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Corrosion
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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]

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
[edit]
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
[edit]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
[edit]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
[edit]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
[edit]
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
[edit]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
[edit]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
[edit]
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
[edit]

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
[edit]
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
[edit]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
[edit]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
[edit]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
[edit]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
[edit]
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
[edit]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
[edit]

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
[edit]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
[edit]
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
[edit]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
[edit]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
[edit]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
[edit]
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
[edit]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
[edit]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
[edit]
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
[edit]
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
[edit]This section needs additional citations for verification. (June 2022) |
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
[edit]
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
[edit]
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
[edit]
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
[edit]- Anaerobic corrosion
- Bacterial anaerobic corrosion
- Chemical hazard label – Warning symbol on locations or products
- Corrosion engineering – Field of engineering dealing with designing materials that resist corrosion
- Corrosion in space – Corrosion of materials occurring in outer space
- Cyclic corrosion testing – Acceleration of real-world corrosion failures
- Dimetcote – Used for steel corrosion resistance
- Electrical resistivity measurement of concrete
- Electronegativity – Tendency of an atom to attract a shared pair of electrons
- Environmental stress fracture – Material failure
- Faraday paradox (electrochemistry) – Resolved paradox in electrochemistry
- Fibre-reinforced plastic tanks and vessels
- Forensic engineering – Investigation of failures associated with legal intervention
- Hydrogen analyzer – Device
- Hydrogen embrittlement – Reduction in ductility of a metal exposed to hydrogen
- Kelvin probe force microscope – Noncontact variant of atomic force microscopy
- Periodic table – Tabular arrangement of the chemical elements
- Pitting resistance equivalent number – Predictive measurement of stainless steel resistance to localized pitting corrosion
- Redox – Chemical reaction with oxidation state changes
- Reduction potential – Measure of the tendency of a substance to gain or lose electrons
- Rouging
- Salt spray test – Corrosion test method
- Scanning vibrating electrode technique
- Stress corrosion cracking – Growth of cracks in a corrosive environment
- Tribocorrosion – Material degradation due to corrosion and wear.
- Zinc pest – Type of corrosion in zinc
References
[edit]- ^ "Corrosion | Oxidation, Electrochemical, Rusting | Britannica". www.britannica.com. 2023-08-03. Retrieved 2023-08-08.
- ^ Jones, Denny A. (1991). Principles and prevention of corrosion. New York : Toronto : New York: Macmillan Pub. Co. ; Collier Macmillan Canada ; Maxwell Macmillan International Pub. Group. ISBN 978-0-02-361215-2.
- ^ Hoffman, Robert S.; Burns, Michele M.; Gosselin, Sophie (2020). "Ingestion of Caustic Substances". New England Journal of Medicine. 382 (18): 1739–1748. doi:10.1056/nejmra1810769. PMID 32348645.
- ^ Nwagha, Nzube. "Statistical study on the corrosion of mild steel in saline mediums".
- ^ "Methods of Protecting Against Corrosion". Piping Technology & Products. Archived from the original on 10 February 2012. Retrieved 31 January 2012.
- ^ Dı́ez-Pérez, I.; Gorostiza, P.; Sanz, F. (2003). "Direct Evidence of the Electronic Conduction of the Passive Film on Iron by EC-STM". Journal of the Electrochemical Society. 150 (7): B348. doi:10.1149/1.1580823.
- ^ Díez-Pérez, I.; Sanz, F.; Gorostiza, P. (2006-10-01). "Electronic barriers in the iron oxide film govern its passivity and redox behavior: Effect of electrode potential and solution pH". Electrochemistry Communications. 8 (10): 1595–1602. doi:10.1016/j.elecom.2006.07.015. ISSN 1388-2481.
- ^ Díez-Pérez, Ismael; Sanz, Fausto; Gorostiza, Pau (2006-06-01). "In situ studies of metal passive films". Current Opinion in Solid State and Materials Science. 10 (3): 144–152. doi:10.1016/j.cossms.2007.01.002. ISSN 1359-0286.
- ^ Díez-Pérez, I.; Vericat, C.; Gorostiza, P.; Sanz, F. (2006-04-01). "The iron passive film breakdown in chloride media may be mediated by transient chloride-induced surface states located within the band gap". Electrochemistry Communications. 8 (4): 627–632. doi:10.1016/j.elecom.2006.02.003. ISSN 1388-2481.
- ^ "Different Types of Corrosion: Pitting Corrosion - Causes and Prevention". corrosionclinic.com. WebCorr Corrosion Consulting Services. Archived from the original on 2022-09-13. Retrieved 2022-09-13.
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- ^ JE Breakell, M Siegwart, K Foster, D Marshall, M Hodgson, R Cottis, S Lyon (2005). Management of Accelerated Low Water Corrosion in Steel Maritime Structures, Volume 634 of CIRIA Series, ISBN 0-86017-634-7
- ^ R. Zuo; D. Örnek; B.C. Syrett; R.M. Green; C.-H. Hsu; F.B. Mansfeld; T.K. Wood (2004). "Inhibiting mild steel corrosion from sulfate-reducing bacteria using antimicrobial-producing biofilms in Three-Mile-Island process water". Appl. Microbiol. Biotechnol. 64 (2): 275–283. doi:10.1007/s00253-003-1403-7. PMID 12898064. S2CID 20734181.
