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.     

Numerical approach to analyze fluid flow in a type C tank for liquefied hydrogen carrier (part 1: Sloshing flow)

The demand for clean energy use has been increasing worldwide, and hydrogen has attracted attention as an alternative energy source. The efficient transport of hydrogen must be established such that hydrogen may be used as an energy source. In this study, we considered the influences of various parameters in the transportation of liquefied hydrogen using type C tanks in shipping vessels. The sloshing and thermal flows were considered in the transportation of liquefied hydrogen, which exists as a cryogenic liquid at ?253 °C. In this study, the sloshing flow was analyzed using a numerical approach. A multiphase sloshing simulation was performed using the volume of fluid method for the observation and analysis of the internal flow. First, a sloshing experiment according to the gas-liquid density ratio performed by other researchers was utilized to verify the simulation technique and investigate the characteristics of liquefied hydrogen. Based on the results of this experiment, a sloshing simulation was then performed for a type C cargo tank for liquefied hydrogen carriers under three different filling level conditions. The sloshing impact pressure inside of the tank was measured via simulation and subjected to statistical analysis. In addition, the influence of sloshing flow on the appendages installed inside of the type C tank (stiffened ring and swash bulkhead) was quantitatively evaluated. In particular, the influence of the sloshing flow inside of the type C tank on the appendages can be utilized as an important indicator at the design stage. Furthermore, if such sloshing impact forces are repeatedly experienced over an extended period of time under cryogenic conditions, the behavior of the tank and appendages must be analyzed in terms of fatigue and brittle failure to ensure the safety of the transportation operation.     

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.     

基于误差估值累加开环校正的诱导式欺骗检测方法

诱导式卫星欺骗干扰可诱导航空器逐渐偏离预定航迹，难以被发现，因此及时有效地检测干扰是飞行安全的保障。在现有紧组合导航体制基础上，设计了一种基于误差估值累加开环校正的紧组合导航结构，并证明了其性能与传统闭环校正紧组合导航性能等效。在此结构中，将紧组合导航系统与自适应序贯概率比检测方法结合，提出了一种基于误差估值累加开环校正的诱导式欺骗检测方法，融合紧组合导航信息与其他不受欺骗影响的导航信息，构建欺骗检测统计量进行诱导式欺骗检测。仿真结果表明，开环校正结构可避免随时间累加的惯性导航系统误差所导致的组合导航滤波器发散问题，同时欺骗检测方法可进一步提高算法对“最坏”情形下微小诱导式欺骗的检测效果。     

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.     

Engineering the hydrogen storage properties of the perovskite hydride ZrNiH3 by uniaxial/biaxial strain

In the present work, the bonding length, electronic structure, stability, and dehydrogenation properties of the Perovskite-type ZrNiH₃ hydride, under different uniaxial/biaxial strains are investigated through ab-initio calculations based on the plane-wave pseudo-potential (PW-PP) approach. The findings reveal that the uniaxial/biaxial compressive and tensile strains are responsible for the structural deformation of the ZrNiH₃ crystal structure, and its lattice deformation becomes more significant with decreasing or increasing the strain magnitude. Due to the strain energy contribution, the uniaxial/biaxial strain not only lowers the stability of ZrNiH₃ but also decreases considerably the dehydrogenation enthalpy and decomposition temperature. Precisely, the formation enthalpy and decomposition temperature are reduced from ?67.73 kJ/mol.H₂ and 521 K for non-strained ZrNiH₃ up to ?33.73 kJ/mol.H₂ and 259.5 K under maximal biaxial compression strain of ε = ?6%, and to ?50.99 kJ/mol.H₂ and 392.23 K for the maximal biaxial tensile strain of ε = +6%. The same phenomenon has been also observed for the uniaxial strain, where the formation enthalpy and decomposition temperature are both decreased to ?39.36 kJ/mol.H₂ and 302.78 K for a maximal uniaxial compressive strain of ε = - 12%, and to ?51.86 kJ/mol.H₂ and 399 K under the maximal uniaxial tensile strain of ε = +12%. Moreover, the densities of states analysis suggests that the strain-induced variation in the dehydrogenation and structural properties of ZrNiH₃ are strongly related to the Fermi level value of total densities of states. These ab-initio calculations demonstrate insightful novel approach into the development of Zr-based intermetallic hydrides for hydrogen storage practical applications.     

Analysis of operating limits and combustion state regulation for low-calorific value gases in industrial burners

The effective and efficient utilization of low-calorific value (LCV) gases has gained increasing attention in scientific research and industrial fields. In this study, the combustion characteristics of three LCV gases in practical devices are analyzed by using a nonadiabatic perfectly stirred reactor model. The complete steady-state solution in the temperature-residence time parameter space is obtained with arc-length continuation. The stable operation region is quantified by the eigenvalue analysis. The transition of solution curves is quantified with heat loss coefficient. Five key system parameters are systematically investigated on their effects on stability limits. With the combustion performance being quantified by a combustion state index, a combustion state regulation method is proposed to find the optimal regulation path of system parameters. Active subspace method is further applied to shorten the regulation step by identifying the active direction. The proposed method and findings are useful for optimal regulation of burning LCV gases in industrial burners.     

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.