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Corrosion is a natural process that converts a refined metal into a more chemically stable
oxide An oxide () is a chemical compound that contains at least one oxygen atom and one other chemical element, element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– (molecular) ion. with oxygen in the oxidation state of ...
. It is the gradual deterioration of materials (usually a
metal A metal (from ancient Greek, Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electrical resistivity and conductivity, e ...
) by chemical or electrochemical reaction with their environment.
Corrosion engineering Corrosion engineering is an engineering specialty that applies scientific, technical, engineering skills, and knowledge of natural laws and physical resources to design and implement materials, structures, devices, systems, and procedures to mana ...
is the field dedicated to controlling and preventing corrosion. In the most common use of the word, this means
electrochemical Electrochemistry is the branch of physical chemistry concerned with the relationship between Electric potential, electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, with the potential dif ...
oxidation Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate (chemistry), substrate change. Oxidation is the loss of Electron, electrons or an increase in the oxidation state, while reduction ...
of metal in reaction with an
oxidant An oxidizing agent (also known as an oxidant, oxidizer, electron recipient, or electron acceptor) is a substance in a redox chemical reaction that gains or "Electron acceptor, accepts"/"receives" an electron from a (called the , , or ). In ot ...
such as
oxygen Oxygen is the chemical element with the chemical symbol, symbol O and atomic number 8. It is a member of the chalcogen Group (periodic table), group in the periodic table, a highly Chemical reaction, reactive nonmetal, and an oxidizing a ...
, hydrogen or hydroxide.
Rusting Rust is an iron oxide, a usually reddish-brown oxide formed by the reaction of iron and oxygen in the catalytic presence of water or air moisture. Rust consists of hydrous ferric oxides, hydrous iron(III) oxides (Fe2O3·nH2O) and iron(III) oxi ...
, the formation of
iron Iron () is a chemical element with Symbol (chemistry), symbol Fe (from la, Wikt:ferrum, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 element, group 8 of the periodic table. It is, Abundance ...
oxides, is a well-known example of electrochemical corrosion. This type of damage typically produces
oxide An oxide () is a chemical compound that contains at least one oxygen atom and one other chemical element, element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– (molecular) ion. with oxygen in the oxidation state of ...
(s) or
salt Salt is a mineral composed primarily of sodium chloride (NaCl), a chemical compound belonging to the larger class of Salt (chemistry), salts; salt in the form of a natural crystallinity, crystalline mineral is known as rock salt or halite. ...
(s) of the original metal and results in a distinctive orange colouration. Corrosion can also occur in materials other than metals, such as
ceramics A ceramic is any of the various hard, brittle, heat-resistant and corrosion-resistant materials made by shaping and then firing an inorganic, nonmetallic material, such as clay, at a high temperature. Common examples are earthenware, porcelain, ...
or
polymers A polymer (; Greek ''wikt:poly-, poly-'', "many" + ''wikt:-mer, -mer'', "part") is a Chemical substance, substance or material consisting of very large molecules called macromolecules, composed of many Repeat unit, repeating subunits. Due to t ...
, although in this context, the term "degradation" is more common. Corrosion degrades the useful properties of materials and structures including strength, appearance and permeability to liquids and gases. Many structural
alloy An alloy is a mixture of chemical elements of which at least one is a metal. Unlike chemical compounds with metallic bases, an alloy will retain all the properties of a metal in the resulting material, such as electrical conductivity, ductility, ...
s corrode merely from exposure to moisture in air, but the process can be strongly affected by exposure to certain substances. Corrosion can be concentrated locally to form a pit or crack, or it can extend across a wide area more or less uniformly corroding the surface. Because corrosion is a diffusion-controlled process, it occurs on exposed surfaces. As a result, methods to reduce the activity of the exposed surface, such as passivation and chromate conversion, can increase a material's corrosion resistance. However, some corrosion mechanisms are less visible and less predictable. The chemistry of corrosion is complex; it can be considered an
electrochemical Electrochemistry is the branch of physical chemistry concerned with the relationship between Electric potential, electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, with the potential dif ...
phenomenon. During corrosion at a particular spot on the surface of an object made of iron,
oxidation Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate (chemistry), substrate change. Oxidation is the loss of Electron, electrons or an increase in the oxidation state, while reduction ...
takes place and that spot behaves as an
anode An anode is an electrode of a polarized electrical device through which conventional current enters the device. This contrasts with a cathode, an electrode of the device through which conventional current leaves the device. A common mnemonic is ...
. The
electron The electron ( or ) is a subatomic particle with a negative one elementary charge, elementary electric charge. Electrons belong to the first generation (particle physics), generation of the lepton particle family, and are generally thought t ...
s released at this anodic spot move through the
metal A metal (from ancient Greek, Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electrical resistivity and conductivity, e ...
and go to another spot on the metal and reduce oxygen at that spot in presence of H+ (which is believed to be available from carbonic acid () formed due to dissolution of
carbon dioxide Carbon dioxide ( chemical formula ) is a chemical compound made up of molecules that each have one carbon Carbon () is a chemical element with the chemical symbol, symbol C and atomic number 6. It is nonmetallic and tetravalence, tetraval ...
from air into water in moist air condition of atmosphere.
Hydrogen ion A hydrogen ion is created when a hydrogen atom loses or gains an electron. A positively charged hydrogen ion (or proton) can readily combine with other particles and therefore is only seen isolated when it is in a gaseous state or a nearly particle ...
in water may also be available due to dissolution of other acidic oxides from the atmosphere). This spot behaves as a
cathode A cathode is the electrode from which a conventional current leaves a polarized electrical device. This definition can be recalled by using the mnemonic ''CCD'' for ''Cathode Current Departs''. A conventional current describes the direction in ...
.


