Innovative method to produce large-area freestanding functional ceramic foils

Using thick and thin films instead of bulk functional materials presents tremendous advantages in the field of flexible electronics and component miniaturization. Here, a low-cost method to grow and release large-area, microscale thickness, freestanding, functional, ceramic foils is reported. It uses evaporation of sodium chloride to silicon wafer substrates as sacrificial layers, upon which functional lead titanate zirconate ceramic films are grown at 710?°C maximum temperature to validate the method. The freestanding, functional foils are then released by dissolution of the sacrificial sodium chloride in water and have the potential to be integrated into low-thermal stability printed circuits and flexible substrates. The optimization of the sodium chloride layer surface quality and bonding strength with the underlying wafer is achieved thanks to pre-annealing treatment.     

基于功能参数的渐进成形件表面质量表征研究

目的 以圆锥台成形件为例，基于粗糙表面的区域支承率曲线，进行了用功能参数表征表面几何形貌的研究，以全面、准确、定量地表征渐进成形件的表面质量，预测表面性能。方法 用渐进成形工艺加工成形角分别为35°、45°和55°的圆锥台件，将各圆锥台的成形面分为顶部、中部和底部三个区域，并使用三维表面轮廓仪，在上述三个区域中随机测量各4个样本。根据ISO 25178-2:2012，将各样本表面的区域支承率曲线分为峰区、核心区和谷区，选用部分功能参数——核心区高度Sk、峰区材料体积Vmp、核心区材料体积Vmc和谷区空隙体积Vvv表征表面，并与常用的高度表征参数——Sa、Sq、Ssk和Sku进行比较。结果 成形件表面的Ssk和Sku的计算值极不稳定，变异系数（标准偏差与均值之比）最高值分别可达127.67%和39.11%，Sa、Sq的最大变异系数分别为4.41%和4.26%，虽然它们的参数计算值较为稳定，但常无法体现表面形貌的实际差异。功能参数独立表征不同功能区，Sk和Vmc的最大变异系数分别为9.32%和7.73%，说明同一表面各处，在长期工作阶段具有较为一致的表面性能，Vmp和Vvv的最大变异系数分别为60.53%和31.25%，说明表面各处峰、谷区的形貌有所不同，因而在磨合时间、磨粒存储等方面会有不同的表现。结论 粗糙表面的三维本质要求用三维表征参数才能全面表征其几何形貌。高度参数虽然计算简单，但常难以解读它们的物理意义，无法定量评价表面性能；功能参数具有明确的物理意义，可为表征表面质量、预测表面性能提供定量、实用的方法。     

后处理对爆轰纳米金刚石表面官能团的影响

分别在高锰酸钾与浓硫酸的混合溶液、空气、氢气、真空以及氩气中对爆轰纳米金刚石进行后处理,研究了后处理方法对其表面官能团的影响。采用X射线衍射仪、高分辨透射电子显微镜、傅立叶变换红外光谱仪和差示扫描量热仪对后处理前后纳米金刚石的微观结构、性能和表面状态进行了研究。结果表明:纳米金刚石颗粒形状为球形或椭球形,平均粒径约为5 nm,在空气中的起始氧化温度约为550 ℃,在氢气、真空和氩气中的石墨化温度分别约为284 ℃、1 146 ℃和1 184 ℃。纳米金刚石在后处理前表面含有大量的官能团,如-OH、-CH₃、-CH₂、CO₂、-C==O、-COOH和-C-O-C等。在氢气中对纳米金刚石进行处理,可使部分官能团从表面解吸而由氢取代,悬键与氢结合可有效防止二次吸附,是去除爆轰纳米金刚石表面官能团的低成本、高效方法。     

A molecular model for ion dehydration in confined water

Although ion dehydration in confined water is ubiquitous in many important processes concerning ion adsorption, transport and separation, and so forth, few theoretical models have been developed to unravel the mechanism of dehydration in confined space. Herein, a molecular model is proposed by weighing the molecular orientation of surrounding water within the first hydration shell, and then this model is applied to predict the hydration numbers and hydrated radii of simple ions with the help of molecular density functional theory. The predictions are rationalized not only with parallel simulations but also with relevant experimental measurements. We find that the ion hydration in confined water is depressed owing to the confinement, and thus the multilayer hydration shell is disturbed, which results in the decline of hydration number and hydrated radius, favoring the ion dehydration. This work provides an insightful route toward the quantitative understanding and prediction of ion dehydration in confined water.     

