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Introduction to Corrosion
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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 SO
2
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
sulfur compounds.
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Corrosion is a major obstacle to overcome when developing many new technologies,
such as in the area of energy generation. The use of controlled nuclear fusion will
require the development of alloys able to withstand corrosion at high temperatures. The
generation of energy from coal by magnetohydrodynamic systems, which pass hot
ionized gas through magnetic fields, involves temperatures and environments that can
destroy materials in contact with the gas. Solar energy systems require alloys to
withstand hot circulating heat-transfer fluids. Geothermal systems must resist
concentrated solutions of corrosive salts at high temperatures and pressures. In order to
drill for previously unrecoverable oil, technology must overcome stress corrosion
cracking, microbiological degradation, and the highly corrosive marine environment.
Corrosion is accelerated by pollution. Priceless works of art, such as the gilded works
of art in Venice, Italy, the stained glass in many churches, and other valuable objects
have been affected.
However, corrosion can have some beneficial effects and is responsible for the
beautiful patinas that form on bronze statues and copper roofs. The corrosion of
weathering steel produces a dark purple-brown protective and decorative layer. Artists
and architects use it in sculptures and the construction of buildings. Curiously, the most
beautiful patina is formed in polluted atmospheres.
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Types of Corrosion
When a metal is exposed to a corrosive environment, its protective film may be
destroyed so that the metal can be damaged. General corrosion is when the entire protective
film is dissolved and the entire metal is subjected to uniform attack. On the other hand,
breakdown of the protective film at specific defective sites results in a highly localized
form of corrosion called pitting, which can penetrate thick sheets of metal. Solid corrosion
products form around those sites and allow damaging chemical species that accelerate
pitting to accumulate underneath. A pile of sand, a barnacle, a gasket, or a collection of
leaves in a gutter act as a similar cover that allows a form of degradation called crevice
corrosion to occur.
Protective films may also fail when metals are exposed to high temperatures in the
presence of corrosive species. Mechanical processes such as tensile stress can also crack
the protective film and expose the metal to the corrosive environment. This type of attack is
called stress corrosion cracking.
Galvanic corrosion results when a more active metal like steel or aluminum comes into
contact with a more noble metal like copper or gold. The more active metal has a greater
tendency to become the anode and the more noble metal to become the cathode. Together
they form a corrosion cell. Therefore, when the aluminum comes into contact with copper
in a corrosive environment, it will corrode more easily than it would by itself under the
protection of its naturally formed oxide film. The cathodic reaction takes place
simultaneously on the copper.
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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
Corrosion has a negative economic impact. It is estimated that in the United
States it is a couple percentage points of the gross national product. Some of the
costs could be avoided implementing proper technology.
Metal implants in the body, such as pacemakers, pins, plates, joints, and other
prosthetic appliances are prone to a variety of corrosion failure mechanisms.
Corrosion can affect our safety and result in injuries and loss of life. An
example is the collapse of the Silver Bridge over the Ohio River in 1976, which
resulted in 46 deaths. It was attributed to stress corrosion cracking. Certain gas
pipeline explosions have also been attributed to stress corrosion. Recent problems
with aging aircrafts can be categorized as the result of corrosion effects and
many less serious failures, often not recognized as corrosion problems, have caused
injury, maiming, and death. Corrosion must also be considered when using metallic
containers for waste disposal, especially of nuclear or other toxic waste.
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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
environment.
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New Approaches for Corrosion Prevention
Life Prediction
Rapid and early assessment of the rate of corrosion for a material in a given
environment plays a crucial role in corrosion prevention. Due to the electrochemical
nature of corrosion, electrochemical science continues to contribute to the prediction of
corrosion life and the establishment of corrosion mechanisms. Whether performed in
the laboratory or in the field, life prediction methodology helps to improve designs.
Corrosion life prediction has become especially important to high-technology areas that
demand high reliability, such as microelectronics and aerospace. Storage of nuclear
and chemical waste also requires accurate life prediction for containment materials.
