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Selective leaching
In metallurgy, selective leaching, also called dealloying, demetalification, parting and selective corrosion, is a corrosion type in some solid solution alloys, when in suitable conditions a component of the alloys is preferentially leached from the initially homogenous material. The less noble metal is removed from the alloy by a microscopic-scale galvanic corrosion mechanism. The most susceptible alloys are the ones containing metals with high distance between each other in the galvanic series, e.g. copper and zinc in brass. The elements most typically undergoing selective removal are zinc, aluminium, iron, cobalt, chromium, and others.
The most common example is selective leaching of zinc from brass alloys containing more than 15% zinc (dezincification) in the presence of oxygen and moisture, e.g. from brass taps in chlorine-containing water. Dezincification has been studied since the 1860s, and the mechanism by which it occurs was under extensive examination by the 1960s. It is believed that both copper and zinc gradually dissolve out simultaneously, and copper precipitates back from the solution. The material remaining is a copper-rich sponge with poor mechanical properties, and a color changed from yellow to red. Dezincification can be caused by water containing sulfur, carbon dioxide, and oxygen. Stagnant or low velocity waters tend to promote dezincification.
To combat this, arsenic or tin can be added to brass, or gunmetal can be used instead. Dezincification resistant brass (DZR), also known as Brass C352 is an alloy used to make pipe fittings for use with potable water. Plumbing fittings that are resistant to dezincification are appropriately marked, with the letters "CR" (Corrosion Resistant) or DZR (dezincification resistant) in the UK, and the letters "DR" (dezincification resistant) in Australia.
Graphitic corrosion is selective leaching of iron, from grey cast iron, where iron is removed and graphite grains remain intact. Affected surfaces develop a layer of graphite, rust, and metallurgical impurities that may inhibit further leaching. The effect can be substantially reduced by alloying the cast iron with nickel.
Dealuminification is a corresponding process for aluminum alloys. Similar effects for different metals are decarburization (removal of carbon from the surface of alloy), decobaltification, denickelification, etc. The prototypical system for dealloying to create nano-porous metals is the np-Au system, which is created by selectively leaching Ag out of an Au-Ag homogenous alloy.
When an initially homogenous alloy is placed in an acid that can preferentially dissolve one or more components out of the alloy, the remaining component will diffuse and organize into a unique, nano-porous microstructure. The resulting material will have ligaments, formed by the remaining material, surrounded by pores, empty space from which atoms were leached/diffused away.
The way that porosity develops during the dealloying process has been studied computationally to understand the diffusional pathways on an atomistic level. Firstly, the less noble atoms must be dissolved away from the surface of the alloy. This process is easiest for the lower coordinated atoms, i.e., those bonded to fewer other atoms, usually found as single atoms sitting on the surface ("adatoms"), but it is more difficult for higher coordinated atoms, i.e., those sitting at "steps" or in the bulk of the material. Thus, the slowest step, and that which is most important for determining rate of porosity evolution is the dissolution of these higher coordinated less noble atoms. Just as the less noble metal is less stable as an adatom on the surface, so is an atom of the more noble metal. Therefore, as dissolution proceeds, any more noble atoms will move to more stable positions, like steps, where its coordination is higher. This diffusion process is similar to spinodal decomposition. Eventually, clusters of more noble atoms form this way, and surrounding less noble atoms dissolve away, leaving behind a "bicontinuous structure" and providing a pathway for dissolution to continue deeper into the metal.
Due to the relatively small sample size achievable with dealloying, the mechanical properties of these materials are often probed using the following techniques:
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Selective leaching
In metallurgy, selective leaching, also called dealloying, demetalification, parting and selective corrosion, is a corrosion type in some solid solution alloys, when in suitable conditions a component of the alloys is preferentially leached from the initially homogenous material. The less noble metal is removed from the alloy by a microscopic-scale galvanic corrosion mechanism. The most susceptible alloys are the ones containing metals with high distance between each other in the galvanic series, e.g. copper and zinc in brass. The elements most typically undergoing selective removal are zinc, aluminium, iron, cobalt, chromium, and others.
The most common example is selective leaching of zinc from brass alloys containing more than 15% zinc (dezincification) in the presence of oxygen and moisture, e.g. from brass taps in chlorine-containing water. Dezincification has been studied since the 1860s, and the mechanism by which it occurs was under extensive examination by the 1960s. It is believed that both copper and zinc gradually dissolve out simultaneously, and copper precipitates back from the solution. The material remaining is a copper-rich sponge with poor mechanical properties, and a color changed from yellow to red. Dezincification can be caused by water containing sulfur, carbon dioxide, and oxygen. Stagnant or low velocity waters tend to promote dezincification.
To combat this, arsenic or tin can be added to brass, or gunmetal can be used instead. Dezincification resistant brass (DZR), also known as Brass C352 is an alloy used to make pipe fittings for use with potable water. Plumbing fittings that are resistant to dezincification are appropriately marked, with the letters "CR" (Corrosion Resistant) or DZR (dezincification resistant) in the UK, and the letters "DR" (dezincification resistant) in Australia.
Graphitic corrosion is selective leaching of iron, from grey cast iron, where iron is removed and graphite grains remain intact. Affected surfaces develop a layer of graphite, rust, and metallurgical impurities that may inhibit further leaching. The effect can be substantially reduced by alloying the cast iron with nickel.
Dealuminification is a corresponding process for aluminum alloys. Similar effects for different metals are decarburization (removal of carbon from the surface of alloy), decobaltification, denickelification, etc. The prototypical system for dealloying to create nano-porous metals is the np-Au system, which is created by selectively leaching Ag out of an Au-Ag homogenous alloy.
When an initially homogenous alloy is placed in an acid that can preferentially dissolve one or more components out of the alloy, the remaining component will diffuse and organize into a unique, nano-porous microstructure. The resulting material will have ligaments, formed by the remaining material, surrounded by pores, empty space from which atoms were leached/diffused away.
The way that porosity develops during the dealloying process has been studied computationally to understand the diffusional pathways on an atomistic level. Firstly, the less noble atoms must be dissolved away from the surface of the alloy. This process is easiest for the lower coordinated atoms, i.e., those bonded to fewer other atoms, usually found as single atoms sitting on the surface ("adatoms"), but it is more difficult for higher coordinated atoms, i.e., those sitting at "steps" or in the bulk of the material. Thus, the slowest step, and that which is most important for determining rate of porosity evolution is the dissolution of these higher coordinated less noble atoms. Just as the less noble metal is less stable as an adatom on the surface, so is an atom of the more noble metal. Therefore, as dissolution proceeds, any more noble atoms will move to more stable positions, like steps, where its coordination is higher. This diffusion process is similar to spinodal decomposition. Eventually, clusters of more noble atoms form this way, and surrounding less noble atoms dissolve away, leaving behind a "bicontinuous structure" and providing a pathway for dissolution to continue deeper into the metal.
Due to the relatively small sample size achievable with dealloying, the mechanical properties of these materials are often probed using the following techniques: