Modeling hardness of polycrystalline materials and bulk metallic glasses

Based on the idea that the hardness of covalent crystal is intrinsic and equivalent to the sum of the resistance to the indenter of each bond per unit area, a semiempirical method for the evaluation of hardness of multicomponent crystals is presented. Applied to beta-BC2N crystal, the predicted value of hardness is in good agreement with the experimental value. It is found that bond density or electronic density, bond length, and degree of covalent bonding are three determinative factors for the hardness of a polar covalent crystal. Our method offers the advantage of applicability to a broad class of materials and initializes a link between macroscopic property and electronic structure from first principles calculation.

Hardness of covalent crystals.

Hardness can be defined microscopically as the combined resistance of chemical bonds in a material to indentation. The current review presents three most popular microscopic models based on distinct scaling schemes of this resistance, namely the bond resistance, bond strength, and electronegativity models, with key points during employing these microscopic models addressed. These models can be used to estimate the hardness of known crystals. More importantly, hardness prediction based on the designed crystal structures becomes feasible with these models. Consequently, a straightforward and powerful criterion for novel superhard materials is provided. The current focuses of research on potential superhard materials are also discussed.

Microscopic theory of hardness and design of novel superhard crystals

Size dependence of nanostructures: Impact of bond order deficiency

The hardness, toughness and chemical stability of the well-known superhard material cubic boron nitride have been improved by using a synthesis technique based on specially prepared ‘onion-like’ precursor materials. Superhard polycrystalline cubic boron nitride, second only to diamond in hardness, is superior to diamond in terms of thermal and chemical stability and is used widely as an abrasive. The hardness of many materials can be improved by decreasing the grain size, and here Yongjun Tian and colleagues use this principle in a new synthesis technique — based on specially prepared 'onion-like' precursor materials — capable of increasing the hardness of cubic boron nitride. The structure of the resulting polycrystalline material is dominated by nanometre-scale twin domains, yielding a solid combining ultrahigh hardness (exceeding that of a synthetic diamond single crystal) with a high oxidization temperature and extreme fracture toughness. If nanotwins at similar scales can be reproduced in polycrystalline diamond, it may be possible to raise diamond itself to new levels of hardness and stability. Cubic boron nitride (cBN) is a well known superhard material that has a wide range of industrial applications. Nanostructuring of cBN is an effective way to improve its hardness by virtue of the Hall–Petch effect—the tendency for hardness to increase with decreasing grain size1,2. Polycrystalline cBN materials are often synthesized by using the martensitic transformation of a graphite-like BN precursor, in which high pressures and temperatures lead to puckering of the BN layers3. Such approaches have led to synthetic polycrystalline cBN having grain sizes as small as ∼14 nm (refs 1, 2, 4, 5). Here we report the formation of cBN with a nanostructure dominated by fine twin domains of average thickness ∼3.8 nm. This nanotwinned cBN was synthesized from specially prepared BN precursor nanoparticles possessing onion-like nested structures with intrinsically puckered BN layers and numerous stacking faults. The resulting nanotwinned cBN bulk samples are optically transparent with a striking combination of physical properties: an extremely high Vickers hardness (exceeding 100 GPa, the optimal hardness of synthetic diamond), a high oxidization temperature (∼1,294 °C) and a large fracture toughness (>12 MPa m1/2, well beyond the toughness of commercial cemented tungsten carbide, ∼10 MPa m1/2). We show that hardening of cBN is continuous with decreasing twin thickness down to the smallest sizes investigated, contrasting with the expected reverse Hall–Petch effect below a critical grain size or the twin thickness of ∼10–15 nm found in metals and alloys.

Ultrahard nanotwinned cubic boron nitride.

Pyrolysis experiments of melamine were carried out under high pressure of 5 GPa and different temperatures. The crystal structure, chemical bonding, and composition of the melamine pyrolysate were studied by X-ray diffraction (XRD), Fourier transform infrared spectra (FTIR), X-ray photoelectron spectroscopy (XPS), X-ray energy-dispersive analysis (EDX), and combustion elemental analysis. A new C–N–H phase was found in the pyrolysate at 5 GPa and 800 °C. The structure is tentatively indexed as a monoclinic symmetry, with the following lattice parameters: a = 8.5368 (±0.0009)A, b = 9.1153 (±0.0010)A, c = 10.2440 (±0.0011)A, α = γ = 90°, and β = 95.5696 (±0.0016)°. The photoluminescence behavior of the pyrolysates was investigated. A blue emission at 421 nm for the C–N–H phase was observed under the ultraviolet light excitation of 365 nm.

Phase transformation of melamine at high pressure and temperature

Barium hexaferrite was synthesized by chemical co-precipitation. Its Mossbauer spectra were obtained. A semi-empirical model, based on the Phillips theory of bonding, has been developed for quantitative explanation of the Mossbauer isomer shifts of Fe ions in BaFe12O19 crystals. The results show that, using the relationship between isomer shifts and covalency, the site assignments in hexaferrites will be resolved easily. This paper provides a powerful tool for studying other members of the hexagonal ferrimagnetic oxides family.

https://iopscience.iop.org/article/10.1088/0953-8984/15/29/319/pdf

Dongchun Li

Papers

Hardness of covalent crystals.

Phase transformation of melamine at high pressure and temperature

Mössbauer spectroscopy and chemical bonds in BaFe12O19 hexaferrite

Orthorhombic B2CN crystal synthesized by high pressure and temperature

First principles study on the properties of p-type conducting In:SnO2