Effect of boron non-stoichiometry on B-site in perovskite type structure ScBxRh3 and CeBxRh3 on charges of atoms on A-site: study by X-ray photoelectron and nuclear magnetic resonance spectroscopies

The solid solutions of ScBRh₃-ScRh₃ and CeBRh₃-CeRh₃ are synthesized by the arc melting method, where RBRh₃ and RRh₃ (R=rare earth element) have perovskite and AuCu₃ type structures, respectively. The binding energy of Sc 2p_3/2 for ScB_xRh₃ increases with the boron concentration. The Knight shift of ⁴⁵Sc observed by nuclear magnetic resonance spectroscopy decreases with increase of boron concentration. The decrement of the Knight shift corresponds the Sc 4s electron density at the Fermi level. The intensity ratio of f²: f¹: f⁰ of Ce 3d XPS spectrum changes with boron concentration of CeB_xRh₃. It is concluded that in both cases of ScB_xRh₃ and CeB_xRh₃ the charge on the atoms on A-site changes with the concentration of the atoms on B-site, where the atoms are not directly bound.     

New quaternary carbon and nitrogen stabilized polyborides: REB15.5CN (RE: Sc, Y, Ho, Er, Tm, Lu), crystal structure and compound formation

A new family of quaternary carbon and nitrogen containing Rare Earth (RE: Sc, Y, Ho, Er, Tm and Lu) borides: REB_15.5CN, has been synthesized and structurally characterized by powder X-ray diffraction data. They are all isotypic with Sc_1−xB_15.5CN whose structure was solved based on single-crystal X-ray data and HRTEM investigations. The structure refinement converged at a R(F²) value of 0.044 for 364 reflections. The new structure type of Sc_1−xB_15.5CN is composed of a three-dimensional network based on interconnected slabs of boron (B₁₂)^ico icosahedra and (B₆)^oct octahedra. A linear [CBC] chain and nitrogen tightly bridges icosahedra. Sc partially occupies voids in the sheets of boron octahedra. It crystallizes with the trigonal space group P³m1, with Z=2. Lattice parameters (nm) are as follows: for RE: Sc, a,b=0.5568(4), c=1.0756(2); Y, a,b=0.55919(6), c=1.0873(2); Ho, a,b=0.55883(7), c=1.0878(6); Er, a,b=0.55889(5), c=1.0880(6); Tm, a,b=0.5580(1), c=1.0850(6); Lu, a,b=0.55771(9), c=1.0839(4). Magnetic characterization of ErB₁₇C_1.3N_0.6 has been performed.     

Unexpected Correlation Between Boron Chain Condensation and Hydrogen Evolution Reaction (HER) Activity in Highly Active Vanadium Borides: Enabling Predictions

Transition‐metal borides (TMBs) have recently attracted attention as excellent hydrogen evolution (HER) electrocatalysts in bulk crystalline materials. Herein, we show for the first time that VB and V₃B₄ have high electrocatalytic HER activity. Furthermore, we show that the HER activity (in 0.5 m H₂SO₄) increases with increasing boron chain condensation in vanadium borides: Using a ?23 mV overpotential decrement derived from ?0.296 mV (for VB at ?10 mA cm^?2 current density) and ?0.273 mV (for V₃B₄) we accurately predict the overpotential of VB₂ (?0.204 mV) as well as that of unstudied V₂B₃ (?0.250 mV) and hypothetical “V₅B₈” (?0.227 mV). We then derived an exponential equation that predicts the overpotentials of known and hypothetical V_xB_y phases containing at least a boron chain. These results provide a direct correlation between crystal structure and HER activity, thus paving the way for the design of even better electrocatalytic materials through structure–activity relationships.     

Experimental Verification of the Theoretical Prediction of High‐Temperature Superconductivity in Phases of Titanium Borides TiB k

Theoretical predictions of hightemperature superconductivity (HTSC) in titanium borides, TiBk, have been experimentally verified. These predictions have been reported previously in the form of theoretical phase diagrams. They predicted the existence of HTSC in TiB _k (1.43 < k < 2.57) phases and in TiB_1.5–1.6. An abrupt decrease at 110 K was found on the temperature curve of conductivity R(T) for titanium samples whose surfaces were coated with diffuse layers of depthvariable boride compositions TiB _k . This indicates that the layers include phases possessing HTSC. This behavior of the R(T) curves is explained assuming that the inclusions of HTSC phases have a strong effect on the resistance of the composite materials at T_c. The composition of the boride layers has been investigated by mass spectrometry. Diffuse boride layers were applied to titanium surface by treating its surface with a B₂H₆ + H₂ gas mixture at 610–700°C followed by annealing in vacuum.     

Amorphous Cobalt Boride Alloy Synthesized by Liquid Phase Methods as Electrode Materials for Electrochemical Capacitors

An amorphous cobalt boride alloy with high electronic conductivity is fabricated through the liquid-phase reduction method. Benefiting from large specific surface area and hierarchical pore structure, the as-synthesized Co-B nanoflakes expose substantial electrochemical active sites, promote the transfer of electrons and ions, and accelerate the redox kinetic process. The as-obtained amorphous Co-B alloy sample displays a specific capacitance of 411 F g⁻¹ at 0.5 A g⁻¹, and with the current density increased to 10 A g⁻¹, it maintains 69% of the initial capacitance. The as-assembled asymmetric supercapacitor device reveals electrochemical properties comprising an excellent specific capacitance of 64.3 F g⁻¹ at 0.25 A g⁻¹, superior cyclical stability of 105% after 20,000 cycles at 3 A g⁻¹, and maximum energy density of 22.9 Wh kg⁻¹ at a power density of 200.3 W kg⁻¹. This study demonstrates great potential in developing high-conductivity materials for an asymmetric supercapacitor through utilizing an amorphous cobalt boride alloy as a promising electrode material.     

