Selective leaching
Encyclopedia
Selective leaching, also called dealloying, demetalification, parting and selective corrosion, is a corrosion
Corrosion
Corrosion is the disintegration of an engineered material into its constituent atoms due to chemical reactions with its surroundings. In the most common use of the word, this means electrochemical oxidation of metals in reaction with an oxidant such as oxygen...

 type in some solid solution
Solid solution
A solid solution is a solid-state solution of one or more solutes in a solvent. Such a mixture is considered a solution rather than a compound when the crystal structure of the solvent remains unchanged by addition of the solutes, and when the mixture remains in a single homogeneous phase...

 alloy
Alloy
An alloy is a mixture or metallic solid solution composed of two or more elements. Complete solid solution alloys give single solid phase microstructure, while partial solutions give two or more phases that may or may not be homogeneous in distribution, depending on thermal history...

s, when in suitable conditions a component of the alloys is preferentially leached
Leaching (metallurgy)
Leaching is a widely used extractive metallurgy technique which converts metals into soluble salts in aqueous media. Compared to pyrometallurgical operations, leaching is easier to perform and much less harmful, because no gaseous pollution occurs...

 from the material. The less noble
Noble metal
Noble metals are metals that are resistant to corrosion and oxidation in moist air, unlike most base metals. They tend to be precious, often due to their rarity in the Earth's crust...

 metal is removed from the alloy by microscopic-scale galvanic corrosion mechanism. The most susceptible alloys are the ones containing metals with high distance between each other in the galvanic series
Galvanic series
The galvanic series determines the nobility of metals and semi-metals. When two metals are submerged in an electrolyte, while electrically connected, the less noble will experience galvanic corrosion. The rate of corrosion is determined by the electrolyte and the difference in nobility...

, eg. copper and zinc in brass. The elements most typically undergoing selective removal are zinc
Zinc
Zinc , or spelter , is a metallic chemical element; it has the symbol Zn and atomic number 30. It is the first element in group 12 of the periodic table. Zinc is, in some respects, chemically similar to magnesium, because its ion is of similar size and its only common oxidation state is +2...

, aluminium
Aluminium
Aluminium or aluminum is a silvery white member of the boron group of chemical elements. It has the symbol Al, and its atomic number is 13. It is not soluble in water under normal circumstances....

, iron
Iron
Iron is a chemical element with the symbol Fe and atomic number 26. It is a metal in the first transition series. It is the most common element forming the planet Earth as a whole, forming much of Earth's outer and inner core. It is the fourth most common element in the Earth's crust...

, cobalt
Cobalt
Cobalt is a chemical element with symbol Co and atomic number 27. It is found naturally only in chemically combined form. The free element, produced by reductive smelting, is a hard, lustrous, silver-gray metal....

, chromium
Chromium
Chromium is a chemical element which has the symbol Cr and atomic number 24. It is the first element in Group 6. It is a steely-gray, lustrous, hard metal that takes a high polish and has a high melting point. It is also odorless, tasteless, and malleable...

, and others.

Leaching of zinc

The most common example is selective leaching of zinc from brass
Brass
Brass is an alloy of copper and zinc; the proportions of zinc and copper can be varied to create a range of brasses with varying properties.In comparison, bronze is principally an alloy of copper and tin...

 alloys containing more than 15% zinc
Zinc
Zinc , or spelter , is a metallic chemical element; it has the symbol Zn and atomic number 30. It is the first element in group 12 of the periodic table. Zinc is, in some respects, chemically similar to magnesium, because its ion is of similar size and its only common oxidation state is +2...

 (dezincification) in presence of oxygen and moisture, eg. from brass taps in chlorine
Chlorine
Chlorine is the chemical element with atomic number 17 and symbol Cl. It is the second lightest halogen, found in the periodic table in group 17. The element forms diatomic molecules under standard conditions, called dichlorine...

-containing water. It is believed that both copper and zinc gradually dissolved out simultaneously and copper precipitates back from the solution. The material remaining is a copper-rich sponge with poor mechanical properties, and color changed from yellow to red. Dezincification can be caused by water containing sulfur
Sulfur
Sulfur or sulphur is the chemical element with atomic number 16. In the periodic table it is represented by the symbol S. It is an abundant, multivalent non-metal. Under normal conditions, sulfur atoms form cyclic octatomic molecules with chemical formula S8. Elemental sulfur is a bright yellow...