- ^ "The sacrificial anode: what is it? When should you replace". hydrosolution.com. Hydro Solution. 20 January 2020. Archived from the original on 2022-09-13. Retrieved 2022-09-13.
Most water heater manufacturers will recommend inspecting the condition of the sacrificial anode every one (1) to three (3) years and replacing it when it has been consumed more than 50%
- ^ Schweitzer, Philip A. (2010). Fundamentals of corrosion – Mechanisms, Causes and Preventative Methods. Taylor and Francis Group. p. 25. ISBN 978-1-4200-6770-5.
- ^ Koch, Gerhardus H.; Brongers, Michiel P.H.; Thompson, Neil G.; Virmani, Y. Paul; Payer, Joe H. (September 2001). "Corrosion costs and preventive strategies in the United States". CC Technologies Laboratories, Inc. Federal Highway Administration (FHWA). Archived from the original on 2011-07-08.
- ^ "NACE Corrosion Costs Study". Cor-Pro.com. NACE. 2013-11-12. Archived from the original on 2014-09-11. Retrieved 16 June 2014.
- ^ Daniel Robles. "Potable Water Pipe Condition Assessment For a High Rise Condominium in The Pacific Northwest". GSG Group, Inc. Dan Robles, PE. Archived from the original on 29 December 2017. Retrieved 10 December 2012.
- ^ Boltres, Bettine (2015). When Glass Meets Pharma: Insights about Glass as Primary Packaging Material. Editio Cantor. ISBN 978-3-87193-432-2.
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- ^ Corrosion of Glass, Ceramics and Ceramic Superconductors. D.E. Clark, B.K. Zoitos (eds.), William Andrew Publishing/Noyes (1992) ISBN 081551283X.
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Further reading
[edit]- Jones, Denny A. (1996). Principles and prevention of corrosion. Upper Saddle River, NJ: Prentice Hall. ISBN 0-13-359993-0. OCLC 32664979.
Corrosion
View on GrokipediaFundamentals of Corrosion
Definition and Overview
Corrosion is the deterioration of a material, usually a metal, resulting from a chemical or electrochemical reaction with its environment, leading to the degradation of physical properties and functionality.[1] This process involves the interaction of the material with substances like oxygen, water, or acids, often producing compounds such as oxides or salts that weaken the structure.[5] While primarily affecting metals and alloys, corrosion can occur under specific conditions in certain environments.[6] The rusting of iron, a classic example of corrosion, has been observed since ancient times, as seen in archaeological iron artifacts that exhibit oxide layers from environmental exposure.[7] A pivotal advancement in understanding corrosion occurred in 1824, when British chemist Sir Humphry Davy demonstrated its electrochemical nature through experiments on protecting copper-sheathed ships from seawater degradation, laying the groundwork for modern corrosion science.[8] 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.[2] Corrosion occurs across diverse environments, including aqueous media like seawater, atmospheric conditions with pollutants and humidity, and soil with varying pH and moisture levels.[9] 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.[10] In everyday life, corrosion manifests as rust on vehicles accelerated by road salts in winter, compromising safety and longevity, or as the gradual decay of infrastructure like bridges and pipelines, where unchecked oxidation leads to structural failures.[11] These impacts underscore corrosion's broad relevance, influencing industries from transportation to construction by necessitating protective measures to mitigate material loss.[12]Electrochemical Principles
Corrosion is fundamentally an electrochemical process that occurs in the presence of an electrolyte, where the deterioration of a metal involves the transfer of electrons from one region of the surface (anode) to another (cathode). At the anode, oxidation takes place, in which metal atoms lose electrons to form positively charged ions, effectively dissolving the metal into the electrolyte. Simultaneously, at the cathode, a reduction reaction consumes these electrons, often involving species from the environment such as oxygen or hydrogen ions. This anodic-cathodic coupling ensures that the overall process is electrically neutral, with electrons flowing through the metal and ions migrating through the electrolyte to complete the circuit.[13][14] 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: 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: In acidic environments, hydrogen evolution predominates: 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.[13][3][15] 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.[16][13] Mixed potential theory explains the kinetics of corrosion by treating the corroding electrode as a superposition of independent anodic and cathodic processes reaching a steady-state mixed potential. At this corrosion potential (E_corr), the anodic current density equals the cathodic current density, resulting in zero net current. Evans diagrams visualize this by plotting logarithmic current density against potential, showing the intersection of anodic and cathodic polarization curves. The anodic curve typically follows the Tafel equation for activation control, while the cathodic may exhibit concentration polarization 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.[3][14]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 temperature, pH, oxygen availability, and the presence of aggressive ions play critical roles in accelerating or mitigating the degradation of metallic materials. Similarly, intrinsic properties 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, temperature exerts a dominant effect on corrosion kinetics, often following an Arrhenius relationship where the rate increases exponentially with rising temperature due to enhanced reaction rates and ion mobility.[17] For many systems, such as mild steel in acidic media, the corrosion rate approximately doubles for every 10°C increase, reflecting the activation energy barrier in the anodic and cathodic reactions.[18] The pH of the electrolyte also significantly impacts the rate; in acidic environments (low pH), the increased availability of H⁺ ions accelerates the cathodic reduction, leading to higher dissolution rates for metals like carbon steel, whereas neutral or alkaline conditions (higher pH) can promote passivation and reduce rates.[19] For instance, in CO₂-saturated solutions, corrosion rates of mild steel at pH 4.0 are higher than those at pH 6.0 due to this mechanism.