MATE1000 Lecture 14 Corrosion and Degradation of Materials

(Callister: Selected parts of Chapter 18)

All materials react with the environment to some extent and this can result in deterioration in
their properties mechanical, physical, chemical and/or aesthetic. Ceramics are relatively
resistant to environmental attack, except at high temperatures or in extreme environments.
Metals can lose material by dissolution in liquids or in moist environments (corrosion) or by
the formation of a non-metallic scale or film (oxidation). Polymers can degrade through
dissolution or swelling in a liquid solvent, under electromagnetic radiation, such as ultraviolet
light, and by changes in their molecular structures at high temperatures.

Corrosion of Metals
Corrosion is is the destructive, unintentional attack of a metal usually at the surface and
involving a form of electrochemical reaction. It has been estimated that ~5% of an
industrialised nations GDP is spent on corrosion protection and the maintenance or
replacement of components affected by corrosion.
Electrochemical corrosion of metals occurs in aqueous solutions or moist environments,
when some of the metal atoms (M) lose their electrons and pass into solution as metal ions
(Mn+). This is an oxidation or anodic reaction of the form:
M Mn+ + ne
The electrons released from the ionisation of the metal atoms can now participate in another
process a reduction or cathodic reaction that generates another chemical species, usually
from the ions present in the surrounding aqueous solution or moisture film. Examples
include:
2H+ + 2e H2 (in acid solutions)

O2 + 4H + 4e 2H2O
+
(in acid solutions with dissolved oxygen)

O2 + 2H2O + 4e 4(OH) (in neutral or basic solutions with dissolved oxygen)
The overall electrochemical reaction must
consist of one oxidation (anodic) reaction
and one reduction (cathodic) reaction.
There is no net electrical charge
accumulation and all the electrons
generated in the oxidation reaction must be
consumed in the reduction reaction.
An example of the combination of these
two reactions is the rusting of iron, ie.
2Fe 2Fe3+ + 6e
O2 + 3H2O + 6e 6(OH)
2Fe + O2 + 3H2O 2Fe(OH)3
Note that it is essential to have a conducting medium an electrolyte to transport the ions
participating in the corrosion process. This can be an aqueous solution or even a moisture
film, but it must be capable of ionic conduction.

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Reactivity of Metals
The tendency of metal atoms to oxidise by forming ions varies from metal to metal. This
tendency is reflected in the standard electromotive force (emf) series, which measures the
ionisation potential relative to the ionisation of hydrogen. Metals with a positive electrode
potential relative to the hydrogen electrode are cathodic and resist ionisation eg. Cu, Ag,
Au and Pt. Metals with a negative electrode potential are anodic and susceptible to
oxidation, with the susceptibility increasing as the electrode potential becomes more negative
- eg. Fe, Zn, Al, Mg, Na and K.
This emf series can be expressed in a more practical way by ranking metals and alloys in a
galvanic series. Materials at the top of the series are increasingly cathodic and inert, while
those at the bottom of the series are increasingly anodic and reactive.
If two dissimilar metals are placed in contact, the more anodic of the two will be
preferentially oxidised and the other less reactive one will be cathodic and will not
corrode. This has two important consequences. Contact between dissimilar metals will
invariably lead to corrosion of one of them and should be avoided. However, this preferential
corrosion can be used to advantage as a form of corrosion protection. If a component to be
protected is placed in electrical contact with another more reactive metal, the reactive metal
corrodes preferentially and acts as a sacrificial anode to prevent the component from
corroding. An example is the use of Mg or Zn sacrificial anodes to prevent corrosion of iron.

Corrosion Rates
The emf series (or the galvanic series) gives an indication of the tendency of a particular
metal to corrode. How fast this corrosion occurs in practice the corrosion rate depends
on other factors. For example, the higher the conductivity of the liquid or moisture film in
contact with the metal, the higher the corrosion rate. This is why corrosion in salt water (eg.
seawater) is more aggressive than in plain water. Another factor is the possible departure of
the corrosion potentials from their equilibrium values process known as polarisation.
Finally the corrosion product may be solid and deposited as a surface film that confers a
measure of protection to the corroding material. In effect the material loses its reactivity and
behaves as if it is inert a phenomenon known as passivity. For this process to be effective
the solid protective film must adhere to the underlying metal, must not be porous, must be
capable of self-healing, if the film becomes broken or damaged, and it must not be a
conductor. The classic examples are Al and stainless steel. Both are very anodic with large
negative emfs. Hence, they oxidise readily, but in doing so produce a tenacious, non-
conducting oxide film that protects the underlying metal. If this film is damaged it reforms
very rapidly and re-instates the protection against further oxidation.

