UMIST

Corrosion and Protection Centre

Introduction to Corrosion

Bob Cottis

January 2002
Chemical and Electrochemical Reactions

Before we consider chemical reactions, you need to be aware of a number of terms that are used in
chemistry. If you are unfamiliar with these, then we suggest that you look at the BBC site on
http://www.bbc.co.uk/worldservice/sci_tech/features/elementary/index.shtml to learn a little more
about them:

Atom In simple terms atoms consist of a central nucleus that has a positive charge, surrounded by
negatively charged electrons that orbit around the nucleus. Atoms are the fundamental
building blocks of chemistry – atoms can be changed in nuclear reaction, but they are not
changed in chemical reactions, except by small changes in the outer (valance) electrons.

Element The chemical nature of an atom is determined by the number of electrons that orbit the
nucleus, and hence by the charge on the nucleus. An element is a mass composed of atoms
with all the same charge on the nucleus.

Molecule A molecule is a collection of atoms held together by chemical bonds (usually covalent).

Ion An ion is an atom or molecule that has lost or gained one or more electrons, such that it has
a net negative or positive charge. Ions that have lost electrons are positively charged and
are known as cations (e.g. sodium ions, Na+, and ammonium ions, NH4+). Ions that have
gained electrons are negatively charged, and are known as anions (e.g. chloride ions, Cl-,
or sulphate ions, SO42-).

Bonds Chemistry is largely about the ways in which atoms can join together to form molecules,
crystals and other structures. Chemical bonds are a result of interactions between the outer
electrons in the atoms. Covalent bonds result when electron pairs are shared between two
atoms, normally with one electron of the pair coming from each atom. Ionic bonds are
produced when anions and cations are held together by electrostatic forces, usually in an
ionic crystal. The metallic bond results from a distributed sharing of electrons between
many atoms. The easy movement of electrons within a metal crystal is the cause of the
characteristic good electrical conductivity of metals.

Chemical reactions

Chemical reactions occur when one or more reactants (which may be atoms, molecules or ions),
combine to produce one or more products.

Chemical reactions only involve changes in the bonding between the atoms that are involved, and the
number of atoms of the various elements will not change.

Chemical reactions may occur between species dissolved in a liquid (including the liquid itself) in a
gas mixture, between components of a ‘solid solution’ or at the interface between solids and liquids,
gases or other solids. Reactions occurring within a single phase (gas, liquid or solid) are known as
homogeneous reactions, while reactions occurring at the interface between two phases are known as
heterogeneous reactions. As a general rule homogenous reactions occur more easily than
heterogeneous reaction, because they can occur throughout the volume, rather than occurring only at
the boundary. However, solid surfaces may assist in the reaction, or ‘catalyse’ it.

Introduction to Corrosion © Bob Cottis 2002 1

Chemical reactions may involve a transfer of electrons from one species to another, but overall they
will not involve a change in the number of electrons.

Types of chemical reaction

Chemical reactions may be classified in a number of types, and some of the common reaction types
are summarized in Table 1, which also gives examples of each type of reaction:

Table 1 – Types of chemical reaction and examples

Type of Reaction General form and examples

Synthesis A+B → AB
Fe + Cl2 → FeCl2
2H2 + C → CH4
Combustion nA + O2 → 2An/2O
CH4 + 2O2 → CO2 + 2H2O
Decomposition AB →A+B
2NaHSO3 → Na2SO3 + H2O + SO2
Replacement A + BC → AB + C
2KBr + Cl2 → 2KCl + Br2
Hydrolysis A + H2 O → AOH- + H+
Al3+ + 3H2O → Al(OH)3 + 3H+

Electrochemical reactions

Electrochemical reactions are heterogeneous reactions that involve the transfer of charge from a
chemical species in solution to a metal. As the charge carriers in a metal are electrons, whereas free
electrons cannot exist in solution, electrochemical reactions may be thought of as reactions that
produce or consume electrons.

Reactions that produce electrons result in the oxidation of the species in solution and are known as
anodic reactions. Reactions that consume electrons result in the reduction of the species in solution,
and are know as cathodic reactions. Examples of anodic and cathodic reactions are given in Table 2.

Table 2 – Example electrochemical reactions

Type of Reaction Examples

Anodic Fe → Fe2+ + 2e-

Zn → Zn2+ + 2e-
Fe2+ → Fe3+ + e-
4OH- → O2 + 2H2O + 4e-
Cathodic O2 + 2H2O + 4e- → 4OH-
2H2O + 2e- → H2 + 2OH-
Fe3+ + e- → Fe2+

Note that for every anodic reaction there is a cathodic reaction that is the reverse (see the two
examples in Table 2).
2 Introduction to Corrosion © Bob Cottis 2002
Corrosion Reactions

One of the first reactions that a child studying chemistry at school will encounter is the reaction of a
metal such as zinc with an acid, with the result that the metal goes into solution as a salt, and hydrogen
gas is liberated. For example zinc with hydrochloric acid gives the reaction:
Zn + HCl → ZnCl2 + H2
metal in solution in solution gas
However this is not always what is observed. If we replace zinc by platinum, we do not see any
reaction, no hydrogen is evolved, and we do not find any platinum in the solution. This is because
platinum is a very non-reactive metal, and does not easily form salts.
We can get further information about the nature of the corrosion reaction if we simultaneously expose
zinc and platinum to the hydrochloric acid, with the two metals electrically connected together. In this
case hydrogen is seen to evolve on the surface of the platinum. However we still find no platinum in
solution. If we connect an ammeter in the circuit between the zinc and the platinum, we find that an
electrical current is flowing from the platinum to the zinc, i.e. electrons are flowing from the zinc to
the platinum. This can be explained in terms of the separation of the corrosion process into two parts;
the dissolution of the zinc and the generation of hydrogen gas:
Zn → Zn2+ + 2 e-
metal in solution in metal

2H + + 2e − → H2
in solution in metal gas
In general corrosion involves an anodic, metal-dissolution reaction (such as zinc dissolution above),
and a cathodic reaction that consumes electrons. The two common cathodic reactions are hydrogen
evolution (above), and the reduction of dissolved oxygen:
O2 + 2 H2O + 4e- → 4OH-

Pourbaix diagrams
In general the chemical stability of a metal exposed to a solution is a function of the potential of the
metal with respect to the solution, and the pH of the solution. The regions where the various species
are stable can be plotted on a map of potential against pH, know as an E-pH or Pourbaix diagram.

