MODULE-2

CORROSION AND METAL FINISHING

(CO 2)
Corrosion: Introduction, Electrochemical theory of corrosion, Factors affecting the rate of corrosion:
ratio of anodic and cathodic areas, nature of metal, nature of corrosion product, nature of medium –
pH, conductivity and temperature. Types of corrosion- Differential metal corrosion, Differential
aeration corrosion (Pitting and water line corrosion).Corrosion control: Inorganic coatings –
Anodizing of Al,Metal coatings – Galvanization, Cathodic protection -Sacrificial anodic and
impressed current methods.

Metal Finishing: Introduction, Technological importance. Electroplating: Introduction, principle

governing- Polarization, decomposition potential and overvoltage. Electroplating of chromium
(decorative and Hard). Electroless plating : Introduction, Electrolessplating of nickel and copper,
distinction between electroplating and electroless plating process.

Introduction: Corrosion is a process of destruction or deterioration of metal by the environment

through chemical or electrochemical reactions.
Most of the metals and alloys undergo corrosion except the noble metals. Corrosion is like
“Cancer”for the metals.
Eg: Rusting of Iron- it is due to formation of hydrated ferric oxide.

Types of corrosion:
1. Dry Corrosion: Corrosion taking place in the absence of moisture that is direct chemical reaction
taking place between metal and dry gases.

2. Wet Corrosion: Corrosion taking place in the presence of moisture or aqueous wet environment.

Electrochemical Theory of Corrosion:

According to electrochemical theory, corrosion of metal takes place due to the formation of
anodic and cathodic regions on the same metal surface or when two different metals are in contact
with each other in the presence of a conducting medium.
• When a metal is exposed to aqueous environment it divides metal into two parts as anode and
cathode on same metal surface.
• At anodic region oxidation takes place where e- are liberated. Corrosion takes place at the
anode.
• Cathodic region is protected as it undergoes reduction where it consumes or accepts liberated
e-.
• Anodic and cathodic reactions are going to take place due to metal impurities in bulk amount
and difference in oxygen concentration on metal surface.
Corrosion reactions:

Anodic reaction: Oxidation of metal takes place where metal converts to metal ion.
M ------→ Mn+ + ne-
Fe Fe2+ + 2e-

Cathodic reaction: Two types of reaction going to take place

1. Liberation of hydrogen: In absence of oxygen

i) In acidic medium cathodic reaction is
2H+ +2e- H2

ii) In neutral or alkaline medium, hydroxide ions are formed.

2H2O + 2e- 2OH- + H2

2. Absorption of Oxygen:
i) In acidic medium water is formed
4H+ +2e- +O2 2H2O

ii) Alkaline medium

2H2O + O2 +4e- 4OH-

This water accepts electrons to form OH- ions. Fe2+ ions and OH- ions defuse towards each other and
forms corrosion product (Ferrous hydroxide).
Fe2+ + 2OH- Fe(OH)2 (insoluble)

This Ferric hydroxide further undergo oxidation in presence of oxygen to form Rust
Fe(OH)2 + H2O + ½ O2 (Fe2O3. 3H2O) Rust
 FACTIORS AFFECTING THE RATE OF CORROSION

1. Ratio of anodic and cathodic areas. The rate of corrosion depends on the size of anodic and cathodic
area. If metal forms small anodic region and larger cathodic region then corrosion is faster and
intensive at anodic region.
At anode oxidation takes place and electrons are liberated. At cathode electrons are consumed. When
anode area is smaller electrons liberated at anode is rapidly consumed at larger cathodic area. This
process makes anodic reaction to take place at maximum rate of corrosion. If cathode area is smaller
than anode area consumption of electrons will be slower and rate of corrosion decrease.

Eg: Broken coating of Tin (larger cathodic area) on iron surface (smaller anodic area)

Zinc plating on Iron gives smaller cathodic region and larger anodic region. If zinc plating peels of at
same point still rapid corrosion does not occur due to smaller cathodic area and larger anodic area.

