CORROSION & ITS PREVENTION

Introduction:
Corrosion is the slow but continuous deterioration of metallic components by Chemical
or electrochemical attack. All metals and alloys are susceptible to corrosion and no
single material is suitable for all applications.

For example, gold known for excellent resistance to atmospheric corrosion will corrode
when exposed to mercury at ambient temperature. On the other hand, iron does not
corrode in mercury but readily “rusts” when exposed to the atmosphere.

Corrosion, in simple terms, occurs in metals because most metals are not in their
natural state and always try to return to their ore – form of an oxide, e.g., iron exists in
nature in the form of haematite ( Fe2 O3) and iron pyrites ( FeS2).

Factors Governing Corrosion

Three factors govern corrosion.
 The metal from which the component is made.
 The protective treatment the component surface receives.
 The environment in which the component is kept.

All metals corrode to a greater or lesser degree; even precious metals like gold and
silver tarnish in time, and this is a form of corrosion. Prevention processes are unable to
prevent the inevitable failure of the component by corrosion; they only slow down the
process to a point where the component will have worn out or been discarded for other
reasons before failing due to corrosion. Let's now look at the three ways in which
metals corrode.

• Dry corrosion
This is the direct oxidation of metals which occurs when a freshly cut surface reacts
with the oxygen of the atmosphere. Most of the corrosion-resistant metals such as lead,
zinc and aluminium form a dry oxide film which protects the metal from further
atmospheric attack.

• Wet corrosion
This occurs in two ways:
a) The oxidation of metals in the presence of air and moisture, as in the rusting of
ferrous metals.
b) The corrosion of metals by reaction with the dilute acids in rain due to the burning of
fossil fuels (acid rain) - for example, the formation of the carbonate 'patina' on copper.
This is the characteristic green film seen on the copper clad roofs of some public
buildings.

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• Galvanic corrosion
This occurs when two dissimilar metals, such as iron and tin or iron and zinc, are in
intimate contact. They form a simple Engineering electrical cell in which rain, polluted
with dilute atmospheric acids, acts as an electrolyte as generated and circulates within
the system. Corrosion occurs with (depending upon its position in the electrochemical
series) being eaten away.

Other metals, in addition to iron and steel, corrode when exposed to the atmosphere.
The green corrosion-product which covers a copper roof, or the white, powdery film
formed on some unprotected aluminium alloys is clear evidence of this.

Fortunately the reactivity of a metal and the rate at which it corrodes is not related. For
example, although aluminium is chemically more reactive than iron, as soon as it is
exposed to the atmosphere, it forms an oxide film which seals the surface and prevents
further corrosion from taking place. On the other hand, iron is less reactive and forms
its oxide film more slowly.
Unfortunately, the iron hydroxide film (rust) is porous and the process continues
unabated until the metal is destroyed.

TYPES OF CORROSION

1. Atmospheric corrosion
Any metal exposed to normal atmospheric conditions become covered with an invisible,
thin film of moisture. This moisture film is invariably contaminated with dissolved
solids and gases which increase the rate of corrosion. The most common example of
corrosion due to dissolved oxygen from the atmosphere is the rapid surface formation
of 'red rust' on unprotected ferrous metals. This 'red rust' is a hydroxide of iron and
should not be confused with the blue-black oxide of iron called 'mill-scale' which is
formed by heating iron in dry air.

Once 'rusting' commences the action is self-generating - that is, it will continue even
after the initial supply of moisture and air is removed. This is why all traces of rust must
be removed or neutralized before painting, otherwise rusting will continue under the
paint, causing it to blister and flake off.

2. Galvanic corrosion
It has already been stated that when two dissimilar metals come into intimate
association in the presence of an electrolyte that a simple electrical cell is formed
resulting in the eating away of one or other of the metals. Metals can be arranged in a
special order called the electrochemical series. This series is listed in Table 1 and it
should be noted that, in this context, hydrogen gas behaves like a metal.

