Chapter - 4

Corrosion control and metal

finishing
 Overview:
• Introduction, causes and different types of corrosion
and effects of corrosion, theories of corrosion –
chemical corrosion, Pilling Bed-worth ratio,
electrochemical corrosion and its mechanism, factors
affecting corrosion –galvanic series. Corrosion control
methods – cathodic protection, sacrificial anode,
impressed current cathode. Surface coatings -
galvanizing, tinning, electroplating of Ni and Cr,
organic surface coatings – paints, constituents and
functions. Anodising and electroplating of Aluminium.
 Corrosion
• The destruction or deterioration of metals or
alloys by chemical or electrochemical reaction
with the environment
 Why do metals corrode?
• Corrosion is the reverse of metallurgic extraction

Metals are naturally in the compound forms

(Thermodynamically stable)
Metals are extracted from ores by providing energy
(unstable)
Extracted metals will have a natural tendency to react
and go to the compound forms when exposed to the
environment
Extraction
Metal ores Metals
Corrosion
(Low energy) (High energy)
 Types of Corrosion
2 fundamental types based on the type of environment
i) Dry Corrosion
ii) Wet Corrosion
Dry Corrosion:
Also known as direct chemical corrosion or direct chemical
attack.
Happens in the dry environment, in the absence of
moisture or electrolytes.
Direct attack by O2 or other corrosive gases like SO2, Cl2 ….
Dry corrosion could be due to oxidation corrosion or liquid
metal corrosion or corrosion by gases
Wet Corrosion
• Also known as the Electro chemical corrosion
• Corrosion occurs in wet conditions through
electrochemical reactions

Wet corrosion occurs when

i) A conducting liquid is in contact with the metal
or
ii) When two dissimilar metal are in contact with
each other in a corrosive medium
 Mechanism of wet corrosion
(Electro-chemical theory of corrosion)
• According to Electro-chemical theory of
corrosion, when a metal or dissimilar metals are
exposed to corrosive medium, separate anodic
and cathodic areas are set up on the metal
surface.
• This leads to the formation of a large number of
galvanic cells on the metal surface
• The wet corrosion involves the flow of electrons
between anodic and cathodic areas
• The anodic reaction involves dissolution of metal liberating free
electrons.
M  Mn+ + n e-
• The cathodic reaction consumes electrons with either evolution of
hydrogen or absorption of oxygen which depends on the nature of
corrosive environment.

a) Cathodic reaction by H2 evolution (acidic medium)

• The electrons released flow through the metal from anode to
cathode, whereas H+ ions of acidic solution are eliminated as
hydrogen gas.
Cathode: 2H+ + 2e- ----> H2 (Reduction)
b) Cathodic reaction by O2 absorption
For Eg: rusting of iron in neutral aqueous solution of
electrolytes in presence of atmospheric oxygen
At anode: Fe ----> Fe2+ + 2e- (Oxidation)
At cathode: ½ O2 + H2O + 2e- ---> 2OH- (Reduction)
Overall reaction: Fe2+ + 2OH- -----> Fe (OH)2
If oxygen is in excess, ferrous hydroxide is easily
oxidized to ferric hydroxide.
4Fe (OH)2 + O2 + 2H2O → 4Fe (OH)3
The product called yellow rust corresponds to Fe2O3.
3H2O
 Factors affecting rate of corrosion
1. Nature of the metals
• Metals with lower electrode potential are more
prone to corrosion. Ex: Mg, Zn
• Noble metals are less prone to corrosion. Ex. Au, Pt
2. Nature of corrosion products
If the corrosion product (oxide layer) is stable, non-
porous and insoluble, then it acts as a protective
layer and prevents further corrosion. Ex: Ti, Al, Cr
If the corrosion product is unstable, porous and
soluble, then corrosion continues even after the
formation of corrosion product layer. Ex: Fe, Zn, Mg
Pilling-Bedworth ratio
PBR = Volume of metal oxide formed / Volume
of metal consumed
This ratio gives the idea about the nature of
the film formed i.e. whether the film is porous
or nonporous.

