High-Entropy Borides under Extreme Environment of Pressures and Temperatures.

The high-entropy transition metal borides containing a random distribution of five or more constituent metallic elements offer novel opportunities in designing materials that show crystalline phase stability, high strength, and thermal oxidation resistance under extreme conditions. We present a comprehensive theoretical and experimental investigation of prototypical high-entropy boride (HEB) materials such as (Hf, Mo, Nb, Ta, Ti)B2 and (Hf, Mo, Nb, Ta, Zr)B2 under extreme environments of pressures and temperatures. The theoretical tools include modeling elastic properties by special quasi-random structures that predict a bulk modulus of 288 GPa and a shear modulus of 215 GPa at ambient conditions. HEB samples were synthesized under high pressures and high temperatures and studied to 9.5 GPa and 2273 K in a large-volume pressure cell. The thermal equation of state measurement yielded a bulk modulus of 276 GPa, in excellent agreement with theory. The measured compressive yield strength by radial X-ray diffraction technique in a diamond anvil cell was 28 GPa at a pressure of 65 GPa, which is a significant fraction of the shear modulus at high pressures. The high compressive strength and phase stability of this material under high pressures and high temperatures make it an ideal candidate for application as a structural material in nuclear and aerospace fields.

Bias-Enhanced Formation of Metastable and Multiphase Boron Nitride Coating in Microwave Plasma Chemical Vapor Deposition.

Boron nitride (BN) is primarily a synthetically produced advanced ceramic material. It is isoelectronic to carbon and, like carbon, can exist as several polymorphic modifications. Microwave plasma chemical vapor deposition (MPCVD) of metastable wurtzite boron nitride is reported for the first time and found to be facilitated by the application of direct current (DC) bias to the substrate. The applied negative DC bias was found to yield a higher content of sp3 bonded BN in both cubic and metastable wurtzite structural forms. This is confirmed by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). Nano-indentation measurements reveal an average coating hardness of 25 GPa with some measurements as high as 31 GPa, consistent with a substantial fraction of sp3 bonding mixed with the hexagonal sp2 bonded BN phase.

Selective Deposition of Hard Boron-Carbon Microstructures on Silicon.

Boron-rich B-C compounds with high hardness have been recently synthesized by the chemical vapor deposition (CVD) method. In this paper, we present our successful efforts in the selective growth of microstructures of boron-carbon compounds on silicon substrates. This was achieved by combining microfabrication techniques such as maskless lithography and sputter deposition with the CVD technique. Our characterization studies on these B-C microstructures showed that they maintain structural and mechanical properties similar to that of their thin-film counterparts. The methodology presented here paves the way for the development of microstructures for microelectromechanical system (MEMS) applications which require custom hardness and strength properties. These hard B-C microstructures are an excellent choice as support structures in MEMS-based devices.

Superhard Boron-Rich Boron Carbide with Controlled Degree of Crystallinity.

Superhard boron-rich boron carbide coatings were deposited on silicon substrates by microwave plasma chemical vapor deposition (MPCVD) under controlled conditions, which led to either a disordered or crystalline structure, as measured by X-ray diffraction. The control of either disordered or crystalline structures was achieved solely by the choice of the sample being placed either directly on top of the sample holder or within an inset of the sample holder, respectively. The carbon content in the B-C bonded disordered and crystalline coatings was 6.1 at.% and 4.5 at.%, respectively, as measured by X-ray photoelectron spectroscopy. X-ray diffraction analysis of the crystalline coating provided a good match with a B50C2-type structure in which two carbon atoms replaced boron in the α-tetragonal B52 structure, or in which the carbon atoms occupied different interstitial sites. Density functional theory predictions were used to evaluate the dynamical stability of the potential B50C2 structural forms and were consistent with the measurements. The measured nanoindentation hardness of the coatings was as high as 64 GPa, well above the 40 GPa threshold for superhardness.