Intergranular Corrosion

Forms of corrosion

General corrosion (uniform corrosion over the whole anode)

Localized Corrosion (corrosion at isolated areas in the anode)
Galvanic corrosion
pitting corrosion
Crevice corrosion
Metallurgically Influenced Corrosion (corrosion is related to microstructure)
intergranular corrosion of stainless steel
Mechanically Assisted Corrosion (corrosion is accelerated due to mechanical
factors)
Erosion corrosion
Corrosion Fatigue
Environmentally Assisted Cracking (corrosion results in cracking)
Stress corrosion cracking
Hydrogen damage

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 Forms of Corrosion

Factors affecting forms of corrosion :

Microstructure Environment Stress Geometry Time

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Intergranular Corrosion
INTERGRANULAR CORROSION (Intergranular Attack.. IGA) is localized attack at and
adjacent to grain boundaries, with relatively little corrosion of the grains. The alloy,
sensitive to IGC, disintegrates and/or loses its strength when exposed to
environments.
Metals are usually “polycrystalline” . . . an
assemblage of single crystal grains
separated by grain boundaries.

Grain boundary in a polycrystalline metal (schematic representation & actual).

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Intergranular Corrosion
The atoms in the grain boundaries are in a distorted lattice (i.e., disordered).

The higher energies of grain boundary atoms make them slightly more reactive than grains.

BUT: difference is NOT NOTICEABLE in general corrosion.

SOMETIMES . . . grain boundaries can become highly reactive by:

concentration of impurity atoms (e.g., Fe in Al has low solubility in metal,
segregates in grain boundaries which corrode more rapidly than grains, and
intergranular attack results);

enrichment of an alloying element (e.g., Zn in brass);

depletion of an alloying element (e.g., Cr in SS).

Causes of intergranular corrosion

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Intergranular Corrosion
IGA (Intergranular Attack) in Austenitic SS (Stainless Steel)
What is austenite?

The lower-left corner

receives prime attention
in heat-treating of steels.
(In calculations, 0.77 %
is commonly rounded to
0.8 %.)

Fe-Fe3C Phase Diagram.

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Intergranular Corrosion
Nomenclature

cast iron / CS . . . . > 2%C / < 4% C;

iron ( ferrite not to be confused with ferrite oxides).. is BCC
iron (ferrite) is also BCC;
iron carbide (cementite) is Fe3C, orthorhombic;
iron (austenite) is FCC.

austenite
is non magnetic;
is unstable below 727 C
decomposes on slow cooling to ferrite + pearlite if hypoeutectoid;
pearlite + eutectic if hyperentectoid
(N.B. pearlite is the lamellar mixture of ferrite and carbide that forms on
cooling austenite of eutectoid composition . . . 0.8% C).

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Intergranular Corrosion

Pearlite.
This microstructure is a lamellar mixture
of ferrite (lighter matrix) and carbide
(darker).
Pearlite forms from austenite of
eutectoid composition. Therefore, the
amount and composition of pearlite are
the same as those of eutectoid austenite.

Pearlite Formation. Carbon must diffuse

from the eutectoid austenite ( 0.8
percent) to form carbide (6.7 percent).
The ferrite that is formed has negligible
carbon.

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Intergranular Corrosion
AUSTENITE decomposes on rapid cooling below 727 C (i.e., quenching) to:
MARTENSITE a metastable forced solution of C in ferrite that is very hard, has BCT
(body centered tetragonal) structure.

N.B. IN STAINLESS STEELS, THE THREE MAJOR CARBON STEEL PHASES (FERRITE, AUSTENITE,
MARTENSITE) CAN ALSO BE FORMED.
Also: · “ferritic austenitic” (duplex)
· “precipitation hardened”.

Stability and mechanical/physical properties depend on combination of alloying

elements.
austenite stabilizers: C, N, Mn, Ni, (q.v. Ni alloys);
ferrite stabilizers: Si, Cr, Mo, Nb (“Columbium” Cb), Ti.

Selection of a steel/alloy for a particular application depends on mechanical or

physical property considered to be most important.