2. Nature of Metal: Metals with lower electrode potential values are more reactive than the metals with
higher electrode potential. Hence more reactive metals are more susceptible for corrosion. The
tendency of a metal to undergo corrosion decreases with increase in electron potential.
Eg: Metals like Sodium, Zinc, Magnesium have low electrode potential values and hence susceptible for
corrosion.
Noble metals like gold, platinum have higher electrode potential value less susceptible for corrosion

3. Nature of corrosion product: When corrosion product deposited is insoluble, stable uniform and non-
porous, it acts like barrier between the metal and corrosion atmosphere, which prevents further
corrosion. On other hand if corrosion product is soluble, unstable non-uniform and porous, rate of
corrosion is fast and continuous
Eg: Aluminium, Titanium and chromium form a protective film of metal oxide on surface and prevents
further corrosion where as in Zinc, Iron and Magnesium corrosion product formed do not form
protective film and corrosion continuous.

4. pH of the medium: In general lower pH of corrosion medium, higher is the corrosion rate. But
 exception case is Al, Zn shows faster corrosion in alkaline medium. In case of Iron rate of corrosion
will be less at greater pH because of the formation of protective coating of hydrous oxides of iron.

5. Conductivity of medium: As the conductivity of the corrosion medium increases, the corrosion rate
also increases. Higher the conductivity of medium , faster the ions can migrate between the anodic and
cathodic regions of the corrosion cell. This facilitate higher corrosion rate.

6. Temperature: In general rate of chemical reaction increases with increase in temperature. Corrosion
is one such chemical reaction. Higher the temperature, higher is the ionic conductivity in corrosion
medium and higher is the corrosion rate.

Types of corrosion
Differential Metal Corrosion (galvanic corrosion):
Differential metal corrosion occurs when two dissimilar metals are in contact with each other and
expose to corrosive environment. The two metals differ in their electrode potential. The metal with
lower electrode potential acts as anode, the metal with higher electrode potential acts as cathode. The
potential difference between two metals is a driving force for corrosion. Here anode undergoes
corrosion.
Eg: When iron is in contact with copper.

Fe++ 2OH-
-
F e Cu

ANODE CATHOD
Fe has lower electrode potential when compared to copper. Hence iron undergo oxidation and get
corroded.
Reactions:
At anode:
Fe Fe2+ + 2e-
At cathode:
H2O + ½ O2 + 2e- 2OH-
Overall Reaction
Fe2+ + 2OH- Fe(OH)2 (insoluble)
Fe(OH)2 + H2O +½ O2 (Fe2O3. 3H2O) Rust
Other examples
1. Steel screws in copper sheet
2. Steel screws with copper washer
3. Nut and bolts made of different metals.
Differential aeration corrosion:

Differential aeration corrosion occurs when a metal surface is exposed different oxygen concentration.
Part of metal exposed to higher oxygen concentration acts as cathode and metal exposed to lower
oxygen concentration acts as anode. The anodic region undergoes oxidation and gets corroded.
Eg: When iron rod partially dipped in water.

Reaction:
At anode:
Fe Fe2+ + 2e-
At cathode:
H2O + ½ O2 + 2e- 2OH-
Overall Reaction
Fe2+ + 2OH- Fe(OH)2 (insoluble)
Fe(OH)2 + H2O +½ O2 (Fe2O3. 3H2O) Rust

Other examples
a) Part of nail inside the wall undergoes corrosion.
b) Partially buried pipeline in soil undergoes corrosion.
c) Partially filled iron tank undergoes corrosion inside water.

This differential aeration corrosion is divided in to two types

Water line corrosion

This is due to differential oxygen concentration
Eg: Water storage tank

Poor oxygenated more oxygenated

Area (anode) area (cathode)

When a steel tank partially filled with water for a long time, the inner portion of the tank below the
water line is exposed only to dissolved oxygen whereas the portion above waterline is exposed to more
oxygen. Thus the portion below the water acts as anode and undergoes corrosion. The upper portion
acts as cathode and it is unaffected.
At anode:
Fe Fe2+ + 2e-
At cathode:
H2O + ½ O2 + 2e- 2OH-
Overall Reaction
Fe2+ + 2OH- Fe(OH)2 (insoluble)
Fe(OH)2 + H2O +½ O2 (Fe2O3.3H2O) Rust

Pitting Corrosion

Corrosion product
More oxygenated cathode
Anode
Iron metal

When a small dust particle gets deposited on metal surface, region below the dust particle is exposed
to less oxygen when compared to remaining part of the metal. Therefore region below dust particle
acts as anode and undergoes corrosion and forms a pit. Here formation of small anodic area and large
cathodic area results in intense corrosion below the dust particle.

