In situ Raman spectroscopic study towards the growth and excellent HER catalysis of Ni/Ni(OH)2 heterostructure

The electrochemical water splitting to produce H₂ in high efficiency with earth-abundant-metal catalysts remains a challenge. Here, we describe a simple “cyclic voltammetry + ageing” protocol at room temperature to activate Ni electrode (AC-Ni/NF) for hydrogen evolution reaction (HER), by which Ni/Ni(OH)₂ heterostructure is formed at the surface. In situ Raman spectroscopy reveals the gradual growth of Ni/Ni(OH)₂ heterostructure during the first 30 min of the aging treatment and combined with polarization measurements, it suggests a positive relation between the Ni/Ni(OH)₂ amount and HER performance of the electrode. The obtained AC-Ni/NF catalyst, with plentiful Ni–Ni(OH)₂ interfaces, exhibits remarkable performance towards HER, with the low overpotential of only 30 mV at a H₂-evolving current density of 10 mA/cm² and 153 mV at 100 mA/cm², as well as a small Tafel slope of 46.8 mV/dec in 1 M KOH electrolyte at ambient temperature. The excellent HER performance of the AC-Ni/NF could be maintained for at least 24 h without obvious decay. Ex situ experiments and in situ electrochemical-Raman spectroscopy along with density functional theory (DFT) calculations reveal that Ni/Ni(OH)₂ heterostructure, although partially reduced, can still persist during HER catalysis and it is the Ni–Ni(OH)₂ interface reducing the energy barrier of H1 adsorption thus promoting the HER performance.     

Adaptive compensation of persistent actuator failures of nonlinear systems

In this article, adaptive compensation designs are developed for nonlinear systems with uncertainties from the system functions and persistent actuator failures of characterizations that (i) some unknown system inputs are stuck at some unknown fixed or varying values at unknown time instants and (ii) the failure pattern always switches from one to another and the switching does not stop. Such a controlled plant is described by an uncertain time-varying nonlinear system, and some robust adaptive feedback linearization based failure compensation results are studied for closed-loop system stabilization and bounded output tracking for some specific conditions. To improve the tracking performance in the presence of persistent actuator failures, a new adaptive control scheme is developed, using the failure indicator function which contains the failure pattern and failure time in the formulation. Detailed stability and tracking performance are shown. Simulation results are shown to verify the effectiveness of the proposed adaptive actuator failure compensation method.     

Structural,optical and electrical properties of indium doped Cu2ZnSn(S,Se)4 thin films synthesized by the DC and RF reactive magnetron cosputtering

Element doping into the Cu₂ZnSn(S,Se)₄ (CZTSSe) absorber is an effective method to optimize the performance of thin film solar cells. In this study, the Cu₂In_xZn_1-xSn(S,Se)₄ (CIZTSSe) precursor film was deposited by magnetron cosputtering technique using indium (In) and quaternary Cu₂ZnSnS₄ (CZTS) as targets. Meanwhile, the In content was controlled using the direct current (DC) power on In target (P_In). A single kesterite CIZTSSe alloy was formed by successfully doping a small number of In³⁺ into the main lattice of CZTSSe. The partial Zn²⁺ cations were substituted by In³⁺ ions, resulting in improving properties of CZTSSe films. Morphological analysis showed that large grain CIZTSSe films could be obtained by doping In. The well-distributed, smooth, and dense film was obtained when the P_In was 30 W. The band gap of CIZTSSe could be continuously adjusted from 1.27 to 1.05 eV as P_In increased from 0 to 40 W. In addition, the CIZTSSe alloy thin film at P_In = 30 W exhibited the best p-type conductivity with Hall mobility of 6.87 cm²V^?1s^?1, which is a potential material as the absorption layer of high-performance solar cells.     

Interfacial Crystallization of Diacylglycerols Rich in Medium‐ and Long‐Chain Fatty Acids in Water‐in‐Oil Emulsions

The effects of diacylglycerols rich in medium‐ and long‐chain fatty acids (MLCD) on the crystallization of hydrogenated palm oil (HPO) and formation of 10% water‐in‐oil (W/O) emulsion are studied, and compared with the common surfactants monostearoylglycerol (MSG) and polyglycerol polyricinoleate (PGPR). Polarized light microscopy reveals that emulsions made with MLCD form crystals around dispersed water droplets and promotes HPO crystallization at the oil‐water interface. Similar behavior is also observed in MSG‐stabilized emulsions, but is absent from emulsions made with PGPR. The large deformation yield value of the test W/O emulsion is increased four‐fold versus those stabilized via PGPR due to interfacial crystallization of HPO. However, there are no large differences in droplet size, solid fat content (SFC), thermal behavior or polymorphism to account for these substantial changes, implying that the spatial distribution of the HPO crystals within the crystal network is the driving factor responsible for the observed textural differences. MLCD‐covered water droplets act as active fillers and interact with surrounding fat crystals to enhance the rigidity of emulsion. This study provides new insights regarding the use of MLCD in W/O emulsions as template for interfacial crystallization and the possibility of tailoring their large deformation behavior. Practical Applications: MLCD is applied in preparing W/O emulsion. It is found that MLCD forms unique interfacial Pickering crystals around water droplets, which promote the surface‐inactive HPO nucleation at the oil‐water interface. Thus MLCD‐covered water droplets act as active fillers and interact with surrounding fat crystals, which can greatly enhance the rigidity of emulsion. This observation would provide a theoretical reference and practical basis for the application of the MLCD with appreciable nutritional properties in lipid‐rich products such as whipped cream, shortenings margarine, butter and ice cream, so as to substitute hydrogenated oil. MLCD‐stabilized emulsions can also be explored for the development of novel confectionery products, lipsticks, or controlled release matrices.     