The introduction of microcomputers has broadened the scope of electrochemical
evaluation of corrosion rates and characterization of mechanism. Electrochemical
impedance spectroscopy (EIS) provides real-time, in situ rate information and
mechanistic details for corroding metals and is particularly applicable for coated,
anodized or slowly corroding metals. Computers allows for the extraction of features in
seemingly random electrochemical noise and offer promise as a means of evaluating
localized corrosion such as pitting, crevice corrosion, stress corrosion cracking (SCC),
and microbiologically influenced corrosion (MIC).
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Ultra-microelectrodes hold advantages for probing electrochemical processes in high
resistivity media and can perform electroanalysis in small volumes of electrolyte. These
features can be exploited to characterize corrosion in high resistivity media and
characterizing localized corrosion.
A number of well established surface analytical techniques such as Auger electron
spectroscopy (AES), X-ray photoelectron spectroscopy (XPS) and surface ion mass
spectroscopy (SIMS) that probe the first few layers of metallic surfaces remain important
tools for corrosion research. However, these methods are limited because they are
restricted to an ex situ ultrahigh vacuum (UHV) environment. Advances in the use of pre-
conditioning cells, have recently been implemented. A number of vibrational
spectroscopies including laser Raman and enhanced Raman spectroscopy can be
applied in situ. Older optical methods such as ellipsometry remain viable tools for in situ
examination of corroding surfaces. Newer non-linear optical methods of second harmonic
generation (SHG) are not yet fully developed as a tool for examining the behavior of a
corroding surface. Increased availability of synchrotron radiation now gives the corrosion
scientist a powerful spectral method of obtaining information on the surface chemistry of
metals with the use of the X-ray absorption near edge structure (XANES) and the surface
extended X-ray adsorption fine structure (SEXAFS) technoques.
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Microscopies such as scanning electron microscopy and transmission electron
microscopy remain important techniques used in corrosion research. Newer
microscopies such as scanning tunneling microscopy (STM) and surface force
microscopy provide the corrosion scientist direct details of the molecular structure.
Acoustic microscopy has also been introduced as an analytical tool for corrosion
research.
The recently developed electrochemical quartz crystal microbalance allows
simultaneous evaluation of mass change in the sub-nanogram range and
electrochemical current. Therefore, it is an important tool for evaluating
fundamental corrosion and passivation mechanisms. This method relies on the
frequency shift of oscillation modes of a quartz crystal coated with the test
electrode. Mass changes as well as viscoelastic coupling to the electrolyte
influence the response. The method can be quite useful for evaluating slow
corrosion rates critical to passivity and microelectronics and for providing
fundamental information on double layer structures. In the future, it may also have
applicability as an atmospheric and gas phase corrosion sensor, although the
method is now limited to thin metallic films.
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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
temperatures.
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Even though corrosion inhibitors cover a broad range of technology, many
studies have been in the anecdotal realm and barely applied scientific tools
available to the electrochemist. One significant exception is the adsorption of
organic compounds to inhibit the corrosion of steel in acidic environments,
where two dimensional films are formed. However, recent work has expanded our
knowledge of neutral media by revealing the detailed role of inorganic and organic
inhibitors in neutral electrolytes, where three dimensional films form. Research on
novel approaches using multiphase organic/inorganic inhibitors is still ongoing.
Environmental concerns are now a greater priority for governments around the
world. Older methods for corrosion protection, particularly those that rely on the
use of hexavalent chromate, are becoming obsolete. It is likely that in the near
future all heavy metal inhibitors, conversion coatings, and pigments will
eventually be outlawed from widespread application and the use of the organic
coating VOC will have to be reduced. Changing environmental regulations will
continue to motivate corrosion research and development in the coming years.
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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).
Advances in Corrosion Protection by Organic Coatings, D. Scantlebury and M. Kending,
Editors, The Electrochemical Society Softbound Proceedings Series, Volume 89-13,
Pennington NJ(1989).
Corrosion Protection by Organic Coatings, M. W. Kendig and H. Leidheiser, Jr., Editors,
The Electrochemical Society Softbound Proceedings Series, Volume 87-2, Pennington
NJ(1987).
Surfaces, Inhibition, and Passivation, E. McCafferty and R. J. Brodd, Editors, The
Electrochemical Society Softbound Proceedings Series, Volume 86-7, Pennington NJ(1986).