Forms of Corrosion
There are a variety of forms of corrosion that depend on the service environment. Uniform
attack occurs with equal intensity over the entire exposed surface and may leave behind a
scale or deposit (eg. rusting of steel sheet, tarnishing of silver). Galvanic corrosion occurs
with dissimilar metals in contact in the presence of an electrolyte (eg. steel screws joining
brass components). It can be avoided by choosing metals close together in the galvanic series
or by electrically insulating dissimilar materials from each other. Crevice corrosion where
there are differences in the concentration of ions or dissolved gases between two regions of
the same component. The crevice region is usually depleted in dissolved gases and becomes

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more anodic relative to the remainder of the metal (eg. in crevices under washers in bolted
metal plates or between riveted sheets of metal). Pitting corrosion is a very localised form of
attack, which generates its own crevices. It often occurs in relatively corrosion resistant
materials where local variations in composition or surface damage (eg. scratches) result in
localised corrosion. Intergranular corrosion occurs preferentially along grain boundaries in
some alloys. It is often associated with the formation of precipitates at the grain boundary and
the consequential depletion of a protective element near the boundary. For example, the
formation of chromium carbide at grain boundaries in stainless steel depletes the boundary
region of chromium and makes it less corrosion resistant. Selective leaching is the
preferential removal of one constituent in an alloy (eg. dezincification of brass). Erosion-
corrosion arises from the combined effects of corrosion and erosion. If the erosion process
mechanical wear or abrasion disrupts any protective surface film, the corrosion rate of the
now unprotected metal will be increased. Stress corrosion is an insidious form of corrosion,
where the combination of an applied (or residual) tensile stress and a corrosive atmosphere
leads to cracking and possibly eventual failure. This can occur in relatively corrosion
resistant, ductile materials at stresses well below the yield stress (eg. stainless steel in chloride
environments and brasses exposed to ammonia).

Corrosion Environments
These include the atmosphere, aqueous solutions, soils, acids, bases, inorganic solvents,
molten salts, liquid metals and even the human body. Atmospheric corrosion is enhanced by
moisture particularly if it contains dissolved oxygen by salt (marine atmospheres) and by
the presence of sulphur or sulphuric acid (acid rain). Aqueous corrosion is more aggressive in
seawater - presence of salt. Soils can be very varied in terms of composition, presence of
oxygen, moisture, salts, acids and even bacteria.

Corrosion Prevention
Passivation via a protective, non-conducting oxide film has already been mentioned Al and
stainless steels. Coatings (metals, ceramics or plastics) can also be used to prevent corrosion,
but the coating must adhere well to the surface of the metal and prevent contact between the
underlying metal and the surrounding corrosive atmosphere. Coatings are inert and purely
protective. Damage to these non-reactive coatings often leads to localised corrosion, which
can be particularly intense, if the coating is a more cathodic metal. For example, damage to
the surface of tinplate (steel sheet coated with tin) results in the tin acting as a large cathode
that accentuates the corrosion of the steel exposed by the scratch. If the metal coating is more
reactive than the substrate, it behaves in a sacrificial fashion, being attacked in preference to
the underlying material and damage to the coating has no detrimental effect. Galvanised steel
is a familiar example the Zn coating is attacked in preference to the steel and confers
protection until no more zinc remains.
Cathodic protection involves changing the potential of the component to be protected so that
it becomes cathodic rather than anodic. This can be done via the application of an external
voltage from battery or rectifier or by establishing a galvanic couple with more anodic metal
a sacrificial anode. Examples include cathodic protection of water heaters, underground
pipelines and underground tanks.

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Degradation of Polymers
Polymers and plastics are normally regarded as being unaffected by the weather, by
household chemicals or by water. However, they are not immune to environmental effects.
The degradation of polymers is not classed as corrosion, because it is not an electrochemical
process (polymers are normally insulators). Polymer degradation involves both physical
and chemical processes.
Chemical attack can lead to the irreversible rupture of the covalent bonds in the molecular
chains (scission). This can occur in environments containing acids, oxygen or ozone and
affects the mechanical properties.
Dissolution involves the physical removal of polymer chains from a solid polymer
particularly when the solvent is similar in chemical structure to the polymer. It does not
change the chemical make-up of the polymer. High molecular weight, more crosslinking and
lower service temperatures help to minimise dissolution.
Swelling also occurs when polymers are exposed to liquids. The liquid or solute diffuses into
the polymer and is absorbed within the polymer. These smaller solute molecules force the
polymer chains apart, causing swelling and the reduction in the secondary intermolecular
bonding forces. This results in the material becoming softer and more ductile with a lower
glass transition temperature. In general, lower service temperatures and increased molecular
weight, crosslinking, and/or crystallinity all serve to reduce swelling.
Radiation with ultraviolet light (sunlight), electrons, x-rays, - and -radiation has enough
energy to penetrate a polymer and interact with the constituent atoms or electrons. For
example, a photon of ultraviolet light has enough energy to remove an electron from a
specific atom like C, and in effect break a C-C bond. This bond breaking can lead to scission
or to local rearrangement, such as crosslinking at the site of the broken bond. Stabilisers (eg.
carbon black or TiO2) can be added to protect polymers from this radiation damage.
Note that if crosslinking does occur, it can be beneficial and result in improved mechanical
properties and degradation characteristics. Hence, -radiation is used commercially to
crosslink polyethylene and improve its resistance to softening and flow at elevated
temperatures.
Scission of the molecular chains at elevated temperatures leads to thermal degradation.
Some polymers undergo chemical reactions that result in the evolution of gaseous species and
weight loss. Thermal stability is a measure of the resistance to this type of decomposition and
is related to the bonding energies in the chains higher bonding energies (eg. the C-F bond
compared with the C-H bond) result in greater thermal stability.
Attack by a variety of insects and microbes may lead to polymer degradation. Most polymers
are immune to this form of attack, but biodegradable polymers including polyesters and
polyurethane are vulnerable to microbial degradation. These polymers are broken down
into small units by chemical attack or radiation and then ingested by microbes. For example,
bacteria attack the starch component of a starch/polyethylene copolymer, which then degrades
rapidly.