, carbon dioxide
Carbon dioxide
Carbon dioxide is a naturally occurring chemical compound composed of two oxygen atoms covalently bonded to a single carbon atom...

 and oxygen
Oxygen
Oxygen is the element with atomic number 8 and represented by the symbol O. Its name derives from the Greek roots ὀξύς and -γενής , because at the time of naming, it was mistakenly thought that all acids required oxygen in their composition...

. Stagnant or low velocity waters tend to promote dezincification.

To combat this, arsenic
Arsenic
Arsenic is a chemical element with the symbol As, atomic number 33 and relative atomic mass 74.92. Arsenic occurs in many minerals, usually in conjunction with sulfur and metals, and also as a pure elemental crystal. It was first documented by Albertus Magnus in 1250.Arsenic is a metalloid...

 or tin
Tin
Tin is a chemical element with the symbol Sn and atomic number 50. It is a main group metal in group 14 of the periodic table. Tin shows chemical similarity to both neighboring group 14 elements, germanium and lead and has two possible oxidation states, +2 and the slightly more stable +4...

 can be added to brass, or gunmetal
Gunmetal
Gunmetal, also known as yellow brass in the United States, is a type of bronze – an alloy of copper, tin, and zinc. Originally used chiefly for making guns, gunmetal was eventually superseded by steel...

 can be used instead. Dezincification resistant brass (DZR) 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

Graphitic corrosion is selective leaching of iron
Iron
Iron is a chemical element with the symbol Fe and atomic number 26. It is a metal in the first transition series. It is the most common element forming the planet Earth as a whole, forming much of Earth's outer and inner core. It is the fourth most common element in the Earth's crust...

 from grey cast iron
Cast iron
Cast iron is derived from pig iron, and while it usually refers to gray iron, it also identifies a large group of ferrous alloys which solidify with a eutectic. The color of a fractured surface can be used to identify an alloy. White cast iron is named after its white surface when fractured, due...

, where iron gets removed and graphite
Graphite
The mineral graphite is one of the allotropes of carbon. It was named by Abraham Gottlob Werner in 1789 from the Ancient Greek γράφω , "to draw/write", for its use in pencils, where it is commonly called lead . Unlike diamond , graphite is an electrical conductor, a semimetal...

 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.

Leaching of other elements

Dealuminification is a corresponding process for aluminum alloys. Similar effects for different metals are decarburization
Decarburization
Decarburization is the process opposite to carburization, namely aimed at decreasing the content of carbon in metals . Decarburization occurs when Carbon in the metal reacts with gasses present in the atmosphere...

 (removal of carbon
Carbon
Carbon is the chemical element with symbol C and atomic number 6. As a member of group 14 on the periodic table, it is nonmetallic and tetravalent—making four electrons available to form covalent chemical bonds...

 from the surface of alloy), decobaltification, denickelification, etc.

Countermeasures

Countermeasures involve using alloys not susceptible to grain boundary depletion, using a suitable heat treatment
Heat treatment
Heat treating is a group of industrial and metalworking processes used to alter the physical, and sometimes chemical, properties of a material. The most common application is metallurgical. Heat treatments are also used in the manufacture of many other materials, such as glass...

, altering the environment (eg. lowering oxygen content), and/or use cathodic protection
Cathodic protection
Cathodic protection is a technique used to control the corrosion of a metal surface by making it the cathode of an electrochemical cell. The simplest method to apply CP is by connecting the metal to be protected with another more easily corroded "sacrificial metal" to act as the anode of the...

.

Uses

Selective leaching can be used to produce powdered materials with extremely high surface area, such as Raney nickel
Raney nickel
Raney nickel is a solid catalyst composed of fine grains of a nickel-aluminium alloy, used in many industrial processes. It was developed in 1926 by American]] engineer Murray Raney as an alternative catalyst for the hydrogenation of vegetable oils in industrial processes...

. Selective leaching can be the pre-final stage of depletion gilding
Depletion gilding
Depletion gilding is a method for producing a layer of nearly pure gold on an object made of gold alloy by removing the other metals from its surface. It is sometimes referred to as a "surface enrichment" process.-Process:...

.
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