Corrosion

Corrosion is a natural process, which converts a refined metal to a more chemically-stable form, such as its oxide, hydroxide, or sulfide. It is the gradual destruction of materials (usually metals) by chemical and/or electrochemical reaction with their environment. Corrosion engineering is the field dedicated to controlling and stopping corrosion.

In the most common use of the word, this means electrochemical oxidation of metal in reaction with an oxidant such as oxygen or sulfates. Rusting, the formation of iron oxides, is a well-known example of electrochemical corrosion. This type of damage typically produces oxide(s) or salt(s) of the original metal, and results in a distinctive orange colouration. 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 strength, appearance and permeability to liquids and gases.

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.

Rust and dirt
Rust, the most familiar example of corrosion
Corroding machinery at old White Island sulphur mine
Volcanic gases have accelerated the extensive corrosion of this abandoned mining machinery, rendering it almost unrecognizable
Rust Bolt
Corrosion on exposed metal, including a bolt and nut
Side view Crow Hall Railway Bridge north of Preston Lancs corroding - general
Side view Crow Hall Railway Bridge north of Preston Lancs corroding – general
Side view Crow Hall Railway Bridge north of Preston Lancs corroding
Side view Crow Hall Railway Bridge north of Preston Lancs corroding

Galvanic corrosion

Galvanic corrosion of aluminum and steel in seawater
Galvanic corrosion of aluminium. A 5-mm-thick aluminium alloy plate is physically (and hence, electrically) connected to a 10-mm-thick mild steel structural support. Galvanic corrosion occurred on the aluminium plate along the joint with the steel. Perforation of aluminium plate occurred within 2 years.[1]

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. 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

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

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

Some metals are more intrinsically resistant to corrosion than others (for some examples, see galvanic series). There are various ways of protecting metals from corrosion (oxidation) including painting, hot dip galvanizing, and combinations of these.[2]

Intrinsic chemistry

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

The materials most resistant to corrosion are those for which corrosion is thermodynamically unfavorable. Any corrosion products of gold or platinum tend to decompose spontaneously into pure metal, which is why these elements can be found in metallic form on Earth and have long been valued. More common "base" metals can only be protected by more temporary means.

Some metals have naturally slow reaction kinetics, even though their corrosion is thermodynamically favorable. These include such metals as zinc, magnesium, and cadmium. While corrosion of these metals is continuous and ongoing, it happens at an acceptably slow rate. An extreme example is graphite, which releases large amounts of energy upon oxidation, but has such slow kinetics that it is effectively immune to electrochemical corrosion under normal conditions.

Passivation

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.

Corrosion in passivated materials

Passivation is extremely useful in mitigating corrosion damage, however even a high-quality alloy will corrode if its ability to form a passivating film is hindered. Proper selection of the right grade of material for the specific environment is important for the long-lasting performance of this group of materials. If breakdown occurs in the passive film due to chemical or mechanical factors, the resulting major modes of corrosion may include pitting corrosion, crevice corrosion, and stress corrosion cracking.

Pitting corrosion

Pitting corrosion-scheme
Diagram showing cross-section of pitting corrosion

Certain conditions, such as low concentrations of oxygen or high concentrations of species such as chloride which complete 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, but it can be prevented by control of the alloy's environment.

Pitting results when a small hole, or cavity, forms in the metal, usually as a result of de-passivation of a small area. This area becomes anodic, while part of the remaining metal becomes cathodic, producing a localized galvanic reaction. The deterioration of this small area penetrates the metal and can lead to failure. This form of corrosion is often difficult to detect due to the fact that it is usually relatively small and may be covered and hidden by corrosion-produced compounds.

Weld decay and knifeline attack

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

Stainless steel can pose special corrosion challenges, since its passivating behavior relies on the presence of a major alloying component (chromium, at least 11.5%). Because of the elevated temperatures of welding and heat treatment, chromium carbides can form in the grain boundaries of stainless alloys. This chemical reaction robs the material of chromium in the zone near the grain boundary, making those areas much less resistant to corrosion. This creates a galvanic couple with the well-protected alloy nearby, which leads to "weld decay" (corrosion of the grain boundaries in the heat affected zones) in highly corrosive environments. This process can seriously reduce the mechanical strength of welded joints over time.