There are three types of region on the Pourbaix diagram:

1. When the metal is the thermodynamically stable state, the metal is immune from
corrosion.

2. When the stable species is a soluble corrosion product, the metal is said to be active, and
will corrode relatively rapidly.

3. When the stable species is an insoluble corrosion product, then the metal is said to be
passive, and will corrode relatively slowly.

Introduction to Corrosion © Bob Cottis 2002 3

Example Pourbaix Diagrams

Water
We can describe the two main cathodic reactions as being concerned with the stability of water:

O2 + 4 H+ + 4 e- ⇌ 2H2O ⇌ H2 + 2 OH- - 2e-

(the right-hand reaction has been written in a slightly 2.0

unconventional way to emphasize the equilibria with 1.6 (a) O2 stable
water). The equilibrium between oxygen and water 1.2
occurs at rather positive potentials, and it is able to 0.8
act as a cathodic reactant for all but the most noble 0.4 (b) H2 O stable
metals. The equilibrium between water and hydrogen Equilibrium
Potential 0
occurs at quite low potentials, and only the more -0.4
active metals are able to displace hydrogen from -0.8
water and thereby suffer from corrosion in oxygen- (b) H2 stable
-1.2
free solution. On the Pourbaix diagram (a map of the
-1.6
stability of the various species as a function of pH 0 7 14
and Electrochemical Potential) both of these pH
equilibria produce a sloping line, because the
equilibrium potential is affected by the hydrogen ion concentration and is hence a function of pH.

Gold
The region of thermodynamic immunity
extends to above the line for oxygen
evolution at all pH values, and consequently
gold cannot corrode either with the reduction
of oxygen in solution or the evolution of
hydrogen. This is the reason why gold is such
a corrosion-resistant metal, and why it is
often found in the form of the metal in nature,
rather than combined with oxygen as an
oxide.

Copper
Cannot corrode with hydrogen evolution at
any pH, but can corrode with dissolved
oxygen reacting to form hydroxyl ions. The
corrosion product is soluble in acids and
strong alkalis, where significant corrosion
may be expected. Protected by a passive film
of oxide in neutral solutions.

4 Introduction to Corrosion © Bob Cottis 2002

Iron
Corrodes both with oxygen reduction and
hydrogen evolution in acid and near neutral
solutions, although it may be passivated at
high potentials in weak acids. It is protected
from corrosion in alkaline solutions by a
passive oxide film, except possibly in very
strongly alkaline conditions.

Aluminium
Corrodes with oxygen reduction or hydrogen
evolution in strongly acid or alkaline
solutions. Protected by a passive film of
aluminium oxide in near-neutral solutions.

Localized Corrosion

The various forms of localized corrosion tend to be a more severe problem than normal general
corrosion, since they lead to more damage to structures for a given loss of metal. Localized corrosion
problems tend to occur most commonly when general corrosion has been limited by various means,
but the protection is incomplete, and fails at local points. Since the rate of corrosion processes is often
controlled by the rate of supply of oxygen to the metal surface, this may result in the same metal loss
as in general corrosion, but only at the points of local breakdown, with consequent rapid attack.

Sources of Localized Corrosion

Localized corrosion may be caused by variations in the environment seen by different regions of the
metal, by inherent variations in the structure or composition of the metal, or by the effects of the
mechanical loading experienced by the component.
Environmental variations that may be important include oxygen concentration, chloride ion
concentration, pH and flow rate.

Important metallurgical variations generally involve segregation of the alloying elements in the metal,
such as the presence of second phase precipitates, inclusions and grain boundary segregation.

Mechanical factors that may be important include both static stress, which leads to stress corrosion
cracking, and fluctuating stress, which results in corrosion fatigue.

Introduction to Corrosion © Bob Cottis 2002 5

Types of Localized Corrosion
Galvanic Corrosion
A extreme form of segregation occurs when two dissimilar
metals are coupled together. For example, if a piece of iron is
connected to a piece of copper in aerated sodium chloride
solution, oxygen reduction will occur on the surface of both the
copper and the iron. However only the iron will be able to
corrode. Consequently if the areas of the two metals are the
same, the iron will corrode twice as fast as it would in the
absence of the connection to the copper.
Similarly in an aluminium alloy containing iron, iron-aluminium
inter-metallic particles will be precipitated in the aluminium.
Unlike the normal aluminium surface, which is protected from
corrosion by an insulating layer of aluminium oxide, the iron-
aluminium particles are good sites for hydrogen evolution, and
this leads to intense local corrosion around the precipitates.

Table 1 Standard emf series Table 2 Galvanic Series in Seawater

Reaction Eo at 25oC,
(V vs NHE)
3+
Au-Au +1.498 Platinum
↑
Pt-Pt2+ +1.2 Gold
Noble or
Pd-Pd2+ +0.987 Graphite
cathodic
Ag-Ag+ +0.799 Titanium
Hg-Hg22+ +0.788 Silver
2+
Cu-Cu +0.337 Chlorimet 3 (62 Ni, 18 Cr, 18 Mo)
Hastelloy C (62 Ni, 17 Cr, 15 Mo)
+
H2-H 0.000 18-8 Mo stainless steel (passive)
18-8 stainless steel (passive)
2+
Pb-Pb -0.126 Chromium stainless steel 11-30% Cr
2+
Sn-Sn -0.136 (passive)
2+
Ni-Ni -0.250 Inconel (passive) (80 Ni, 13 Cr, 7 Fe)
2+
Co-Co -0.277 Nickel (passive)
2+
Cd-Cd -0.403 Silver solder
2+
Fe-Fe -0.440 Monel (70 Ni, 30 Cu)
Cr-Cr3+ -0.744 Cupronickels (60-90 Cu, 40-10 Ni)
Zn-Zn2+ -0.763 Bronzes (Cu-Sn)
Al-Al3+ -1.662 Copper
Mg-Mg2+ -2.363 Brasses (Cu-Zn)
+
Na-Na -2.714 Chlorimet 2 (66 Ni, 32 Mo, 1 Fe)
+
K-K -2.925 Hastelloy B (60 Ni, 30 Mo, 6 Fe, 1 Mn)
Inconel (active)
Nickel (active)
Lead-tin solders
18-8 Mo stainless steel (active)
Ni-Resist (high Ni cast iron)
Chromium stainless steel, 13% Cr
(active)
Cast iron
Steel or iron
2024 aluminium (4.5 Cu, 1.5 Mg, 0.6 Mn)
Active or
Cadmium
anodic
Commercially pure aluminium (1100)
↓
Zinc
Magnesium and magnesium alloys
After de Bethune and Loud from INCO test results

