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Corrosion
Corrosion
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Corrosion on exposed metal, including a bolt and nut

Corrosion is a natural process that converts a refined metal into a more chemically stable oxide. It is the gradual deterioration of materials (usually a metal) by chemical or electrochemical reaction with their environment. Corrosion engineering is the field dedicated to controlling and preventing corrosion.[1][2]

Riveted connection of elements of the cooling tower of a power plant from 1904. Increased material volume caused by corrosion.

In the most common use of the word, this means electrochemical oxidation of a metal reacting with an oxidant such as oxygen (O2, gaseous or dissolved), or H3O+ ions (H+, hydrated protons) present in aqueous solution. Rusting, the formation of red-orange iron oxides, is perhaps the most familiar example of electrochemical corrosion. This type of corrosion typically produces oxides or salts of the original metal and results in a distinctive coloration. Corrosion can also occur in materials other than metals, such as ceramics or polymers, although, in this context, the term degradation is more common. Corrosion degrades the useful properties of materials and structures including mechanical strength, appearance, and permeability to liquids and gases. Corrosive is distinguished from caustic: the former implies mechanical degradation, the latter chemical.[3]

Many structural alloys 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 phenomenon. During corrosion at a particular spot on the surface of an object made of iron, oxidation takes place and that spot behaves as an anode. The electrons released at this anodic spot move through the metal to another spot on the object and reduce oxygen at that spot in the presence of hydrogen ions (H+, which are believed to be available from carbonic acid (H2CO3) formed by dissolution of atmospheric carbon dioxide or other acidic oxides in the presence of water vapor. This spot then behaves as a cathode.

Galvanic corrosion

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Galvanic corrosion of an aluminium plate occurred when the plate was connected to a mild steel structural support.

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.

Factors such as relative size of anode, types of metal, and operating conditions (temperature, humidity, salinity, etc.) affect galvanic corrosion.[4] The surface area ratio of the anode and cathode directly affects the corrosion rates of the materials. Galvanic corrosion is often prevented by the use of sacrificial anodes.

Galvanic series

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In any given environment (one standard medium is aerated, room-temperature seawater), 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

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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.

Resistance to corrosion

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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 galvanization, cathodic protection, and combinations of these.[5]

Intrinsic chemistry

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Gold nuggets do not naturally corrode, even on a geological time scale.

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 extreme example is graphite, which releases large amounts of energy upon oxidation, but has such slow kinetics that it is effectively immune to electrochemical corrosion under normal conditions.

Passivation

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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, stainless steel, titanium, and silicon.

Passivation is primarily determined by metallurgical and environmental factors. The effect of pH is summarized using Pourbaix diagrams, 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 ions for stainless steel, high temperature for titanium (in which case the oxide dissolves into the metal, rather than the electrolyte) and fluoride 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 does for steel rebar. Exposure to a liquid metal such as mercury or hot solder can often circumvent passivation mechanisms.

It has been shown using electrochemical scanning tunneling microscopy that during iron passivation, an n-type semiconductor Fe(III) oxide grows at the interface with the metal that leads to the buildup of an electronic barrier opposing electron flow and an electronic depletion region that prevents further oxidation reactions. These results indicate a mechanism of "electronic passivation".[6][7][8] The electronic properties of this semiconducting oxide film also provide a mechanistic explanation of corrosion mediated by chloride, which creates surface states at the oxide surface that lead to electronic breakthrough, restoration of anodic currents, and disruption of the electronic passivation mechanism.[9]

Corrosion in passivated materials

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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

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Diagram showing cross-section of 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 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,[10] 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 because it is usually relatively small and may be covered and hidden by corrosion-produced compounds.

Weld decay and knifeline attack

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Normal microstructure of Type 304 stainless steel surface
Sensitized metallic microstructure, showing wider intergranular boundaries

Stainless steel can pose special corrosion challenges, since its passivating behavior relies on the presence of a major alloying component (chromium, at least 11.5%). Because of the elevated temperatures of welding and heat treatment, chromium carbides can form in the grain boundaries 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 "getters" such as titanium and niobium (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

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Corrosion in the crevice between the tube and tube sheet (both made of type 316 stainless steel) of a heat exchanger in a seawater desalination plant

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[further explanation needed] 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

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In the chemical industry, hydrogen grooving is the corrosion of piping at grooves created by the interaction of a corrosive agent, corroded pipe constituents, and hydrogen gas bubbles.[11] 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 can be formed by a travelling bubble, exposing more steel to the acid, causing a vicious cycle. The grooving is exacerbated by the tendency of subsequent bubbles to follow the same path.

High-temperature corrosion

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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 ("sulfidation"), 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 must resist sustained periods at high temperature, during which they may be exposed to an atmosphere containing the potentially highly-corrosive products of combustion.

Some 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 glazes, prevent or reduce wear during high-temperature sliding contact of metallic (or metallic and ceramic) surfaces. Thermal oxidation is also commonly used to produce controlled oxide nanostructures, including nanowires and thin films.

Microbial corrosion

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Microbial corrosion, or commonly known as microbiologically influenced corrosion (MIC), is a corrosion caused or promoted by microorganisms, usually chemoautotrophs. It can apply to both metallic and non-metallic materials, in the presence or absence of oxygen. Sulfate-reducing bacteria are active in the absence of oxygen (anaerobic); they produce hydrogen sulfide, causing sulfide stress cracking. 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. Concentration cells 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.[12] 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

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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.

Protection from corrosion

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The US military shrink-wraps equipment such as helicopters to protect them from corrosion, thus saving millions of dollars

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.

Surface treatments

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When surface treatments are used to reduce 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 extensive damage even while the outer protective layer remains apparently intact for a period of time.

Applied coatings

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Galvanized surface
Corroding steel gantry on an electrified railway line

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, 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.

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 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.

Reactive coatings

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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 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 systems are known 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

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This climbing descender is anodized with a yellow finish.

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.

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 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

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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.[13]

Controlled permeability formwork

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Controlled permeability formwork (CPF) is a method of preventing the corrosion of reinforcement by naturally enhancing the durability of the cover during concrete placement. CPF has been used in environments to combat the effects of carbonation, chlorides, frost, and abrasion.

Cathodic protection

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Cathodic protection (CP) is a technique to control the corrosion of a metal surface by making it 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.

Sacrificial anode protection

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Sacrificial anode attached to the hull of a ship

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 is caused by the current flow from the anode to the cathode, driven by the difference in electrode potential 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 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.[14]

Impressed current cathodic protection

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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). Anodes for ICCP systems are tubular and solid rod shapes of various specialized materials. These include high silicon cast iron, graphite, mixed metal oxide or platinum coated titanium or niobium coated rod and wires.

Anodic protection

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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

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These neodymium magnets corroded extremely rapidly after only five months of outside exposure

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.[15] 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

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

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The collapsed Silver Bridge, as seen from the Ohio side

In 2002, the US Federal Highway Administration 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 US roughly $276 billion (or 3.2% of the US gross domestic product at the time).[16] 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.[17]

Rust is one of the most common causes of bridge accidents. As rust displaces a much higher volume than the originating mass of iron, its build-up can also cause failure by forcing apart adjacent components. It was the cause of the collapse of the Mianus River Bridge in 1983, when support 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 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 disaster of 1967 in West Virginia, when a steel suspension bridge collapsed within a minute, killing 46 drivers and passengers who were on the bridge at the time.

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.[18] The economic impact on homeowners, condo dwellers, and the public infrastructure is estimated at $22 billion as the insurance industry braces for a wave of claims due to pipe failures.

Corrosion in nonmetals

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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.

Corrosion of polymers

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Ozone cracking in natural rubber tubing

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 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) 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

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Glass corrosion

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 pharmaceutical industry since most medicines are preserved in a watery solution.[19] 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 solutions. It is governed by two mechanisms: diffusion-controlled leaching (ion exchange) and hydrolytic dissolution of the glass network.[20] 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.[21]

Mathematically, corrosion rates of glasses are characterized by normalized corrosion rates of elements NRi (g/cm2·d) which are determined as the ratio of total amount of released species into the water Mi (g) to the water-contacting surface area S (cm2), time of contact t (days), and weight fraction content of the element in the glass fi:

.

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 ith 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.[22] 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 to 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

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Effect of addition of a certain glass component on the chemical durability against water corrosion of a specific base glass (corrosion test ISO 719).[23]

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,[24] and under other conditions.

The standard procedure ISO 719[25] 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.

Amount of 0.01M HCl needed to neutralize extracted basic oxides, mL Extracted Na2O
equivalent, μg
Hydrolytic
class
< 0.1 < 31 1
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
> 3.5 > 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.