Galvanic corrosion

Galvanic corrosion occurs when two different metals have physical or electrical contact with each other and are immersed in a common
electrolyte An electrolyte is a medium containing ions that is electrically conducting through the movement of those ions, but not conducting electron The electron ( or ) is a subatomic particle with a negative one elementary charge, elementary electr ...
, 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 A noble metal is ordinarily regarded as a metallic chemical element that is generally resistant to corrosion and is usually found in nature in its native element, raw form. Gold, platinum, and the other platinum group metals (ruthenium, rhodium ...
(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 The galvanic series (or electropotential series) determines the noble metal, nobility of metals and semi-metals. When two metals are submerged in an electrolyte, while also electrically connected by some external conductor, the less noble (base) wi ...
. 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. Factors such as relative size of
anode An anode is an electrode of a polarized electrical device through which conventional current enters the device. This contrasts with a cathode, an electrode of the device through which conventional current leaves the device. A common mnemonic is ...
, types of metal, and operating conditions (
temperature Temperature is a physical quantity that expresses quantitatively the perceptions of hotness and coldness. Temperature is measurement, measured with a thermometer. Thermometers are calibrated in various Conversion of units of temperature, temp ...
,
humidity Humidity is the concentration of water vapor present in the air. Water vapor, the gaseous state of water, is generally invisible to the human eye. Humidity indicates the likelihood for precipitation (meteorology), precipitation, dew, or fog t ...
,
salinity Salinity () is the saltiness or amount of salt (chemistry), salt dissolved in a body of water, called saline water (see also soil salinity). It is usually measured in g/L or g/kg (grams of salt per liter/kilogram of water; the latter is dimensio ...
, etc.) affect galvanic corrosion. The surface area ratio of the anode and
cathode A cathode is the electrode from which a conventional current leaves a polarized electrical device. This definition can be recalled by using the mnemonic ''CCD'' for ''Cathode Current Departs''. A conventional current describes the direction in ...
directly affects the corrosion rates of the materials. Galvanic corrosion is often prevented by the use of
sacrificial anode A galvanic anode, or sacrificial anode, is the main component of a galvanic cathodic protection system used to protect buried or submerged metal structures from corrosion. They are made from a metal alloy with a more "active" voltage (more n ...
s.


Galvanic series

In any given environment (one standard medium is aerated, room-temperature
seawater Seawater, or salt water, is water from a sea or ocean. On average, seawater in the world's oceans has a salinity of about 3.5% (35 g/L, 35 ppt, 600 mM). This means that every kilogram (roughly one liter by volume) of seawater has approx ...
), one metal will be either more ''noble'' or more ''active'' than others, based on how strongly its ions are bound to the surface. Two metals in electrical contact share the same electrons, so that the "tug-of-war" at each 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.


Corrosion removal

Often it is possible to chemically remove the products of corrosion. For example,
phosphoric acid Phosphoric acid (orthophosphoric acid, monophosphoric acid or phosphoric(V) acid) is a colorless, odorless phosphorus-containing solid, and inorganic compound with the chemical formula . It is commonly encountered as an 85% aqueous solution, w ...
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 Electropolishing, also known as electrochemical polishing, anodic polishing, or electrolytic polishing (especially in the metallography field), is an electrochemical process that removes material from a metallic workpiece, reducing the surface roug ...
, 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.


Resistance to corrosion

Some metals are more intrinsically resistant to corrosion than others (for some examples, see
galvanic series The galvanic series (or electropotential series) determines the noble metal, nobility of metals and semi-metals. When two metals are submerged in an electrolyte, while also electrically connected by some external conductor, the less noble (base) wi ...
). There are various ways of protecting metals from corrosion (oxidation) including painting,
hot-dip galvanization Hot-dip galvanization is a form of galvanization. It is the process of coating iron and steel with zinc, which alloys with the surface of the base metal when immersing the metal in a bath of molten zinc at a temperature of around . When expose ...
,
cathodic protection Cathodic protection (CP; ) is a technique used to control the corrosion of a metal surface by making it the cathode of an electrochemical cell. A simple method of protection connects the metal to be protected to a more easily corroded "sacrific ...
, and combinations of these.


Intrinsic chemistry

The materials most resistant to corrosion are those for which corrosion is thermodynamically unfavorable. Any corrosion products of
gold Gold is a chemical element with the Symbol (chemistry), symbol Au (from la, aurum) and atomic number 79. This makes it one of the higher atomic number elements that occur naturally. It is a Brightness, bright, slightly orange-yellow, dense, s ...
or
platinum Platinum is a chemical element with the Symbol (chemistry), symbol Pt and atomic number 78. It is a density, dense, malleable, ductility, ductile, highly unreactive, precious metal, precious, silverish-white transition metal. Its name origina ...
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 Chemical kinetics, also known as reaction kinetics, is the branch of physical chemistry Physical chemistry is the study of macroscopic scale, macroscopic and Microscopic scale, microscopic phenomena in chemistry, chemical systems in terms of t ...
, even though their corrosion is thermodynamically favorable. These include such metals as
zinc Zinc is a chemical element with the Symbol (chemistry), symbol Zn and atomic number 30. Zinc is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 eleme ...
,
magnesium Magnesium is a chemical element with the Symbol (chemistry), symbol Mg and atomic number 12. It is a shiny gray metal having a low density, low melting point and high chemical reactivity. Like the other alkaline earth metals (group ...
, and
cadmium Cadmium is a chemical element with the Symbol (chemistry), symbol Cd and atomic number 48. This soft, silvery-white metal is chemically similar to the two other stable metals in group 12 element, group 12, zinc and mercury (element), mercury. Li ...
. While corrosion of these metals is continuous and ongoing, it happens at an acceptably slow rate. An extreme example is
graphite Graphite () is a crystalline A crystal or crystalline solid is a solid material whose constituents (such as atoms, molecules, or ions) are arranged in a highly ordered microscopic structure, forming a crystal lattice that extends in al ...
, which releases large amounts of energy upon
oxidation Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate (chemistry), substrate change. Oxidation is the loss of Electron, electrons or an increase in the oxidation state, while reduction ...
, but has such slow kinetics that it is effectively immune to electrochemical corrosion under normal conditions.


