CORROSION & Its CONTROL

Corrosion:
Is a slow but spontaneous chemical
interaction of metal or an alloy with its
environment, resulting in the formation of
one of its compound such as oxide, hydrate
oxide, carbonate, sulphide, sulphate, etc.
or
The destruction of metals or alloys by surrounding environment through
chemical or electrochemical changes.
Causes of Corrosion

Corrosion is the deterioration of materials by chemical interaction with their

environment. The term corrosion is sometimes also applied to the degradation
of plastics, concrete and wood, but generally refers to metals. The most
familiar example of corrosion is rusting of iron exposed to the atmospheric
conditions.
The destruction of metals or alloys by surrounding environment
through chemical or electrochemical changes.
• Example: Formation of rust on the surface of
iron, formation of green film on the surface of
copper.

• The responsible factors for the corrosion of a

metal are the metal itself, the environmental
chemicals, temperature and the design.

4
It is an oxidation process. It
causes loss of metal.

Hence, disintegration of a metal by its

surrounding chemicals through a chemical
reaction on the surface of the metal is called
corrosion.
 Loss of metal

Loss of time

Reduction of value of goods

Effects of Corrosion
Contamination of fluids due to
chemical reaction

Changes in surface properties

Mechanical damage
 Dry corrosion
Dry corrosion means attack of gas (like O2) on
the metal in absence of moisture.

The corrosion media is vapors/ gasses in

perfectly dry condition.

There are main three types of Dry corrosion.

• (i) Oxidation corrosion (Reaction with oxygen)

• (ii) Corrosion by other gases

• (iii) Liquid metal corrosion

7
Types of Corrosion:
Dry Corrosion (Direct Chemical Attack)

Direct effect of atmospheric gases on the metal in the absence of moisture

liquid phase.

There are three main types of dry corrosion.

1. Oxidation corrosion (reaction with oxygen): direct attack of oxygen on

metal at low/high temperature in absence of moisture

The overall reaction can be given by

Mechanism for oxidation corrosion

The oxide layer formed can be

1. Stable: Oxides of Al, Cu, Pb, Sn
2. Unstable: Ag, Pt, Au
3. Volatile: Molybdenum oxide
4. Porous: Oxide of Li, Na, Mg
 Pilling and Bedworth rule
• Predicting oxide film formed is porous or non-
porous
• “Volume of Oxide of metal formed is less than
the metal volume then the oxide film is non-
protective or porous”
• Eg. Na, K, Mg volume of oxide is less- non-
protective
• Oxides of Al, Zn, Cr, Ni- volume is equal or
greater- Protective
2. Corrosion by other gases such as Cl2, SO2, H2S, NOx: In dry
atmosphere, these gases react with metal and form
corrosion products, which may be protective or non-
protective. Dry Cl2 reacts with Ag and forms AgCl which is a
protective layer, while SnCl4 is volatile. In petroleum
industries at high temperatures, H2S attacks steel forming FeS
scale which is porous and interferes with normal operations.

3. Liquid metal corrosion: In several industries, molten metal

passes through metallic pipes and causes corrosion due to
dissolution or internal penetration. For example, liquid
metal mercury dissolves most metals by forming amalgams,
thereby corroding them.
Wet corrosion (Electrochemical theory of
corrosion)
It occurs when metal comes in contact with a conducting liquid
or when two dissimilar metals are immersed /dipped partly in a
solution.

Wet corrosion involves electrochemical attack on metals in

aqueous environment.
The reactions involved in the galvanic cell are as follows:

1. Anodic reaction: Metal undergoes oxidation (corrosion) with positive

release of electrons:

2. Cathodic reactions: These reactions are dependent on the constituents

of the corrosion medium.

• If the solution is aerated and almost neutral, oxygen is reduced in

presence of H2O to OH− ions.

• If the solution is de-aerated and almost neutral, H2 is liberated along

with OH− ions.

