Density functional theory study of the hydrogen evolution reaction in haeckelite boron nitride quantum dots

To satisfy arising energy needs and to handle the forthcoming worldwide climate transformation, the major research attention has been drawn to environmentally friendly, renewable and abundant energy resources. Hydrogen plays an ideal and significant role is such resources, due to its non-carbon based energy and production through clean energy. In this work, we have explored catalytic activity of a newly predicted haeckelite boron nitride quantum dot (haeck-BNQD), constructed from the infinite BN sheet, for its utilization in hydrogen production. Density functional theory calculations are employed to investigate geometry optimization, electronic and adsorption mechanism of haeck-BNQD using Gaussian16 package, employing the hybrid B3LYP and wB97XD functionals, along with 6–31G(d,p) basis set. A number of physical quantities such as HOMO/LUMO energies, density of states, hydrogen atom adsorption energies, Mulliken populations, Gibbs free energy, work functions, overpotentials, etc., have been computed and analysed in the context of the catalytic performance of haeck-BNQD for the hydrogen-evolution reaction (HER). Based on our calculations, we predict that the best catalytic performance will be obtained for H adsorption on top of the squares or the octagons of haeck-BNQD. We hope that our prediction of most active catalytic sites on haeck-BNQD for HER will be put to test in future experiments.     

B4C–TiB2 composites fabricated by hot pressing TiC–B mixtures: The effect of B excess

Previous research have reported that B₄C–TiB₂ composites could be prepared by the reactive sintering of TiC–B powder mixtures. However, due to spontaneous oxidation of raw powders, using TiC–B powder mixtures with a B/TiC molar ratio of 6: 1 introduced an intermediate phase of C during the sintering process, which deteriorated the hardness of the composites. In this report, the effects of B excess on the phase composition, microstructure, and mechanical properties of B₄C–TiB₂ composites fabricated by reactive hot pressing TiC–B powder mixtures were investigated. XRD and Raman spectra confirmed that lattice expansion occurred in B-rich boron carbide and B_xC–TiB₂ (x > 4) composites were obtained. The increasing B content improved the hardness and fracture toughness but decreased the flexural strength of B_xC–TiB₂ (x > 4) composites. When the molar ratio of B/TiC increased from 6.6:1 to 7.8:1, the Vickers hardness and the fracture toughness of the composites were enhanced from 26.7 GPa and 4.53 MPa m^1/2 to 30.4 GPa and 5.78 MPa m^1/2, respectively. The improved hardness was attributed to the microstructural improvement, while the toughening mechanism was crack deflection, crack bridging and crack branching.     

Green preparation of vanadium carbide through one-step molten salt electrolysis

Vanadium carbide (VC) as excellent ceramic and functional material is usually prepared by carbothermal reduction of V₂O₅ which must be extracted from a typical V slag by complex processes. Pollutants, such as ammonia-nitrogen wastewater, NH₃ and CO₂ are inevitably discharged. A novel and green method for VC preparation was proposed by one-step co-electrolysis of soluble NaVO₃ and CO₂ in molten salt. It was found that VC with high purity was easily obtained by reducing electrolysis temperature and CO₂ flow rate to 600 °C and 10 mL min⁻¹ at 3.0 V. Besides VC with particles and layered stacking structure in products, a small amount of carbon and oxygen elements existed. The atomic percentage contents of C, V, and O elements in VC were about 50.0%, 44.5% and 3.8%, respectively. During electrolysis, CO₃²⁻ and VO₃⁻ was reduced at about −0.55 V (vs. Ag/AgCl) and −1.38 V (vs. Ag/AgCl), respectively. CO₃²⁻ ions were more easily reduced than VO₃⁻, and was firstly reduced to CO₂²⁻ and then converted to C. Then, VC was prepared by two routes from CO₂ and NaVO₃. One route is that VO₃⁻ ions are firstly electroreduced to VO₂⁻ ions and then are further electroreduced to VC with C. Another route is that VO₃⁻ ions are electroreduced to V which in-situ reacted with C to VC. Both VO₃⁻ and CO₃²⁻ ions are electroreduced by two-step process. In final, VC is in-situ deposited on cathode. It provides a novel and green way to prepare VC and also achieves the high value-added utilization of vanadium slag and CO₂.     

