Superhard material

A superhard material is a material with a hardness value exceeding 40 gigapascals (GPa) when measured by the Vickers hardness test. They are highly incompressible solids with high electron density and high bond covalency. As a result of their unique properties, these materials are of great interest in many industrial areas including, but not limited to, abrasives, polishing and cutting tools and wear-resistant and protective coatings. A superhard material is a material with a hardness value exceeding 40 gigapascals (GPa) when measured by the Vickers hardness test. They are highly incompressible solids with high electron density and high bond covalency. As a result of their unique properties, these materials are of great interest in many industrial areas including, but not limited to, abrasives, polishing and cutting tools and wear-resistant and protective coatings. Diamond is the hardest known material to date, with a Vickers hardness in the range of 70–150 GPa. Diamond demonstrates both high thermal conductivity and electrically insulating properties and much attention has been put into finding practical applications of this material. However, diamond has several limitations for mass industrial application, including its high cost and oxidation at temperatures above 800 °C. In addition, diamond dissolves in iron and forms iron carbides at high temperatures and therefore is inefficient in cutting ferrous materials including steel. Therefore, recent research of superhard materials has been focusing on compounds which would be thermally and chemically more stable than pure diamond. The search for new superhard materials has generally taken two paths. In the first approach, researchers emulate the short, directional covalent carbon bonds of diamond by combining light elements like boron, carbon, nitrogen, and oxygen. This approach became popular in the late 1980s with the exploration of C3N4 and B-C-N ternary compounds. The second approach towards designing superhard materials incorporates these lighter elements (B, C, N, and O), but also introduces transition metals with high valence electron densities to provide high incompressibility. In this way, metals with high bulk moduli but low hardness are coordinated with small covalent-forming atoms to produce superhard materials. Tungsten carbide is an industrially-relevant manifestation of this approach, although it is not considered superhard. Alternatively, borides combined with transition metals have become a rich area of superhard research and have led to discoveries such as ReB2, OsB2, and WB4. Superhard materials can be generally classified into two categories: intrinsic compounds and extrinsic compounds. The intrinsic group includes diamond, cubic boron nitride (c-BN), carbon nitrides and ternary compounds such as B-N-C, which possess an innate hardness. Conversely, extrinsic materials are those that have superhardness and other mechanical properties that are determined by their microstructure rather than composition. An example of extrinsic superhard material is nanocrystalline diamond known as aggregated diamond nanorods. The hardness of a material is directly related to its incompressibility, elasticity and resistance to change in shape. A superhard material has high shear modulus, high bulk modulus and does not deform plastically. Ideally superhard materials should have a defect-free, isotropic lattice. This greatly reduces structural deformations that can lower the strength of the material. However, defects can actually strengthen some covalent structures. Traditionally, high-pressure and high-temperature (HPHT) conditions have been used to synthesize superhard materials, but recent superhard material syntheses aim at using less energy and lower cost materials. Historically, hardness was first defined as the ability of one material to scratch another and quantified by an integer (sometimes half-integer) from 0 to 10 on the Mohs scale. This scale was however quickly found too discrete and non-linear. Measuring the mechanical hardness of materials changed to using a nanoindenter (usually made of diamond) and evaluating bulk moduli, and the Brinell, Rockwell, Knoop and Vickers scales have been developed. Whereas the Vickers scale is widely accepted as a most common test, there remain controversies on the weight load to be applied during the test. This is because Vickers hardness values are load-dependent. An indent made with 0.5N will indicate a higher hardness value than an indent made with 50N. This phenomenon is known as the indentation size effect (ISE). Thus, hardness values are not meaningful unless the load is also reported. Some argue that hardness values should consistently be reported in the asymptotic (high-load region), as this is a more standardized representation of a material’s hardness. Bulk moduli, shear moduli, and elasticity are the key factors in the superhard classification process. The incompressibility of a material is quantified by the bulk modulus B, which measures the resistance of a solid to volume compression under hydrostatic stress as B = −Vdp/dV. Here V is the volume, p is pressure, and dp/dV is the partial derivative of pressure with respect to the volume. The bulk modulus test uses an indenter tool to form a permanent deformation in a material. The size of the deformation depends on the material’s resistance to the volume compression made by the tool. Elements with small molar volumes and strong interatomic forces usually have high bulk moduli. Bulk moduli was the first major test of hardness and originally shown to be correlated with the molar volume (Vm) and cohesive energy (Ec) as B ~ Ec/Vm Bulk modulus was believed to be a direct measure of a material’s hardness but this no longer remains the dominant school of thought. For example, some alkali and noble metals (Pd, Ag) have anomalously high ratio of the bulk modulus to the Vickers of Brinell hardness. In the early 2000s, a direct relationship between bulk modulus and valence electron density was found as the more electrons were present the greater the repulsions within the structure were. Bulk modulus is still used as a preliminary measure of a material as superhard but it is now known that other properties must be taken into account. In contrast to bulk modulus, shear modulus measures the resistance to shape change at a constant volume, taking into account the crystalline plane and direction of shear. The shear modulus G is defined as ratio of shear stress to shear strain: G = stress/strain = F·L/(A·dx), where F is the applied force, A is the area upon which the force acts, dx is the resulting displacement and L is the initial length. The larger the shear modulus, the greater the ability for a material to resist shearing forces. Therefore, the shear modulus is a measure of rigidity. Shear modulus is related to bulk modulus as 3/G = 2B(1 − 2v)(1 + v), where v is the Poisson’s ratio, which is typically ~0.1 in covalent materials. If a material contains highly directional bonds, the shear modulus will increase and give a low Poisson ratio. A material is also considered hard if it resists plastic deformation. If a material has short covalent bonds, atomic dislocations that lead to plastic deformation are less likely to occur than in materials with longer, delocalized bonds. If a material contains many delocalized bonds it is likely to be soft. Somewhat related to hardness is another mechanical property fracture toughness, which is a material's ability to resist breakage from forceful impact (note that this concept is distinct from the notion of toughness). A superhard material is not necessarily 'supertough'. For example, the fracture toughness of diamond is about 7–10 MPa·m1/2, which is high compared to other gemstones and ceramic materials, but poor compared to many metals and alloys – common steels and aluminium alloys have the toughness values at least 5 times higher.