Usual glasses are differentiated into the following classes:

  • Hydrolytic class 1 (Type I): 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.
  • 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 and calcium oxide.
  • 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

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References

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Further reading

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Revisions and contributorsEdit on WikipediaRead on Wikipedia
from Grokipedia
Corrosion is the deterioration of a metal or due to chemical reactions with its environment, resulting in the loss of material properties such as strength and appearance. This process primarily occurs through electrochemical mechanisms, where oxidation at anodic sites on the metal surface leads to the release of electrons, coupled with reduction reactions at cathodic sites, often involving oxygen or other environmental . Metals corrode because they are thermodynamically unstable in most environments, tending to revert to their more stable oxidized forms, such as ores, driven by a decrease in free energy. The kinetics of corrosion are influenced by factors like temperature, pH, and the presence of electrolytes, which accelerate the rate of electron transfer and ion diffusion. Common forms include uniform corrosion, which evenly degrades the surface; galvanic corrosion, occurring when dissimilar metals are in electrical contact in an electrolyte; and pitting corrosion, which creates localized deep holes. A classic example is the rusting of iron in the presence of water and oxygen, forming hydrated iron(III) oxide, which weakens structures like bridges and vehicles. Other notable cases include the tarnishing of silver to silver sulfide and the development of a protective patina on copper, as seen on the Statue of Liberty. Corrosion poses significant economic and safety challenges, costing approximately $2.5 trillion globally each year in maintenance and replacement, particularly in sectors like , marine, and . Prevention strategies include the use of protective coatings like or with , alloying with elements such as to form passive oxide layers (e.g., in ), and via sacrificial anodes. These methods disrupt the by isolating the metal from the environment or shifting the corrosion to a more reactive material.

Fundamentals of Corrosion

Definition and Overview

Corrosion is the deterioration of a , usually a metal, resulting from a chemical or electrochemical reaction with its environment, leading to the degradation of physical properties and functionality. This process involves the interaction of the with substances like oxygen, , or acids, often producing compounds such as oxides or salts that weaken the structure. While primarily affecting metals and alloys, corrosion can occur under specific conditions in certain environments. The rusting of iron, a classic example of corrosion, has been observed since ancient times, as seen in archaeological iron artifacts that exhibit layers from environmental exposure. A pivotal advancement in understanding corrosion occurred in 1824, when British chemist Sir demonstrated its electrochemical nature through experiments on protecting copper-sheathed ships from seawater degradation, laying the groundwork for modern corrosion science. These early insights highlighted corrosion as an inevitable consequence of metals' thermodynamic instability in natural settings, where they tend to revert to more stable ore-like states. Common manifestations include rusting, where iron forms hydrated iron(III) oxide in the presence of moisture and oxygen, and tarnishing, such as the black silver sulfide layer on silver exposed to sulfur-containing air. Corrosion occurs across diverse environments, including aqueous media like seawater, atmospheric conditions with pollutants and humidity, and soil with varying pH and moisture levels. Unlike erosion, which involves mechanical wear from particle abrasion or fluid flow, or general wear from friction, corrosion is fundamentally a chemical or electrochemical degradation without direct mechanical forces. In everyday life, corrosion manifests as on accelerated by road salts in winter, compromising and longevity, or as the gradual decay of like bridges and pipelines, where unchecked oxidation leads to structural failures. These impacts underscore corrosion's broad relevance, influencing industries from transportation to by necessitating protective measures to mitigate material loss.

Electrochemical Principles

Corrosion is fundamentally an electrochemical process that occurs in the presence of an , where the deterioration of a metal involves the transfer of electrons from one region of the surface () to another (). At the , oxidation takes place, in which metal atoms lose electrons to form positively charged ions, effectively dissolving the metal into the . Simultaneously, at the , a reduction reaction consumes these electrons, often involving from the environment such as oxygen or ions. This anodic-cathodic coupling ensures that the overall process is electrically neutral, with electrons flowing through the metal and ions migrating through the to complete the circuit. The key half-cell reactions define the specific chemistry of corrosion. For iron, a common example, the anodic reaction is the oxidation of the metal: FeFe2++2e\text{Fe} \rightarrow \text{Fe}^{2+} + 2\text{e}^- This releases ferrous ions into the solution. The corresponding cathodic reaction depends on the environmental conditions; in neutral or alkaline aerated solutions, it is typically the reduction of oxygen: O2+2H2O+4e4OH\text{O}_2 + 2\text{H}_2\text{O} + 4\text{e}^- \rightarrow 4\text{OH}^- In acidic environments, hydrogen evolution predominates: 2H++2eH22\text{H}^+ + 2\text{e}^- \rightarrow \text{H}_2 These reactions form the basis of corrosion cells, requiring three essential elements: an anode and cathode connected by a metallic path for electron conduction, and an electrolyte to facilitate ion transport. The metallic path, often the metal substrate itself, allows electrons to flow from anodic to cathodic sites, while the electrolyte—such as water containing dissolved salts—enables the movement of ions to balance charge. Without any of these, the cell cannot operate, preventing corrosion. Pourbaix diagrams provide a thermodynamic framework for predicting the stability of metal ions and their corrosion products as a function of pH and electrode potential. These diagrams plot potential (E, in volts versus the standard hydrogen electrode) against pH, delineating regions where the metal is immune (stable), corrodes (dissolves as ions), or passivates (forms protective oxides). For instance, in the iron-water system at 25°C, corrosion occurs in acidic conditions below approximately -0.6 V, while passivation dominates in neutral to alkaline pH with oxide layers like Fe₂O₃. The boundaries are derived from the Nernst equation and Gibbs free energy data, with water stability limits (hydrogen evolution at lower potentials and oxygen evolution at higher) marking the edges. These diagrams are invaluable for forecasting corrosion susceptibility without kinetic considerations. Mixed potential theory explains the kinetics of corrosion by treating the corroding as a superposition of independent anodic and cathodic processes reaching a steady-state mixed potential. At this corrosion potential (E_corr), the anodic equals the cathodic , resulting in zero net current. Evans diagrams visualize this by plotting logarithmic against potential, showing the intersection of anodic and cathodic polarization curves. The anodic curve typically follows the for activation control, while the cathodic may exhibit limits, such as oxygen reduction plateaus. This graphical approach quantifies corrosion rates; for example, shifting the cathodic curve (e.g., via deaeration) alters E_corr and increases the anodic dissolution rate, illustrating kinetic dependencies.

Factors Influencing Corrosion Rate

The rate of corrosion is profoundly influenced by both environmental and material factors, which dictate the kinetics of the electrochemical processes involved. Environmental variables such as , , oxygen availability, and the presence of aggressive ions play critical roles in accelerating or mitigating the degradation of metallic materials. Similarly, intrinsic of the material, including its composition, microstructure, and surface state, determine susceptibility to corrosive attack. Understanding these factors is essential for predicting corrosion behavior across diverse conditions. Among environmental factors, exerts a dominant effect on corrosion kinetics, often following an Arrhenius relationship where the rate increases exponentially with rising due to enhanced reaction rates and mobility. For many systems, such as mild in acidic media, the corrosion rate approximately doubles for every 10°C increase, reflecting the barrier in the anodic and cathodic reactions. The of the also significantly impacts the rate; in acidic environments (low ), the increased availability of H⁺ ions accelerates the cathodic reduction, leading to higher dissolution rates for metals like , whereas neutral or alkaline conditions (higher ) can promote passivation and reduce rates. For instance, in CO₂-saturated solutions, corrosion rates of mild at 4.0 are higher than those at 6.0 due to this mechanism. Oxygen concentration further modulates the corrosion rate by influencing the cathodic reaction, particularly in aerobic environments where O₂ acts as the primary depolarizer; higher dissolved oxygen levels elevate the corrosion current, as seen in systems where rates increase proportionally with O₂ up to saturation points. In low-oxygen settings, such as deaerated waters, rates drop markedly, though residual oxygen can still sustain localized attack. Pollutants, exemplified by chloride s (Cl⁻), exacerbate corrosion by disrupting passive films and promoting pitting or uniform attack; in , Cl⁻ penetration thresholds as low as 0.3% by weight of can initiate rapid reinforcement corrosion by adsorbing to layers and facilitating ingress. This effect is pronounced in marine or industrial atmospheres, where Cl⁻ concentrations accelerate rates by orders of magnitude compared to chloride-free conditions. Material factors are equally pivotal, with alloy composition altering the thermodynamic stability and kinetics of corrosion. Additions of elements like (≥12 wt%) in stainless steels form protective Cr₂O₃ layers, reducing rates by promoting passivation, while higher content in alloys like enhances resistance in acidic media. Microstructure influences localized susceptibility; for example, in carbon steels, pearlitic phases corrode faster than ferritic ones due to galvanic between carbide lamellae and matrix, increasing overall rates in CO₂ environments. Uniform microstructures, as in heat-treated alloys, minimize such couples and lower rates by fostering coherent oxide films. Surface condition, including roughness and cleanliness, affects initial attack; rougher surfaces (higher Ra values) trap electrolytes and increase active area, elevating rates in both stagnant and flowing conditions, with studies on low-carbon showing up to 50% higher corrosion in turbulent flows over polished surfaces. Corrosion rates are quantified using standardized units to enable comparison and prediction. Penetration rates are commonly expressed in millimeters per year (mm/year) for practical engineering assessments, while electrochemical metrics like the corrosion current density (i_corr) in amperes per square centimeter (A/cm², often microamperes per cm²) provide kinetic insights from polarization . The describes the relationship in overpotential (η) and current density (i) for high overpotentials, allowing extrapolation of i_corr from linear regions of polarization curves: η=a+blogi\eta = a + b \log i Here, a is the Tafel intercept (related to exchange current), and b is the Tafel slope (typically 0.06–0.12 V/decade), reflecting charge transfer kinetics. This equation underpins techniques like Tafel extrapolation for rate determination. To link electrochemical measurements to material loss, Faraday's quantifies mass loss (m) from the total charge passed (I t), incorporating the (M), number of electrons transferred (n), and Faraday's constant (F = 96,485 C/mol): m=ItMnFm = \frac{I t M}{n F} This relation, applied to integrated corrosion currents, predicts mass loss in grams, convertible to penetration rates; for example, an i_corr of 10 μA/cm² for iron (n=2, M=55.85 g/mol) yields approximately 0.12 mm/year. Synergistic effects arise when multiple factors interact to amplify rates beyond additive contributions, notably in flow-accelerated scenarios like , where fluid velocity removes protective films and enhances mass transport, increasing total loss by 2–5 times the sum of pure and corrosion components. In pipes, velocities exceeding 3 m/s in chloride-laden waters can elevate rates through this interplay, emphasizing the need for integrated assessments.

