Pure CuBi2O4 Photoelectrodes with Increased Stability by Rapid Thermal Processing of Bi2O3/CuO Grown by Pulsed Laser Deposition

A new method for enhancing the charge separation and photo‐electrochemical stability of CuBi₂O₄ photoelectrodes by sequentially depositing Bi₂O₃ and CuO layers on fluorine‐doped tin oxide substrates with pulsed laser deposition (PLD), followed by rapid thermal processing (RTP), resulting in phase‐pure, highly crystalline films after 10 min at 650 °C, is reported. Conventional furnace annealing of similar films for 72 h at 500 °C do not result in phase‐pure CuBi₂O₄. The combined PLD and RTP approach allow excellent control of the Bi:Cu stoichiometry and results in photoelectrodes with superior electronic properties compared to photoelectrodes fabricated through spray pyrolysis. The low photocurrents of the CuBi₂O₄ photocathodes fabricated through PLD/RTP in this study are primarily attributed to their low specific surface area, lack of CuO impurities, and limited, slow charge transport in the undoped films. Bare (without protection layers) CuBi₂O₄ photoelectrodes made with PLD/RTP shows a photocurrent decrease of only 26% after 5 h, which represents the highest stability reported to date for this material. The PLD/RTP fabrication approach offers new possibilities of fabricating complex metal oxides photoelectrodes with a high degree of crystallinity and good electronic properties at higher temperatures than the thermal stability of glass‐based transparent conductive substrates would allow.     

铜吡啶配合物催化合成1-甲氧基-2,2,6,6-四甲基哌啶-4-醇

目前1-烷氧基-2,2,6,6-四甲基哌啶基化合物的合成主要是以醛酮法为主。醇法合成虽然醇价格便宜，但合成效率很低。为解决这一问题，本文对醇法合成工艺进行了深入探讨，并以乙醇和4-羟基-2,2,6,6-四甲基哌啶氮氧自由基（ZJ-701）为原料，30%过氧化氢为氧化剂，氯化铜和吡啶配合物为催化剂，通过氧化和自由基偶合合成了1-甲氧基-2,2,6,6-四甲基哌啶-4-醇，通过红外光谱、核磁共振谱和质谱表征了其结构。通过实验进一步优化了反应时间、温度等一系列合成条件。研究结果表明：当反应时间为12h，反应温度为78℃，n(ZJ-701)∶n(乙醇)∶n(H₂O₂)∶n(CuCl₂)∶n(吡啶)=1∶39.25∶17.01∶0.034∶0.36时，产品产率最高，为60.6%，质量分数为98.8%，熔点为87～90℃。该方法具有原料乙醇便宜易得、反应条件温和、产品提纯容易等优点。     

Impacts of layout,surface condition and alloying elements on diffusion welding of micro process devices

The formation of a monolithic part during diffusion bonding is accompanied by the diffusion of atoms across the bonding planes. At sufficient low roughness, it mainly depends on the temperature and dwell time. At the same time, the diffusion process competes against grain growth. By adjusting an appropriate level of bearing pressure, it is possible to control deformation taking into account additional parameters resulting from mechanical microstructures and the design and aspect ratio of the part. Furthermore, material properties, such as the content of alloying elements, the degree of cold work hardening and the grain size, have an impact on diffusion and deformation behavior. Also the surface condition of mating surfaces is important to diffusion kinetics and the quality of the joint. Especially passivation layers of corrosion‐resistant alloys, such as stainless steels and nickel‐based alloys, impair diffusion. In contrast to this, cold work hardening at low depth below the surface, e. g. by means of a blasting processes, may facilitate formation of a good bond and help to limit grain size. For oxide dispersion‐strengthened materials, additional impacts on diffusion bonding behavior applies.     

Investigations of geometrical structure and morphology of samples made of hard machinable materials after wire electrical discharge machining and vibro‐abrasive finishing

In this article the results concerned influence of processing conditions of the wire electrical discharge machining and vibro‐abrasive machining on the surface layer and morphology of samples made of hard machinable materials used in aircraft industry like: Titanium 5553 β, Inconel 617, Hastelloy X and Magnesium AZ31 have been presented. For this purpose the cubic and cylindrical samples made of hard machinable alloys have been prepared using optimal electric parameters of wire‐cut electrical discharge machining and finally they have been polished using circular vibratory finishing technology and different ceramic shaped stones.     

DOPO‐Based Phosphorus‐Containing Methacrylic (Co)Polymers: Glass Transition Temperature Investigation

A two‐step synthetic procedure is designed for preparing new flame‐retardant methacrylic monomers containing 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) as a substituent side group. DOPO and methacrylate moieties are linked by linear aliphatic hydrocarbon spacers (3 to 11 carbon atoms). Copolymerization with methyl methacrylate is carried out leading to copolymers containing between 2 and 10 wt% phosphorus. All homo‐ and copolymers exhibit a unique glass transition temperature (T_g ). A new group contribution for DOPO‐based substituent is extracted that leads to reasonable estimations of T_g s of other published polymers. The Fox equation provides a good estimation of T_g s for most copolymers and for physical blends of poly(methyl methacrylate) (PMMA) and DOPO. When using monomers having three and four carbon atoms in the hydrocarbon spacer, the T_g of copolymers remains close to that of PMMA over a wide range of composition.     

