Corrosion
Corrosion
Corrosion
org/wiki/Corrosion
Corrosion removal
Resistance to corrosion
Intrinsic chemistry
Passivation
Corrosion in passivated materials
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Pitting corrosion
Weld decay and knifeline attack
Crevice corrosion
Hydrogen grooving
High-temperature corrosion
Microbial corrosion
Metal dusting
Side view of Crow Hall Railway
Protection from corrosion
Bridge, north of Preston, Lancashire
Surface treatments rusting
Applied coatings
Reactive coatings
Anodization
Biofilm coatings
Controlled permeability formwork
Cathodic protection
Sacrificial anode protection
Impressed current cathodic protection
Anodic protection
Rate of corrosion
Economic impact
Corrosion in nonmetals
Corrosion of polymers
Corrosion of glass
Glass corrosion tests
See also
References
Further reading
External links
Galvanic corrosion occurs when two different metals have physical or electrical contact with each
other and are immersed in a common electrolyte, or when the same metal is exposed to electrolyte
with different concentrations. In a galvanic couple, the more active metal (the anode) corrodes at
an accelerated rate and the more noble metal (the cathode) corrodes at a slower rate. When
immersed separately, each metal corrodes at its own rate. What type of metal(s) to use is readily
determined by following the galvanic series. For example, zinc is often used as a sacrificial anode
for steel structures. Galvanic corrosion is of major interest to the marine industry and also
anywhere water (containing salts) contacts pipes or metal structures.
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Galvanic series
In any given environment (one standard medium is aerated,
room-temperature seawater), one metal will be either more
Galvanic corrosion of an aluminium
noble or more active than others, based on how strongly its plate occurred when the plate was
ions are bound to the surface. Two metals in electrical contact connected to a mild steel structural
share the same electrons, so that the "tug-of-war" at each support.
surface is analogous to competition for free electrons between
the two materials. Using the electrolyte as a host for the flow of
ions in the same direction, the noble metal will take electrons from the active one. The resulting
mass flow or electric current can be measured to establish a hierarchy of materials in the medium
of interest. This hierarchy is called a galvanic series and is useful in predicting and understanding
corrosion.
Often it is possible to chemically remove the products of corrosion. For example, phosphoric acid
in the form of naval jelly is often applied to ferrous tools or surfaces to remove rust. Corrosion
removal should not be confused with electropolishing, which removes some layers of the
underlying metal to make a smooth surface. For example, phosphoric acid may also be used to
electropolish copper but it does this by removing copper, not the products of copper corrosion.
Some metals are more intrinsically resistant to corrosion than others (for some examples, see
galvanic series). There are various ways of protecting metals from corrosion (oxidation) including
painting, hot dip galvanizing, cathodic protection, and combinations of these.[1]
Intrinsic chemistry
The materials most resistant to corrosion are those for which corrosion is thermodynamically
unfavorable. Any corrosion products of gold or platinum tend to decompose spontaneously into
pure metal, which is why these elements can be found in metallic form on Earth and have long
been valued. More common "base" metals can only be protected by more temporary means.
Some metals have naturally slow reaction kinetics, even though their corrosion is
thermodynamically favorable. These include such metals as zinc, magnesium, and cadmium. While
corrosion of these metals is continuous and ongoing, it happens at an acceptably slow rate. An
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Passivation
Passivation refers to the spontaneous formation of an ultrathin
film of corrosion products, known as a passive film, on the Gold nuggets do not naturally
corrode, even on a geological time
metal's surface that act as a barrier to further oxidation. The
scale.
chemical composition and microstructure of a passive film are
different from the underlying metal. Typical passive film
thickness on aluminium, stainless steels, and alloys is within 10 nanometers. The passive film is
different from oxide layers that are formed upon heating and are in the micrometer thickness
range – the passive film recovers if removed or damaged whereas the oxide layer does not.
Passivation in natural environments such as air, water and soil at moderate pH is seen in such
materials as aluminium, stainless steel, titanium, and silicon.
Passivation is extremely useful in mitigating corrosion damage, however even a high-quality alloy
will corrode if its ability to form a passivating film is hindered. Proper selection of the right grade
of material for the specific environment is important for the long-lasting performance of this group
of materials. If breakdown occurs in the passive film due to chemical or mechanical factors, the
resulting major modes of corrosion may include pitting corrosion, crevice corrosion, and stress
corrosion cracking.
