CORROSION

The loss of materials or its useful properties, by chemical or electrochemical

interaction with its environment is known as corrosion. Ex: Rusting of iron,
tarnishing of silver etc.

Units of Corrosion:
Mils per year (MPY)
Milligram per decimeter square per day (MDD)
1 mil = 1/1000 inch

REASON / CAUSES OF CORROSION

Extraction of metal (+energy)
ORES OR METAL COMPOUND METAL (PURE)
Stable form with lower energy Corrosion (- energy) unstable due to higher
energy
FACTORS AFFECTING CORROSION: Rate and extent of corrosion depends
upon :
1. Nature of metal
2. Nature of environment

1. NATURE OF METAL :

i. Position of metals in galvanic series:

a) If two metals are in electrical contact, then the metal placed higher in galvanic
series acts as anode and get corroded.

b) More is the difference in the position of the metals in the galvanic series, faster
is the rate of corrosion.

ii. Relative areas of anode and cathode:

Rate of corrosion α Cathodic area/ Anodic area
iii. Purity of metal: The impurities present in metal results in setting up
small electrochemical cells leading to corrosion.

iv. Nature of oxide film: If the oxide film formed on metal surface is porous and
loosely held , then the corrosion of the metal takes place very rapidly.

v. Solubility of corrosion products: If corrosion products are soluble then metal

corrodes rapidly and continuously.

vi. Volatility of corrosion products: If the corrosion products formed are

volatile, then there is rapid and continuous corrosion.
Nature of the oxide formed:
It plays an important role in further oxidation corrosion process. When the oxide film
formed is:

i) Stable layer: - A stable layer is fine grained in structure and can get adhered
tightly to the parent metal surface. Such a layer will be impervious in nature and
hence behaves as protective coating, thereby shielding the metal surface.
Consequently further oxidation corrosion is prevented. E.g.: Al, Sn. Pb, Cu, etc. form
stable oxide layers on surface thus preventing further oxidation.
ii) Unstable Layer: The oxide layer formed decomposes back into metal and O2.

Metal oxide metal + oxygen

Consequently oxidation corrosion is not possible in such cases. Eg: Ag, Au and Pt
do not undergo oxidation corrosion.
iii) Volatile Layer: The oxide layer formed is volatile in nature and evaporates as
soon as it is formed. There by leaving the under lying metal surface exposed for
further attack. This causes rapid continuous corrosion, leading to excessive
corrosion eg: Mo- molybdenum forms volatile MoO3 layer.
iv) Porous Layer: Contains pores and cracks. In such a case the atmospheric
oxygen has access to the underlying surface of the metal through the pores or
cracks of the layer, there by corrosion continues until the entire metal is converted
to its oxide.
Eg: Iron when attacked by H2S at high temperature forms porous FeS layer.
.

2. NATURE OF CORRODING ENVIRONMENT:

i. Temperature: Rate of corrosion α Temperature

ii. Moisture: Moisture acts as solvent for corrosion.

So, Rate of corrosion α Moisture

iii. PH: Generally acidic medium leads to more corrosion.

iv. Nature of corroding medium: Nature of anions, cations and their conducting
nature affects the rate of corrosion.

v. Presence of impurities and suspended particles in atmosphere: Corrosive

gases, fumes of sulphuric acid and hydrochloric acid, suspended particles like
NaCl, charcoal, etc. increases the rate of corrosion.
 CORROSION LAW – PILLING BEDWORTH RULE

The oxide layer acts as a protective or non–porous barrier, if the volume of the
oxide is at least as great as the volume of the metal from which it is formed.
On the other hand -if the volume of the oxide layer is less than the volume of
metal, the oxide layer is porous and hence non-protective.

Specific volume ratio = volume of metal oxide

volume of metal

Volume of metal oxide < Volume of metal consumed (Porous layer)

Volume of metal oxide > Volume of metal consumed (Non-Porous layer)

 TYPES OF CORROSION
There occurs two types of corrosion processes:
1) Dry corrosion or Chemical corrosion: Occurs due to direct chemical action of an oxidising gas
eg: O2 ,S2 ,Halogens, H2S , etc in the absence of moisture.

2) Wet corrosion or Electrochemical corrosion: when corrosion takes place by the transfer of
electrons from anodic parts of metal to cathode part through a conducting solution . It is known as wet
corrosion.

