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At least 19 records

Oxidative Deboronation of Boronic Acids by Hydrogen Peroxide in Planta Generates Borate for Cross-Linking of Rhamnogalacturonan II

Vascular plants require boron to cross-link the rhamnogalacturonan-II (RG-II) domain of pectin to form functional cell walls. Boronic acids, which form reversible esters with cis-diols like borate, have been proposed to influence RG-II cross-linking, though the mechanism remains unclear. We used suspension-cultured rose cells adapted to grow without boron to investigate the effect of boronic acids on RG-II dimerization. When grown with phenylboronic acid (PBA) as the sole boron source, nearly all RG-II was crosslinked, whereas methylboronic acid (MBA) only partially restored cross-linking. In contrast, in vitro assays showed that homogeneous RG-II monomers did not dimerize with alkyl or aryl boronic acids unless supplemented with hydrogen peroxide (H2O2), which oxidatively converts boronic acids to boric acid. Real-time NMR spectroscopy and density functional theory calculations provided insight into the reaction mechanism and energetics of oxidation respectively. Together, our data show that exogenous boronic acids are a source of boric acid for plants, and that the deboronation reaction generates aryl or alkyl alcohol byproducts that can undergo further chemical modification in planta. The fate and potential roles of these byproducts in planta remain to be determined.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Glow Discharge Boronization and Real-Time Boronization Using an Impurity Powder Dropper in LHD

In the Large Helical Device (LHD), boronization is utilized for wall conditioning, employing two distinct methods: glow discharge using diborane gas and the injection of boron powder into the plasma via an impurity powder dropper (IPD). Glow discharge boronization is conducted after maintenance when the vacuum vessel is exposed to air and just before the start of an experimental campaign. In contrast, real-time boronization using the IPD is performed during discharges. The distribution of boron on plasma-facing components was assessed through long-term material probes in the case of glow discharge and through numerical simulations for the IPD method. Results indicated non-uniform boron distributions in both cases. The impact of these boronization techniques on impurity levels and the lifetime of their effects were also examined. Both methods effectively reduced oxygen and iron in the plasma, with the iron impurities originating from the first wall. For glow discharge boronization, the reduction in oxygen levels persisted until the end of the experimental campaign, whereas the reduction in iron levels only lasted a few days. In the case of boron injection during long pulse discharges exceeding 200 s, the suppression of oxygen and iron was observed. The effect on iron quickly diminished within several seconds after the injection ended, whereas the effect on oxygen lasted more than 100 s. The difference in the lifetimes of the boronization effects is further discussed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY

Boron Arsenide and Boron Phosphide for High Temperature and Luminescent Devices

The crystal growth of boron arsenide and boron phosphide in the form of bulk crystals and epitaxial layers on suitable substrates is discussed. The physical, chemical, and electrical properties of the crystals and epitaxial layers are examined. Bulk crystals of boron arsenide were prepared by the chemical transport technique, and their carrier concentration and Hall mobility were measured. The growth of boron arsenide crystals from high temperature solutions was attempted without success. Bulk crystals of boron phosphide were also prepared by chemical transport and solution growth techniques. Techniques required for the fabrication of boron phosphide devices such as junction shaping, diffusion, and contact formation were investigated. Alloying techniques were developed for the formation of low-resistance ohmic contacts to boron phosphide. Four types of boron phosphide devices were fabricated: (1) metal-insulator-boron phosphide structures, (2) Schottky barriers; (3) boron phosphide-silicon carbide heterojunctions; and (4) p-n homojunctions. Easily visible red electroluminescence was observed from both epitaxial and solution grown p-n junctions.

Chu, T. L.

ReaxFF Parameter Set for Boron Clusters and Icosahedral Boron Crystals: Comparison with Density Functional Theory and Machine-Learning Potentials

