Section 1

Corrosion
1 Corrosion
Corrosion can be generally defined as degradation of a metal by chemical or
electro-chemical means.

From this definition it is obvious that two mechanisms are involved, firstly an
electrical circuit and secondly a chemical reaction.

1.1 Electrical circuit

In a corrosion circuit the current is always direct current (DC). It is
conventionally thought that a current passes from positive + to negative -, ie
from anode to cathode. In fact electrons are flowing in exactly the opposite
direction, from cathode to anode. For corrosion circuit to exist three things are
needed:

Anode
An anode is a positively charged area. It becomes positively charged because
the atoms release two electrons each, thus causing an imbalance between
protons and electrons, positive and negatively charged units. In its passive
state, the iron atom has 26 of each, protons and electrons, when the two
electrons are released the atom still has 26 protons, but now only 24 electrons.
In this state the atom is now an ion, overall positively charged by two units and
written as Fe++. (An ion is a charged particle and can be positive or negative, a
single atom or a group of atoms, known as a molecule.) This losing of electrons
can be shown as: -Fe  Fe++ +2e. The Fe++ is called a positive iron ion. An
ion can be positive or negative and is a charged particle, an atom or a group of
atoms.

A passive iron atom Fe 26 An iron ion Fe++, 26 protons

protons and 26 electrons. and only 24 electrons

Nucleus

Figure 1.1 Iron atoms.

Cathode
A cathode is a negatively charged area where there are more electrons than
needed in its passive state. These are electrons released from the anode. At the
cathode the electrons enter into the electrolyte to pass back to the anode.

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 Electrolyte
An electrolyte is a substance, which will conduct a current and be broken down
by it, (dissociate into ions). Water is the most abundant electrolyte and also
very efficient. Acids, alkalis and salts in solution are also very efficient
electrolytes. As the electrons pass into the electrolyte it is dissociated into
positive and negative ions, as shown by the formula: -2H2O2H+ + 2OH-.
Simultaneously the electrons couple back with the hydrogen ions to form two
full Hydrogen atoms, which join together diatomically to form hydrogen gas.
This is termed as being evolved, or given off from the cathode. The hydroxyl
ions return to the anode through the electrolyte carrying the electrons.

The corrosion triangle, as shown below, can illustrate the electrical circuit. The
electron circuit can be seen to be from anode A, to cathode C, through the
electrolyte E, back to A.

A C
Figure 1.2 The corrosion triangle.

1.2 The chemical reaction

From the above we can see that no chemical reaction, (combination of
elements) has occurred at the cathode, or in the electrolyte. The chemical
reaction, the formation of corrosion products, only occurs at the anode. The
positive iron ions, Fe++, receive the returning hydroxyl ions and ionically bond
together to form iron hydroxide, which is hydrous iron oxide, rust and is shown
by the formula: Fe++ + 2OH- Fe (OH)2 It is now apparent that corrosion only
occurs at the anode, never at the cathode, hence the term cathodic protection.
If a structure can be made to be the cathode in a circuit, it will not corrode.

The corrosion triangle shows the three elements needed for corrosion to occur,
anode, cathode and electrolyte. If any one of these three is removed from the
triangle, corrosion cannot occur. The one most commonly eliminated is the
electrolyte. Placing a barrier between the electrolyte and the anodic and
cathodic areas, in the form of a coating or paint system does this. If electrolyte
is not in direct contact with anode and cathode, there can be no circuit and so
no corrosion.

The basic corrosion reaction, as explained above, occurs fairly slowly at ambient
temperatures. In common with all chemical reactions certain factors can
increase the reaction rate, listed below are some of these.

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 1 Temperature. Steel, in common with most metals, is thermodynamically
unstable. The hotter the steel is the faster the corrosion will occur.

2 Hygroscopic salts. Will attract water and dissolve in it. When salts are
present on a substrate and a coating is applied over them, water will be
drawn through the film and the resulting solution builds up a pressure
under the film. Eventually the film is forced up to form blisters. These
blisters are called osmotic or hygroscopic blisters and are defined as
pinhead sized water filled blisters. Sulphates and chlorides are the two most
common salts, chlorides predominant in marine environments and
sulphates in industrial areas and sometimes agricultural.

3 Aerobic conditions, (presence of oxygen): By introducing oxygen into the

cathodic reaction the number of Hydroxyl ions doubles. This means that
double the number of iron ions will be passivated and therefore double the
corrosion rate. Shown by :-2H2O + O2 + 4e  4OH-

4 Presence of some types of bacteria on the metal surface, for example

sulphur reducing bacteria, better known as SRBs, or, metal eating microbes
(MEMs).

5 Acids and alkalis.

6 Bi-metallic contact. Also known as bi-metallic corrosion.

Metals can be listed in order of nobility. A noble metal is one, which will not
corrode. In descending order, the further down the list the metal is, the more
reactive it is and so, the more anodic it is, the metal loses its electrons to
become reactive ions. The degree of activity can be expressed as potential, in
volts. The list can be called a galvanic list, but when the free potentials of the
metals are known it can also be called the electro motive forces series or the
electro-chemical series. On the following page is a table of some metals in order
of nobility with potentials as measured using a copper/copper sulphate half-cell
reference electrode, in seawater at 25°C.

Material Known potential av.

values
Graphite + 0.25 v
Titanium 0.0 v
Silver - 0.1 v
Nickel 200 - 0.15 v
Lead - 0.2 v
Admiralty brass - 0.3 v
Copper - 0.35 v
Tin - 0.35 v
Mill scale - 0.4 v
Low alloy steel - 0.7 v
Mild steel - 0.7 v
Aluminium alloys - 0.9 v
Zinc - 1.0 v
Magnesium - 1.6 v

From the list above it can be seen that millscale is immediately above steel on
the galvanic list. This means that millscale is cathodic to steel and if left on the
surface of steel will accelerate the corrosion of the steel substrate.

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 Mill scale is formed during the rolling operation of steel sections eg RSC, RSA,
RSJ. The oxides of iron form very quickly at temperatures in excess of 580°C.
The first oxide formed is FeO, iron oxide, the next is Fe3O4 and last of all
Fe2O3. Common names in order are wustite, magnetite and haematite. These
oxides are compressed during the rolling operation to produce blue millscale.
The thickness of millscale varies from 25-100m. Because millscale is only
produced during rolling, when it has been removed by any surface preparation
method, it can never recur.

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