You are on page 1of 13

CORROSION

Definition
Corrosion is defined as the destruction of metals or alloys by the surrounding
environment through chemical or electrochemical changes.
Ex:-Rusting of iron & green scales formation on copper vessels.

Depending upon the corrosion medium, corrosion is classified into

1. Dry corrosion & 2.Wet corrosion

1. Dry corrosion

Dry corrosion involves the direct attack of metals by dry gases mainly through chemical
reactions. Dry corrosion is less common.

Ex:-Attack of dry air or oxygen on a metal to form an oxide layer.

2. Wet corrosion

It occurs due to electrochemical reaction of metals with air (O2) in aqueous medium

Ex:-Rusting of iron

Wet corrosion is explained on the basis of electrochemical theory.

Electrochemical theory of corrosion


When metal like iron is exposed to atmosphere, the following electrochemical change takes
place

1. Formation of galvanic cells :Anodic and cathodic areas are formed resulting in minute
galvanic cells.
2. Anodic reaction :At the anodic area, oxidation takes place resulting in the corrosion of
iron. At anode (oxidation reaction): M →Mn+ + ne-
When iron undergoes corrosion: Fe → Fe+2 + 2e-
3. Cathodic reaction: The electrons flow from the anodic to cathodic area and cause reduction.
There are different ways in which the reduction can take place.

At cathodic region
1. Liberation of hydrogen takes place in the absence of oxygen

2. Absorption of oxygen takes place in the presence of oxygen


1. Liberation of hydrogen

If the medium is acidic, in the absence of dissolved oxygen: 2H+ + 2e-→ H2
In neutral and alkaline medium in the absence of dissolved oxygen 2H2O+2e-→ 2OH- + H2

2. Absorption of oxygen takes place in the presence of oxygen

In acidic medium in the presence of oxygen 4H+ + O2 + 4e-→2H2O

In neutral or alkaline medium and in the presence of oxygen 2H2O+ O2 + 4e-→ 4 OH-

Corrosion of iron produces Fe+2 and OH- ions at the anode and cathode sites respectively.
These ions diffuse towards each other.
2Fe2+ +4OH- →2Fe (OH) 2(ferrous hydroxide)

4Fe (OH) 2+O2 +2H2O →2 Fe2O3.3 H2O


Hydrated ferric oxide (yellow rust)

In the presence of limited oxygen, ferrous hydroxide is converted into magnetic oxide of iron
(Fe3O4)

3Fe (OH) 2+½ O2→Fe3O4.3H2O


(Black rust)

Factors influencing the corrosion rate


Primary Factors
1. Nature of the metal

*The metals with lower electrode potential values are more reactive than the metals
with higher electrode potential values.
*The more reactive metals are more susceptible for corrosion.

Thus the tendency of a metal to undergo corrosion decreases with increase in


electrode potential. Ex:-Active metals like K,Na,Mg,Zn with low electrode potential
values are highly susceptible for corrosion.

*The noble metals such as Silver,Gold,Platinum with higher electrode potential values are
less susceptible for corrosion.

*There are few exceptions for this general trend as some metals show the property
of passivity.

*Larger the potential difference between the anodic and cathodic region of the
corrosion cell,higher is the corrosion rate.

*The more active metal undergoes corrosion very fast.

For Ex:-The potential difference between iron and copper is 0.78V which is more than
between iron and tin (0.3V).Therefore, iron corrodes faster in contact with copper than with
tin.

2. Relative size of anodic and cathodic areas

*Corrosion of a metal occurs fast if the anodic area is small and the cathodic area is larger.

*When cathodic area is large, demand for electrons for reduction reaction will be high. To
meet this demand, oxidation reaction occurs more intensely at anodic area.

Ex:-In the plating of tin on iron, if some areas are not covered or some pin holes are left,a
small anode and large cathode areas are formed. An intense localized corrosion occurs at the
exposed anodic area.

Zinc plating on iron gives an anodic coating to iron. Even if zinc plating peels off at some
points, the rate of corrosion of iron is low. This is because of the formation of large anodic and
small cathodic area.
3. Nature of the metal and corrosion product

*The product of corrosion is usually the oxide of the metal.

