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Corrosion and Its Control
Corrosion and Its Control
Concentration cell
Differential metallic
corrosion or differential
corrosion
aeration corrosion
• Pitting corrosion
• Waterline corrosion
• Stress corrosion
Galvanic corrosion
• Corrosion under a drop of water,
leaf, stone, block of wood, etc.
• Caustic embrittlement, etc.
Galvanic corrosion: It is also called bimetallic
corrosion or differential metallic corrosion.
It occurs when two dissimilar metals (for example, Zn
and Cu) are electrically connected and exposed to an
electrolyte and then the metal higher in the
electrochemical series undergoes corrosion.
For example, if Zn and Cu are connected, Zn acts as
anode and undergoes corrosion, whereas Cu acts as
cathode.
Mechanism: In a Zn – Cu couple
(At anode) Zn Zn2+ + 2e–
The reaction at the cathode depends upon the
environment.
Acidic environment 2H+ + 2e– H2 (evolution of hydrogen)
Alkaline or neutral environment
½O2 + H2O + 2e– 2OH– (absorption of oxygen)
Zn2+ and 2OH– ions interact to form Zn(OH)2. Hence, Zn
dissolves and Cu is protected.
The common examples of galvanic corrosion are as follows
• Use of Cu pipes in conjunction with iron pipes in water distribution
system.
• A steel propeller shaft in a bronze bearing.
• Steel screw in brass marine hardware.
• Lead–antimony solder around Cu wire.
Concentration cell: corrosion Concentration cell corrosion
takes place when different areas of a metal surface are in
contact with an electrolyte of different concentration
(caustic embrittlement) or varying aeration (pitting
corrosion, waterline corrosion, corrosion under a block of
wood or a drop of water, etc). The difference in
electrolyte/air concentration may be because of local
temperature differences or inadequate stirring or slow
diffusion of metal ions.
Differential aeration corrosion (DAC): This is the most
common type of concentration cell corrosion. It occurs
when one part of the metal is exposed to a different air
concentration than the other. There will be a difference of
potential between differently aerated areas.
Experimental observations have shown that
• Poorly oxygenated areas become anodic and
• Highly oxygenated areas become cathodic.
Waterline corrosion:
Pitting corrosion:
Corrosion under a block of wood, leaf, metal,
stone, etc:
Stress corrosion Crevice corrosion
Intergranular corrosion
a more reliable series for predicting the corrosion
behaviour in different environments is the galvanic
series.
It has been prepared by studying the corrosion of
metals and alloys in a given environment like sea water.
Thus, the galvanic series gives real and useful information for studying
the corrosion of metals and alloys.
The rate and extent of corrosion depend on the following
• Nature of the metal
• Nature of the corroding environment.
Nature of metal
• Position in the galvanic series: When two metals or alloys are in
contact in the presence of an electrolyte, the metal that is higher in the
galvanic series undergoes corrosion. The rate and severity of corrosion
depends on the difference in their position. Greater the difference in
the position of the two metals greater is the corrosion of the anodic
metal.
• Purity of the metal :Pure metals are less prone to corrosion.
Impurities in a metal cause ‘heterogeneity’ and forms minute/tiny
electrochemical cells, where the anodic part gets corroded. For
example, very pure and smooth zinc metal will not corrode in very pure
hydrochloric acid. However, zinc metal containing impurities of Fe and
Pb corrodes rapidly.
The figures below show the effect of impurities on corrosion of
aluminium by hydrochloric acid.
% Aluminium 99.998 99.97 99.2
Relative corrosion rate 1 1000 30,000
Physical state of the metal: Rate of corrosion is
greatly influenced by the physical state of the metal like
particle size, orientation of grains, localised stresses,
smooth or rough surface, etc. Smaller the grain size
greater will be the corrosion; similarly, areas under
stress, even in a pure metal, are likely to be anodic and
corrosion takes place at these areas.
Nature of surface film: In the presence of air, all
metals are covered with a thin film of metal oxide. If the
specific volume ratio of the metal is greater than one the
metal will be protected from corrosion, and if the
specific volume ratio is less than unity the film will be
unstable and the underlying metal will be corroded
(Pilling–Bedworth rule). The specific volume ratios of
Ni, Cr and W are 1.7, 2.0 and 3.6, respectively.
Relative areas of anodic and cathodic parts : Rate of corrosion is
high if anodic areas are small and cathodic areas are large. If the
cathodic areas are large, then it will demand more electrons, which will
be met by the brisk and rapid corrosion of the anodic area. For example,
in copper plates (cathode) with steel (anode) rivets, the steel rivets are
almost completely corroded because the smaller steel rivets are coupled
to larger copper cathodic area.
Solubility of corrosion products: Corrosion is faster if the corrosion
product is soluble in the corroding medium. If the corrosion product is
insoluble in the corroding medium, or it reacts with the corroding
medium to form insoluble product; the product acts as a physical barrier
and suppresses further corrosion. For example, the corrosion of Pb in
H2SO4 proceeds at a much slower rate due to the formation of insoluble
PbSO4.
Volatility of the corrosion product: If the corrosion product is
volatile, it leaves the surface as soon as it is formed, leaving the
underlying metal surface exposed for further attack. This causes rapid,
continuous and excessive corrosion. MoO3 is the volatile corrosion
product formed on the oxidation of Mo. It volatilizes, causing extensive
corrosion of the underlying metal.
Temperature: As the rate of all chemical reactions
increases with the rise in temperature, rate of
corrosion also increases as temperature rises. At higher
temperatures, even the passive metal can become
active and get corroded. However, differential aeration
corrosion slows down at higher temperatures. This is
because of the faster diffusion of O2 into pits and
crevices. Moreover, corrosion also occurs due to the
formation of differential temperature cells.