Types of Corrosion

Uniform Corrosion

Uniform corrosion, also known as general corrosion, is the most common form of corrosion characterized by a uniform attack across the entire exposed surface of a metal, resulting in even material thinning without localized penetration. This process occurs through electrochemical reactions where anodic dissolution of the metal (oxidation) is balanced by cathodic reactions, such as hydrogen evolution or oxygen reduction, distributed uniformly over the surface. The metal acts as a single electrode supporting both half-reactions, leading to a consistent recession of the surface rather than concentrated damage. A classic example is the rusting of unprotected exposed to atmospheric or aqueous environments, where the iron oxidizes evenly to form a layer of ( hydrate), gradually reducing the material thickness. Another representative case is the dissolution of in acidic solutions, such as , where the metal surface erodes uniformly due to the reaction with ions. Unlike localized corrosion forms, uniform corrosion does not produce pits or deep penetrations, allowing for straightforward assessment of material loss as a general surface thinning. The rate of uniform corrosion is typically quantified using weight loss methods, as outlined in ASTM G1, which involves exposing a test specimen to the corrosive environment, cleaning it to remove corrosion products, measuring the mass loss, and calculating the penetration rate in units such as mils per year (mpy) or millimeters per year (mm/y). The formula for corrosion rate CRCR based on ΔW\Delta W (in milligrams), exposure time tt (in hours), specimen area AA (in cm²), and metal ρ\rho (in g/cm³) is given by: CR=ΔW×KA×t×ρCR = \frac{\Delta W \times K}{A \times t \times \rho} where K=3.45×103K = 3.45 \times 10^3 for mpy or K=87.6K = 87.6 for mm/y, providing a reliable metric for even attack. This uniformity offers predictability in engineering design, enabling corrosion allowances to be incorporated into material thickness calculations to account for expected thinning over the service life, thus ensuring structural integrity without overdesign. For instance, if a predicted uniform corrosion rate is 0.1 mm/y, designers can add an extra thickness margin to maintain minimum required dimensions.

Galvanic Corrosion

Galvanic corrosion occurs when two dissimilar metals are electrically connected in the presence of an , forming an that accelerates the corrosion of the more anodic metal. In this process, the metal with the more negative acts as the , where oxidation occurs, leading to preferential dissolution, while the more cathodic metal serves as the , where reduction reactions take place and experiences protection from corrosion. This mechanism is driven by the flow of electrons from the anode to the cathode through the metallic path, with ions moving through the electrolyte to complete the circuit. The driving force behind is the potential difference between the two metals, quantified using the (EMF) series, which ranks metals and alloys based on their standard electrode potentials in a given environment. This difference creates a galvanic current that sustains the corrosion reaction until the anodic material is depleted or the circuit is interrupted. For instance, in applications like aircraft construction, rivets fastened into aluminum structures can lead to rapid pitting and degradation of the aluminum due to its more anodic nature relative to . Similarly, intentional galvanic setups, such as coatings on ship hulls, exploit this principle for , where the sacrificially corrodes to shield the underlying . In marine environments, galvanic corrosion is particularly pronounced due to the conductive nature of seawater acting as the electrolyte. A notable case involves the coupling of copper alloys, such as brass or bronze propellers, with carbon steel hulls on ships, where the steel anode corrodes at rates up to several millimeters per year, leading to structural weakening and requiring frequent maintenance. Studies on such couples in simulated seawater have shown corrosion rates increasing with the cathode-to-anode area ratio, emphasizing the need for design considerations in naval architecture. Basic prevention strategies include avoiding direct contact between dissimilar metals by selecting compatible materials or inserting non-conductive insulators like gaskets or coatings, though comprehensive protection methods are addressed in dedicated sections on corrosion mitigation.

Pitting Corrosion

is a form of localized corrosion that results in the formation of small cavities or pits on the metal surface, particularly in materials that form a protective passive film, such as stainless steels and aluminum alloys. This type of corrosion is highly dangerous because the pits can penetrate deeply into the metal while the surrounding surface appears relatively unaffected, leading to unexpected structural failure. It typically occurs in environments containing aggressive anions like chloride ions, which disrupt the passive film integrity. The mechanism of pitting corrosion begins with the initiation phase, where chloride ions adsorb onto the passive film and penetrate it, accumulating at the metal-film interface and causing local lattice expansion and structural inhomogeneity. This penetration leads to a breakdown of the passive film at vulnerable sites, such as inclusions or defects, allowing localized metal dissolution. Once initiated, the pit grows autocatalytically: the dissolution of metal ions inside the pit hydrolyzes to produce hydrogen ions, drastically lowering the local (often to 1-2) and enriching chloride concentration, which further dissolves the protective film cover and accelerates corrosion. The low environment sustains the aggressive conditions, preventing repassivation and promoting continued pit deepening. Pitting corrosion progresses through distinct stages, starting with metastable pits, which are small (micron-scale) transient events that form below the pitting potential and last only seconds before repassivating due to insufficient aggressive conditions. In contrast, stable pits develop when the potential exceeds the , allowing sustained growth without repassivation; these pits can reach the repassivation potential only after significant depth is achieved. Repassivation occurs at a lower potential than pit initiation, influenced by factors like pit geometry and composition, effectively halting further propagation if conditions shift. Representative examples of pitting corrosion include its occurrence on exposed to , where ions from the marine environment initiate pits at manganese inclusions, compromising the passive layer. Similarly, aluminum alloys suffer pitting when exposed to deicing salts containing , which infiltrate soil or runoff and attack the natural film, leading to localized penetration in infrastructure like culverts. Detection methods for pitting corrosion often rely on electrochemical noise analysis, which monitors fluctuations in potential and current to identify transient events associated with pit initiation and growth, distinguishing pitting from uniform corrosion. Salt spray tests, such as those specified in ASTM B117, simulate chloride-rich environments to accelerate and visually assess pit formation on coated or uncoated metals, providing a standardized evaluation of susceptibility. The consequences of pitting corrosion are severe, as pits can cause of thin-walled components, allowing leakage in pipelines or vessels, and act as stress concentrators that initiate cracks under mechanical loading, ultimately leading to .

Crevice Corrosion

Crevice corrosion is a form of localized corrosion that occurs within confined spaces or crevices on metal surfaces, where the restricts the flow of oxygen and , leading to accelerated attack compared to surrounding areas. This phenomenon is particularly prevalent in chloride-containing environments, such as , and affects materials like stainless steels and nickel-based alloys. Unlike uniform corrosion, it results in deep, narrow cavities that can compromise structural integrity without visible external signs. The mechanism of begins with differential aeration: oxygen is rapidly depleted inside the crevice due to limited , establishing it as an anodic site where metal dissolution occurs, while the external surface acts as a cathodic site for oxygen reduction. As metal ions hydrolyze within the crevice, the local drops significantly (often to 2-3), and ions concentrate to maintain electroneutrality, creating an aggressive, autocatalytic environment that depassivates the protective film. This process, described in the critical crevice solution theory, stabilizes once the product of crevice depth (x) and (i) exceeds a critical value, allowing propagation. plays a crucial role, with narrow gaps (typically 0.1–100 μm) and sufficient depth promoting stagnation and ion buildup; a critical crevice depth of at least 0.025 mm is often required for initiation in testing scenarios. Common examples include corrosion under gaskets or seals, within bolt threads, and beneath surface deposits on components exposed to marine or industrial atmospheres. In such sites, like incomplete welds in or assemblies on coastal structures, the confined spaces trap and salts, exacerbating the attack. To evaluate susceptibility, standardized testing employs ASTM G78, which outlines procedures for immersing iron- and nickel-base in or solutions using multiple crevice assemblies to simulate confined geometries and measure maximum attack depth after 30 days. This guide emphasizes factors like crevice former materials and environmental conditions to rank resistance reliably. Crevice corrosion differs from pitting in that it requires physical confinement for initiation via oxygen depletion and limitations, rather than direct passive breakdown often triggered by localized factors like ions on open surfaces; while propagation mechanisms are similar, crevice attack typically initiates more slowly but at lower critical temperatures (20–50°C below pitting thresholds).