Origin of the temperature stability of dielectric constant in CaCu3Ti4O12

The temperature and dc bias stability of the dielectric constant and loss tangent of CaCu₃Ti₄O₁₂ samples sintered under different oxygen atmospheres are discussed. The results suggest that the metal-oxygen vacancy related defects not only provide the charge carriers for the conduction (defect doping) but also contribute to the huge permittivity in the way of defect dipoles repositioning under charge carrier hopping. The charge localization in a specific copper-oxygen vacancy defect complex is the reason of the huge and stable permittivity and low dielectric loss in the middle temperature range, 90 K-200 K (20 Hz), while the implementation of the large barrier layer height needs a contribution by the titanium oxygen vacancy related trap charges in the grain boundaries, which also lead to a second permittivity stable range in a higher temperature range 200 K–300 K.     

正电子湮没研究Al、Nb共掺CaCu3Ti4O12陶瓷高介电常数机理

关于CaCu₃Ti₄O₁₂陶瓷的高介电常数机理，目前广泛接受的是非本征的内阻挡层电容模型。该模型认为在多晶中元素变价、缺陷和非化学计量比等导致的半导化晶粒被绝缘晶界层，即内阻挡层所包围。其中内阻挡层的厚度对材料的介电性能影响较大，而扫描电子显微镜（SEM）测试表明样品晶界呈稀烂的果酱状，SEM难以测量晶界区域绝缘内阻挡层厚度。本文采用正电子湮没技术表征其厚度，通过对CaCu₃Ti₄O₁₂陶瓷共掺不同浓度的Al、Nb（CaCu₃Ti_4-xAl_0.5xNb_0.5xO₁₂，x=0.2%、0.5%、5.0%）改变其晶粒和晶界的微观结构，研究CaCu₃Ti₄O₁₂陶瓷高介电常数机理。正电子湮没结果显示，掺杂样品符合多普勒展宽谱S参数的变化趋势与平均寿命的变化趋势一致。x=0.5%掺杂样品的介电常数最高，其平均寿命、S参数和湮没长寿命成分均最小，阻挡层最薄。实验结果验证了描述CaCu₃Ti₄O₁₂陶瓷高介电常数机理的内阻挡层电容模型的预测。     

石墨烯增强钛基复合材料制备工艺与性能研究

以多层石墨烯为增强体,通过熔炼锻造(MF)和粉末冶金(PM) 2种工艺分别制备出规格为Φ10 mm的石墨烯增强钛基复合材料棒材。石墨烯在凝固过程中以TiC枝晶形态析出,变形后呈细小颗粒,其中Ti和C原子比约为2∶1。石墨烯和球形钛粉经过机械合金化和变形加工,在基体中反应形成薄片层。MF工艺对应的棒材拉伸强度可达476 MPa,延伸率保持在28%; PM工艺对应的棒材拉伸强度可达487 MPa,延伸率保持在30%。PM工艺可形成尺寸较小的薄片状石墨烯增强体,强化作用提升,同时塑性没有显著下降。     

Stabilizing temperature-capacitance dependence of (Sr,Pb, Bi)TiO3-Bi4Ti3O12 solutions for energy storage

(1-x)Sr_0.7Pb_0.15Bi_0.1TiO₃-xBi₄Ti₃O₁₂ ((1-x)SPBT-xBIT, x = 0-0.125) bulk ceramics were developed and calcined via the solid-state method, aimed at the application of pulsed power capacitors. The phase structures, temperature stability, hysteresis loop, and discharge properties were systematically investigated. Considering both the temperature stability and dielectric properties, 0.925SPBT-0.075BIT bulk ceramics with a capacitance variation satisfying the X7R specification were developed for pulsed power capacitors. The energy storage density was 0.252 J/cm³, and the ceramics showed high temperature stability at 80 kV/cm. The discharge current waveforms of the 0.925SPBT-0.075BIT ceramics were recorded. A high discharge power density of approximately 1.01 × 10⁸ W/kg with an 8 Ω load resistor and short discharge period of 84 ns were achieved at 50 kV/cm. The good temperature stability properties and high power density show that the 0.925SPBT-0.075BIT ceramics are well suited for pulsed power capacitors with a wide temperature range.     

Fabrication of composites from different carbon content ferrous powders adopting thermomechanical processes

In this research, deep consolidation technique is utilized for processing of low and high carbon content ferrous powders to manufacture composite material. High carbon content ferrous powders were used as reinforcing material. The powder particles were allowed to mix with low carbon content ferrous powders in 50:50 weight percent for fabrication of composites. The composites were heat treated at three different temperatures (i.e., 800°C, 900°C, and 1000°C). The changes in microstructure, microhardness, the grain size, and bonding among powder particles were studied. Refinement of grains was observed and this led to improved hardness enabling the processed material to be used as a suitable composite. Abrasive wear tests were carried out using a laboratory tribometer in dry reciprocating sliding contact against Sic abrasive paper. The outcomes demonstrate that the abrasive wear resistance was notably affected by the treatment temperature and hardness of the composites.