Passivation

Passivation refers to the spontaneous formation of an ultrathin film of corrosion products, known as a passive film, on the metal's surface that act as a barrier to further oxidation. The 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 Aluminium (aluminum in American and Canadian English) is a chemical element A chemical element is a species of atoms that have a given number of protons in their atomic nucleus, nuclei, including the pure Chemical substance, substan ...
,
stainless steel Stainless steel is an alloy of iron that is resistant to rusting and corrosion. It contains at least 11% chromium and may contain elements such as carbon, other nonmetals and metals to obtain other desired properties. Stainless steel's corros ...
,
titanium Titanium is a chemical element with the Symbol (chemistry), symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resista ...
, and
silicon Silicon is a chemical element with the Symbol (chemistry), symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic luster, and is a Tetravalence, tetravalent metalloid and semiconductor. It is a member ...
. Passivation is primarily determined by metallurgical and environmental factors. The effect of pH is summarized using
Pourbaix diagram In electrochemistry Electrochemistry is the branch of physical chemistry concerned with the relationship between Electric potential, electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, ...
s, but many other factors are influential. Some conditions that inhibit passivation include high pH for aluminium and zinc, low pH or the presence of
chloride The chloride ion is the anion (negatively charged ion) Cl−. It is formed when the chemical element, element chlorine (a halogen) gains an electron or when a chemical compound, compound such as hydrogen chloride is dissolved in water or o ...
ions for stainless steel, high temperature for titanium (in which case the oxide dissolves into the metal, rather than the electrolyte) and
fluoride Fluoride (). According to this source, is a possible pronunciation in British English. is an Inorganic chemistry, inorganic, Monatomic ion, monatomic Ion#Anions and cations, anion of fluorine, with the chemical formula (also written ), whose ...
ions for silicon. On the other hand, unusual conditions may result in passivation of materials that are normally unprotected, as the alkaline environment of
concrete Concrete is a composite material composed of fine and coarse construction aggregate, aggregate bonded together with a fluid cement (cement paste) that hardens (cures) over time. Concrete is the second-most-used substance in the world after wa ...
does for
steel Steel is an alloy made up of iron with added carbon to improve its strength of materials, strength and fracture toughness, fracture resistance compared to other forms of iron. Many other elements may be present or added. Stainless steels that ...
rebar Rebar (short for reinforcing bar), known when massed as reinforcing steel or reinforcement steel, is a steel bar used as a Tension (physics), tension device in reinforced concrete and reinforced masonry structures to strengthen and aid the concr ...
. Exposure to a liquid metal such as mercury or hot
solder Solder (; North American English, NA: ) is a fusible alloy, fusible metal alloy used to create a permanent bond between metal workpieces. Solder is melted in order to wet the parts of the joint, where it adheres to and connects the pieces afte ...
can often circumvent passivation mechanisms.


Corrosion in passivated materials

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 Pitting corrosion, or pitting, is a form of extremely localized corrosion that leads to the random creation of small holes in metal. The driving power for pitting corrosion is the depassivation of a small area, which becomes anodic (oxidation ...
, crevice corrosion, and
stress corrosion cracking Stress corrosion cracking (SCC) is the growth of crack formation in a corrosion, corrosive environment. It can lead to unexpected and sudden failure of normally ductile metal alloys subjected to a tensile stress, especially at elevated temper ...
.


Pitting corrosion

Certain conditions, such as low concentrations of oxygen or high concentrations of species such as chloride which compete as
anion An ion () is an atom or molecule with a net electric charge, electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be po ...
s, 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 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 In solid mechanics, a stress concentration (also called a stress raiser or a stress riser) is a location in an object where the stress (mechanics), stress is significantly greater than the surrounding region. Stress concentrations occur when the ...
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 environment. 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.


Weld decay and knifeline attack

Stainless steel can pose special corrosion challenges, since its passivating behavior relies on the presence of a major alloying component (
chromium Chromium is a chemical element with the Symbol (chemistry), symbol Cr and atomic number 24. It is the first element in Group 6 element, group 6. It is a steely-grey, Luster (mineralogy), lustrous, hard, and brittle transition metal. Chromium me ...
, at least 11.5%). Because of the elevated temperatures of
welding Welding is a fabrication process that joins materials, usually metals or thermoplastics, by using high heat to melt the parts together and allowing them to cool, causing fusion. Welding is distinct from lower temperature techniques such as b ...
and heat treatment, chromium carbides can form in the
grain boundaries In materials science, a grain boundary is the interface between two grains, or crystallites, in a polycrystalline material. Grain boundaries are two-dimensional crystallographic defect, defects in the crystal structure, and tend to decrease the ...
of stainless alloys. This chemical reaction robs the material of chromium in the zone near the grain boundary, making those areas much less resistant to corrosion. This creates a galvanic couple with the well-protected alloy nearby, which leads to "weld decay" (corrosion of the grain boundaries in the heat affected zones) in highly corrosive environments. This process can seriously reduce the mechanical strength of welded joints over time. A stainless steel is said to be "sensitized" if chromium carbides are formed in the microstructure. A typical microstructure of a normalized type 304 stainless steel shows no signs of sensitization, while a heavily sensitized steel shows the presence of grain boundary precipitates. The dark lines in the sensitized microstructure are networks of chromium carbides formed along the grain boundaries. Special alloys, either with low carbon content or with added carbon "
getter A getter is a deposit of reactive material that is placed inside a vacuum A vacuum is a space devoid of matter. The word is derived from the Latin adjective ''vacuus'' for "vacant" or "Void (astronomy), void". An approximation to such vacuu ...
s" such as titanium and
niobium Niobium is a chemical element with chemical symbol Nb (formerly columbium, Cb) and atomic number 41. It is a light grey, crystalline, and ductile transition metal. Pure niobium has a Mohs scale of mineral hardness, Mohs hardness rating similar ...
(in types 321 and 347, respectively), can prevent this effect, but the latter require special heat treatment after welding to prevent the 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. Crevice corrosion is influenced by the crevice type (metal-metal, metal-non-metal), crevice geometry (size, surface finish), and metallurgical and environmental factors. The susceptibility to crevice corrosion can be evaluated with ASTM standard procedures. A critical crevice corrosion temperature is commonly used to rank a material's resistance to crevice corrosion.


