mg or Al or their alloys. These are maintained in
electrical contact with the metal.