Intergranular Corrosion

Intergranular corrosion is a form of localized attack that preferentially occurs along the grain boundaries of polycrystalline metals, particularly in alloys like austenitic stainless steels, where it leads to rapid degradation without significant overall material loss. The primary mechanism involves the depletion of key alloying elements, such as , at grain boundaries due to the formation of chromium carbides (Cr23C6) during exposure to specific temperature ranges, typically 425–870 °C, rendering these zones anodic and susceptible to corrosive media. This process creates chromium-depleted regions with reduced passivation ability, promoting anodic dissolution along the boundaries while the grain interiors remain relatively protected. In welding applications, manifests as weld decay, where the (HAZ) adjacent to the weld experiences from transient heating in the critical temperature range, leading to carbide precipitation and chromium depletion parallel to the weld bead. This form of attack is particularly problematic in unstabilized austenitic stainless steels like Type 304, as the uneven heating during welding exacerbates boundary precipitation without allowing full homogenization. Stabilized alloys, such as Type 321 stainless steel containing , are designed to mitigate by forming titanium carbides that preferentially bind carbon, but they can still suffer from knifeline attack—a narrow band of at the weld fusion line. This occurs because high temperatures dissolve existing stabilizers, and upon cooling through the sensitizing range, carbon competes with titanium for , resulting in localized depletion at the knifeline. Another variant is hydrogen grooving in austenitic s, where absorbed facilitates intergranular cracking and grooving along boundaries, often under combined environmental and mechanical influences, by promoting decohesion and accelerating anodic attack in sensitized regions. Practical examples include failures in piping systems made of sensitized Type 304 or 347 , where intergranular attack in the HAZ led to leaks and operational shutdowns after exposure to corrosive process fluids like or chlorides. Susceptibility to intergranular corrosion is commonly assessed using ASTM A262 standard practices, which include oxalic acid etching for screening and copper-copper (Strauss test) for confirmation of attack depth in sensitized austenitic s. Prevention often relies on low-carbon variants or post-weld heat treatments to restore passivation and minimize boundary depletion.

Stress Corrosion Cracking

Stress corrosion cracking (SCC) is a brittle mechanism in metals and alloys that arises from the synergistic interaction of tensile stress—either applied or residual—and exposure to a specific corrosive environment, resulting in the and of cracks without significant overall loss. This process often leads to sudden, under conditions where the material would otherwise be ductile, distinguishing it from purely mechanical or uniform corrosion processes. The primary mechanism of SCC involves anodic dissolution at the crack tip, where localized corrosion accelerates under the influence of stress, promoting crack advancement. According to the film rupture theory, a protective passive film on the metal surface ruptures due to tensile strain, exposing fresh metal to the corrosive medium and initiating localized anodic dissolution; subsequent repassivation occurs, but repeated ruptures under ongoing stress allow the crack to propagate. This electrochemical process is strain-rate dependent, with crack growth rates typically ranging from 10^{-10} to 10^{-6} m/s in susceptible systems. Susceptibility to SCC varies by and environment, with notable examples including chloride-induced cracking in austenitic stainless steels, where concentrations above 20-50 ppm Cl^- at temperatures exceeding 50°C can trigger transgranular cracks in types 304 and 316. In high-strength steels, such as those with yield strengths over 1000 MPa, contributes to SCC, where atomic generated by corrosion diffuses into the lattice, reducing and facilitating intergranular or quasi-cleavage in moist environments or under . Another critical case is sulfide stress cracking in sour gas environments containing H2S, affecting carbon and low- steels, where partial pressures as low as 0.05 psia H2S promote cracking at pH 3-4 and temperatures up to 80°C. Crack propagation in SCC exhibits a threshold stress intensity factor, K_{ISCC}, below which cracks do not advance; typical values range from 5-30 MPa√m depending on the alloy-environment pair, such as 10-20 MPa√m for austenitic stainless steels in chlorides. Fracture paths can be transgranular, following slip planes in face-centered cubic metals like austenitic steels, or intergranular, along grain boundaries in body-centered cubic steels, influenced by environmental chemistry and microstructure. Standard testing methods for SCC susceptibility include slow strain rate testing per ASTM G129, which applies a controlled extension rate (e.g., 10^{-6} to 10^{-8} s^{-1}) in the corrosive environment to measure metrics like elongation reduction and time-to-failure compared to air-exposed controls. approaches, using precracked specimens under constant , determine K_{ISCC} and crack growth rates, while NACE TM0177 outlines specific protocols for H2S environments, including tensile and bent-beam tests to qualify materials for sour service.

Erosion Corrosion

Erosion corrosion is a form of material degradation that occurs when the mechanical action of a moving corrosive fluid or removes or damages protective surface , thereby accelerating the underlying electrochemical corrosion process. This combined effect is particularly prevalent in systems involving high-velocity flows, such as pipelines, pumps, and valves, where the between and corrosion can increase material loss rates by up to 50 times compared to either process alone in certain materials like grey . The mechanism involves the fluid's abrasive action—often enhanced by , , or —disrupting passive layers on metals, exposing fresh substrate to corrosive attack, and abrading away corrosion products that might otherwise form a barrier. A key aspect of the in corrosion is the mutual enhancement: exposes new metal surfaces that corrode more rapidly, while corrosion weakens the material, making it more susceptible to mechanical removal by the flow. This interaction is quantified in standards like ASTM G119-93, which distinguishes -enhanced corrosion (ΔE_c) from corrosion-enhanced (ΔC_e), with positive dominating in aggressive environments. Common examples include the formation of grooves and pits in at pipe bends due to turbulent impingement attack from high-velocity flows, and damage in pump impellers where collapsing vapor bubbles generate localized high-pressure impacts that strip protective films. In marine applications, such as ship propellers and rudders made from nickel-aluminium , exposure to with entrained particulates leads to accelerated degradation through this mechanism. Flow regimes play a critical role, with laminar flows generally causing less damage due to smoother transport, while turbulent flows increase rates and impingement forces, often initiating sudden corrosion rate increases. thresholds vary by and ; for instance, velocities exceeding 5 ft/s (1.5 m/s) in systems can trigger corrosion in , whereas copper-nickel alloys tolerate up to 15 ft/s (4.6 m/s) in before significant film removal occurs. Mitigation strategies focus on enhancing resistance through harder alloys or coatings that maintain integrity under flow, such as high-velocity oxygen (HVOF) applied for pumps, and design modifications like rounding pipe edges to reduce and impingement. Increasing hardness, as seen in friction stir-processed composites with reinforcement, also forms more durable oxide films to counter film removal.

High-Temperature Corrosion

High-temperature corrosion encompasses the chemical degradation of metals and alloys through reactions with gaseous environments at elevated temperatures, often exceeding 400°C, as encountered in industrial furnaces, gas turbines, and boilers. These processes differ from ambient-temperature corrosion by relying on direct gas-solid interactions rather than electrolytes, leading to the formation of surface scales that can either protect or accelerate material loss. The primary reactions involve oxidation by oxygen or , but contaminants like and carbon introduce additional degradation modes, compromising structural integrity and efficiency in high-performance applications. A key mechanism in high-temperature corrosion is the formation of oxide scales, where the metal reacts with oxygen to produce a layer whose growth is governed by of ions and electrons across the scale. This process typically adheres to the parabolic growth law, expressed as x2=ktx^2 = k t where xx is the oxide thickness, kk is the temperature-dependent rate constant, and tt is exposure time; the parabolic nature reflects decreasing growth rates as the scale thickens, limiting further . Carl Wagner's theory underpins this behavior, modeling oxidation as a diffusion-controlled process in a compact scale, with of cations, anions, and electrons through point defects driving growth under local equilibrium at the scale interfaces. The theory assumes that interface reactions are faster than bulk , resulting in the observed parabolic kinetics for many pure metals and alloys.[](https://home.agh.edu.pl/~grzesik/FHTC/6_Wagner%20 theory%20of%20metal%20oxidation.pdf) Common types of high-temperature corrosion include gaseous oxidation, carburization, and sulfidation. Gaseous oxidation involves direct reaction with oxygen or to form metal oxides, often protective if adherent and slow-growing. Carburization occurs when metals absorb carbon from environments rich in CO, CH₄, or other hydrocarbons, forming internal carbides that embrittle the material and reduce . Sulfidation, typically more aggressive than oxidation, arises from exposure to sulfur-bearing gases like H₂S or SO₂, producing non-adherent scales with higher growth rates and leading to rapid metal wastage. Illustrative examples highlight the practical impacts: in gas turbine blades, Ni-based superalloys face oxidation and sulfidation in hot gases containing O₂ and SO₂ at around 900°C, forming alumina or scales but risking and degradation after prolonged cyclic exposure. tubes in power plants, operating in supercritical at 700–760°C, undergo oxidation where initial layers provide protection, yet chromium volatilization as CrO₂(OH)₂ above 700°C causes depletion and accelerated internal oxidation. Resistance to these processes is enhanced through strategic alloying, particularly with and aluminum, which promote selective formation of stable scales. additions of 16–20 wt% enable chromia (Cr₂O₃) scale development below 1000°C, serving as an effective oxygen barrier in Ni-based alloys; however, its volatility limits utility at higher temperatures. Aluminum, at 5–15 wt%, fosters alumina (Al₂O₃) scales above 900°C, offering superior thermodynamic stability and minimal growth rates due to low defect concentrations, thus extending service life in severe conditions. In Ni-superalloys for applications, combined Cr and Al alloying ensures continuous protective layers, mitigating carburization and sulfidation as well.

