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Chromium(II) carbide is a
ceramic A ceramic is any of the various hard, brittle, heat-resistant and corrosion-resistant materials made by shaping and then firing an inorganic, nonmetallic material, such as clay, at a high temperature. Common examples are earthenware, porcelain, ...
compound that exists in several chemical compositions: Cr3C2, Cr7C3, and Cr23C6. At standard conditions it exists as a gray solid. It is extremely hard and
corrosion Corrosion is a natural process that converts a refined metal into a more chemically stable oxide. It is the gradual deterioration of materials (usually a metal) by chemical or electrochemical reaction with their environment. Corrosion engi ...
resistant. It is also a
refractory In materials science, a refractory material or refractory is a material that is resistant to decomposition by heat, pressure, or chemical attack, and retains strength and form at high temperatures. Refractories are polycrystalline, polyphase, ...
compound, which means that it retains its strength at high temperatures as well. These properties make it useful as an additive to metal
alloys An alloy is a mixture of chemical elements of which at least one is a metal. Unlike chemical compounds with metallic bases, an alloy will retain all the properties of a metal in the resulting material, such as electrical conductivity, ductility, ...
. When chromium carbide crystals are integrated into the surface of a metal it improves the wear resistance and corrosion resistance of the metal, and maintains these properties at elevated temperatures. The hardest and most commonly used composition for this purpose is Cr3C2. The mineral form of the Cr3C2 compound is
tongbaite Tongbaite is a rare mineral that has the chemical formula Cr3C2, or chromium carbide. It was first described in 1983 for an occurrence in Liu village, Tongbai County (桐柏县), Henan Province, China and named for the locality. It occurs in an ...
. Isovite, , is a related mineral. Both are extremely rare. Yet another chromium-rich carbide mineral is yarlongite, Cr4Fe4NiC4.Mindat, http://www.mindat.org/min-35899.html


Properties

There are three different crystal structures for chromium carbide corresponding to the three different chemical compositions. Cr23C6 has a cubic crystal structure and a Vickers hardness of 976 kg/mm2. Cr7C3 has a hexagonal crystal structure and a microhardness of 1336 kg/mm2. Cr3C2 is the most durable of the three compositions, and has an orthorhombic crystal structure with a microhardness of 2280 kg/mm2. For this reason Cr3C2 is the primary form of chromium carbide used in surface treatment.


Synthesis

Synthesis of chromium carbide can be achieved through
mechanical alloying Mechanical alloying (MA) is a solid-state and powder processing technique involving repeated cold welding, fracturing, and re-welding of blended powder particles in a high-energy ball mill to produce a homogeneous material. Originally developed to p ...
. In this type of process metallic
chromium Chromium is a chemical element with the symbol Cr and atomic number 24. It is the first element in group 6. It is a steely-grey, lustrous, hard, and brittle transition metal. Chromium metal is valued for its high corrosion resistance and hard ...
and pure carbon in the form of
graphite Graphite () is a crystalline form of the element carbon. It consists of stacked layers of graphene. Graphite occurs naturally and is the most stable form of carbon under standard conditions. Synthetic and natural graphite are consumed on la ...
are loaded into a
ball mill A ball mill is a type of grinder used to grind or blend materials for use in mineral dressing processes, paints, pyrotechnics, ceramics, and selective laser sintering. It works on the principle of impact and attrition: size reduction is done ...
and ground into a fine powder. After the components have been ground they are pressed into a pellet and subjected to hot
isostatic press Hot isostatic pressing (HIP) is a manufacturing process, used to reduce the porosity of metals and increase the density of many ceramic materials. This improves the material's mechanical properties and workability. The process can be used to p ...
ing. Hot isostatic pressing utilizes an inert gas, primarily
argon Argon is a chemical element with the symbol Ar and atomic number 18. It is in group 18 of the periodic table and is a noble gas. Argon is the third-most abundant gas in Earth's atmosphere, at 0.934% (9340 ppmv). It is more than twice a ...
, in a sealed oven. This pressurized gas applies pressure to the sample from all directions while the oven is heated. The heat and pressure cause the graphite and metallic chromium to react and form chromium carbide. Decreasing the percentage of carbon content in the initial mixture results in an increase in the yield of the Cr7C3, and Cr23C6 forms of chromium carbide. Another method for the synthesis of chromium carbide utilizes chromium oxide, pure aluminum, and graphite in a self-propagating
exothermic reaction In thermochemistry, an exothermic reaction is a "reaction for which the overall standard enthalpy change Δ''H''⚬ is negative." Exothermic reactions usually release heat. The term is often confused with exergonic reaction, which IUPAC defines ...
that proceeds as follows: :3Cr2O3 + 6Al + 4C → 2Cr3C2 + 3Al2O3 In this method the reactants are ground and blended in a ball mill. The blended powder is then pressed into a pellet and placed under an inert atmosphere of argon. The sample is then heated. A heated wire, a spark, a laser, or an oven may provide the heat. The exothermic reaction is initiated, and the resulting heat propagates the reaction throughout the rest of the sample.


Uses

Chromium carbide is useful in the surface treatment of metal components. Chromium carbide is used to coat the surface of another metal in a technique known as
thermal spraying Thermal spraying techniques are coating processes in which melted (or heated) materials are sprayed onto a surface. The "feedstock" (coating precursor) is heated by electrical (plasma or arc) or chemical means (combustion flame). Thermal sprayi ...
. Cr3C2 powder is mixed with solid nickel-chromium. This mixture is then heated to very high temperatures and sprayed onto the object being coated where it forms a protective layer. This layer is essentially its own metal matrix composite, consisting of hard ceramic Cr3C2 particles embedded in a nickel-chromium matrix. The matrix itself contributes to the corrosion resistance of the coating because both
nickel Nickel is a chemical element with symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive but large pieces are slow t ...
and chromium are corrosion resistant in their metallic form. After over spraying the coating, the coated part must run through a diffusion heat treatment to reach the best results in matter of coupling strength to the base metal and also in matter of hardness. Another technique utilizes chromium carbide in the form of overlay plates. These are prefabricated chromium carbide-coated steel plates, which are meant to be welded onto existing structures or machinery in order to improve performance. Chromium carbide is used as an additive in cutting tools made of
cemented carbide Cemented carbides are a class of hard materials used extensively for cutting tools, as well as in other industrial applications. It consists of fine particles of carbide cemented into a composite by a binder metal. Cemented carbides commonly us ...
s, in order to improve
hardness In materials science, hardness (antonym: softness) is a measure of the resistance to localized plastic deformation induced by either mechanical indentation or abrasion. In general, different materials differ in their hardness; for example hard ...
by preventing the growth of large grains. The primary constituent in most extremely hard cutting tools is
tungsten carbide Tungsten carbide (chemical formula: WC) is a chemical compound (specifically, a carbide) containing equal parts of tungsten and carbon atoms. In its most basic form, tungsten carbide is a fine gray powder, but it can be pressed and formed into ...
. The tungsten carbide is combined with other carbides such as titanium carbide, niobium carbide, and chromium carbide and
sintered Clinker nodules produced by sintering 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 ...
together with a cobalt matrix. Cr3C2 prevents large grains from forming in the composite, which results in a fine-grained structure of superior hardness. Undesired formation of chromium carbides in stainless steel and other alloys can lead to intergranular corrosion.


References


External links


National Pollutant Inventory - Chromium (III) compounds fact sheet
{{Chromium compounds Carbides Chromium(II) compounds Refractory materials Superhard materials