SEMINAR ON

DETECTING SUSCEPTIBILITY TO INTERGRANULAR CORROSION

PREPARED BY: NAME: TRUSHIT K. NASHIKKAR ROLL NO. : 913

INTERGRANULAR CORROSION

The microstructure of metals and alloys is made up of grains, separated by grain boundaries. Intergranular corrosion is localized attack along the grain boundaries, or immediately adjacent to grain boundaries, while the bulk of the grains remain largely unaffected. This form of corrosion is usually associated with chemical segregation effects (impurities have a tendency to be enriched at grain boundaries) or specific phases precipitated on the grain boundaries. Such precipitation can produce zones of reduced corrosion resistance in the immediate vicinity.

MECHANISM

Microscope view of a polished cross section of a material attacked by intergranular corrosion What causes intergranular corrosion?

This type of attack results from local differences in composition, such as coring commonly encountered in alloy castings. Grain boundary precipitation, notably chromium carbides in stainless steels, is a well recognized and accepted mechanism of intergranular corrosion. The precipitation of chromium carbides consumed the alloying element - chromium from a narrow band along the grain boundary and this makes the zone anodic to the unaffected grains. The chromium depleted zone becomes the preferential path for corrosion attack or crack propagation if under tensile stress.

CHROMIUM PROFILE ACROSS GRAIN:

In nickel alloys and austenitic stainless steels, where chromium is added for corrosion resistance, the mechanism involved is formation of chromium carbide at the grain boundaries, forming chromiumdepleted zones (this process is called sensitization).

Around 12% chromium is minimally required to ensure passivation, mechanism by which a thin invisible layer forms at the surface of stainless steels. This layer protects the metal from environments and it is, thus, stainless.

corrosive boundary

Selective leaching often depletion mechanisms.

involve

grain

These zones also act as local galvanic couples, causing local galvanic corrosion.

This condition happens when the material is heated to temperature around 700 C for too long time, and often happens during welding or an improper heat treatment.

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 oftitanium, niobium, or tantalum, which form titanium carbide, niobium carbide and tantalum carbide preferentially to chromium carbide, by lowering the content of carbon 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 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.

Other related kind of intergranular termed knifeline attack (KLA).

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Knifeline attack impacts steels stabilized by niobium, such as 347 stainless steel.

Titanium, niobium, and their carbides dissolve in steel at very high temperatures.

At some cooling regimes, 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 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.

The photos above show the microstructure of a type 304 stainless steel. The figure on the left is the normalized microstructure and the one on the right is the "sensitized" structure and is susceptible to intergranular corrosion or intergranular stress corrosion cracking.

Figure : Intergranular corrosion of a failed aircraft component made of 7075-T6 aluminum

Many aluminum base alloys are susceptible to intergranular corrosion on account of either phases anodic to aluminum being present along grain boundaries or due to depleted zones of copper adjacent to grain boundaries in copper-containing alloys. High strength aluminium alloys, especially when extruded or otherwise subjected to high degree of working, can undergo exfoliation corrosion. Here 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.

Other kinds of alloys can undergo exfoliation as well; the sensitivity of cupronickel increases together with its nickel content. A broader term for this class of corrosion is lamellar corrosion. Alloys of iron are susceptible to lamellar corrosion, as the volume of iron oxides is about seven times higher than the volume of original metal, leading to formation of internal tensile stresses 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 alloys, where extrusion or heavy working leads to formation of long, flat grains, are especially prone to intergranular corrosion. Intergranular corrosion induced by environmental stresses is termed as stress corrosion cracking.

Intergranular corrosion can be detected by ultrasonic and eddy current methods.

SENSITIZATION EFFECT

Sensitization of metals involves the creation of galvanic corrosion cells within the microstructure of an alloy. 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 an adjacent to grain boundaries with relatively little corrosion of the grains themselves.

The alloy disintegrates (grains fall out) and/or loses its strength.

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 alloys, small amounts of iron have been shown to segregate in the grain boundaries and cause intergranular corrosion. Also, it has been shown that the zinc content of a brass is higher at the grain boundaries and subject to such corrosion.

High-strength aluminium alloys such as the Duralumintype alloys (Al-Cu) which depend upon precipitated phases for strengthening are susceptible to intergranular corrosion following sensitization at temperatures of about 120C. Nickel-rich alloys such as Inconel 600 and Incoloy 800 show similar susceptibility. Die-cast zinc alloys containing aluminum intergranular corrosion by steam in a atmosphere. exhibit marine

Cr-Mn and Cr-Mn-Ni steels are also susceptible to intergranular corrosion following sensitization in the temperature range of 400-850C. In the case of the austenitic stainless steels, when these steels are sensitized by being heated in the temperature range of about 500 to 800C, 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 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.

Thus a high-temperature solutionheat treatment, commonly termed solution-annealing, quenchannealing or solution-quenching, has been used.

The alloy is heated to a temperature of about 1,060 to 1,120C 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 formers or stabilizing elements such as niobium or titanium in the stainless steels.

Such elements have a much greater affinity for carbon than does chromium; carbide formation with these elements reduces the carbon available in the alloy for formation of chromium carbides.

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.

REFERENCES: 1. en.wikipedia.org/wiki/Intergranular_corrosion 2. corrosion-doctors.org/FormsIntergranular/intergranular.htm 3. www.corrosionclinic.com