Harivandana College

Fundamentals of Corrosion
Dept. of Industrial Chemistry
Dr. Govind V Vagadiya
Fundamentals of Corrosion – Dept. of Industrial Chemistry 1

Contents
Introduction ..................................................................................................................................................... 2
Causes of corrosion ....................................................................................................................................... 3
Factors Influencing Corrosion: ................................................................................................................. 4
Classification of corrosion .......................................................................................................................... 5
Mechanisms of corrosion ............................................................................................................................ 9
Corrosion Mechanism of Iron oxide (Rust) Formation ................................................................. 10
Prevention of corrosion ............................................................................................................................. 11

DR. GOVIND V VAGADIYA

Fundamentals of Corrosion – Dept. of Industrial Chemistry 2

Introduction
Corrosion is a natural process that converts a refined metal into a
more chemically-stable form such as oxide, hydroxide, or sulfide. It is the
gradual destruction of materials (usually metals) by chemical and/or
electrochemical reaction with their environment. Corrosion engineering is
the field dedicated to controlling and stopping corrosion.

In the most common use of the word, this means electrochemical

oxidation of metal in reaction with an oxidant such as oxygen or sulfates.
Rusting, the formation of iron oxides, is a well-known example of
electrochemical corrosion. This type of damage typically produces oxide(s)
or salt(s) of the original metal and results in a distinctive orange
coloration. Corrosion can also occur in materials other than metals, such as
ceramics or polymers, although in this context, the term "degradation" is
more common. Corrosion degrades the useful properties of materials and
structures including strength, appearance and permeability to liquids and
gases.

Many structural alloys corrode merely from exposure to moisture in

air, but the process can be strongly affected by exposure to certain
substances. Corrosion can be concentrated locally to form a pit or crack, or
it can extend across a wide area more or less uniformly corroding the
surface. Because corrosion is a diffusion-controlled process, it occurs on
exposed surfaces. As a result, methods to reduce the activity of the
exposed surface, such as passivation and chromate conversion, can
increase a material's corrosion resistance. However, some corrosion
mechanisms are less visible and less predictable.

DR. GOVIND V VAGADIYA

Fundamentals of Corrosion – Dept. of Industrial Chemistry 3

Causes of corrosion
Following are the factors which are responsible for causing corrosion
especially to the reinforcing bars in concrete:

• Congested reinforcement in small concrete sections,

• Excessive water-cement ratio,
• Improper construction methods,
• Inadequate design procedure,
• Incompetent supervising staff or contractor,
• Initially rusted reinforcement before placing concrete,
• Insufficient cover to steel from the exposed concrete surfaces,
• Permeability of concrete which depends on various factors such as
water- cement ratio, size of aggregate, curing, grading of aggregates,
etc.,
• Poor workmanship,
• Presence of moisture in concrete,
• Presence of salts,
• Type of atmospheric conditions surrounding the region of concrete,
• Unequal distribution of oxygen over the steel surface,
• Weak and porous cover blocks which are tied directly to the
reinforcement or stirrups, etc.

DR. GOVIND V VAGADIYA

Fundamentals of Corrosion – Dept. of Industrial Chemistry 4

Factors Influencing Corrosion:

The corrosion is influenced by the following factors:

Blow holes, inclusions and trapped gases,

Chemical nature of the metal,

Distribution of secondary phases,

Factors Influencing Corrosion

Eddy electric currents,

Internal structure of metal,

Nature of engineering application,

Presence of dust, dirt or other foreign matter,

Surface film,

Working conditions or environment like temperature, concentration of

stresses, etc.

DR. GOVIND V VAGADIYA

Fundamentals of Corrosion – Dept. of Industrial Chemistry 5

Classification of corrosion
The classification of corrosion is done on the basis of its mechanism.

General Attack Corrosion:

Also known as uniform attack corrosion, general attack corrosion is the

most common type of corrosion and is caused by a chemical or
electrochemical reaction that results in the deterioration of the entire
exposed surface of a metal. Ultimately, the metal deteriorates to the point of
failure.

General attack corrosion accounts for the greatest amount of metal

destruction by corrosion but is considered as a safe form of corrosion, due to
the fact that it is predictable, manageable and often preventable.

Galvanic Corrosion:

Galvanic corrosion, or dissimilar metal corrosion, occurs when two

different metals are located together in a corrosive electrolyte. A galvanic
couple forms between the two metals, where one metal becomes the anode
and the other the cathode. The anode, or sacrificial metal, corrodes and
deteriorates faster than it would alone, while the cathode deteriorates more
slowly than it would otherwise.