A stainless steel is said to be "sensitized" if chromium carbides are formed in the microstructure. A typical microstructure of a normalized type 304 stainless steel shows no signs of sensitization, while a heavily sensitized steel shows the presence of grain boundary precipitates. The dark lines in the sensitized microstructure are networks of chromium carbides formed along the grain boundaries.[3]

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

Crevice corrosion of 316 stainless steel in desalination
Corrosion in the crevice between the tube and tube sheet (both made of type 316 stainless steel) of a heat exchanger in a seawater desalination plant[4]

Crevice corrosion is a localized form of corrosion occurring in confined spaces (crevices), to which the access of the working fluid from the environment is limited. Formation of a differential aeration cell leads to corrosion inside the crevices. Examples of crevices are gaps and contact areas between parts, under gaskets or seals, inside cracks and seams, spaces filled with deposits and under sludge piles.

Crevice corrosion is influenced by the crevice type (metal-metal, metal-nonmetal), 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.

Microbial corrosion

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.[5] 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.

High-temperature corrosion

High-temperature corrosion is chemical deterioration of a material (typically a metal) as a result of heating. This non-galvanic form of corrosion can occur when a metal is subjected to a hot atmosphere containing oxygen, sulfur, or other compounds capable of oxidizing (or assisting the oxidation of) the material concerned. For example, materials used in aerospace, power generation and even in car engines have to resist sustained periods at high temperature in which they may be exposed to an atmosphere containing potentially highly corrosive products of combustion.

The products of high-temperature corrosion can potentially be turned to the advantage of the engineer. The formation of oxides on stainless steels, for example, can provide a protective layer preventing further atmospheric attack, allowing for a material to be used for sustained periods at both room and high temperatures in hostile conditions. Such high-temperature corrosion products, in the form of compacted oxide layer glazes, prevent or reduce wear during high-temperature sliding contact of metallic (or metallic and ceramic) surfaces.

Metal dusting

Metal dusting is a catastrophic form of corrosion that occurs when susceptible materials are exposed to environments with high carbon activities, such as synthesis gas and other high-CO environments. The corrosion manifests itself as a break-up of bulk metal to metal powder. The suspected mechanism is firstly the deposition of a graphite layer on the surface of the metal, usually from carbon monoxide (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

Corrosion protection
The US military shrink wraps equipment such as helicopters to protect them from corrosion and thus save millions of dollars

Various treatments are used to slow corrosion damage to metallic objects which are exposed to the weather, salt water, acids, or other hostile environments. Some unprotected metallic alloys are extremely vulnerable to corrosion, such as those used in neodymium magnets, which can spall or crumble into powder even in dry, temperature-stable indoor environments unless properly treated to discourage corrosion.

Surface treatments

When surface treatments are used to retard corrosion, great care must be taken to ensure complete coverage, without gaps, cracks, or pinhole defects. Small defects can act as an "Achilles' heel", allowing corrosion to penetrate the interior and causing extensive damage even while the outer protective layer remains apparently intact for a period of time.

Applied coatings

Galvanized surface
Galvanized surface

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.

Corroding Steel Electrification Gantry
Corroding Steel Electrification Gantry

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

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 famous for their mineral deposits), chromates, phosphates, polyaniline, other conducting polymers and a wide range of specially-designed chemicals that resemble surfactants (i.e. long-chain organic molecules with ionic end groups).

Anodization

Belaying8
This climbing descender is anodized with a yellow finish.

Aluminium alloys often undergo a surface treatment. Electrochemical conditions in the bath are carefully adjusted so that uniform pores, several nanometers wide, appear in the metal's oxide film. These pores allow the oxide to grow much thicker than passivating conditions would allow. At the end of the treatment, the pores are allowed to seal, forming a harder-than-usual surface layer. If this coating is scratched, normal passivation processes take over to protect the damaged area.

Anodizing is very resilient to weathering and corrosion, so it is commonly used for building facades and other areas where the surface will come into regular contact with the elements. While being resilient, it must be cleaned frequently. If left without cleaning, panel edge staining will naturally occur. Anodization is the process of converting an anode into cathode by bringing a more active anode in contact with it.

Biofilm coatings

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.[6]

Controlled permeability formwork

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

Cathodic protection (CP) is a technique to control the corrosion of a metal surface by making that surface the cathode of an electrochemical cell. Cathodic protection systems are most commonly used to protect steel, and pipelines and tanks; steel pier piles, ships, and offshore oil platforms.

Sacrificial anode protection

Sacrificial anode
Sacrificial anode attached to the hull of a ship

For effective CP, the potential of the steel surface is polarized (pushed) more negative until the metal surface has a uniform potential. With a uniform potential, the driving force for the corrosion reaction is halted. For galvanic CP systems, the anode material corrodes under the influence of the steel, and eventually it must be replaced. The polarization is caused by the current flow from the anode to the cathode, driven by the difference in electrode potential between the anode and the cathode. The most common sacrificial anode materials are aluminum, zinc, magnesium and related alloys. Aluminum has the highest capacity, and magnesium has the highest driving voltage and is thus used where resistance is higher. Zinc is general purpose and the basis for galvanizing.

Impressed current cathodic protection

For larger structures, galvanic anodes cannot economically deliver enough current to provide complete protection. Impressed current cathodic protection (ICCP) systems use anodes connected to a DC power source (such as a cathodic protection rectifier). 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

Anodic protection impresses anodic current on the structure to be protected (opposite to the cathodic protection). It is appropriate for metals that exhibit passivity (e.g. stainless steel) and suitably small passive current over a wide range of potentials. It is used in aggressive environments, such as solutions of sulfuric acid.

Rate of corrosion

NdFeB corrosion
These neodymium magnets corroded extremely rapidly after only 5 months of outside exposure

A simple test for measuring corrosion is the weight loss method.[7] 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

Silver Bridge collapsed, Ohio side
The collapsed Silver Bridge, as seen from the Ohio side

In 2002, the US Federal Highway Administration released a study titled "Corrosion Costs and Preventive Strategies in the United States" on the direct costs associated with metallic corrosion in the US industry. In 1998, the total annual direct cost of corrosion in the U.S. was ca. $276 billion (ca. 3.2% of the US gross domestic product).[8] 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.[9]

Rust is one of the most common causes of bridge accidents. As rust has a much higher volume than the originating mass of iron, its build-up can also cause failure by forcing apart adjacent parts. It was the cause of the collapse of the Mianus river bridge in 1983, when the bearings rusted internally and pushed one corner of the road slab off its support. Three drivers on the roadway at the time died as the slab fell into the river below. The following NTSB 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 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.[10] The economic impact on homeowners, condo dwellers, and the public infrastructure is estimated at 22 billion dollars as the insurance industry braces for a wave of claims due to pipe failures.

Corrosion in nonmetals

Most ceramic 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

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

Glaskorrosion
Glass corrosion

Glass is characterized by a high degree of corrosion-resistance. Because of its high water-resistance it is often used as primary packaging material in the pharma industry since most medicines are preserved in a watery solution.[11] 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.[12] 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.[13]

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 i-th cation effective diffusion coefficient (cm2/d), which depends on pH of contacting water as Di = Di0·10–pH, and ρ is the density of the glass (g/cm3).

Glass network dissolution is characteristic of the later phases of corrosion and causes a congruent release of ions into the water solution at a time-independent rate in dilute solutions (g/cm2·d):

,

where rh is the stationary hydrolysis (dissolution) rate of the glass (cm/d). In closed systems the consumption of protons from the aqueous phase increases the pH and causes a fast transition to hydrolysis.[14] However, a further saturation of solution with silica impedes hydrolysis and causes the glass to return to an ion-exchange, e.g. diffusion-controlled regime of corrosion.

In typical natural conditions normalized corrosion rates of silicate glasses are very low and are of the order of 10−7–10−5 g/(cm2·d). The very high durability of silicate glasses in water makes them suitable for hazardous and nuclear waste immobilisation.

Glass corrosion tests

Spidergraph ChemDurab
Effect of addition of a certain glass component on the chemical durability against water corrosion of a specific base glass (corrosion test ISO 719).[15]

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,[16] and under other conditions.

The standard procedure ISO 719[17] 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

References

  1. ^ Galvanic Corrosion. Corrosionclinic.com. Retrieved on 2012-07-15.
  2. ^ Methods of Protecting Against Corrosion Piping Technology & Products, (retrieved January 2012)
  3. ^ Intergranular Corrosion. Corrosionclinic.com. Retrieved on 2012-07-15.
  4. ^ Crevice Corrosion. Corrosionclinic.com. Retrieved on 2012-07-15.
  5. ^ 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
  6. ^ 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.
  7. ^ [Fundamentals of corrosion – Mechanisms, Causes and Preventative Methods]. Philip A. Schweitzer, Taylor and Francis Group, LLC (2010) ISBN 978-1-4200-6770-5, p. 25.
  8. ^ Gerhardus H. Koch, Michiel P.H.Brongers, Neil G. Thompson, Y. Paul Virmani and Joe H. Payer. CORROSION COSTS AND PREVENTIVE STRATEGIES IN THE UNITED STATES – report by CC Technologies Laboratories, Inc. to Federal Highway Administration (FHWA), September 2001.
  9. ^ "NACE Corrosion Costs Study". Cor-Pro.com. NACE. 2013-11-12. Retrieved 16 June 2014.
  10. ^ Daniel Robles. "Potable Water Pipe Condition Assessment For a High Rise Condominium in The Pacific Northwest". GSG Group, Inc. Dan Robles, PE. Retrieved 10 December 2012.
  11. ^ Bettine Boltres (2015) When Glass Meets Pharma: Insights about Glass as Primary Packaging Material. Editio Cantor. ISBN 978-3-87193-432-2
  12. ^ A.K. Varshneya (1994). Fundamentals of inorganic glasses. Gulf Professional Publishing. ISBN 0127149708.
  13. ^ M.I. Ojovan, W.E. Lee. New Developments in Glassy Nuclear Wasteforms. Nova Science Publishers, New York (2007) ISBN 1600217834 pp. 100 ff.
  14. ^ Corrosion of Glass, Ceramics and Ceramic Superconductors. D.E. Clark, B.K. Zoitos (eds.), William Andrew Publishing/Noyes (1992) ISBN 081551283X.
  15. ^ Calculation of the Chemical Durability (Hydrolytic Class) of Glasses. Glassproperties.com. Retrieved on 2012-07-15.
  16. ^ Vapor Hydration Testing (VHT) Archived December 14, 2007, at the Wayback Machine. Vscht.cz. Retrieved on 2012-07-15.
  17. ^ International Organization for Standardization, Procedure 719 (1985). Iso.org (2011-01-21). Retrieved on 2012-07-15.

Further reading

External links

Anodizing

Anodizing (also spelled anodising in British English) is an electrolytic passivation process used to increase the thickness of the natural oxide layer on the surface of metal parts.

The process is called anodizing because the part to be treated forms the anode electrode of an electrolytic cell. Anodizing increases resistance to corrosion and wear, and provides better adhesion for paint primers and glues than bare metal does. Anodic films can also be used for a number of cosmetic effects, either with thick porous coatings that can absorb dyes or with thin transparent coatings that add interference effects to reflected light.

Anodizing is also used to prevent galling of threaded components and to make dielectric films for electrolytic capacitors. Anodic films are most commonly applied to protect aluminium alloys, although processes also exist for titanium, zinc, magnesium, niobium, zirconium, hafnium, and tantalum. Iron or carbon steel metal exfoliates when oxidized under neutral or alkaline microelectrolytic conditions; i.e., the iron oxide (actually ferric hydroxide or hydrated iron oxide, also known as rust) forms by anoxic anodic pits and large cathodic surface, these pits concentrate anions such as sulfate and chloride accelerating the underlying metal to corrosion. Carbon flakes or nodules in iron or steel with high carbon content (high-carbon steel, cast iron) may cause an electrolytic potential and interfere with coating or plating. Ferrous metals are commonly anodized electrolytically in nitric acid or by treatment with red fuming nitric acid to form hard black ferric oxide. This oxide remains conformal even when plated on wire and the wire is bent.

