Formation and properties of high entropy oxides in Co-Cr-Fe-Mg-Mn-Ni-O system: Novel (Cr,Fe,Mg,Mn,Ni)3O4 and (Co,Cr,Fe,Mg,Mn)3O4 high entropy spinels

Possibility of formation of quinary and senary equimolar high entropy oxides from the Co-Cr-Fe-Mg-Mn-Ni-O system is presented. Different proposed compositions are synthesized using the solid-state reaction route at high temperatures (900−1100 °C) and quenched to room temperature. Phase composition of the samples is studied, showing tendency toward formation of two main phases: rock salt-structured Fm-3 m and spinel-structured Fd-3 m. It is documented that the annealing temperature has a profound effect on stability of both structures, and at 1100 °C usually the highest content of Fm-3 m phase is usually observed. Three different oxides, namely, (Co,Cr,Fe,Mn,Ni)₃O₄, (Co,Cr,Fe,Mg,Mn)₃O₄ and (Cr,Fe,Mg,Mn,Ni)₃O₄ are obtained as single-phase materials, which structure can be described as the high entropy Fd-3 m spinel one. The latter two compounds have not been previously reported in the literature. Activated character of the electrical conductivity dependence on temperature is observed, with relatively high total conductivity at high temperatures and corresponding high absolute values of Seebeck coefficient.     

Influence of the porous transport layer properties on the mass and charge transfer in a segmented PEM electrolyzer

A titanium Porous Transport Layer (PTL) is usually used at the anode side of PEM water electrolyzers to ensure both the gas/water transport and the electric charges transfer. In this paper, four different sintered Ti powder PTLs were characterized to determine some properties, such as the pore size distribution, the porosity, and the permeability. Their influence on the electrolysis performance was investigated by using a 30 cm² segmented cell which allowed measuring the current density distribution, while controlling temperature and pressure conditions. For a better understanding, in-situ techniques such as the Polarization Curves and the Electrochemical Impedance Spectroscopy (EIS) were used. A local characterization of mass transport limitations caused by oxygen saturation was carried out, paying special attention to the pressure influence when using a PTL with very small pores. The results showed that current density heterogeneities can be explained by microstructure changes along the PTL. The optimal geometric characteristics of the PTL depend not only on the operating conditions such as current density, pressure, and temperature but also on the catalyst layer properties. A new model for the constriction resistance between the catalyst layer and the PTL was proposed.     

Separators for alkaline water electrolysis prepared by plasma-initiated grafting of acrylic acid on microporous polypropylene membranes

Highly hydrophilic separators for alkaline water electrolysis were prepared by plasma-initiated grafting of acrylic acid on porous polypropylene (PP) membranes. The membranes were activated in a low-pressure radio-frequency discharge in oxygen and subsequently graft polymerization of acrylic acid was performed in aqueous solution. The membranes were characterized by gravimetric grafting degree (GD), SEM, FTIR, critical wetting surface tension (CWST) test, mechanical strength, and electrolytic conductivity. Moreover, the membranes were applied as separators in alkaline electrolysis cell, and content of hydrogen in the produced oxygen was measured to determine membrane permeability to hydrogen dissolved in the electrolyte. It was observed that increasing GD improves performance of membranes as separators in alkaline electrolysis, although the particular effects on the electrolytic conductivity and hydrogen permeability strongly depend on structure the of initial PP substrate. Ageing test conducted in 30 wt% KOH at 60 °C revealed that although considerable degrafting took place at beginning of the test, the remaining polyacrylic acid provided highly hydrophilic character to membrane for 7000 h of the test.     

Optimization of self-regulated hydrogen production from photovoltaic energy

The use of photovoltaic energy (PV) for the production of hydrogen by using autonomous modular self-regulated systems is studied. Results are compared with those obtained for controlled systems. It was proved that for small and low-cost applications, it is possible to eliminate any control system with yields as high as 91.2% in the PV-electrolyzer interface for a sunny day. Self-regulated systems are thus an excellent, safe, cheap and environmentally friendly alternative for applications in isolated sites, especially in emerging countries.     

Fabrication of platinum thin films for ultra-high electrocatalytic hydrogen evolution reaction

While the noble metals (e.g., platinum, (Pt)) remain the benchmark electrocatalyst for the hydrogen evolution reaction (HER), their mass production require a reduced metal loading and faster fabrication protocols. The aim of the present work is to prepare Pt thin films by simple and fast fabrication technique, and to evaluate their performance for HER. The thin films of Pt are grown on two substrates, namely titanium foil (Ti) and nickel foam (NF), using a single step aerosol assisted chemical vapor deposition (AACVD) method. The film deposition time are varied from 20 to 60 min. Microscopic analyses suggest a gradual evolution of the films into percolated and/or porous nanostructures, a feature that remains highly desired to allow the maximum access of active sites. The performance of the as-prepared electrodes is evaluated by monitoring the HER in acidic electrolyte. The Pt film on nickel foam (Pt/NF) exhibits better electrical conductivity and smaller charge transfer resistance, while the film deposited on the Ti foil (Pt/Ti) demonstrates superior catalytic activity per active sites. The as-prepared Pt/Ti and Pt/NF electrodes produce 10 mA cm⁻² at overpotential of 28 mV and 26 mV, respectively, better in performance than commercial Pt/C electrode (~39 mV), set a new bench mark electrocatalyst for the HER.     

