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 Civil War era[ when? ], [1] 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. [2]
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. [3]
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. [4] 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. [3] 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. [3] This diffusion process is similar to spinodal decomposition. [3] 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. [3]
Due to the relatively small sample size achievable with dealloying, the mechanical properties of these materials are often probed using the following techniques: [5]
A common concept in materials science is that, at ambient conditions, smaller features (like grain size or absolute size) generally lead to stronger materials (see Hall-Petch strengthening, Weibull statistics). However, due to the high-level of porosity in the dealloyed materials, their strengths and stiffnesses are relatively low compared to the bulk counterparts. [3] The decrease in strength due to porosity can be described with the Gibson-Ashby (GA) relations, [3] which give the yield strength and Young's modulus of a foam according to the following equations: [6]
where and are geometric constants, and are microstructure dependent exponents, and is the relative density of the foam.
The GA relations can be used to estimate the strength and stiffness of a given dealloyed, porous material, but more extensive study has revealed an additional factor: ligament size. When the ligament diameter is greater than 100 nm, increasing ligament size leads to greater agreement between GA predictions and experimental measurements of yield stress and Young's modulus. [7] However, when the ligament size is under 100 nm, which is very common in many dealloying processes, there is an addition to the GA strength that looks similar to Hall-Petch strengthening of bulk polycrystalline metals (i.e., the yield stress increases with the inverse square root of grain size). Combining this relationship with the GA relation from before, an expression for the yield stress of dealloyed materials with ligaments smaller than 100 nm can be determined: [3]
where A and m are empirically determined constants, and is the ligament size. The represents the Hall-Petch-like contribution.
There are two theories for why this increase in strength occurs: 1) dislocations are less common in smaller sample volumes, so deformation requires activation of sources (which is a more difficult process), or 2) dislocations pile-up, which strengthens the material. Either way, there would be significant surface and small volume effects in the ligaments <100 nm, which lead to this increase in yield stress. [7] A relationship between ligament size and Young's modulus has not been studied past the GA relation. [3]
Occasionally, the metastable nature of these materials means that ligaments in the structure may "pinch off" due to surface diffusion, which decreases the connectivity of the structure, and reduces the strength of the dealloyed material past what would be expected from simply porosity (as predicted by the Gibson-Ashby relations). [8]
Because the ligaments of these materials are essentially small metallic samples, they are themselves expected to be quite ductile; although, the entire nano-porous material is often observed to be brittle in tension. [3] Dislocation behavior is extensive within the ligaments (just as would be expected in a metal): a high density. of partial dislocations, stacking faults and twins have been observed both in simulation and in TEM. [3] However, the morphology of the ligaments makes bulk dislocation motion very difficult; the limited size of each ligament and complex connectivity within the nano-porous structure means that a dislocation cannot freely travel long distances and thus induce large-scale plasticity. [3]
Countermeasures involve using alloys not susceptible to grain boundary depletion, using a suitable heat treatment, altering the environment (e.g. lowering oxygen content), and/or use cathodic protection.
Selective leaching can be used to produce powdered materials with extremely high surface area, such as Raney nickel and other heterogeneous catalysts. [9] Selective leaching can be the pre-final stage of depletion gilding.
Electrical resistivity is a fundamental specific property of a material that measures its electrical resistance or how strongly it resists electric current. A low resistivity indicates a material that readily allows electric current. Resistivity is commonly represented by the Greek letter ρ (rho). The SI unit of electrical resistivity is the ohm-metre (Ω⋅m). For example, if a 1 m3 solid cube of material has sheet contacts on two opposite faces, and the resistance between these contacts is 1 Ω, then the resistivity of the material is 1 Ω⋅m.
Sintering or frittage is the process of compacting and forming a solid mass of material by pressure or heat without melting it to the point of liquefaction. Sintering happens as part of a manufacturing process used with metals, ceramics, plastics, and other materials. The nanoparticles in the sintered material diffuse across the boundaries of the particles, fusing the particles together and creating a solid piece.
Corrosion is a natural process that converts a refined metal into a more chemically stable oxide. It is the gradual deterioration of materials by chemical or electrochemical reaction with their environment. Corrosion engineering is the field dedicated to controlling and preventing corrosion.
In physics and materials science, plasticity is the ability of a solid material to undergo permanent deformation, a non-reversible change of shape in response to applied forces. For example, a solid piece of metal being bent or pounded into a new shape displays plasticity as permanent changes occur within the material itself. In engineering, the transition from elastic behavior to plastic behavior is known as yielding.
In materials science, creep is the tendency of a solid material to undergo slow deformation while subject to persistent mechanical stresses. It can occur as a result of long-term exposure to high levels of stress that are still below the yield strength of the material. Creep is more severe in materials that are subjected to heat for long periods and generally increase as they near their melting point.