Humidity: Corrosion increases with the increase in
humidity of the atmosphere. The effect of humidity on
corrosion of enameled steel is given in the table below.
This is due to the fact that moisture acts as a solvent for
O2, H2S, SO2, NaCl, and so on to furnish the
electrolyte for setting up a corrosion cell.
Presence of impurities in atmosphere: Gases like
H2S, SO2 and CO2 increase acidity of the liquid
closer to the metal surface and hence increases the
rate of corrosion. Salts like NaCl present in marine
environment increase the conductivity of the
electrolyte, thus speeding up the corrosion process.
Presence of even trace amount of H2S in atmosphere
tarnishes silver (due to formation of Ag2S) and
copper (due to formation of a mixture of Cu2S + CuS
+ Cu2O).
Effect of pH: Generally, acidic media (pH < 7 ) are
more corrosive than alkaline or neutral media.
However, amphoteric metals like Al, Zn, Pb form
complexes in alkaline medium.
Conductance of the corroding medium:
Conductance of the corroding medium has a vital
role in corrosion. Dry sandy soils have lower
conductance compared with clay or mineralized
soils. Hence, metallic structures buried under clay or
mineralized soils undergo corrosion faster than
under dry sandy soils.
Formation of oxygen concentration cell: Owing
to differential aeration “oxygen concentration cell” is
set up and the anodic parts having less oxygen
concentration suffers corrosion. The corrosion by
differential aeration has already been discussed in
detail.
Material selection and design
Cathodic protection
Corrosion inhibitors
Protective Coatings
metallic coatings
paints
Use of pure metals or alloys
Select metal with low reactivity.
When two dissimilar metals in direct contact are to be
used then, they should be as close as possible in the
galvanic series.
Avoid direct contact of two dissimilar metals in a
corroding medium.
Joints should be welded with same metal/alloy
Sharp corners should be avoided
Wherever possible, equipment should be supported on
legs to allow free circulation of air
The anodic metal should not be painted or coated.
The principle involved is that the metal to be
protected is made to behave like a cathode.
Alloys/metals like steel, brass, copper and lead can be
protected in all types of soils and almost all sorts of
aqueous media by cathodic protection method.
Sacrificial Anode Cathodic Protection Method
(SACP): In this method, the metal structure to be protected is
connected to a more reactive metal. For example, if an iron
structure is to be protected it is connected to a more reactive
metal like Zn or Mg. The more reactive metal behaves as an
anode and the iron structure becomes cathodic. Thus, the iron
structure is protected and the anode undergoes corrosion. After
sometime, the anode is corroded completely and is replaced with
a fresh anode. This type of protection method is used in industry
to protect buried pipelines, underground cables, ship hulls and
even in railway tracks.
In this method direct current from an external source is
impressed (applied in opposite direction) to nullify the corrosion
current and convert the corroding metal from anode to cathode.
e positive terminal of the direct current source is connected to
the anode and the negative terminal to the structure to be
protected. Anode is made of inert material like graphite, carbon,
stainless steel and is buried in a backfill like gypsum to increase
electrical contact between itself and the surrounding soil
PROTECTIVE
COATINGS
Inorganic
Organic Coatings
Coatings
Non-
Metallic Paints
Metallic
Paint
Pigment
Vehicle/
Thinner Drier Additives
Binder
Requisites of a good paint:
A good paint should the following properties, it should
have a high hiding power
form a good and uniform film on the metal surface
the film should not crack on drying
give a glossy film
the film produced should be washable
give a stable and decent colour on the metal surface
have good resistance to the atmospheric conditions
be fluid enough to spread easily over the surface
possess high adhesion capacity to the material over which it
is intended to be used
dry quickly or in a reasonable duration.
the colour of the paint should not fade
Constituents of paint:
a) Pigment
b) Vehicle or medium or drying oil
c) Thinner
d) Driers
e) Fillers or Extenders
f) Plasticizers
g) Antiskinning agents
Driers: These are the oxygen carrier catalysts. They accelerate the drying of
the oil-film through oxidation, polymerization and condensation. The main
function of the drier is to improve the drying quality of the oil film.
Eg: Resinates, linoleates, tungstates and naphthenates of Co, Mn, Pb and Zn.
Extenders or fillers: These are low refractive indices
materials. These are added to reduce the cost, increase
durability, to provide negligible covering power to the paint
and to reduce the cracking of dry paint film. These fill the
voids in the film, increase random arrangement of pigment
and acts as the carrier for pigment color.
Eg: Barytes (BaSO4), talc, asbestos, ground silica, gypsum
ground mica, slate powder, china-clay, calcium sulphate.
Plasticizers: Plasticizers are added to the paint to provide
elasticity to the film and to minimize its cracking.
Eg: Tricresyl phosphate, tri phenyl phosphate, tri butyl
phthalate.
Anti skinning agents: These are added to prevent gelling and
skinning of the paint film.
Eg: Poly hydroxy phenols.
VARNISHES
OIL Spirit
Varnish Varnish
OIL VARNISH:
• They contain linseed oil or other drying oils, dryers, synthetic or natural resins and
solvents such as white spirit or turpentine.
• They dry by evaporation of the solvent and oxidation of the oil.
• The relative proportions of the oil and the resins control the usage, if the oil is
predominant a more elastic varnish reserved for external work.
• If the solvent is the major ingredient a high gloss, which dries out rapidly, is obtained for
internal work.
• Copal varnish is a good quality type.
SPIRIT VARNISH
• Spirit varnish is a solutions of shellac and spirit resins dissolved in commercial
alcohol(methylated spirits).
• The are only suitable for internals surfaces like furniture(e.g. in French
polishing).
• Polyurethane varnish is a type of resin varnish producing a very durable finish.
• Its cost is RS- 230/kg
Thank you
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