Thermal desorption and pyrolysis direct analysis in real time mass spectrometry of Nafion membrane

Perfluorosulfonic acid ionomer membranes have been widely used as proton conducting membranes in various electrochemical processes such as polymer electrolyte fuel cells and water electrolysis. While their thermal stability has been studied by thermogravimetry and analysis of low molecular weight products, their decomposition mechanism is little understood. In this study a newly developed methodology of thermal desorption and pyrolysis in combination with direct analysis in real time mass spectrometry is applied for Nafion membrane. An ambient ionization source and a high-resolution time-of-flight mass spectrometer enabled unambiguous assignment of gaseous products. Thermal decomposition is initiated by side chain detachment above 350°C, which leaves carbonyls on the main chain at the locations of the side chains. Perfluoroalkanes are released above 400°C by main chain scission and their further decomposition products dominate above 500 °C. DFT calculation of reaction energies and barrier heights of model compounds support proposed decomposition reactions.     

An ultrasonic study on ternary xPbO–(45-x)CuO–55B2O3 glasses

A series of xPbO–(45-x)CuO–55B₂O₃ glasses (5 ≤ x ≥ 40 mol %) were prepared by the melt-quenching technique. The X-ray diffraction (XRD) patterns of the prepared glasses are found to have amorphous structure. An extensive ultrasonic study has been made to explore the structural role of PbO and CuO in the borate network. Various elastic properties were calculated from the measured data of density and ultrasonic velocity. Ultrasonic velocity and elastic moduli revealed broad humps at about 20 mol % PbO, which are attributed to the borate anomaly. Below 20 mol % PbO, all Pb²⁺ ions are considered to be entering the borate network as a glass modifier. This results in the transforms the borate network from an open structure to a denser three-dimensional structure due to BO₃ → BO₄ conversion. Beyond 20 mol, addition of PbO results in the formation of metaborate, pyroborate, and orthoborate units with NBOs. This weakness the glass structure and decrease both ultrasonic velocity and elastic moduli. The elastic properties were predicted and quantitatively analyzed by taking into account the effect of boron coordination number on the compositional and structural parameters involved in Makishima–Mackenzie's theory, ring deformation model and bond compression model. An excellent agreement between the computed theoretical and experimental elastic moduli, micro-harness and Poisson's ratio was achieved for majority of samples.     

Chemical bond characteristics and infrared reflectivity spectrum of a novel microwave dielectric ceramic CaIn2O4 with near-zero τf

Orthorhombic-structured CaIn₂O₄ ceramics with a space group Pca2₁ were synthesized via a solid-state reaction method. A high relative density (95.6 %) and excellent microwave dielectric properties (ε_r ～11.28, Qf = 74,200 GHz, τ_f ～ ?4.6 ppm/°C) were obtained when the ceramics were sintered at 1375 °C for 6 h. The dielectric properties were investigated on the basis of the Phillips–Van Vechten–Levine chemical bond theory. Results indicated that the dielectric properties were mainly determined by the InO bonds in the CaIn₂O₄ ceramics. These bonds contributed more (74.65 %) to the dielectric constant than the CaO bonds (25.35 %). Furthermore, the intrinsic dielectric properties of the CaIn₂O₄ ceramics were investigated via infrared reflectivity spectroscopy. The extrapolated microwave dielectric properties were ε_r ～10.12 and Qf = 112,200 GHz. Results indicated that ion polarization is the main contributor to the dielectric constant in microwave frequency ranges.     

一类分数阶微积分的中值定理及应用

Riemann-Liouville分数阶微积分算子是一类带有一个函数的分数阶微积分算子的特殊情形，以Riemann-Liouville分数阶微积分算子的积分中值定理和微分中值定理为基础，我们得到了一类带有一个函数的分数阶微积分算子的积分中值定理和微分中值定理，并给出其在计算方面的一些应用。     

Scaling analysis of hydrogen flow with carbon dioxide cushion gas in subsurface heterogeneous porous media

Subsurface hydrogen (H₂) storage in geological formations is of growing interest for decarbonization. However, there is a knowledge gap in understanding the multiphase flow involved in this process, which can have a significant impact on the recovery performance of H₂. Therefore, a full-compositional modeling study was conducted to analyze potential issues and to understand the fundamental hydrodynamic mechanisms of H₂ storage. We performed a range of 2D vertical simulations at the decametre scale with a very fine cell size (0.1 m) to observe the detailed flow behaviour of H₂ with carbon dioxide (CO₂) as cushion gas in various flow regimes. Issues such as viscous instability, capillary bypassing, gas trapping and gravity segregation are analysed here. To generalize our calculations, we have validated and applied the scaling theory in the context of subsurface H₂ storage. Since this study is focused on the hydrodynamic behaviour, three dimensionless groups, including aspect factor, capillary/viscous ratio and gravity/viscous ratio were identified to correlate recovery performance between various scales in a fixed heterogeneous system. It was found that H₂ could infiltrate the cushion gas in the proximity of the injectors, meaning that CO₂ is not displaced away from the injectors in a piston-like fashion. As a result, the purity of the back produced H₂ is much degraded, particularly in a viscous-dominated scenario. On the other hand, the injected H₂ mostly accumulates at the top forming a highly restricted mixing zone with CO₂ in the gravity-dominated case. The recovery performance is therefore much improved in this case. Although the gas distribution can be significantly altered by capillary forces leading to bypassed zones, the recovery performance of H₂ is hardly influenced. This is because the back-produced H₂ recovery is not dependent on the sweep efficiency of the gas. H₂ can be back produced following the same paths which were formed during injection.     

