The surface carboxyl group of carbonaceous microspheres effects on the synthesis and structure of SiOC ceramics

In this study, C/SiOC and C/SiO₂ composites were prepared by using carbonaceous microspheres with different surface functional groups. Carbonaceous microspheres based on hydrothermal reaction of glucose contains hydroxyl group, while the surface carboxyl group increases after NaOH etching. The hydroxyl group increases the oxygen-enriched structural units of SiOC ceramics, and the C spheres are closely enwrapped in SiOC matrix after pyrolysis at 900 °C. However, the interfacial reaction of surface carboxyl with Si–OH results in the formation of cristobalite SiO₂, and C spheres are not only encased inside the SiOC matrix, but also dispersed outside of SiOC ceramics. After removal of C via calcination at 500 °C for 5 h, C/SiOC and C/SiO₂ composites are transformed into amorphous SiO₂ and cristobalite SiO₂, respectively. The thermogravimetric analysis indicates the oxidation resistance of SiOC is superior to that of C and SiO₂.     

A novel approach for bulk micromachining of 4H-SiC by tool-based electrolytic plasma etching in HF-free aqueous solution

Bulk micromachining of single-crystal SiC has been challenging due to its extreme stability both mechanically and chemically. To address this issue, a novel tool-based electrolytic plasma etching method is proposed, with which micropatterns and micro-holes are fabricated in SiC in a hydrofluoric acid-free aqueous solution with no need for masks. The material removal is the result of the combined effects of electrolytic plasma chemistry and physics. The chemistry refers to the reaction of Si with hydroxyl radical to form various SiO_x and with H to form silanes, and the reactions of C to form volatile carbon oxides or hydrocarbons, all of which are accomplished and enhanced under the electrolytic plasma atmosphere. Besides, the local high temperature of plasma thermally promotes the evaporation or dissolution of SiO₂ in NaOH solution. The tool-based electrolytic plasma etching method provides alternative approaches for the fabrication of SiC-based MEMS and devices.     

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。     

3D CaP porous scaffolds with grooved surface topography obtained by the sol-gel method

The influence of surface topography on cellular behaviour and its importance for the development of three-dimensional scaffolds for bone tissue engineering are a topic of growing interest. To date, the introduction of topographical patterns into the surface of 3D porous ceramic scaffolds has proven difficult, due partly to the brittle nature of ceramic materials as well as the currently available fabrication technologies. In this study, a grooved pattern was introduced into the surface of 3D multilayer porous ceramic scaffolds by the chemical etching technique. The patterned scaffolds were characterised by X-Ray Diffraction (XRD), Scanning Electron Microscopy with Energy Dispersive X-Ray Spectroscopy (SEM-EDX) and Digital Holographic Microscopy (DHM). Their bioactivity was also evaluated in vitro by immersion in simulated body fluid (SBF) for 12 h, 1, 7, 14 and 21 days. Scaffolds were constituted mainly with a mixture of the calcium pyrophosphate (Ca₂O₇P₂) and β-tricalcium phosphate (Ca?(PO?)?) phases. The pyrophosphate on the external layer was dissolved as a result of the etching process, leaving grooves on the surface. Ridges and grooves were nano-/micrometric, with dimensions of around 900 nm–1.5 μm in width and 200 nm–300 nm in depth. Moreover, the mechanical properties and bioactive capacity of the patterned scaffolds were not affected by chemical etching, making them suitable to be used in bone tissue engineering.     

Investigation of La0.6Sr0.4Co1-xNixO3-δ (x=0, 0.2, 0.4, 0.6, 0.8) catalysts on solid oxide fuel cells anode for biogas dry reforming

The introduction of catalyst on anode of solid oxide fuel cell (SOFC) has been an effective way to alleviate the carbon deposition when utilizing biogas as the fuel. A series of La_0.6Sr_0.4Co_1-xNi_xO_3-δ (x = 0, 0.2, 0.4, 0.6, 0.8) oxides are synthesized by sol-gel method and used as catalysts precursors for biogas dry reforming. The phase structure of La_0.6Sr_0.4Co_1-xNi_xO_3-δ oxides before and after reduction are characterized by X-ray diffraction (XRD). The texture properties, carbon deposition, CH₄ and CO₂ conversion rate of La_0.6Sr_0.4Co_1-xNi_xO_3-δ catalysts are evaluated and compared. The peak power density of 739 mW cm^?2 is obtained by a commercial SOFC with La_0.6Sr_0.4Co_0.4Ni_0.6O_3-δ catalyst at 850 °C when using a mixture of CH₄: CO₂ = 2:1 as fuel. This shows a great improvement from the cell without catalyst for internal dry reforming, which is attributed to the formation of NiCo alloy active species after reduction in H₂ atmosphere. The results indicate the benefits of inhibiting the carbon deposition on Ni-based anode through introducing the La_0.6Sr_0.4Co_0.4Ni_0.6O_3-δ catalyst precursor. Additionally, the dry reforming technology will also help to convert part of the exhaust heat into chemical energy and improve the efficiency of SOFC system with biogas fuel.     