Microbial Corrosion

Microbial corrosion, also known as microbiologically influenced corrosion (MIC), refers to the deterioration of metals accelerated by the metabolic activities of microorganisms, primarily through the modification of electrochemical reactions at the metal surface. Unlike purely abiotic processes, MIC involves biofilms that create localized environments conducive to corrosion, often leading to pitting or formation. A primary mechanism of MIC involves sulfate-reducing bacteria (SRB), such as species, which reduce ions to (H₂S) under anaerobic conditions, using or as electron donors. The produced H₂S reacts with metal ions to form insoluble sulfides, like , which deposit on the surface and enhance cathodic reactions, thereby accelerating anodic metal dissolution. Another key mechanism is driven by acid-producing bacteria (APB), including species like Acidithiobacillus, which generate organic acids such as acetic or through metabolic processes, locally lowering the pH to values as low as 2-4 and dissolving protective oxide layers on metals. Biofilms, composed of microbial communities embedded in extracellular polymeric substances, play a central role in MIC by forming heterogeneous layers on metal surfaces. These biofilms create microenvironments with differential , where oxygen-depleted areas beneath the biofilm act as anodes prone to corrosion, while oxygenated edges serve as cathodes, establishing galvanic cells similar to effects. Notable examples of MIC include internal corrosion of oil and gas pipelines by SRB, where biofilms lead to localized pitting and failures in pipes transporting . On ship hulls, marine algae such as species contribute to , fostering anaerobic zones that promote SRB activity and accelerate degradation in . Detection of MIC relies on molecular methods, such as quantitative (qPCR), which targets specific genetic markers to identify and quantify corrosive bacteria like SRB without requiring cultivation. This technique offers rapid results, detecting microbial densities as low as 10² cells per gram, enabling early intervention. MIC predominantly occurs in anaerobic soils, where SRB thrive on sulfate-rich , and in cooling water systems, where biofilms form on surfaces due to availability and stagnation. Standards such as NACE SP0775 provide guidelines for preparing and analyzing corrosion coupons to assess MIC risk in oilfield environments, including measurements and microbial enumeration.

Metal Dusting

Metal dusting is a catastrophic form of high-temperature corrosion that causes the disintegration of metals and alloys into fine metal particles and carbon dust in environments with high carbon activity. This process occurs in carbon-supersaturated gaseous atmospheres, such as those containing (CO), (H₂), and hydrocarbons, where the thermodynamic driving force for carbon ingress exceeds the stability of the metal matrix. The mechanism involves the deposition of carbon on the metal surface, leading to , formation, and subsequent fragmentation of the material. It proceeds in distinct stages: first, and dissolution of carbon into the metal lattice, forming a carbon-expanded phase (γ_C) with up to 5.3 wt% carbon at lower temperatures; second, of stable s such as M_{23}C_6 and M_7C_3 along grain boundaries and the surface, creating a brittle network; and third, disintegration where the s decompose into metal particles and , often via or direct intercalation of metal atoms into layers, resulting in pitting and wastage. For iron-based systems, metastable (Fe_3C) may form initially before dissociating, while and systems favor direct formation without intermediate s. Primarily affecting nickel (Ni), iron (Fe), and cobalt (Co)-based alloys, metal dusting is most severe in the temperature range of 400–800°C (673–1073 K), where carbon solubility is high but carbide stability allows fragmentation. Austenitic stainless steels like AISI 316 and 316L, as well as Ni-based alloys such as Alloy 600 and 601, are particularly susceptible due to their catalytic activity for carbon deposition and limited ability to form protective oxide scales in carburizing conditions. Common in plants, including reformers and hydro-dealkylation units, as well as furnaces in heat-treating industries, metal dusting leads to rapid material loss in components exposed to process gases like CO-H_2 mixtures. The process is governed by the carbon activity (a_c) of the atmosphere, defined by the equilibrium of reactions such as CO + H_2 ⇌ C + H_2O, where a_c > 1 promotes carbon deposition and accelerates dusting kinetics; this activity can be quantified using thermodynamic models analogous to Wagner's for inward carbon transport, emphasizing the role of gas composition and temperature in driving .

Corrosion Resistance Mechanisms

Intrinsic Material Properties

Intrinsic material properties play a fundamental role in determining a 's inherent resistance to corrosion, stemming from its atomic and electronic , thermodynamic stability, and phase composition. These properties dictate how readily a material undergoes oxidation or dissolution in various environments, without reliance on external modifications. Noble metals exemplify this through their electrochemical nobility, while reactive metals like aluminum and exhibit conditional stability based on pH-dependent behavior. Alloying elements and microstructural features further tailor these traits, enhancing overall durability in applications. Noble metals such as (Au) and (Pt) demonstrate exceptional corrosion resistance due to their highly positive standard reduction potentials, which make oxidation thermodynamically unfavorable. For instance, the Au³⁺/Au couple has a potential of +1.50 V, and Pt²⁺/Pt is +1.18 V versus the , positioning them at the noble end of the electromotive series and preventing reaction with oxygen or most aqueous species under ambient conditions. This electrochemical stability arises from the high energy required to form their ions, rendering them inert in environments where base metals corrode readily. Amphoteric metals like aluminum (Al) and zinc (Zn) possess intrinsic corrosion resistance in neutral environments but dissolve in acidic or alkaline conditions due to their ability to form soluble hydroxo complexes. Aluminum remains stable near pH 7 because its protective oxide layer persists, but it corrodes amphoterically in strong bases (e.g., NaOH) via formation of aluminate ions (Al(OH)₄⁻) or in acids via Al³⁺ dissolution. Similarly, zinc exhibits passivity in neutral water but amphoteric attack in pH extremes, with solubility increasing below pH 5 or above pH 10 due to Zn²⁺ or zincate (Zn(OH)₄²⁻) formation. This pH-dependent behavior highlights the role of solution chemistry in modulating their inherent oxide solubility. In alloy design, elements like (Cr) and (Ni) are strategically incorporated to enhance corrosion stability in iron-based alloys such as s. Austenitic stainless steels typically contain 17-25% Cr, which promotes thermodynamic favorability for Cr₂O₃ formation over iron oxides, conferring bulk resistance to oxidation in aqueous and gaseous media. Nickel additions (e.g., 8-10% in 304 stainless steel) stabilize the austenitic phase and improve resistance to reducing environments by shifting the alloy's potential to more noble values, reducing susceptibility to pitting or general corrosion. These alloying strategies leverage solid-solution strengthening and phase stabilization to achieve balanced mechanical and corrosion performance. Microstructural features, including and secondary phases, significantly influence corrosion susceptibility by altering local galvanic interactions and diffusion paths. Finer s generally improve resistance by increasing density, which can distribute corrosion more uniformly and reduce propagation rates, as observed in ultrafine-grained aluminum alloys where severe deformation refines structure to enhance pitting resistance. However, coarse grains or heterogeneous phase distributions, such as β-phase precipitates in magnesium alloys, create galvanic couples that accelerate localized attack by acting as cathodes relative to the matrix. precipitation, particularly carbides in nickel alloys, heightens intergranular corrosion risk by depleting adjacent regions of protective elements like Cr, though controlled heat treatments can mitigate this through homogenization. Titanium (Ti) illustrates intrinsic resistance through its strong oxygen affinity, forming a tenacious TiO₂ layer that imparts stability in aqueous environments like and . This affinity, rooted in Ti's high heat of oxide formation (ΔH_f ≈ -944 kJ/mol for TiO₂), ensures rapid, self-limiting oxidation upon exposure, rendering the metal virtually immune to uniform corrosion under neutral to mildly acidic conditions. The oxide's thermodynamic stability prevents further degradation, with Ti exhibiting corrosion rates below 0.01 mm/year in at ambient temperatures. This property underpins titanium's use in and biomedical applications where long-term durability is essential.

Passivation Processes

Passivation processes refer to the electrochemical formation of a thin, protective film on metal surfaces that significantly reduces the corrosion rate by acting as a barrier to transport and . In corrosion-resistant alloys such as , this passive film is typically composed of (Cr₂O₃) and achieves a thickness of 1-5 nm, providing a stable, self-healing layer under appropriate conditions. The formation of the passive occurs through anodic polarization, where the metal surface is exposed to an oxidizing environment that promotes the growth of the layer via metal dissolution and subsequent oxidation. This process involves the migration of metal cations outward and oxygen anions inward, resulting in a compact, adherent that maintains low corrosion currents in the passive region of the polarization curve. At sufficiently high anodic potentials, however, the undergoes transpassive breakdown, where the becomes unstable, leading to accelerated dissolution and loss of protectiveness. Key electrochemical parameters characterizing passivation stability include the pitting potential (E_pit), the potential above which localized breakdown initiates, and the repassivation potential (E_rep), the threshold below which the film can reform and halt propagation. These values are determined from cyclic potentiodynamic polarization curves, where the forward scan identifies E_pit as the sharp rise in , and the reverse scan reveals E_rep at the crossover point where the current decreases. If E_rep is more positive than the open-circuit potential, the material exhibits good resistance to sustained pitting. A practical example of controlled passivation is the treatment of , as specified in ASTM A967, which involves immersion in 20-25% at 50-60°C for 20-30 minutes to remove surface contaminants and enrich the layer. This chemical passivation enhances the film's uniformity and corrosion resistance in industrial applications. Limitations arise when aggressive species, such as halide ions (e.g., ), adsorb onto the film, causing localized thinning or defects that lead to breakdown and subsequent localized corrosion.

