Boron: a Hunt for Superhard Polymorphs

Boron is a unique element, being the only element, all known polymorphs of which are superhard, and all of its crystal structures are distinct from any other element. The electron-deficient bonding in boron explains its remarkable sensitivity to even small concentrations of impurity atoms and allows boron to form peculiar chemical compounds with very different elements. These complications made the study of boron a great challenge, creating also a unique and instructive chapter in the history of science. Strange though it may sound, the discovery of boron in 1808 was ambiguous, with pure boron polymorphs established only starting from the 1950s-1970s, and only in 2007 was the stable phase at ambient conditions determined. The history of boron research from its discovery to the latest discoveries pertaining to the phase diagram of this element, the structure and stability of beta-boron, and establishment of a new high-pressure polymorph, gamma-boron, is reviewed

High pressure synthesis of FeO-ZnO solid solutions with rock salt structure: in situ X-ray diffraction studies

X-ray diffraction with synchrotron radiation has been used for the first time to study chemical interaction in the FeO-ZnO system at 4.8 GPa and temperatures up to 1300 K. Above 750 K, the chemical reaction between FeO and ZnO has been observed that resulted in the formation of rock salt (rs) Fe1-xZnxO solid solutions (0.3 \leq x \leq 0.85). The lattice parameters of these solid solutions have been in situ measured as a function of temperature under pressure, and corresponding thermal expansion coefficients have been calculated.Comment: 9 pages, 2 figures, 1 tabl

On the Hardness of a New Boron Phase, Orthorhombic {\gamma}-B28

Measurements of the hardness of a new high-pressure boron phase, orthorhombic {\gamma}-B28, are reported. According to the data obtained, {\gamma}-B28 has the highest hardness (~50 GPa) of all known crystalline modifications of boron

Superhard Phases of Simple Substances and Binary Compounds of the B-C-N-O System: from Diamond to the Latest Results (a Review)

The basic known and hypothetic one- and two-element phases of the B-C-N-O system (both superhard phases having diamond and boron structures and precursors to synthesize them) are described. The attention has been given to the structure, basic mechanical properties, and methods to identify and characterize the materials. For some phases that have been recently described in the literature the synthesis conditions at high pressures and temperatures are indicated.Comment: Review on superhard B-C-N-O phase

On the crystal lattice parameters of graphite-like phases of the B-C system

The structure of graphite-like BCx phases (x = 1, 1.5, 3, 4, 32) has been studied using conventional X-ray diffraction. The results have been obtained, which unambiguously point to turbostratic (one- dimensionally disordered) structure of all phases under study. The crystal lattice parameters, sizes of coherent scattering domains, and microstrain values have been defined, which have allowed us to find a correlation between the structure and stoichiometry of the phases synthesized at the same temperature

High-pressure synthesis of rock salt LiMeO2-ZnO (Me = Fe3+, Ti3+) solid solutions

Metastable LiMeO2-ZnO (Me = Fe3+, Ti3+) solid solutions with rock salt crystal structure have been synthesized by solid state reaction of ZnO with LiMeO2 complex oxides at 7.7 GPa and 1350-1450 K. Structure, phase composition, thermal stability and thermal expansion of the recovered samples have been studied by X-ray diffraction with synchrotron radiation. At ambient pressure rock salt LiMeO2-ZnO solid solutions are kinetically stable up to 670-800 K depending on the composition.Comment: 11 pages, 3 figures, 1 tabl

Effect of nanostructuration on compressibility of cubic BN

Compressibility of high-purity nanostructured cBN has been studied under quasi-hydrostatic conditions at 300 K up to 35 GPa using diamond anvil cell and angle-dispersive synchrotron X-ray powder diffraction. A data fit to the Vinet equation of state yields the values of the bulk modulus B0 of 375(4) GPa with its first pressure derivative B0' of 2.3(3). The nanometer grain size (\sim20 nm) results in decrease of the bulk modulus by ~9%

Thermodynamic aspects of materials' hardness: prediction of novel superhard high-pressure phases

In the present work we have proposed the method that allows one to easily estimate hardness and bulk modulus of known or hypothetical solid phases from the data on Gibbs energy of atomization of the elements and corresponding covalent radii. It has been shown that hardness and bulk moduli of compounds strongly correlate with their thermodynamic and structural properties. The proposed method may be used for a large number of compounds with various types of chemical bonding and structures; moreover, the temperature dependence of hardness may be calculated, that has been performed for diamond and cubic boron nitride. The correctness of this approach has been shown for the recently synthesized superhard diamond-like BC5. It has been predicted that the hypothetical forms of B2O3, diamond-like boron, BCx and COx, which could be synthesized at high pressures and temperatures, should have extreme hardness