In materials science, a dislocation or Taylor's dislocation is a linear crystallographic defect or irregularity within a crystal structure that contains an abrupt change in the arrangement of atoms. The movement of dislocations allow atoms to slide over each other at low stress levels and is known as glide or slip. The crystalline order is restored on either side of a glide dislocation but the atoms on one side have moved by one position. The crystalline order is not fully restored with a partial dislocation. A dislocation defines the boundary between slipped and unslipped regions of material and as a result, must either form a complete loop, intersect other dislocations or defects, or extend to the edges of the crystal. A dislocation can be characterised by the distance and direction of movement it causes to atoms which is defined by the Burgers vector. Plastic deformation of a material occurs by the creation and movement of many dislocations. The number and arrangement of dislocations influences many of the properties of materials.
In materials science, work hardening, also known as strain hardening, is the strengthening of a metal or polymer by plastic deformation. Work hardening may be desirable, undesirable, or inconsequential, depending on the context.
In materials science and engineering, the yield point is the point on a stress-strain curve that indicates the limit of elastic behavior and the beginning of plastic behavior. Below the yield point, a material will deform elastically and will return to its original shape when the applied stress is removed. Once the yield point is passed, some fraction of the deformation will be permanent and non-reversible and is known as plastic deformation.
A nanocrystalline (NC) material is a polycrystalline material with a crystallite size of only a few nanometers. These materials fill the gap between amorphous materials without any long range order and conventional coarse-grained materials. Definitions vary, but nanocrystalline material is commonly defined as a crystallite (grain) size below 100 nm. Grain sizes from 100 to 500 nm are typically considered "ultrafine" grains.
Material selection is a step in the process of designing any physical object. In the context of product design, the main goal of material selection is to minimize cost while meeting product performance goals. Systematic selection of the best material for a given application begins with properties and costs of candidate materials. Material selection is often benefited by the use of material index or performance index relevant to the desired material properties. For example, a thermal blanket must have poor thermal conductivity in order to minimize heat transfer for a given temperature difference. It is essential that a designer should have a thorough knowledge of the properties of the materials and their behavior under working conditions. Some of the important characteristics of materials are : strength, durability, flexibility, weight, resistance to heat and corrosion, ability to cast, welded or hardened, machinability, electrical conductivity, etc. In contemporary design, sustainability is a key consideration in material selection. Growing environmental consciousness prompts professionals to prioritize factors such as ecological impact, recyclability, and life cycle analysis in their decision-making process.
Ceramic foam is a tough foam made from ceramics. Manufacturing techniques include impregnating open-cell polymer foams internally with ceramic slurry and then firing in a kiln, leaving only ceramic material. The foams may consist of several ceramic materials such as aluminium oxide, a common high-temperature ceramic, and gets insulating properties from the many tiny air-filled voids within the material.
In metallurgy, solid solution strengthening is a type of alloying that can be used to improve the strength of a pure metal. The technique works by adding atoms of one element to the crystalline lattice of another element, forming a solid solution. The local nonuniformity in the lattice due to the alloying element makes plastic deformation more difficult by impeding dislocation motion through stress fields. In contrast, alloying beyond the solubility limit can form a second phase, leading to strengthening via other mechanisms.
Radiation damage is the effect of ionizing radiation on physical objects including non-living structural materials. It can be either detrimental or beneficial for materials.
Sedimentation potential occurs when dispersed particles move under the influence of either gravity or centrifugation or electricity in a medium. This motion disrupts the equilibrium symmetry of the particle's double layer. While the particle moves, the ions in the electric double layer lag behind due to the liquid flow. This causes a slight displacement between the surface charge and the electric charge of the diffuse layer. As a result, the moving particle creates a dipole moment. The sum of all of the dipoles generates an electric field which is called sedimentation potential. It can be measured with an open electrical circuit, which is also called sedimentation current.
Methods have been devised to modify the yield strength, ductility, and toughness of both crystalline and amorphous materials. These strengthening mechanisms give engineers the ability to tailor the mechanical properties of materials to suit a variety of different applications. For example, the favorable properties of steel result from interstitial incorporation of carbon into the iron lattice. Brass, a binary alloy of copper and zinc, has superior mechanical properties compared to its constituent metals due to solution strengthening. Work hardening has also been used for centuries by blacksmiths to introduce dislocations into materials, increasing their yield strengths.
Melting-point depression is the phenomenon of reduction of the melting point of a material with a reduction of its size. This phenomenon is very prominent in nanoscale materials, which melt at temperatures hundreds of degrees lower than bulk materials.
The Bresler–Pister yield criterion is a function that was originally devised to predict the strength of concrete under multiaxial stress states. This yield criterion is an extension of the Drucker–Prager yield criterion and can be expressed on terms of the stress invariants as
Porosity or void fraction is a measure of the void spaces in a material, and is a fraction of the volume of voids over the total volume, between 0 and 1, or as a percentage between 0% and 100%. Strictly speaking, some tests measure the "accessible void", the total amount of void space accessible from the surface.
Dislocation creep is a deformation mechanism in crystalline materials. Dislocation creep involves the movement of dislocations through the crystal lattice of the material, in contrast to diffusion creep, in which diffusion is the dominant creep mechanism. It causes plastic deformation of the individual crystals, and thus the material itself.
Nuclear magnetic resonance (NMR) in porous materials covers the application of using NMR as a tool to study the structure of porous media and various processes occurring in them. This technique allows the determination of characteristics such as the porosity and pore size distribution, the permeability, the water saturation, the wettability, etc.
