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IGC - 304 - Lecture 7
IGC - 304 - Lecture 7
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Intergranular Corrosion
INTERGRANULAR CORROSION
(INTERGRANULAR ATTACK.. IGA)
Metals are usually “polycrystalline” . . . an assemblage of single-crystal grains
separated by grain boundaries.
Grain boundary in a
polycrystalline metal (two-
dimensional representation).
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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.
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IGA (Intergranular Attack) in Austenitic SS (Stainless Steel)
What is austenite?
austenite
• is non-magnetic;
• is unstable below 727C
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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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.
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AUSTENITE decomposes on rapid cooling below 727C (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”.
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Diagrammatic representation
of a grain boundary in sensitized
type 304 stainless steel.
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Electron photomicrograph of carbides isolated from sensitized type 304 stainless steel.
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Sensitization by welding, or “Weld Decay”
During welding, the weld “bead” and the metal on either side pass through
the temperature range for sensitization.
Temperature AND time are crucial for carbide precipitation: sensitized areas
are on either side of the bead.
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Actual measurements made with thermocouples at points ABCD. Fontana
says metal at and between points B and C within sensitizing range for some
time.
Discuss
Minimizing IGA of SS
(1) Heat Treatment “Quench-Annealing”
or ... “Solution-Annealing”
or .... “Solution-Quenching”
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(2) Alloy “Stabilization”
Elements that are strong carbide formers are added:
Nb (or Nb+Ta) type 347 SS
Ti type 327 SS
Melting point, F C
Cr + Nb carbides
dissolve
2250 1230
Cr carbide dissolves
Nb carbide precipitates 790
1450 Schematic chart showing solution
and precipitation reactions in types
Cr carbide precipitates 304 and 347 SS.
950 510
No reactions
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70 20
Stabilized SS from supplier usually heat-treated by quenching from ~1070C.
- Nb carbide has precipitated,
- Cr left in solution, hence no C available for any reactions with Cr at
lower temperatures.
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“Knife-Line-Attack” (KLA) may now occur in narrow band next to weld if exposed to
corrosive environment.
Knife-line attack on
type 347 stainless
steel.
Should have been heat-treated between 790 & 1230 C (Nb carbide precipitates, Cr
dissolves).
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(3) Use “Low-Carbon” (< 0.03%) Alloy.
At concentrations < 0.03%, not enough C can precipitate as Cr carbide to
sensitize. Get L-Grade or ELC alloys e.g., “type 304L”.
N.B. Must take care to avoid C contamination during casting, welding, etc.
Other Alloys and IGA
Alloy with precipitated phases may also show IGA:
• Duralumin(um) Al-Cu can precipitate CuAl2 and deplete Cu locally;
• Die-cast Zn alloys containing Al... IGA in steam, marine environments;
• Minor IGA effects in many Al alloys.
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Selective leaching
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Selective Leaching
SELECTIVE LEACHING (“Dealloying”, “Parting”)
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Combinations of alloys and environments subject to dealloying and elements
preferentially removed
Alloy Environment Element removed
Many waters, especially under stagnant
Brasses Zn (dezincification)
conditions
Grey iron Soils, many waters Fe (graphitic corrosion)
Aluminium bronzes HCl, acids containing Chloride Al (dealuminification)
Silicon bronzes High-temperature steam and acidic species Si (desiliconification)
Hot brine or steam
Tin bronzes Sn (destannification)
High heat flux and low water velocity
Copper-nickels Ni (denickelification)
(in refinery condenser tubes)
Copper-gold single crystals Ferric chloride Cu
Monels Hydrofluoric and other acids Cu in some acids, and Ni in others
Gold alloys with copper or
Sulfide solutions, human saliva
silver Cu, Ag, Cr, Fe, Mo and T
Molten salts
High-nickel alloys
Medium- and high-carbon Oxidizing atmospheres, hydrogen at high
C (decarburization)
steels temperatures
Iron-chromium alloys High-temperature oxidizing atmospheres Cr, which forms a protective film
Nickel-molybdenum alloys Oxygen at high temperature Mo
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Dezincification
All Cu-Zn alloys (Brasses) containing > 15% Zn are susceptible . . .
e.g. common yellow brass . . . 30 Zn 70 Cu, dezincifies to red copper-rich
structure. Dezincification can be uniform...
- potable water inside
Uniform dezincification of
brass pipe.
Uniform dezincification...
- usually found in high brasses (high[Zn]), acid environments;
Plug-type dezincification...
- usually found in low brasses, alkaline, neutral or slightly acid environments.
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Mechanism
(1) Zn atoms leave lattice sites . . .
“are leached into the environment selectively’’
Discuss . . . w.r.t. last picture.
- Cathodically protect;
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“Graphitization” (misnomer . . . graphitization is the breakdown of pearlite to
ferrite + C at high temperature)
Grey cast iron is the cheapest engineering metal . . . 2-4% C, 1-3% Si.
Hard, brittle, easily cast; carbon present as microscopic flakes of matrix
graphite within microstructure.
100 m
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In some environments (notably mild, aqueous soils affecting buried pipe) the
Fe leaches out slowly and leaves graphite matrix behind . . appears graphitic . .
.soft . . . can be cut with a knife. Pores usually filled with rust. Original
dimensions are retained.
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(a) External surface of a grey-iron pipe
exhibiting severe graphitic corrosion.
20 m 28
Selective Dissolution in Liquid Metals
In liquid metal coolants (LMFBR with Na or Na-K coolant), austenitic alloys
can lose Ni and Cr and revert to the ferrite phase...
Corrosion of Inconel* alloy 706 exposed to liquid sodium for 8,000 hours at 700C
(1290F); hot leg circulating system. A porous surface layer has formed with a
composition of 95% Fe, 2% Cr and < 1% Ni. The majority of the weight loss
encountered can be accounted for by this surface degradation. Total damage depth:
45 m. (a) Light micrograph. (b) SEM of the surface of the porous layer.
* Alloy 706 ... 39-44% Ni, 14.5-17.5% Cr, 0.06% C.
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Also in fusion-reactor environments (Li as coolant)....
Corrosion of type 316 stainless steel exposed to thermally convective lithium for
7488 hours at the maximum loop temperature of 600C.
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Usually, the transport and deposition of leached elements is of more concern
than the actual corrosion.
(a) (b)
SEM micrographs of chromium mass transfer deposits found at the 460C (860C)
position in the cold leg of a lithium/type-316-stainless-steel thermal convection loop
after 1700 hours. Mass transfer deposits are often a more serious result of corrosion
than wall thinning. (a) Cross section of specimen on which chromium was deposited.
(b) Top view of surface.
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100 m
Molten salts are ionic conductors (like aqueous solutions) and can promote
anodic-cathodic electrolytic cells . . . they can be aggressive to metals.
ALSO . . . some molten salts (notably fluorides) are “Fluxes” and dissolve surface
deposits that would otherwise be protective: dealloying of Cr from Ni-base
alloys and stainless steels can occur in the surface layers exposed to molten
fluorides; the vacancies in the metal lattice then coalesce to form subsurface
voids which agglomerate and grow with increasing time and temperature.
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(a) (b)
(a) microstructure of type 304L SS exposed to LiF-BeF2-ZrF4-ThF4- UF4 (70-23-5-1-1
mole % respectively) for 5700 hours at 688C.
(b) microstructure of type 304L SS exposed to LiF-BeF2-ZrF4-ThF4- UF4 (70-23-5-1-1
mole % respectively) for 5724 hours at 685C.
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