A high-throughput chaotic advection microreactor for preparation of uniform and aggregated barium sulfate nanoparticles

A high-throughput (105.5 g/h) passive four-stage asymmetric oscillating feedback microreactor using chaotic mixing mechanism was developed to prepare aggregated Barium sulfate (BaSO₄) particles of high primary nanoparticle size uniformity. Three-dimensional unsteady simulations showed that chaotic mixing could be induced by three unique secondary flows (i.e., vortex, recirculation, and oscillation), and the fluid oscillation mechanism was examined in detail. Simulations and Villermaux–Dushman experiments indicate that almost complete mixing down to molecular level can be achieved and the prepared BaSO₄ nanoparticles were with narrow primary particle size distribution (PSD) having geometric standard deviation, σ_g, less than 1.43 when the total volumetric flow rate Q_total was larger than 10 ml/min. By selecting Q_total and reactant concentrations, average primary particle size can be controlled from 23 to 109 nm as determined by microscopy. An average size of 26 nm with narrow primary PSD (σ_g = 1.22) could be achieved at Q_total of 160 ml/min.     

一种“KooN”结构的马尔可夫简并建模和简化计算的方法

IEC61508等标准提出了几种计算安全仪表系统需求时平均失效概率的方法,但是,对于具有冗余配置的复杂系统,随着组件数量的增加,系统的中间状态数量快速增长,用户难以构建马尔可夫模型,即便借助计算机来建模运算也较为耗时。提出了一种同型“K oo N”简并状态的马尔可夫建模的通用方法,首先是根据降级状态进行判断,将符合条件的状态进行简并,然后对标记为危险失效状态的概率进行计算。通过严格的理论推导,该简并状态方法可以在不损失精度的前提下简化马尔可夫建模。     

Spin-state regulating of cobalt assisted by iron doping and coordination for enhanced oxygen evolution reaction

Customizing catalysts from the electronic structure, such as spin state, is an effective but challenging strategy for oxygen evolution reaction (OER). Herein, an ultrafine Co–Fe material highly dispersed on nitrogen carbide matrix is fabricated by coordination polymer and self-templating method to scrutinize the impact of spin state of Co on OER through Fe doping. The optimized catalyst shows boosted OER performance, which only requires overpotential of 333 mV at 10 mA cm^?2, outperforming other control samples and commercial RuO₂. The elevated local spin states of Co by Fe doping lead to charge transfer acceleration and fast generation of oxygenated intermediates, which is proved to account for the OER elevation. In addition, the long-term stability of Co–Fe material is guaranteed by the strong coordination of Co/Fe to the melamine-formaldehyde resin, which is used to adsorb metal ions, contributing to the high dispersion of active sites during the OER process.     

Photoluminescence properties of Eu-doped WO3-Eu2(WO4)3 composites and single-phase Eu2(WO4)3 powders

The development of highly stable and efficient oxide-based red phosphors is urgently required for next-generation lighting devices. Herein, we report the micro/crystal structures and luminescent properties of single-phase Eu₂(WO₄)₃ and Eu³⁺-doped WO₃-Eu₂(WO₄)₃ composite phosphors prepared by a one-step conventional solid-state reaction method in air atmosphere. As increasing Eu contents in the mixtures of WO₃ and Eu₂O₃, the intensities of the X-ray diffraction peaks of Eu₂(WO₄)₃ increased while that of WO₃ decreased. The photoluminescence intensity of the synthesized phosphors increased with increase in the Eu content when calcined at 900 °C, while it degraded at a higher temperature. Red-emitting single-phase Eu₂(WO₄)₃ powders were successfully obtained when the WO₃ and Eu₂O₃ powders were calcined in the ratio of 3:1. The intensity of the red emission spectra of the Eu₂(WO₄)₃ phosphor was higher than those of the 6, 12, and 24 at.% Eu-added WO₃ composites at excitation wavelengths of 394 and 465 nm. On the other hand, the intensity of emission from the single-phase phosphor was lower than that of the Eu-doped WO₃-Eu₂(WO₄)₃ composites under excitation of UV light at 254 nm. Thus, we propose two prospective phosphors for application as red phosphors at various wavelengths.     

Description of the thermodynamic properties and fluid-phase behavior of aqueous solutions of linear,branched, and cyclic amines

The SAFT-γ Mie group-contribution equation of state is used to represent the fluid-phase behavior of aqueous solutions of a variety of linear, branched, and cyclic amines. New group interactions are developed in order to model the mixtures of interest, including the like and unlike interactions between alkyl primary, secondary, and tertiary amine groups (NH₂, NH, N), cyclic secondary and tertiary amine groups (cNH, cN), and cyclic methine-amine groups (cCHNH, cCHN) with water (H₂O). The group-interaction parameters are estimated from appropriate experimental thermodynamic data for pure amines and selected mixtures. By taking advantage of the group-contribution nature of the method, one can describe the fluid-phase behavior of mixtures of molecules comprising those groups over broad ranges of temperature, pressure, and composition. A number of aqueous solutions of amines are studied including linear, branched aliphatic, and cyclic amines. Liquid–liquid equilibria (LLE) bounded by lower critical solution temperatures (LCSTs) have been reported experimentally and are reproduced here with the SAFT-γ Mie approach. The main feature of the approach is the ability not only to represent accurately the experimental data employed in the parameter estimation, but also to predict the vapor–liquid, liquid–liquid, and vapor–liquid–liquid equilibria, and LCSTs with the same set of parameters. Pure compound and binary phase diagrams of diverse types of amines and their aqueous solutions are assessed in order to demonstrate the main features of the thermodynamic and fluid-phase behavior.     