[20] 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 carbon steel systems where rates increase proportionally with O₂ up to saturation points.[1] In low-oxygen settings, such as deaerated waters, rates drop markedly, though residual oxygen can still sustain localized attack.[21] Pollutants, exemplified by chloride ions (Cl⁻), exacerbate corrosion by disrupting passive films and promoting pitting or uniform attack; in reinforced concrete, Cl⁻ penetration thresholds as low as 0.3% by weight of cement can initiate rapid reinforcement corrosion by adsorbing to oxide layers and facilitating ion ingress.[22] This effect is pronounced in marine or industrial atmospheres, where Cl⁻ concentrations accelerate rates by orders of magnitude compared to chloride-free conditions.[23] Material factors are equally pivotal, with alloy composition altering the thermodynamic stability and kinetics of corrosion. Additions of elements like chromium (≥12 wt%) in stainless steels form protective Cr₂O₃ layers, reducing rates by promoting passivation, while higher nickel content in alloys like Inconel enhances resistance in acidic media.[24] Microstructure influences localized susceptibility; for example, in carbon steels, pearlitic phases corrode faster than ferritic ones due to galvanic coupling 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.[25] 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 steel showing up to 50% higher corrosion in turbulent flows over polished surfaces.[26] 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 data.[27] The Tafel equation describes the relationship in overpotential (η) and current density (i) for high overpotentials, allowing extrapolation of i_corr from linear regions of polarization curves: 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.[28] This equation underpins techniques like Tafel extrapolation for rate determination. To link electrochemical measurements to material loss, Faraday's first law quantifies mass loss (m) from the total charge passed (I t), incorporating the molar mass (M), number of electrons transferred (n), and Faraday's constant (F = 96,485 C/mol): 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.[29] Synergistic effects arise when multiple factors interact to amplify rates beyond additive contributions, notably in flow-accelerated scenarios like erosion-corrosion, where fluid velocity removes protective films and enhances mass transport, increasing total loss by 2–5 times the sum of pure erosion and corrosion components. In carbon steel pipes, velocities exceeding 3 m/s in chloride-laden waters can elevate rates through this interplay, emphasizing the need for integrated assessments.[30]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.[31] 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.[32] A classic example is the rusting of unprotected carbon steel exposed to atmospheric or aqueous environments, where the iron oxidizes evenly to form a layer of rust (iron oxide hydrate), gradually reducing the material thickness.[33] Another representative case is the dissolution of zinc in acidic solutions, such as hydrochloric acid, where the metal surface erodes uniformly due to the reaction with hydrogen ions.[34] 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.[31] 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 based on weight loss (in milligrams), exposure time (in hours), specimen area (in cm²), and metal density (in g/cm³) is given by: where for mpy or for mm/y, providing a reliable metric for even attack.[35] 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.[36] 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.[33]Galvanic Corrosion
Galvanic corrosion occurs when two dissimilar metals are electrically connected in the presence of an electrolyte, forming an electrochemical cell that accelerates the corrosion of the more anodic metal. In this process, the metal with the more negative electrode potential acts as the anode, where oxidation occurs, leading to preferential dissolution, while the more cathodic metal serves as the cathode, 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.[34][33] The driving force behind galvanic corrosion is the potential difference between the two metals, quantified using the electromotive force (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, steel rivets fastened into aluminum structures can lead to rapid pitting and degradation of the aluminum due to its more anodic nature relative to steel. Similarly, intentional galvanic setups, such as zinc coatings on steel ship hulls, exploit this principle for cathodic protection, where the zinc sacrificially corrodes to shield the underlying steel.[37][38] 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.[39][40]Pitting Corrosion
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.[41] 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.[41] 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 pH (often to 1-2) and enriching chloride concentration, which further dissolves the protective film cover and accelerates corrosion. The low pH environment sustains the aggressive conditions, preventing repassivation and promoting continued pit deepening.[42] 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 pitting potential, 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 electrolyte composition, effectively halting further propagation if conditions shift. Representative examples of pitting corrosion include its occurrence on stainless steel exposed to seawater, where chloride ions from the marine environment initiate pits at manganese sulfide inclusions, compromising the passive oxide layer.[43] Similarly, aluminum alloys suffer pitting when exposed to deicing salts containing chlorides, which infiltrate soil or runoff and attack the natural oxide film, leading to localized penetration in infrastructure like culverts.[44] 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.[45] 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.[46] The consequences of pitting corrosion are severe, as pits can cause perforation of thin-walled components, allowing leakage in pipelines or vessels, and act as stress concentrators that initiate cracks under mechanical loading, ultimately leading to catastrophic failure.Crevice Corrosion
Crevice corrosion is a form of localized corrosion that occurs within confined spaces or crevices on metal surfaces, where the geometry restricts the flow of oxygen and electrolyte, leading to accelerated attack compared to surrounding areas.[47] This phenomenon is particularly prevalent in chloride-containing environments, such as seawater, and affects materials like stainless steels and nickel-based alloys.[48] Unlike uniform corrosion, it results in deep, narrow cavities that can compromise structural integrity without visible external signs.[49] The mechanism of crevice corrosion begins with differential aeration: oxygen is rapidly depleted inside the crevice due to limited diffusion, establishing it as an anodic site where metal dissolution occurs, while the external surface acts as a cathodic site for oxygen reduction.[50] As metal ions hydrolyze within the crevice, the local pH drops significantly (often to 2-3), and chloride ions concentrate to maintain electroneutrality, creating an aggressive, autocatalytic environment that depassivates the protective oxide film.[47] This process, described in the critical crevice solution theory, stabilizes once the product of crevice depth (x) and current density (i) exceeds a critical value, allowing propagation.[50] Geometry 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.[47] Common examples include corrosion under gaskets or seals, within bolt threads, and beneath surface deposits on stainless steel components exposed to marine or industrial atmospheres.[48] In such sites, like incomplete welds in piping or fastener assemblies on coastal structures, the confined spaces trap moisture and salts, exacerbating the attack.[48] To evaluate susceptibility, standardized testing employs ASTM G78, which outlines procedures for immersing iron- and nickel-base stainless alloys in seawater or chloride solutions using multiple crevice assemblies to simulate confined geometries and measure maximum attack depth after 30 days.[51] This guide emphasizes factors like crevice former materials and environmental conditions to rank alloy resistance reliably.[51] Crevice corrosion differs from pitting in that it requires physical confinement for initiation via oxygen depletion and diffusion limitations, rather than direct passive film breakdown often triggered by localized factors like chloride 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).[49][47]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.[52] The primary mechanism involves the depletion of key alloying elements, such as chromium, 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.[53] This sensitization process creates chromium-depleted regions with reduced passivation ability, promoting anodic dissolution along the boundaries while the grain interiors remain relatively protected.[54] In welding applications, intergranular corrosion manifests as weld decay, where the heat-affected zone (HAZ) adjacent to the weld experiences sensitization from transient heating in the critical temperature range, leading to carbide precipitation and chromium depletion parallel to the weld bead.[55] 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.[56] Stabilized alloys, such as Type 321 stainless steel containing titanium, are designed to mitigate sensitization by forming titanium carbides that preferentially bind carbon, but they can still suffer from knifeline attack—a narrow band of intergranular corrosion at the weld fusion line.[57] This occurs because high welding temperatures dissolve existing stabilizers, and upon cooling through the sensitizing range, carbon competes with titanium for chromium, resulting in localized depletion at the knifeline.[58] Another variant is hydrogen grooving in austenitic stainless steels, where absorbed hydrogen facilitates intergranular cracking and grooving along boundaries, often under combined environmental and mechanical influences, by promoting decohesion and accelerating anodic attack in sensitized regions.[59] Practical examples include failures in chemical plant piping systems made of sensitized Type 304 or 347 stainless steel, where intergranular attack in the HAZ led to leaks and operational shutdowns after exposure to corrosive process fluids like nitric acid or chlorides.[60] Susceptibility to intergranular corrosion is commonly assessed using ASTM A262 standard practices, which include oxalic acid etching for screening and copper-copper sulfate (Strauss test) for confirmation of attack depth in sensitized austenitic stainless steels.[61] Prevention often relies on low-carbon variants or post-weld heat treatments to restore passivation and minimize boundary depletion.[53]Stress Corrosion Cracking
Stress corrosion cracking (SCC) is a brittle failure 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 initiation and propagation of cracks without significant overall material loss.[62] This process often leads to sudden, catastrophic failure under conditions where the material would otherwise be ductile, distinguishing it from purely mechanical or uniform corrosion processes.[63] 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.[62] This electrochemical process is strain-rate dependent, with crack growth rates typically ranging from 10^{-10} to 10^{-6} m/s in susceptible systems.[64] Susceptibility to SCC varies by alloy 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.[65] In high-strength steels, such as those with yield strengths over 1000 MPa, hydrogen embrittlement contributes to SCC, where atomic hydrogen generated by corrosion diffuses into the lattice, reducing ductility and facilitating intergranular or quasi-cleavage fracture in moist environments or under cathodic protection.[66] Another critical case is sulfide stress cracking in sour gas environments containing H2S, affecting carbon and low-alloy steels, where partial pressures as low as 0.05 psia H2S promote cracking at pH 3-4 and temperatures up to 80°C.[67] 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.[68] 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.[69] 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.[70] Fracture mechanics approaches, using precracked specimens under constant K, 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.[71]Erosion Corrosion
Erosion corrosion is a form of material degradation that occurs when the mechanical action of a moving corrosive fluid or slurry removes or damages protective surface films, thereby accelerating the underlying electrochemical corrosion process.[33] This combined effect is particularly prevalent in systems involving high-velocity flows, such as pipelines, pumps, and valves, where the synergy between erosion and corrosion can increase material loss rates by up to 50 times compared to either process alone in certain materials like grey cast iron.[72] The mechanism involves the fluid's abrasive action—often enhanced by suspended solids, turbulence, or cavitation—disrupting passive oxide layers on metals, exposing fresh substrate to corrosive attack, and abrading away corrosion products that might otherwise form a barrier.[73] A key aspect of the synergy in erosion corrosion is the mutual enhancement: erosion exposes new metal surfaces that corrode more rapidly, while corrosion weakens the material, making it more susceptible to mechanical removal by the flow.[72] This interaction is quantified in standards like ASTM G119-93, which distinguishes erosion-enhanced corrosion (ΔE_c) from corrosion-enhanced erosion (ΔC_e), with positive synergy dominating in aggressive environments.[72] Common examples include the formation of grooves and pits in copper tubing at pipe bends due to turbulent impingement attack from high-velocity water flows, and cavitation damage in pump impellers where collapsing vapor bubbles generate localized high-pressure impacts that strip protective films.[33] In marine applications, such as ship propellers and rudders made from nickel-aluminium bronze, exposure to seawater with entrained particulates leads to accelerated degradation through this mechanism.[73] Flow regimes play a critical role, with laminar flows generally causing less damage due to smoother transport, while turbulent flows increase mass transfer rates and impingement forces, often initiating sudden corrosion rate increases.[74] Velocity thresholds vary by material and fluid; for instance, velocities exceeding 5 ft/s (1.5 m/s) in water systems can trigger erosion corrosion in copper, whereas copper-nickel alloys tolerate up to 15 ft/s (4.6 m/s) in seawater before significant film removal occurs.[75][33] Mitigation strategies focus on enhancing material resistance through harder alloys or coatings that maintain integrity under flow, such as high-velocity oxygen fuel (HVOF) applied aluminium bronze for pumps, and design modifications like rounding pipe edges to reduce turbulence and impingement.[72] Increasing material hardness, as seen in friction stir-processed composites with chromium reinforcement, also forms more durable oxide films to counter film removal.[73]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 steam, but contaminants like sulfur and carbon introduce additional degradation modes, compromising structural integrity and efficiency in high-performance applications.[76] 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 diffusion of ions and electrons across the scale. This process typically adheres to the parabolic growth law, expressed as where is the oxide thickness, is the temperature-dependent rate constant, and is exposure time; the parabolic nature reflects decreasing growth rates as the scale thickens, limiting further diffusion.[77] Carl Wagner's theory underpins this behavior, modeling oxidation as a diffusion-controlled process in a compact scale, with ambipolar diffusion of cations, anions, and electrons through point defects driving growth under local equilibrium at the scale interfaces.[78] The theory assumes that interface reactions are faster than bulk diffusion, 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 steam 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 ductility. Sulfidation, typically more aggressive than oxidation, arises from exposure to sulfur-bearing gases like H₂S or SO₂, producing non-adherent sulfide scales with higher growth rates and leading to rapid metal wastage.[76][79] Illustrative examples highlight the practical impacts: in gas turbine blades, Ni-based superalloys face oxidation and sulfidation in hot combustion gases containing O₂ and SO₂ at around 900°C, forming alumina or chromia scales but risking porosity and degradation after prolonged cyclic exposure. Boiler tubes in power plants, operating in supercritical steam at 700–760°C, undergo oxidation where initial chromia layers provide protection, yet chromium volatilization as CrO₂(OH)₂ above 700°C causes alloy depletion and accelerated internal oxidation.[80][81] Resistance to these processes is enhanced through strategic alloying, particularly with chromium and aluminum, which promote selective formation of stable oxide scales. Chromium additions of 16–20 wt% enable chromia (Cr₂O₃) scale development below 1000°C, serving as an effective oxygen diffusion 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.[82] In Ni-superalloys for turbine applications, combined Cr and Al alloying ensures continuous protective layers, mitigating carburization and sulfidation as well.[82]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.[83] Unlike purely abiotic processes, MIC involves biofilms that create localized environments conducive to corrosion, often leading to pitting or tubercle formation.[84] A primary mechanism of MIC involves sulfate-reducing bacteria (SRB), such as Desulfovibrio species, which reduce sulfate ions to hydrogen sulfide (H₂S) under anaerobic conditions, using organic matter or hydrogen as electron donors.[85] The produced H₂S reacts with metal ions to form insoluble sulfides, like iron sulfide, which deposit on the surface and enhance cathodic reactions, thereby accelerating anodic metal dissolution.[86] Another key mechanism is driven by acid-producing bacteria (APB), including species like Acidithiobacillus, which generate organic acids such as acetic or sulfuric acid through metabolic processes, locally lowering the pH to values as low as 2-4 and dissolving protective oxide layers on metals.[87] Biofilms, composed of microbial communities embedded in extracellular polymeric substances, play a central role in MIC by forming heterogeneous layers on metal surfaces.[84] These biofilms create microenvironments with differential aeration, where oxygen-depleted areas beneath the biofilm act as anodes prone to corrosion, while oxygenated edges serve as cathodes, establishing galvanic cells similar to crevice corrosion effects.[83] Notable examples of MIC include internal corrosion of oil and gas pipelines by SRB, where biofilms lead to localized pitting and failures in carbon steel pipes transporting produced water.[88] On ship hulls, marine algae such as Shewanella species contribute to biofouling, fostering anaerobic zones that promote SRB activity and accelerate steel degradation in seawater.