Synthesis and Characterization of Single-Phase Metal Dodecaboride Solid Solutions: Zr1- xY xB12 and Zr1- xU xB12.

Single-phase metal dodecaboride solid solutions, Zr0.5Y0.5B12 and Zr0.5U0.5B12, were prepared by arc melting from pure elements. The phase purity and composition were established by powder X-ray diffraction (PXRD), energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and 10B and 11B solid-state nuclear magnetic resonance (NMR) spectroscopy. The effects of carbon addition to Zr1- xY xB12 were studied and it was found that carbon causes fast cooling and as a result rapid nucleation of grains, as well as "templating" and patterning effects of the surface morphology. The hardness of the Zr0.5Y0.5B12 phase is 47.6 ± 1.7 GPa at 0.49 N load, which is ∼17% higher than that of its parent compounds, ZrB12 and YB12, with hardness values of 41.6 ± 2.6 and 37.5 ± 4.3 GPa, respectively. The hardness of Zr0.5U0.5B12 is ∼54% higher than that of its UB12 parent. The dodecaborides were confirmed to be metallic by band structure calculations, diffuse reflectance UV-vis, and solid-state NMR spectroscopies. The nature of the dodecaboride colors-violet for ZrB12 and blue for YB12-can be attributed to charge-transfer. XPS indicates that the metals are in the following oxidation states: Y3+, Zr4+, and U5+/6+. The superconducting transition temperatures ( Tc) of the dodecaborides were determined to be 4.5 and 6.0 K for YB12 and ZrB12, respectively, as shown by resistivity and superconducting quantum interference device (SQUID) measurements. The Tc of the Zr0.5Y0.5B12 solid solution was suppressed to 2.5 K.

Effects of Variable Boron Concentration on the Properties of Superhard Tungsten Tetraboride.

Tungsten tetraboride is an inexpensive, superhard material easily prepared at ambient pressure. Unfortunately, there are relatively few compounds in existence that crystallize in the same structure as tungsten tetraboride. Furthermore, the lack of data in the tetraboride phase space limits the discovery of any new superhard compounds that also possess high incompressibility and a three-dimensional boron network that withstands shear. Thus, the focus of the work here is to chemically probe the range of thermodynamically stable tetraboride compounds with respect to both the transition metal and the boron content. Tungsten tetraboride alloys with a variable concentration of boron were prepared by arc-melting and investigated for their mechanical properties and thermal stability. The purity and phase composition were confirmed by energy dispersive X-ray spectroscopy and powder X-ray diffraction. For variable boron WBx, it was found that samples prepared with a metal to boron ratio of 1:11.6 to 1:9 have similar hardness values (∼40 GPa at 0.49 N loading) as well as having a similar thermal oxidation temperature of ∼455 °C. A nearly single phase compound was successfully stabilized with tantalum and prepared with a nearly stoichiometric amount of boron (4.5) as W0.668Ta0.332B4.5. Therefore, the cost of production of WB4 can be decreased while maintaining its remarkable properties. Insights from this work will help design future compounds stable in the adaptable tungsten tetraboride structure.

Stabilization of LnB12 (Ln = Gd, Sm, Nd, and Pr) in Zr1-xLnxB12 under Ambient Pressure.

We report ambient pressure stabilization of a previously synthesized high-pressure (6.5 GPa) phase, GdB12, in a Zr1-xGdxB12 solid solution (with ∼54 at. % Gd solubility, as determined by both powder X-ray diffraction and energy-dispersive spectroscopy). Limited solubilities of Sm (∼15 at. % Sm), Nd (∼7 at. % Nd), and Pr (∼4 at. % Pr), in ZrB12 were also achieved. Previous attempts at preparing these rare-earth borides were unsuccessful even under high pressure. On the basis of insights provided from the unit cell sizes observed via solid solutions, at least 6.5 GPa of pressure would be needed to synthesize these rare-earth borides since Sm, Nd, and Pr atomic radii are larger than that of Gd. The solid-solution formation for Zr1-xGdxB12 and Zr1-xSmxB12 can be seen in the change of the unit cell of each of the solid solutions relative to their pure parent compounds as well as in the change of color of the respective alloys. For Zr0.45Gd0.55B12 and Zr0.70Sm0.30B12, the cubic unit cell parameter (a) reached a value of 7.453 and 7.428 Å, respectively, compared to 7.412 Å for pure ZrB12.

Investigation of ternary metal dodecaborides (M1M2M3)B12 (M1, M2 and M3 = Zr, Y, Hf and Gd).

Samples of metal borides with a nominal composition of ((M1)(1-x-z)(M2)(x)(M3)(z)) : 20B (M1, M2 and M3 = Zr, Y, Hf and Gd) were prepared by arc-melting and studied for phase composition (using powder X-ray diffraction (PXRD) and energy dispersive X-ray spectroscopy (EDS)) and mechanical properties (Vickers hardness). Ternary metal dodecaboride phases were successfully synthesized for the majority of compositions, including stabilization of two high-pressure (6.5 GPa) phases (cubic-UB12 structure), HfB12 and GdB12, in (Zr1-x-zHfxGdz) : 20B and (Y1-x-zHfxGdz) : 20B nominal alloy compositions. Unit cell refinement for the samples showed solid solution formation in most cases. Vickers hardness measurements indicated that most samples possess enhanced hardness in comparison to their parent phases, with the alloy (Zr0.50Y0.25Gd0.25) : 20B having a hardness of 46.9 ± 2.4 GPa compared to 41.3 ± 1.1 and 41.6 ± 1.3 GPa for alloy compositions of 1.0 Zr : 20B and 1.0 Y : 20B, respectively, at 0.49 N of applied load. Using the data from this manuscript as well as previous work, pseudo-ternary phase diagrams (at a constant boron content) have been constructed.