*The nature of oxide layer determines the corrosion rate.

*If its composition is stoichiometric, highly insoluble and nonporous with low ionic
and electronic conductivities, the layer effectively prevents further corrosion.

Ex:-Al,Ti,Cr

*Metals like Ta,Zr,Mo not only form such protective layers but are also capable of self-
repairing the oxide film when it is damaged.

These metals are extremely resistant to corrosion.

*Stainless steel builds up a thin but a highly protective film of Cr2O3 which resists attack in
a highly corrosive environment.

*If the oxide layer is non stoichiometric, highly porous with high ionic and
electronic conductivity, it cannot control further corrosion. Ex:-Fe,Zn.

Secondary factors
4. pH

*The rate of corrosion increases with decrease in pH

*At pH greater than 10, corrosion of iron practically ceases due to the formation of a
protective coating of hydrous oxide of iron.

*Between pH 10 and 3 presence of oxygen is essential for corrosion.

Ex:-Ships submerged in sea water unaffected

*If pH is lower than 3, severe corrosion occurs even in the absence of air due to the
continuous evolution of hydrogen at the cathodic region.
Types of Corrosion
According to electrochemical theory, corrosion occurs due to formation of large number
of minute galvanic cells. There are different ways in which galvanic cell can be formed on
the metal surface. Accordingly, the following types of corrosion have been observed.

1) Differential Metal corrosion:

When two dissimilar metals are in contact with each other, the metal with lower reduction
potential becomes anodic and undergoes corrosion. Whereas, the metal with higher
potential becomes cathodic and remains unaffected. This kind of corrosion is called
differential metal corrosion or galvanic corrosion. The rate of corrosion depends primarily on
the amount of current passing from the anode to the cathode. and also on the difference in
potential between the metals. Higher the difference, faster is the rate of corrosion.

Example
a) Std. potential of Fe(-0.44V) is less than that of Cu(0.34V). Therefore, when iron
is in contact with copper, iron becomes anodic and undergoes corrosion
whereas copper becomes cathodic and remains unaffected.

b) Std. potential of Zn(-0.76V) is less than that of Fe(0.44V). therefore , when iron
is in contact with Zn, Zinc undergoes corrosion whereas Fe remains unaffected.

2. Differential aeration corrosion

When metal is exposed to different concentrations of air(O2), part of the metal exposed to
lower concentration of O2 becomes anodic and undergoes corrosion. Whereas, other part
of the metal exposed to higher concentration of O2 becomes cathodic and remains
unaffected. This kind of corrosion is called as differential aeration corrosion.e:
Iron rod partially immersed in NaCl solution. The part of the metal immersed in solution is
exposed to lower concentration of oxygen becomes anodic area and undergoes corrosion.
Whereas, part of the metal outside water is exposed to more oxygen becomes cathodic
and remains unaffected.
Examples of differential aeration corrosion, a) Waterline corrosion, & b) Pitting corrosion.

a) Water line corrosion

It is observed in steel or iron water tanks partially filled with water. Metal just below the
water line which is exposed to lower concentration of O2, becomes anodic and undergoes
corrosion. Part of the tank just above the water line which is exposed to higher concentration
of o2 becomes cathodic and remains unaffected. This type of corrosion is also observed in
ships floating in sea water for long time.
b) Pitting corrosion

Pitting corrosion results when dust particles get deposited on a metal surface. The portion
covered by the dust will be less aerated compared to the exposed surface. The covered portion
thus becomes anodic with respect to the exposed surface. In the presence of electrolytes and
moisture corrosion starts beneath the dust resulting in a pit. Once a pit is formed, the
corrosion progress rapidly. This is because of the formation of small anodic area (pit) compared
to a large cathodic area (surface).

