Transient liquid phase sintering of high-purity mullite for high-temperature structural ceramics

High-purity mullite ceramics, promising engineering ceramics for high-temperature applications, were fabricated using transient liquid phase sintering to improve their high-temperature mechanical properties. Small amounts of ultrafine alumina or silica powders were uniformly mixed with the mullite precursor depending on the silica-alumina ratio of the resulting ceramics to allow for the formation of a transient liquid phase during sintering, thus, enhancing densification at the early stage of sintering and mullite formation by the reaction between additional alumina and the residual glassy phase (mullitization) at the final stage of sintering. The addition of alumina powder to the silica-rich mullite precursor resulted in a reaction between the glassy silica and alumina phases during sintering, thereby forming a mullite phase without inhibiting densification. The addition of fine silica powder to the mullite single-phase precursor led to densification with an abnormal grain growth of mullite, whereas some of the added silica remained as a glassy phase after sintering. The resulting mullite ceramics prepared using different powder compositions showed different sintering behaviors, depending on the amount of alumina added. Upon selecting an optimum process and the amount of alumina to be added, the pure mullite ceramics obtained via transient liquid phase sintering exhibited high density (approximately 99%) and excellent high-temperature flexural strength (approximately 320 MPa) at 1500 °C in air. These results clearly demonstrate that pure mullite ceramics fabricated via transient liquid phase sintering with compositions close to those of stoichiometric mullite could be a promising process for the fabrication of high-temperature structural ceramics used in an ambient atmosphere. The transient liquid phase sintering process proposed in this study could be a powerful processing tool that allows for the preparation of superior high-temperature structural ceramics used in the ambient processing atmosphere.     

Optimization of hydrogen enrichment via palladium membrane in vacuum environments using Taguchi method and normalized regression analysis

In this study, the separation of hydrogen from gas mixtures using a palladium membrane coupled with a vacuum environment on the permeate side was studied experimentally. The gas mixtures composed of H₂, N₂, and CO₂ were used as the feed. Hydrogen permeation fluxes were measured with membrane operating temperature in the range of 320–380 °C, pressures on the retentate side in the range of 2–5 atm, and vacuum pressures on the permeate side in the range of 15–51 kPa. The Taguchi method was used to design the operating conditions for the experiments based on an orthogonal array. Using the measured H₂ permeation fluxes from the Taguchi approach, the stepwise regression analysis was also employed for establishing the prediction models of H₂ permeation flux, followed by the analysis of variance (ANOVA) to identify the significance and suitability of operating conditions. Based on both the Taguchi approach and ANOVA, the H₂ permeation flux was mostly affected by the gas mixture composition, followed by the retentate side pressure, the vacuum degree, and the membrane temperature. The predicted optimal operating conditions were the gas mixture with 75% H₂ and 25% N₂, the membrane temperature of 320 °C, the retentate side pressure of 5 atm, and the vacuum degree of 51 kPa. Under these conditions, the H₂ permeation flux was 0.185 mol s^?1 m^?2. A second-order normalized regression model with a relative error of less than 7% was obtained based on the measured H₂ permeation flux.     

Co2FeO4@rGO composite: Towards trifunctional water splitting in alkaline media

Development of efficient, low cost and multifunctional electrocatalysts for water splitting to harvest hydrogen fuels is a challenging task, but the combination of carbon materials with transition metal-based compounds is providing a unique and attractive strategy. Herein, composite systems based on cobalt ferrite oxide-reduced graphene oxide (Co₂FeO₄) @(rGO) using simultaneous hydrothermal and chemical reduction methods have been prepared. The proposed study eliminates one step associated with the conversion of GO into rGO as it uses direct GO during the synthesis of cobalt ferrite oxide, consequently rGO based hybrid system is achieved in-situ significantly, the optimized Co₂FeO₄@rGO composite has revealed an outstanding multifunctional applications related to both oxygen evolution reaction (OER) and hydrogen counterpart (HER). Various metal oxidation states and oxygen vacancies at the surface of Co₂FeO₄@rGO composites guided the multifunctional surface properties. The optimized Co₂FeO₄@rGO composite presents excellent multifunctional properties with onset potential of 0.60 V for ORR, an overpotential of 240 mV at a 20 mAcm^?2 for OER and 320 mV at a 10 mAcm^?2 for HER respectively. Results revealed that these multifunctional properties of the optimized Co₂FeO₄@ rGO composite are associated with high electrical conductivity, high density of active sites, crystal defects, oxygen vacancies, and favorable electronic structure arisinng from the substitution of Fe for Co atoms in binary spinel oxide phase. These surface features synergistically uplifted the electrocatalytic properties of Co₂FeO₄@rGO composites. The multifunctional properties of the Co₂FeO₄@ rGO composite could be of high interest for its use in a wide range of applications in sustainable and renewable energy fields.     

