Definition

Corrosion is the degradation of a material through contact with its environment. It is the deterioration of
a metal as a result of electrochemical chemical reaction(s) between materials (e.g., metal) and
substances present in the environment (e.g, moisture).

Do All Metals Corrode?

All metals can corrode. Some, like pure iron, corrode quickly. Stainless steel, however, which combines
iron and other alloys, is slower to corrode and is therefore used more frequently.

A common type of corrosion is rust, which is found on iron and steel structures. In this type of corrosion,
the iron is reacting with oxygen (present in air/moisture) to form ‘iron oxide hydroxide’ [FeO(OH)]
compounds.

However, Noble Metals (e.g., silver, platinum, gold etc.) are much less reactive than others. As a result,
they corrode rarely. They are, in fact, the only metals that can be found in nature in their pure form.

Mechanism of Corrosion

Several theories have been advanced to explain it over the period of time. However, the modern view
which is known as the electrochemical theory seems more practical. Let’s understand this theory with
the help of an example of rusting of iron.

Water containing oxygen a and carbon dioxide acts as an electrolyte and helps in the flow of electrons.
The formation of rust on the surface of iron occurs through the following steps.

(i) At the anodic region

Iron in contact with water forms an anode and gets oxidized to Fe2+.

Anodic region: Fe(s) →Fe2+(aq) + 2e– E0 Fe2+ /Fe = –0.44 V

The released electrons move to another portion of the iron sheet. This portion of the iron sheet serves
as a cathode.
(ii) At the cathodic region

At this cathodic portion of the surface, oxygen in the presence of H+ ions (produced due to the
ionization of water molecules) gets reduced to form H2O.

Cathodic region: O2(g) + 4H+(aq) + 4e– →2H2O(l) EoO2/H+ ,H2O = +1.23 V

The overall reaction of the local cell is the sum of the cathodic and anodic reactions.

Overall cell reaction: 2Fe(s) + O2(g) + 4H+(aq) →2Fe2+(aq) + 2H2O(l) E0 cell = 1.67 V

Fe2+ ions move through the water on the surface of the iron sheet. Presence of electrolytes (e.g.,
sodium chloride, SO2, CO2 etc.) in water helps in carrying more current through the local cell on the
surface of the iron. The increased flow of current enhances the rate of corrosion. The Fe 2+ ions are
further oxidized by atmospheric oxygen to Fe3+, and form hydrated iron(III) oxide, expressed as
Fe2O3.xH2O. The hydrated ferric oxide is called rust.

4Fe2+ (aq)+O2(g)+4H2O(l) →2Fe2O3(s)+8H+

Fe2O3(s) + xH2O (l) → Fe2O3.xH2O rust

H+ ions produced in the above reaction help further in the rusting of iron. Impurities present in iron also
enhance rusting by setting a number of localized cells. Pure iron does not rust.

Types of Corrosion

In general, Corrosion can be divided into three main groups:

 Wet Corrosion
 Dry Corrosion
 Corrosion in other fluids

“Wet corrosion” refers to metal corrosion occurring in a wet/aqueous environment. This process is
almost always electrochemical, and it occurs when two or more electrochemical reactions take place on
a metal surface. This electrochemical process can occur uniformly or nonuniformly across the metal
surface, which is called the “electrode” and the conducting liquid is called the “electrolyte.” A classic
example of this process is the rusting of a steel substrate: the iron metal is converted into a nonmetallic
form called “rust.”
“Dry corrosion” (basically an oxidation of metal) occurs when oxygen in the air reacts with metal
without the presence of a liquid. Typically, dry corrosion is not as detrimental as wet corrosion, but it is
very sensitive to temperature. Most engineering metals have a slow oxidation rate in the atmosphere at
ambient temperature. It is worth noting that once dry corrosion starts to occur, an oxide layer forms on
the metal surface which acts ac as a protective layer since it inhibits gaseous oxygen to reach the metal
surface for further degradation.

M  Mz+ + z e
O2 + 4 e  2 O2
M + O2  2MO (for z = 4)

e.g. 4Fe + 3 O2 + 2H2O = 4 FeO(OH)

“Corrosion in other fluids” refers to the corrosion of metals/alloys in nonaqueous environments, such
as fused salts sometimes referred to as molten salts. In addition corrosion can also occur in liquid
metals. Corrosion in fused salts such as nitrates, halides, carbonates, sulfates, hydroxides, and oxides
can cause profound attack on metal alloys via several mechanisms (such as pitting, degradation of
alloy with fused salts, ).

The most common types of wet corrosion are described below.