Corrosion Protection Methods

Surface Treatments and Coatings

Surface treatments and coatings serve as physical and chemical barriers to inhibit corrosive agents from reaching the underlying substrate, thereby extending the of metals and other materials. These methods involve applying layers that either block environmental exposure or react to form protective films, commonly used in industries such as , automotive, and . Applied coatings include organic and metallic types designed to provide sacrificial or barrier protection. Paints and epoxies form impermeable barriers that prevent moisture and oxygen diffusion to the substrate, with epoxies particularly effective due to their adhesion and chemical resistance in harsh environments. Metallic coatings, such as hot-dip galvanizing with zinc, offer cathodic protection where the zinc sacrificially corrodes preferentially to the base metal, forming stable zinc corrosion products like zinc carbonate that further seal the surface. These zinc coatings can provide corrosion protection for decades in atmospheric exposure, depending on environmental severity. Reactive coatings, such as conversion layers, chemically alter the substrate surface to create adherent or films that enhance corrosion resistance and serve as primers for subsequent coatings. conversion coatings involve immersing the metal in a solution to form crystalline iron layers, which improve paint adhesion and provide mild corrosion protection on . Chromate conversion coatings, historically used on aluminum and , deposit a complex chromate film that passivates the surface and offers self-healing properties by releasing inhibiting ions at corrosion sites, though their use is declining due to toxicity. Anodization is an electrolytic process that grows a thick, porous layer on metals like aluminum and , significantly enhancing their corrosion resistance through barrier protection. For aluminum, anodizing produces an film up to 25 micrometers thick, which can be sealed to block ion ingress and is widely used in architectural and applications. On , anodization in alkaline electrolytes forms a denser layer, improving resistance to pitting and in biomedical and marine environments. Emerging biofilm coatings incorporate antimicrobial agents to prevent microbial-induced corrosion (MIC) by disrupting biofilm formation on surfaces. These coatings, often embedded with silver or copper nanoparticles, inhibit bacterial adhesion and metabolic activity, reducing sulfate-reducing bacteria proliferation in pipelines and marine structures. Such layers have demonstrated up to 99.999% reduction in microbial colonization in laboratory tests against Pseudomonas aeruginosa. Recent advances include graphene sheets for hydrophobic barrier coatings and metal-organic frameworks (MOFs) for smart release of inhibitors, offering improved sustainability and efficiency as of 2025. For concrete structures, controlled permeability formwork (CPF) uses porous liners during casting to extract excess water and air from the surface zone, resulting in denser cover with reduced and ingress, thereby protecting embedded from corrosion. CPF can reduce ingress by 46–56% compared to traditional , enhancing long-term in chloride-rich environments like bridges. Application methods for these coatings vary by type and substrate, with dipping used for uniform coverage in galvanizing—where is immersed in molten at 450°C—and spraying for paints and epoxies to achieve thin, controlled layers on complex geometries. Durability is assessed through standardized tests like the salt fog test (ASTM B117), which exposes coated samples to a 5% mist at 35°C to evaluate corrosion resistance over hours to thousands of hours, simulating accelerated marine exposure.

Electrochemical Protection Techniques

Electrochemical protection techniques mitigate corrosion by applying external electrical currents or potentials to alter the electrochemical environment at the metal surface, thereby suppressing anodic reactions or promoting passivity. These methods are particularly effective for structures in aggressive environments, such as marine or industrial settings, where natural corrosion rates are high. Unlike passive barriers, electrochemical approaches actively control the corrosion potential to protect the substrate metal. Cathodic protection is the most widely used electrochemical technique, operating on the principle of making the protected metal a in an , which prevents oxidation. In sacrificial anode systems, more reactive metals such as , aluminum, or magnesium are electrically connected to the ; these s corrode preferentially, providing electrons to the protected metal. For instance, anodes are commonly attached to ship hulls and propellers to prevent corrosion in , while magnesium anodes are favored in less conductive environments like freshwater systems due to their more negative potential in the . Anode selection relies on the , which ranks metals by nobility to ensure the anode is sufficiently active relative to the protected . Impressed current cathodic protection (ICCP) employs an external DC power source, typically a transformer-rectifier, to supply protective current through inert , offering greater control and longevity for large-scale applications. This method is ideal for buried , where rectifiers convert AC to DC and deliver current via ground beds to maintain the pipeline at a protective potential. ICCP systems are scalable and adjustable, making them suitable for extended structures without frequent anode replacement. A key criterion for effective of structures is maintaining a potential of at least -850 mV versus the copper-copper sulfate electrode (CSE), as established by early empirical studies on buried pipelines; this ensures sufficient polarization to halt . More negative potentials may be required in aerated soils, but overprotection risks . Anodic protection, in contrast, polarizes the metal to a more positive potential within its passive region, where a stable forms to inhibit corrosion; this technique is applied in environments supporting passivity, such as concentrated . For storage tanks, low-voltage DC current from platinum-activated anodes maintains the steel at +0.5 to +1.0 V versus a , dramatically reducing iron dissolution and contamination. Anodic systems require precise control to avoid breakdown of the passive layer. Monitoring electrochemical protection systems involves periodic assessment to verify potential levels and corrosion rates. Corrosion coupons, typically strips of the protected metal exposed for fixed periods, allow weight-loss measurements to calculate average corrosion rates, providing a simple baseline for system efficacy. Electrical resistance probes and resistance (LPR) sensors offer real-time data on instantaneous corrosion rates and potentials, enabling automated adjustments in ICCP setups. Reference electrodes, such as CSE, are used alongside probes to measure structure-to-electrolyte potentials accurately. In practice, offshore platforms often utilize ICCP systems to protect steel jackets and risers from seawater corrosion, with rectifier outputs up to 500 A distributed via mixed-metal oxide anodes for uniform current coverage over expansive structures. These installations have demonstrated corrosion rate reductions to below 0.01 mm/year, extending asset life in harsh marine conditions.

Corrosion Inhibitors and Controlled Environments

Corrosion inhibitors are chemical compounds added to environments in low concentrations to reduce the corrosion rate of metals by interfering with electrochemical reactions at the surface. These additives form protective layers or alter the local chemistry to suppress anodic or cathodic processes, thereby extending the of materials in aggressive conditions. Unlike physical barriers, inhibitors act through dissolution and adsorption, making them suitable for dynamic systems like fluids. Corrosion inhibitors are classified into three main types based on their interaction with corrosion mechanisms: anodic, cathodic, and mixed. Anodic inhibitors, such as chromates, promote passivation by oxidizing the metal surface to form a stable layer that blocks further dissolution; however, their use has declined due to concerns. Cathodic inhibitors, exemplified by (CaCO₃), precipitate on the surface to limit access of cathodic reactants like oxygen or ions, often inducing scaling to hinder reduction reactions. Mixed inhibitors, including amines, simultaneously retard both anodic and cathodic reactions through broad-spectrum adsorption, providing versatile protection in neutral or mildly acidic media. The primary mechanisms of corrosion inhibitors involve adsorption onto the metal surface and subsequent film formation, which physically separates the substrate from the corrosive . Adsorption occurs via (electrostatic interactions) or (electron sharing), leading to or multilayer coverage that reduces the active sites for corrosion. For many organic inhibitors, this process follows the Langmuir adsorption isotherm, which models surface coverage (θ) as a function of inhibitor concentration (C): θ=KC1+KC\theta = \frac{K C}{1 + K C} where K is the adsorption equilibrium constant, indicating the inhibitor's affinity for the surface; this isotherm assumes uniform sites and no interactions between adsorbed molecules, commonly verified in electrochemical studies for efficiencies exceeding 90% at optimal dosages. Film formation enhances this by creating a hydrophobic or insoluble barrier, often synergizing with natural passivation to amplify protection. In practical applications, corrosion inhibitors are widely used in coolants and fuels to safeguard components and pipelines from degradation. In automotive and industrial coolants, organic phosphates or silicates maintain stability and prevent corrosion in radiators, achieving corrosion rates below 0.1 mm/year in mixed-metal systems. For fuels, such as diesel or kerosene, amine-based inhibitors mitigate microbial-induced corrosion and water contamination effects, ensuring compliance with standards like ASTM D665. Emerging since the , green inhibitors derived from plant extracts—such as from or alkaloids from neem leaves—offer biodegradable alternatives with inhibition efficiencies up to 95% in acidic media, driven by sustainable sourcing and reduced environmental impact. Controlled environments complement inhibitors by modifying ambient conditions to minimize corrosion drivers like and acidity. Dehumidification systems, targeting relative humidity below 40%, prevent and electrolytic film formation on stored metals, commonly applied in warehouses and marine settings to extend asset life by factors of 5-10. pH adjustment, often via alkaline additives like , shifts the solution toward passivity for metals like aluminum, reducing general corrosion in systems. In concrete admixtures, calcium nitrite inhibitors are incorporated during mixing to delay chloride-induced corrosion of in aggressive exposures. The effectiveness of corrosion inhibitors is evaluated using linear polarization resistance (LPR), an electrochemical technique that measures the polarization resistance (Rp) from small potential perturbations (±10-20 mV) around the corrosion potential. LPR provides instantaneous corrosion rates via the Stern-Geary equation, Rp = β_a β_c / (2.303 I_corr (β_a + β_c)), where β_a and β_c are Tafel slopes and I_corr is the corrosion current; inhibitor efficiency (η) is then calculated as η (%) = (1 - I_corr^inh / I_corr^blank) × 100, often yielding real-time data for optimization in field trials. This method is favored for its non-destructive nature and sensitivity to low concentrations, typically detecting efficiencies above 80% in controlled tests.