Hydrogen grooving

In the
chemical A chemical substance is a form of matter having constant chemical composition and characteristic properties. Some references add that chemical substance cannot be separated into its constituent Chemical element, elements by physical separation m ...
industry Industry may refer to: Economics * Industry (economics), a generally categorized branch of economic activity * Industry (manufacturing), a specific branch of economic activity, typically in factories with machinery * The wider industrial sect ...
, hydrogen grooving is the corrosion of piping by grooves created by the interaction of a corrosive agent, corroded pipe constituents, and
hydrogen Hydrogen is the chemical element with the Symbol (chemistry), symbol H and atomic number 1. Hydrogen is the lightest element. At standard temperature and pressure, standard conditions hydrogen is a gas of diatomic molecules having the chemical ...
gas Gas is one of the four fundamental states of matter In physics, a state of matter is one of the distinct forms in which matter can exist. Four states of matter are observable in everyday life: solid, liquid, gas, and Plasma (physics), pl ...
bubbles. For example, when
sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid (English in the Commonwealth of Nations, Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen ...
() flows through
steel Steel is an alloy made up of iron with added carbon to improve its strength of materials, strength and fracture toughness, fracture resistance compared to other forms of iron. Many other elements may be present or added. Stainless steels that ...
pipes, the
iron Iron () is a chemical element with Symbol (chemistry), symbol Fe (from la, Wikt:ferrum, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 element, group 8 of the periodic table. It is, Abundance ...
in the steel reacts with the
acid An acid is a molecule or ion capable of either donating a proton (i.e. hydrogen ion, H+), known as a Brønsted–Lowry acid, or forming a covalent bond with an electron pair, known as a Lewis acid A Lewis acid (named for the American p ...
to form a passivation coating of
iron sulfate Iron sulfate may refer to: * Ferrous sulfate, Iron(II) sulfate Iron(II) sulfate (British English British English (BrE, en-GB, or BE) is, according to Oxford Dictionaries, " English as used in Great Britain, as distinct from that used el ...
() and hydrogen gas (). 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 travelling bubble, exposing more steel to the acid: a
vicious cycle A vicious circle (or cycle) is a complex chain of events that reinforces itself through a feedback loop, with detrimental results. It is a system with no tendency toward equilibrium (social Social organisms, including human(s), live collec ...
. The grooving is exacerbated by the tendency of subsequent bubbles to follow the same path.


High-temperature corrosion

High-temperature corrosion is chemical deterioration of a material (typically a metal) as a result of heating. This non-galvanic form of corrosion can occur when a metal is subjected to a hot atmosphere containing oxygen, sulfur, or other compounds capable of oxidizing (or assisting the oxidation of) the material concerned. For example, materials used in aerospace, power generation and even in car engines have to resist sustained periods at high temperature in which they may be exposed to an atmosphere containing potentially highly corrosive products of combustion. 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 both room and high temperatures in hostile conditions. Such high-temperature corrosion products, in the form of
compacted oxide layer glaze Compacted oxide layer glaze describes the often shiny, wear-protective layer of oxide formed when two Metal, metals (or a metal and ceramic) are slid against each other at high temperature in an oxygen-containing atmosphere. The layer forms on eith ...
s, prevent or reduce wear during high-temperature sliding contact of metallic (or metallic and ceramic) surfaces.
Thermal oxidation In microfabrication, thermal oxidation is a way to produce a thin layer of oxide (usually silicon dioxide) on the surface of a wafer (electronics), wafer. The technique forces an oxidizing agent to diffuse into the wafer at high temperature and r ...
is also commonly used as a route towards the obtainment of controlled oxide nanostructures, including
nanowires A nanowire is a nanostructure in the form of a wire with the diameter of the order of a nanometre (10−9 metres). More generally, nanowires can be defined as structures that have a thickness or diameter constrained to tens of nanometers or less ...
and thin films.


Microbial corrosion

Microbial corrosion, or commonly known as microbiologically influenced corrosion (MIC), is a corrosion caused or promoted by
microorganism A microorganism, or microbe,, ''mikros'', "small") and ''organism'' from the el, ὀργανισμός, ''organismós'', "organism"). It is usually written as a single word but is sometimes hyphenated (''micro-organism''), especially in olde ...
s, usually chemoautotrophs. It can apply to both metallic and non-metallic materials, in the presence or absence of oxygen.
Sulfate-reducing bacteria Sulfate-reducing microorganisms (SRM) or sulfate-reducing prokaryotes (SRP) are a group composed of sulfate-reducing bacteria Bacteria (; singular: bacterium) are ubiquitous, mostly free-living organisms often consisting of one biologica ...
are active in the absence of oxygen (anaerobic); they produce
hydrogen sulfide Hydrogen sulfide is a chemical compound with the chemical formula, formula . It is a colorless Chalcogen hydride, chalcogen-hydride gas, and is poisonous, corrosive, and flammable, with trace amounts in ambient atmosphere having a characteristic ...
, causing
sulfide stress cracking Sulfide stress cracking (SSC) is a form of hydrogen embrittlement Hydrogen embrittlement (HE), also known as hydrogen-assisted cracking or hydrogen-induced cracking (HIC), is a reduction in the ductility of a metal due to absorbed hydrogen ...
. In the presence of oxygen (aerobic), some bacteria may directly oxidize iron to iron oxides and hydroxides, other bacteria oxidize sulfur and produce sulfuric acid causing
biogenic sulfide corrosion Biogenic sulfide corrosion is a bacteria Bacteria (; singular: bacterium) are ubiquitous, mostly free-living organisms often consisting of one biological cell. They constitute a large domain of prokaryotic microorganisms. Typically a fe ...
.
Concentration cell In Battery (electricity), battery technology, a concentration cell is a limited form of a galvanic cell that has two equivalent half-cells of the same composition differing only in concentrations. One can calculate the potential developed by such ...
s can form in the deposits of corrosion products, leading to localized corrosion. 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. 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

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 Carbon monoxide (chemical formula CO) is a colorless, poisonous, odorless, tasteless, flammable gas that is slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the simple ...
(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.


