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Stress corrosion cracking (SCC) is the growth of crack formation in a
corrosive A corrosive substance is one that will damage or destroy other substances with which it comes into contact by means of a chemical reaction. Etymology The word ''corrosive'' is derived from the Latin verb ''corrodere'', which means ''to gnaw'', ...
environment. It can lead to unexpected and sudden failure of normally
ductile Ductility is a mechanical property commonly described as a material's amenability to drawing (e.g. into wire). In materials science, ductility is defined by the degree to which a material can sustain plastic deformation under tensile stres ...
metal
alloy An alloy is a mixture of chemical elements of which at least one is a metal. Unlike chemical compounds with metallic bases, an alloy will retain all the properties of a metal in the resulting material, such as electrical conductivity, ductility, ...
s subjected to a
tensile stress In continuum mechanics, stress is a physical quantity. It is a quantity that describes the magnitude of forces that cause deformation. Stress is defined as ''force per unit area''. When an object is pulled apart by a force it will cause elonga ...
, 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 A corrosive substance is one that will damage or destroy other substances with which it comes into contact by means of a chemical reaction. Etymology The word ''corrosive'' is derived from the Latin verb ''corrodere'', which means ''to gnaw'', ...
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.ASM International, ''Metals Handbook (Desk Edition)'' Chapter 32 (Failure Analysis), American Society for Metals The stresses can be the result of the crevice loads due to
stress concentration In solid mechanics, a stress concentration (also called a stress raiser or a stress riser) is a location in an object where the stress is significantly greater than the surrounding region. Stress concentrations occur when there are irregularitie ...
, or can be caused by the type of assembly or
residual stress In materials science and solid mechanics, residual stresses are Stress (physics), stresses that remain in a solid material after the original cause of the stresses has been removed. Residual stress may be desirable or undesirable. For example, l ...
es from fabrication (e.g. cold working); the residual stresses can be relieved by annealing or other surface treatments. Unexpected and premature failure of chemical process equipment, for example, due to stress corrosion cracking constitutes a serious hazard in terms of safety of personnel, operating facilities and the environment. By weakening the reliability of these types of equipment, such failures also adversely affect productivity and profitability.


Mechanisms

Stress corrosion cracking mainly affects
metal A metal (from Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typicall ...
s and metallic alloys. A comparable effect also known as
environmental stress cracking Environmental Stress Cracking (ESC) is one of the most common causes of unexpected brittle failure of thermoplastic (especially amorphous) polymers known at present. According to ASTM D883, stress cracking is defined as "an external or intern ...
also affects other materials such as
polymer A polymer (; Greek '' poly-'', "many" + ''-mer'', "part") is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
s,
ceramic A ceramic is any of the various hard, brittle, heat-resistant and corrosion-resistant materials made by shaping and then firing an inorganic, nonmetallic material, such as clay, at a high temperature. Common examples are earthenware, porcelain ...
s and
glass Glass is a non-crystalline, often transparent, amorphous solid that has widespread practical, technological, and decorative use in, for example, window panes, tableware, and optics. Glass is most often formed by rapid cooling (quenching) of ...
.