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Intergranular Corrosion
COMMON STANDARD WROUGHT AUSTENITIC SS
AISI type UNS Cr Ni Mo C Si Mn Other

304 S30400 18 20 8 10.5 0.08 1.0 2.0

304L S30403 18 20 8 12 0.03 1.0 2.0
304N S30451 18 20 8 10.5 0.08 1.0 2.0 0.10 0.16N
316 S31600 16 18 10 14 2.0 3.0 0.08 1.0 2.0
316L S31603 16 18 10 14 2.0 3.0 0.03 1.0 2.0
316N S31651 16 18 10 14 2.0 3.0 0.08 1.0 2.0 0.10 0.16N
347 S34700 17 19 9 13 0.08 1.0 2.0 (10xC)(Cb+Ta)

COMMON STANDARD WROUGHT FERRITIC SS

AISI type UNS Cr C Mn Si P S Other

405 S40500 11.5 14.5 0.08 1.0 1.0 0.04 0.03 0.1 0.3Al

430 S43000 16 18 0.12 1.0 1.0 0.04 0.03

COMMON STANDARD WROUGHT MARTENSITIC SS

AISI type UNS Cr Ni Mo C Other
403 S40300 11.5 13.0 0.15
410 S41000 11.5 13.0 0.15
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Intergranular Corrosion
Sensitization:
Cr is added to steels to make them “stainless”. The Cr rich oxide film (based on
Cr2O3) is thin, adherent and very protective. BUT if heated into range 425 815 C, the
steels “sensitize” and become prone to IGA.
Sensitization involves the precipitation of Cr carbide (Cr23C6) at the grain boundaries;
at the high temperature range its solubility is virtually zero.
Sensitization causes IG corrosion in austenitic stainless steel (such as 304 and 316
SS).
Stainless steels corrosion resistance depends on the availability of Cr dissolved in
iron (at least 12 wt. %).
Between 425 815°C, Cr near the GB react with Carbon and form carbides Cr23C6
Heating for stress relief
During welding
Cr concentration at GB drops below 12 wt.% and the metal is said to be sensitized
(sensitive to IG corrosion)
GB will be more anodic than the grain interiors (galvanic action)
Corrosion rates at the GB will be higher than in the grain interiors
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Sensitization of S. Steel

Above 815oC: Cr-carbides are soluble (so they don’t precipitate) and below 425oC the
diffusion rate of Cr is very low. Sensitization is a pre-requisite for Intergranular corrosion.

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Effects of Cr content on the anodic Effects of Cr content on corrosion
polarization behavior of Fe Cr alloy rate of Fe-Cr alloy

Effects of % C on senitization time of 304

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Weld Decay and Knifeline Attack(KLA)

Sensitization of stainless steels is frequently

developed during improper gas welding.
Sensitization frequently occurs in the heat
affected zone during welding, and the
resultant corrosion is called weld decay
The thermal cycle at the heat affected zone in
thick sections can expose the HAZ of the weld
to the range of sensitization temperature
(425 815 C).
Thin sections (<3mm) need single welds
and will cool rapidly and sensitization
can be avoided
Heavy sections (>3mm) need multiple
passes and cool slowly and may be
subject to sensitization and weld decay.

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Weld Decay and Knifeline Attack(KLA)
An intergranular attack in welded structures. The weld decay zone is within the heat
affected zone(HAZ) somewhat removed from the weld bead itself. At position B in figure
below, the alloy is in the critical temperature range for sufficient time to produce
sensitization. KLA is a highly localized form of IGC that occurs for only a few grain
diameters immediately adjacent to the weld bead in Type 321 and 347 austenitic stainless
steels.

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Weld Decay and Knifeline Attack(KLA)

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Control of Intergranular Corrosion

Metallurgical measures :
Solution annealing : heating the alloy to 1050 C where all Cr carbides are
dissolved, followed by rapid cooling.
Low carbon alloy modifications : lower the carbon content to below 0.03%
for austenitic stainless steels(304L, 316L) or to below 50ppm for ferritic
stainless steels.
Stabilization treatment : add strong carbide former (Ti, Nb) in melt:
321 stabilized SS (Ti is added 0.4 0.8%)
347 stabilized SS (Niobium is added)
Environmental measures : lower acidity and less oxidizing conditions will
generally reduce the susceptibility to IGC.

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