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.     

Microstructural and mechanical properties assessment of transient liquid phase bonding of CoCuFeMnNi high entropy alloy

The transient liquid phase (TLP) bonding of CoCuFeMnNi high entropy alloy (HEA) was studied. The TLP bonding was performed using AWS BNi-2 interlayer at 1050 °C with the TLP bonding time of 20, 60, 180 and 240 min. The effect of bonding time on the joint microstructure was characterized by SEM and EDS. Microstructural results confirmed that complete isothermal solidification occurred approximately at 240 min of bonding time. For samples bonded at 20, 60 and 180 min, athermal solidification zone was formed in the bonding area which included Cr-rich boride and Mn₃Si intermetallic compound. For all samples, the γ solid solution was formed in the isothermal solidification zone of the bonding zone. To evaluate the effect of TLP bonding time on mechanical properties of joints, the shear strength and micro-hardness of joints were measured. The results indicated a decrement of micro-hardness in the bonding zone and an increment of micro-hardness in the adjacent zone of joints. The minimum and maximum values of shear strength were 100 and 180 MPa for joints with the bonding time of 20 and 240 min, respectively.     

高熵形状记忆合金的研究进展

高熵形状记忆合金是在等原子比NiTi合金的基础上,结合高熵合金的概念,逐渐发展起来的一种新型高温形状记忆合金。近年来,已开发出了综合性能优异的(TiZrHf)50(NiCoCu)50系和(TiZrHf)50(NiCuPd)50系高熵形状记忆合金,引起了广泛的关注和研究兴趣。本文从物相组成、微观组织、马氏体相变行为、形状记忆效应和超弹性等角度出发,综述了高熵形状记忆合金的研究进展,并对高熵形状记忆合金未来的研究重点进行了展望。     

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.     

Machine learning of phases and mechanical properties in complex concentrated alloys

The mechanical properties of complex concentrated alloys (CCAs) depend on their formed phases and corresponding microstructures.The data-driven prediction of the phase formation and associated mechanical properties is essential to discovering novel CCAs.The present work collects 557 samples of various chemical compositions,comprising 61 amorphous,167 single-phase crystalline,and 329 multi-phases crystalline CCAs.Three classification models are developed with high accuracies to category and understand the formed phases of CCAs.Also,two regression models are constructed to predict the hard-ness and ultimate tensile strength of CCAs,and the correlation coefficient of the random forest regression model is greater than 0.9 for both of two targeted properties.Furthermore,the Shapley additive expla-nation (SHAP) values are calculated,and accordingly four most important features are identified.A significant finding in the SHAP values is that there exists a critical value in each of the top four fea-tures,which provides an easy and fast assessment in the design of improved mechanical properties of CCAs.The present work demonstrates the great potential of machine learning in the design of advanced CCAs.     

Investigation the effect of FeNiCoCrMo HEA addition on properties of B4C ceramic prepared by spark plasma sintering

In this study, monolithic B₄C and B₄C-based ceramics incorporating FeNiCoCrMo dual-phase (FCC and BCC) high entropy alloys (HEAs) were produced by spark plasma sintering (SPS). The effect of additives on the densification behavior, mechanical properties, microstructures, and phase evaluation of the samples were investigated. X-ray analysis confirmed the existence of FCC structured HEA and depletion of BCC structured HEA, after high-temperature reaction between B₄C-HEAs. The addition of HEAs enhanced the densification behavior by liquid phase sintering. Furthermore, hardness and fracture toughness values of the samples increased with increasing HEAs content. Fracture toughness and hardness values for all composites were higher than the monolithic B₄C. A combination of the highest density (∼99.22 %) and the best mechanical properties (32.3 GPa hardness and 4.53 MPa m^1/2 fracture toughness) was achieved with 2.00 vol.% HEA addition.     

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。