Selective Leaching

SELECTIVE LEACHING (Dealloying, Parting)

Corrosion in which one constituent of an alloy is
preferentially removed, leaving behind an altered
(weakened) residual structure.

Can occur in several systems.

Combinations of alloys and environments subject to dealloying and
elements preferentially removed

Alloy Environment Element removed
Brasses
Many waters, especially under stagnant
conditions
Zn (dezincification)
Grey iron
Aluminium bronzes
Soils, many waters
HCl, acids containing Chloride
Fe (graphitic corrosion)
Al (dealuminification)
Silicon bronzes High-temperature steam and acidic species Si (desiliconification)
Tin bronzes
Copper-nickels
Hot brine or steam
High heat flux and low water velocity
(in refinery condenser tubes)
Sn (destannification)
Ni (denickelification)
Copper-gold single crystals
Monels
Ferric chloride
Hydrofluoric and other acids
Cu
Cu in some acids, and Ni in others
Gold alloys with copper or
silver
High-nickel alloys
Sulfide solutions, human saliva
Molten salts
Cu, Ag, Cr, Fe, Mo and T
Medium- and high-carbon
steels
Oxidizing atmospheres, hydrogen at high
temperatures
C (decarburization)
Iron-chromium alloys High-temperature oxidizing atmospheres Cr, which forms a protective film
Nickel-molybdenum alloys Oxygen at high temperature Mo
Dezincification (Characteristics)
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






- or plug-type.... (boiler water inside, combustion gases
outside)
Uniform dezincification of
brass pipe.
Plug-type
dezincification.
Overall dimensions of original material tend to be retained . . . residual is
spongy and porous . . . often brittle.
Can go unnoticed, especially if covered with dirt/deposit, etc.

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.
Section of one of the plugs shown before
Mechanism
(1) Zn atoms leave lattice sites . . .
are leached into the environment selectively

(2) Generally accepted . . .
- brass dissolves;
- Zn stays in solution;
- Cu re-deposits.

N.B. possibility for local anode-cathode couples .. Cu deposits
accelerate attack.
N.B. dezincified areas generally 90-95% Cu; some Cu
2
O/CuO present if
O
2
in the environment.
Prevention
- Make environment less aggressive (e.g., reduce O
2
content);

- Cathodically protect;

- Use a better alloy (common cure - above not usually feasible)...
- red brass (<15% Zn) almost immune
- Admiralty Brass. . . 70 Cu, 29 Zn, 1 Sn;
- arsenical Admiralty. . . 70 Cu, 29 Zn, 1 Sn, 0.04 As
(Sn and Sn-As in deposited films hinder redeposition of Cu);

- For very corrosive environments likely to provoke dezincification, or
for critical components, use . . .
- cupronickels 70-90 Cu, 30-10 Ni.
Graphitization (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.
Microstructure of grey cast
iron.
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.
A 200-mm (8-in.) diameter grey-iron pipe
that failed because of graphitic corrosion.
The pipe was part of a subterranean fire
control system. The external surface of the
pipe was covered with soil; the internal
surface was covered with water. Severe
graphitic corrosion occurred along the
bottom external surface where the pipe
rested on the soil.

The small-diameter piece in the foreground
is a grey-iron pump impeller on which the
impeller vanes have disintegrated because
of graphitic corrosion.
(a) External surface of a grey-iron pipe
exhibiting severe graphitic corrosion.
(b) Close-up of the graphitically-corroded
region shown in (a).
(c) Micrograph of symmetrical envelopes of
graphitically-corroded iron surrounding flakes
of graphite.
Selective Dissolution in Liquid Metals
In liquid metal coolants (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.
Also in fusion-reactor environments (Li as coolant)....









Light micrograph of cross-section. SEM of surface showing porous layer.


Corrosion of type 316 stainless steel exposed to thermally convective lithium for
7488 hours at the maximum loop temperature of 600C.
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.
Iron crystals found in a plugged region of a failed pump channel of
a lithium processing test loop.
Selective Leaching in Molten Salts

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.










(a) (b)
(a) microstructure of type 304L SS exposed to LiF-BeF
2
-ZrF
4
-ThF
4
- UF
4

(70-23-5-1-1 mole % respectively) for 5700 hours at 688C.
(b) microstructure of type 304L SS exposed to LiF-BeF
2
-ZrF
4
-ThF
4
- UF
4

(70-23-5-1-1 mole % respectively) for 5724 hours at 685C.