Epitaxial Growth of 2D Materials on High-Index Substrate Surfaces

Recently, the successful synthesis of wafer-scale single-crystal graphene, hexagonal boron nitride (hBN), and MoS₂ on transition metal surfaces with step edges boosted the research interests in synthesizing wafer-scale 2D single crystals on high-index substrate surfaces. Here, using hBN growth on high-index Cu surfaces as an example, a systematic theoretical study to understand the epitaxial growth of 2D materials on various high-index surfaces is performed. It is revealed that hBN orientation on a high-index surface is highly dependent on the alignment of the step edges of the surface as well as the surface roughness. On an ideal high-index surface, well-aligned hBN islands can be easily achieved, whereas curved step edges on a rough surface can lead to the alignment of hBN along with different directions. This study shows that high-index surfaces with a large step density are robust for templating the epitaxial growth of 2D single crystals due to their large tolerance for surface roughness and provides a general guideline for the epitaxial growth of various 2D single crystals.     

Investigation of thermal residual stresses during laser ablation of tantalum carbide coated graphite substrates using micro-Raman spectroscopy and COMSOL multiphysics

Laser ablation of high-temperature ceramic coatings results in thermal residual stresses due to which the coatings fail by cracking and debonding. Hence, the measurement of such residual stresses during laser ablation process holds utmost importance from the view of performance of coatings in extreme conditions. The present research aims at investigating the effect of laser parameters such as laser pulse energy, scanning speed and line spacing on thermal residual stresses induced in tantalum carbide-coated graphite substrates. Residual stresses were measured using micro-Raman spectroscopy and correlated with Raman peak shifts. Transient thermal analysis was performed using COMSOL Multiphysics to model the single ablated track and residual stresses were reported at low, moderate and high pulse energy regimes. The results showed that the initial laser conditions caused higher tensile residual stresses. Moderate pulse energy regime comprised higher compressive residual stresses due to off centre overlapping of the laser pulses. Higher pulse energy (250 μJ), higher scanning speed (1000 mm/s) and moderate line spacing (20 μm) caused accumulation of tensile residual stresses during the final stage of laser ablation. The deviation of experimental residual stresses from COMSOL numerical model was attributed to unaccounted additional stresses induced during thermal spraying process and deformation potentials in the numerical model.     

Novel TiC-based composites with enhanced mechanical properties

Novel TiC-based composites were synthesized by reactive hot-pressing at 1800 °C for 1 h with ZrB₂ addition as a sintering aid for the first time. The effects of ZrB₂ contents on the phase composition, microstructure evolution, and mechanical properties were reported. Based on the reaction and solid solution coupling effects between ZrB₂ and TiC, the product ZrC may be partially or completely dissolved into the TiC matrix, and then phase separation within the miscibility gap is observed to form lamellar nanostructured ZrC-rich (Zr, Ti)C. The TiC-10 mol.% ZrB₂ (starting batch composition) exhibits good comprehensive mechanical properties of hardness 27.7 ± 1.3 GPa, flexural strength 659 ± 48 MPa, and fracture toughness of 6.5 ± 0.6 MPa m^1/2, respectively, which reach or exceed most TiC-based composites using ceramics as sintering aids in the previous reports.     

Influence of SiC microstructure on its corrosion behavior in molten FLiNaK salt

The influence of the microstructure on the corrosion rate of three monolithic SiC samples in FLiNaK salt at 900 °C for 250 h was studied. The SiC samples, labeled as SiC-1, SiC-2, and SiC-3, had corrosion rates of 0.137, 0.020, and 0.043 mg/cm²h, respectively. Compared with grain size and the presence of special grain boundaries (i.e., Σ3), the content of high-angle grain boundaries (HAGBs) appeared to have the strongest influence on the corrosion rate of SiC in FLiNaK salt, since the corrosion rate increased six times as the concentration of high-angle grain boundaries increased from 19 to 32% for SiC-2 and SiC-1, respectively. These results stress the importance of controlling the content of HAGBs during the production process of SiC.     

