Module-2

Corrosion and Metal Finishing

Corrosion
Definition:

“Corrosion is the deterioration or destruction of metals by chemical or electrochemical

reaction with their environment that converts a refined metal into a more chemically stable
form such as metal oxide, metal hydroxide, or metal sulfide”.

Electrochemical theory of corrosion:

(Theory or Mechanism of rusting of iron)
According to electrochemical theory, corrosion of metals occurs due to the following
changes, when they are exposed to the environment.

1) A large number of minute galvanic cells are formed which acts as anodic and cathodic
areas.

2) At anode the metal undergoes oxidation and electrons are liberated which migrates towards
cathodic region

3) Oxygen of the atmosphere undergoes reduction at cathodic area in the presence of moisture
forming hydroxyl ions at the cathode.

4) Moisture or water acts as electrolyte.

5) The anodic part of the metal undergoes oxidation and suffers from corrosion, cathodic part

undergo reduction and protected from corrosion.

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At Anode: At anode the metal undergoes oxidation-liberating electrons

Ex: when iron is exposed to the environment it undergoes oxidation as

Fe  Fe2+ + 2 e- (oxidation)

At cathode:

The electrons released at anode migrate to the cathodic area and reduces oxygen to hydroxyl
ions.

a) In acidic medium (absence of oxygen): In acidic medium and in the absence of oxygen
(deaerated), hydrogen ions are reduced to hydrogen gas.

2 H+ + 2 e-  H2  (reduction)

b) In neutral (absence of oxygen): Hydroxide ions are formed with simultaneous liberation of
hydrogen.

2 H2O + 2 e-  2 OH- + H2 

c) In neutral and aerated medium (absorption of oxygen): When the solution is neutral
and aerated (in presence of oxygen), hydroxyl ions are formed as follows

-
H2O + 1/2 O2 + 2 e-  2 OH
2+
d) Formation of corrosion product: Thus corrosion of iron produces Fe ions at the anode
-
and OH ions at the cathode sites respectively and these ions diffuse towards each other, and
their combination forms insoluble (ferrous hydroxide) Fe (OH)
2

Fe2+ + 2 OH-  Fe (OH)2 

e) In the presence of moisture and atmospheric oxygen ferrous hydroxide Fe (OH) is

2

oxidized to hydrated ferric oxide

2Fe (OH)2 + ½ O2 + x H2O  Fe2O3. xH2O (Rust) (yellow or orange brown color)
(Hydrated ferric oxide)

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Galvanic series:

“The arrangement of metals and alloys in order of their corrosion tendencies

in a corrosive environment is called as galvanic series”.

a) Galvanic series helps in judging

the relative corrosion tendencies.
Simple galvanic table series is shown
in table.

b) A negative value indicates

oxidation tendency and a positive
value indicates reduction tendency
with respect to hydrogen

c) Lesser is the electrode potential

value in galvanic series, the metal
becomes anodic and corrodes. The
metal with lesser electrode potential is more reactive

d) More is the electrode potential value in galvanic series, the metal becomes cathodic and
remains unaltered. As the electrode potential increases, the reactivity decreases and they are
nobler.

e) Metals with lower electrode potentials have the tendency to replace metals with higher
electrode potential from their solutions, for example, Zn displaces Cu, Cu displaces Ag

Note:

Electrode Potential: When a metal is placed in a solution of its ions, the metal
acquires either a positive or negative charge with respect to the solution. On account of
this, a definite potential difference is developed between the metal and the solution. This
potential difference is called electrode potential.

Example: The electrode potential for copper is +0.34 V and for zinc -0.76

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Factors affecting the rate of corrosion:
1. Ratio of cathodic to anodic areas:
a) The rate of corrosion (x) is directly proportional to the ratio of area of cathode to the area
of anode. i.e.,

x = area of cathode/ area of anode

or

b) Higher the value of x, greater is the rate of corrosion.

c) If the metal has small anode and large cathodic region, corrosion rate is very high, this is
because at anode electrons are liberated and are consumed at cathodic region.

d) When the cathodic area is smaller, demand for electrons will be less and this result
decrease in the rate of dissolution of metal at the anodic region

2. Nature of corrosion product:

The corrosion product is usually the oxide layer formed on metal surface determines the
corrosion rate.

a) If the corrosion product formed is stable, insoluble, uniform, non-porous, non-conducting,

and non-volatile and thus it acts as protective film and prevents further corrosion by acting as
barrier between metal surface and corrosion medium.

For E.g: Aluminium forms insoluble oxide layer (Al2O3) on its surface, which is protective
film. and prevents from corrosion , and other metals like Chromium, Titanium, etc., are
highly stable as their oxides as corrosion products form protective films on the metal surface,
preventing further corrosion.

b) On the other hand, if the oxide layer is unstable, non-stoichiometric and porous with high
conductivity then it acts as non-protective film. In such case the fresh metal is exposed for
further attack. Hence corrosion takes place continuously.

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For E.g: Iron forms iron oxide on its surface which is destructive oxide layer in which
corrosion takes place continuously and other metals like zinc, magnesium etc., do not form
any protective film and are highly corrosive

3. Nature of medium
(i) pH : Higher the acidic nature of the environment (lower the pH of corrosion medium),
higher is the rate of corrosion.

a) Iron does not undergo corrosion at pH greater than 10. This is due to the formation of a
protective coating of hydrous oxides of iron.

b) Between pH 3 and 10, the presence of oxygen is essential for corrosion.

c) If the pH is less than 3, severe corrosion occurs even in the absence of oxygen/air, due to
the continuous evolution of hydrogen at the cathodic region. This is because, more H2
evolution, more electrons accept at cathode which in turn more electrons release from anode.
Hence the rate of corrosion is high.