Metals

Lower pH and lower applied
redox potential Redox potential (also known as oxidation / reduction potential, ''ORP'', ''pe'', ''E_'', or E_) is a measure of the tendency of a chemical species to acquire electrons from or lose electrons to an electrode and thereby be reduced or oxidised respe ...
facilitate the evolution and the enrichment of hydrogen during the process of SCC, thus increasing the SCC intensity. * Certain
austenitic Austenite, also known as gamma-phase iron (γ-Fe), is a metallic, non-magnetic allotrope of iron or a solid solution of iron with an alloying element. In plain-carbon steel, austenite exists above the critical eutectoid temperature of 1000 K ...
stainless steel Stainless steel is an alloy of iron that is resistant to rusting and corrosion. It contains at least 11% chromium and may contain elements such as carbon, other nonmetals and metals to obtain other desired properties. Stainless steel's corros ...
s and
aluminium Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. I ...
alloy An alloy is a mixture of chemical elements of which at least one is a metal. Unlike chemical compounds with metallic bases, an alloy will retain all the properties of a metal in the resulting material, such as electrical conductivity, ductility, ...
s crack in the presence of
chloride The chloride ion is the anion (negatively charged ion) Cl−. It is formed when the element chlorine (a halogen) gains an electron or when a compound such as hydrogen chloride is dissolved in water or other polar solvents. Chloride salts ...
s. This limits the usefulness of austenitic stainless steel for containing water with higher than a few parts per million content of chlorides at temperatures above ; * mild
steel Steel is an alloy made up of iron with added carbon to improve its strength and fracture resistance compared to other forms of iron. Many other elements may be present or added. Stainless steels that are corrosion- and oxidation-resistant ty ...
cracks in the presence of
alkali In chemistry, an alkali (; from ar, القلوي, al-qaly, lit=ashes of the saltwort) is a basic, ionic salt of an alkali metal or an alkaline earth metal. An alkali can also be defined as a base that dissolves in water. A solution of a ...
(e.g. boiler cracking and caustic stress corrosion cracking) and
nitrate Nitrate is a polyatomic ion A polyatomic ion, also known as a molecular ion, is a covalent bonded set of two or more atoms, or of a metal complex, that can be considered to behave as a single unit and that has a net charge that is not zer ...
s; *
copper alloys Copper alloys are metal alloys that have copper as their principal component. They have high resistance against corrosion. The best known traditional types are bronze, where tin is a significant addition, and brass, using zinc instead. Both of th ...
crack in
ammonia Ammonia is an inorganic compound of nitrogen and hydrogen with the formula . A stable binary hydride, and the simplest pnictogen hydride, ammonia is a colourless gas with a distinct pungent smell. Biologically, it is a common nitrogenous was ...
cal solutions (
season cracking Season cracking is a form of stress-corrosion cracking of brass cartridge cases originally reported from British forces in India. During the monsoon season, military activity was temporarily reduced, and ammunition was stored in stables until the ...
); *
high-tensile steel Carbon steel is a steel with carbon content from about 0.05 up to 2.1 percent by weight. The definition of carbon steel from the American Iron and Steel Institute (AISI) states: * no minimum content is specified or required for chromium, cobalt ...
s have been known to crack in an unexpectedly brittle manner in a whole variety of aqueous environments, especially when chlorides are present. With the possible exception of the latter, which is a special example of hydrogen cracking, all the others display the phenomenon of subcritical crack growth, i.e. small surface flaws propagate (usually smoothly) under conditions where
fracture mechanics Fracture mechanics is the field of mechanics concerned with the study of the propagation of cracks in materials. It uses methods of analytical solid mechanics to calculate the driving force on a crack and those of experimental solid mechanics t ...
predicts that failure should not occur. That is, in the presence of a corrodent, cracks develop and propagate well below critical stress intensity factor (K_\mathrm). The subcritical value of the stress intensity, designated as K_\mathrm, may be less than 1% of K_\mathrm.