Ni,Cr, and Fe surfaces corroded by molten ZnCl2

Understanding the corrosion of molten ZnCl₂ on metal surfaces is significant for the corrosion protection of metals, sustainable use of molten salts, preparation of ZnO coatings, and so on. In this paper, surfaces of pure Ni, Cr, and Fe corroded by molten ZnCl₂ were investigated. The results show that Ni suffered very slight corrosion, while Cr experienced more serious corrosion than Ni, but lighter corrosion than Fe. The morphology of the corrosion of Cr and Fe, respectively, presented pitting and intergranular corrosion characteristics. Furthermore, nanostructured ZnO coatings were obtained on the surfaces of Ni and Fe, but not on the surface of Cr. The ZnO coating on the Ni surface was doped with a small amount of Zn₅(OH)₈Cl₂, and the ZnO coating on the Fe surface was doped with ZnFe₂O₄ and Zn₂OCl₂. The coatings on the Ni and Fe surfaces had an average thickness of 1.5 and 50 μm, respectively.     

盐溶液种类和浓度对α-半水脱硫石膏合成的影响

为了解决脱硫石膏的大量堆存对环境造成的潜在危害,同时提高脱硫石膏的附加值,采用常压盐溶液水热法以电厂脱硫石膏为原料探究α-半水石膏的最佳合成工艺,重点研究了盐溶液种类及浓度对α-半水石膏的合成过程、合成产物组成及结构的影响。结果表明：在氯化钙、氯化镁盐溶液中,由于同离子效应和硫酸镁离子对的形成,导致半水石膏的形成过程受阻。较高浓度氯化钾和氯化钠盐溶液可使二水石膏发生转晶,其中氯化钾会致使半水石膏过度脱水生成无水钾石膏,氯化钠盐溶液可以使二水石膏转变为半水石膏并维持较长时间,通过比较得出最佳合成工艺为氯化钠溶液质量分数为15%、体系反应温度为95 ℃、固液质量比为1∶4、搅拌速率为150 r/min、合成时间为3 h,可以制得长径比约为5∶1的六方短柱状α-半水石膏。     

喷涂功率对YSZ涂层的力学性能和抗铝硅熔体腐蚀性能的影响

热浸镀Al–Si合金涂层是一种有效的现代钢铁防腐涂层，但熔融Al–Si合金腐蚀已成为热浸镀Al–Si合金生产线沉没辊及其备件亟待解决的关键问题之一。本工作采用大气等离子喷涂技术制备Y2O3部分稳定ZrO2(YSZ)/NiCrAlY防护涂层，研究了喷涂功率对YSZ涂层组织和力学性能的影响和涂层在700℃下Al–Si熔体中的腐蚀行为。结果表明，YSZ涂层是由板条和层间柱状晶粒组成的典型层状结构，随着喷涂功率从37 kW增至46 kW，层间柱状结晶呈长大趋势；YSZ涂层主要由t-ZrO2相和少量m-ZrO2相组成，喷涂功率对涂层相组成无明显影响；喷涂功率为40 kW的YSZ涂层具有较高的显微硬度642.4 HV0.3和结合强度62 MPa。此外，当带有涂层的样品在700℃的Al–Si熔液中腐蚀240 h后，YSZ涂层与高温Al–Si熔液之间的界面没有反应层生成，同时Al–Si合金熔液中的Al和Si元素也未渗透进YSZ涂层内部，表明YSZ/NiCrAlY防护涂层有效地将Al–Si合金熔体阻挡在涂层表面。     

高速激光热丝钎焊表面成形质量的控制

高速激光钎焊会引起熔池流动紊乱导致焊缝成形质量恶化,从而限制了其在汽车制造领域的应用。通过正交试验研究了高速下激光功率、送丝角度等工艺参数对焊缝成形质量的影响,发现焊缝成形质量随激光功率增加和送丝角度减小而提升。激光功率是通过影响熔池获得的热输入,从而影响熔池表面扰动的铺展来影响焊缝成形质量的。送丝角度是通过影响焊丝送入熔池的位置,从而影响焊丝对熔池的扰动强度和扰动的铺展速度来影响焊缝成形质量的。采用正交试验获得的最优工艺参数组合进行试验,获得了表面光滑平整无缺陷的高质量焊缝,为激光钎焊在高速下的应用发展奠定了基础。     

Anodic process on Cu−Al alloy in KF−AlF3−Al2O3 melts and suspensions

Anodic processes on Cu−10Al electrode in molten KF−AlF₃−Al₂O₃ (saturated) and suspensions were characterized using chronopotentiometric and cyclic voltammetric techniques. Effects of cryolite ratio (CR= x(KF)/x(AlF₃)), temperature and particle volume fraction (ϕ) on the electrochemical behaviour of the anode were demonstrated. Initially, the anode was polarised in the galvanostatic mode in melt and suspensions (ϕ=0.12, 0.15) at 750 °C with 0.4 A/cm² current density. The anode potential in melt varied between 2.5 and 3.2 V and in suspensions (ϕ= 0.12) between 3.3 and 3.4 V. XRD analysis was conducted to study the oxide phases on the anode surface. Anode limiting current densities and mass transfer coefficients drastically decreased with the increase of ϕ in the suspension. The results suggest that the Cu−10Al electrode works better in suspensions with CR of 1.4 and particle volume fraction of 0.09 at 800 °C.