BASICS OF CORROSION

1
Metal Corrosion

“the destruction/degradation of a
material by chemical or electrochemical
reaction to its environment”
typically a transfer of electrons from
one metal to another through an
Oxidation-Reduction Reaction.
 The Nature of Corrosion Reactions
 The special characteristic of most corrosion
processes is that the oxidation and reduction
steps occur at separate locations on the metal.
 This is possible because metals are conductive,
so the electrons can flow through the metal from
the anodic to the cathodic regions.
 The presence of water is necessary in order to
transport ions to and from the metal, but a thin
film of adsorbed moisture can be sufficient.
The Nature of Corrosion Reactions
 Galvanic Series
 The galvanic series determines the nobility of metals and semi-metals.
 When two metals are submerged in an electrolyte, while also
electrically connected by some external conductor, the less noble
(base) will experience galvanic corrosion.
 Acidity and Alkalinity (pH)
 The atoms of a molecule are held together by a force referred to as
chemical bonding. It is this chemical bonding that defines many of the
properties of a substance.
 When discussing an aqueous medium (including soil), the question
often arises as to how acid or alkaline the solution is.
 Referring to whether there is an excess of hydrogen (H+) or hydroxyl
(OH-) ions present.
 When acids dissociate, the cation produced is the hydrogen ion, H+.
 Acidity and Alkalinity (pH)
 A medium is said to be acidic when there is an excess of H+ ions.
 The strength of an acid is a measure of the hydrogen ion concentration
in an aqueous solution and is classified according to the pH scale.
 The definition of pH is the negative logarithm to the base 10 of the
hydrogen ion concentration, or: pH = -log [H+]
 The neutral pH point is 7.
 Acid solutions have a pH below 7 and alkaline, or basic, solutions
have a pH above 7.
 Acidity and Alkalinity (pH)
 Since the pH scale is logarithmic, for each unit of pH the environment
becomes ten times more acid or alkaline.
 This concept is better understood if we look at pure water, H2O.

 Pure water will ionize into equal parts of hydrogen ions (H+) and
hydroxyl ions (OH-).
 An understanding of pH is important in corrosion and cathodic
protection work.
 For many metals, the rate of corrosion increases appreciably below a
pH of about 4.
 Between 4 and 8 corrosion rate is fairly independent of pH.
 Above 8, the environment becomes passive and corrosion rates tend
to decrease.
 Acidity and Alkalinity (pH)
 The corrosion rate of aluminum and lead, on the other hand, tends to
increase in environments above a pH of about 8.
 This is because the protective oxide film on the surface of these
metals is dissolved in most strong acids and alkalis and the metals
corrode.
 Metals that corrode under low and high pH levels are termed
amphoteric metals.
 An understanding of the effect of pH is also important in the
application of cathodic protection.
 The pH of the environment around the cathode (the protected
structure) becomes more alkaline due to the production of hydroxyl
ions or removal of hydrogen ions.
 Electrochemistry
 One branch of electrochemistry deals with solid state reactions that
take place in semiconductors such as transistors and diodes.
 Another branch deals with chemical changes that accompany the
passage of an electric current.
 Or a process in which a chemical reaction produces an electric current.
• Corrosion and cathodic protection pertain to the branch of
electrochemistry concerned with chemical changes that
accompany the transfer of electric charge, or reactions that
produces electric current in aqueous or other liquid environments.
 Electrochemical Reactions
• Metallic corrosion is almost always an electrochemical process.

• An electrochemical reaction is a chemical reaction:

o involving the transfer of electrons.
o involves oxidation and reduction.

• Battery or an electrochemical cell is generating electrical

energy from chemical reactions.

• The principle of a Daniell cell shown here.

o Zinc loses electrons and copper gains electrons.

o Electrons is transferred through an electrically path.

Zinc anode: Zn(s) → Zn2+ + 2e-

Copper cathode: Cu2+ + 2e- → Cu(s)
 Electrochemical Reactions
• A piece of zinc immersed in hydrochloric acid solution is undergoing
corrosion.
o Zinc is transformed to zinc ions.
o This reaction produces electrons and these pass through the metal to other site
where hydrogen ions are reduced to hydrogen gas.
 Anodic Processes
• The individual anodic reactions for iron, nickel, and aluminum are
listed as follows:

• The corrosion of metal M results in the oxidation of metal M to an

ion with a valence charge of n+ and the release of n electrons.
 Cathodic Processes
• The reduction of hydrogen ions at a cathodic surface will make the
solution less acidic or more alkaline or basic at the corroding
interface.
 Cathodic Processes
• In neutral waters the anodic corrosion of some active metals will split
water directly as shown:

• Cathodic reactions encountered during the corrosion of metals are:

 Cathodic Processes
• Oxygen reduction is a very common cathodic reaction.

• Although less common, metal ion reduction and metal deposition,

can cause severe corrosion problems in special situations.