Fracture behavior of solid electrolyte LATP material based on micro-pillar splitting method

The NASICON type solid electrolyte LATP is a promising candidate for all-solid-state Li-ion batteries considering energy density and safety aspects. To ensure the performance and reliability of batteries, crack initiation and propagation within the electrolyte need to be suppressed, which requires knowledge of the fracture characteristics. In the current work, micro-pillar splitting was applied to determine the fracture toughness of LATP material for different grain orientations. The results are compared with data obtained using a conventional Vickers indentation fracture (VIF) approach. The fracture toughness obtained via micro-pillar splitting test is 0.89 ± 0.13 MPa?m^1/2, which is comparable to the VIF result, and grain orientation has no significant effect on the intrinsic fracture toughness. Being a brittle ceramic material, the effect of pre-existing defects on the toughness needs to be considered.     

Modulation of electrical transport in calcium cobaltite ceramics and thick films through microstructure control and doping

Ca₃Co₄O₉ is a promising p-type thermoelectric oxide material having intrinsically low thermal conductivity. With low cost and opportunities for automatic large scale production, thick film technologies offer considerable potential for a new generation of micro-sized thermoelectric coolers or generators. Here, based on the chemical composition optimized by traditional solid state reaction for bulk samples, we present a viable approach to modulating the electrical transport properties of screen-printed calcium cobaltite thick films through control of the microstructural evolution by optimized heat-treatment. XRD and TEM analysis confirmed the formation of high-quality calcium cobaltite grains. By creating 2.0 at% cobalt deficiency in Ca_2.7Bi_0.3Co₄O_9+δ, the pressureless sintered ceramics reached the highest power factor of 98.0 μWm^?1 K^-2 at 823 K, through enhancement of electrical conductivity by reduction of poorly conducting secondary phases. Subsequently, textured thick films of Ca_2.7Bi_0.3Co_3.92O_9+δ were efficiently tailored by controlling the sintering temperature and holding time. Optimized Ca_2.7Bi_0.3Co_3.92O_9+δ thick films sintered at 1203 K for 8 h exhibited the maximum power factor of 55.5 μWm^?1 K^-2 at 673 K through microstructure control.     

Effects of the joining process on the microstructure and properties of liquid-phase-sintered SiC-SiC joints formed with Ti foil

The joining of liquid-phase sintered SiC (LPS-SiC) ceramics was conducted using spark plasma sintering (SPS), through solid state diffusion bonding, with Ti-metal foil as a joining interlayer. Samples were joined at 1400 °C, under applied pressures of either 10 or 30 MPa, and with different atmospheres (argon, Ar, vs. vacuum). It was demonstrated that the shear strength of the joints increased with an increase in the applied joining pressure. The joining atmosphere also affected on both the microstructure and shear strength of the SiC joints. The composition and microstructure of the interlayer were examined to understand the mechanism. As a result, a SiC-SiC joining with a good mechanical performance could be achieved under an Ar environment, which in turn could provide a cost-effective approach and greatly widen the applications of SiC ceramic components with complex shape.     

Compositional design,structure stability,and microwave dielectric properties in Ca3MgBGe3O12 (B = Zr,Sn) garnet ceramics with tetravalent cations on B-site

Two garnet-structured Ca₃MgBGe₃O₁₂ (B = Zr, Sn) ceramics with tetravalent cations at B-site were prepared by conventional solid state reaction. The crystal structure, microstructure evolution, and microwave dielectric performance were investigated using X-ray powder diffraction, Rietveld refinement, scanning electron microscopy, Raman spectroscopy, and infrared spectroscopy techniques. Dense Ca₃MgZrGe₃O₁₂ and Ca₃MgSnGe₃O₁₂ ceramics were obtained at sintering temperatures of 1420 and 1400 °C, respectively. The dielectric constant, unloaded quality factor, and temperature coefficient of resonance frequency of Ca₃MgZrGe₃O₁₂ were 10.80 ± 0.2; 79,600 ± 1000 GHz (f = 12.61 GHz); and ?66.8 ± 1 ppm/°C, respectively, and the corresponding values for Ca₃MgSnGe₃O₁₂ were 9.68 ± 0.2; 83,400 ± 1000 GHz (f = 14.19 GHz); and ?57.9 ± 1 ppm/°C, respectively. The dielectric performances of the two ceramics were compared by analyzing the ionic polarizability, packing fraction, and bond valence. The intrinsic dielectric properties were predicted by fitting the infrared reflectivity spectra.