Tungsten tetraboride (WB 4 ) is an interesting candidate as a less expensive member of the growing group of superhard transition metal borides. WB 4 was successfully synthesized by arc melting from the elements. Characterization using powder X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDX) indicates that the as-synthesized material is phase pure. The zeropressure bulk modulus, as measured by high-pressure X-ray diffraction for WB 4 , is 339 GPa. Mechanical testing using microindentation gives a Vickers hardness of 43.3 AE 2.9 GPa under an applied load of 0.49 N. Various ratios of rhenium were added to WB 4 in an attempt to increase hardness. With the addition of 1 at.% Re, the Vickers hardness increased to approximately 50 GPa at 0.49 N. Powders of tungsten tetraboride with and without 1 at.% Re addition are thermally stable up to approximately 400°C in air as measured by thermal gravimetric analysis.dispersion hardening | indentation hardness | intrinsic hardness | nano-indentation hardness | solid solutions I n many manufacturing processes, materials must be cut, formed, or drilled, and their surfaces protected with wearresistant coatings. Diamond has traditionally been the material of choice for these shaping operations, due to its superior mechanical properties (e.g., hardness > 70 GPa) (1, 2). However, diamond is rare in nature and difficult to synthesize artificially due to the need for a combination of high temperature and high pressure. Industrial applications of diamond are thus generally limited by cost. Moreover, diamond is not a good option for high-speed cutting of ferrous alloys due to its graphitization on the material's surface and formation of brittle carbides, which leads to poor cutting performance (3). Other hard or superhard (hardness ≥ 40 GPa) substitutes for diamond include compounds of light elements such as cubic boron nitride (4) and BC 2 N (5) or transition metals combined with light elements such as WC (6), HfN (7), and TiN (8). Although the compounds of the first group (B, C, or N) possess high hardness, their synthesis requires high pressure and high temperature and is thus nontrivial (9, 10). On the other hand, most of the compounds of the second group (transition metal-light elements) are not superhard although their synthesis is more straightforward.To overcome the shortcomings of diamond and its substitutes, we have been pursuing the synthesis of dense transition metal borides, which combine high hardness with synthetic conditions that do not require high pressure (11,12). For example, arc melting and metathesis reactions have been used to synthesize the transition metal diborides OsB 2 (13, 14), RuB 2 (15), and ReB 2 (16-20). Among these, rhenium diboride (ReB 2 ) with a hardness of approximately 48 GPa under a load of 0.49 N has proven to be the hardest (16, 21). The boron atoms are needed to build the strong covalent metal-boron and boron-boron bonds that are responsible for the high hardness of these materials (12). Because of this, it is expected th...

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 .

By creation of solid solutions of the recently explored low-cost superhard boride, tungsten tetraboride (WB4), the hardness can be increased. To illustrate this concept, various concentrations of molybdenum (Mo) in WB4, that is, W1–x Mo x B4 (x = 0.00–0.50), were systematically synthesized by arc melting from the pure elements. The as-synthesized samples were characterized using energy-dispersive X-ray spectroscopy (EDS) for elemental analysis, powder X-ray diffraction (XRD) for phase identification, Vickers microindentation for hardness testing, and thermal gravimetric analysis for determining the thermal stability limit. While the EDS analysis confirmed the elemental purity of the samples, the XRD results indicated that Mo is completely soluble in WB4 over the entire concentration range studied (0–50 at. %) without forming a second phase. When 3 at. % Mo is added to WB4, Vickers hardness values increased by about 15% from 28.1 ± 1.4 to 33.4 ± 0.9 GPa under an applied load of 4.90 N and from 43.3 ± 2.9 to 50.3 ± 3.2 GPa under an applied load of 0.49 N. Thermal gravimetric analysis revealed that the powders of this superhard solid solution, W0.97Mo0.03B4, are thermally stable in air up to ∼400 °C. These results indicate that the hardness of superhard transition-metal borides may be enhanced by making solid solutions with small amounts of other transition metals, without introducing a second phase to their structures.

In this work, we examine the lattice behavior of the economically interesting superhard material, tungsten tetraboride (WB 4 ), in a diamond anvil cell under non-hydrostatic compression up to 48.5 GPa. From the measurements of lattice-supported differential stress, significant strength anisotropy is observed in WB 4 . The (002) planes are found to support the highest differential stress of 19.7 GPa within the applied pressure range. This result is in contrast to ReB 2 , one of the hardest transition metal borides known to date, where the same planes support the least differential stress. A discontinuous change in the slope of c/a ratio is seen at 15 GPa, suggesting a structural phase transition that has also been observed under hydrostatic compression. Speculations on the possible relationship between the observed structural changes, the strength anisotropy, and the orientation of boron-boron bonds along the c direction within the WB 4 structure are included.