Pitting corrosion
Certain conditions, such as low concentrations of oxygen or high concentrations of species such as
chloride which compete as anions, can interfere with a given alloy's ability to re-form a passivating
film. In the worst case, almost all of the surface will remain protected, but tiny local fluctuations
will degrade the oxide film in a few critical points. Corrosion at these points will be greatly
amplified, and can cause corrosion pits of several types, depending upon conditions. While the
corrosion pits only nucleate under fairly extreme circumstances, they can continue to grow even
when conditions return to normal, since the interior of a pit is naturally deprived of oxygen and
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locally the pH decreases to very low values and the corrosion rate
increases due to an autocatalytic process. In extreme cases, the sharp
tips of extremely long and narrow corrosion pits can cause stress
concentration to the point that otherwise tough alloys can shatter; a
thin film pierced by an invisibly small hole can hide a thumb sized pit
from view. These problems are especially dangerous because they are
difficult to detect before a part or structure fails. Pitting remains
among the most common and damaging forms of corrosion in
passivated alloys, but it can be prevented by control of the alloy's
Diagram showing cross-
environment.
section of pitting corrosion
Pitting results when a small hole, or cavity, forms in the metal, usually
as a result of de-passivation of a small area. This area becomes
anodic, while part of the remaining metal becomes cathodic, producing a localized galvanic
reaction. The deterioration of this small area penetrates the metal and can lead to failure. This
form of corrosion is often difficult to detect due to the fact that it is usually relatively small and may
be covered and hidden by corrosion-produced compounds.
Special alloys, either with low carbon content or with added Sensitized metallic microstructure,
showing wider intergranular
carbon "getters" such as titanium and niobium (in types 321
boundaries
and 347, respectively), can prevent this effect, but the latter
require special heat treatment after welding to prevent the
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similar phenomenon of "knifeline attack". As its name implies, corrosion is limited to a very
narrow zone adjacent to the weld, often only a few micrometers across, making it even less
noticeable.
Crevice corrosion
Crevice corrosion is a localized form of corrosion occurring in
confined spaces (crevices), to which the access of the working
fluid from the environment is limited. Formation of a
differential aeration cell leads to corrosion inside the crevices.
Examples of crevices are gaps and contact areas between parts,
under gaskets or seals, inside cracks and seams, spaces filled
with deposits and under sludge piles.
Hydrogen grooving
In the chemical industry, hydrogen grooving is the corrosion of piping by grooves created by the
interaction of a corrosive agent, corroded pipe constituents, and hydrogen gas bubbles.[2] For
example, when sulfuric acid (H2SO4) flows through steel pipes, the iron in the steel reacts with the
acid to form a passivation coating of iron sulfate (FeSO4) and hydrogen gas (H2). The iron sulfate
coating will protect the steel from further reaction; however, if hydrogen bubbles contact this
coating, it will be removed. Thus, a groove will be formed by a traveling bubble, exposing more
steel to the acid: a vicious cycle. The grooving is exacerbated by the tendency of subsequent
bubbles to follow the same path.
The products of high-temperature corrosion can potentially be turned to the advantage of the
engineer. The formation of oxides on stainless steels, for example, can provide a protective layer
preventing further atmospheric attack, allowing for a material to be used for sustained periods at
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both room and high temperatures in hostile conditions. Such high-temperature corrosion
products, in the form of compacted oxide layer glazes, prevent or reduce wear during high-
temperature sliding contact of metallic (or metallic and ceramic) surfaces. Thermal oxidation is
also commonly used as a route towards the obtainment of controlled oxide nanostructures,
including nanowires and thin films.
Accelerated low-water corrosion (ALWC) is a particularly aggressive form of MIC that affects steel
piles in seawater near the low water tide mark. It is characterized by an orange sludge, which
smells of hydrogen sulfide when treated with acid. Corrosion rates can be very high and design
corrosion allowances can soon be exceeded leading to premature failure of the steel pile.[3] Piles
that have been coated and have cathodic protection installed at the time of construction are not
susceptible to ALWC. For unprotected piles, sacrificial anodes can be installed locally to the
affected areas to inhibit the corrosion or a complete retrofitted sacrificial anode system can be
installed. Affected areas can also be treated using cathodic protection, using either sacrificial
anodes or applying current to an inert anode to produce a calcareous deposit, which will help
shield the metal from further attack.
Metal dusting is a catastrophic form of corrosion that occurs when susceptible materials are
exposed to environments with high carbon activities, such as synthesis gas and other high-CO
environments. The corrosion manifests itself as a break-up of bulk metal to metal powder. The
suspected mechanism is firstly the deposition of a graphite layer on the surface of the metal,
usually from carbon monoxide (CO) in the vapor phase. This graphite layer is then thought to form
metastable M3C species (where M is the metal), which migrate away from the metal surface.
