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Corrosion
Corrosion
Corrosion
Even in modern technology, corrosion still remains a very destructive
problem. It not only costs the economy billions of dollars by affecting the
industry, businesses and homes, but also endangers the health and safety of the
general population. Electrochemists and materials scientists continue to investigate
the causes of corrosion and develop methods for preventing but new challenges
are always emerging.
With the exception of gold, metals are naturally unstable. Corrosion occurs
when metals react with oxygen, water, and other substances in the environment.
Even metallic gold will corrode under the certain conditions. Fortunately, most
metals form protective films in reaction to their initial exposure to a normal,
benign environment, that slow down the corrosion process.
Most corrosion reactions are electrochemical in nature. From anodic sites,
where oxidation of the metal occurs, electric currents flow to cathodic sites, where
reduction of oxygen dissolved in water, hydrogen ions in acids, or SO2 in the
atmosphere takes place. The electrochemical nature of corrosion is very similar,
whether the reaction takes place in an aqueous or dry environment. For example,
aluminum corroding in sea water or silver tarnishing in air both contain traces of
2
sulfur compounds.
Types of Corrosion
When there is an electrical potential difference between two pieces of metal and a path
that a current can flow over, electrolytic corrosion occurs . On thin film or integrated
circuits or on printed wiring boards, adjacent conductor paths are normally at different
applied potentials; ionic transport occurs if moisture is adsorbed on the substrate to act as a
transport medium. Moisture reaches the surface of a device by diffusing through the cover
coat or by entering through a faulty seal. Ionic contaminants that increase the conductivity
of the adsorbed moisture layer also greatly increase the corrosion rate .
Thin tarnish films, such as oxides or sulfides, may have sufficient resistance to give an
effective open circuit in electrical contacts. Furthermore, in some applications, e.g.,
communications, even films just a few monolayers in thickness can introduce unacceptable
noise into circuits.
The corrosion of many metals and alloys is limited by the initial stages of the
corrosion process itself. Fortunately, the initial reaction of a metal with its environment
results in a very thin corrosion product film (<50) that passivates or protects the metal
from further attack. Corrosion then can only occur at defects in this film. For example,
aluminum metal is unstable in air and wants to react with atmospheric oxygen to form
stable aluminum oxide. However, the initial layer of aluminum oxide that forms on the
surface effectively protects the aluminum from further contact and reaction with oxygen.
Therefore, aluminum and its alloys have many uses, from pots and pans to window frames
and aircraft skin.
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Damage
z Prevention
Research into the characteristics and causes of corrosion has produced methods for
preventing or slowing it. For example, the addition of alloying elements to steel,
aluminum, etc., has produced many corrosion-resistant alloys, such as stainless steel.
Protective coatings are very useful for controlling corrosion. Among these are:
1. organics, such as paints, plastics, waxes, and grease,
2. silicones,
3. inorganic compounds, such as silicon nitride, glasses, and ceramics,
4. metallic coatings, such as chrome plate, which is more corrosion resistant than the
metal it covers. Zinc plate or galvanizing, does not act as a barrier, but reduces the
tendency of the underlying metal to corrode by forming a galvanic cell. Zinc is more
active than the steel to which it is coupled so it acts as the anode of the corrosion cell and
undergoes galvanic corrosion. In the process, it protects the steel by making it the cathode.
The zinc is called a sacrificial anode, the term for this process is cathodic protection.
Corrosion may be prevented by chemicals called inhibitors. Some inhibitors, mainly
certain organic molecules, adhere to the metals surface and form a single layer barrier to
the environment. Other inhibitors control the corrosiveness of the environment by acting
as a buffer.
In anodic protection, a protective or passivating film is induced electrochemically on
metals (such as steel) which do not form these films naturally by exposure to the
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environment.
Surface Treatments
Surface treatments include the work of surface modification, coating, and alloy
development. Surface modification allows the use of base metals with advantageous
structural properties but unattractive environmental resistance and continues to be a focus
of active research. Ion implantation also remains an active area. Its primary objective is to
identify implanted ions that will alter the passive film to make it more protective. Concepts
related to the charge state (the Zeta potential or pH of zero change) of the resulting
electrolyte-immersed passive oxide and the susceptibility of attack by the chloride ion
have directed the search for particular elements to implant.
The chemical modification of surfaces through conversion coatings is an important
approach to corrosion protection, although environmental concerns now make the use of
chromates less attractive. A number of alternative conversion coatings including those
containing cerium, tungstate, molybdate, and silicate are currently being investigated.