Polymers

A similar process (
environmental stress cracking Environmental Stress Cracking (ESC) is one of the most common causes of unexpected brittle failure of thermoplastic (especially amorphous) polymers known at present. According to ASTM D883, stress cracking is defined as "an external or intern ...
) occurs in
polymer A polymer (; Greek '' poly-'', "many" + ''-mer'', "part") is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic a ...
s, when products are exposed to specific solvents or aggressive chemicals such as
acids In computer science, ACID ( atomicity, consistency, isolation, durability) is a set of properties of database transactions intended to guarantee data validity despite errors, power failures, and other mishaps. In the context of databases, a sequ ...
and
alkalis In chemistry, an alkali (; from ar, القلوي, al-qaly, lit=ashes of the saltwort) is a basic, ionic salt of an alkali metal or an alkaline earth metal. An alkali can also be defined as a base that dissolves in water. A solution of a so ...
. As with metals, attack is confined to specific polymers and particular chemicals. Thus
polycarbonate Polycarbonates (PC) are a group of thermoplastic polymers containing carbonate groups in their chemical structures. Polycarbonates used in engineering are strong, tough materials, and some grades are optically transparent. They are easily work ...
is sensitive to attack by alkalis, but not by acids. On the other hand,
polyesters Polyester is a category of polymers that contain the ester functional group in every repeat unit of their main chain. As a specific material, it most commonly refers to a type called polyethylene terephthalate (PET). Polyesters include natural ...
are readily degraded by acids, and SCC is a likely
failure Failure is the state or condition of not meeting a desirable or intended objective (goal), objective, and may be viewed as the opposite of Success (concept), success. The criteria for failure depends on context, and may be relative to a parti ...
mechanism. Polymers are susceptible to
environmental stress cracking Environmental Stress Cracking (ESC) is one of the most common causes of unexpected brittle failure of thermoplastic (especially amorphous) polymers known at present. According to ASTM D883, stress cracking is defined as "an external or intern ...
where attacking agents do not necessarily degrade the materials chemically.
Nylon Nylon is a generic designation for a family of synthetic polymers composed of polyamides ( repeating units linked by amide links).The polyamides may be aliphatic or semi-aromatic. Nylon is a silk-like thermoplastic, generally made from petro ...
is sensitive to degradation by acids, a process known as
hydrolysis Hydrolysis (; ) is any chemical reaction in which a molecule of water breaks one or more chemical bonds. The term is used broadly for substitution reaction, substitution, elimination reaction, elimination, and solvation reactions in which water ...
, and nylon mouldings will crack when attacked by strong acids. For example, the fracture surface of a fuel connector showed the progressive growth of the crack from acid attack (Ch) to the final cusp (C) of polymer. In this case the failure was caused by
hydrolysis Hydrolysis (; ) is any chemical reaction in which a molecule of water breaks one or more chemical bonds. The term is used broadly for substitution reaction, substitution, elimination reaction, elimination, and solvation reactions in which water ...
of the polymer by contact with
sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid ( Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen and hydrogen, with the molecular formu ...
leaking from a
car battery An automotive battery or car battery is a rechargeable battery that is used to start a motor vehicle. Its main purpose is to provide an electric current to the electric-powered starting motor, which in turn starts the chemically-powered intern ...
. The degradation reaction is the reverse of the synthesis reaction of the polymer: : : image:amide hydrolysis.svg Cracks can be formed in many different
elastomers An elastomer is a polymer with viscoelasticity (i.e. both viscosity and elasticity) and with weak intermolecular forces, generally low Young's modulus and high failure strain compared with other materials. The term, a portmanteau of ''elastic po ...
by
ozone Ozone (), or trioxygen, is an inorganic molecule with the chemical formula . It is a pale blue gas with a distinctively pungent smell. It is an allotrope of oxygen that is much less stable than the diatomic allotrope , breaking down in the lo ...
attack, another form of SCC in polymers. Tiny traces of the gas in the air will attack double bonds in rubber chains, with
natural rubber Rubber, also called India rubber, latex, Amazonian rubber, ''caucho'', or ''caoutchouc'', as initially produced, consists of polymers of the organic compound isoprene, with minor impurities of other organic compounds. Thailand, Malaysia, and ...
,
styrene-butadiene Styrene-butadiene or styrene-butadiene rubber (SBR) describe families of synthetic rubbers derived from styrene and butadiene (the version developed by Goodyear is called Neolite). These materials have good abrasion resistance and good aging st ...
rubber, and
nitrile butadiene rubber Nitrile rubber, also known as nitrile butadiene rubber, NBR, Buna-N, and acrylonitrile butadiene rubber, is a synthetic rubber derived from acrylonitrile (ACN) and butadiene. Trade names include Perbunan, Nipol, Krynac and Europrene. This rubber is ...
being most sensitive to degradation. Ozone cracks form in products under tension, but the critical strain is very small. The cracks are always oriented at right angles to the strain axis, so will form around the circumference in a rubber tube bent over. Such cracks are dangerous when they occur in fuel pipes because the cracks will grow from the outside exposed surfaces into the bore of the pipe, so fuel leakage and fire may follow.
Ozone cracking Cracks can be formed in many different elastomers by ozone attack, and the characteristic form of attack of vulnerable rubbers is known as ozone cracking. The problem was formerly very common, especially in tires, but is now rarely seen in those ...
can be prevented by adding anti-ozonants to the rubber before
vulcanization Vulcanization (British: Vulcanisation) is a range of processes for hardening rubbers. The term originally referred exclusively to the treatment of natural rubber with sulfur, which remains the most common practice. It has also grown to include ...
. Ozone cracks were commonly seen in automobile
tire A tire (American English) or tyre (British English) is a ring-shaped component that surrounds a Rim (wheel), wheel's rim to transfer a vehicle's load from the axle through the wheel to the ground and to provide Traction (engineering), t ...
sidewalls, but are now seen rarely thanks to the use of these additives. On the other hand, the problem does recur in unprotected products such as rubber tubing and seals.


Ceramics

This effect is significantly less common in ceramics which are typically more resilient to chemical attack. Although phase changes are common in ceramics under stress these usually result in toughening rather than failure (see
Zirconium dioxide Zirconium dioxide (), sometimes known as zirconia (not to be confused with zircon), is a white crystalline oxide of zirconium. Its most naturally occurring form, with a monoclinic crystalline structure, is the mineral baddeleyite. A dopant stabi ...
). Recent studies have shown that the same driving force for this toughening mechanism can also enhance oxidation of reduced cerium oxide, resulting in slow crack growth and spontaneous failure of dense ceramic bodies.