[89] Detection of MIC relies on molecular methods, such as quantitative polymerase chain reaction (qPCR), which targets specific genetic markers to identify and quantify corrosive bacteria like SRB without requiring cultivation.[90] This technique offers rapid results, detecting microbial densities as low as 10² cells per gram, enabling early intervention.[91] MIC predominantly occurs in anaerobic soils, where SRB thrive on sulfate-rich groundwater, and in cooling water systems, where biofilms form on heat exchanger surfaces due to nutrient availability and stagnation.[92] Standards such as NACE SP0775 provide guidelines for preparing and analyzing corrosion coupons to assess MIC risk in oilfield environments, including weight loss measurements and microbial enumeration.[93]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 carbon monoxide (CO), hydrogen (H₂), and hydrocarbons, where the thermodynamic driving force for carbon ingress exceeds the stability of the metal matrix.[94][95] The mechanism involves the deposition of carbon on the metal surface, leading to supersaturation, carbide formation, and subsequent fragmentation of the material. It proceeds in distinct stages: first, nucleation and dissolution of carbon into the metal lattice, forming a carbon-expanded austenite phase (γ_C) with up to 5.3 wt% carbon solubility at lower temperatures; second, precipitation of stable carbides 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 carbides decompose into metal particles and graphite, often via spinodal decomposition or direct intercalation of metal atoms into graphite layers, resulting in pitting and wastage.[95][94] For iron-based systems, metastable cementite (Fe_3C) may form initially before dissociating, while nickel and cobalt systems favor direct graphite formation without intermediate carbides.[94] 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.[95][96] Common in petrochemical plants, including syngas reformers and hydro-dealkylation units, as well as carburizing 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 diffusion theory for inward carbon transport, emphasizing the role of gas composition and temperature in driving supersaturation.[96][95]Corrosion Resistance Mechanisms
Intrinsic Material Properties
Intrinsic material properties play a fundamental role in determining a material's inherent resistance to corrosion, stemming from its atomic and electronic structure, 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 zinc exhibit conditional stability based on pH-dependent behavior. Alloying elements and microstructural features further tailor these traits, enhancing overall durability in engineering applications. Noble metals such as gold (Au) and platinum (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 standard hydrogen electrode, positioning them at the noble end of the electromotive series and preventing reaction with oxygen or most aqueous species under ambient conditions.[97] This electrochemical stability arises from the high energy required to form their ions, rendering them inert in environments where base metals corrode readily.[98] 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.[99] 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.[100] This pH-dependent behavior highlights the role of solution chemistry in modulating their inherent oxide solubility.[101] In alloy design, elements like chromium (Cr) and nickel (Ni) are strategically incorporated to enhance corrosion stability in iron-based alloys such as stainless steels. 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.[102] 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.[103][104] These alloying strategies leverage solid-solution strengthening and phase stabilization to achieve balanced mechanical and corrosion performance.[105] Microstructural features, including grain size and secondary phases, significantly influence corrosion susceptibility by altering local galvanic interactions and diffusion paths. Finer grain sizes generally improve resistance by increasing grain boundary density, which can distribute corrosion more uniformly and reduce propagation rates, as observed in ultrafine-grained aluminum alloys where severe plastic deformation refines structure to enhance pitting resistance.[106] 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.[107] Grain boundary 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.[108] Titanium (Ti) illustrates intrinsic resistance through its strong oxygen affinity, forming a tenacious TiO₂ layer that imparts stability in aqueous environments like water and seawater. 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.[109] The oxide's thermodynamic stability prevents further degradation, with Ti exhibiting corrosion rates below 0.01 mm/year in distilled water at ambient temperatures.[110] This property underpins titanium's use in aerospace and biomedical applications where long-term durability is essential.[111]Passivation Processes
Passivation processes refer to the electrochemical formation of a thin, protective oxide film on metal surfaces that significantly reduces the corrosion rate by acting as a barrier to ion transport and electron transfer. In corrosion-resistant alloys such as stainless steel, this passive film is typically composed of chromium oxide (Cr₂O₃) and achieves a thickness of 1-5 nm, providing a stable, self-healing layer under appropriate conditions.[112][113] The formation of the passive film occurs through anodic polarization, where the metal surface is exposed to an oxidizing environment that promotes the growth of the oxide 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 film that maintains low corrosion currents in the passive region of the polarization curve. At sufficiently high anodic potentials, however, the film undergoes transpassive breakdown, where the oxide becomes unstable, leading to accelerated dissolution and loss of protectiveness.[114] 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 current density, 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.[115][116] A practical example of controlled passivation is the nitric acid treatment of stainless steel, as specified in ASTM A967, which involves immersion in 20-25% nitric acid at 50-60°C for 20-30 minutes to remove surface contaminants and enrich the chromium oxide 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., chloride), adsorb onto the film, causing localized thinning or defects that lead to breakdown and subsequent localized corrosion.[117][118]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 service life 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 aerospace, automotive, and construction.