Reaction:
At anode:
Fe Fe2+ + 2e-
At cathode:
H2O + ½ O2 + 2e- 2OH-
Overall Reaction
Fe2+ + 2OH- Fe(OH)2 (insoluble)
Fe(OH)2 + H2O +½ O2 (Fe2O3. 3H2O) Rust

Corrosion Control: Corrosion can be controlled by protecting the surface of the metal or by
preventing the formation of galvanic cells.

Protective Coatings: Application of protective coating is one of the important methods of corrosion
control. The protective coating protects the metal from corrosion by acting as a barrier between the
metal and the corrosion environment. The principle types of coatings applied on the metal surface are
a) Metal coating b) Inorganic coating c) Organic coating

a) Metal coating : The process of covering base metal with a layer of protective metal is known as
 metal coating. They are divided into two types,
i) Anodic coatings: It is produced by coating a metal surface with more active metals which acts as anodic
to base metal.
Eg: Galvanization
Galvanization is a process of coating base metal like iron or its alloy surface with anodic and active
Zn metal. One of the important characteristic of anodic coating is even if coating is ruptured base metal
does not undergo corrosion because base metal exposed to environment will be cathodic in nature with
respect to coating metal.
Galvanization process involves following steps:
• Metal surface is washed with organic solvents to remove organic matter.
• Rust and other deposits removed by washing with hot dil H2SO4 is called pickling
process.
• Then it is well washed with water.
• It is air dried by passing hot air.
• Then it is dipped in molten zinc, maintained at 430-4500C and covered with flux of
ammonium chloride and zinc chloride to increase adhesion property.
• Excess of zinc on surface is removed by passing a pair of hot rollers, which removes
excess of zinc and produces thin coating.
Application: Galvanized materials are used in fencing wire, buckets, bolts, nuts, nails, screw etc.

Inorganic coating: It is chemical conversion coatings where metal surface is converted to a compound
by chemical or electrochemical process which forms barrier. There are two types

a) Anodizing (Anodizing of aluminium)

It is a electrochemical process which forms protective passive (non reactive) oxide film on metal surface.
Here aluminium metal is made as anode in a suitable oxidizing electrolyte like sulphuric acid, chromic
acid, oxalic acid bath at a temperature of 30 - 400 C and moderate current density. A thin film of Al2O3
is deposited on surface, this acts as protective layer preventing the corrosion. This film tend to be
porous and provides good adherence for paint and dyes.

Uses: It is used as soap boxes, tiffin boxes, window frames etc. Anodic films are also used for number of
cosmetic effects.

Cathodic protection: It is a method of protecting a metal or alloy from corrosion by converting

metal completely into cathodic and no part of the metal is allowed to act as anode.
There are two types,
a) Sacrifical anodic method:

• Protected metal structure is converted to cathode by connecting to more active metal

• This active metal acts as anode Eg: Mg,Al,Zn etc
• This active metals undergo preferential corrosion, protecting the metal structure
• Since the anodic metals are sacrificed to protect the metal structure, hence the name.
• Exhausted sacrificial anodes are replaced when required.

Eg: Mg block connected to buried pipe tank in water

Mg block connected to underground oil storage tank.

b) Impressed current method:

• Applying direct current larger than the corrosion current

• Protected metal is made cathodic by connecting it to cathode of external source of current
• Anode of electric source is connected to inert electrode(anode)
• Metal structure being cathode does not undergo corrosion.
• Anode being inert remains unaffected
Eg: Platinum, graphite, silicon, iron are used as anodes
 Assignment Questions:

1. Explain electrochemical theory of corrosion taking iron as an example.

2. Describe differential metal corrosion
3. Explain differential aeration corrosion
4. Describe pitting corrosion
5. Explain waterline corrosion
6. Explain the factors affecting rate of corrosion.
7. Define anodizing? Explain anodizing of aluminium
8. Explain the process of galvanization
9. Define cathodic protection? Explain sacrificial anode and impressed current method.