(ii) Conductivity:

Rate of corrosion increases with the increase in conductivity of the medium. Higher the
conductivity of the medium, faster the ions can migrate between the anodic and cathodic
regions. This facilitates higher corrosion rate.

For example, near industrial areas, the atmosphere contains corrosive gases like CO2, H2S,
SO2, HCl and H2SO4 fumes. In presence of these gases, the acidity of the liquid adjacent to
the metal surfaces increases and its conductivity increases. As a result, corrosion increases.

Similarly, in the marine atmosphere, the presence of sodium and other chlorides leads to
increased conductivity of the liquid layer in contact with the metal surface, thereby increases
corrosion. For another example, the rate of corrosion is more in the

i) Clayed and mineralized soils than those in dry sandy soils

ii) Ocean water than the river water

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(iii) Temperature:

As temperature increases, diffusion of ions increases due to increase in the ionic conductivity
of the corrosive medium. Therefore, the rate of corrosion is high.

As temperature decreases, diffusion of ions will be less. Therefore, the rate of corrosion is
also less.

Types of corrosion
1. Differential metal corrosion or Galvanic Corrosion
This type of corrosion occurs when two
dissimilar metals are in contact with each other
and are exposed to a corrosive environment.

Metal with lower electrode potential will acts as

an anode and it undergoes oxidation and gets
corrode

Metal with higher electrode potential will acts as

an cathode and it undergoes reduction and metal
does not undergo corrosion

Iron acts as an anode when it is in contact with Cu, Sn, Ni etc. and iron acts as a cathode in
presence of Mg, Zn etc.

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The reactions may be represented as follows:

At anode: Fe → Fe+2 + 2e- (oxidation)

At cathode: 2 H2O + ½ O2 + 2 e-  2 OH- (reduction)

Fe2+ + 2 OH-  Fe (OH)2  (ferrous hydroxide )

2Fe (OH)2 + ½ O2 + x H2O  Fe2O3. xH2O (Rust)

(Hydrated ferric oxide)
Example.: 1) Steel pipe connected to copper

2) Zinc coating on mild steel

3) When screws & washers and bolts & nuts are made of different metals,

2. Differential aeration corrosion

This type of corrosion occurs when same metal is exposed to different concentrations of
oxygen.

a) The part of the metal which is exposed to less oxygen

concentration acts as an anode.

b) The part, which is exposed to more oxygen

concentration, acts as a cathode.

c) The anodic region undergoes corrosion and the

cathodic region is unaffected.

d) The difference in oxygen concentration produces a

potential difference and causes corrosion. This type of corrosion is called differential aeration
corrosion.

Ex.: Nail inside the wall corrodes, Window frame inside wall corrodes

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The reactions may be represented as follows:

At anode: Fe → Fe+2 + 2e- (oxidation)

At cathode: 2 H2O + ½ O2 + 2 e-  2 OH- (reduction)

Fe2+ + 2 OH-  Fe (OH)2  (ferrous hydroxide )

2Fe (OH)2 + ½ O2 + x H2O  Fe2O3. xH2O (Rust)

(Hydrated ferric oxide)

Examples for Differential aeration corrosion are:

1) Pitting corrosion

2) Water line corrosion

1) Pitting corrosion:
a) Pitting corrosion is observed when dust particles get deposited over the metal surface.
Pitting corrosion is one of the most damaging forms of corrosion.

b) When dust settles on the surface of a metal, the portion of the metal covered by dust is less
aerated and acts as anode, where the rate of corrosion is high.

c) The rest of the metal is exposed to atmosphere and is more aerated. This portions acts as
cathode, where the rate of corrosion is less.

d) The large cathodic area requires large number of electrons for reduction. This has to be
supplied by small anodic area and hence corrosion takes place fast. This localized corrosion
leads to formation of a Pit. This type of corrosion is called pitting corrosion.

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The reactions may be represented as follows:

At anode: Fe → Fe+2 + 2e- (oxidation)

At cathode: 2 H2O + ½ O2 + 2 e-  2 OH- (reduction)

Fe2+ + 2 OH-  Fe (OH)2  (ferrous hydroxide )

2Fe (OH)2 + ½ O2 + x H2O  Fe2O3. xH2O (Rust)

(Hydrated ferric oxide)

Pitting is vigorous when the solution on the metal surface contains chloride, hypochlorite or
bromide ions. Other harmful solutions are those that contain fluorides and iodides. Sulphides
and water are also known to enhance the pitting process.

The most common pitting corrosion causes are;

a) Cracks in protective coating

b) Scratches, scuffs & small chips

c) Non-uniform stress

d) Defective metal substrate

e) Chemical attack on protective coating

f) Non-uniform protective coating

g) Turbulent fluid flow

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2. Water line corrosion
In steel tanks half filled with water, the
portion which is above the level of
water is exposed to atmospheric oxygen
and hence is more aerated. This part acts
as cathode and undergoes less corrosion.

The bottom portion is exposed to Oxygen dissolved in water, hence acts as anode and
undergoes more corrosion. Therefore corrosion begins at this portion and moves slowly
upwards until the entire tank corrodes.

The area below the water level is corroded and area above water level is protected. Example:
water storage tanks, floating ships

The reactions may be represented as follows:

At anode: Fe → Fe+2 + 2e- (oxidation)

At cathode: 2 H2O + ½ O2 + 2 e-  2 OH- (reduction)

Fe2+ + 2 OH-  Fe (OH)2  (ferrous hydroxide )

2Fe (OH)2 + ½ O2 + x H2O  Fe2O3. xH2O (Rust)

(Hydrated ferric oxide)

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