However, in some regimes no M3C species is observed indicating a direct transfer of metal atoms
into the graphite layer.
Various treatments are used to slow corrosion damage to metallic objects which are exposed to the
weather, salt water, acids, or other hostile environments. Some unprotected metallic alloys are
extremely vulnerable to corrosion, such as those used in neodymium magnets, which can spall or
crumble into powder even in dry, temperature-stable indoor environments unless properly treated
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to discourage corrosion.
Surface treatments
When surface treatments are used to retard corrosion, great
care must be taken to ensure complete coverage, without gaps,
cracks, or pinhole defects. Small defects can act as an "Achilles'
heel", allowing corrosion to penetrate the interior and causing
The US military shrink wraps
extensive damage even while the outer protective layer
equipment such as helicopters to
remains apparently intact for a period of time.
protect them from corrosion and
thus save millions of dollars
Applied coatings
Plating, painting, and the application of enamel are the most
common anti-corrosion treatments. They work by providing a
barrier of corrosion-resistant material between the damaging
environment and the structural material. Aside from cosmetic
and manufacturing issues, there may be tradeoffs in
mechanical flexibility versus resistance to abrasion and high
temperature. Platings usually fail only in small sections, but if
the plating is more noble than the substrate (for example,
Galvanized surface
chromium on steel), a galvanic couple will cause any exposed
area to corrode much more rapidly than an unplated surface
would. For this reason, it is often wise to plate with active metal such as zinc or cadmium. If the
zinc coating is not thick enough the surface soon becomes unsightly with rusting obvious. The
design life is directly related to the metal coating thickness.
Reactive coatings
If the environment is controlled (especially in recirculating
systems), corrosion inhibitors can often be added to it. These
chemicals form an electrically insulating or chemically
impermeable coating on exposed metal surfaces, to suppress
electrochemical reactions. Such methods make the system less Corroding Steel Electrification
Gantry
sensitive to scratches or defects in the coating, since extra
inhibitors can be made available wherever metal becomes
exposed. Chemicals that inhibit corrosion include some of the salts in hard water (Roman water
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systems are famous for their mineral deposits), chromates, phosphates, polyaniline, other
conducting polymers and a wide range of specially-designed chemicals that resemble surfactants
(i.e. long-chain organic molecules with ionic end groups).
Anodization
Aluminium alloys often undergo a surface treatment.
Electrochemical conditions in the bath are carefully adjusted
so that uniform pores, several nanometers wide, appear in the
metal's oxide film. These pores allow the oxide to grow much
thicker than passivating conditions would allow. At the end of
the treatment, the pores are allowed to seal, forming a harder-
than-usual surface layer. If this coating is scratched, normal
passivation processes take over to protect the damaged area.
This climbing descender is anodized
Anodizing is very resilient to weathering and corrosion, so it is
with a yellow finish.
commonly used for building facades and other areas where the
surface will come into regular contact with the elements. While
being resilient, it must be cleaned frequently. If left without cleaning, panel edge staining will
naturally occur. Anodization is the process of converting an anode into cathode by bringing a more
active anode in contact with it.
Biofilm coatings
A new form of protection has been developed by applying certain species of bacterial films to the
surface of metals in highly corrosive environments. This process increases the corrosion resistance
substantially. Alternatively, antimicrobial-producing biofilms can be used to inhibit mild steel
corrosion from sulfate-reducing bacteria.[4]
Cathodic protection
Cathodic protection (CP) is a technique to control the corrosion of a metal surface by making that
surface the cathode of an electrochemical cell. Cathodic protection systems are most commonly
used to protect steel pipelines and tanks; steel pier piles, ships, and offshore oil platforms.
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Anodic protection
Anodic protection impresses anodic current on the structure to be protected (opposite to the
cathodic protection). It is appropriate for metals that exhibit passivity (e.g. stainless steel) and
suitably small passive current over a wide range of potentials. It is used in aggressive
environments, such as solutions of sulfuric acid.
Rate of corrosion
The formation of an oxide layer is described by the Deal–Grove
model, which is used to predict and control oxide layer
formation in diverse situations. A simple test for measuring
corrosion is the weight loss method.[5] The method involves
exposing a clean weighed piece of the metal or alloy to the
corrosive environment for a specified time followed by
cleaning to remove corrosion products and weighing the piece
to determine the loss of weight. The rate of corrosion (R) is These neodymium magnets
calculated as corroded extremely rapidly after only
5 months of outside exposure
where k is a constant, W is the weight loss of the metal in time t, A is the surface area of the metal
exposed, and ρ is the density of the metal (in g/cm³).