• If the solution is de-aerated and acidic, H+ ions are reduced to

hydrogen gas
• Evolution of Hydrogen
• In Acidic solution

• 2H+ +2e-  H2 gas

• Overall reaction
• Fe + 2H+  Fe2+ + + H2 gas
3. The metal ions formed at the anode combine with
hydroxyl ions and form the corresponding metallic
hydroxide Fe(OH)2, which further gets oxidized to
hydrated ferric oxide [rust].

In the presence of limited oxygen, black rust is formed as

follows:
Dry Corrosion Wet Corrosion

Involves direct attack of atmospheric

Involves electrochemical attack on
gases on metal in the absence of
metals in aqueous environments
moisture liquid phase

Less prevalent More prevalent

The corrosive media include vapours, The corrosive media is conducting

gases, etc. liquid (aqueous) phase

It is of various types: Oxidation

It is of three types: differential metal
corrosion, corrosion by other gases
corrosion, differential aeration
such as Cl2, SO2, H2S, NOx and liquid
corrosion and crevice corrosion
metal corrosion
Types of Electrochemical Corrosion

Differential Metal Corrosion (Galvanic Corrosion)

When two dissimilar metals are in contact with each other in

corrosive environment.

Metal having low reduction potential undergo oxidation (anode),

and vice versa (cathode), anodic metal always undergo
corrosion.
Types of Electrochemical Corrosion

Differential Metal Corrosion (Galvanic Corrosion)

When two dissimilar metals are in contact in corrosive environment.

Depending on their electrode potential value (position on
electrochemical series) the metal which has lesser E0 would undergo
oxidation (anodic part), other one would act as cathodic part. Corrosion
will happen only in the anodic region.
In Fe-Cu couple, Fe (-0.44 V) would act as anode and Cu (+0.34V)
acts as cathode. Corrosion happens only on Fe (anode).
In Zn-Fe couple, the corrosion happens only on Zn, as Zn has
lower E0, Zn acts as anode.
Higher the difference between E0 value, higher is the corrosion.
Other examples of differential metal corrosion (galvanic
corrosion) include the following:

1. Buried iron pipeline connected to zinc bar.

2. Steel pipe connected to copper plumbing.
3. Steel propeller shaft in bronze bearing.
4. Zinc coating on mild steel.
5. Lead–tin solder around copper wires.

Preventive Measures

1. Placing a thin layer of an insulator between two metals or

materials.
2. Selecting materials having very less potential difference.
Differential Aeration Corrosion (Concentration Cell
Corrosion)
When metal is exposed to differential air or oxygen concentration.
Part exposed to higher oxygen conc. acts as Cathodic region and vice versa

Anodic

Cathodic
The examples of differential aeration corrosion include:

1. Half-immersed iron plate in aqueous solution.

2. Steel pipe carrying any liquid exposed to atmosphere.
3. Ocean going ships.
4. Steel storage tanks.

Preventive Measures

1. Using metallic coating, electro-less plating or chemical

conversion methods.
2. Maintaining the material’s own protective film.
3. Controlling the chemistry of fluids and using inhibitors.
Waterline Corrosion
Is a form of differential aeration corrosion

Waterline corrosion: (a) Water storage tank and (b) ocean going ship.
Pitting corrosion
Localized attack on iron surface forming pit like structures /porous
and usually in Chloride medium.
Preventive Measures
1. Preparing surfaces with best possible finish. Mirror-finish
resists pitting best.
2. Removing all contaminants, especially free-iron by
passivation (coating).
3. Designing and fabricating to avoid trapped and pooled
liquids.
 Other Types of Corrosion

1. Inter-granular corrosion:
Generally observed in alloys,
Attack on the grain boundary of a metal or alloy, where the
formation of a corrosion product takes place eg. Stainless steel
(18% C Ni), if carbon more than 0.1 % Sudden anticipated failure

2. Soil corrosion:
Underground pipes, cables, tank bottoms, etc., get corroded due to
moisture, pH of soil, ionic species like chlorides and micro-
organisms like bacteria. It is further enhanced by differential aeration
of various parts of the soil.
 Nature of the metal