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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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Types of Localized Corrosion Initially
Associated with the Environment
(a) Crevice corrosion (b) Deposit corrosion
Narrow
gap
Paint film or debris
(d) Filiform corrosion
(C) Waterline attack
Low [O
2
]
Severe
attack
High [O
2
]
Air
Corrosion products form a
network under a coating
Water
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Types of Localized Corrosion Initially
Associated with the Environment
(f) Drop corrosion
(e) Erosion corrosion
Flow
High [O
2
] Low [O
2
]
High [O
2
]
(g) Turbulent-flow corrosion
(h) Fretting
Turbulent flow
Very small, frequent movement
Loss of metal via surface disruption
caused by collapse of gas bubble
cavitation
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Types of Corrosion
Grain boundary
attack
Crystalline
grains
(b) Intergranular corrosion
Attack
Metal
(a) General, uniform attack corrosion
(c) Selective corrosion, e.g.
dezincification of brass
Porous Cu
Load
Cracks
Stress
(d) Stress corrosion cracking
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Types of Corrosion
(e) Pitting
Oxide film or noble metal
Pit
(f) Layer corrosion (exfoliation)
Cracks
Stress
(h) Corrosion fatigue
(g) Graphitic corrosion
Anodic loss
of metal
Graphite inclusions
acting as cathodes
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The overall corrosion process is a chemical reaction
representing the spontaneous dissolution of a metal (M)
through a reaction with the environment. This can be
described schematically by one of the following processes:
M + n/4 O
2
+ n/2 H
2
O M
n+
+ n OH
-
(10.1)
M + n H
2
O M
n+
+ n/2 H
2
+ n OH
-
(10.2)
M + n H
+
M
n+
+ n/2 H
2
(10.3)
M + n H
+
+ n/4 O
2
M
n+
+ n/2 H
2
O (10.4)
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In reality, these chemical reactions do not occur by
direct interaction between a metal and an oxidizing
agent in the environment (e.g. O
2
, H
2
O or H
+
). Instead,
each of these cell reactions is the result of an anodic and
a cathodic reaction occurring simultaneously at
identical rates on the corroding surface, i.e.:
Anode: M - ne
-
M
n+
(10.5)
Cathode: O
2
+ 2 H
2
O + 4 e
-
4 OH
-
(10.6)
Or cathode: O
2
+ 4 H
+
+ 4 e
-
2 H
2
O (10.7)
Or cathode: 2 H
2
O + 2 e
-
H
2
+ 2 OH
-
(10.8)
Or cathode: 2 H
+
+ 2 e
-
H
2
(10.9)
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Thus, the corrosion process represented by reactions
(10.1)-(10.4) are overall cell reactions, each being the sum
of the anode reaction (10.5) and appropriate cathode
reaction, e.g.:
Anode: M - ne
-
M
n+
(10.5)
Cathode: n/4O
2
+ n/2H
2
O + n e
-
n OH
-
(10.6)
Cell: M + n/4O
2
+ n/2H
2
O M
n+
+ nOH
-
(10.1)
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A Simplified Summary of the Step Involved in a
Corrosion Process
2
4
2
4
1
5
O
2
OH
-
OH
-
O
2
1
5
3B
3B
3A
e
-
e
-
Fe
2+
Fe
2+
Fe
2+
5
4
Metal surface
(electrodes)
Fe
Bulk solution
(electrolyte)
H
2
O
,
OH
-
, O
2
Reaction layer
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The corrosion of iron via oxygen reduction in an
alkaline medium is considered
1. Mass transport of reactant O
2
to the surface via convection
and diffusion.
2. Adsorption of reactant O
2
and H
2
O.
3. Electrochemical reactions:
4. Desorption of products (Fe
2+
and OH
-
) or reaction between
products: e.g.
5. Mass transport of products Fe
2+
and OH
-
away from the
surface by migration and convective diffusion.
3A anode Fe - 2e
-
Fe
2+
3B cathode 1/2 O
2
+ H
2
O + 2 e
-
2 OH
-
Cell Fe + 1/2 O
2
+ H
2
O Fe
2+
+ 2 OH
-
2Fe
2+
+ 4OH
-
2Fe(OH)
2
then
2Fe(OH)
2
+ O
2
+ (n-2)H
2
O Fe
2
O
3
nH
2
O
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This simplified treatment indicates some of the factors
influencing corrosion; the following points are noteworthy:
1. The anodic process results in metal dissolving from the 0 to the
n+ oxidation state; M
n+
may be a simple, hydrated metal ion
or it may represent a more complex soluble or insoluble species.