Glass

Subcritical crack propagation in glasses falls into three regions. In region I, the velocity of crack propagation increases with ambient humidity due to stress-enhanced chemical reaction between the glass and water. In region II, crack propagation velocity is diffusion controlled and dependent on the rate at which chemical reactants can be transported to the tip of the crack. In region III, crack propagation is independent of its environment, having reached a critical stress intensity. Chemicals other than water, like ammonia, can induce subcritical crack propagation in silica glass, but they must have an
electron donor In chemistry, an electron donor is a chemical entity that donates electrons to another compound. It is a reducing agent that, by virtue of its donating electrons, is itself oxidized in the process. Typical reducing agents undergo permanent chem ...
site and a
proton donor A proton is a stable subatomic particle, symbol , H+, or 1H+ with a positive electric charge of +1 ''e'' elementary charge. Its mass is slightly less than that of a neutron and 1,836 times the mass of an electron (the proton–electron mass ...
site.


Prevention

The compressive residual stresses imparted
laser peening Laser peening (LP), or laser shock peening (LSP), is a surface engineering process used to impart beneficial residual stresses in materials. The deep, high-magnitude compressive residual stresses induced by laser peening increase the resistance o ...
are precisely controlled both in location and intensity and can be applied to mitigate sharp transitions into tensile regions. Laser peening imparts deep compressive residual stresses on the order of 10 to 20 times deeper than conventional shot peening, making them significantly more beneficial at preventing SCC. Laser peening is widely used in the aerospace and power generation industries in gas fired turbine engines.


Notable failures

* A 32-inch diameter gas transmission pipeline, north of
Natchitoches, Louisiana Natchitoches ( ; french: link=no, Les Natchitoches) is a small city and the parish seat of Natchitoches Parish, Louisiana, United States. Established in 1714 by Louis Juchereau de St. Denis as part of French Louisiana, the community was named ...
, belonging to the Tennessee Gas Pipeline exploded and burned from SCC on March 4, 1965, killing 17 people. At least 9 others were injured, and 7 homes 450 feet from the rupture were destroyed. * SCC caused the catastrophic collapse of the
Silver Bridge The Silver Bridge was an eyebar-chain suspension bridge built in 1928 and named for the color of its aluminum paint. The bridge carried U.S. Route 35 over the Ohio River, connecting Point Pleasant, West Virginia, and Gallipolis, Ohio. On Dece ...
in December 1967, when an
eyebar In structural engineering and construction, an eyebar is a straight bar, usually of metal, with a hole ("eye") at each end for fixing to other components. Eyebars are used in structures such as bridges, in settings in which only tension, and ne ...
suspension bridge A suspension bridge is a type of bridge in which the deck (bridge), deck is hung below suspension wire rope, cables on vertical suspenders. The first modern examples of this type of bridge were built in the early 1800s. Simple suspension bridg ...
across the
Ohio river The Ohio River is a long river in the United States. It is located at the boundary of the Midwestern and Southern United States, flowing southwesterly from western Pennsylvania to its mouth on the Mississippi River at the southern tip of Illino ...
at Point Pleasant,
West Virginia West Virginia is a state in the Appalachian, Mid-Atlantic and Southeastern regions of the United States.The Census Bureau and the Association of American Geographers classify West Virginia as part of the Southern United States while the Bur ...
, suddenly failed. The main chain joint failed and the entire structure fell into the river, killing 46 people who were traveling in vehicles across the bridge. Rust in the eyebar joint had caused a stress corrosion crack, which went critical as a result of high bridge loading and low temperature. The failure was exacerbated by a high level of
residual stress In materials science and solid mechanics, residual stresses are Stress (physics), stresses that remain in a solid material after the original cause of the stresses has been removed. Residual stress may be desirable or undesirable. For example, l ...
in the eyebar. The disaster led to a nationwide reappraisal of bridges.Lewis, Peter Rhys, Reynolds, K., and Gagg, C., (2004). ''Forensic Materials Engineering: Case studies'', CRC Press.


See also

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


References

;Notes ;Sources * ASM International, Metals Handbook (Desk Edition) Chapter 32 (Failure Analysis), American Society for Metals, (1997) pp 32–24 to 32-26 * ASM Handbook Volume 11 "Failure Analysis and Prevention" (2002) "Stress-Corrosion Cracking" Revised by W.R. Warke, American Society of Metals. Pages 1738-1820 * * "Mechanical Properties of Ceramics" by John B. Wachtman, W. Roger Cannon, and M. John Matthewson. Chapter 8. {{DEFAULTSORT:Stress Corrosion Cracking Corrosion Fracture mechanics Engineering failures Materials degradation