Modulation of electrical transport in calcium cobaltite ceramics and thick films through microstructure control and doping

Ca₃Co₄O₉ is a promising p-type thermoelectric oxide material having intrinsically low thermal conductivity. With low cost and opportunities for automatic large scale production, thick film technologies offer considerable potential for a new generation of micro-sized thermoelectric coolers or generators. Here, based on the chemical composition optimized by traditional solid state reaction for bulk samples, we present a viable approach to modulating the electrical transport properties of screen-printed calcium cobaltite thick films through control of the microstructural evolution by optimized heat-treatment. XRD and TEM analysis confirmed the formation of high-quality calcium cobaltite grains. By creating 2.0 at% cobalt deficiency in Ca_2.7Bi_0.3Co₄O_9+δ, the pressureless sintered ceramics reached the highest power factor of 98.0 μWm^?1 K^-2 at 823 K, through enhancement of electrical conductivity by reduction of poorly conducting secondary phases. Subsequently, textured thick films of Ca_2.7Bi_0.3Co_3.92O_9+δ were efficiently tailored by controlling the sintering temperature and holding time. Optimized Ca_2.7Bi_0.3Co_3.92O_9+δ thick films sintered at 1203 K for 8 h exhibited the maximum power factor of 55.5 μWm^?1 K^-2 at 673 K through microstructure control.     

西藏燕麦主要种植区灌溉定额空间分布及影响因素

燕麦为西藏自治区典型牧草之一,由于种植区地域辽阔,灌溉试验结果受限,西藏燕麦主要种植区的灌溉定额尚不明确。本文在西藏燕麦主要种植区内选取28个典型站点进行资料收集,遵循农业气候相似原则进行区域划分,基于水量平衡法揭示了西藏燕麦主要种植区灌溉定额的空间分布特征,并根据统计学原理分析了其影响因素。研究表明:燕麦主要种植区的灌溉定额呈由西藏中部至东部呈现先递增后递减的趋势,50%水文年下的燕麦灌溉定额在56~265 mm之间变化。降雨量是影响研究区内燕麦灌溉定额的主要因素(R²为0.515),ET₀次之(R²为0.152);其它气象因素中,日照时数对研究区燕麦灌溉定额影响较大(R²为0.462),且呈正相关关系;相对湿度对燕麦灌溉定额影响较小。西藏燕麦主要种植区的灌溉定额及其空间分布可为西藏自治区灌溉用水管理提供支撑。     

25%小偏置碰撞策略及测试评估研究

随着汽车事故的增加,且小重叠碰撞事故死亡率居高不下,小偏置碰撞试验逐渐成为焦点。基于IIHS公布的最新车辆碰撞试验结果,统计超过100余款不同类型的25%小偏置碰撞车辆,建立碰撞转角与碰撞区域的数学模型,将25%小偏置碰撞归结为三种不同的碰撞策略,分别是吸能策略、掠过策略和掠过与吸能策略;并进行试验验证,对三种策略的优缺点进行分析。结果表明,小偏置碰撞试验可运用合理的碰撞策略达到法规要求,对25%小偏置碰撞试验具有一定的参考价值。     

浸渍剂和压紧系数对全膜电容器端部电场分布的影响研究

全膜电容器边缘处的电场畸变是影响电容器元件击穿的重要因素之一.为研究浸渍情况和压紧系数对全膜电容器电场分布的影响,对电容器端部进行建模,通过改变浸渍情况和压紧系数,计算不同参数下电容器端部的电场分布情况,结果表明:未浸渍情况下电场最大值集中在折边处两侧,浸渍情况下场强在折边圆弧处分布较为均匀.同时发现,在浸渍情况下增大压紧系数K可以明显改善全膜电容器端部电场的分布情况.     

Strong tribocatalytic dye degradation by tungsten bronze Ba4Nd2Fe2Nb8O30

The triboelectric effect has recently demonstrated its great potential in environmental remediation and even new energy applications for triggering a number of catalytic reactions by utilizing trivial mechanical energy. In this study, Ba₄Nd₂Fe₂Nb₈O₃₀ (BNFN) submicron powders were used to degrade organic dyes via the tribocatalytic effect. Under the frictional excitation of three PTFE stirring rods in a 5 mg/L RhB dye solution, BNFN demonstrates a high tribocatalytic degradation efficiency of 97% in 2 h. Hydroxyl radicals (?OH) and superoxide radicals (?O₂－) were also detected during the catalysis process, which proves that triboelectric energy stimulates BNFN to generate electron-hole pairs. The tribocatalysis of tungsten bronze BNFN submicron powders provides a novel and efficient method for the degradation of wastewater dye by utilizing trivial mechanical energy.     

Synergistic effect of bulk phase doping and layered-spinel structure formation on improving electrochemical performance of Li-Rich cathode material

In this study, La was doped into the lithium layer of Li-rich cathode material and formed a layered-spinel hetero-structure. The morphology, crystal structure, element valence and kinetics of lithium ion migration were studied by field emission scanning electron microscope (FESEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). The La doped lithium-rich cathode material exhibited similar initial discharge capacity of 262.8 mAh g^?1 at 0.1 C compared with the undoped material, but the discharge capacity retention rate can be obviously improved to 90% after 50 cycles at 1.0 C. Besides that, much better rate capability and Li⁺ diffusion coefficient were observed. The results revealed that La doping not only stabilized the material structure and reduced the Li/Ni mixing degree, but also induced the generation of spinel phase to provide three-dimensional diffusion channels for lithium ion migration. Moreover, the porous structure of the doped samples also contributed to the remarkable excellent electrochemical performance. All of these factors combined to significantly improve the electrochemical performance of the material.     