Protection from corrosion

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 magnet file:Neodymag.jpg, A Nickel-plated neodymium magnet on a bracket from a hard disk drive file:Nd-magnet.jpg, Nickel-plated neodymium magnet cubes file:Neodymium Crystal Structure Nd2Fe14B.jpg, Left: high-resolution transmission electron microscopy ...
s, which can
spall Spall are fragments of a material that are broken off a larger solid physical object, body. It can be produced by a variety of mechanisms, including as a result of projectile impact, corrosion, weathering, cavitation, or excessive rolling pressu ...
or crumble into powder even in dry, temperature-stable indoor environments unless properly treated to discourage corrosion.


Surface treatments

When surface treatments are used to deter corrosion, great care must be taken to ensure complete coverage, without gaps, cracks, or pinhole defects. Small defects can act as an "
Achilles' heel An Achilles' heel (or Achilles heel) is a weakness in spite of overall strength, which can lead to downfall. While the mythological origin refers to a physical vulnerability, idiomatic references to other attributes or qualities that can lead to ...
", allowing corrosion to penetrate the interior and causing extensive damage even while the outer protective layer remains apparently intact for a period of time.


Applied coatings

Plating Plating is a surface covering in which a metal is deposited on a conductive surface. Plating has been done for hundreds of years; it is also critical for modern technology. Plating is used to decorate objects, for corrosion inhibition, to impr ...
,
paint Paint is any pigmented liquid, liquefiable, or solid mastic composition that, after application to a substrate in a thin layer, converts to a solid film. It is most commonly used to protect, color, or provide texture. Paint can be made in ma ...
ing, and the application of enamel are the most common
anti-corrosion In chemistry Chemistry is the scientific study of the properties and behavior of matter. It is a natural science that covers the elements that make up matter to the compounds made of atoms, molecules and ions: their composition, struct ...
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, 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 Zinc is a chemical element with the Symbol (chemistry), symbol Zn and atomic number 30. Zinc is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 eleme ...
or
cadmium Cadmium is a chemical element with the Symbol (chemistry), symbol Cd and atomic number 48. This soft, silvery-white metal is chemically similar to the two other stable metals in group 12 element, group 12, zinc and mercury (element), mercury. Li ...
. 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. Painting either by roller or brush is more desirable for tight spaces; spray would be better for larger coating areas such as steel decks and waterfront applications. Flexible
polyurethane Polyurethane (; often abbreviated PUR and PU) refers to a class of polymers composed of organic chemistry, organic units joined by carbamate (urethane) links. In contrast to other common polymers such as polyethylene and polystyrene, polyurethan ...
coatings, like Durabak-M26 for example, can provide an anti-corrosive seal with a highly durable slip resistant membrane. Painted coatings are relatively easy to apply and have fast drying times although temperature and humidity may cause dry times to vary. Nowadays, organic coatings made using petroleum based polymer are being replaced with many renewable source based organic coatings. Among various vehicles or binders, polyurethanes are the most explored polymer in such a attempts.


Reactive coatings

If the environment is controlled (especially in recirculating systems),
corrosion inhibitor In chemistry, a corrosion inhibitor or anti-corrosive is a chemical compound that, when added to a liquid or gas, decreases the corrosion rate of a material, typically a metal or an alloy, that comes into contact with the fluid. The effectiveness ...
s 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 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 Hard water is water that has high mineral content (in contrast with "soft water"). Hard water is formed when water percolation, percolates through deposits of limestone, chalk or gypsum, which are largely made up of calcium and magnesium carbona ...
(Roman water systems are famous for their
mineral deposits In geology and mineralogy, a mineral or mineral species is, broadly speaking, a solid chemical compound with a fairly well-defined chemical composition and a specific crystal structure that occurs naturally in pure form.John P. Rafferty, ed. (2 ...
),
chromates Chromate salts contain the chromate anion, . Dichromate salts contain the dichromate anion, . They are oxyanions of chromium in the +6 oxidation state and are moderately strong oxidizing agents. In an aqueous solution, chromate and dichroma ...
,
phosphate In chemistry, a phosphate is an anion, salt (chemistry), salt, functional group or ester derived from a phosphoric acids and phosphates, phosphoric acid. It most commonly means orthophosphate, a derivative of phosphoric acid, orthophosphoric a ...
s,
polyaniline Polyaniline (PANI) is a Conductive polymer, conducting polymer and organic semiconductor of the semi-flexible rod polymer family. The compound has been of interest since the 1980s because of its electrical conductivity and mechanical properties. P ...
, other conducting polymers and a wide range of specially designed chemicals that resemble
surfactant Surfactants are chemical compounds that decrease the surface tension between two liquids, between a gas and a liquid, or interfacial tension between a liquid and a solid. Surfactants may act as detergents, wetting agents, emulsion#Emulsifiers , ...
s (i.e. long-chain organic molecules with ionic end groups).


Anodization

Aluminium alloy An aluminium alloy (or aluminum alloy; see American and British English spelling differences, spelling differences) is an alloy in which aluminium (Al) is the predominant metal. The typical alloying elements are copper, magnesium, manganese, sil ...
s often undergo a surface treatment. Electrochemical conditions in the bath are carefully adjusted so that uniform pores, several
nanometer file:EM Spectrum Properties edit.svg, 330px, Different lengths as in respect to the electromagnetic spectrum, measured by the metre and its derived scales. The nanometre is often used to express dimensions on an atomic scale and mostly in the Mol ...
s 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. Anodizing is very resilient to weathering and corrosion, so it is 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 Panel edge staining is a naturally occurring problem that occurs to anodized aluminium and stainless steel panelling and façades. It is semi-permanent staining that dulls the panel or façade's surface (in particular the edges of the panelling ...
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 A biofilm comprises any syntrophic consortium of microorganisms in which cells stick to each other and often also to a surface. These adherent cells become embedded within a slimy extracellular matrix In biology Biology is the ...
can be used to inhibit mild steel corrosion from
sulfate-reducing bacteria Sulfate-reducing microorganisms (SRM) or sulfate-reducing prokaryotes (SRP) are a group composed of sulfate-reducing bacteria Bacteria (; singular: bacterium) are ubiquitous, mostly free-living organisms often consisting of one biologica ...
.