Synthesis,Characterization, and Magnetic Properties of the New Boride Solid Solutions M0.5Ru6.5B3 (M = Cr,Mn, Co,Ni)

Powder samples and single crystals of the borides M_0.5Ru_6.5B₃ (M = Cr, Mn, Co, Ni) were synthesized by arc‐melting the elements in a water‐cooled copper crucible under argon. The new phases were structurally characterized by single‐crystal and powder X‐ray diffraction as well as EDX‐Analyses. They crystallize in the hexagonal Th₇Fe₃ structure type (space group P6₃mc, no. 186, Z = 2) and a pronounced site preferential M/Ru substitution is observed. Magnetic properties of the compounds were investigated and Pauli paramagnetism was observed in all cases. However, a strong temperature dependency is subsequently observed in Mn_0.5Ru_6.5B₃ below 250 K, but no hint of magnetic ordering was found.     

Electrochemical synthesis of rare-earth metal (Eu,Nd) borides in molten salts

Rare-earth metal borides are widely used in different fields of modern techniques. Electrochemical synthesis at moderate temperatures (973–1023 K) is a cost-effective alternative to direct reaction techniques. The present work reports the mechanism and kinetics of boron and europium, boron and neodymium joint electrodischarge in chloride-fluoride molten systems. The optimum regimes of europium and neodymium borides electrodeposition are worked out on the base of voltammetric experiments. Europium compound is synthesized as a single-phase EuB₆ product, while neodymium compounds is co-deposited as NdB₄ and NdB₆. Published in Russian in Elektrokhimiya, 2007, Vol. 43, No. 8, pp. 978–984. The article was translated by the authors.     

Study on the microstructure and wear resistance of the composite coatings fabricated on Ti-6Al-4V under different processing conditions

Composite coatings mainly containing titanium carbides and borides were produced by laser surface alloying of Ti-6Al-4V with graphite and boron mixed powders. The test results show that the coatings have higher hardness (1600-1700 HV_0.1) and are more resistant to wear than the as-received sample. Laser scanning speed and the content of alloying elements (weight ratio of graphite to boron) have an effect on both the microstructure and the wear resistance of the coatings. TEM results show that strip titanium carbides and borides grow alternately and thus restrain the formation of coarse needle-like TiB and dendritic TiC crystals produced by laser alloying of titanium alloys with boron and graphite separately.     

Theoretical investigation of the crystallographic structure,anisotropic elastic response,and electronic properties of the major borides in Ni-based superalloys

ABSTRACT

In Ni-based superalloys, it is usually found that borides can strengthen the grain boundaries, thereby resulting in an increase in mechanical strength and high-temperature creep properties. Due to their importance and prevalence in Ni-based superalloys, this study employs first-principles methods to investigate the crystallographic structure, anisotropic elastic response, and electronic properties of the major borides, such as M₂B, M₅B₃ and M₃B₂ (M: Cr, Mo, W), respectively, which is necessary for the assessment of complex mechanical responses of Ni-based superalloys. The results demonstrate that the studied borides are all thermodynamically and mechanically stable. Among the M _x B _y binary borides analysed, Cr _x B _y exhibits the largest shear modulus, Young’s modulus, and Vicker hardness values, and these properties increase with the increase of B contents. The studied borides display nearly isotropic elastic properties except for W₅B₃ and W₃B₂. The electronic structure analysis of M _x B _y shows that the strong hybridisation between M-d and B-p orbitals leads to these borides exhibiting higher theoretical hardness, and the overlapping peaks of M-d and B-p orbitals move to a lower energy area with the increase of B contents, which leads to the increase of shear and Young’s moduli of M _x B _y . Furthermore, for M₃B₂ borides, the Cr-B bonds and Cr–Cr bonds are much stronger than the W-B & Mo-B bonds, and W-W & Mo-Mo bonds, respectively, which leads to Cr _x B _y yielding the largest values of elastic moduli.     

Zn11Rh18B8 and Zn10MRh18B8 with M = Sc,Ti, V,Cr, Mn,Fe, Co,Ni, Cu,Al, Si,Ge, Sn – New Ternary and Quaternary Zinc Rhodium Borides

Zn₁₁Rh₁₈B₈ and Zn₁₀MRh₁₈B₈ with M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Al, Si, Ge and Sn are obtained by reaction of the elemental components in sealed tantalum tubes at 1500 K. They crystallize tetragonally with Z = 2 in the spacegroup P4/mbm with lattice constants a = 1771.2(2) pm, c = 286.40(4) pm for Zn₁₁Rh₁₈B₈ and in the range a = 1767.65(9) pm, c = 285.96(3) pm (Zn₁₀NiRh₁₈B₈) to a = 1774.04(9) pm, c = 286.79(2) pm (Zn₁₀SnRh₁₈B₈) for the quaternary compounds. According to powder photographs all compounds are isotypic. Struture determinations based on single crystal X-ray data were performed with Zn₁₁Rh₁₈B₈, Zn₁₀FeRh₁₈B₈ and Zn₁₀NiRh₁₈B₈. The structure of Zn₁₁Rh₁₈B₈ is related to the Ti₃Co₅B₂ type. Along the short axis planar nets of rhodium atoms composed of triangles, squares, pentagons and elongated hexagons alternate with layers containing the boron and zinc atoms. The rhodium atoms form trigonal prisms centered by boron atoms, two kinds of tetragonal and pentagonal prisms centered by zinc atoms and elongated hexagonal prisms containing pairs of zinc atoms. In the quaternary compounds Zn₁₀MRh₁₈B₈ the zinc atoms in one sort of tetragonal prisms are replaced by M atoms.