If PBR ≥ 1, then corrosion product formed will be

protective
3. Potential difference between anodic and cathodic areas
(OCPD- Open circuit potential difference)
Larger the p.d. between the anodic and cathodic areas,
higher will be the rate of corrosion. Therefore use of
dissimilar metals should be avoided
4. Size of anodic and cathodic areas
Smaller the anodic area and larger the cathodic area
exposed, severe will be the corrosion – Unfavorable area
effect.
When the anode is smaller and cathode larger, the electrons
produced at the anode will be consumed rapidly prompting
more metal dissolution at the anode.
Ex. A small steel tap fitted in large copper tank will create
intense corrosion
 Unfavorable area effect…?

5. pH
a) No corrosion above pH 10 (due to protective
OH layer)
b) Between pH 3 -10, presence of O2 is essential
c) Below pH 3, severe corrosion (due to excess
of H+ ions)
Common types of corrosion- Based on the
mechanism
1. Dissimilar metal or galvanic corrosion
When two dissimilar metals (eg., zinc and copper) are
electrically connected and exposed to an electrolyte,
the metal higher in electrochemical series undergoes
corrosion. In this process, the more active metal acts as
a anode while the less active metal acts as cathode.
2. Differential aeration or concentration cell
corrosion.
It is due to electrochemical attack on the metal surface, exposed
to an electrolyte of varying concentrations or of varying
aeration. It occurs when one part of metal is exposed to a
different air concentration from the other part. This causes a
difference in potential between differently aerated areas. It has
been found experimentally that poor-oxygenated parts are
anodic.
Examples for Differential aeration corrosion are
1) Pitting or localized corrosion
2) Crevice corrosion
3) Pipeline corrosion
4) Corrosion on wire fence
3. Stress Corrosion Cracking
Due to the combined effects of tensile stress and
corrosive medium
Ex. 1: Caustic embrittlement

Caustic embrittlement in a boiler is a process in which

the boiler material becomes brittle due to the
accumulation of caustic substances.

In high-pressure boilers, sodium carbonate is used in

the water softening and it undergoes hydrolysis to
form sodium hydroxide. This alkaline water enters
minute cracks present in the inner walls of the boiler
by capillary action and starts eating away the metal as
sodium ferroate
Stress + NAOH on steel
Ex. 2: Season Cracking

Environmental cracking phenomenon of brass 

cartridges stored in stables during the
monsoon season.
 A type of stress-corrosion cracking of brass 
cartridge cases originally reported from British
forces in India.
 
NH3 + Stress on Copper
 Corrosion Control Techniques
1. Cathodic protection Techniques-
The reduction or prevention of corrosion by making
metallic structure as cathode in the electrolytic cell
is called cathodic protection. Since there will not be
any anodic area on the metal, corrosion does not
occur.
There are two methods of applying cathodic
protection to metallic structures.
• a) Sacrificial anodic method
• b) Impressed current method
a) Sacrificial anode method
In this method, the metallic structure to be protected is
made cathode by connecting it with a ymore active metal
(anodic metal). Hence, all the corrosion will concentrate
only on the active metal. The parent structure is thus
protected. The more active metal so employed is called
sacrificial anode. The corroded sacrificial anode block is
replaced by a fresh one. Metals commonly employed as
sacrificial anodes are magnesium, zinc, aluminium and
their alloys.
b) Impressed Current Method:
In this method, an impressed current is applied in opposite
direction to nullify the corrosion current and convert the
corroding metal from anode to cathode. Usually the impressed
current is derived from a direct current sources (like battery or
AC line) with an insoluble, inert anode (like graphite). This kind
of protection technique is particularly useful for large structures
for long term operations.
 Metallic coatings
The surface of the base metal is coated with another metal (coating
metal). Metallic coatings are broadly classified into anodic and
cathodic coatings.
1. Anodic coating: the metal used for the surface coating is more
anodic than the base metal which is to be protected.
• For example, coating of Al, Cd and Zn on steel surface are anodic
because their electrode potentials are lower than that of the
base metal iron. Therefore, anodic coatings protect the
underlying base metal sacrificially
2. Cathodic coating: obtained by coating a more noble metal (i.e.
metals having higher electrode potential like Sn, Au, Ag, Pt etc.)
than the base metal. They protect the base metal as they have
higher corrosion resistance than the base metal due to cathodic
nature. Cathodic coating protects the base metal only when the
coating is uniform and free from pores.
Methods of application of metallic coatings

