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.     

Extraction and characterization of hydroxyapatite-based materials from grey triggerfish skin and black scabbardfish bones

The conversion of food industry by-products to compounds with high added value is nowadays a significant topic, for social, environmental, and economic reasons. In this paper, calcium phosphate-based materials were obtained from black scabbardfish (Aphanopus carbo) bones and grey triggerfish (Balistes capriscus) skin, which are two of the most abundant fish by-products of Madeira Island. Different calcination temperatures between 400 and 1000°C were employed. Materials obtained from calcination of bones of black scabbard fish were composed by homogeneous mixtures of hydroxyapatite (Ca₁₀(PO4)₆(OH)₂, HAp) and β-tricalcium phosphate (β-Ca₃(PO₄)₂, β-TCP). Because of the high biocompatibility of HAp and the good resorbability of β-TCP, these natural biphasic materials could be very relevant in the field of biomaterials, as bone grafts. The ratio between HAp and β-TCP in the biphasic compound was dependent on the calcination temperature. Differently, the material obtained from skin of grey triggerfish contained HAp as the main phase, together with small amounts of other mineral phases, such as halite and rhenanite, which are known to enhance osteogenesis when used as bone substitutes. In both cases, the increase of calcination temperature led to an increase in the particles size with a consequent decrease in their specific surface area. These results demonstrate that from the fish by-products of the most consumed fishes in Madeira Island it is possible to obtain bioceramic materials with tunable composition and particle morphology, which could be promising materials for the biomedical field.     

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.     

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.     

Thermal transport and chemical conversion in single reacting sorbent particles

The effects of particle size and carbon dioxide concentration on chemical conversion in engineered spherical particles undergoing calcium oxide looping are investigated. Particles are thermochemically cycled in a furnace under different carbon dioxide concentrations. Changes in composition due to chemical reactions are measured using thermogravimetric analysis. Gas composition at the furnace exit is evaluated with mass spectroscopy. A numerical model of thermal transport phenomena developed previously is adapted to match the physical system investigated in the present study. The model is used to elucidate effects of reacting medium characteristics on particle temperature and reaction extent. Experimental and numerical results show that (1) an increase in particle size results in a decrease in carbonation extent, and (2) the carbonation step consists of fast and slow reaction regimes. The reaction rates in the fast and slow carbonation regimes increase with increasing carbon dioxide concentration. The effect of carbon dioxide concentration and the distinction between the fast and slow regimes become more pronounced with increasing particle size.     

Structural Basis for the Function of the C-Terminal Proton Release Pathway in the Calcium Pump

The calcium pump (sarco/endoplasmic reticulum Ca²⁺-ATPase, SERCA) plays a major role in calcium homeostasis in muscle cells by clearing cytosolic Ca²⁺ during muscle relaxation. Active Ca²⁺ transport by SERCA involves the structural transition from a low-Ca²⁺ affinity E2 state toward a high-Ca²⁺ affinity E1 state of the pump. This structural transition is accompanied by the countertransport of protons to stabilize the negative charge and maintain the structural integrity of the transport sites and partially compensate for the positive charges of the two Ca²⁺ ions passing through the membrane. X-ray crystallography studies have suggested that a hydrated pore located at the C-terminal domain of SERCA serves as a conduit for proton countertransport, but the existence and function of this pathway have not yet been fully characterized. We used atomistic simulations to demonstrate that in the protonated E2 state and the absence of initially bound water molecules, the C-terminal pore becomes hydrated in the nanosecond timescale. Hydration of the C-terminal pore is accompanied by the formation of water wires that connect the transport sites with the cytosol. Water wires are known as ubiquitous proton-transport devices in biological systems, thus supporting the notion that the C-terminal domain serves as a conduit for proton release. Additional simulations showed that the release of a single proton from the transport sites induces bending of transmembrane helix M5 and the interaction between residues Arg762 and Ser915. These structural changes create a physical barrier against full hydration of the pore and prevent the formation of hydrogen-bonded water wires once proton transport has occurred through this pore. Together, these findings support the notion that the C-terminal proton release pathway is a functional element of SERCA and also provide a mechanistic model for its operation in the catalytic cycle of the pump.     

Impact of gypsum on flotation of scheelite and fluorite using sodium oleate as collector

ABSTRACT

In this study, effect of calcium and gypsum on scheelite and fluorite was investigated using sodium oleate as collector. Micro-flotation and contact angle results showed that the adsorption of calcium could inhibit the hydrophobicity of scheelite and fluorite. Moreover, sulfate could enhance the inhibition. FT-IR results showed that calcium could be priori precipitated into calcium oleate and adsorb on mineral surface. The adsorption of calcium could increase the scheelite potential to IEP, while it showed limited effect on fluorite potential. However, the interaction of calcium on scheelite and fluorite in gypsum solution was more complex than that in calcium solution.     

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.