1. Uniform (General) Corrosion:

General corrosion occurs when most or all of the atoms on the same metal surface are oxidized,
damaging the entire surface. In this type of corrosion, the electrochemical reactions (in aqueous
or atmospheric media) proceed uniformly over the entire exposed metal surface over a large
area. As such, general corrosion represents the greatest destruction of metal on a tonnage
basis. However, general corrosion is less dangerous than the other types of corrosion.

The occurrence of general corrosion in magnesium alloys is quite common. Corrosion of a Mg-
alloy (AZ31D) after 1 week of immersion in NaCl solution is an example of General corrosion.
Using more corrosion-resistant materials or protective coatings is the most effective approach to
control such corrosion.

2. Galvanic Corrosion: This can occur when two different metals are located together in a liquid
electrolyte such as salt water. In essence, one metal's molecules are drawn toward the other
metal, leading to corrosion in only one of the two metals.
 3. Localized Corrosion:

This corrosion attacks only portions of a metal structure. There are three types of localized
corrosion:

a. Pitting: the creation of small holes in the surface of a metal.

b. Crevice corrosion: corrosion that occurs in stagnant locations such as those found under gaskets.
c. Filiform corrosion: corrosion that occurs when water gets under a coating such as paint.

4. Environmental induced Cracking: When environmental conditions are stressful enough, some
metal can begin to crack, fatigue, or become brittle and weakened.

Corrosion Prevention

An effective prevention system begins in the design stage with a proper understanding of the
environmental conditions and metal properties. Engineers work with metallurgical experts to select the
proper metal or alloy for each situation. They must also be aware of possible chemical interactions
between metals used for surfaces, fittings, and fastenings.

Although corrosion is a natural process, it can be controlled by using effective methods and strategies.
There are mainly five primary ways to control corrosion. These are:

 Coating
 Cathodic and anodic protection
 Inhibitors
1. Coating
 The basic feature of coating is to prevent the metal surface from exposure towards moisture or
air. To perform this Nickel, gold and silver are often used as decorative coatings as they are
very unreactive so they will not corrode as well as they look attractive too.
 Some metals react with oxygen to form metal oxides that are robust and protect the metal
underneath. The most common metals that do this are chromium (forms Cr 2O3), aluminium
(forms Al2O3) and nickel (forms NiO). This is why aluminium is such a good metal to be used for
window frames.
 The most common method of protection is simply painting the metal object. However, coatings
such as plastic (PVC), rubber and bitumen can also be used. They all simply stop the oxygen
and/or the water from coming into contact with the metal.
2a. Electroplating

Plating involves using electric currents to coat a metal with a thin layer of another metal that acts as a
protective barrier. The process is known as electroplating. In order to coat a metal (e.g. steel) in
another metal to prevent corrosion, an electrolytic cell must be set-up. For example, if one wanted to
coat a substance in chromium (i.e. chrome plating), the following set-up is to be needed to consider.

The electrochemical reactions that occur here are:

2b. Using a sacrificial (more reactive) metal

Iron that is coated in zinc (i.e. galvanised iron) is also protected, even if the surface is scratched.
This is because of the increased reactivity of zinc. Firstly, it forms its own zinc oxide (ZnO) coating.
Secondly, if the iron is exposed, the zinc will oxidise in preference to the iron (because its more
reactive), hence giving electrons to the iron, preventing corrosion. The redox reactions are as
follows:
Anode: Zn(s) → Zn2+(aq) + 2e-
Cathode: Fe2+(aq) + 2e- → Fe(s)
Overall: Zn(s) + Fe2+(aq) → Zn2+(aq) + Fe(s)

The zinc donates its electrons to the iron, thus sacrificing itself to ensure that the iron doesn’t
corrode. When all of the zinc is used up it will need to be replaced with another piece. This technique
will work as long as the metal being used is more reactive, and hence willing to lose its electrons,
more readily than iron.
Magnesium metal blocks are often attached to the outside of the hull of boats to help prevent
corrosion. The magnesium blocks must be replaced every 2 – 3 years (depending on the size of the
ship and the size of the piece of Mg attached to it).

3. Inhibitor

An inhibitor can be considered as a retarding catalyst that reduces the rate of corrosion. The
mechanism of inhibition is quite complex and it is not well understood. An inhibitor that acts both in a
cathodic and anodic manner is termed a mixed inhibitor.

It is established that inhibitors function in more than one way:

(a) by adsorption of a thin film on the corroding surface of a metal;
(b) by forming a thick corrosion product, or
(c) by changing the properties of the environment and thereby retards the corrosion rate.

Inhibitors can be broadly classified as :

1. Passivators
2. Organic inhibitors
3. Vapor phase inhibitors

Examples:

Volatile amines are used in boilers to minimize the effects of acid and acts as an anodic
inhibitor.
Benzotriazole inhibits the corrosion and staining of copper surfaces.