The quest to create superhard materials rarely strays from the use of high-pressure synthetic methods, which typically require gigapascals of applied pressure. We report that rhenium diboride (ReB2), synthesized in bulk quantities via arc-melting under ambient pressure, rivals materials produced with high-pressure methods. Microindentation measurements on ReB2 indicated an average hardness of 48 gigapascals under an applied load of 0.49 newton, and scratch marks left on a diamond surface confirmed its superhard nature. Its incompressibility along the c axis was equal in magnitude to the linear incompressibility of diamond. In situ high-pressure x-ray diffraction measurements yielded a bulk modulus of 360 gigapascals, and radial diffraction indicated that ReB2 is able to support a remarkably high differential stress. This combination of properties suggests that this material may find applications in cutting when the formation of carbides prevents the use of traditional materials such as diamond.

To enhance the hardness of tungsten tetraboride (WB(4)), a notable lower cost member of the late transition-metal borides, we have synthesized and characterized solid solutions of this material with tantalum (Ta), manganese (Mn), and chromium (Cr). Various concentrations of these transition-metal elements, ranging from 0.0 to 50.0 at. %, on a metals basis, were made. Arc melting was used to synthesize these refractory compounds from the pure elements. Elemental and phase purity of the samples were examined using energy-dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD), and microindentation was utilized to measure the Vickers hardness under applied loads of 0.49-4.9 N. XRD results indicate that the solubility limit is below 10 at. % for Cr and below 20 at. % for Mn, while Ta is soluble in WB(4) above 20 at. %. Optimized Vickers hardness values of 52.8 ± 2.2, 53.7 ± 1.8, and 53.5 ± 1.9 GPa were achieved, under an applied load of 0.49 N, when ~2.0, 4.0, and 10.0 at. % Ta, Mn, and Cr were added to WB(4) on a metals basis, respectively. Motivated by these results, ternary solid solutions of WB(4) were produced, keeping the concentration of Ta in WB(4) fixed at 2.0 at. % and varying the concentration of Mn or Cr. This led to hardness values of 55.8 ± 2.3 and 57.3 ± 1.9 GPa (under a load of 0.49 N) for the combinations W(0.94)Ta(0.02)Mn(0.04)B(4) and W(0.93)Ta(0.02)Cr(0.05)B(4), respectively. In situ high-pressure XRD measurements collected up to ~65 GPa generated a bulk modulus of 335 ± 3 GPa for the hardest WB(4) solid solution, W(0.93)Ta(0.02)Cr(0.05)B(4), and showed suppression of a pressure-induced phase transition previously observed in pure WB(4).

Abstract:In this work, we examine the high pressure behavior of superhard material candidate WB 4 using high-pressure synchrotron X-ray diffraction in a diamond anvil cell up to 58.4 GPa. The zero-pressure bulk modulus, K 0 , obtained from fitting the pressure-volume data using the second-order Birch-Murnaghan equation of state is 326 ± 3 GPa. A reversible, discontinuous change in slope in the c/a ratio is further observed at ~42 GPa, suggesting that lattice softening occurs in the c direction above this pressure. This softening is not observed in other superhard transition metal borides such as ReB 2 compressed to similar pressures. Speculation on the possible relationship between this softening and the orientation of boronboron bonds in the c direction in the WB 4 structure is included. Finally, the shear and Young's modulus values are calculated using an isotropic model based on the measured bulk modulus and an estimated Poisson's ratio for WB 4 .