Effect of micro-cracks on the in-plane electronic conductivity of proton exchange membrane fuel cell catalyst layers based on lattice Boltzmann method

Micro-cracks commonly occur on the catalyst layers (CLs) during the manufacturing of catalyst coated membranes (CCMs). However, the crack shape parameters effect on CLs in-plane (IP) electronic conductivity λ_s is not clear. In this work, the relationship between crack parameters and the λ_s is obtained based on the two-dimensional (2D) multiple-relaxation time (MRT) lattice Boltzmann method (LBM). The LBM numerical model is validated by the normalized λ_s experiment applied on three different home-made cracked CLs, and the parameter study focus on crack width, length, quantity and phase angle are carried out. The results show that the decrease of λ_s has different sensitivity |k| to the parameters above. The crack width has little effect on λ_s decrease, and the |k_w| is 0.038. However, crack arm length and quantity show more significant impact, which |k_l| and |k_N| are 0.753 and 0.725, respectively. The CLs with different crack propagation directions show significant anisotropy on λ_s, and a 53.53% decrease in λ_s is observed between 0° and 90° crack phase angle change. To manufacture a high electronic conductivity CL, crack initiation and migration mitigation are highly encouraged.     

Finite-time adaptive fuzzy control for a class of output constrained nonlinear systems with dead-zone

The article investigates the finite-time adaptive fuzzy control for a class of nonlinear systems with output constraint and input dead-zone. First, by skillfully combining the barrier Lyapunov function, backstepping design method, and finite-time control theory, a novel adaptive state-feedback tracking controller is constructed, and the output constraint of the nonlinear system is not violated. Second, the fuzzy logic system is used to approximate unknown function in the nonlinear system. Third, the finite-time command filter is introduced to avoid the problem of “complexity explosion” caused by repeated differentiations of the virtual control signal in conventional backstepping control schemes. Meanwhile, a new saturation function is added in the compensating signal for filter error to improve control accuracy. Finally, based on Lyapunov stability analysis, all the signals of the closed-loop are proved to be semi-globally uniformly ultimately bounded, and the tracking error converges to a small neighborhood region of the origin in a finite time. A simulation example is presented to demonstrate the effectiveness for the proposed control scheme.     

PID Control of Planar Nonlinear Uncertain Systems in the Presence of Actuator Saturation

This paper investigates PID control design for a class of planar nonlinear uncertain systems in the presence of actuator saturation. Based on the bounds on the growth rates of the nonlinear uncertain function in the system model, the system is placed in a linear differential inclusion. Each vertex system of the linear differential inclusion is a linear system subject to actuator saturation. By placing the saturated PID control into a convex hull formed by the PID controller and an auxiliary linear feedback law, we establish conditions under which an ellipsoid is contractively invariant and hence is an estimate of the domain of attraction of the equilibrium point of the closed-loop system. The equilibrium point corresponds to the desired set point for the system output. Thus, the location of the equilibrium point and the size of the domain of attraction determine, respectively, the set point that the output can achieve and the range of initial conditions from which this set point can be reached. Based on these conditions, the feasible set points can be determined and the design of the PID control law that stabilizes the nonlinear uncertain system at a feasible set point with a large domain of attraction can then be formulated and solved as a constrained optimization problem with constraints in the form of linear matrix inequalities (LMIs). Application of the proposed design to a magnetic suspension system illustrates the design process and the performance of the resulting PID control law.      

Magnetic properties,phase evolution,hollow structure and biomedical application of hematite (α-Fe2O3) and QUAIPH