Corrosion Removal and Mitigation

Mechanical and Chemical Removal Techniques

Mechanical removal techniques involve the physical abrasion or dislodgement of corrosion products from metal surfaces to restore integrity without chemical alteration. Abrasive blasting, also known as grit blasting, propels abrasive media such as steel grit or at high velocities to strip , , and coatings, commonly applied to large structures like ship hulls where uniform corrosion products accumulate. This method achieves a clean surface profile essential for subsequent treatments, with steel grit providing angular particles for aggressive removal on metals. Grinding and cleaning employ rotary tools, wire brushes, or sanding equipment to mechanically eliminate loose , , and scale from localized areas, suitable for spot repairs on intricate components. Defined under SSPC-SP 3, this technique removes all loose detrimental foreign matter but leaves tightly adherent material intact, ensuring minimal substrate damage. High-pressure jetting uses pressurized streams, often exceeding 5,000 psi, to dislodge corrosion without abrasives, preserving surface details on sensitive substrates like . An emerging mechanical technique is cleaning, which employs high-powered to ablate corrosion layers through or thermal ejection, offering precise, non-contact removal without abrasives or residues. This method is particularly effective for delicate or hard-to-reach surfaces, minimizing substrate damage and environmental impact, and has gained adoption in industries like and heritage conservation as of 2025. Chemical removal techniques dissolve corrosion products through reactive solutions, targeting specific metal types. Acid pickling immerses steel in (HCl) solutions to remove and oxides via , widely used in industrial batch processes for components. Concentrations typically range from 5-15% HCl, with immersion times of 10-30 minutes depending on thickness, followed by rinsing to neutralize residues. Alkaline derusting employs or other bases in heated solutions to saponify organic contaminants and loosen , particularly effective for initial cleaning of heavily soiled metals before acid stages. Mechanical methods like abrasive blasting and grinding prepare rusted surfaces for repainting, ensuring and preventing under-film corrosion recurrence. For historic artifact restoration, such as corroded iron tools or statues, conservators combine gentle mechanical scraping with chemical baths to preserve while removing active corrosion layers. Safety considerations include the use of corrosion inhibitors during water-based processes to prevent flash rust formation on freshly cleaned surfaces exposed to moisture. Environmental regulations govern chemical disposal, with restrictions on phosphate-based inhibitors due to risks in waterways, prompting shifts to non-phosphate alternatives. Industry standards like SSPC-SP 10 define near-white blast cleaning, requiring removal of at least 95% of and stains for high-performance applications.

Post-Corrosion Repair Strategies

Post-corrosion repair strategies aim to restore structural integrity and functionality to damaged metallic components after corrosion products have been removed, focusing on techniques that rebuild material loss while mitigating risks of further degradation. These methods are essential in industries such as and gas, infrastructure, and , where premature failure can lead to significant safety and economic consequences. Key approaches include and patching, which are selected based on the extent of , material type, and environmental exposure. Welding repairs are commonly employed for corroded metals, involving the deposition of filler material to rebuild lost sections, but they require stringent precautions to prevent hydrogen-induced cracking in the (HAZ), particularly in hardenable steels like SA-516 Gr. 70. To mitigate this, preheating to several hundred degrees is applied to slow cooling rates and reduce HAZ hardness below 22 HRC, while low- processes—such as those using basic-coated electrodes or fluxes—are utilized to limit diffusible hydrogen levels. Post-weld (PWHT) further tempers the HAZ and relieves residual stresses, ensuring long-term durability in corrosive environments. Non-destructive testing (NDT), such as , is integrated pre-repair to assess remaining wall thickness and detect subsurface defects, enabling precise excavation of damaged areas before . Patching techniques provide an alternative or complementary method, especially for pipelines and pressure vessels, where composite wraps reinforced with materials like E-glass fabric and epoxy resin restore strength without full replacement. For instance, epoxy-based fillers, such as those incorporating 20% aluminum powder, are used to fill pits and gaps, achieving tensile strengths up to 214 MPa and effectively reducing strain by 50% at corrosion edges when applied in multi-layer sleeves adhering to standards like ISO 24817. These repairs limit axial and circumferential displacements, enhancing integrity in oil and gas applications. In bridge rehabilitation, and patching have been successfully applied to corroded girders, including for distorted structures due to fire or corrosion, as seen in rapid restorations of fire-damaged bridges like the using partial member replacement and heat-straightening techniques without extensive downtime. Similarly, aircraft components benefit from patching corroded aluminum alloys with doublers—Alclad sheets secured by rivets and sealants—following corrosion removal, while requires controlled post-weld to preserve corrosion resistance and avoid . For long-term , especially after , systems are often implemented, using galvanic anodes or impressed current to shield repaired areas from ongoing electrochemical corrosion in aggressive soils or waters.

Economic and Societal Impact

Global Costs and Case Studies

Corrosion imposes a substantial economic burden on global economies, with estimates indicating an annual cost of approximately $2.5 trillion, equivalent to about 3.4% of the world's based on 2013 data. As of 2025, these costs are estimated to exceed $2.5 trillion annually. This figure encompasses direct expenses such as maintenance, replacement, and repair of corroded assets, and it has remained a benchmark in recent analyses. In the United States, a detailed 2001 study calculated direct corrosion costs at $276 billion annually, representing 3.1% of the GDP at that time, with modern assessments maintaining the 3-4% GDP range despite the lack of a comprehensive national update. These costs are distributed across key sectors, particularly , transportation, and , where corrosion accelerates degradation of critical assets. In the U.S., for instance, utilities account for the largest share at $47.9 billion (34.7% of the subtotal for major sectors), driven by corrosion in systems, electrical grids, and gas distribution networks. Transportation contributes $29.7 billion (21.5%), primarily from vehicle and corrosion in and ships, while adds $22.6 billion (16.4%), including bridges and pipelines. Energy-related elements, such as gas and liquid transmission pipelines, represent a significant portion within at $7 billion. The following table summarizes the U.S. sector breakdown from the 2001 study for five major categories, totaling $137.9 billion (approximately 50% of the national $276 billion total) and serving as a representative illustration of global patterns:
SectorAnnual Cost ($ billion)Percentage of Subtotal
Utilities47.934.7%
Transportation29.721.5%
20.114.6%
22.616.4%
Production/Manufacturing17.612.8%
Subtotal137.9100%
Indirect costs amplify the financial impact, including production downtime, lost from asset failures, and environmental cleanup efforts, which can equal or exceed direct expenses in severe cases. For example, corrosion-induced shutdowns in energy pipelines can halt operations for weeks, costing millions daily in forgone output, while remediation of contaminated sites from corroded storage tanks adds substantial cleanup expenses under regulatory mandates. Notable case studies underscore these costs through catastrophic failures. The Silver Bridge collapse on December 15, 1967, over the in , resulted from and corrosion fatigue in a critical chain link, leading to the structure's sudden failure during rush-hour traffic and claiming 46 lives. The incident caused immediate economic losses estimated at $1 million per month due to disrupted commerce and transportation, with long-term regional impacts including business closures and heightened infrastructure inspection costs that influenced national bridge safety standards. Similarly, the platform disaster in the on July 6, 1988, involved chronic corrosion problems affecting equipment, including condensate pumps, which—combined with procedural and errors—triggered a , , and that destroyed the facility and killed 167 workers. The event incurred direct costs exceeding $3 billion for , encompassing platform reconstruction, insurance payouts, and immediate operational halts, while indirect effects included over a year of lost production—equivalent to 10% of U.K. oil output—and extensive environmental cleanup from oil spills and debris. These cases highlight how corrosion in energy infrastructure can escalate from localized degradation to widespread economic and societal disruption.

Prevention Strategies in Industry

In the oil and gas sector, systems and corrosion inhibitors are primary strategies to protect pipelines, well casings, and offshore platforms from aggressive environments involving CO2, H2S, and saline conditions. CP involves applying an external current or sacrificial anodes to shift the metal potential, preventing anodic dissolution, while inhibitors form protective films on metal surfaces to reduce reaction rates. These measures extend asset life and minimize downtime in upstream and operations. The marine industry employs marine-grade coatings and sacrificial s to combat , saltwater immersion, and atmospheric corrosion on ship hulls, offshore rigs, and subsea structures. Epoxy-based coatings provide a barrier against and ions, often combined with or aluminum anodes in galvanic CP setups to preferentially corrode the anode material. This approach is critical for vessels operating in C5 (very high) corrosivity categories per international guidelines. In construction, particularly for structures like bridges and buildings, admixtures such as calcium are integrated into the mix to inhibit chloride-induced corrosion of embedded . These admixtures delay the breakdown of the passive layer on , enhancing in de-icing salt-exposed environments without altering concrete's mechanical properties significantly. Industry standards ensure consistent application of these strategies. ISO 12944 specifies protective paint systems for structures, classifying environments by corrosivity (C1 to C5) and recommending thicknesses and types for expected service lives of 5 to 25+ years. NACE International standards, such as SP0169, provide criteria for external CP design on buried or submerged pipelines, including requirements and interference mitigation to achieve protective potentials of -850 mV or more versus copper-copper sulfate reference. Life-cycle costing (LCC) evaluates corrosion prevention by comparing initial capital expenditures—such as application or CP installation—against ongoing and replacement costs over an asset's 20-50 year lifespan. For instance, higher upfront costs for durable systems like hot-dip galvanizing often yield lower total ownership expenses due to reduced repainting intervals and failure risks, with LCC incorporating discount rates and to present net savings. Emerging post-2020 developments include smart coatings embedded with sensors for real-time corrosion detection, such as pH-sensitive or strain-responsive that trigger self-healing or alerts via wireless signals. These coatings, often incorporating oxide or conducting polymers, enable in oil/gas and marine applications by monitoring early degradation without invasive inspections. Proactive implementation of these strategies delivers strong returns on , with industry analyses estimating 15-35% savings in corrosion-related costs through avoided repairs and extended asset ; for example, U.S. Army projects have achieved ROI ratios exceeding 10:1 via targeted CP retrofits.