CHEMICAL (DRY) CORROSION ELECTROCHEMICAL (WET) CORROSION

Takes place in dry condition . Gases and vapours Takes place in presence of water or an electrolyte .
are corrodants.
It involves direct chemical attack on the metal by It involves setting up of large number of galvanic
environment. cells on metal surface.
It is explained by absorption mechanism. It is explained by mechanism of electrochemical
reaction.
Corrosion is uniform. Corrosion is not uniform.
It occurs on both homogeneous and heterogeneous It occurs only on heterogeneous surfaces.
surfaces.
Also known as high temperature corrosion. Also known as low temperature corrosion.
It is a slow process. It is a fast process.
Corrosion products accumulate at the same place Corrosion occurs at the anode but products
where corrosion occurs. accumulated near cathode.
CHEMICAL CORROSION OR DRY CORROSION

Corrosion that takes place in the absence of electrolyte, due to direct attack
of gases on metals is called dry corrosion.

This type of corrosion takes place at elevated temperature and corrosion is

uniform over metal surface. E.g. attack of oxygen on iron.

Mechanism:
At anode (oxidation): 2 M 2M n+ + 2ne –
At cathode (Reduction): O2 + 2ne - nO2-

Overall Reaction: 2M + O2 2Mn + + nO2- or (M2On)

Oxidation occurs first at the surface of the metal and a scale of metal oxide
is formed on the surface of the metal and it tends to act as a barrier for
further oxidation.
 ELECTROCHEMICAL / WET THEORY OF CORROSION

Electrochemical corrosion involves flow of electrons between anode and

cathode. For Ex: Rusting of iron.
Electrochemical theory of corrosion is explained by two mechanisms:
1. Oxygen absorption mechanism (in neutral and alkaline medium).
2. Hydrogen evolution mechanism (in acidic medium).

Mechanisms:

OXYGEN ABSORPTION MECHANISM (in basic or neutral medium)

Reaction at anode (OXIDATION) Fe Fe2+ + 2e-

Reaction at cathode (REDUCTION)

½ O2 + H2O + 2e- 2OH-
OVERALL REACTION
Fe + ½ O2 + H2O Fe2+ + 2OH- Or Fe(OH)2
ferrous hydroxide
i) If enough O2 is present: Fe(OH)2 is oxidised to rust: Fe2O3.xH2O (Yellow rust)

ii) In limited supply of oxygen Black Magnetite is formed:

Fe2O3 .FeO.6H2O (Black magnetite)

Mechanism of wet corrosion by oxygen absorption mechanism

(Small anodic area and large cathodic area, so higher rate of corrosion)
HYDROGEN EVOLUTION MECHAINSM (In acidic medium)
All the metals placed above H2 in electrochemical series, corrodes in acidic
solution by hydrogen evolution mechanism.

Anodic reaction: Fe Fe +2 + 2 e –
Cathodic reaction : 2H+ + 2e- H2

Overall reaction: Fe + 2H + Fe2+ + H2

PREVENTION OF CORROSION
Corrosion can be prevented by the following methods:

1.PROPER DESIGN
a) Avoid sharp bends and sharp corners.
b) Avoid contact of dissimilar metals in presence of corroding medium.
c) There should be proper drainage.
d) When the two dissimilar metals are to be used in contact, anodic area should be
large and cathodic area should be small.
e) If two dissimilar metals have to be used in contact, their position in
electrochemical series should as close as possible.
f) If two metals have to be coupled use insulation between them.

2. MODIFICATION OF ENVIRONMENT
Removing moisture by using silica gel.
Removing oxygen by adding oxygen scavengers like hydrazine
By adjusting pH using pourbaix diagram.
3. BY USING INHIBITORS: The substances which are added from outside to
inhibit the corrosion are known as inhibitors.

There are two types of inhibitors: Anodic Inhibitors and Cathodic Inhibitors.

a) ANODIC INHIBITORS
They react with the metallic ions of anode and form insoluble precipitate which is
adsorbed on metal surface forming a protective film/barrier. Ex: alkalis,
phosphates, chromates, etc.

b) CATHODIC INHIBITORS
They decrease the rate of reaction thereby reducing rate of overall corrosion.

i) In acidic medium
Cathodic reaction:
2H+ +2 e- H2
Cathodic inhibitors slow down the diffusion of H+ ions through cathode and
thus reduces corrosion rate.