The EMF Series (Table 1) and the Galvanic Series (Table 2) are often used to determine which metal
of a couple is liable to corrode. The EMF Series has the advantage of being based on a precisely
quantifiable parameter, but unfortunately passive metals may operate as stable cathodes at potentials
well above the equilibrium potential, consequently it gives a rather poor indication of the behaviour to
6 Introduction to Corrosion © Bob Cottis 2002
be expected. The Galvanic Series has been derived
from exposure of samples in the specified
environment, and therefore gives a better indication
of practical performance. However, even the
Galvanic Series should be used with some caution, as
the severity of any galvanic corrosion since this
depends on such factors as the electrical resistance of
any passive films, the conductivity of the electrolyte
and the kinetics of the cathodic reaction on the
cathodic half of the couple.
Differential Aeration
Differential aeration occurs when two areas of a
piece of metal are exposed to regions of solution of
different oxygen content. In this case the cathodic
reaction of oxygen reduction only occurs at the site at which oxygen is readily available, while the
metal dissolution occurs over the entire surface of the sample. At the site of the oxygen reduction
excess hydroxyl ions are produced, causing the pH to rise. For many metals, such as iron and copper,
this results in the deposition of a passive film of metal oxide or hydroxide, with the result that the rate
of metal dissolution at this site is retarded. Correspondingly the metal dissolution reaction is
accelerated in the oxygen-free region of the solution.

Crevice Corrosion and Deposit Attack

For metals that are normally protected by a passive oxide
film, such as stainless steel, the formation of forms of
differential aeration cell by the presence of crevices in the
structure can lead to very severe corrosion. Considering, for
example, the use of stainless steel in seawater, when the
structure is first immersed in seawater, the solution both
inside and outside the crevice will be oxygenated, and the
corrosion rate of the steel will be low due to the protective
action of the passive oxide film. However, the oxygen
inside the crevice will eventually be used up by the slow
corrosion occurring, while the steel outside the crevice will
continue to be in contact with aerated solution. The steel
inside the crevice will continue to corrode, leading to the
production of positively-charged metal ions inside the
crevice. These react with hydroxyl ions to precipitate iron
hydroxide. Because of the removal of hydroxyl ions from
solution by this process, the pH in the crevice goes down.
Thus the solution in the crevice becomes more and more
acid, until eventually the passive oxide film can no longer
be maintained, and the steel starts to dissolve actively. This
further reinforces the acidification of the crevice, and
severe corrosion occurs inside the crevice. Similar
problems may also occur under deposits of dirt, sand etc.,
and in this case the resulting corrosion is called deposit
attack.
It should be emphasized that crevice corrosion requires a passive external surface in order to proceed.
For metals that are actively corroding, such as carbon steels in seawater, the conditions in a crevice do
Introduction to Corrosion © Bob Cottis 2002 7
not become acidic, because the accumulation of metal ions stifles further corrosion, and in this case
the crevice is protected from corrosion. Problems are experienced in crevices in carbon steel structures
exposed in the atmosphere, but these are due to the retention of moisture in the crevice, not
conventional crevice corrosion.

Pitting
Under suitable circumstances a corrosion mechanism
similar to crevice corrosion can occur on plain metal
surfaces. For various reasons the passive film breaks down
locally, the region of solution in contact with the metal
becomes acidic and starts to corrode rapidly. The resultant
hole is known as a pit, and the process as pitting corrosion.

Pitting corrosion of stainless steel

(left) and copper (right).
Dealloying

Plug-type dezincification
Alloys are inherently made of dissimilar metals, which may have very different corrosion properties.
For example cast iron consists of iron, which is relatively easily corroded, and carbon, which is
essentially inert. In normal carbon steels the carbon is dispersed in the steel as fine precipitates of iron
carbide, which leaves a deposit of very finely divided carbon when it dissolves. However in grey cast
iron the carbon is present as flakes of graphite. When this corrodes, the graphite is left behind, and
retains the shape of the original casting. This process is known as graphitic corrosion or graphitisation
(some workers argue that the latter term relates to another form of degradation and should not be used
here, but it is widely used), and may be quite dangerous, since the component appears to be intact,
although the graphite has little strength.
A similar process can occur with alloys such brass, from which the zinc can dissolve, leaving a
spongy mass of copper behind. Again this does not change the shape of the object, but the strength is
markedly reduced.

Intergranular Corrosion
Grain boundaries in metals and alloys tend to be sites of significant
changes in composition. Because of the irregular structure of the
grain boundary it is easier to fit impurity atoms in, and also diffusion
of atoms is faster. Consequently grain boundaries tend to have
different properties from the bulk of grain. This leads to enhanced
corrosion either at the grain boundary (if it is less corrosion resistant
than the grain), or immediately next to it (if the grain boundary is
more noble).