Three conditions must exist for galvanic corrosion to occur:

• Electrochemically dissimilar metals must be present

• The metals must be in electrical contact, and
• The metals must be exposed to an electrolyte

DR. GOVIND V VAGADIYA

Fundamentals of Corrosion – Dept. of Industrial Chemistry 6

Environmental Cracking:

Environmental cracking is a corrosion process that can result from a

combination of environmental conditions affecting the metal. Chemical,
temperature and stress-related conditions can result in the following types of
environmental corrosion:

• Stress Corrosion Cracking (SCC)

• Corrosion fatigue
• Hydrogen-induced cracking
• Liquid metal embrittlement

DR. GOVIND V VAGADIYA

Fundamentals of Corrosion – Dept. of Industrial Chemistry 7

Localized Corrosion:

Unlike general attack corrosion, localized corrosion specifically targets one

area of the metal structure. Localized corrosion is classified as one of three
types:

• Crevice corrosion: Similar to pitting, crevice corrosion occurs at a

specific location. This type of corrosion is often associated with a
stagnant micro-environment, like those found under gaskets and
washers and clamps. Acidic conditions or a depletion of oxygen in a
crevice can lead to crevice corrosion.
• Filiform corrosion: Occurring under painted or plated surfaces when
water breaches the coating, filiform corrosion begins at small defects in
the coating and spreads to cause structural weakness.
• Pitting: Pitting results when a small hole, or cavity, forms in the metal,
usually as a result of de-passivation of a small area. This area becomes
anodic, while part of the remaining metal becomes cathodic, producing
a localized galvanic reaction. The deterioration of this small area
penetrates the metal and can lead to failure. This form of corrosion is
often difficult to detect due to the fact that it is usually relatively small
and may be covered and hidden by corrosion-produced compounds

DR. GOVIND V VAGADIYA

Fundamentals of Corrosion – Dept. of Industrial Chemistry 8

Flow-Assisted Corrosion (FAC):

Flow-assisted corrosion, or flow-accelerated corrosion, results when a

protective layer of oxide on a metal surface is dissolved or removed by wind
or water, exposing the underlying metal to further corroding and deteriorate.

• Erosion-assisted corrosion
• Impingement
• Cavitation

Intergranular corrosion

Intergranular corrosion is a chemical or electrochemical attack on the

grain boundaries of a metal. It often occurs due to impurities in the metal,
which tend to be present in higher contents near grain boundaries. These
boundaries can be more vulnerable to corrosion than the bulk of the metal.

De-Alloying:

De-alloying, or selective leaching, is the selective corrosion of a specific

element in an alloy. The most common type of de-alloying is de-zincification
of unsterilized brass. The result of corrosion in such cases is a deteriorated
and porous copper.

Fretting corrosion:

Fretting corrosion occurs as a result of repeated wearing, weight and/or

vibration on an uneven, rough surface. Corrosion, resulting in pits and
grooves, occurs on the surface. Fretting corrosion is often found in rotation
and impact machinery, bolted assemblies and bearings, as well as to surfaces
exposed to vibration during transportation.

High-Temperature Corrosion:

Fuels used in gas turbines, diesel engines and other machinery, which
contain vanadium or sulfates can, during combustion, form compounds with a
low melting point. These compounds are very corrosive towards metal alloys
normally resistant to high temperatures and corrosion, including stainless
steel.

High-temperature corrosion can also be caused by high-temperature

oxidization, sulfidation, and carbonization.

DR. GOVIND V VAGADIYA

Fundamentals of Corrosion – Dept. of Industrial Chemistry 9

Mechanisms of corrosion

The electrochemical nature of corrosion can be illustrated by the attack of

zinc by hydrochloric acid. When zinc is placed in dilute hydrochloric acid a
vigorous reaction occurs; hydrogen gas is evolved and the zinc is dissolves
forming a solution of zinc chloride. The reaction is as follows

Zn + 2HCl → ZnCl2 + H2

From the above equation, it is found that the chloride ion is not involved in
the reaction. Hence the above equation can be rewritten as follows

Zn + 2H+ →Zn +2 + H2

From this equation when the zinc ion reacts with the hydrogen ions in the
acid solution to form zinc ions and hydrogen gas. During the reaction, zinc is
oxidized to zinc ions and hydrogen ion is reduced to hydrogen. The reaction
can be divided into two reactions.

• Oxidation
• Reduction

In the above reaction oxidation (Anodic reaction)

Zn → Zn+2 + 2e

The reduction reaction (Cathodic reaction)

2H+ + 2e → H2

An oxidation or anodic reaction is indicated by an increase in valence or a

production of an electron. A decrease in valence charge or the consumption of
electrons signifies a reduction or cathodic reaction. During metallic
corrosion, the rate of oxidation will equal to the rate of reduction.

The above concept is illustrated in the figure below. Here the zinc atom has
been transformed into Zinc ion and two electrons. These electrons which
remain in the metal are immediately consumed during the reduction of
hydrogen ions. These two reactions will occur simultaneously at the same
point on the surface of the metal.