Ex – Amines, Mercaptons, ureas, thioureas, etc.

ii) In neutral/alkaline medium
Cathodic reaction:
½ O2 + H2O + 4e- 2OH-

Cathodic inhibitors remove O2 that is being used at cathode, thereby reducing

corrosion.
Ex: O2 scavengers like Na2SO3, N2H4, etc.

4. CHANGINING THE OPERATING VARIABLES: lowering the temperature,

selecting suitable pH.

5. PROTECTIVE COATINGS
(a)Organic coating: includes use of paints, varnishes, etc. which acts as organic
barrier between metal and environment.
(b)Inorganic coating: inorganic surface barriers produced by chemical/
electrochemical reactions at the surface of base metal coatings are used for paints.
Ex – phosphates, chromates , etc.
(c)Metallic coatings: In metallic coatings one metal is coated over another metal.
There are two types of metallic coatings: i) anodic coating and ii) cathodic coating.
i) ANODIC COATING or SACRIFICIAL COATING
1. Base metal is coated with a metal which is more reactive.
2. Protects the underlying base metal sacrificially.
3. Known as anodic coating as the reduction potential of coated metal is less than
that of base metal.
4. If there are pores, cracks, or breaks in such a coating base metal is not corroded
till all the coated metal is consumed.
5. Zn, Cd, Al are generally used as sacrificial coatings.
6. Ex: galvanised iron (coating of Zn on Fe)

SACRIFICIAL PROTECTION OF IRON BY ZINC

 ii) CATHODIC COATING or NOBLE COATING
1. Base metal is coated with a metal which is less reactive (more noble) in its comparison.
2. Protects the base metal due to its noble character.
3. Also known as Cathodic coating as reduction potential of coated metal is more than that of
base metal.
4. If there are pores, break, etc. corrosion takes place because of small anodic area and large
cathodic area.
5. Ni, Ag, Cr, Pb, etc. are used generally for noble coating.
6. Ex: coating of Sn on Fe.
6. MODIFICATION OF METAL
Metal can be modified by annealing, refining and alloying.

Annealing is the heat treatment process that changes the physical and sometimes
also the chemical properties of a material. It is used mostly to increase the ductility,
reduce the hardness and to help to eliminate the internal stress of a material .

Refining consists of purifying an impure metal.

Alloying is a process in which two or more metal elements are melted together in a
precise combination to form a specific material or alloy.

7. CATHODIC PROTECTION
The method of protecting the base metal by making it to behave like a cathode is
called as cathodic protection.

There are two types of cathodic protection:

(a) Sacrificial anodic protection.
(b) Impressed current method.
a) SACRIFICIAL ANODIC PROTECTION
Base metal is connected by a wire to a more reactive metal so that the base metal
becomes cathode and more reactive metal becomes anode.
The anodic metal gets corroded slowly, while the base metal (cathodic) is protected.
The more active metal is called sacrificial anode and is replaced by a fresh one,
when it is completely consumed. Mg, Zn, Al and their alloys are generally used as
sacrificial anodes.
Ex: 1. A ship-hull which is made up of steel is connected to sacrificial anode (Zn-
blocks) which undergoes corrosion leaving the base metal protected.
2. The underground water pipelines and water tanks are also protected by
sacrificial anode method.
 DIFFERENT TYPES OF CORROSION

Corrosion due to difference in temperature: Usually, a temperature or

pressure increase directly leads to a higher corrosion rate because
electrochemical reactions generally occur faster at
higher temperatures. Temperature increases add energy to the reactions,
which increases the corrosion rate.
Galvanic corrosion: also known as bimetallic corrosion: is an
electrochemical process whereby one metal corrodes in preference to
another metal that it is in contact with through an electrolyte. Galvanic
corrosion occurs when two dissimilar metals are immersed in a
conductive solution and are electrically connected.
Crevice corrosion: Occurs between different metallic objects e.g., bolts,
nuts, and rivets in contact with liquid.
Crevice area has lack of oxygen, and thus becomes anodic region. The
exposed areas act as the cathode.
Concentration cell corrosion or Differential aeration corrosion: is a type of
corrosion that occurs when oxygen concentrations vary across a metal's surface.
The area with the higher oxygen concentration becomes the cathode. The area with
the lower oxygen concentration becomes the anode. Consequently, the portion of
the metal that has the lower oxygen concentration is the portion subject to
corrosion.
Waterline corrosion: occurs when one portion of a base material is
submersed in the water and another portion is in contact with the air. This
creates a differential of the amount of oxygen in contact with the material's
surface above and below the waterline and results in a corrosive reaction.
Pitting corrosion is a localized form of corrosion by which cavities or
"holes" are produced in the material. Pitting is considered to be more
dangerous than uniform corrosion damage because it is more difficult to
detect, predict and design against. Corrosion products often cover the
pits.
 Corrosion Issues in specific Industries