Anodizing changes the microscopic texture of the surface and the crystal structure of the metal near the surface. Thick coatings are normally porous, so a sealing process is often needed to achieve corrosion resistance. Anodized aluminium surfaces, for example, are harder than aluminium but have low to moderate wear resistance that can be improved with increasing thickness or by applying suitable sealing substances. Anodic films are generally much stronger and more adherent than most types of paint and metal plating, but also more brittle. This makes them less likely to crack and peel from aging and wear, but more susceptible to cracking from thermal stress.

Antifreeze

An antifreeze is an additive which lowers the freezing point of a water-based liquid and increases its boiling point.

An antifreeze mixture is used to achieve freezing-point depression for cold environments and also achieves boiling-point elevation ("anti-boil") to allow higher coolant temperature. Freezing and boiling points are colligative properties of a solution, which depend on the concentration of the dissolved substance.

Because water has good properties as a coolant, water plus antifreeze is used in internal combustion engines and other heat transfer applications, such as HVAC chillers and solar water heaters. The purpose of antifreeze is to prevent a rigid enclosure from bursting due to expansion when water freezes. Commercially, both the additive (pure concentrate) and the mixture (diluted solution) are called antifreeze, depending on the context. Careful selection of an antifreeze can enable a wide temperature range in which the mixture remains in the liquid phase, which is critical to efficient heat transfer and the proper functioning of heat exchangers.

Salts are frequently used for de-icing, but salt solutions are not used for cooling systems because they can cause severe corrosion to metals. Instead, non-corrosive antifreezes are commonly used for critical de-icing, such as for aircraft wings.

Coating

A coating is a covering that is applied to the surface of an object, usually referred to as the substrate. The purpose of applying the coating may be decorative, functional, or both. The coating itself may be an all-over coating, completely covering the substrate, or it may only cover parts of the substrate. An example of all of these types of coating is a product label on many drinks bottles- one side has an all-over functional coating (the adhesive) and the other side has one or more decorative coatings in an appropriate pattern (the printing) to form the words and images.

Paints and lacquers are coatings that mostly have dual uses of protecting the substrate and being decorative, although some artists paints are only for decoration, and the paint on large industrial pipes is presumably only for the function of preventing corrosion.

Functional coatings may be applied to change the surface properties of the substrate, such as adhesion, wettability, corrosion resistance, or wear resistance. In other cases, e.g. semiconductor device fabrication (where the substrate is a wafer), the coating adds a completely new property, such as a magnetic response or electrical conductivity, and forms an essential part of the finished product.

A major consideration for most coating processes is that the coating is to be applied at a controlled thickness, and a number of different processes are in use to achieve this control, ranging from a simple brush for painting a wall, to some very expensive machinery applying coatings in the electronics industry. A further consideration for 'non-all-over' coatings is that control is needed as to where the coating is to be applied. A number of these non-all-over coating processes are printing processes.

Many industrial coating processes involve the application of a thin film of functional material to a substrate, such as paper, fabric, film, foil, or sheet stock. If the substrate starts and ends the process wound up in a roll, the process may be termed "roll-to-roll" or "web-based" coating. A roll of substrate, when wound through the coating machine, is typically called a web.

Coatings may be applied as liquids, gases or solids.

Corrosion inhibitor

A corrosion inhibitor is a chemical compound that, when added to a liquid or gas, decreases the corrosion rate of a material, typically a metal or an alloy. The effectiveness of a corrosion inhibitor depends on fluid composition, quantity of water, and flow regime. A common mechanism for inhibiting corrosion involves formation of a coating, often a passivation layer, which prevents access of the corrosive substance to the metal. Permanent treatments such as chrome plating are not generally considered inhibitors, however. Instead corrosion inhibitors are additives to the fluids that surround the metal or related object.

Corrosion inhibitors are common in industry, and also found in over-the-counter products, typically in spray form in combination with a lubricant and sometimes a penetrating oil.