Stainless steels are corrosion resistant because of the chromium Intergranular corrosion (weld
content, which permits the formation of a thin, highly protective decay) of stainless steel. The
left-hand plate is stabilized with
film of chromium oxide on the steel surface. In order for the steel to titanium
be corrosion resistant, the chromium content must be greater than
8 Introduction to Corrosion © Bob Cottis 2002
about 9%. For this reason stainless steels have chromium contents that are typically in the range 13 to
20 %. Unfortunately however, if the steel also contains carbon, it is possible, if the steel is heated to a
certain temperature range, for the chromium and carbon to combine to form precipitates of chromium
carbide. Because of the faster diffusion in the grain boundary the precipitates form preferentially here.
Furthermore, because of the much faster diffusion of carbon than chromium, this precipitation tends to
consume most of the chromium in the neighbourhood of the grain boundary, and the effective grain
boundary chromium concentration is insufficient to keep the metal protected. The resulting corrosion
is known as intergranular corrosion, and is a serious problem in welded structures. It can be controlled
either by reducing the carbon content to a very low level, or by adding elements such as titanium or
niobium, which form carbides in preference to the chromium.
During rolling the grains in a metal tend to be flattened into a pancake shape, and if such an alloy is
subject to intergranular corrosion, the structure can separate into a series of layers. This is known as
exfoliation, and often occurs with aluminium alloys.

Flow Effects
Flow of solution tends to accelerate corrosion processes by increasing
the rate at which oxygen gets to the surface of the metal (an exception
to this occurs for passive metals, when the improved oxygen supply
can help to maintain passivity). When flow conditions become
turbulent, the corrosion problems can become much more severe, and
serious localized corrosion is often observed at joints and bends in
pipework carrying water.
Erosion corrosion of stainless
steel pump impeller

More serious problems can occur if the fluid contains entrained air bubbles or particles of solids, both
of which further enhance the transport of oxygen to the metal surface, and also tend to mechanically
damage and remove protective films of corrosion product. These processes are known as impingement
and erosion-corrosion.
If the solution velocity becomes high enough, vapour bubbles may form at low-pressure regions. The
subsequent collapse of these leads to a combination of corrosion and mechanical damage known as
cavitation.

Introduction to Corrosion © Bob Cottis 2002 9

Mechanical Aspects of Corrosion

It is often found that the joint action of corrosion and mechanical stress is more damaging than either
alone. One aspect of this aspect of this interaction is the enhanced failure of metals by cracking in the
presence of stress. In the case of a static stress the resultant failure is termed stress corrosion cracking,
while for alternating stresses the process is called corrosion fatigue. Additionally, the action of
mechanical stress can enhance corrosion and related processes. Thus mechanically deformed metal
tends to corrode more rapidly, while rubbing surfaces may suffer from accelerated corrosion known as
fretting corrosion.

The Effect of Stress and Strain on Corrosion

Elastic stress does not usually cause much change in corrosion behaviour, but as soon as plastic
deformation occurs, the metal tends to become significantly more active, either because the oxide film
which normally limits the rate of corrosion is disrupted by the deformation, or because the greater
number of dislocations in the strained metal make the corrosion process easier.

Stress Corrosion Cracking

If the rate of corrosion at sites at which the protective oxide film is ruptured is sufficient to cause more
plastic strain at the tip of a notch or crack, it is possible for this enhanced corrosion to propagate into
the metal, with the corrosion causing the plastic strain, and the plastic strain causing the corrosion.
This process is called stress corrosion cracking. Because of the need for a fairly delicate balance
between the tendency to corrosion and the generation of plastic strain, this phenomenon is observed
only in specific combinations of metal and environment, although as our knowledge of the subject
increases, so we find more cases of problems. A general requirement is that the metal should be
protected by a good passive film, but one that reforms slowly when damaged.
Common systems giving rise to stress corrosion cracking are:
• Brass and ammonia (often in local atmospheres).
• Austenitic stainless steels and chloride solutions (70°C).
• Carbon steels in caustic, carbonate/bicarbonate, nitrate and phosphate solutions.
• High strength aluminium alloys in water or water vapour.

Hydrogen Embrittlement
Many metals are made brittle by the presence of dissolved hydrogen. The reasons for this are not
known, but this leads to many problems that are similar in result to stress corrosion cracking (indeed
the latter term is often used to cover both types of failure). The hydrogen may come from many
sources, such as:
• Welding.
• Electroplating.
• Contact with gaseous hydrogen.
• Corrosion, especially in the presence of sulphides.

10 Introduction to Corrosion © Bob Cottis 2002

In general higher strength materials are more susceptible to hydrogen embrittlement, the major
problems occurring with high strength steels. As a general rule face centred cubic materials, such as
austenitic stainless steels, are less susceptible to hydrogen embrittlement, although it seems probable
that the stress corrosion cracking of high strength aluminium alloys in water is a hydrogen
embrittlement process.

Liquid Metal Embrittlement

A process similar to stress corrosion cracking can occur if liquid metals come into contact with a
metal. For example mercury will cause brass to crack, and stainless steel will crack in liquid zinc.

Corrosion Fatigue
The process of metal fatigue is responsible for the majority of mechanical failures. When combined
with a corrosive environment the process is known as corrosion fatigue. The effects of corrosion on
fatigue crack initiation and growth are still not fully understood, but in general the effect is to increase
the rate of both processes. The mechanisms by which this is thought to happen are similar to those of
stress corrosion cracking and hydrogen embrittlement, but because of the more extreme mechanical
damage, the environments in which the effects are seen are far less specific.

Fretting Corrosion
If two metal surfaces are rubbed together, the oxide film which is normally present, and which reduces
the rate of corrosion, may be removed, thereby allowing corrosion to occur more quickly. The oxide
debris may also act as an abrasive, particularly if the amount of movement is small, and the oxide
remains in the joint. This process, which can lead to very rapid wear of mating surfaces, is known as
fretting corrosion.

Methods of Corrosion Control

There are relatively few methods for controlling corrosion:

1. Coat the metal

• paint
• metal e.g. galvanizing (zinc), chrome plate (Cr+Ni)
• conversion coating, e.g. anodising of aluminium (Al2O3), phosphating (FePO4)
• glass (vitreous enamel)

2. Modify the electrochemical potential of the metal

• into a region of immunity (cathodic protection)
• into a region of passivity (anodic protection)

3. Modify the environment

• remove oxygen
• change the pH
• add inhibitors

4. Use corrosion resistant materials

• polymers
• passive alloys (aluminium, stainless steel, nickel-base alloys, titanium)
• noble metals (gold, platinum)
Introduction to Corrosion © Bob Cottis 2002 11
 5. Design
• avoid crevices
• avoid galvanic couples
• allow for good drainage

6. Use corrosion monitoring to detect corrosion problems

7. Live with it – if it is the most cost effective approach, then this is the best method of
corrosion control.

Coatings
Paint

A paint consists of a mixture of different materials each constituent possessing. a specific function.