Adding alloys, such as chromium, to ferrous materials provides improved corrosion
resistance by improving the stability of the passive film. The synergistic influence of
molybdenum and nitrogen in improving the pitting resistance of stainless steels has been
the subject of considerable research. Alloy development for non-ferrous materials has
focused on removing heterogeneous components that provide catalytic sites for the
cathodic half of the corrosion reaction, typically the reduction of oxygen. In addition, rare
earth elements added to magnesium improve the oxidation resistance of the alloy.
However, the search for stainless aluminum and magnesium still continues.
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Organic coatings are still the most popular choice for protecting base metals in a
number of environments. Organic coatings provide a mass transport barrier, but
their primary function is to act as a barrier for ionic charge transport and to
block surface reactions. As a result, organic coatings must maintain adhesion in
corrosive environments. Methods for pretreating surfaces, including conversion
coating and using adhesion promoters, are very important. Novel approaches,
including ion implantation and corona discharge, have been considered as
methods to promote adhesion. Organic coatings can also provide a matrix for
corrosion inhibitors, such as inhibiting pigments. Use of time/stress-released
pigments represents a current area of active research. As with conversion coatings,
environmental concerns demand radical reformulations of organic coatings to
eliminate heavy metal pigments and most of the volatile organic chemicals (VOC).
The application of conducting polymers is something relatively new and used
very rarely to prevent corrosion. However, conducting polymers will continue to be
an important area of research, especially since they are able to provide active
protection rather than just serve as barrier films.
Sol-gel technologies to form protective inorganic oxide films have not been
fully exploited. Since they hold a great deal of promise, they are expected to have
the greatest future impact on the development of coatings that can withstand high
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temperatures.
Additional Reading
Transient Techniques in Corrosion Science and Engineering W. H. Smyrl, D. D.
Macdonald, and W. J. Lorenz, Editors, The Electrochemical Society Softbound Proceeding
Series, Volume 89-1, Pennington, NJ (1989).
Corrosion
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Definition of Corrosion
The corrosion of metal is an electrochemical phenomenon in nature.
Corrosion reactions are redox reactions in which a metal is
attacked by some substance in its environment and converted to an
unwanted compound.
All metallic corrosion involves an anodic process, which is an
oxidation reaction that releases electrons into the metal, and a
cathodic process, which is a reduction reaction that consumes
electrons at exactly the same site.
The corrosion of metals may appear as:
1. general material loss with discoloration and scaling;
2. the formation of deep gouges,
3. uncontrolled enlargement of cracks and crevices ;
4. inexplicable pinhole formations.
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Narrow
gap
High [O2]
Water
Low [O2]
Severe
attack
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Flow
(h) Fretting
Very small, frequent movement
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Types of Corrosion
(a) General, uniform attack corrosion
Attack
Metal
Crystalline
grains
Stress
Cracks
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Types of Corrosion
(e) Pitting
Pit
Anodic loss
of metal
Stress
Graphite inclusions
acting as cathodes
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(10.1)
(10.2)
M + n H+ Mn+ + n/2 H2
(10.3)
(10.4)
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Anode:
M - ne- Mn+
(10.5)
Cathode:
O2 + 2 H2O + 4 e- 4 OH-
(10.6)
Or cathode: O2 + 4 H+ + 4 e- 2 H2O
(10.7)
(10.8)
Or cathode: 2 H+ + 2 e- H2
(10.9)
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Anode:
M - ne- Mn+
(10.5)
Cathode:
(10.6)
Cell:
(10.1)
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2
4
e-
5
3A
Bulk solution
(electrolyte)
H2O, OH-, O2
1
5
O2
OH-
Fe2+
Fe2+
Fe2+
e2
3B 4
1
5
O2
OH24
Environmental causes
Non-aqueous
Emulsions
Chemical
properties of
metals and
alloys
(heterogeneities
may be
submicroscopic,
microscopic, or
macroscopic)
Natural
Aqueous (wet)
Chemical streams
Distillation columns
Atmospheric
Sea water
River and estuarine water
Potable water
Underground water
Biochemical
Wet
Damp
Foodstuffs
Cooling water
Engines
Nuclear power stations
Plant
Acid
Ambient or
Alkaline
evaluated
Neutral
temperature
Complex-forming
High temperature
Ambient
Artificial
Chemical process streams
Paint films and polymer
coatings
Aerosols
Atmospheric
Chemical fumes
Gases and vapours
(wet or dry)
Oxygen
Nitrogen, CO2
Contamination, H2S, SO2,
SO3,NH3, HCl, NH4Cl, etc.
Solid particle
Steam
Dry
Wet
Flue gases
Reducing
Oxidizing
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