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In materials science, intergranular corrosion (IGC), also known as intergranular attack (IGA), is a form of
corrosion 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 engi ...
where the boundaries of
crystallite A crystallite is a small or even microscopic crystal which forms, for example, during the cooling of many materials. Crystallites are also referred to as grains. Bacillite is a type of crystallite. It is rodlike with parallel longulites. Stru ...
s of the material are more susceptible to corrosion than their insides. (''Cf.'' transgranular corrosion.)


Description

This situation can happen in otherwise corrosion-resistant alloys, when the grain boundaries are depleted, known as ', of the corrosion-inhibiting elements such as chromium by some mechanism. In
nickel Nickel is a chemical element with symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive but large pieces are slow ...
alloys and austenitic stainless steels, where
chromium Chromium is a chemical element with the symbol Cr and atomic number 24. It is the first element in group 6. It is a steely-grey, lustrous, hard, and brittle transition metal. Chromium metal is valued for its high corrosion resistance and h ...
is added for corrosion resistance, the mechanism involved is precipitation of chromium carbide at the grain boundaries, resulting in the formation of chromium-depleted zones adjacent to the grain boundaries (this process is called
sensitization Sensitization is a non-associative learning process in which repeated administration of a stimulus results in the progressive amplification of a response. Sensitization often is characterized by an enhancement of response to a whole class of st ...
). Around 12% chromium is minimally required to ensure passivation, a mechanism by which an ultra thin invisible film, known as passive film, forms on the surface of stainless steels. This passive film protects the metal from corrosive environments. The self-healing property of the passive film make the steel stainless. Selective leaching often involves grain boundary depletion mechanisms. These zones also act as local
galvanic couple Electrochemistry is the branch of physical chemistry concerned with the relationship between electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, with the potential difference as an outco ...
s, causing local
galvanic corrosion Galvanic corrosion (also called bimetallic corrosion or dissimilar metal 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 sim ...
. This condition happens when the material is heated to temperatures around 700 °C for too long a time, and often occurs during
welding Welding is a fabrication process that joins materials, usually metals or thermoplastics, by using high heat to melt the parts together and allowing them to cool, causing fusion. Welding is distinct from lower temperature techniques such as br ...
or an improper
heat treatment Heat treating (or heat treatment) is a group of industrial, thermal and metalworking processes used to alter the physical, and sometimes chemical, properties of a material. The most common application is metallurgical. Heat treatments are al ...
. When zones of such material form due to welding, the resulting corrosion is termed weld decay. Stainless steels can be stabilized against this behavior by addition of
titanium Titanium is a chemical element with the Symbol (chemistry), symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resista ...
,
niobium Niobium is a chemical element with chemical symbol Nb (formerly columbium, Cb) and atomic number 41. It is a light grey, crystalline, and ductile transition metal. Pure niobium has a Mohs hardness rating similar to pure titanium, and it ha ...
, or
tantalum Tantalum is a chemical element with the symbol Ta and atomic number 73. Previously known as ''tantalium'', it is named after Tantalus, a villain in Greek mythology. Tantalum is a very hard, ductile, lustrous, blue-gray transition metal that is ...
, which form
titanium carbide Titanium carbide, Ti C, is an extremely hard ( Mohs 9–9.5) refractory ceramic material, similar to tungsten carbide. It has the appearance of black powder with the sodium chloride (face-centered cubic) crystal structure. It occurs in nature ...
,
niobium carbide Niobium carbide ( Nb C and Nb2C) is an extremely hard refractory ceramic material, commercially used in tool bits for cutting tools. It is usually processed by sintering and is a frequent additive as grain growth inhibitor in cemented carbide ...
and
tantalum carbide Tantalum carbides (TaC) form a family of binary compound, binary chemical compounds of tantalum and carbon with the empirical formula TaC''x'', where ''x'' usually varies between 0.4 and 1. They are extremely hardness, hard, brittle, refraction (m ...
preferentially to chromium carbide, by lowering the content of
carbon Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent—its atom making four electrons available to form covalent chemical bonds. It belongs to group 14 of the periodic table. Carbon makes ...
in the steel and in case of welding also in the filler metal under 0.02%, or by heating the entire part above 1000 °C and
quenching In materials science, quenching is the rapid cooling of a workpiece in water, oil, polymer, air, or other fluids to obtain certain material properties. A type of heat treating, quenching prevents undesired low-temperature processes, such as ...
it in water, leading to dissolution of the chromium carbide in the grains and then preventing its precipitation. Another possibility is to keep the welded parts thin enough so that, upon cooling, the metal dissipates heat too quickly for chromium carbide to precipitate. The ASTM A923, ASTM A262,ASTM A262 Intergranular Corrosion Testing of Stainless Steels
/ref> and other similar tests are often used to determine when stainless steels are susceptible to intergranular corrosion. The tests require etching with chemicals that reveal the presence of intermetallic particles, sometimes combined with Charpy V-Notch and other mechanical testing. Another related kind of intergranular corrosion is termed knifeline attack (KLA). Knifeline attack impacts steels stabilized by niobium, such as 347 stainless steel. Titanium, niobium, and their
carbide In chemistry, a carbide usually describes a compound composed of carbon and a metal. In metallurgy, carbiding or carburizing is the process for producing carbide coatings on a metal piece. Interstitial / Metallic carbides The carbides of th ...
s dissolve in steel at very high temperatures. At some cooling regimes (depending on the rate of cooling), niobium carbide does not precipitate and the steel then behaves like unstabilized steel, forming chromium carbide instead. This affects only a thin zone several millimeters wide in the very vicinity of the weld, making it difficult to spot and increasing the corrosion speed. Structures made of such steels have to be heated in a whole to about 1065 °C (1950 °F), when the chromium carbide dissolves and niobium carbide forms. The cooling rate after this treatment is not important, as the carbon that would otherwise pose risk of formation of chromium carbide is already sequestered as niobium carbide