We investigate synthesis, phase evolution, hollow and porous structure and magnetic properties of quasi-amorphous intermediate phase (QUAIPH) and hematite (α-Fe₂O₃) nanostructure synthesized by annealing of akaganeite (β-FeOOH) nanorods. It is found that the annealing temperature determines the phase composition of the products, the crystal structure/size dictates the magnetic properties whereas the final nanorod morphology is determined by the starting material. Annealing of β-FeOOH at ～300 °C resulted in the formation of hollow QUAIPH nanorods. The synthesized material shows low-cytotoxicity, superparamagnetism and good transverse relaxivity, which is rarely reported for QUAIPH. The QUAIPH nanorods started to transform to porous hematite nanostructures at ～350 °C and phase transformation was completed at 600 °C. During the annealing, the crystal structure changed from monoclinic (akaganeite) to quasi-amorphous and rhombohedral (hematite). Unusually, the crystallite size first decreased (akaganeite → QUAIPH) and then increased (QUAIPH → hematite) during annealing whereas the nanorods retained particle shape. The magnetic properties of the samples changed from antiferromagnetic (akaganeite) to superparamagnetic with blocking temperature T_B = 84 K (QUAIPH) and finally to weak-ferromagnetic with the Morin transition at T_M = 244 K and high coercivity H_C = 1652 Oe (hematite). The low-cytotoxicity and MRI relaxivity (r₂ = 5.80 mM^?1 s^?1 (akaganeite), r₂ = 4.31 mM^?1 s^?1 (QUAIPH) and r₂ = 5.17 mM^?1 s^?1 (hematite)) reveal potential for biomedical applications.     

基于特征建模的TDD系统大气波导干扰控制体系研究

大气波导干扰是特定气象条件下发生的时分双工（time-division duplex，TDD）系统内干扰，是TDD移动通信系统大规模组网面临的顽疾。在总结分析大气波导干扰成因和分类等的基础上，对大气波导干扰进行建模和表征，验证了海量干扰源在时域和频域的功率集总特征，并结合大量4G/5G现网实测数据给出了典型条件下内陆波导和海面波导的量化干扰信号传播模型，对于干扰的预测和预防具有重要意义。基于干扰特征，给出了TDD系统预防大气波导干扰的帧结构与组网的4项设计原则，5G现网数据表明干扰控制方案有效，上行干扰下降10 dB以上，相关原则对于6G系统的设计也具有指导意义。     

Silver-substituted (Ag1-xCux)2ZnSnS4 solar cells from aprotic molecular inks

To battle the high open-circuit voltage deficit (V_OC,def) in kesterite (Cu₂ZnSnS₄ or CZTS) solar cells, a current field of research relates to point defect engineering by cation substitution. For example, by partly replacing Cu with an element of a larger ionic radius, such as Ag, the degree of Cu/Zn disorder decreases, and likewise does the associated band tailing. In this paper, solution-processed (Ag_1-xCu_x)₂ZnSnS₄ (ACZTS) samples are prepared through the aprotic molecular ink approach using DMSO as the solvent. The successful incorporation of silver into the CZTS lattice is demonstrated with relatively high silver concentrations, namely Ag/(Ag+Cu) ratios of 13% and 26%. The best device was made with 13% Ag/(Ag+Cu) and had an efficiency of 4.9%. The samples are compared to the pure CZTS sample in terms of microstructure, phase distribution, photoluminescence, and device performance. In the XRD patterns, a decrease in the lattice parameter c/a ratio is observed for ACZTS, as well as significant peak splitting with Ag addition for several of the characteristic kesterite XRD reflections. In addition to the improvement in efficiency, other advantageous effects of Ag-incorporation include enhanced grain growth and an increased band gap. A too high concentration of Ag leads to the formation of secondary phases such as SnS and Ag₂S as detected by XRD.     

Synthesis of Hollow Three-Dimensional Channels LiNi_(0.5)Mn_(1.5)O_4 Microsphere by PEO Soft Template Assisted with Solvothermal Method

A appropriate size with three-dimension(3 D) channels for lithium diffusion plays an important role in constructing highperforming LiNi_(0.5)Mn_(1.5)O_4(LNMO) cathode materials, as it can not only reduce the transport path of lithium ions and electrons, but also reduce the side effects and withstand the structural strain in the process of repetitive Li~+ intercalation/deintercalation. In this work, an e fficient method for designing the hollow LNMO microsphere with 3 D channels structure by using polyethylene oxide(PEO) as soft template agent assisted solvothermal method is proposed. Experimental results indicate that PEO can make the reagents mingle evenly and nucleate slowly in the solvothermal process, thus obtaining a homogeneous distribution of carbonate precursors. In the final LNMO products, the hollow 3 D channels structure obtained by the decomposition of PEO and carbonate precursor in the calcination can provide abundant electroactive zones and electron/ion transport paths during the charge/discharge process, which benefits to improve the cycling performance and rate capability. The LNMO prepared by adding 1 g PEO possesses the most outstanding electrochemical performance, which presented an excellent discharge capacity of 143.1 mAh g~(-1) at 0.1 C and with a capacity retention of 92.2% after 100 cycles at 1 C. The superior performance attributed to the 3 D channels structure of hollow microspheres, which provide uninterrupted conductive systems and therefore achieve the stable transfer for electron/ion.