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Table 1. Electrochemical series

3. Corrosion accelerated by mechanical stresses

We have seen that failure of a component may take place due to corrosion arising from
electrolytic action between two different phases in a microstructure, or between two
different materials in a fabricated structure. Failure of a component may also occur as a
result of the complementary effects of chemical corrosion and mechanical stress. The
methods of stress application may vary and this will affect the extent of corrosion which
occurs. Forms of corrosion in which stress plays a part can be classified as follows:

3.1 Stress Corrosion - cracking

The combined action of a tensile stress and corrosive environment results in the
corrosion of a metal alloy. Stresses that cause cracking arise either due to residual cold
work, welding thermal treatment or may be externally applied during service. The
cracks can follow inter-granular or transgranular paths and there is often a tendency for
crack branching.
A similar process may take place in components in which unequal heating or cooling has
given rise to the presence of locked-up stresses, as, for example, near to welded joints.

3.2 Corrosion Fatigue. As might be expected, any component which is subjected to

alternating stresses and is working in conditions which promote corrosion may fail at a
stress well below the normal fatigue limit. The action of the corrosive medium will tend
to be concentrated at any surface flaw and behave as a focal point for the initiation of a
fatigue crack. Once a crack has been formed it will spread more rapidly as a result of the
corrosive action combined with alternating stress.

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3.3 Fretting Corrosion is allied to corrosion fatigue and occurs particularly where
closely fitting machine parts are subjected to vibrational stresses. In steel this form of
corrosion appears as patches of finely divided ferric oxide¿ ¿).

3.4 Impingement Corrosion refers to the combined effects of mechanical abrasion and
chemical corrosion on a metallic surface. Mechanical wear can be caused by the
impingement of entrained air bubbles or abrasive particles suspended in the liquid.
The impingement of such media may lead to the perforation of any protective film
existing on the surface. This film may be an oxide, which is cathodic to the exposed
metal beneath. This type of corrosion is encountered in pump mechanism turbine and
tuber carrying sea-water.

Impingement failure of an elbow that was part of a steam condensate line

3.5 Pitting Corrosion Pitting is another form of much localized corrosion attack in
which small pits or holes form. They ordinarily penetrate from the top of a horizontal
surface downward in a nearly vertical direction. It is an extremely insidious type of
corrosion, often going undetected and with very little material loss until failure occurs.

Fretting corrosion
It occurs when two surfaces under load, rub against each other, e.g. during vibrations.
Lubricating to lower the friction between the two surfaces, or roughening to increase
friction to a point of no movement are methods of avoiding the problem.

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FACTORS AFFECTING CORROSION
1. Structural design
The following factors should be observed during the design stage of a component or
assembly to reduce corrosion to a minimum.
• The design should avoid crevices and corners where moisture may become trapped
and adequate ventilation and drainage should be provided.
• The design should allow for easy washing down and cleaning.
• Joints which are not continuously welded should be sealed, for example, by the use of
mastic compounds or impregnated tapes.
• Where dissimilar metals have to be joined, high-strength epoxy adhesives should be
considered since they insulate the metals from each other and prevent galvanic
corrosion.
• Materials which are inherently corrosion resistant should be chosen or, if this is not
possible, an anti-corrosive treatment should be specified.

2. Environment
The environment in which the component or assembly is to spend its service life must
be carefully studied so that the materials chosen, or the anticorrosion treatment
specified, will provide an adequate service life at a reasonable cost. It would be
unnecessary and uneconomical to provide a piece of office equipment which will be
used indoors whit a protective finish suitable for heavy-duty contractors plant which is
going to work on construction sites in all kinds of weather conditions.

3. Applied or internal stresses

Chemical and electrochemical corrosion is intensified when a metal is under stress. This
applies equally to externally applied and internal stresses, although more common in
the latter case. Internal stresses are usually caused by cold working and, if not removed
by stress-relief heat treatment, results in corrosive attack along the crystal boundaries.
This weakens the metal considerably more than simple surface corrosion. An example
of intercrystalline corrosion is the 'season cracking' of a brass after severe cold working.
Intercrystalline corrosion occurs at the grain boundaries of crystals not only when
impurities are present but also when stress concentrations are present. Grain
boundaries are regions of high energy levels, even in very pure metals, so corrosion
tends to occur more quickly at the grain boundaries.
Severely cold-worked α brasses are prone to ‘season cracking'. Here, intercrystalline
corrosion follows the grain boundaries until the component is no longer able to sustain
the internal stresses due to cold working. The component then cracks. This can be
prevented by a low temperature stress relief annealing process. This low temperature
does not cause recrystallisation but is sufficient to remove the locked up stresses by
allowing the atoms to move small distances nearer to their equilibrium positions.