自重湿陷性黄土地基预钻孔浸水处理的可靠度设计方法

为解决传统预浸水法存在的浸水时间长、浸水处理范围难以确定等不足,基于土体中水分运移规律,依据可靠度理论、极限状态设计方法及复合 Poisson 过程原理,提出一种消除黄土湿陷性的处理浸水方法——预钻孔浸水法。给出了利用预钻孔浸水法对自重湿陷性黄土地基进行浸水时,水平向及竖直向浸水影响范围的确定模型;在此基础上结合达西定律给出了浸水孔设计参数如孔深、孔间距及浸水孔个数的确定方法。结合铜川某工程,设计进行了现场预钻孔浸水试验,对该方法的合理性进行了验证,并通过现场钻探、现场勘探、室内湿陷性试验等方法对该方法的处理效果进行了评价。该浸水方法具有浸水时间短、浸水影响范围可根据浸水孔布设进行控制等优点,且浸水处理效果良好,完全符合施工要求。     

基于设计事理学的儿童情感陪伴玩具研究

目的 从设计事理学视角，探讨儿童情感陪伴玩具的设计方法。方法 通过社会调研结合理论分析，提炼7～12岁城市留守儿童情感陪伴玩具中“事”的各外部因素与内部因素，建立合理的儿童情感陪伴玩具设计模型及评价体系。运用案例分析法，结合儿童情感陪伴玩具设计案例与实践，验证设计事理学在实际儿童情感陪伴玩具设计中的应用价值。结论 探索儿童情感陪伴玩具的设计路径，以Combot——具有情感陪伴与寓教于乐功能的儿童情感陪伴玩具为实践案例，证明了基于设计事理学的儿童情感陪伴玩具设计方法是有效可行的，可有效指导儿童玩具设计，满足父母与孩子的情感需求，促进儿童健康成长。     

基于心流理论的民艺体验产品设计要素研究

目的 探索民艺体验产品的设计方法，帮助用户实现沉浸式体验，提高用户对民艺产品的认同感，促进民艺的活态传承。方法 以竹编体验产品为例，通过用户观察、访谈并以用户体验地图的方式提取出“乌镇竹编”民艺产品在用户体验上的优点和痛点，结合心流理论，提出民艺体验产品的设计策略，同时优化“乌镇竹编”民艺体验产品。结论 经用户测试验证，最优的民艺体验产品除了要具备符合现代审美、工艺流程简化以及材料工具模块化等特征之外，还应具备以下设计要素:产品选择层次化、目标设置精细化、学习形式交互化、背景知识通俗化、作品分享社区化。     

基于Logistic回归的老年人APP用户体验优化设计

目的 提升老年人APP的用户体验水平。方法 提出一种基于Logistic回归的老年人APP用户体验优化设计研究方法。首先，通过文献研究和焦点小组法确定APP的设计模式，并选择合适的正交表确定设计模式的组合方式；其次，构建以行为体验、感知体验和情感体验为基础的用户体验评价体系，邀请被试者对试验样本执行具有代表性的任务，并对用户体验进行评价研究，收集试验数据；再次，运用序次Logistic回归建立APP设计模式与用户体验之间的关系模型，确定APP的最佳设计方案；最后，运用A/B测试方法对得到的试验结果进行验证。结论 以老年人移动医疗APP为例进行研究，结果表明所提出的方法可以有效地对老年人APP的用户体验进行优化设计，有助于设计师了解老年用户的偏好，设计出适合老年人使用的APP。     

“新国潮”设计要素对受众关注度的影响研究

目的 针对“新国潮”这一新兴的设计现象进行受众关注度研究，旨在剖析“新国潮”设计风格，发现影响“新国潮”受众关注度的设计要素，并展开实验分析，为设计领域的实证研究提供方法层面上的启示，为“新国潮”风格的推广提供设计策略。方法 在从字体、符号和色彩三方面解构“新国潮”设计要素的基础上，通过因素分析方法确定实验数据的信度、效度，运用眼动实验系统和方差分析法从无意注意和有意注意两个阶段实证研究“新国潮”设计要素对受众关注度的影响，并对原因展开分析。结果 在无意注意阶段，书法体、有色彩渐变、高纯度色彩、非象征符号能够获得较高关注度;在有意注意阶段，受众对宋体、有色彩渐变、高纯度色彩、象征符号的关注度更高。结论 研究在提高受众对“新国潮”画面的关注度、发现关注度影响机理和构建设计要素有效表达方面具有重要意义。