Icosahedral boron materials, which include regular icosahedra of 12 boron atoms have gained increasing attention due to their potential applications as superhard materials, semiconductors, and energy storage media. However, the synthesis of high quality crystals of these materials has been a major barrier to the development of these applications. To enable computational prediction of synthesis conditions yielding high-quality icosahedral boron crystals, herein we tested and refined a set of ReaxFF parameters for the nucleation and growth of such crystals. We focused on matching the relative energies of small boron clusters obtained by density functional theory since such small clusters and similar motifs are likely present in crystal nuclei and at the interface of growing crystals. Using a training set of B 80 clusters, including a low-energy core–shell structure containing a B 12 icosahedron core and a high-energy single-shell structure produced in preliminary ReaxFF simulations, the ReaxFF parameter set was refined to better reproduce energies calculated by density functional theory (DFT). Among existing ReaxFF parameter sets and the machine-learning interatomic potentials MACE-MP-0, MACE-MP-0b3, MACE-MPA-0, PFP v7.0.0, and SevenNet-MF-ompa, only our new parameter set and PFP v7.0.0 correctly ranked these B 80 clusters. This refinement led to improved agreement with DFT for a test set of 58 clusters consisting of 8–103 boron atoms. Furthermore, our refined parameter set yielded greater local icosahedral structure than the previously existing ReaxFF parameter set for larger scale simulations of crystallization from supercooled liquid boron. Additionally, simulations of solid boron in contact with molten nickel using our refined ReaxFF parameters yielded a boron solubility value that agrees moderately well with experimental expectations, while the previous boron parameters gave a value that was much too low.

boron

High pressure Raman spectroscopy of boron-rich boron carbides up to 50 GPa

We investigated the effects of increased boron content on the resistance to non-hydrostatic stress-induced (NHSI) local amorphous zones in boron-rich boron carbide (BxC) compounds. Using high-pressure Raman spectroscopy, we subjected B 4.3 C, B 6.4 C, and B 10.4 C to pressures up to 50 GPa and monitored their responses. Our results show that higher boron content delays the onset of NHSI local amorphous zone formation, shifting it from 35 GPa in B 4.3 C to approximately 50 GPa in B 10.4 C. This enhanced resistance is attributed to a reduction in the formation of the B 12 (CCC) polytype, which is susceptible to amorphization, and the greater flexibility of B–B–B chains. Furthermore, alternative mechanisms, such as boron vacancy-driven C–C bond formation, provide additional insights into defect-mediated structural changes that may influence the amorphization process. In conclusion, these findings highlight the dual role of boron content and defect mechanisms in improving the structural stability of B x C materials under extreme environments.

36 MATERIALS SCIENCE

The structure of boron in boron fibres

The structure of noncrystalline, chemically vapour-deposited boron fibres was investigated by computer modelling the experimentally obtained X-ray diffraction patterns. The diffraction patterns from the models were computed using the Debye scattering equation. The modelling was done utilizing the minimum nearest-neighbour distance, the density of the model, and the broadening and relative intensity of the various peaks as boundary conditions. The results suggest that the fibres consist of a continuous network of randomly oriented regions of local atomic order, about 2 nm in diameter, containing boron atoms arranged in icosahedra. Approximately half of these regions have a tetragonal structure and the remaining half a distorted rhombohedral structure. The model also indicates the presence of many partial icosahedra and loose atoms not associated with any icosahedra. The partial icosahedra and loose atoms indicated in the present model are in agreement with the relaxing sub-units which have been suggested to explain the anelastic behavior of fibre boron and the loosely bound boron atoms which have been postulated to explain the strengthening mechanism in boron fibres during thermal treatment.

Bhardwaj, J.

Ceramic silicon-boron-carbon fibers from organic silicon-boron-polymers

Novel high strength ceramic fibers derived from boron, silicon, and carbon organic precursor polymers are discussed. The ceramic fibers are thermally stable up to and beyond 1200 C in air. The method of preparation of the boron-silicon-carbon fibers from a low oxygen content organosilicon boron precursor polymer of the general formula Si(R2)BR(sup 1) includes melt-spinning, crosslinking, and pyrolysis. Specifically, the crosslinked (or cured) precursor organic polymer fibers do not melt or deform during pyrolysis to form the silicon-boron-carbon ceramic fiber. These novel silicon-boron-carbon ceramic fibers are useful in high temperature applications because they retain tensile and other properties up to 1200 C, from 1200 to 1300 C, and in some cases higher than 1300 C.

Riccitiello, Salvatore R.

Boron Nitride Nanoribbons from Exfoliation of Boron Nitride Nanotubes

Two types of boron nitride nanotubes (BNNTs) were exfoliated into boron nitride nanoribbons (BNNR), which were identified using transmission electron microscopy: (1) commercial BNNTs with thin tube walls and small diameters. Tube unzipping was indicated by a large decrease of the sample's surface area and volume for pores less than 2 nm in diameter. (2) BNNTs with large diameters and thick walls synthesized at NASA Glenn Research Center. Here, tube unraveling was indicated by a large increase in external surface area and pore volume. For both, the exfoliation process was similar to the previous reported method to exfoliate commercial hexagonal boron nitride (hBN): Mixtures of BNNT, FeCl3, and NaF (or KF) were sequentially treated in 250 to 350 C nitrogen for intercalation, 500 to 750 C air for exfoliation, and finally HCl for purification. Property changes of the nanosized boron nitride throughout this process were also similar to the previously observed changes of commercial hBN during the exfoliation process: Both crystal structure (x-ray diffraction data) and chemical properties (Fourier-transform infrared spectroscopy data) of the original reactant changed after intercalation and exfoliation, but most (not all) of these changes revert back to those of the reactant once the final, purified products are obtained.