Electrode potential difference

Primary Factors
Surface state of the metal
Formation of protective films
by metals

Factors Influencing
Rate of Corrosion

pH

Temperature
Anodic and Cathodic area
Secondary Factors effect
Conductance of the medium

Humidity
Open circuit potential difference
 Primary factors
• Nature of metal- low reduction potential-high reactivity-
more corrosion(Li, Na, Mg, Zn,)
• High reduction potential- less reactivity (Ag, Au, Pt,) - less
corrosion
• Ele. Potential difference- Iron and silver =1.04V (more
corrosion) & Iron and Tin- 0.3V

• Surface state of metal- oil, dust, water leads corrosion

• Formation of protective film- The passive layer(Oxides)

formation around the metal
• Unstable, soluble, non-uniform, porous oxides not able to
control the corrosion
 Secondary Factors

• pH- lower pH medium----higher corrosion

• Temperature- rate of reaction increases with

increasing temp., reduces passivity, increases
corrosion.

• Anodic and cathodic area- Sizes of Anodic and

cathodic area
Small ratio of anodic to cathodic region leading to high rate
of corrosion

Large ratio of anodic to cathodic region leading to low rate of

corrosion.
 Secondary Factors----------

• Conductance of the medium -more

conductance medium in the atmosphere
increases corrosion-
• Humidity- Low humidity –low rate of
corrosion and vice versa.
 Passivity/Passivation
• Means metal or an alloy shows very high corrosion
resistant than expected

• Galvanic series
• In electrochemical series a metal is higher in the series
is more anodic and undergoes corrosion faster than
metal below it
• Zn corrodes faster than Fe, Fe than Sn.

• This series gives useful information for studying

corrosion of metals and alloys.
Corrosion Control Methods

1. Design and material selection: number of angles, corners, edges etc.

should be minimized

2. Protective coatings: prevents surface corrosion

3. Cathodic protection: metal at cathodic region is
unprotected
Sacrificial anode method: metal surface is converted
into a cathode by connecting into a more active metal,
acting as an auxiliary anode.

Impressed current method: Using direct current

larger than the corrosion current
 Cementation
• It is a diffusion process
• Base metal heated after coating with powder of
coating metal
• On heating metal powder get diffused into base
metal resulting into form layer of alloy at the
surface.
• Zn over Fe -----Sherardising
• Cr over Fe ------Chromising
• Al over Fe ------Calorizing
• Si over Fe-------Siliconising
 Heat Treatment
• Heating of metal to definite temperature and
cooling at suitable rate to develop desired
mechanical and physical properties

• Quenching/Hardening
• Heated to brightness and cooled suddenly in
water or oil metal becomes hard called
quenching
• Annealing
• Metal or quenched metal heated to brightness
and cooled slowly to room temp----metal become
soft called annealing
 Ceramic Coatings(Inorganic coating)
• Thin film coating
• Material include carbides, nitrides, borides,
silicide's of gr 14, 15, 16 elements.
• Common ceramic coatings are TiN, CrN, TiCN,
TiAlN.
• Multilayered coating improves properties of
ceramic coating
Electroplating Process

Deposition of metal on substrate by electrochemical process.

Engineering Chemistry (revised edition)

ISBN: 978-81-265-4475-2
Copyright©2014 Wiley India Pvt. Ltd. All Rights Reserved
Purpose and Applications of Electroplating

1. Improving appearance.
2. Increasing protection.
3. Special surface properties.
4. Engineering or mechanical properties.

Engineering Chemistry (revised edition)

ISBN: 978-81-265-4475-2
Copyright©2014 Wiley India Pvt. Ltd. All Rights Reserved
The applications of electroplating are as
follows:

1. Steel parts on automobiles are often plated with

chrome to help them resist corrosion.
2. Steel and aluminium components in light fixtures are
coated with nickel and either chromium or brass to
enhance their appearance.
3. Steel bolts are coated with zinc and cadmium to help
them last longer, and copper and brass connectors
are often plated with silver to prevent tarnishing and
increase conductivity.