a. Galvanizing
Galvanizing is a process in which the iron article is protected from corrosion by
coating it with a thin layer of zinc.
It is the anodic protection offered by the zinc. In this process, at first iron or
steel is cleaned by pickling with dilute sulphuric acid solution at a temperature
range of 60-90oC for 15 to 20 minutes. Therefore, it removes scale, rust and
other impurities present and then washed well in a water bath and dried.
Then after dipped in the bath containing molten zinc which is at 425-450 oC. To
prevent it from oxide formation, the surface of bath is covered with a
ammonium chloride flux. When the iron sheet is taken out it is coated with a
thin layer of zinc.
b. Tinning
The process of coating tin over the iron or steel
articles to protect them from undergoing
corrosion is known as tinning. In this process,
iron sheet is treated in dilute sulphuric acid
(pickling) to remove any oxide film, if present.
A cleaned iron sheet is passed through a bath
ZnCl2 molten flux followed by molten tin and
finally through a suitable vegetable oil. The
ZnCl2 flux helps the molten metal to adhere to
the base metallic surface.
• Electroplating
• Electroplating is the process of coating metals and protects
them from corrosion, wear and chemical attack. It is the
method of electro-deposition of metal by means electrolysis
over surface of metals and alloys.
• The base metal is first subjected to acid pickling to remove any
scales, oxides etc. The base metal is made as cathode of the
electrolytic cell and the coating metal is made as anode.
• The two electrodes are dipped in the electrolyte solution
which contains the metal ions to be deposited on the base
metal.
• When a direct current is passed from an external source, the
coating metal ions migrate towards cathode and get deposited
over the surface of base metal in the form of a thin layer.
 Organic surface coatings
Organic surface coatings are applied over the metallic surfaces to prevent from the
corrosion. Provide Chemical inertness to the corrosive environment,
Impermeability to water, gases and salts
Eg. Paints
Paint is a mechanical dispersion mixture of several constituents in a vehicle oil or
drying oil.
The following are the constituents of paints and their functions.
1. Pigment
It is a major constituent of the paint. Provides desired colour to the paint
It protects the paint by reflecting harmful U.V radiation.
Gives strength and increases weather resistance of the film.
Ex: white lead, ZnO , Ferric Oxide

2. Vehicle oil/ Drying oil

It forms the film forming constituent of the paint and acts as medium for the
dispersion of various constituents. It gives durability, adhesion and water
proofness to the paint.
Ex: Sunflower oil, Mustard oil, Soya bean oil.
3. Thinners : Reduces the viscosity and increases the elasticity of the Paint film.
Ex: Turpentine, Kerosene, Naphtha.

4. Driers : Driers are oxygen carrying catalysts. They accelerate the drying of the
paint film through oxidation, polymerization and condensation.
Ex: Tungstates and nahthalates of Pb, Zn and Co.

5. Extenders/ Fillers
Low refractive indices materials. They reduce the cost and cracking nature of
the paint film.
Ex: BaSO4, gypsum,

6. Plasticizers: They provide elasticity to the film and minimize cracking.

Ex: Tributylphosphate, triphenylphosphate

7. Anti skinning agents

They prevent the gelling nature the paint film.
Ex: Polyhydroxy phenols