4. Composition and structure

The presence of impurities in non-ferrous metals reduces their corrosion resistance.
Hence the high level of corrosion resistance exhibited by high purity copper, aluminium
and zinc. The importance of grain structure has also been mentioned above, and a fine-
grain structure is generally less susceptible to corrosion than a coarse-grain structure.
The inclusion of certain alloying elements such as nickel and chromium can also
improve corrosion resistance - for example, the stainless steels and cupro-nickel alloys.

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5. Temperature
For all chemical reactions there is a critical temperature below which they will not take
place. Since corrosion is the result of chemical or electrochemical reactions, corrosion is
retarded or stopped altogether at low temperatures. On the other hand, corrosion is at
its worst in the hot. Humid atmosphere of the tropical rain forests and equipment for
use in such environments has to be 'tropicalised' if it is to have a reasonable service
life. High temperatures alone do not increase the rate of corrosion, and corrosion is
virtually nonexistent in arid desert areas of the world. Failure of mechanical devices in
desert environments is due generally to the abrasive effect of the all-pervasive sand.

Metals which resist corrosion

It has already been made clear that metals combine with atmospheric oxygen and or
atmospheric pollutants to a greater or lesser extent. The following metals, which resist
corrosion, react to form impervious, homogeneous coatings on their surfaces which
prevent further corrosion from taking place, as long as these coatings remain
undisturbed. Metals such as copper, zinc, aluminium, lead, stainless steel, nickel and
chromium are good examples of metals that are inherently uncorrodable.

CORROSION PREVENTION
There are three principal methods by which corrosion may be prevented or minimized.

1. Use of protective coating.

First, the metallic surface can be insulated from the corrosive medium by some form of
protective coating. The objective of a protective coating is to isolate the metal from the
corrosive environment. Such coatings include various types of paints and varnishes,
metallic films having good corrosion-resistance and artificially thickened oxide films. All
of these are generally effective in protecting surfaces from atmospheric corrosion,
though zinc coatings are used to protect iron from the rusting action of water, whilst tin
coatings offer protection against most animal and vegetable juices encountered in the
canning industry.
Underground pipe work is usually given a thick bituminous coating before installation
but this coating may be damaged during pipe laying and cathodic protection is used to
minimise corrosion of any exposed surface.

2. Cathodic protection.

Cathodic protection is widely used to protect structures in circumstances where

corrosive action is severe, where abrasion is likely to damage a surface coating or where
the renewal of a corroded structure could prove very expensive. It is particularly useful
for the protection of ships’ hulls, steel piers, and harbour installations, buried steel work
in building foundations and buried pipelines.

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A block of highly anodic material, magnesium, aluminium or zinc is placed adjacent to
the structure to be protected and connected electrically. A galvanic cell is created
deliberately and the sacrificial anode will corrode, protecting the structure.

Cathodic (sacrificial) protection of an underground pipeline using a magnesium sacrificial

anode.

3. Inhibitors and passifying agents

Inhibitors and passifying agents are widely used for the reduction of corrosion in closed cooling
systems where cooling water is recircullated. They may take the form of PH regulators or they
may help to form a protective film on metal surfaces within the system. Chromate slats
are widely used as inhibitors within car radiator systems. Any iron ions generated at a
steel anode surface will combine with chromate ions to form an insoluble iron chromate
which will create a protective coating over the steel surface. Certain tungstens and
phosphates may also be used as inhibitors

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ASSIGNEMENT I (C8/6)

DUE DATE: Monday, 28th September, 2020.

Time: 16:00Hrs

Describe in detail the following metal protection mechanisms;

(a) Cementation
(b) Painting
(c) Chromating
(d) Phosphating
(e) Anodising

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