Other common expressions for the corrosion rate is penetration depth and change of mechanical
properties.
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Similarly, corrosion of concrete-covered steel and iron can cause the concrete to spall, creating
severe structural problems. It is one of the most common failure modes of reinforced concrete
bridges. Measuring instruments based on the half-cell potential can detect the potential corrosion
spots before total failure of the concrete structure is reached.
Until 20–30 years ago, galvanized steel pipe was used extensively in the potable water systems for
single and multi-family residents as well as commercial and public construction. Today, these
systems have long ago consumed the protective zinc and are corroding internally resulting in poor
water quality and pipe failures.[8] The economic impact on homeowners, condo dwellers, and the
public infrastructure is estimated at 22 billion dollars as the insurance industry braces for a wave
of claims due to pipe failures.
Most ceramic materials are almost entirely immune to corrosion. The strong chemical bonds that
hold them together leave very little free chemical energy in the structure; they can be thought of as
already corroded. When corrosion does occur, it is almost always a simple dissolution of the
material or chemical reaction, rather than an electrochemical process. A common example of
corrosion protection in ceramics is the lime added to soda-lime glass to reduce its solubility in
water; though it is not nearly as soluble as pure sodium silicate, normal glass does form sub-
microscopic flaws when exposed to moisture. Due to its brittleness, such flaws cause a dramatic
reduction in the strength of a glass object during its first few hours at room temperature.
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Corrosion of polymers
Polymer degradation involves several complex and often
poorly understood physiochemical processes. These are
strikingly different from the other processes discussed here,
and so the term "corrosion" is only applied to them in a loose
sense of the word. Because of their large molecular weight,
very little entropy can be gained by mixing a given mass of
polymer with another substance, making them generally quite Ozone cracking in natural rubber
difficult to dissolve. While dissolution is a problem in some tubing
A more common and related problem is "swelling", where small molecules infiltrate the structure,
reducing strength and stiffness and causing a volume change. Conversely, many polymers (notably
flexible vinyl) are intentionally swelled with plasticizers, which can be leached out of the structure,
causing brittleness or other undesirable changes.
The most common form of degradation, however, is a decrease in polymer chain length.
Mechanisms which break polymer chains are familiar to biologists because of their effect on DNA:
ionizing radiation (most commonly ultraviolet light), free radicals, and oxidizers such as oxygen,
ozone, and chlorine. Ozone cracking is a well-known problem affecting natural rubber for example.
Plastic additives can slow these process very effectively, and can be as simple as a UV-absorbing
pigment (e.g. titanium dioxide or carbon black). Plastic shopping bags often do not include these
additives so that they break down more easily as ultrafine particles of litter.
Corrosion of glass
Glass is characterized by a high degree of corrosion-resistance.
Because of its high water-resistance it is often used as primary
packaging material in the pharma industry since most medicines are
preserved in a watery solution.[9] Besides its water-resistance, glass is
also robust when exposed to certain chemically aggressive liquids or
gases.
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The overall corrosion rate is a sum of contributions from both mechanisms (leaching + dissolution)
NRi=NRxi+NRh. Diffusion-controlled leaching (ion exchange) is characteristic of the initial phase
of corrosion and involves replacement of alkali ions in the glass by a hydronium (H3O+) ion from
the solution. It causes an ion-selective depletion of near surface layers of glasses and gives an
inverse square root dependence of corrosion rate with exposure time. The diffusion-controlled
normalized leaching rate of cations from glasses (g/cm2·d) is given by:
where t is time, Di is the i-th cation effective diffusion coefficient (cm2/d), which depends on pH of
contacting water as Di = Di0·10–pH, and ρ is the density of the glass (g/cm3).
Glass network dissolution is characteristic of the later phases of corrosion and causes a congruent
release of ions into the water solution at a time-independent rate in dilute solutions (g/cm2·d):
where rh is the stationary hydrolysis (dissolution) rate of the glass (cm/d). In closed systems the
consumption of protons from the aqueous phase increases the pH and causes a fast transition to
hydrolysis.[12] However, a further saturation of solution with silica impedes hydrolysis and causes
the glass to return to an ion-exchange, e.g. diffusion-controlled regime of corrosion.
In typical natural conditions normalized corrosion rates of silicate glasses are very low and are of
the order of 10−7–10−5 g/(cm2·d). The very high durability of silicate glasses in water makes them
suitable for hazardous and nuclear waste immobilisation.