Corrosion of Conformity

Corrosion of Conformity (also known as C.O.C.) is an American heavy metal band from Raleigh, North Carolina formed in 1982. This band has undergone multiple line-up changes throughout its existence with guitarist Woody Weatherman as the sole constant member. Weatherman, founding bassist Mike Dean, founding drummer Reed Mullin, and vocalist and rhythm guitarist Pepper Keenan (who joined the band in 1989) are widely regarded as its classic line-up. After a hiatus in 2006, Corrosion of Conformity returned in 2010 without Keenan, who had been busy touring and recording with Down, but announced their reunion with him in December 2014.The band started as a hardcore punk band but later moved towards a slower and blues-tinged heavy metal sound. To date, the band has released ten studio albums, four EPs, one compilation, and one live album. Their first three studio albums―Eye for an Eye (1984), Animosity (1985) and Blind (1991)―attracted the attention of Columbia Records, who signed the band in 1993. Corrosion of Conformity found success with the release of their 1994 fourth studio album, Deliverance, which peaked at number 155 on the Billboard 200 and spawned the hits "Albatross" and "Clean My Wounds". Their 1996 follow-up Wiseblood was also successful, and at the time, it was Corrosion of Conformity's highest-charting album in the United States, peaking at number 104 on the Billboard 200. Their latest album, No Cross No Crown, was released on January 12, 2018 on Nuclear Blast Records, and became the band's first album to enter the Top 100 on the Billboard 200, where it peaked at number 67.

Duralumin

Duralumin (also called duraluminum, duraluminium, duralum, dural(l)ium, or dural) is a trade name for one of the earliest types of age-hardenable aluminium alloys. Its use as a trade name is obsolete, and today the term mainly refers to aluminium–copper alloys, designated as the 2000 series by the International Alloy Designation System (IADS), as with 2014 and 2024 alloys used in airframe fabrication.

Electrolysis

In chemistry and manufacturing, electrolysis is a technique that uses a direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of elements from naturally occurring sources such as ores using an electrolytic cell. The voltage that is needed for electrolysis to occur is called the decomposition potential.

Galvanic corrosion

Galvanic corrosion (also called bimetallic corrosion) is an electrochemical process in which one metal corrodes preferentially when it is in electrical contact with another, in the presence of an electrolyte. A similar galvanic reaction is exploited in primary cells to generate a useful electrical voltage to power portable devices.

Galvanization

Galvanization or galvanizing is the process of applying a protective zinc coating to steel or iron, to prevent rusting. The most common method is hot-dip galvanizing, in which the parts are submerged in a bath of molten zinc.

Intercalation (chemistry)

In chemistry, intercalation is the reversible inclusion or insertion of a molecule (or ion) into materials with layered structures. Examples are found in graphite and transition metal dichalcogenides.

List of blade materials

Blade materials are those used to make the blade of a knife or other simple edged hand tool or weapon, such as a hatchet or sword.

The blade of a knife can be made from a variety of materials, the most common being carbon steel, stainless steel, tool steel and alloy steel. Other less-common materials used in knife blades include: cobalt and titanium alloys, ceramics, obsidian, and plastic.

The hardness of steel is usually stated as a number on the Rockwell C scale (HRC). The Rockwell scale is a hardness scale based on the resistance to indentation of a material, as opposed to other scales such as the Mohs scale (scratch resistance) testing used in mineralogy. As hardness increases, the blade becomes capable of taking and holding a better edge, but is more difficult to sharpen and more brittle (commonly called less "tough"). Laminating a softer steel between a harder one is an expensive process that to some extent gives the benefits of both types (see Damascus steel).

Passivation (chemistry)

Passivation, in physical chemistry and engineering, refers to a material becoming "passive," that is, less affected or corroded by the environment of future use. Passivation involves creation of an outer layer of shield material that is applied as a microcoating, created by chemical reaction with the base material, or allowed to build from spontaneous oxidation in the air. As a technique, passivation is the use of a light coat of a protective material, such as metal oxide, to create a shell against corrosion. Passivation can occur only in certain conditions, and is used in microelectronics to enhance silicon. The technique of passivation strengthens and preserves the appearance of metallics. In electrochemical treatment of water, passivation reduces the effectiveness of the treatment by increasing the circuit resistance, and active measures are typically used to overcome this effect, the most common being polarity reversal, which results in limited rejection of the fouling layer. Other proprietary systems to avoid electrode passivation, several discussed below, are the subject of ongoing research and development.