[119] 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.[120] 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.[121] These zinc coatings can provide corrosion protection for decades in atmospheric exposure, depending on environmental severity.[122] Reactive coatings, such as conversion layers, chemically alter the substrate surface to create adherent oxide or phosphate films that enhance corrosion resistance and serve as primers for subsequent coatings. Phosphate conversion coatings involve immersing the metal in a phosphoric acid solution to form crystalline iron phosphate layers, which improve paint adhesion and provide mild corrosion protection on steel.[123] Chromate conversion coatings, historically used on aluminum and zinc, 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 hexavalent chromium toxicity.[124] Anodization is an electrolytic process that grows a thick, porous oxide layer on metals like aluminum and titanium, significantly enhancing their corrosion resistance through barrier protection. For aluminum, sulfuric acid anodizing produces an oxide film up to 25 micrometers thick, which can be sealed to block ion ingress and is widely used in architectural and aerospace applications.[125] On titanium, anodization in alkaline electrolytes forms a denser rutile oxide layer, improving resistance to pitting and crevice corrosion in biomedical and marine environments.[126] 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.[127] Such layers have demonstrated up to 99.999% reduction in microbial colonization in laboratory tests against Pseudomonas aeruginosa.[128] 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.[129][130] 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 concrete with reduced porosity and chloride ingress, thereby protecting embedded steel reinforcement from corrosion.[131] CPF can reduce chloride ingress by 46–56% compared to traditional formwork, enhancing long-term durability in chloride-rich environments like bridges.[131] Application methods for these coatings vary by type and substrate, with dipping used for uniform coverage in galvanizing—where steel is immersed in molten zinc at 450°C—and spraying for paints and epoxies to achieve thin, controlled layers on complex geometries.[132] Durability is assessed through standardized tests like the salt fog test (ASTM B117), which exposes coated samples to a 5% sodium chloride mist at 35°C to evaluate corrosion resistance over hours to thousands of hours, simulating accelerated marine exposure.[133]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.[134] Cathodic protection is the most widely used electrochemical technique, operating on the principle of making the protected metal a cathode in an electrochemical cell, which prevents oxidation. In sacrificial anode systems, more reactive metals such as zinc, aluminum, or magnesium are electrically connected to the structure; these anodes corrode preferentially, providing electrons to the protected metal. For instance, zinc anodes are commonly attached to ship hulls and propellers to prevent corrosion in seawater, while magnesium anodes are favored in less conductive environments like freshwater systems due to their more negative potential in the galvanic series. Anode selection relies on the galvanic series, which ranks metals by nobility to ensure the anode is sufficiently active relative to the protected structure.[135][136][137] Impressed current cathodic protection (ICCP) employs an external DC power source, typically a transformer-rectifier, to supply protective current through inert anodes, offering greater control and longevity for large-scale applications. This method is ideal for buried pipelines, 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.[138][134] A key criterion for effective cathodic protection of steel 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 corrosion. More negative potentials may be required in aerated soils, but overprotection risks hydrogen embrittlement.[139][140] Anodic protection, in contrast, polarizes the metal to a more positive potential within its passive region, where a stable oxide film forms to inhibit corrosion; this technique is applied in environments supporting passivity, such as concentrated sulfuric acid. For sulfuric acid storage tanks, low-voltage DC current from platinum-activated titanium anodes maintains the steel at +0.5 to +1.0 V versus a reference electrode, dramatically reducing iron dissolution and contamination. Anodic systems require precise control to avoid breakdown of the passive layer.[141][142] 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 linear polarization 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.[143][144] 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.[145][138]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 service life of materials in aggressive conditions. Unlike physical barriers, inhibitors act through dissolution and adsorption, making them suitable for dynamic systems like fluids.[146] 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 oxide layer that blocks further dissolution; however, their use has declined due to toxicity concerns. Cathodic inhibitors, exemplified by calcium carbonate (CaCO₃), precipitate on the surface to limit access of cathodic reactants like oxygen or hydrogen 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.[147][146][148] The primary mechanisms of corrosion inhibitors involve adsorption onto the metal surface and subsequent film formation, which physically separates the substrate from the corrosive electrolyte. Adsorption occurs via physisorption (electrostatic interactions) or chemisorption (electron sharing), leading to monolayer 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): 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.[149][146][150] In practical applications, corrosion inhibitors are widely used in coolants and fuels to safeguard engine components and pipelines from degradation. In automotive and industrial coolants, organic phosphates or silicates maintain pH stability and prevent cavitation corrosion in radiators, achieving corrosion rates below 0.1 mm/year in mixed-metal systems. For fuels, such as diesel or aviation kerosene, amine-based inhibitors mitigate microbial-induced corrosion and water contamination effects, ensuring compliance with standards like ASTM D665. Emerging since the 2010s, green inhibitors derived from plant extracts—such as tannins from grape pomace 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.