1. The main constituent is known as the binder, a continuous polymeric phase which is responsible
for the cohesion of the dried film either by a physical polymer, polymer interaction in the dry
state or by further polymerisation during the drying process, Further, the binder is the
component in the paint which is responsible for the adhesion of the paint to a substrate.
2. The second major constituent is the pigment, solid particles dispersed in the binder which
originally were designed to provide colour and opacity but with anti-corrosive paints imparts to
the final dried film a specific anti-corrosion function.
3. Extenders are solid particles whose main function is to lower the overall unit cost. They may
also provide mechanical reinforcement to the dried film, to adjust the viscosity of the wet paint.
4. Solvents and thinners are low molecular weight highly volatile compounds which make the
liquid paint less viscous and evaporate during the drying process.
5. Plasticisers are non polymeric compounds and are sometimes added to improve the flexibility of
the final dried film.
6. Driers are salts of transition metals added to catalyse the autoxidation drying reaction for air-
drying systems.

Paint is typically applied as several layers. This allows the properties of the various interfaces to be
optimised, and helps to avoid pinholes that penetrate the coating (known as ‘holidays’).

• A primer is applied to the metal, and is designed for good adhesion. It may also include
corrosion inhibitors.

• A top coat provides a weather resistant surface, and a decorative appearance.

Metal Coatings

Metal used for coatings may either be more active than the substrate (e.g. zinc on steel), or more noble
(e.g. Ni-Cr plate on steel). More active coatings tend to corrode relatively quickly, but provide
galvanic protection to the underlying metal when the coating is penetrated. More noble coating metals
are usually more corrosion resistant, but create a galvanic corrosion problem when the coating is
penetrated or damaged.

12 Introduction to Corrosion © Bob Cottis 2002

A common method for the protection of outdoor steel work is to use galvanized (zinc coated) steel,
and then to paint it before the zinc is completely lost.

Conversion Coatings and Inorganic Coatings

Conversion coatings are produced by reaction of the metal being coated with a suitable chemical
solution, sometimes with an applied current to drive the reaction. Common conversion coatings are:

• anodising of aluminium (the formation of an artificially thickened aluminium oxide)

• phosphating of steel or galvanized steel (the formation of an iron or zinc-iron phopsphate by

reaction with a mixture of phosphoric acid and phosphates) – this is often used as a pre-
treatment before painting (e.g. car bodies).

Glass is also used as a coating in the form of vitreous enamel. It is very protective and resistant to
most chemicals, but it is brittle and easily damaged.

Environment Modification and Inhibitors

The simplest modification to the environment is the removal of oxygen. In neutral solution this
reduces the rate of corrosion of iron and steel to a very low value. Increasing the pH to above about 10
will also reduce the corrosion rate of iron and steel, as the iron will passivate. If this methods are not
applicable, then chemicals may be added to the environment to interfere with the corrosion process,
usually by forming a film of some kind.
Definition
‘A corrosion inhibitor is a substance which, when added in small quantities to a normally corrosive
environment, reduces the corrosion rate of the metal, without significantly changing the concentration
of corrosive species.’

Broadly, there are only two ways in which inhibitors can exert their action:

• by forming an adsorbed layer on the metal surface, or,

• by forming a three-dimensional film, either a passive film or a precipitated film.

Inhibitors for Acids

In this case the corrosion reactions are metal dissolution with hydrogen evolution as the cathodic
reaction. These reactions occur in the absence of surface films of oxides or corrosion products,
because of their solubility in acid, and both reactions are under activation control. Even a small
reduction in the kinetics of either process will reduce the corrosion rate.

Inhibitors for acid solutions usually function by adsorption on the metal surface, and typically contain
elements in Groups V or VI of the periodic table, e.g. N, P, O, S or As, which can interact with the
metal by a process known as chemisorption.

Introduction to Corrosion © Bob Cottis 2002 13

Inhibitors for Near-Neutral and Alkaline Environments

This section considers inhibitors that work in the presence of oxygen, since inhibitors for oxygen-free
near-neutral solutions, as may be found, for example, in oil production, are of the type discussed
above.

There are essentially two ways of reducing the corrosion rate in these environments. For an actively
corroding steel surface the corrosion rate is under cathodic control, i.e. the rate is determined by the
transport of oxygen to the metal surface. The two ways of reducing corrosion rate are

(a) to reduce the rate of this rate determining step, oxygen transport, by the formation of a
electronically non-conducting film on the metal surface (cathodic inhibitors, common
examples are zinc and calcium, both of which precipitate as hydroxides at cathodic sites),
or

(b) to cause the steel to form or retain a protective oxide film which acts as a barrier to metal
dissolution, so that the corrosion rate is now controlled by the anodic process (anodic
passivating inhibitors, common examples are chromate and nitrite).

Cathodic Protection

Cathodic protection is a useful and practical example of an electrochemical cell. The cell may pass
current spontaneously, as in a sacrificial cathodic protection system, or the cell may be driven using a
DC source in an Impressed current cathodic protection system.

1. The structure needing protection, usually mild steel, is one electrode and receives electrons.

2. In the sacrificial anode the other electrode is a reactive metal, usually alloys of zinc, aluminium or
magnesium. The electrochemical reaction generates electrons. The sacrificial anode cathodic
protection case may be thought of as a useful case of galvanic corrosion.

3. In the impressed current system the other electrode is usually an inert metal (sometimes graphite).
The current is provided by a power supply.

4. There must be electron conduction between the two electrodes.

5. There must be electrolyte contact between the two electrodes.

The anodic reaction in the sacrificial anode case is electrochemical oxidation of the anode itself; in the
impressed current case, it is the electrochemical oxidation of the environment. In both cases the
cathodic reaction that occurs on the structure being protected is reduction of oxygen, together with
some evolution of hydrogen. Excessive hydrogen evolution would be considered as overprotection – it
will waste power, and may cause problems with coatings.