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0.1-0.2 31-62 2
0.2-0.85 62-264 3
0.85-2.0 264-620 4
2.0-3.5 620-1085 5
The standardized test ISO 719 is not suitable for glasses with poor or not extractable alkaline
components, but which are still attacked by water, e.g. quartz glass, B2O3 glass or P2O5 glass.
This class, which is also called neutral glass, includes borosilicate glasses (e.g. Duran, Pyrex,
Fiolax).
Glass of this class contains essential quantities of boron oxides, aluminium oxides and alkaline
earth oxides. Through its composition neutral glass has a high resistance against temperature
shocks and the highest hydrolytic resistance. Against acid and neutral solutions it shows high
chemical resistance, because of its poor alkali content against alkaline solutions.
This class usually contains sodium silicate glasses with a high hydrolytic resistance through surface
finishing. Sodium silicate glass is a silicate glass, which contains alkali- and alkaline earth oxide
and primarily sodium oxide and Calcium oxide.
Glass of the 3rd hydrolytic class usually contains sodium silicate glasses and has a mean hydrolytic
resistance, which is two times poorer than of type 1 glasses.
Acid class DIN 12116 and alkali class DIN 52322 (ISO 695) are to be distinguished from the
hydrolytic class DIN 12111 (ISO 719).
Anaerobic corrosion
Chemical hazard label
Corrosion in space
Corrosive substance
Cyclic corrosion testing
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Dimetcote
Electronegativity
Electrical resistivity measurement of concrete
Environmental stress fracture
Faraday paradox (electrochemistry)
Forensic engineering – Investigation of failures associated with legal intervention
Fibre-reinforced plastic tanks and vessels
Hydrogen analyzer
Hydrogen embrittlement
Kelvin probe force microscope
Reduction potential – measure of tendency of a substance to gain or lose electrons
Pitting resistance equivalent number
Redox – Chemical reaction
Reduction potential – measure of tendency of a substance to gain or lose electrons
Periodic table – Tabular arrangement of the chemical elements ordered by atomic number
Rouging
Salt spray test
Scanning vibrating electrode technique
Stress corrosion cracking
Tribocorrosion – Material degradation due to corrosion and wear.
Zinc pest
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8. Daniel Robles. "Potable Water Pipe Condition Assessment For a High Rise Condominium in
The Pacific Northwest" (http://crmanage.com/potable-water-pipe-condition-assessment-for-a-hi
gh-rise-structure-in-the-pacific-northwest/). GSG Group, Inc. Dan Robles, PE. Retrieved
10 December 2012.
9. Bettine Boltres (2015) When Glass Meets Pharma: Insights about Glass as Primary Packaging
Material. Editio Cantor. ISBN 978-3-87193-432-2
10. A.K. Varshneya (1994). Fundamentals of inorganic glasses (https://books.google.com/books?id
=P8g_Mm-VayYC&printsec=frontcover). Gulf Professional Publishing. ISBN 0127149708.
11. M.I. Ojovan, W.E. Lee. New Developments in Glassy Nuclear Wasteforms (https://books.googl
e.com/books?id=rAL-7GU0ec8C&printsec=frontcover). Nova Science Publishers, New York
(2007) ISBN 1600217834 pp. 100 ff.
12. Corrosion of Glass, Ceramics and Ceramic Superconductors (https://books.google.com/books?
id=xBkP6wVu_VgC&printsec=frontcover). D.E. Clark, B.K. Zoitos (eds.), William Andrew
Publishing/Noyes (1992) ISBN 081551283X.
13. Calculation of the Chemical Durability (Hydrolytic Class) of Glasses (http://glassproperties.com/
chemical_durability/). Glassproperties.com. Retrieved on 2012-07-15.
14. Vapor Hydration Testing (VHT) (http://www.vscht.cz/sil/english/chemtech_ag/vht.htm) Archived
(https://web.archive.org/web/20071214030744/http://www.vscht.cz/sil/english/chemtech_ag/vh
t.htm) December 14, 2007, at the Wayback Machine. Vscht.cz. Retrieved on 2012-07-15.
15. International Organization for Standardization, Procedure 719 (1985) (http://www.iso.org/iso/iso
_catalogue/catalogue_tc/catalogue_detail.htm?csnumber=4948). Iso.org (2011-01-21).
Retrieved on 2012-07-15.
Jones, Denny (1996). Principles and Prevention of Corrosion (2nd ed.). Upper Saddle River,
New Jersey: Prentice Hall. ISBN 978-0-13-359993-0.
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