Controlled permeability formwork

Controlled permeability formwork (CPF) is a method of preventing the corrosion of
reinforcement In behavioral psychology, reinforcement is a consequence applied that will strengthen an organism's future behavior whenever that behavior is preceded by a specific antecedent stimulus. This strengthening effect may be measured as a higher fr ...
by naturally enhancing the durability of the cover during concrete placement. CPF has been used in environments to combat the effects of
carbonation Carbonation is the chemical reaction A chemical reaction is a process that leads to the IUPAC nomenclature for organic transformations, chemical transformation of one set of chemical substances to another. Classically, chemical reactions en ...
, chlorides,
frost Frost is a thin layer of ice on a solid surface, which forms from water vapor in an above-freezing atmosphere coming in contact with a solid surface whose temperature is below freezing, and resulting in a phase transition, phase change from wa ...
and abrasion.


Cathodic protection

Cathodic protection (CP) is a technique to control the corrosion of a metal surface by making it the cathode of an
electrochemical cell An electrochemical cell is a device capable of either generating electrical energy from chemical reactions or using electrical energy to cause chemical reactions. The electrochemical cells which generate an electric current are called voltaic o ...
. Cathodic protection systems are most commonly used to protect steel pipelines and tanks; steel pier piles, ships, and offshore
oil platform An oil platform (or oil rig, offshore platform, oil production platform, and similar terms) is a large structure with facilities to extract and process petroleum and natural gas that lie in rock formations beneath the seabed. Many oil platfor ...
s.


Sacrificial anode protection

For effective CP, the potential of the steel surface is polarized (pushed) more negative until the metal surface has a uniform potential. With a uniform potential, the driving force for the corrosion reaction is halted. For galvanic CP systems, the anode material corrodes under the influence of the steel, and eventually it must be replaced. The
polarization Polarization or polarisation may refer to: Mathematics *Polarization of an Abelian variety, in the mathematics of complex manifolds *Polarization of an algebraic form, a technique for expressing a homogeneous polynomial in a simpler fashion by ...
is caused by the current flow from the anode to the cathode, driven by the difference in
electrode potential In electrochemistry Electrochemistry is the branch of physical chemistry concerned with the relationship between Electric potential, electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, w ...
between the anode and the cathode. The most common sacrificial anode materials are aluminum, zinc, magnesium and related alloys. Aluminum has the highest capacity, and magnesium has the highest driving voltage and is thus used where resistance is higher. Zinc is general purpose and the basis for galvanizing. A number of problems are associated with sacrificial anodes. Among these, from an environmental perspective, is the release of zinc, magnesium, aluminum and heavy metals such as
cadmium Cadmium is a chemical element with the Symbol (chemistry), symbol Cd and atomic number 48. This soft, silvery-white metal is chemically similar to the two other stable metals in group 12 element, group 12, zinc and mercury (element), mercury. Li ...
into the environment including seawater. From a working perspective, sacrificial anodes systems are considered to be less precise than modern cathodic protection systems such as Impressed Current Cathodic Protection (ICCP) systems. Their ability to provide requisite protection has to be checked regularly by means of underwater inspection by divers. Furthermore, as they have a finite lifespan, sacrificial anodes need to be replaced regularly over time.


Impressed current cathodic protection

For larger structures, galvanic anodes cannot economically deliver enough current to provide complete protection. Impressed current cathodic protection (ICCP) systems use anodes connected to a DC power source (such as a
cathodic protection rectifier Cathodic protection (CP; ) is a technique used to control the corrosion Corrosion is a Erosion, natural process that converts a refined metal into a more chemically stable oxide. It is the gradual deterioration of materials (usually a met ...
). Anodes for ICCP systems are tubular and solid rod shapes of various specialized materials. These include high silicon
cast iron Cast iron is a class of iron–carbon alloys with a carbon content more than 2%. Its usefulness derives from its relatively low melting temperature. The alloy constituents affect its color when fractured: white cast iron has carbide impuriti ...
, graphite, mixed metal oxide or platinum coated titanium or niobium coated rod and wires.


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. Anodic protection is an electrochemical method of corrosion protection by keeping metal in passive state


Rate of corrosion

The formation of an oxide layer is described by the
Deal–Grove model The Deal–Grove model mathematically describes the growth of an oxide An oxide () is a chemical compound that contains at least one oxygen atom and one other chemical element, element in its chemical formula. "Oxide" itself is the dianion of ox ...
, which is used to predict and control oxide layer formation in diverse situations. A simple test for measuring corrosion is the weight loss method. 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 calculated as :R = \frac 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.