boron nitride nanotube

Spin qubit properties of the boron-vacancy/carbon defect in the two-dimensional hexagonal boron nitride

Spin qubit defects in two-dimensional materials have a number of advantages over those in three-dimensional hosts including simpler technologies for defect creation and control, as well as qubit accessibility. In this work, we select the V B C B defect in the hexagonal boron nitride (hBN) as a possible optically controllable spin qubit and explain its triplet ground state and neutrality. In this defect a boron vacancy is combined with a carbon dopant substituting the closest boron atom to the vacancy. Our density-functional-theory calculations confirmed that the system has dynamically stable spin triplet and singlet ground states. As revealed from our linear response GW calculations, the spin-sensitive electronic states are localized around the three undercoordinated N atoms and make local peaks in the density of electronic states within the bandgap. Using the triplet and singlet ground state energies, as well as the energies of the optically excited states, obtained from solution to the Bethe–Salpeter equation, we construct the spin-polarization cycle, which is found to be favorable for the spin qubit initialization. The calculated zero-field splitting parameters ensure that the splitting energy between the spin projections in the triplet ground state is comparable to that of the known spin qubits. We thus propose the V B C B defect in hBN as a promising spin qubit.

2D BN

Isotopic Enrichment of Boron in the Sputtering of Boron Nitride with Xenon Ions

An experimental study is described to measure the isotopic enrichment of boron. Xenon ions from 100 eV to 1.5 keV were used to sputter a boron nitride target. An ion gun was used to generate the ion beam. The ion current density at the target surface was approximately 30 microA/sq cm. Xenon ions impinged on the target surface at 50 deg angle to the surface normal. Since boron nitride is an insulator, a flood electron gun was used in our experiments to neutralize the positive charge buildup on the target surface. The sputtered secondary ions of boron were detected by a quadrupole mass spectrometer. The spectrometer entrance aperture was located perpendicular to the ion beam direction and 10 mm away from the target surface. The secondary ion flux was observed to be enriched in the heavy isotopes at lower ion energies. The proportion of heavy isotopes in the sputtered secondary ion flux was found to decrease with increasing primary ion energy from 100 to 350 eV. Beyond 350 eV, light isotopes were sputtered preferentially. The light isotope enrichment factor was observed to reach an asymptotic value of 1.27 at 1.5 keV. This trend is similar to that of the isotopic enrichment observed earlier when copper was sputtered with xenon ions in the same energy range.

Ray, P. K.

Subterahertz Spin Relaxation Dynamics of Boron-Vacancy Centers in Hexagonal Boron Nitride

Quantum sensors based on spin defects have become powerful tools for detecting faint magnetic signals, yet their operation remains confined to low magnetic fields and gigahertz frequencies. Extending such sensors into high-field (>0.3 T) and subterahertz regimes would enable quantum metrology across a wide range of electromagnetic phenomena and scientific applications, but has proven challenging. Here, we demonstrate that negatively charged boron vacancies ($V^−_B$) in hexagonal boron nitride can function as relaxation-based quantum sensors operating up to 0.2 terahertz and 7 T fields. Their uniform spin-orientation and persistent spin-contrast at high fields enable measurement of intrinsic spin relaxation across unexplored field regimes. We reveal a crossover in relaxation behavior, initially decreasing at low fields before rising at higher fields, consistent with the emergence of single-phonon-induced resonant noise at subterahertz frequencies. These results establish $V^−_B$ centers as a versatile platform for quantum sensing in the subterahertz, high-field regime.

boron-vacancies

Kinetics of boron deposition by the hydrogen reduction of boron trichloride

The chemical vapor deposition of boron filament is generally considered to be limited by the diffusion of the reactive species to the hot substrate. From concentration gradient considerations and from experimental measurements it is concluded that the product species (HCl) is more likely to be involved in limiting the deposition rate. Comparison of theoretically calculated and experimentally measured deposition rates show that the rate is generally partially limited by diffusion and partially by the surface reaction rate (desorption) of HCl. The relative amounts of surface reaction or diffusion rate impedance were determined as a function of temperature and gas velocity. The temperature coefficient for the desorption of HCl was found to be 52 Kcal/mole.

Mehalso, R. M.