Recent advances during CH4 dry reforming for syngas production: A mini review

Given the continuing issues of environment and energy, methane dry reforming for syngas production have sparked interest among researchers, but struggled with the process immaturity owing to catalyst deactivation. This review summarizes the recent advances in the development of efficient and stable catalysts with strong resistance to coking and metal sintering, including the application of novel materials, the assessment of advanced characterizations and the compatibility to improved reaction system. One feasible option is the crystalline oxide catalysts (perovskite, pyrochlore, spinel and LDHs), which feature a fine metal dispersion and surface confinement effect via a metal exsolution strategy and exhibit superior reactivity and stability. Some new materials (h-BN, clays and MOFs) also extend the option because of their unique morphology and microstructure. It also is elaborated that progresses were achieved in advanced characterizations application, leading to success in the establishment of reaction mechanisms and attributions to the formed robust catalysts. In addition, the perspective described the upgrade of reaction system to a higher reaction efficiency and milder reaction conditions. The combination of efficient reaction systems and robust catalysts paves a way for a scaling-up application of the process.     

单晶硅表层机械力学特性的各向异性分析

为探究挠性筋结构单晶硅材料的各向异性特性以及KOH腐蚀工艺对其力学性能的影响规律,进行纳米压痕实验,并结合原子力显微镜观察单晶硅表层3个主晶面上压痕裂纹形貌随晶向的变化规律,分析单晶硅材料表层弹性模量、硬度、断裂韧性等机械力学特性参数在(001)、(110)及(111)3个主要晶面上沿各个晶向的变化规律;分析挠性筋结构单晶硅材料(001)晶面的KOH腐蚀工艺对其材料表面机械特性的影响规律.结果表明:挠性筋单晶硅在(001)晶面上弹性模量的各向异性变化幅度明显,硬度及断裂韧性各向异性的变化幅度不大;挠性筋单晶硅在(110)晶面弹性模量和断裂韧性的各向异性变化幅度明显,硬度各向异性变化幅度不大;挠性筋单晶硅在(111)晶面硬度值、弹性模量及断裂韧性参数的变化幅度幅值均较小;确定了单晶硅表层3个晶面裂纹最易扩展的晶向方向,KOH腐蚀工艺使得单晶硅表面质量降低,腐蚀后暴露的表面微裂纹、缺陷等会使得单晶硅(001)晶面表层硬度、断裂韧性降低,从而降低了挠性筋结构的实际断裂强度.     

Synthesis of Ti3C2Fx MXene with controllable fluorination by electrochemical etching for lithium-ion batteries applications

Ti₃C₂T_x MXene has attracted remarkable attention due to its promising applications in energy storage and sensors. However, traditional MXene preparation methods used HF as etchant, which was highly toxic and harmful to human and environment. Moreover, the aqueous etchants will also result in the combination of OH, O and F groups on the surfaces, making it difficult to control the varieties and contents of the surface terminations. In this paper, a green and mild electrochemical exfoliation method was proposed to synthesize Ti₃C₂F_x and synchronously control its fluorination degree on the surface. A non-aqueous ionic liquid, [BMIM][PF₆]-based solution was used as electrolyte. The as-prepared Ti₃C₂F_x was fluorinated with the CF and TiF₃ groups, which were electrochemically active and contributed to the excellent cycling stability of the MXene anode-based Li-ion batteries. These findings provided a facile strategy to prepare MXene materials and dope MXene with tailored property for MXene-based energy devices applications.     

Nitrogen dry deposition to Lake Superior and Lake Michigan

Nitrate (NO₃^?) levels in Lake Superior have increased from historic levels of about 5?μM to its current concentration of about 25?μM. The atmosphere makes a substantial contribution to the nitrogen budgets for Lake Superior and Lake Michigan. This study provides a more well-defined estimate of nitrogen dry deposition rates derived from the measurement of over-water concentrations, and in situ meteorological measurements, which were input into the Resistance Model. We obtained a nitrogen dry deposition rate of [(3.41?±?2.26)?×?10⁷?kg?N/yr; (5.90?±?3.91)?kg?N/ha/yr] over Lake Michigan, and [(1.54?±?1.06)?×?10⁷?kg?N/yr; (1.87?±?1.27)?kg?N/ha/yr] over Lake Superior. Nitric acid (HNO₃), which originates from the combustion of fossil fuels, contributes 84% of the total nitrogen dry deposition to Lake Michigan; and 66% to Lake Superior. Ammonia (NH₃), which originates from agricultural activities and gasoline combustion, is the second highest contributor of nitrogen dry deposition to both lakes: contributing 13% to Lake Michigan and 32% to Lake Superior. The nitrogen dry deposition is approximately 68% of the nitrogen wet deposition over Lake Superior, and approximately 80% of wet deposition over Lake Michigan. The over-water dry deposition velocity of HNO₃ and NH₃ were also evaluated. We obtained morning deposition velocities of 0.099?cm/s for NH₃ and 0.095?cm/s for HNO₃; and afternoon values of 0.137?cm/s for NH₃ and 0.132?cm/s for HNO₃. Another key finding is that the atmospheric concentrations of nitrogen compounds near Lake Michigan and Lake Superior have decreased since 2003.     

山银花中绿原酸类化合物的提取工艺优化

目的优化山银花中绿原酸类化合物的提取工艺。方法取一定量粉碎过筛后的山银花,通过单因素实验比较提取溶剂、提取料液比及提取次数对提取物的影响,以绿原酸类化合物的含量及干膏得率为评定指标,探讨适宜的提取工艺。结果以水为提取溶剂,按料液比1:20(m:V)煎煮2次,每次1h,煎液过滤,合并滤液,减压浓缩至相对密度为1.13～1.18(60℃),干燥后的山银花提取物,绿原酸类化合物的含量(95.04%)及干膏得率(42.17%)均较高。结论该提取方法简便可行,可作为山银花的粗取工艺。