Economic impact

In 2002, the US
Federal Highway Administration The Federal Highway Administration (FHWA) is a division of the United States Department of Transportation that specializes in highway transportation. The agency's major activities are grouped into two programs, the Federal-aid Highway Program a ...
released a study titled "Corrosion Costs and Preventive Strategies in the United States" on the direct costs associated with metallic corrosion in the US industry. In 1998, the total annual direct cost of corrosion in the U.S. was ca. $276 billion (ca. 3.2% of the US
gross domestic product Gross domestic product (GDP) is a money, monetary Measurement in economics, measure of the market value of all the final goods and services produced and sold (not resold) in a specific time period by countries. Due to its complex and subjec ...
). Broken down into five specific industries, the economic losses are $22.6 billion in infrastructure; $17.6 billion in production and manufacturing; $29.7 billion in transportation; $20.1 billion in government; and $47.9 billion in utilities. Rust is one of the most common causes of bridge accidents. As rust has a much higher volume than the originating mass of iron, its build-up can also cause failure by forcing apart adjacent parts. It was the cause of the collapse of the Mianus River Bridge in 1983, when the bearings rusted internally and pushed one corner of the road slab off its support. Three drivers on the roadway at the time died as the slab fell into the river below. The following
NTSB The National Transportation Safety Board (NTSB) is an Independent agencies of the United States government, independent U.S. government investigative agency responsible for civil transportation accident investigation. In this role, the NTSB inv ...
investigation showed that a drain in the road had been blocked for road re-surfacing, and had not been unblocked; as a result, runoff water penetrated the support hangers. Rust was also an important factor in the
Silver Bridge The Silver Bridge was an eyebar-chain suspension bridge built in 1928 and named for the color of its aluminum Aluminium (aluminum in American and Canadian English Canadian English (CanE, CE, en-CA) encompasses the Variety (l ...
disaster of 1967 in
West Virginia West Virginia is a U.S. state, state in the Appalachian Mountains, Appalachian, Mid-Atlantic (United States), Mid-Atlantic and Southeastern United States, Southeastern regions of the United States.The United States Census Bureau, Census Burea ...
, when a steel
suspension bridge A suspension bridge is a type of bridge in which the deck (bridge), deck is hung below suspension wire rope, cables on vertical suspenders. The first modern examples of this type of bridge were built in the early 1800s. Simple suspension bridg ...
collapsed within a minute, killing 46 drivers and passengers on the bridge at the time. Similarly, corrosion of concrete-covered steel and iron can cause the concrete to
spall Spall are fragments of a material that are broken off a larger solid physical object, body. It can be produced by a variety of mechanisms, including as a result of projectile impact, corrosion, weathering, cavitation, or excessive rolling pressu ...
, creating severe structural problems. It is one of the most common failure modes of
reinforced concrete Reinforced concrete (RC), also called reinforced cement concrete (RCC) and ferroconcrete, is a composite material in which concrete's relatively low tensile strength and ductility are compensated for by the inclusion of reinforcement having ...
bridge A bridge is a structure built to span a physical obstacle (such as a body of water, valley, road, or rail) without blocking the way underneath. It is constructed for the purpose of providing passage over the obstacle, which is usually someth ...
s. 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. 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.


Corrosion in nonmetals

Most
ceramic A ceramic is any of the various hard, brittle, heat-resistant and corrosion-resistant materials made by shaping and then firing an inorganic, nonmetallic material, such as clay, at a high temperature. Common examples are earthenware, porcelain, ...
materials are almost entirely immune to corrosion. The strong
chemical bond A chemical bond is a lasting attraction between atoms or ions that enables the formation of Molecule, molecules and crystals. The bond may result from the Coulomb's law, electrostatic force between oppositely charged ions as in Ionic bonding, ...
s 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 Glass is a non-Crystallinity, crystalline, often transparency and translucency, transparent, amorphous solid that has widespread practical, technological, and decorative use in, for example, window panes, tableware, and optics. Glass is most ...
to reduce its solubility in water; though it is not nearly as soluble as pure
sodium silicate Sodium silicate is a generic name for chemical compounds with the formula or ·, such as sodium metasilicate , sodium orthosilicate , and sodium pyrosilicate . The anions are often polymeric. These compounds are generally colorless transparent ...
, normal glass does form sub-microscopic flaws when exposed to moisture. Due to its
brittle A material is brittle if, when subjected to stress (physics), stress, it fractures with little elastic deformation and without significant plastic deformation. Brittle materials absorb relatively little energy prior to fracture, even those of h ...
ness, such flaws cause a dramatic reduction in the strength of a glass object during its first few hours at room temperature.


Corrosion of polymers

Polymer degradation Polymer degradation is the reduction in the physical properties of a polymer A polymer (; Greek ''wikt:poly-, poly-'', "many" + ''wikt:-mer, -mer'', "part") is a Chemical substance, substance or material consisting of very large molecules c ...
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 Entropy is a scientific concept, as well as a measurable physical property, that is most commonly associated with a state of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodynam ...
can be gained by mixing a given mass of polymer with another substance, making them generally quite difficult to dissolve. While dissolution is a problem in some polymer applications, it is relatively simple to design against. 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 Vinyl may refer to: Chemistry * Polyvinyl chloride (PVC), a particular vinyl polymer * Vinyl cation, a type of carbocation * Vinyl group, a broad class of organic molecules in chemistry * Vinyl polymer, a group of polymers derived from vinyl mo ...
) are intentionally swelled with
plasticizer A plasticizer (British English, UK: plasticiser) is a substance that is added to a material to make it softer and more flexible, to increase its plasticity (physics), plasticity, to decrease its viscosity, and/or to decrease friction during its ...
s, 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 Ionizing radiation (or ionising radiation), including nuclear radiation, consists of subatomic particles or electromagnetic waves that have sufficient energy to ionization, ionize atoms or molecules by detaching electrons from them. Some particles ...
(most commonly
ultraviolet Ultraviolet (UV) is a form of electromagnetic radiation with wavelength from 10 nanometer, nm (with a corresponding frequency around 30 Hertz, PHz) to 400 nm (750 Hertz, THz), shorter than that of visible light, but longer than ...
light),
free radical A daughter category of ''Ageing'', this category deals only with the biological aspects of ageing. Ageing Ailments of unknown cause Biogerontology Biological processes Causes of death Cellular processes Geron ...
s, and
oxidizer An oxidizing agent (also known as an oxidant, oxidizer, electron recipient, or electron acceptor) is a substance in a redox chemical reaction that gains or "Electron acceptor, accepts"/"receives" an electron from a (called the , , or ). In ot ...
s such as oxygen,
ozone Ozone (), or trioxygen, is an inorganic molecule with the chemical formula . It is a pale blue gas with a distinctively pungent smell. It is an allotrope of oxygen that is much less stable than the diatomic Allotropy, allotrope , breaking down i ...
, and
chlorine Chlorine is a chemical element with the Symbol (chemistry), symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate betwee ...
.
Ozone cracking Cracks can be formed in many different elastomers by ozone attack, and the characteristic form of attack of vulnerable rubbers is known as ozone cracking. The problem was formerly very common, especially in tires, but is now rarely seen in those ...
is a well-known problem affecting
natural rubber Rubber, also called India rubber, latex, Amazonian rubber, ''caucho'', or ''caoutchouc'', as initially produced, consists of polymers of the organic compound isoprene, with minor impurities of other organic compounds. Thailand, Malaysia, and ...
for example. Plastic additives can slow these process very effectively, and can be as simple as a UV-absorbing
pigment A pigment is a colored material that is completely or nearly Solubility, insoluble in water. In contrast, dyes are typically soluble, at least at some stage in their use. Generally dyes are often organic compounds whereas pigments are often inorg ...
(e.g.
titanium dioxide Titanium dioxide, also known as titanium(IV) oxide or titania , is the inorganic compound with the chemical formula . When used as a pigment, it is called titanium white, Pigment White 6 (PW6), or Colour Index International, CI 77891. It is a w ...
or
carbon black Carbon black (subtypes are acetylene black, channel black, furnace black, lamp black and thermal black) is a material produced by the Combustion#Incomplete, incomplete combustion of coal and coal tar, vegetable matter, or petroleum products, inc ...
).
Plastic shopping bag Plastic shopping bags, carrier bags, or plastic grocery bags are a type of plastic bag A plastic bag, poly bag, or pouch is a type of container made of thin, flexible, plastic film, nonwoven fabric, or plastic textile. Plastic bags are use ...
s often do not include these additives so that they break down more easily as ultrafine particles of
litter Litter consists of Waste, waste products that have been discarded incorrectly, without consent, at an unsuitable location. Litter can also be used as a verb; to litter means to drop and leave objects, often man-made, such as aluminum cans, pape ...
.