Aluminium Aluminium (aluminum in AmE, American and CanE, Canadian English) is a chemical element with the Symbol (chemistry), symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately o ...
-based alloys may be sensitive to intergranular corrosion if there are layers of materials acting as
anode An anode is an electrode of a polarized electrical device through which conventional current enters the device. This contrasts with a cathode, an electrode of the device through which conventional current leaves the device. A common mnemoni ...
s between the aluminium-rich crystals. High strength aluminium alloys, especially when extruded or otherwise subjected to high degree of working, can undergo exfoliation corrosion (metallurgy), where the corrosion products build up between the flat, elongated grains and separate them, resulting in lifting or leafing effect and often propagating from edges of the material through its entire structure

Intergranular corrosion is a concern especially for alloys with high content of
copper Copper is a chemical element with the symbol Cu (from la, cuprum) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pinkish ...
. Other kinds of alloys can undergo exfoliation as well; the sensitivity of
cupronickel Cupronickel or copper-nickel (CuNi) is an alloy of copper that contains nickel and strengthening elements, such as iron and manganese. The copper content typically varies from 60 to 90 percent. ( Monel is a nickel-copper alloy that contains a minim ...
increases together with its nickel content. A broader term for this class of corrosion is lamellar corrosion. Alloys of
iron Iron () is a chemical element with symbol Fe (from la, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, right in ...
are susceptible to lamellar corrosion, as the volume of
iron oxide Iron oxides are chemical compounds composed of iron and oxygen. Several iron oxides are recognized. All are black magnetic solids. Often they are non-stoichiometric. Oxyhydroxides are a related class of compounds, perhaps the best known of w ...
s is about seven times higher than the volume of original metal, leading to formation of internal
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 ...
es tearing the material apart. Similar effect leads to formation of lamellae in stainless steels, due to the difference of thermal expansion of the oxides and the metal