Differential aeration corrosion is observed in

1) Less aerated areas in machinery


2) Less aerated areas in metals as for example cracks
3) Less aerated points of contact in a wire screen

2. Stress Corrosion

If two samples of steel, one of which is under stress, are placed in a corrosive environment,
the stressed specimen corrodes at a faster rate. Stress may be due to mechanical operations
such as poor design, riveting, cold working, welding, bending, pressing and quenching. In a
corrosive environment, the stressed portion is anodic with respect to the unstressed portion
and undergoes corrosion. At the stressed portion, the atoms are slightly displaced creating an
anodic zone of higher potential. These zones are very active and are attacked even by mild
corrosive agents.
An example of stress corrosion is intercrystalline corrosion (or) caustic embrittlement.

Mild steel boilers under corrosion at the stressed portion when the pressure is 10 to 20 atm. Fine
hair-line cracks may be present at the stressed portion of the boiler. Boiler water containing
alkaline impurities passes into the cracks by capillary action. Later water evaporates leaving behind
caustic soda in the cracks. When the concentration of caustic soda reaches 10%, an
electrochemical cell is set up between the iron under stress and the iron in the main body.

The iron surrounded by dilute sodium hydroxide is the cathode and the iron under stress acts
as the anode and gets corroded resulting in boiler failure.

Iron under conc. NaOH Dil. NaOH Iron (cathode)


Stress (in the cracks) (in boiler water) (Main body)

Na2CO3+ H2O 2NaOH + CO2

3Na2FeO2+4H2O 6NaOH + Fe3O4 + H2

Caustic embrittlement can be prevented by the addition of compounds such as sodium sulphate,
tannin, ligin, phosphates which block the cracks, thereby preventing the infiltration of alkali.

Corrosion control
Corrosion can be controlled by preventing the formation of galvanic cells

Methods:
1)Design and selection of materials.

2)Protective coatings

A) Metal coatings - anodic and cathodic


B) Surface conversion coatings – anodizing and phosphating

3)Organic coatings.
1) Design and selection of materials.

Design and selection of materials:Corrosion can be comtrolled by selecting proper materials


which resist the corrosion environment and designing them suitably during
fabrication.Some practical considerations are given below.

A)Differential metal corrosion can be reduced by avoiding use of two dissimilar metals.If
their use is unavoidable,the positions of the metals chosen shall be as close as possible in
the galvanic series.

B) To reduce the rate of corrosion ,the anode material must be as large as possible while the
cathode should be small.For example,bolt and nut,washer and rivets of a cathodic metal may
be used in contact with an anodic sheet of large area.

C)While joining metals,care should be taken not to leave gaps between them,where some liquid
or air can be trapped resulting in differential aeration corrosion.The gaps can be avoided by
proper designing.

D)An insulator should preferably be used at the contact point of two dissimilar
metals.However, porous insulators such as asbestos,magnesia and wood should not be used
since they absorb and hold liquids which act as electrolytic

2) Protective coatings
A) Metal coatings

Corrosion of metals can be controlled by isolating them from the environment. This can
be brought about by covering the substrate or base metal with a layer of another metal.
The process is referred to as metal coating. Metal coatings are of two types

a) Anodic metal coating


b) Cathodic metal coating

a) Anodic metal coating

Anodic metal coatings are coatings which are anodic to the base metals. Examples are
Aluminum, magnesium, Zinc and cadmium coatings on iron. These metals are above iron in the
galvanic series and undergo corrosion thereby protecting iron. A characteristics feature of
anodic coatings is that the base metal on which the coating is done will not get corroded even if
the coatings peal off. This is due to the formation of large anodic and small cathodic areas. Hot
dipping or galvanising is an example of metal coating
HOT DIPPING: Galvanizing

The process of coating zinc on iron by hot dipping is called galvanizing. It involves the
following steps. The metal surface is washed with organic solvents to remove organic matter
on the surface.

1. Rust and other deposits are removed by washing with dilute sulphuric acid.
2. Finally the article is well washed with water and air dried.
3. The article is then dipped in a bath of molten zinc, maintained at 430-470 c and
covered with a flux of ammonium chloride to prevent the oxidation of molten zinc.
4. The excess zinc on the surface is removed by passing through a pair of hot
rollers, which wipes out excess zinc coating and produces a thin coating .

Galvanization is used extensively to protect iron from corrosion in the form of roofing
sheets, fencing wire, buckets, nuts, nails, pipes, tubes ,etc..