2. The rate of the anodic process may be significantly altered if
M
n+
builds up in solution or if M
n+
undergoes further reactions,
e.g. hydrolysis.
3. The same anodic process (reaction(10.5)) may be supported by
one or more of the four different cathode reactions (10.6)-(10.9).
4. The cathodic process may determine the nature of the
corrosion products (as well as the rate of reaction), e.g. the local
increase in pH due to reactions (10.6)-(10.9) may result in the
metal being coated by an oxide of hydroxide film.
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This simplified treatment indicates some of the factors
influencing corrosion; the following points are noteworthy:
5. The corrosion products are varied; they include dissolved
species or dissolved ions (e.g. M
n+
, OH
-
); insoluble solids (e.g.
M
2
O
n
, M(OH)
n
) and gaseous (H
2
) species.
6. The reactants for corrosion may include a solid (e.g. M),
solvent or dissolved ions (e.g. H
2
O, OH
-
, H
+
) and dissolved
gases, e.g. O
2
.
7. The cathodic process (and, hence, the corrosion reaction)
depends upon the supply of a cathodic reactant. Hence,
reaction (10.6) involves dissolved oxygen and the solvent, water;
reaction (10.8) requires only water; reaction (10.9) necessitates
protons; and reaction (10.7) involves protons and dissolved
oxygen. This has at least two further implications: (1) dissolved
oxygen is often supplied by convective diffusion resulting in the
possibility of mass transport control; and (2) the electrolyte
composition (in particular pH) is very important as it
determines the cathodic reaction which occurs and its rate.
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This simplified treatment indicates some of the factors
influencing corrosion; the following points are noteworthy:
8. The progress of a corrosion process usually results in compositional
changes in the electrolyte; in particular, the local pH near the cathodic
zones usually experiences an increase (due to reactions
(10.6)-(10.9)). The significance of this effect depends upon the electrode
and electrolyte conditions; possible implications are the saponification
of paint films or the precipitation of basic metal oxides or hydroxides.
9. So far, reactions between the corrosion products themselves and
between the metal and the corrosion products have been ignored. It will
be seen later that the formation of metal oxides and hydroxides via
chemical reaction may be critical in determining the thermodynamics
(section 10.2) and kinetics (section 10.3) of corrosion processes.
Additionally, in the case of acid electrolytes, hydrogen evolution
(reaction(10.9)) may result in the blistering of paint films or hydrogen
embrittlement.
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Environmental causes
Oils and greases
Fused salts
Liquid metal
Organic liquids
and solutions
Natural
Artificial
Atmospheric
Chemical fumes
Steam
Flue gases
Chemical streams
Distillation columns
Atmospheric
Sea water
River and estuarine water
Potable water
Underground water
Biochemical
Foodstuffs
Cooling water
Chemical process streams
Paint films and polymer
coatings
Oxygen
Nitrogen, CO
2
Contamination, H
2
S, SO
2
,
SO
3
,NH
3
, HCl, NH
4
Cl, etc.
Solid particle
Dry
Wet
Reducing
Oxidizing
Wet
Damp
Engines
Nuclear power stations
Plant
Acid
Alkaline
Neutral
Complex-forming
High temperature
Ambient
Ambient or
evaluated
temperature
Non-aqueous
Emulsions
Aqueous (wet)
Aerosols
Gases and vapours
(wet or dry)
Chemical
properties of
metals and
alloys
(heterogeneities
may be
submicroscopic,
microscopic, or
macroscopic)
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Are Some Environments More Corrosive
Than Others?
1. Moist air is more corrosive than dry air.
2. Hot air is more corrosive than cold air.
3. Hot water is more corrosive than cold water.
4. Polluted air is more corrosive than clean air.
5. Acids are more corrosive than bases (alkalies).
6. Salt water is more corrosive than fresh water.
7. Stainless steel will outlast ordinary steel.
8. No corrosion will occur in a vacuum, even at very high
temperatures, etc.

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