Copper-based alloys become sensitive when depletion of copper content in the grain boundaries occurs.
Anisotropic Anisotropy () is the property of a material which allows it to change or assume different properties in different directions, as opposed to isotropy. It can be defined as a difference, when measured along different axes, in a material's phys ...
alloys, where
extrusion Extrusion is a process used to create objects of a fixed cross-sectional profile by pushing material through a die of the desired cross-section. Its two main advantages over other manufacturing processes are its ability to create very complex ...
or heavy working leads to formation of long, flat grains, are especially prone to intergranular corrosion

Intergranular corrosion induced by environmental stresses is termed
stress corrosion cracking Stress corrosion cracking (SCC) is the growth of crack formation in a corrosive environment. It can lead to unexpected and sudden failure of normally ductile metal alloys subjected to a tensile stress, especially at elevated temperature. SCC ...
. Inter granular corrosion can be detected by ultrasonic and eddy current methods.


Sensitization effect

''Sensitization'' refers to the precipitation of carbides at grain boundaries in a stainless steel or alloy, causing the steel or alloy to be susceptible to intergranular corrosion or intergranular stress corrosion cracking. Certain alloys when exposed to a temperature characterized as a sensitizing temperature become particularly susceptible to intergranular corrosion. In a corrosive atmosphere, the grain interfaces of these sensitized alloys become very reactive and intergranular corrosion results. This is characterized by a localized attack at and adjacent to
grain boundaries In materials science, a grain boundary is the interface between two grains, or crystallites, in a polycrystalline material. Grain boundaries are two-dimensional defects in the crystal structure, and tend to decrease the electrical and thermal ...
with relatively little
corrosion 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 engi ...
of the grains themselves. The alloy disintegrates (grains fall out) and/or loses its strength. The photos show the typical microstructure of a normalized (unsensitized) type 304 stainless steel and a heavily sensitized steel. The samples have been polished and etched before taking the
photos A photograph (also known as a photo, image, or picture) is an image created by light falling on a photosensitive surface, usually photographic film or an electronic image sensor, such as a CCD or a CMOS chip. Most photographs are now create ...
, and the sensitized areas show as wide, dark lines where the etching fluid has caused corrosion. The dark lines consist of carbides and corrosion products. Intergranular corrosion is generally considered to be caused by the segregation of impurities at the grain boundaries or by enrichment or depletion of one of the alloying elements in the grain boundary areas. Thus in certain
aluminium alloy An aluminium alloy (or aluminum alloy; see spelling differences) is an alloy in which aluminium (Al) is the predominant metal. The typical alloying elements are copper, magnesium, manganese, silicon, tin, nickel and zinc. There are two princip ...
s, small amounts of
iron Iron () is a chemical element with symbol Fe (from la, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, right in ...
have been shown to segregate in the grain boundaries and cause intergranular corrosion. Also, it has been shown that the
zinc Zinc is a chemical element with the symbol Zn and atomic number 30. Zinc is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodic t ...
content of a
brass Brass is an alloy of copper (Cu) and zinc (Zn), in proportions which can be varied to achieve different mechanical, electrical, and chemical properties. It is a substitutional alloy: atoms of the two constituents may replace each other wit ...
is higher at the grain boundaries and subject to such corrosion. High-strength
aluminium Aluminium (aluminum in AmE, American and CanE, Canadian English) is a chemical element with the Symbol (chemistry), symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately o ...
alloys such as the
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. The term is a combination of ''Dürener'' and ''aluminium''. Its use as a tra ...
-type alloys (Al-Cu) which depend upon precipitated phases for strengthening are susceptible to intergranular corrosion following sensitization at temperatures of about 120 °C.
Nickel Nickel is a chemical element with symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive but large pieces are slow ...
-rich alloys such as