Corrosion is the degradation of materials caused by environmental agencies

through chemical or electrochemical reactions or wear and tear.
Corrosion Issues in Power Generation Industries
OXIDATION is a type of corrosion that occurs when metal reacts with air or oxygen at
high temperature in presence of water. (dry corrosion)

HOT CORROSION is defined high speed corrosion due to the presence of salts
such as Na2SO4, NaCl and V2O5 that which damage protective surface oxides.

GALVANIC CORROSION occurs when two different metals come in contact in

humid environment, where one metal become anode and undergo corrosion.

EROSION is a type of corrosion caused by high fluid surface velocities in high

chemical environment. The reaction erodes the protective scale of metal object and
surface become thin as it erodes.

Power plant component failures due to corrosion

Feed water lines, ductwork, stacks, steel liners coal handling areas, scrubber
modules, boilers etc.
 Corrosion issues in Chemical Processing Industry

Chemical process operations are frequently depend on highly corrosive chemicals and
high- temperature.

Due to this, high damage to the pipelines occurred. At high temperature and in chemical
environment corrosion cause serious problem to the pipeline system.
Chemical firms deal with storage and transportation of caustic materials, hazardous acids and
oxidizers that are harmful to metals.
.
To overcome all these problems, high quality CPVC (Chlorinated Polyvinyl chloride)
pipes can withstand high chemicals - caustic soda, nitric acid, HCl, LiCl, Phosphoric acid,
sulphuric acid.
Pipes valves and fittings are made of easy to install, durable, high performance CPVC
materials that provide mechanical strength and chemical resistance required by chemical
processing operations. CPVC piping offers greater resistance to acids, bases, salts and
aliphatic hydrocarbons.
 Corrosion Issues in oil and Gas Industries

Crude oil and natural gas contain a variety of high impurity products CO2, H2S and
free water causehigh corrosion in oil and gas wells and pipeline. Metal lost its
mechanical properties like strength, ductility, impact strength and so on.

Major Types of corrosion in oil and gas industry

CO2 CORROSION (SWEET CORROSION) CO2 when dissolved aqueous phase

promote electrochemical corrosion of steel and contact surface. CO2 react with water to
form carbonic acid making the fluid acidic.

SOUR CORROSION is the deterioration of metal caused by H2S and

moisture, and most demanding to drill pipe. When H2S dissolved in water forms
a weak acid which is corrosive and source of H+. Uniform pitting and stepwise
cracking are example of sour corrosion.

OXYGEM CORROSION Oxygen is a strong oxidant and reacts with metal. The
presence of dissolved oxygen in drilling fluids cause drill pipe corrosion.
EROSION CORROSION This destructive process is highly increased by high
velocities and presence of corrodents in drilling and produced fluids.

Microbiologically induced corrosion Bacterial activity causes this type of corrosion..

Bacteria produce waste products such as CO2, H2S, organic acids which promotes
corrosion.

Prevention of Corrosion in oil and gas Industry

▪ Choosing appropriate materials,
▪ Use inhibitors (acetylene alcohols, quaternary ammonium
salt, aldehydes, amines etc.
▪ Coatings of Polypropylene (PP)
 Corrosion Issues in Pulp and Paper Industries

Corrosion is a chronic problem in the pulp and paper industry. H2S is a common by
product that cause corrosion. Gases like H2S, mercaptans, dimethyl sulphide cause
corrosion

Proper material section is very important to prevent corrosion.

The mentioned gases cause smell of rotten cabbage and rotten egg around paper mills.

The primary contaminant emitted by sulphite pulp mills is SO2 which has strong
choking odour and cause severe corrosion.

In addition to proper construction, better ventilation and proper drainage system is very
essential in pulp and paper industry.