DR. GOVIND V VAGADIYA

Fundamentals of Corrosion – Dept. of Industrial Chemistry 10

Corrosion Mechanism of Iron oxide (Rust) Formation

The rusting of iron is an electrochemical process that begins with the

transfer of electrons from iron to oxygen. The iron is the reducing agent (gives
up electrons) while the oxygen is the oxidizing agent (gains electrons). The
rate of corrosion is affected by water and accelerated by electrolytes, as
illustrated by the effects of road salt on the corrosion of automobiles. The key
reaction is the reduction of oxygen:

O2 + 4  e− + 2 H
2O → 4  OH−

Because it forms hydroxide ions, this process is strongly affected by the

presence of acid. Indeed, the corrosion of most metals by oxygen is
accelerated at low pH. Providing the electrons for the above reaction is the
oxidation of iron that may be described as follows:

Fe → Fe2+ + 2  e−

The following redox reaction also occurs in the presence of water and is
crucial to the formation of rust:

4 Fe2+ + O2 → 4 Fe3+ + 2 O2−

In addition, the following multistep acid–base reactions affect the course

of rust formation:

Fe2+ + 2  H2O → Fe(OH)2 + 2  H+

Fe3+ + 3  H2O → Fe(OH)3 + 3  H+

as do the following dehydration equilibria:

Fe(OH)2 → FeO + H2O

Fe(OH)3 → FeO(OH) + H2O
2 FeO(OH) → Fe2O3 + H2O

DR. GOVIND V VAGADIYA

Fundamentals of Corrosion – Dept. of Industrial Chemistry 11

Prevention of corrosion
You can prevent corrosion by selecting the right:

• Metal Type
• Protective Coating
• Environmental Measures
• Sacrificial Coatings
• Corrosion Inhibitors
• Design Modification

Metal Type

One simple way to prevent corrosion is to use a corrosion resistant metal

such as aluminum or stainless steel. Depending on the application, these
metals can be used to reduce the need for additional corrosion protection.

Protective Coatings

The application of a paint coating is a cost-effective way of preventing

corrosion. Paint coatings act as a barrier to prevent the transfer of
electrochemical charge from the corrosive solution to the metal underneath.

Another possibility is applying a powder coating. In this process, a dry

powder is applied to the clean metal surface. The metal is then heated which
fuses the powder into a smooth unbroken film. A number of different powder
compositions can be used, including acrylic, polyester, epoxy, nylon, and
urethane.

Environmental Measures

Corrosion is caused by a chemical reaction between the metal and gases in

the surrounding environment. By taking measures to control the
environment, these unwanted reactions can be minimized. This can be as
simple as reducing exposure to rain or seawater, or more complex measures,
such as controlling the amounts of sulfur, chlorine, or oxygen in the
surrounding environment. An example of this would be would be treating the
water in water boilers with softeners to adjust hardness, alkalinity, or oxygen
content.

DR. GOVIND V VAGADIYA

Fundamentals of Corrosion – Dept. of Industrial Chemistry 12

Sacrificial Coatings

Sacrificial coating involves coating the metal with an additional metal type
that is more likely to oxidize; hence the term “sacrificial coating.”

There are two main techniques for achieving sacrificial coating: cathodic
protection and anodic protection.

Cathodic Protection

The most common example of cathodic protection is the coating of iron

alloy steel with zinc, a process known as galvanizing. Zinc is a more active
metal than steel, and when it starts to corrode it oxides which inhibits the
corrosion of the steel. This method is known as cathodic protection because it
works by making the steel the cathode of an electrochemical cell. Cathodic
protection is used for steel pipelines carrying water or fuel, water heater
tanks, ship hulls, and offshore oil platforms.

Anodic Protection

Anodic protection involves coating the iron alloy steel with a less active
metal, such as tin. Tin will not corrode, so the steel will be protected as long as
the tin coating is in place. This method is known as anodic protection because
it makes the steel the anode of an electrochemical cell.

Anodic protection is often applied to carbon steel storage tanks used to store
sulfuric acid and 50% caustic soda. In these environments cathodic protection
is not suitable due to extremely high current requirements.

Corrosion Inhibitors

Corrosion inhibitors are chemicals that react with the surface of the metal
or the surrounding gases to suppress the electrochemical reactions leading to
corrosion. They work by being applied to the surface of a metal where they
form a protective film. Inhibitors can be applied as a solution or as a
protective coating using dispersion techniques. Corrosion inhibitors are
commonly applied via a process known as passivation.

DR. GOVIND V VAGADIYA

Fundamentals of Corrosion – Dept. of Industrial Chemistry 13

Passivation

In passivation, a light coat of a protective material, such as metal oxide,

creates a protective layer over the metal which acts as a barrier against
corrosion. The formation of this layer is affected by environmental pH,
temperature, and surrounding chemical composition. A notable example of
passivation is the Statue of Liberty, where a blue-green patina has formed
which actually protects the copper underneath. Corrosion inhibitors are used
in petroleum refining, chemical production, and water treatment works.

Design Modification

Design modifications can help reduce corrosion and improve the

durability of any existing protective anti-corrosive coatings. Ideally, designs
should avoid trapping dust and water, encourage movement of air, and avoid
open crevices. Ensuring the metal is accessible for regular maintenance will
also increase longevity.

DR. GOVIND V VAGADIYA