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. Besides its water-resistance, glass is also robust when exposed to certain chemically aggressive liquids or gases. Glass disease is the corrosion of silicate glasses in
aqueous solution An aqueous solution is a Solution (chemistry), solution in which the solvent is water. It is mostly shown in chemical equations by appending (aq) to the relevant chemical formula. For example, a solution of table salt, or sodium chloride (NaCl), ...
s. It is governed by two mechanisms:
diffusion Diffusion is the net movement of anything (for example, atoms, ions, molecules, energy) generally from a region of higher concentration to a region of lower concentration. Diffusion is driven by a gradient in Gibbs free energy or chemical p ...
- controlled leaching (ion exchange) and hydrolytic dissolution of the glass network. Both mechanisms strongly depend on the pH of contacting solution: the rate of ion exchange decreases with pH as 10−0.5pH whereas the rate of hydrolytic dissolution increases with pH as 100.5pH. Mathematically, corrosion rates of glasses are characterized by normalized corrosion rates of elements NR''i'' (g/cm2·d) which are determined as the ratio of total amount of released species into the water M''i'' (g) to the water-contacting surface area S (cm2), time of contact t (days) and weight fraction content of the element in the glass f''i'': :\mathrm_i = \frac. The overall corrosion rate is a sum of contributions from both mechanisms (leaching + dissolution) NR''i''=NR''x''''i''+NR''h''. 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: :\mathrmx_i = 2\rho \sqrt, where t is time, ''D''''i'' is the i-th cation effective diffusion coefficient (cm2/d), which depends on pH of contacting water as ''D''''i'' = D''i''0·10–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): :\mathrmh = \rho r_h , where rh is the stationary
hydrolysis Hydrolysis (; ) is any chemical reaction in which a molecule of water breaks one or more chemical bonds. The term is used broadly for substitution reaction, substitution, elimination reaction, elimination, and solvation reactions in which water ...
(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. 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.


Glass corrosion tests

There exist numerous standardized procedures for measuring the corrosion (also called chemical durability) of glasses in neutral, basic, and acidic environments, under simulated environmental conditions, in simulated body fluid, at high temperature and pressure, and under other conditions. The standard procedure ISO 719International Organization for Standardization, Procedure 719 (1985)
Iso.org (2011-01-21). Retrieved on 2012-07-15. describes a test of the extraction of water-soluble basic compounds under neutral conditions: 2 g of glass, particle size 300–500 μm, is kept for 60 min in 50 mL de-ionized water of grade 2 at 98 °C; 25 mL of the obtained solution is titrated against 0.01 mol/L HCl solution. The volume of HCl required for neutralization is classified according to the table below. 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. Usual glasses are differentiated into the following classes: Hydrolytic class 1 (Type I): This class, which is also called neutral glass, includes
borosilicate glass Borosilicate glass is a type of glass with silicon dioxide, silica and boron trioxide as the main glass-forming constituents. Borosilicate glasses are known for having very low coefficient of thermal expansion, coefficients of thermal expansion ( ...
es (e.g. Duran,
Pyrex Pyrex (trademarked as ''PYREX'' and ''pyrex'') is a brand introduced by Corning Inc. in 1915 for a line of clear, low-thermal-expansion borosilicate glass used for laboratory glassware and kitchenware. It was later expanded to include kitchenwa ...
, Fiolax). Glass of this class contains essential quantities of
boron oxide Boron oxide may refer to one of several oxide An oxide () is a chemical compound that contains at least one oxygen atom and one other chemical element, element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– (molecular) ...
s, 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. Hydrolytic class 2 (Type II): 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 Sodium oxide is a chemical compound with the formula Sodium, Na2Oxygen, O. It is used in ceramics and glasses. It is a white solid but the compound is rarely encountered. Instead "sodium oxide" is used to describe components of various materials ...
and
Calcium oxide Calcium oxide (CaO), commonly known as quicklime or burnt lime, is a widely used chemical compound. It is a white, Caustic (substance), caustic, alkaline, crystalline solid at room temperature. The broadly used term "''lime (material), lime''" co ...
. Hydrolytic class 3 (Type III): 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).


See also

* * * * * * * * * * * * * * * * * * * * * * * * * * *


References


Further reading

* {{Authority control Glass chemistry Metallurgy