Cathodically protected structures are often painted to reduce the current demand, and prolong the life
of sacrificial anodes.

14 Introduction to Corrosion © Bob Cottis 2002

Corrosion Resistant Materials

Most corrosion resistant materials are protected by a passive corrosion product film. Common
corrosion resistant materials are:

• Stainless steel: these are iron-based alloys with the passive film being formed by chromium.
Several classes of astainless steel are available: ferritic steels are basically iron-chromium
alloys, with about 13% Cr; austenitic steels contain nickel to stabilise the austenitic structure, a
common composition is 18% Cr, 8% Ni; martensitic steels can be hardened by precipitation of
iron carbide in the same way as carbon steels.

• Aluminium and its alloys are protected by a film of alumina, Al2O3, which is very insoluble
and protective. Many of the alloys are, however, susceptible to pitting associated with copper
or iron containing precipitates.

• Nickel base alloys are similar to stainless steels, but tend to be more corrosion resistant
because nickel is a somewhat more noble metal (it is also much more expecnsive!).

• Titanium is protected by a passive film of TiO2. This is one of the most resistant alloys to
localized corrosion, and it is also relatively light but strong. It is relatively expensive.

Design against corrosion

Design features can have an important influence on corrosion behaviour. The ideal design will have
smooth surfaces, with no crevices or regions where liquid will accumulate, or from which liquid
cannot be drained. It will not normally used mixtures of different metals (in order to avoid galvanic
corrosion), and it will avoid highly stressed regions (to prevent stress corrosion cracking).

Corrosion Monitoring
There are several reasons for corrosion monitoring and testing. The methods used are broadly similar,
but testing is generally applied in the laboratory whereas monitoring is applied to a system. It is of
course possible to carry out testing in an actual plant or system. Reasons for monitoring and testing
include

1. To establish the corrosion rate of a component of a system

2. To check on the application of control measures such as corrosion inhibitors
3. To plan maintenance
4. To select appropriate materials
5. To select appropriate control measures

Note that corrosion monitoring does not change the corrosion behaviour, and it is therefore only an
indirect method of controlling corrosion. It does, however, provide a method for minimizing the cost
of corrosion control, for example by allowing the control of inhibitor additions so that just enough is
provided to prevent corrosion.

Introduction to Corrosion © Bob Cottis 2002 15

Monitoring methods include

1. Weight loss methods, where the corrosion is directly measured by the loss in weight of a
sample. This is appropriate for all systems but may require a long exposure time if the
corrosion rate is low.
2. Electrochemical corrosion rate methods such as linear polarisation, ac impedance and
electrochemical noise. These require a conducting solution and so are not appropriate for gases
or for non-aqueous systems, such as almost dry hydrocarbons.
3. Electrical resistance measurement, where the loss of metal is followed by the increase in
electrical resistance as the metal thins. This is appropriate for all systems.
4. Fluid analysis, for example the measurement of the increase in dissolved iron levels as a fluid
passes through a pipeline.

It is important that the monitoring is representative, so location of corrosion probes should reflect the
worst expected corrosion, for example at high flow rates or at areas where water may separate.

Similar methods can be used for testing in the laboratory. Here it is important to reproduce the actual
exposure conditions as far as possible. Factors of importance include

1. Metal composition and heat treatment

2. Solution composition
3. Temperature
4. Flow rate

In general testing procedures start with comparatively simple tests, and as selection of materials an/or
control measures proceeds develop into more complex and realistic tests.

Corrosion Management

Corrosion is not fundamentally a technical problem. Gold will solve most corrosion problems
(although gold aircraft might not fly very well), but, of course, this solution is economically
impossible in most cases. Corrosion management may be defined as the control of corrosion
problems in a
• safe,
• economic, and
• predictable fashion.

Here we look at some examples of good corrosion management, and also the way in which failure to
apply simple principles have given rise to major corrosion problems.

Examples of Good Corrosion Management

Electronic contacts
Electronic contacts are usually exposed to reasonably mild environments, but even very small
amounts of corrosion may have very serious effects, since films of corrosion product can present a
very high resistance. For high power contacts silver or tin coatings or many metals such as brass can
be used, as the arcing due to the switching action will blast a conductive path through the corrosion
product films. For low power signal contacts that must make reliable, low resistance connections,
very corrosion resistant contacts are used, typically based on gold coatings, as even thin oxide films
will give poor contacts.
16 Introduction to Corrosion © Bob Cottis 2002
This is an example of one approach to corrosion management − use a high cost material when the cost
of failure or replacement is more significant than the cost of the material.

Off-shore platforms
An offshore platform is a large structure that must support large loads and withstand massive wave
and tidal forces. It is very expensive to repair or repaint the structure once it has been placed in the
sea. For the submerged structure it is most common to use a low cost weldable carbon-manganese
steel. This would corrode at a rather high rate (about 1 mm per year near the surface), so the steel is
protected by the application of cathodic protection.

Above the water-line the steel is painted to restrict the rate of corrosion, as cathodic protection won’t
work.

This represents a second approach to corrosion management − when the cost of the material is an
important part of the total cost of the system use a low cost material with corrosion protection.

Corrosion ‘disasters’
Replacement of steel water tank by stainless steel

Stainless steel water storage tanks and detail of pitting corrosion

A dairy company decided to replace the steel tanks used for storing desalinated drinking water with
type 304L stainless steel, in order to eliminate corrosion problems. However, after only one month
the circumferential site welds perforated by pitting corrosion. This was attributed to faulty welding,
and the welds were repaired by re-welding. After four months the longitudinal factory welds also
perforated by pitting corrosion. Subsequent inspection revealed that the parent plate and the piping
was also pitting.

The problem was eventually attributed to sulphide (or possibly thiosulphate) in the water. This was
derived from lake water used to make up the desalinated water, together with around 70 ppm of
chloride.