Colossal dielectric response and relaxation behavior in novel system of Zr4+ and Nb5+ co-substituted CaCu3Ti4O12 ceramics

In this work, we developed a novel system of isovalent Zr⁴⁺ and donor Nb⁵⁺ co-doped CaCu₃Ti₄O₁₂ (CCTO) ceramics to enhance dielectric response. The influences of Zr⁴⁺ and Nb⁵⁺ co-substituting on the colossal dielectric response and relaxation behavior of the CCTO ceramics fabricated by a conventional solid-phase synthesis method were investigated methodically. Co-doping of Zr⁴⁺ and Nb⁵⁺ ions leads to a significant reduction in grain size for the CCTO ceramics sintered at 1060 °C for 10 h. XRD and Raman results of the CaCu₃Ti_3.8-xZr_xNb_0.2O₁₂ (CCTZNO) ceramics show a cubic perovskite structure with space group Im-3. The first principle calculation result exhibits a better thermodynamic stability of the CCTO structure co-doped with Zr⁴⁺ and Nb⁵⁺ ions than that of single-doped with Zr⁴⁺ or Nb⁵⁺ ion. Interestingly, the CCTZNO ceramics exhibit greatly improved dielectric constant (~10⁵) at a frequency range of 10²–10⁵ Hz and at a temperature range of 20–210 °C, indicating a giant dielectric response within broader frequency and temperature ranges. The dielectric properties of CCTZNO ceramics were analyzed from the viewpoints of defect-dipole effect and internal barrier layer capacitance (IBLC) model. Accordingly, the immensely enhanced dielectric response is primarily ascribed to the complex defect dipoles associated with oxygen vacancies by co-doping Zr⁴⁺ and Nb⁵⁺ ions into CCTO structure. In addition, the obvious dielectric relaxation behavior has been found in CCTZNO ceramics, and the relaxation process in middle frequency regions is attributed to the grain boundary response confirmed by complex impedance spectroscopy and electric modulus.     

Nanovaccine-Mediated Cell Selective Delivery of Neoantigens Potentiating Adoptive Dendritic Cell Transfer for Personalized Immunization

Neoantigen vaccines and adoptive dendritic cell (DC) transfer are major clinical approaches to initiate personalized immunity in cancer patients. However, the immunization efficacy is largely limited by the in vivo trajectory including neoantigens’ access to resident DCs and DCs’ access to lymph nodes (LNs). Herein, an innovative strategy is proposed to improve personalized immunization through neoantigen-loaded nanovaccines synergized with adoptive DC transfer. It is found that it enables selective delivery of neoantigens to resident DCs and macrophages by coating cancer cell membranes onto neoantigen-loaded nanoparticles. In addition, the nanovaccines promote the secretion of chemokine C-C motif ligand 2 (CCL2), CCL3, and C-X-C motif ligand 10 from macrophages, thus potentiating the access of transferred DCs to LNs. This immunization strategy enables coordinated delivery of identified neoantigens and autologous tumor lysate-derived undefined antigens, leading to initiation of antitumor T cell immunity in a personalized manner. It significantly inhibits tumor growth in prophylactic and established mouse tumor models. The findings provide a new vision for potentiating adoptive cell transfer by nanovaccines, which may open the door to a transformative possibility for improving personalized immunization.     

Phase and microstructure evolution of Sc2O3–CeO2 –ZrO2ceramics in Na2SO4 + V2O5 molten salts

In this study, the destabilization resistance of Sc₂O₃ and CeO₂ co-stabilized ZrO₂ (SCZ) ceramics was tested in Na₂SO₄ + V₂O₅ molten salts at 750°C–1100 °C. The phase structure and microstructure evolution of the samples during the hot corrosion testing were analyzed with X-ray diffraction (XRD), Raman spectra, scanning electron microscopy (SEM), energy dispersive X-ray spectrum (EDS), and X-ray photoelectron spectroscopy (XPS). Results showed that the destabilization of SCZ ceramics at 750 °C was the result of the chemical reaction with V₂O₅ to produce m-ZrO₂ and CeVO₄, and little ScVO₄ was detected in the Sc₂O₃-rich SCZ ceramics. The primary corrosion products at 900 °C and 1100 °C were CeO₂ and m-ZrO₂ due to the mineralization effect. The Sc₂O₃-rich SCZ ceramics exhibited excellent degradation resistance and phase stability owing to the enhanced bond strength and the decreased size misfit between Zr⁴⁺ and Sc³⁺. The destabilization mechanism of SCZ ceramic under hot corrosion was also discussed.     

A Highly Sensitive,Reversible, and Bidirectional Humidity Actuator by Calcium Carbonate Ionic Oligomers Incorporated Poly(Vinylidene Fluoride)

Sensitivity and multi-directional motivation are major two factors for developing optimized humidity-response materials, which are promising for sensing, energy production, etc. Organic functional groups are commonly used as the water sensitive units through hydrogen bond interactions with water molecules in actuators. The multi-coordination ability of inorganic ions implies that the inorganic ionic compounds are potentially superior water sensitive units. However, the particle forms of inorganic ionic compounds produced by classical nucleation limit the number of exposed ions to interact with water. Recent progress on the inorganic ionic oligomers has broken through the limitation of classical nucleation, and realized the molecular-scaled incorporation of inorganic ionic compounds into an organic matrix. Here, the incorporation of hydrophilic calcium carbonate ionic oligomers into hydrophobic poly(vinylidene fluoride) (PVDF) is demonstrated. The ultra-small calcium carbonate oligomers within a PVDF film endow it with an ultra-sensitive, reversible, and bidirectional response. The motivation ability is superior to other bidirectional humidity-actuators at present, which realizes self-motivation on an ice surface, converting the chemical potential energy of the humidity gradient from ice to kinetic energy.