Galvanized articles are not used for preparing and storing food stuffs, since zinc dissolves
in dilute acids producing toxic zinc compounds.

b) Cathodic Metal Coating

Cathodic metal coatings are coatings which are cathodic to the base metal. Examples are tin,
nickel, chromium and copper on iron. The coating is given in such a way that the applied coat
completely covers the surface without leaving even pin holes. Otherwise rapid corrosion of
the base metal takes due to the formation of large cathodic and small anodic areas.

Tinning, the process of coating tin on iron is described below.

1. The sheet is first washed with organic solvents to remove grease or oil deposits.
2. Then treated with dilute sulphuric acid to remove rust and scale deposits. Finally it
is washed well with and air dried.
3. Then clean and is passed through molten zinc chloride flux. The flux helps the molten to
adhere on the metal surface.
4. It is passed through a tank that contains molten tin.
5. Finally passed through a series of rollers immersed in palm oil.
The rollers wipe the excess tin deposits and produce a continuous,
thin coating of tin on the sheet. The oil prevents the oxidation of the tin coated surface.
The largest single use of tin is in coating of steel for manufacturing containers used for
storing food stuffs like jam, instant food, milk products, pickles, etc….copper utensils are
coated with tin to prevent contamination of food stuffs with poisonous copper salts.

B) Surface conversion coatings


a) Anodizing
b) Phosphating

a) Anodizing

Aluminium when made the cathode allows the passage of electrons but ceases to conduct
when made the anode in aqueous solutions of chromic acid and sulphuric acid (anodic
passivity) . The passivity of aluminium is due to the formation of a thin and compact layer of
aluminium oxide over the metal.

This phenomenon is known as anodizing or anodic oxidation other metals such as magnisium ,
titanium, tantalum, vanadium, zirconium also form anodic films . But these have not found
commercial application.

Anodizing is carried out as follows:

The article is degreased, polished and connected to anode.steel or copper is made the cathode.
The electrolyte consists of 5-10% chromic acid. The temperature of both is maintained at 35 c. A
potential is applied and gradually increased from 0 to 40v during the first 10mins. Anodizing is
continued for 20mins at 40v. After 20mins, the potential is increased to 50V and held at this
potential for 5mins. An opaque oxide layer of 2-5 micrometer thickness is obtained. For higher
thickness, 10% sulphuric acid is used as the electrolyte at 22 oC and at a potential of 24V.

The article is dyed immersing for about 20mins in a solution of the dye at 50-60oC . Finally
the article is treated with nickel acetate followed by boiling water.
Anodized aluminium is also used in computer hardware exhibit displays, scientific instruments
and in a range of home appliances and consumer products. It also finds applications in
satellites for their protection in space environment.

b) Phosphating

Phosphating is the process of depositing a coating of metal phosphate on metal surface. Steel,
zinc and aluminium objects which are to be provided with a paint finish are generally given a
phosphate undercoat. Phosphating improves corrosion resistance and also imparts the surface
a good paint adhesion quality. An example is coating of mixed iron and zinc phosphates on
steel sheet fabrications such as refrigerators, washing machines and car bodies.

Phosphating bath solutions contain a mixture of free phosphoric acid , a metal phosphate and
an accelerator.

Accelerators speed up the reaction and reduce the crystal size. Nitrites are commonly used as
accelerators. The pH is maintained between 1.8-3.2 and the electrolysis is carried out at about
35oC .

Phosphating involves:-

1. Dissolution of metal as metal ions.

2. Reaction of the metal ions with the phosphates ions to form metal phosphate.

3. Deposition of the metal phosphate on the surface of the metal.


ORGANIC COATINGS:
Organic coatings such as paints,enamel,varnishes,applied on clean metal surface act as inert
protective barriers.These coatings not only protect metal from corrosion but also offer decorative
appeal.
Paints are the mixture of pigments,drying oils,synthetic resins,thinners,and driers.Enamels are
pigmented varnishes gives a hard and glossy finish.Porcelain enamels offer corrosion resistance
at elevated temperatures.

You might also like