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.     

The effects of washing a collagen sample prior to TEM examination

Transmission electron microscopy (TEM) is an important analysis technique to visualize (bio)macromolecules and their assemblies, including collagen fibers. Many protocols for TEM sample preparation of collagen involve one or more washing steps to remove excess salts from the dispersion that could hamper analysis when dried on a TEM grid. Such protocols are not standardized and washing times as well as washing solvents vary from procedure to procedure, with each research group typically having their own protocol. Here, we investigate the influence of washing with water, ethanol, but also methanol and 2-propanol, for both mineralized and unmineralized collagen samples via a protocol based on centrifugation. Washing with water maintains the hydrated collagen structure and the characteristic banding pattern can be clearly observed. Conversely, washing with ethanol results in dehydration of the fibrils, often leading to aggregation of the fibers and a less obvious banding pattern, already within 1 min of ethanol exposure. As we show, this process is fully reversible. Similar observations were made for methanol and propanol. Based on these results, a standardized washing protocol for collagenous samples is proposed.     

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.     

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.     

基于滚动摩擦作用下玉米颗粒在模拟筒仓卸料中的力链分析（网络首发、推荐阅读）

针对颗粒滚动摩擦作用对筒仓中玉米颗粒的力链空间分布进行研究，通过EDEM离散元软件建立筒仓模型与仿真玉米颗粒模型进行卸粮仿真模拟，并与筒仓卸料实验作流态对比，验证模型与仿真结果的准确性。通过对模拟仓进行切片观察和数据处理，对比分析了不同摩擦情况下力链的细观参数随时间演化规律。模拟结果表明：颗粒间摩擦系数越大，卸粮完成的最终时间越长；颗粒间滚动摩擦系数越小，颗粒由整体流转变为管状流的时间越早。对于有漏斗的筒仓来说，减小颗粒间摩擦会改变整体流和管状流之间的极限，从而增加产生管状流的面积。标准滚动摩擦系数下玉米颗粒在卸料过程中会出现起拱-塌陷效应；减小滚动摩擦，玉米颗粒卸料较稳定，未出现起拱的应力突增、以及拱塌陷的应力衰减；增大颗粒间滚动摩擦不但会增加拱效应，且出现成拱高度距离漏斗口更高。     

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.     

High-temperature oxidation behavior of monolithic Zr3[Al(Si)]4C6 and its composite incorporating 30vol% ZrB2-SiC: Providing a basis for broadening the service temperature

To provide a basis for the high-temperature oxidation of ultra-high temperature ceramics (UHTCs), the oxidation behavior of Zr₃[Al(Si)]₄C₆ and a novel Zr₃[Al(Si)]₄C₆-ZrB₂-SiC composite at 1500 °C were investigated for the first time. From the calculation results, the oxidation kinetics of the two specimens follow the oxidation dynamic parabolic law. Zr₃[Al(Si)]₄C₆ exhibited a thinner oxide scale and lower oxidation rate than those of the composite under the same conditions. The oxide scale of Zr₃[Al(Si)]₄C₆ exhibited a two-layer structure, while that of the composite exhibited a three-layer structure. Owing to the volatilization of B₂O₃ and the active oxidation of SiC, a porous oxide layer formed in the oxide scale of the composite, resulting in the degradation of its oxidation performance. Furthermore, the cracks and defects in the oxide scale of the composite indicate that the reliability of the oxide scale was poor. The results support the service temperature of the obtained ceramics.