溶胀嵌入脂肪酸分子制备高脱硼反渗透膜

采用“溶胀-嵌入-收缩”方法改性聚酰胺反渗透膜，制备了一种高脱硼反渗透膜。通过甲醇溶胀增加了高分子链之间的距离，为疏水性癸酸分子的嵌入提供了场所，然后在压力和浓差极化共同作用下，改性分子选择性嵌入聚酰胺膜的孔内；当甲醇分子离开后，聚酰胺膜收缩将癸酸分子固定在高分子网络中。实验借助溶胀和分子嵌入以及溶胀后的收缩调节聚酰胺膜的孔径大小；利用脂肪酸的疏水性降低聚酰胺膜的极性，从而实现增加空间位阻和减少氢键结合位点数量的目的。实验结果显示，改性膜的脱硼率和截盐率均明显升高，截盐率从90.36%增加到96.46%，脱硼率从未改性膜的47.85%增加到77.32%，渗透液的硼含量达到WTO的使用标准。虽然水和硼的渗透性均下降，但是水和硼的渗透选择性增加，证明该方法有利于提高水硼选择性。     

Improvement of polyamide/thermoplastic polyurethane blends with polyamide 6-polyurethane copolymer prepared via suspension polymerization as compatibilizer

The polyamide 6-polyurethane copolymer (PA6-b-PU-b-PA6) was synthesized through anionic suspension polymerization and then mixed with polyamide 6/thermoplastic polyurethane (PA6/TPU) and polyamide 6, 6/thermoplastic polyurethane (PA66/TPU) blends using as the compatibilizer. The results show that the PA6-b-PU-b-PA6 copolymers powders several can be obtained through suspension polymerization using dimethicone as disperse medium. The average diameter of PA6-b-PU-b-PA6 copolymer powders decreased with the increasing of PU content. With the addition of PA6-b-PU-b-PA6, the TPU phase dispersed more uniformly in PA6 or PA66 matrix, and the size of TPU dispersed phase decreased obviously. The PA6-b-PU-b-PA6 copolymer with higher PU content shows better compatibilizing effect. Addition of PA6-b-PU-b-PA6 can improve both strength and toughness of the PA/TPU blends. When the amount of PA6-PU25% copolymer was 5 phr, the tensile strength and notched impact strength of PA6/TPU/PA6-PU25% blends increased 29 and 159.4%, respectively, compared to the PA6/TPU blend without compatibilizer.     

超细粉在内循环流化床中的流态化特性

在内径120 mm的半圆柱形内循环流化床中,以平均粒径387 nm的Ti O2为原料,考察了单独通入流化气、射流气和同时通入流化气和射流气三种流化方式下超细粉的流化特性以及射流气速对超细粉聚团尺寸的影响。结果表明:同时通入流化气和射流气时,流化气能促进粉体循环,消除环隙死区;高速射流能有效破碎聚团,显著减小聚团尺寸,从而使超细粉在环隙区与导流管之间形成稳定循环,小聚团在环隙区实现平稳流态化。随着射流气速的增大,聚团尺寸减小,粒度分布变窄,在射流气速分别为60,90,120,150 m/s的条件下,聚团平均直径分别为194,158,147,135μm。     

Wear mechanism of a novel AlSiMgAl2O4Al2O3 composite used in the low vessel of an RH secondary refining furnace

A novel AlSiMgAl₂O₄Al₂O₃ composite brick was prepared and evaluated in the low vessel of an RH (the initials of Ruhrstahl and Hereaeus) secondary refining furnace; it was characterized by X-ray diffraction, scanning electron microscopy, and energy-dispersive spectroscopy. The results show that after use, the AlSiMgAl₂O₄Al₂O₃ composite has a functional gradient with an erosion zone–reinforced zone–original zone phase distribution, in which the phases in the erosion zone (0–1.8?cm) are a Mg-hercynite spinel solid solution, α-Al₂O₃, and minor amount of Al₃Fe₅O₁₂. Furthermore, the phases in the reinforced zone (1.8–5.0?cm) are γ-AlON, 21RSiAlON, SiC, Mg_0.388Al_2.408O₄, and α-Al₂O₃; i.e., the Al and Si in the composite are completely converted into non-oxide reinforced phases. Finally, the phases in the original zone (>5.0?cm) show no change. The reaction mechanism is as follows. During operation, a Mg-hercynite spinel solid solution is formed in the erosion zone due to a reaction between MgAl₂O₄ and FeO from a refinery operation. Therefore, the slag erosion of the material is improved. The Al and Si metals undergo active oxidation, and 21RSiAlON flakes are subsequently formed from the products of the metastable Al₂O(g), SiO(g), and N₂(g) in the ambient. The γ-AlON is formed by a carbothermal reduction nitridation of the α-Al₂O₃ and residual active carbon from the resin binder. The 21RSiAlON and γ-AlON reinforce the composite brick and improve its high temperature performance accordingly. Its service life is 110% that of the magnesia-chrome bricks used in the same period. The reaction model was also established.