Introduction to Corrosion © Bob Cottis 2002 17

Change to all-stainless steel heat exchanger
A stainless steel heat exchanger was used to evaporate liquefied natural gas from cryogenic storage.
The heating fluid was water that was heated directly with a submerged gas-air flame. This tended to
pick up chloride from impurities in the gas, and was there moderately corrosive. The original design
used carbon steel tube plates for low cost, these suffered from corrosion (but the life was acceptable as
they were thick). The new design used all stainless steel to eliminate tube plate corrosion. However,
this design failed more rapidly by crevice corrosion between tubes and tube supports. The original
design had accidentally provided cathodic protection to the stainless steel by connection to the carbon
steel, which therefore did not corrode.

Causes of corrosion ‘disasters’

In general these corrosion disasters result from a lack of knowledge or understanding of the effects of
design decisions.

Hence the primary weapon for good corrosion management is knowledge

• knowledge of corrosion processes
• knowledge of corrosion control methods
• knowledge of economic implications
• knowledge of sources of corrosion information
• knowledge of the limits to knowledge

In this course we shall cover the knowledge that is needed for good corrosion management, and then
see how it can be applied in practical situations.

Corrosion of Concrete Structures

Introduction
Steel-reinforced concrete is widely used as a constructional material because of its low cost,
compressive strength and easy fabrication on-site. The reinforcing steel is normally protected from
corrosion by the alkalinity of the concrete, which renders the steel passive. An understanding of the
reasons for the corrosion of steel therefore rests on understanding the processes that led to the loss of
passivity. This is an important problem, as many reinforced concrete structures have been built
without an adequate awareness of the possibility of steel corrosion, and it has been suggested that
more money is now being spent on the repair of old reinforced concrete structures than on the
construction of new structures.
Concrete
Concrete is produced by mixing three components:

Cement - this is produced by calcining a mixture of minerals based on chalk and clay. When
water is added to cement a series of hydration reactions take place that result in the formation
of a strong structure of interlocking crystals.
Aggregate - this is added to fill space in the concrete, and thereby reduce the cost. It also modifies
the mechanical properties of the concrete. It is usual to add aggregates of various sizes, with
the fine aggregate filling the spaces between the coarse aggregate.
Water - this provides an essential part of the chemical requirements for the setting of the concrete,
and also makes the mix easy to manipulate by pouring and casting.

18 Introduction to Corrosion © Bob Cottis 2002

Once a concrete mix has been cast the chemical reactions (known as curing) cause it to harden into a
solid mass with a high compressive strength. The water does not react completely, and some (known
as pore water) will be left in pores in the concrete. The pore water in fresh concrete is very alkaline,
with a pH of around 13.5 as a result of the presence of potassium and sodium hydroxides released by
the curing process.
Steel-Reinforced Concrete
Concrete is strong in compression but brittle and weak in tension. In order to produce structures that
can resist forces with tensile elements, steel is embedded in the concrete. If this steel is initially
unstressed the material is known as reinforced concrete, and is liable to suffer some cracking of the
concrete when a tensile stress is applied (since the concrete will crack as a result of the elastic strain in
the steel). Structures with a better resistance to tensile stresses can be produced by placing the steel in
tension either before or after the concrete is cast (known as prestressed and post-tensioned concrete
respectively). These variants suffer from additional corrosion-related problems that are largely
associated with the higher strength of the steel that is used, and these will be discussed further below.
Corrosion of Steel in Concrete
Steel is normally passive in fresh concrete, and corrosion usually results from either or both of two
processes:
Carbonation - when concrete is exposed to an atmosphere containing carbon dioxide, the latter
gas will diffuse into the concrete and react with the alkaline species according to reactions of
the form:
Ca(OH)2 + CO2 = CaCO3 + H2O
This causes the pH to fall, and when it falls to around 9 or 10, the corrosion of steel may
commence (although it will usually occur earlier as a result of chlorides that are present in the
concrete).
Chloride entry - chloride ions can cause pitting corrosion of the normally passive steel in much
the same way that they cause pitting corrosion of stainless steels in neutral solutions. However,
the hydroxyl ions that are present in alkaline solutions act as an inhibitor of pitting corrosion,
since they compete with the chloride to migrate into the pit, and thereby tend to stop the pH
falling. Thus it has been found that a critical ratio of chloride to hydroxyl ions is necessary
before pitting corrosion can occur. The critical ratio is generally found to be around 0.6.
Chlorides in concrete may be derived from two sources, the initial mix or the external
environment. Chloride in the initial mix is relatively inert to start with, as is it bound to the
cement in complex chloro-aluminates, but it can be released if the alkalinity drops through
carbonation. In modern practice chloride should not be added to concrete mixes, although poor
quality control may result in the use of sea-washed aggregate or even sea water being used for
mix water. In the past chloride has been deliberately added as calcium chloride to accelerate
the cure of the concrete, and this has been responsible for many problems. Chloride diffusing
in from the environment is less easily avoided, and it does not bind very strongly to the cement
matrix, and is therefore liable to cause more severe corrosion if it reaches the steel. However,
the rate of diffusion is rather low, and with sufficient cover (the thickness of concrete over the
reinforcement steel) and good design and concrete quality, reinforced concrete can give a good
life even in aggressive marine conditions.
When corrosion of the reinforcement does start to occur, the corrosion product formed occupies a
larger volume than the steel from which it has been produced, and this tends to create a tensile stress
in the surrounding concrete, which consequently cracks. The cracks then allow easy access of the
corrosive environment to the steel, and the corrosion therefore accelerates.

