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.     

多晶硅表面金属催化化学腐蚀法制绒研究现状

在多晶硅太阳能电池的生产过程中, 金刚线切割技术(Diamond wire sawn, DWS)具有切割速度快、精度高、原材料损耗少等优点, 受到了广泛关注。金刚线切割多晶硅表面形成的损伤层较浅, 与传统的酸腐蚀制绒技术无法匹配, 金属催化化学腐蚀法应运而生。金属催化化学腐蚀法制绒具有操作简单、结构可控且易形成高深宽比的绒面等优点, 具有广阔的应用前景。本文总结了不同类型的金属催化剂在制绒过程中的腐蚀机理及其形成的绒面结构, 深入分析和讨论了具有代表性的银、铜的单一及复合催化腐蚀过程及绒面结构和电池片性能。最后对金刚线切割多晶硅片表面的金属催化化学腐蚀法存在的问题进行了分析, 并展望了未来的研究方向。     

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.     

Investigation on thermal conductivity and mechanical properties of Si3N4 ceramics via one-step sintering

High thermal conductivity Si₃N₄ ceramics were fabricated using a one-step method consisting of reaction-bonded Si₃N₄ (RBSN) and post-sintering. The influence of Si content on nitridation rate, β/(α+β) phase rate, thermal conductivity and mechanical properties was investigated in this work. It is of special interest to note that the thermal conductivity showed a tendency to increase first and then decrease with increasing Si content. This experimental result shows that the optimal thermal conductivity and fracture toughness were obtained to be 66 W (m K)^-1 and 12.0 MPa m^1/2, respectively. As a comparison, the nitridation rate and β/(α+β) phase rate in a static pressure nitriding system, i.e., 97% (MS10), 97% (MS15), 97% (MS20) and 8.3% (MS10), 8.3% (MS15), 8.9% (MS20), respectively, have obvious advantages over those in a flowing nitriding system, i.e., 91% (MS10), 91% (MS15), 93% (MS20) and 3.1% (MS10), 3.3% (MS15), 3.3% (MS20), respectively. Moreover, high lattice integrity of the β-Si₃N₄ phase was observed, which can effectively confine O atoms into the β-Si₃N₄ lattice using MgO as a sintering additive. This result indicates that one-step sintering can provide a new route to prepare Si₃N₄ ceramics with a good combination of thermal conductivity and mechanical properties.     

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.     

Etching characteristics of thin SiON films using a liquefied perfluorocarbon precursor of C6F12O with a low global warming potential

Perfluorocarbon gas is widely used in the semiconductor industry. However, perfluorocarbon has a negative effect on the global environment owing to its high global warming potential (GWP) value. An alternative solution is essential. Therefore, we evaluated the possibility of replacing conventional perfluorocarbon etching gases such as CHF₃ with C₆F₁₂O, which has a low GWP and is in a liquid state at room temperature. In this study, silicon oxynitride (SiON) films were plasma-etched using inductively coupled CF₄ +C₆F₁₂O+O₂ mixed plasmas. Subsequently, the etching characteristics of the film, such as etching rate, etching profile, selectivity over Si, and photoresist, were investigated. A double Langmuir probe was used and optical emission spectroscopy was performed for plasma diagnostics. In addition, a contact angle goniometer and x-ray photoelectron spectroscope were used to confirm the change in the surface properties of the etched SiON film surface. Consequently, the etching characteristics of the C₆F₁₂O mixed plasma exhibited a lower etching rate, higher SiON/Si selectivity, lower plasma damage, and more vertical etched profiles than the conventional CHF₃ mixed plasma. In addition, the C₆F₁₂O gas can be recovered in the liquid state, thereby decreasing global warming. These results confirmed that the C₆F₁₂O precursor can sufficiently replace the conventional etching gas.     

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.     

Deposition,opto-electronic and structural characterization of polymorphous silicon thin films to be applied in a solar cell structure

In this study we analyze the optoelectronic properties and structural characterization of hydrogenated polymorphous silicon thin films as a function of the deposition parameters. The films were grown by plasma enhanced chemical vapor deposition (PECVD) using a gas mixture of argon (Ar), hydrogen (H₂) and dichlorosilane (SiH₂Cl₂). High-resolution transmission electron microscopy images and Raman measurements confirmed the existence of very different internal structures (crystalline fractions from 12% to 54%) depending on the growth parameters. Variations of as much as one order of magnitude were observed in both the photoconductivity and effective absorption coefficient between the samples deposited with different dichlorosilane/hydrogen flow rate ratios. The optical and transport properties of these films depend strongly on their structural characteristics, in particular the average size and densities of silicon nanocrystals embedded in the amorphous silicon matrix. From these results we propose an intrinsic polymorphous silicon bandgap grading thin film to be applied in a p–i–n junction solar cell structure. The different parts of the solar cell structure were proposed based on the experimental optoelectronic properties of the pm-Si:H thin films studied in this work.