When exposed to air, many metals naturally form a hard, relatively inert surface, as in the tarnish of silver. In the case of other metals, such as iron, a somewhat rough porous coating is formed from loosely adherent corrosion products. In this case, a substantial amount of metal is removed, which is either deposited or dissolved in the environment. Corrosion coating reduces the rate of corrosion by varying degrees, depending on the kind of base metal and its environment, and is notably slower in room-temperature air for aluminium, chromium, zinc, titanium, and silicon (a metalloid); the shell of corrosion inhibits deeper corrosion, and operates as one form of passivation. The inert surface layer, termed the ‘’native oxide layer‘’, is usually an oxide or a nitride, with a thickness of a monolayer of 0.1-0.3 nm (1-3 Å) for a noble metal such as platinum, about 1.5 nm (15 Å) for silicon, and nearer to 5 nm (50 Å) for aluminium after several years.

Reinforced concrete

Reinforced concrete (RC) (also called reinforced cement concrete or RCC) is a composite material in which concrete's relatively low tensile strength and ductility are counteracted by the inclusion of reinforcement having higher tensile strength or ductility. The reinforcement is usually, though not necessarily, steel reinforcing bars (rebar) and is usually embedded passively in the concrete before the concrete sets. Reinforcing schemes are generally designed to resist tensile stresses in particular regions of the concrete that might cause unacceptable cracking and/or structural failure. Modern reinforced concrete can contain varied reinforcing materials made of steel, polymers or alternate composite material in conjunction with rebar or not. Reinforced concrete may also be permanently stressed (concrete in compression, reinforcement in tension), so as to improve the behaviour of the final structure under working loads. In the United States, the most common methods of doing this are known as pre-tensioning and post-tensioning.

For a strong, ductile and durable construction the reinforcement needs to have the following properties at least:

High relative strength

High toleration of tensile strain

Good bond to the concrete, irrespective of pH, moisture, and similar factors

Thermal compatibility, not causing unacceptable stresses (such as expansion or contraction) in response to changing temperatures.

Durability in the concrete environment, irrespective of corrosion or sustained stress for example.

Rust

Rust is an iron oxide, a usually red oxide formed by the redox reaction of iron and oxygen in the presence of water or air moisture. Several forms of rust are distinguishable both visually and by spectroscopy, and form under different circumstances. Rust consists of hydrated iron(III) oxides Fe2O3·nH2O and iron(III) oxide-hydroxide (FeO(OH), Fe(OH)3).

Given sufficient time, oxygen, and water, any iron mass will eventually convert entirely to rust and disintegrate. Surface rust is flaky and

friable, and it provides no protection to the underlying iron, unlike the formation of patina on copper surfaces. Rusting is the common term for corrosion of iron and its alloys, such as steel. Many other metals undergo similar corrosion, but the resulting oxides are not commonly called rust.Other forms of rust exist, like the result of reactions between iron and chloride in an environment deprived of oxygen. Rebar used in underwater concrete pillars, which generates green rust, is an example. Although rusting is generally a negative aspect of iron, a particular form of rusting, known as "stable rust," causes the object to have a thin coating of rust over the top, and if kept in low relative humidity, makes the "stable" layer protective to the iron below, but not to the extent of other oxides, such as aluminum.

Salt spray test

The salt spray (or salt fog) test is a standardized and popular corrosion test method, used to check corrosion resistance of materials and surface coatings. Usually, the materials to be tested are metallic (although stone, ceramics, and polymers may also be tested) and finished with a surface coating which is intended to provide a degree of corrosion protection to the underlying metal.

Salt spray testing is an accelerated corrosion test that produces a corrosive attack to coated samples in order to evaluate (mostly comparatively) the suitability of the coating for use as a protective finish. The appearance of corrosion products (rust or other oxides) is evaluated after a pre-determined period of time. Test duration depends on the corrosion resistance of the coating; generally, the more corrosion resistant the coating is, the longer the period of testing before the appearance of corrosion/ rust.