Introduction to Corrosion © Bob Cottis 2002 19

Detection of Corrosion
Often the first sign of corrosion of the reinforcement is rust staining of the surface of the concrete.
When this is seen, it implies that the concrete has cracked, and repair will require significant work. It
is preferable to detect corrosion before it has reached this stage, as it then becomes possible to apply
preventative measures without major repair work. The best method for this is probably potential
mapping. This entails measuring the potential of the steel relative to a reference electrode that is
moved over the surface of the concrete. Then a local minimum in potential implies high local currents
and hence local corrosion. The absolute potential of the steel can also be used as an indication of
possible corrosion, although there is a range of potentials over which the behaviour of the steel is
uncertain.
Hydrogen Embrittlement of Pre-stressing Steel
Owing to its high tensile strength (usually around 1500 MPa), pre-stressing steel is quite susceptible to
hydrogen embrittlement (although it is more resistant than other steels of a similar strength by virtue
of its highly directional drawn structure). When the steel is in the passive state in alkaline concrete
little hydrogen enters the steel. Problems are usually experienced when the steel is exposed to neutral
environments, such as sea water, or, more severely, when the steel is in contact with a more active
metal such as zinc or aluminium. This problem tends to produce failure with little warning, as little
corrosion is needed to produce sufficient hydrogen. A number of major failures have occurred as a
result of hydrogen embrittlement of pre-stressing steel, including the collapse of the roof of the Berlin
Convention Centre.
Prevention of Concrete Corrosion by Design
At the design stage there is much that can be done to limit potential corrosion problems. Some of the
approaches that may be used include:
Use adequate cover - the diffusion of both CO2 and chloride into the concrete is controlled by
diffusion, and the time taken for these species to reach a given depth will increase as the
square of the depth. Therefore, doubling the cover will, in theory, give a four times increase in
life. In practise the observed effects may not be quite this large as some diffusion occurs down
cracks and other defects in the concrete. Additionally, the extra cover will cost money, and
there is an economic trade-off to take into account. Typical cover depths will range from 25
mm in benign environments to 75 mm or more for long life in severe conditions.
Use good-quality concrete - the porosity of the concrete will be influenced by several factors, the
most significant being the water-cement ratio. If this is too high, a high porosity concrete will
be produced, and chloride diffusion will be rapid. On the other hand it must not be so low that
the concrete cannot be compacted properly, and there must be sufficient water to allow the
cement to cure adequately (note that concrete does not harden by drying, and it is important
that it is not allowed to dry out during the curing process).
Coat the concrete to restrict access of chloride and CO2 - by coating the concrete with an
alkali-resistant paint, the rate of entry of chloride and CO2 can be greatly reduced. The major
difficulty with this approach is the difficulty of getting good adhesion of the coating to the
concrete, as any loss of adhesion eliminates most of the benefits of the coating.
Use epoxy-coated reinforcement - if the reinforcement is coated with a good-quality epoxy
coating (usually applied by melt-curing an epoxy resin power onto the hot steel), the epoxy
coating can further retard the onset of serious corrosion.
Use galvanised reinforcement - a zinc coating on the reinforcement may be able to delay the
onset of serious corrosion. It might be thought that the zinc corrosion products would be as
likely to cause cracking of the concrete in the same way as rust on the steel. While there is
some evidence that this can happen if corrosion rates are very high, zinc salts are more soluble
in the alkaline pore solution, and appear to be able to diffuse into the concrete are thereby
relieve the stresses resulting from moderate rates of corrosion.
20 Introduction to Corrosion © Bob Cottis 2002
 Use stainless steel reinforcement - stainless steels can tolerate a much higher chloride to
hydroxide ratio before pitting corrosion occurs, and stainless steel reinforcement is expected to
give a very long life, although at the expense of a much higher initial cost.
Repair of Corroding Steel in Concrete
Unless the structure is left for a long time after the signs of corrosion of the steel become apparent, the
corrosion of the steel is not usually sufficient to reduce the strength of the reinforcement, and the loss
of the concrete integrity is more important. If the concrete has cracked, it is necessary to remove the
cracked cover back to the reinforcing steel, and then to recover with a suitable material.
If the corrosion is detected before cracking of the concrete has occurred, it is possible to prolong the
life of a structure by the application of cathodic protection using external anodes. Both the impressed
current and the sacrificial anode methods have been used:
Sacrificial anode - this has been achieved by flame-spraying zinc onto the surface of the concrete,
and then bonding the zinc coating to the reinforcement.
Impressed current - again the anode is placed on the surface of the concrete, but in this case it is
either a carbon-based paint or a platinized titanium mesh held on to the surface with mortar.
The latter method is much more expensive, but also more durable.
Where the structure is immersed in the sea or buried in soil, a conventional anode outside the structure
may be used, rather than needing to be placed on the surface of the concrete. Whichever form of
cathodic protection is used, it is also important to ensure that all of the reinforcement steel is
electrically bonded together, otherwise the cathodic protection system may cause locally enhanced
corrosion by stray current effects.

Cathodic protection aims to lower the potential of the steel to such a low value that corrosion is
thermodynamically impossible. However, providing the steel has not started to corrode too
extensively, it may be sufficient to apply much smaller currents than are needed for conventional
cathodic protection. The cathodic reaction occurring on the reinforcement produces hydroxyl ions and
raises the pH, while the applied current causes chloride ions to move away from the reinforcement.
The potential will be lowered somewhat (though not into the region of thermodynamic immunity), and
the overall effect of this treatment is to reduce the possibility of pitting corrosion of the steel, which
will remain passive. This method is known as cathodic prevention.

Cathodic protection tends to draw the chloride ions away from the steel and to generate alkalinity at
the surface of the steel (since the latter is behaving as a cathode). A variant of conventional cathodic
protection, known as chloride extraction, aims to enhance these effects to restore the protective
properties of the concrete by using larger cathodic protection currents for a relatively short time.

Web Resources
General
Corrosion and Protection Centre
http://www.umist.ac.uk/corrosion
Corrosion and Protection Centre Course Notes
http://www.umist.ac.uk/corrosion/civils
Corrosion Source
http://www.corrosionsource.com
Corrosion Doctors
http://www.corrosion-doctors.org

Introduction to Corrosion © Bob Cottis 2002 21

Corrosion of Steel in Concrete
Corrosion Doctors
http://www.corrosion-doctors.org/Concrete/Introduction.htm
G.M Iborn Consult
http://www.gmic.dk/deter_corr.htm
NASA
http://corrosion.ksc.nasa.gov/html/corrincon.htm
Southern Cathodic Protection
http://www.cathodicprotection.com/concrete/mainconcrete.htm

22 Introduction to Corrosion © Bob Cottis 2002