Multi-discharge EDM coring of single crystal SiC ingot by electrostatic induction feeding method

A new technique of EDM coring of single crystal silicon carbide (SiC) ingot was proposed in this paper. Currently single crystal SiC devices are still of high cost due to the high cost of bulk crystal SiC material and the difficulty in the fabrication process of SiC. In the manufacturing process of SiC ingot/wafer, localized cracks or defects occasionally occur due to thermal or mechanical causes resulted from fabrication processes which may waste the whole piece of material. To save the part of ingot without defects and maximize the material utilization, the authors proposed EDM coring method to cut out a no defect ingot from a larger diameter ingot which has localized defects. A special experimental setup was developed for EDM coring of SiC ingot in this study and its feasibility and machining performance were investigated. Meanwhile, in order to improve the machining rate, a novel multi-discharge EDM coring method by electrostatic induction feeding was established, which can realize multiple discharges in single pulse duration. Experimental results make it clear that EDM coring of SiC ingot can be carried out stably using the developed experimental setup. Taking advantage of the newly developed multi-discharge EDM method, both the machining speed and surface integrity can be improved.     

Heat propagation in thermally conductive polymers of PA6 and hexagonal boron nitride

Thermally conductive polymers offer new possibilities for the heat dissipation in electric and electronic components, for example, by a three‐dimensional shaping of the heat sinks. To face safety regulations, improved fire performance of those components is required. In contrast to unfilled polymers, those materials exhibit an entirely different thermal behavior. To investigate the flammability, a phosphorus flame retardant was incorporated into thermally conductive composites of polyamide 6 and hexagonal boron nitride. The flame retardant decreased the thermal conductivity only slightly. However, the burning behavior changed significantly, due to a different heat propagation, which was investigated using a thermographic camera. An optimum content of hexagonal boron nitride for a sufficient thermal conductivity and fire performance was found between 20 and 30 vol%. The improvement of the fire performance was due to a faster heat release out of the pyrolysis zone and an earlier decomposition of the flame retardant. For higher contents of hexagonal boron nitride, the heat was spread faster within the part, promoting an earlier ignition and increasing the decomposition rate of the flame retardant.     

Study of the synergistic effect of boron nitride and carbon nanotubes in the improvement of thermal conductivity of epoxy composites

The enhancement of the thermal conductivity, keeping the electrical insulation, of epoxy thermosets through the addition of pristine and oxidized carbon nanotubes (CNTs) and microplatelets of boron nitride (BN) was studied. Two different epoxy resins were selected: a cycloaliphatic (ECC) epoxy resin and a glycidylic (DGEBA) epoxy resin. The characteristics of the composites prepared were evaluated and compared in terms of thermal, thermomechanical, rheological and electrical properties. Two different dispersion methods were used in the addition of pristine and oxidized CNTs depending on the type of epoxy resin used. Slight changes in the kinetics of the curing reaction were observed in the presence of the fillers. The addition of pristine CNTs led to a greater enhancement of the mechanical properties of the ECC composite whereas the oxidized CNTs presented a greater effect in the DGEBA matrix. The addition of CNTs alone led to a marked decrease of the electrical resistivity of the composites. Nevertheless, in the presence of BN, which is an electrically insulating material, it was possible to increase the proportion of pristine CNTs to 0.25 wt% in the formulation without deterioration of the electrical resistivity. A small but significant synergic effect was determined when both fillers were added together. Improvements of about 750% and 400% in thermal conductivity were obtained in comparison to the neat epoxy matrix for the ECC and DGEBA composites, respectively. © 2019 Society of Chemical Industry