Inconel Inconel is a registered trademark of Special Metals Corporation for a family of austenitic nickel-chromium-based superalloys. Inconel alloys are oxidation- corrosion-resistant materials well suited for service in extreme environments subjected ...
600 and
Incoloy Incoloy refers to a range of superalloys now produced by the Special Metals Corporation (SMC) group of companies and created with a trademark by the Inco company in 1952. Originally Inco protected these alloys by patent. In 2000, the SMC publishe ...
800 show similar susceptibility. Die-cast
zinc Zinc is a chemical element with the symbol Zn and atomic number 30. Zinc is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodic t ...
alloys containing aluminum exhibit intergranular corrosion by
steam Steam is a substance containing water in the gas phase, and sometimes also an aerosol of liquid water droplets, or air. This may occur due to evaporation or due to boiling, where heat is applied until water reaches the enthalpy of vaporizat ...
in a marine atmosphere. Cr-Mn and Cr-Mn-Ni steels are also susceptible to intergranular corrosion following sensitization in the temperature range of 420 °C–850 °C. In the case of the austenitic stainless steels, when these steels are sensitized by being heated in the temperature range of about 520 °C to 800 °C, depletion of chromium in the grain boundary region occurs, resulting in susceptibility to intergranular corrosion. Such sensitization of austenitic stainless steels can readily occur because of temperature service requirements, as in steam generators, or as a result of subsequent
welding Welding is a fabrication process that joins materials, usually metals or thermoplastics, by using high heat to melt the parts together and allowing them to cool, causing fusion. Welding is distinct from lower temperature techniques such as br ...
of the formed structure. Several methods have been used to control or minimize the intergranular corrosion of susceptible alloys, particularly of the
austenitic stainless steels 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 ...
. For example, a high-temperature solution
heat treatment Heat treating (or heat treatment) is a group of industrial, thermal and metalworking processes used to alter the physical, and sometimes chemical, properties of a material. The most common application is metallurgical. Heat treatments are al ...
, commonly termed solution- annealing,
quench In materials science, quenching is the rapid cooling of a workpiece in water, oil, polymer, air, or other fluids to obtain certain material properties. A type of heat treating, quenching prevents undesired low-temperature processes, such as phas ...
-annealing or solution-quenching, has been used. The alloy is heated to a temperature of about 1,060 °C to 1,120 °C and then water quenched. This method is generally unsuitable for treating large assemblies, and also ineffective where welding is subsequently used for making repairs or for attaching other structures. Another control technique for preventing intergranular corrosion involves incorporating strong
carbide In chemistry, a carbide usually describes a compound composed of carbon and a metal. In metallurgy, carbiding or carburizing is the process for producing carbide coatings on a metal piece. Interstitial / Metallic carbides The carbides of th ...
formers or stabilizing elements such as
niobium Niobium is a chemical element with chemical symbol Nb (formerly columbium, Cb) and atomic number 41. It is a light grey, crystalline, and ductile transition metal. Pure niobium has a Mohs hardness rating similar to pure titanium, and it ha ...
or
titanium Titanium is a chemical element with the Symbol (chemistry), symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resista ...
in the stainless steels. Such elements have a much greater affinity for
carbon Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent—its atom making four electrons available to form covalent chemical bonds. It belongs to group 14 of the periodic table. Carbon makes ...
than does
chromium Chromium is a chemical element with the symbol Cr and atomic number 24. It is the first element in group 6. It is a steely-grey, lustrous, hard, and brittle transition metal. Chromium metal is valued for its high corrosion resistance and h ...
; carbide formation with these elements reduces the carbon available in the alloy for formation of chromium carbides. Such a stabilized titanium-bearing austenitic chromium-nickel-copper stainless steel is shown in U.S. Pat. No. 3,562,781. Or the stainless steel may initially be reduced in carbon content below 0.03 percent so that insufficient carbon is provided for carbide formation. These techniques are expensive and only partially effective since sensitization may occur with time. The low-carbon steels also frequently exhibit lower strengths at high temperatures.


See also

* Intergranular fracture


References

{{Reflist Corrosion