Self-supported multidimensional Ni–Fe phosphide networks as novel and robust water splitting catalyst

The water splitting has become one of the most promising hydrogen production methods. The Ni–Fe–P materials were first synthesized and in situ grown on nickel foam by typical hydrothermal and phosphating methods. The Ni–Fe–P-300 catalyst shows excellent water splitting activity (cell voltage of 1.59 V @10 mA cm⁻²) and stability after phosphating. The results of density functional theory (DFT) demonstrate that the water molecules preferentially adsorbed on the Fe site and Fe might be the real catalytic active site. A series of characterization indicated that a small amount of phosphorus loss was probably caused on the catalyst surface, but the electrocatalytic activity was not affected by the small amount of oxide species formation. This study offers a promising way to design and optimize electrocatalysts for the water splitting in alkaline solution.     

Transition metal atom doped C2N as catalyst for the oxygen reduction reaction: A density functional theory study

The catalytic mechanism and activity of transition metal atom doped C₂N (M-C₂N, M = Fe, Co, Ni, and Cu) for the oxygen reduction reaction (ORR) are investigated in detail by density functional theory method. All the screened M-C₂N are thermodynamically stable based on the binding energy calculations. The adsorption energy results indicate that the adsorption strength of O₂ and ORR intermediates are decreased in the order of Fe-C₂N ˃ Co-C₂N ˃ Ni-C₂N ˃ Cu-C₂N, in which the adsorption energy values on Cu-C₂N are most close to those on the Pt(111). Based on the relative energy diagram of ORR, the energetically favorable pathway on Fe-C₂N and Co-C₂N is direct 4e⁻ mechanism, in which the O–O bond is directly dissociated after the second electron transfer. While for Ni-C₂N and Cu-C₂N, the most favorable pathway is indirect 4e⁻ mechanism, in which the H₂O₂ is formed as the intermediate product. For all studied M-C₂N, the Ni-C₂N and Cu-C₂N hold better catalytic activity, which could attribute to the contribution of metal atom and part of its activated nitrogen atoms.     

玻璃沉积物对La2Ce2O7/YSZ涂层高温下热冲击性能的影响

目的 为了探究玻璃沉积物CMAS(CaO-MgO-Al2O3-SiO2)对新型结构热障涂层在1250 ℃下的热冲击寿命的影响，揭示热障涂层的失效行为。方法 通过火焰喷涂技术将制备的CMAS粉体均匀地沉积到铈酸镧/氧化钇部分稳定二氧化锆双陶瓷层热障涂层(LC/YSZ DCL-TBCs)和梯度热障涂层(LC/YSZ FGM-TBCs)的表面，于1250 ℃热冲击实验中进行涂层样品的抗热冲击性能及失效机理研究。利用扫描电镜(SEM)和能谱仪(EDS)追踪CMAS的位置，观察CMAS与涂层反应层的厚度与形貌。采用X射线衍射仪(XRD)测试反应层产物，并总结其失效方式。结果 高温热冲击结果显示梯度涂层的热冲击寿命(435次)远高于双陶瓷层热障涂层的寿命(229次)，约为铈酸镧/氧化锆双陶瓷层热障涂层寿命的1.9倍。铈酸镧层与梯度层都能在一定程度上阻碍CMAS渗入涂层内部，提高其CMAS腐蚀条件下的热冲击寿命。双陶瓷层热障涂层与梯度热障涂层的失效均是以层状剥落为主，剥落层主要是CMAS与LC的反应层以及反应层下的烧结层，反应层是由Ca2(LaxCe1-x)8(SiO4)6O6-4x、萤石相和MgAl2O4等难熔氧化物组成，这层致密氧化物类似于密封层，能阻止CMAS继续渗入。结论 功能梯度结构具有比双陶瓷层结构更优异的抗CMAS热冲击性能和更好的应力耐受性。     

Density functional theory and machine learning guided search for RE2Si2O7 with targeted coefficient of thermal expansion

Density functional theory (DFT) calculations and machine learning (ML) methods are used to establish a relationship between the crystal structures of rare-earth (RE) disilicates (RE₂Si₂O₇) and their coefficient of thermal expansion (CTE). The DFT total energy data predict the presence of several energetically competing crystal structures, which is rationalized as one of the reasons for observing polymorphism. An ensemble of support vector regression models is trained to rapidly predict the CTE as a function of RE₂Si₂O₇ crystal chemistry. Experiments subsequently validated the structure and CTE predictions for Sm₂Si₂O₇.