The salt spray test is one of the most widespread and long established corrosion tests. ASTM B117 was the first internationally recognized salt spray standard, originally published in 1939. Other important relevant standards are ISO9227, JIS Z 2371 and ASTM G85.

Stainless steel

In metallurgy, stainless steel, also known as inox steel or inox from French inoxydable (inoxidizable), is a steel alloy, with highest percentage contents of iron, chromium, and nickel, with a minimum of 10.5% chromium content by mass and a maximum of 1.2% carbon by mass.Stainless steels are most notable for their corrosion resistance, which increases with increasing chromium content. Additions of molybdenum increase corrosion resistance in reducing acids and against pitting attack in chloride solutions. Thus, there are numerous grades of stainless steel with varying chromium and molybdenum contents to suit the environment the alloy must endure. Stainless steel's resistance to corrosion and staining, low maintenance, and familiar luster make it an ideal material for many applications where both the strength of steel and corrosion resistance are required.

Stainless steels are rolled into sheets, plates, bars, wire, and tubing to be used in: cookware, cutlery, surgical instruments, major appliances; construction material in large buildings, such as the Chrysler Building; industrial equipment (for example, in paper mills, chemical plants, water treatment); and storage tanks and tankers for chemicals and food products (for example, chemical tankers and road tankers). Stainless steel's corrosion resistance, the ease with which it can be steam cleaned and sterilized, and no need for surface coatings has also influenced its use in commercial kitchens and food processing plants.

Stress corrosion cracking

Stress corrosion cracking (SCC) is the growth of crack formation in a corrosive environment. It can lead to unexpected sudden failure of normally ductile metals subjected to a tensile stress, especially at elevated temperature. SCC is highly chemically specific in that certain alloys are likely to undergo SCC only when exposed to a small number of chemical environments. The chemical environment that causes SCC for a given alloy is often one which is only mildly corrosive to the metal. Hence, metal parts with severe SCC can appear bright and shiny, while being filled with microscopic cracks. This factor makes it common for SCC to go undetected prior to failure. SCC often progresses rapidly, and is more common among alloys than pure metals. The specific environment is of crucial importance, and only very small concentrations of certain highly active chemicals are needed to produce catastrophic cracking, often leading to devastating and unexpected failure.The stresses can be the result of the crevice loads due to stress concentration, or can be caused by the type of assembly or residual stresses from fabrication (e.g. cold working); the residual stresses can be relieved by annealing or other surface treatments.

Sulfide

Sulfide (British English sulphide) is an inorganic anion of sulfur with the chemical formula S2− or a compound containing one or more S2− ions. Solutions of sulfide salts are corrosive. Sulfide also refers to chemical compounds large families of inorganic and organic compounds, e.g. lead sulfide and dimethyl sulfide. Hydrogen sulfide (H2S) and bisulfide (SH-) are the conjugate acids of sulfide.

Water cooling

Water cooling is a method of heat removal from components and industrial equipment. Water may be a more efficient heat transfer fluid where air cooling is ineffective. In most occupied climates water offers the thermal conductivity advantages of a liquid with unusually high specific heat capacity and the option of evaporative cooling. Low cost often allows rejection as waste after a single use, but recycling coolant loops may be pressurized to eliminate evaporative loss and offer greater portability and improved cleanliness. Unpressurized recycling coolant loops using evaporative cooling require a blowdown waste stream to remove impurities concentrated by evaporation. Disadvantages of water cooling systems include accelerated corrosion and maintenance requirements to prevent heat transfer reductions from biofouling or scale formation. Chemical additives to reduce these disadvantages may introduce toxicity to wastewater. Water cooling is commonly used for cooling automobile internal combustion engines and large industrial facilities such as nuclear and steam electric power plants, hydroelectric generators, petroleum refineries and chemical plants. Other uses include cooling the barrels of machine guns, cooling of lubricant oil in pumps; for cooling purposes in heat exchangers; cooling products from tanks or columns, and recently, cooling of various major components inside high-end personal computers such as CPUs, GPUs, and motherboards. The main mechanism for water cooling is convective heat transfer.

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