Corrosion in Non-Metallic Materials

Degradation of Polymers

refers to the chemical and physical breakdown of polymeric materials due to environmental exposures, distinct from metallic corrosion as it lacks electrochemical processes and relies primarily on diffusion-driven mechanisms. Unlike metals, which corrode via and migration, polymers degrade through bond cleavage and chain scission induced by reactive penetrating the material matrix. This section examines key degradation types, influencing factors, practical examples, and standard testing methods for polymers in corrosive environments. Hydrolysis is a prominent degradation mechanism in polymers containing ester or amide linkages, such as polyesters and polyamides, where molecules react with these bonds to form hydroxyl and groups, leading to chain shortening and reduced mechanical integrity. For instance, in poly(lactic acid) biomaterials, hydrolysis proceeds via random chain scission, insensitive to pH variations, and accelerates under humid conditions. Oxidation, often triggered by (UV) radiation or thermal exposure, involves free radical formation that propagates chain scission and crosslinking, particularly in polyolefins like , resulting in embrittlement and surface cracking. Swelling occurs when solvents or aggressive fluids, such as hydrocarbons, diffuse into the network, causing volumetric expansion, loss of dimensional stability, and eventual stress cracking without immediate bond breakage. Practical examples illustrate these mechanisms in applied settings. In chlorinated water distribution systems, pipes undergo oxidative degradation from disinfectants, leading to depletion, surface oxidation, and brittle cracking that compromises pressure resistance. Similarly, coatings on metals, such as epoxy-based systems, experience due to hydrolytic and oxidative attack at the interface, allowing corrosive ingress and reducing protective . These failures highlight how degradation initiates at the surface and propagates inward via , contrasting with the uniform or localized electrochemical pitting in metals. Degradation rates in polymers are strongly influenced by environmental factors like temperature and intensity. Elevated temperatures increase molecular mobility and reaction kinetics, often following the , where the rate constant kk is given by k=Aexp(Ea/RT)k = A \exp(-E_a / RT), with AA as the , EaE_a the , RR the , and TT the absolute temperature; this enables lifetime predictions by extrapolating accelerated aging data to service conditions, assuming consistent mechanisms. UV radiation exacerbates photo-oxidation by generating peroxyl radicals, while factors like humidity amplify in susceptible polymers. Unlike metallic corrosion, which involves equilibria, polymer degradation emphasizes non-electrochemical of reactants, making barrier properties and additive stabilizers critical for mitigation. Standard testing evaluates resistance to these degradants. ASTM D543 outlines practices for immersing specimens in chemical reagents at specified temperatures, measuring changes in , dimensions, tensile strength, and appearance to quantify resistance; it applies to various plastics, including molded and laminated types, simulating end-use exposures without electrochemical setups. This diffusion-focused approach underscores the mechanistic differences from metal corrosion testing, prioritizing and over conductivity.

Corrosion of Glass

Glass corrosion primarily occurs through a multi-stage process involving , network , and potential , particularly in aqueous environments. In the initial stage, ions (H⁺) from the solution exchange with alkali ions such as sodium (Na⁺) in the glass network, leading to a hydrated surface layer formation without significant loss. This ion-exchange mechanism is followed by of the silicate network, where water molecules react with silicon-oxygen bonds, breaking them and forming groups (Si-OH), which can further condense or dissolve. In some compositions, may occur, where alkali-rich droplets form within the glass matrix, accelerating localized dissolution. Aggressive environments that promote glass corrosion include alkaline solutions, where hydroxyl ions (OH⁻) enhance network , and high-humidity conditions that facilitate vapor-phase hydration. A critical application is in nuclear waste storage, where borosilicate es encapsulating radioactive materials are exposed to or repository atmospheres, potentially leading to radionuclide release if corrosion rates exceed design limits. For instance, in unsaturated geological repositories, humidity-driven corrosion can form alteration layers that control long-term durability. Key factors influencing glass corrosion rates include composition and temperature. Borosilicate glasses, commonly used for their enhanced durability, exhibit lower dissolution rates due to the incorporation of , which strengthens the network and reduces mobility compared to soda-lime-silica glasses. Higher temperatures accelerate both and kinetics, often following Arrhenius behavior, with activation energies typically ranging from 50 to 80 kJ/mol depending on the type. Solution pH also plays a role, with corrosion minimized near neutrality but increasing in acidic or alkaline conditions. Standardized tests evaluate durability under controlled conditions. The Materials Characterization Center Test 1 (MCC-1), a static leach test, measures normalized loss (NL) of elements like or over time (e.g., up to 28 days at 90°C) in deionized , providing insights into initial ion-exchange rates. The Product Consistency Test (PCT), based on ASTM C1285, assesses long-term performance by leaching monolithic samples in borosilicate-buffered solution at 90°C for 7 days, yielding a normalized release (r_B) as a index, often below 1 g/m²/day for glasses. These tests establish durability indices that correlate with field performance, guiding material selection. Consequences of unchecked glass corrosion include surface cracking due to stress buildup in the hydrated layer and bulk dissolution, which compromises structural and . Surface cracking arises from volume expansion during and , potentially leading to fragmentation, while prolonged exposure results in progressive material loss, as observed in weathered archaeological . In nuclear contexts, this can elevate leach rates, necessitating robust predictive models.

Corrosion of Concrete

Corrosion of concrete primarily affects reinforced structures, where the degradation arises from the ingress of external agents that compromise the protective alkaline environment around embedded , leading to its corrosion and subsequent structural damage. In , the high (typically 12-13) of the pore solution forms a passive layer on the , preventing oxidation; however, environmental factors can disrupt this passivity, initiating corrosion that expands products up to six times the volume of the original , causing cracking, spalling, and of the . This process is a major concern in , particularly for infrastructure exposed to aggressive environments. Degradation in non-reinforced concrete primarily involves direct chemical attacks on the cement matrix and aggregates. Key mechanisms include , where exposure to acidic environments ( < 5.5) dissolves cementitious components, leading to mass loss and reduced compressive strength; alkali-silica reaction (ASR), in which reactive silica in aggregates reacts with alkalis in the presence of moisture (>80% relative humidity) to form an expansive gel that induces cracking; and leaching of [Ca(OH)₂] in aggressive waters, which increases and permeability. and sulfate attack, while primarily discussed in the context of , also contribute to gradual strength reduction and expansion-induced damage in plain . The main mechanisms of corrosion in include , ingress, and sulfate attack. occurs when (CO₂) from the atmosphere diffuses into the concrete pores and reacts with to form , progressively lowering the to around 9 or below, which depassivates the and initiates uniform corrosion. ingress, often from salts or , involves the diffusion of ions (Cl⁻) through the to the surface; once the concentration exceeds a threshold (typically 0.4-1% by weight), it breaks down the passive layer, leading to localized on the . Sulfate attack, common in soils or rich in sulfates, reacts with hydration products to form expansive ettringite and , causing internal pressure, cracking, and increased permeability that facilitates further ingress of corrosive agents. Chloride ingress in is commonly modeled using , particularly the second law, which describes the time-dependent concentration profile of ions: Ct=D2Cx2\frac{\partial C}{\partial t} = D \frac{\partial^2 C}{\partial x^2} where CC is the concentration, tt is time, xx is depth, and DD is the apparent diffusion coefficient (typically 10⁻¹² to 10⁻¹⁰ m²/s for normal , decreasing with lower ). This in the , as referenced in discussions of pitting mechanisms, results in deep localized pits that weaken the more severely than uniform corrosion. Notable examples include bridge decks exposed to salts, where penetration accelerates deterioration, and marine structures like piers and seawalls, where splash zones experience high concentrations from , often reducing if not mitigated. Key factors influencing corrosion include concrete porosity, which governs the rate of ion diffusion (higher porosity increases DD and vulnerability), and the thickness of the concrete cover over the rebar (minimum 40-75 mm recommended to delay initiation). Service life modeling, often based on probabilistic approaches incorporating these factors, targets 50-100 years for durable structures, with initiation time estimated via the time for aggressive agents to reach the rebar. Testing methods assess these risks: the Rapid Chloride Permeability Test (RCPT) per ASTM C1202 measures electrical conductance of saturated concrete discs under a 60 V DC voltage for 6 hours, classifying permeability as high (>4000 coulombs), moderate (2000-4000), low (1000-2000), very low (100-1000), or negligible (<100), providing an indicator of Cl⁻ ingress potential. Half-cell potential mapping, using a copper-copper sulfate electrode (CSE) referenced to the rebar, measures corrosion probability: potentials more negative than -350 mV CSE indicate >90% likelihood of active corrosion, guiding inspections and repairs.

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