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.
Electrical circuit
In a corrosion circuit the current is always_ direct current1C). It is conventionally thought that d current
passes from positive + to negative -, ie from anode to cathode. In fact electrons are flowing in exactly
the oposite 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 on is acharged p_article and
can be positive or_ne__ga_tima, a single atomor 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 protons and 26 electrons.
An iron ion Fe++, 26 protons and only 24 electrons
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.
Rev 1 January 2010 Corrosion Copyright 6 TWI Ltd 2010
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: -2H2042H+ + 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.
Figure 1.2 The corrosion triangle.
corrosion
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 eon hydroxide, which is hydr us iron oxide, rust and is shown by the formula: Fe+1 + 20F1--> 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.
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 iform blisters. These blisters are called
osmotic or hygroscoic ers and are defined as pinhead sized water filled b isters. 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 :-2H20 + 02 + 4e 40H-
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. Below is a list of some
metals in order of nobility with potentials as measured using a copper/copper sulphate half cell
reference electrode, in seawater at 25C.
corrosion
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Rev 1 2010 6 TWI 2010
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