[151][152][153] Controlled environments complement inhibitors by modifying ambient conditions to minimize corrosion drivers like moisture and acidity. Dehumidification systems, targeting relative humidity below 40%, prevent condensation 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 sodium hydroxide, shifts the solution toward passivity for metals like aluminum, reducing general corrosion in water systems. In concrete admixtures, calcium nitrite inhibitors are incorporated during mixing to delay chloride-induced corrosion of rebar in aggressive exposures.[154][155] 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.[156][157][158]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 garnet at high velocities to strip rust, mill scale, and coatings, commonly applied to large structures like ship hulls where uniform corrosion products accumulate.[159] This method achieves a clean surface profile essential for subsequent treatments, with steel grit providing angular particles for aggressive removal on ferrous metals.[160] Grinding and power tool cleaning employ rotary tools, wire brushes, or sanding equipment to mechanically eliminate loose rust, paint, and scale from localized areas, suitable for spot repairs on intricate components.[161] Defined under SSPC-SP 3, this technique removes all loose detrimental foreign matter but leaves tightly adherent material intact, ensuring minimal substrate damage.[162] High-pressure water jetting uses pressurized water streams, often exceeding 5,000 psi, to dislodge corrosion without abrasives, preserving surface details on sensitive substrates like stainless steel.[163] An emerging mechanical technique is laser cleaning, which employs high-powered lasers to ablate corrosion layers through vaporization 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 aerospace and heritage conservation as of 2025.[164] Chemical removal techniques dissolve corrosion products through reactive solutions, targeting specific metal types. Acid pickling immerses steel in hydrochloric acid (HCl) solutions to remove rust and oxides via chemical reaction, widely used in industrial batch processes for carbon steel components.[165] Concentrations typically range from 5-15% HCl, with immersion times of 10-30 minutes depending on rust thickness, followed by rinsing to neutralize residues.[166] Alkaline derusting employs sodium hydroxide or other bases in heated solutions to saponify organic contaminants and loosen rust, particularly effective for initial cleaning of heavily soiled ferrous metals before acid stages.[167] Mechanical methods like abrasive blasting and grinding prepare rusted surfaces for repainting, ensuring adhesion and preventing under-film corrosion recurrence.[168] For historic artifact restoration, such as corroded iron tools or bronze statues, conservators combine gentle mechanical scraping with chemical baths to preserve patina while removing active corrosion layers.[169] Safety considerations include the use of corrosion inhibitors during water-based processes to prevent flash rust formation on freshly cleaned ferrous surfaces exposed to moisture.[170] Environmental regulations govern chemical disposal, with restrictions on phosphate-based inhibitors due to eutrophication risks in waterways, prompting shifts to non-phosphate alternatives.[165] Industry standards like SSPC-SP 10 define near-white blast cleaning, requiring removal of at least 95% of rust and stains for high-performance applications.[171]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 oil and gas, infrastructure, and aerospace, where premature failure can lead to significant safety and economic consequences. Key approaches include welding and patching, which are selected based on the extent of damage, material type, and environmental exposure.[172][173] 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 heat-affected zone (HAZ), particularly in hardenable steels like SA-516 Gr. 70. To mitigate this, preheating to several hundred degrees Fahrenheit is applied to slow cooling rates and reduce HAZ hardness below 22 HRC, while low-hydrogen welding processes—such as those using basic-coated electrodes or fluxes—are utilized to limit diffusible hydrogen levels. Post-weld heat treatment (PWHT) further tempers the HAZ and relieves residual stresses, ensuring long-term durability in corrosive environments. Non-destructive testing (NDT), such as ultrasonic testing, is integrated pre-repair to assess remaining wall thickness and detect subsurface defects, enabling precise excavation of damaged areas before welding.[172][174][173] 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 pipeline integrity in oil and gas applications.[175] In bridge rehabilitation, welding and patching have been successfully applied to corroded steel girders, including for distorted structures due to fire or corrosion, as seen in rapid restorations of fire-damaged bridges like the MacArthur Maze 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 welding requires controlled post-weld heat treatment to preserve corrosion resistance and avoid sensitization. For long-term protection, especially after welding, cathodic protection systems are often implemented, using galvanic anodes or impressed current to shield repaired areas from ongoing electrochemical corrosion in aggressive soils or waters.[176][177][178]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 gross domestic product based on 2013 data. As of 2025, these costs are estimated to exceed $2.5 trillion annually.[4][179] 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.[180] These costs are distributed across key sectors, particularly infrastructure, transportation, and energy, 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 drinking water systems, electrical grids, and gas distribution networks. Transportation contributes $29.7 billion (21.5%), primarily from vehicle rust and corrosion in aircraft and ships, while infrastructure 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 infrastructure 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 $276 billion total) and serving as a representative illustration of global patterns:| Sector | Annual Cost ($ billion) | Percentage of Subtotal |
|---|---|---|
| Utilities | 47.9 | 34.7% |
| Transportation | 29.7 | 21.5% |
| Government | 20.1 | 14.6% |
| Infrastructure | 22.6 | 16.4% |
| Production/Manufacturing | 17.6 | 12.8% |
| Subtotal | 137.9 | 100% |