New horizon in mechanochemistry—high-temperature,high-pressure mechanical synthesis in a planetary ball mill—with magnesium hydride synthesis as an example

A new route of materials synthesis, namely, high-temperature, high-pressure reactive planetary ball milling (HTPRM), is presented. HTPRM allows for the mechanosynthesis of materials at fully controlled temperatures of up to 450 °C and pressures of up to 100 bar of hydrogen. As an example of this application, a successful synthesis of magnesium hydride is presented. The synthesis was performed at controlled temperatures (room temperature (RT), 100, 150, 200, 250, 300, and 325 °C) while milling in a planetary ball mill under hydrogen pressure ($>$50 bar). Very mild milling conditions (250 rpm) were applied for a total milling time of 2 h, and a milling vial with a relatively small diameter (φ = 53 mm, V = ～0.06 dm³) was used. The effect of different temperatures on the synthesis kinetics and outcome were examined. The particle morphology, phase composition, reaction yield, and particle size were measured and analysed by scanning electron microscopy, X-ray diffraction, differential scanning calorimetry (DSC) techniques. The obtained results showed that increasing the temperature of the process significantly improved the reaction rate, which suggested the great potential of this technique for the mechanochemical synthesis of materials.     

Model of reactive precipitation process of preparation nano-ZnO in rotating packed bed: Contribution ratio

With excellent micromixing characteristic of rotating packed bed (RPB), many nanoparticles with small average size, narrower distribution and good morphology had been successfully and continuously prepared. To reveal complex crystal process, an empirical model were developed to simulate nano-ZnO by considering mass changed, population balance equation, growth rate G, nucleation rate B, drop sizes D_i, and resident time t. The predicted particle sizes were shown good agreement with experimental data with error of ±10%. Therefore, it was further adopted to predict the effects of rotating speed, liquid flow rate and reactant concentration on the mean particle size. To look more deeply insight in this process, their contribution ratios were further analyzed. The proposed empirical models were of great helpful to obtain suitable operation conditions for preparing much better properties of nanoparticles with fewer experiments. It was also beneficial to produce other nanoparticles in RPB.     

Novel TiC-based composites with enhanced mechanical properties

Novel TiC-based composites were synthesized by reactive hot-pressing at 1800 °C for 1 h with ZrB₂ addition as a sintering aid for the first time. The effects of ZrB₂ contents on the phase composition, microstructure evolution, and mechanical properties were reported. Based on the reaction and solid solution coupling effects between ZrB₂ and TiC, the product ZrC may be partially or completely dissolved into the TiC matrix, and then phase separation within the miscibility gap is observed to form lamellar nanostructured ZrC-rich (Zr, Ti)C. The TiC-10 mol.% ZrB₂ (starting batch composition) exhibits good comprehensive mechanical properties of hardness 27.7 ± 1.3 GPa, flexural strength 659 ± 48 MPa, and fracture toughness of 6.5 ± 0.6 MPa m^1/2, respectively, which reach or exceed most TiC-based composites using ceramics as sintering aids in the previous reports.     

Grain orientation evolution and multi-scale interfaces enhanced thermoelectric properties of textured Sr0.9La0.1TiO3 based ceramics

Sr_0.9La_0.1TiO₃ based textured ceramics (SLTT-S3T) with a texture fraction of 0.81 are successfully fabricated by the reactive template grain growth method, in which Sr_0.9La_0.1TiO₃/20 wt%Ti was used as matrix and 10 wt% plate-like Sr₃Ti₂O₇ template seeds were used as templates. The phase transition, microstructure evolution, and the anisotropic thermoelectric properties of SLTT-S3T ceramics were investigated. The results show that the ceramics are mainly composed of Sr_0.9La_0.1TiO₃ and rutile TiO₂ phases. Grains grow with a preferred orientation along (h00). A maximum ZT of 0.26 at 1073 K was achieved in the direction perpendicular to the tape casting direction. The low lattice thermal conductivity of 1.9 W/(m K) at 1073 K was obtained decreased by 34%, 40%, and 38% compared with non-textured, SrTiO₃ and Sr_0.9La_0.1TiO₃ ceramics prepared by the same process, can be attributed to the enhanced phonon scattering by the complex multi-scale boundaries and interfaces. This work provides a strategy of microstructural design for thermoelectric oxides to decrease intrinsic lattice thermal conductivity and further regulate thermoelectric properties via texture engineering.     

Evaluation of hydrodynamic behavior of the perforated gas distributor of industrial gas phase polymerization reactor using CFD-PBM coupled model

A 2D computational fluid dynamics (Eulerian–Eulerian) multiphase flow model coupled with a population balance model (CFD-PBM) was implemented to investigate the fluidization structure in terms of entrance region in an industrial-scale gas phase fluidized bed reactor. The simulation results were compared with the industrial data, and good agreement was observed. Two cases including perforated distributor and complete sparger were applied to examine the flow structure through the bed. The parametric sensitivity analysis of time step, number of node, drag coefficient, and specularity coefficient was carried out. It was found that the results were more sensitive to the drag model. The results showed that the entrance configuration has significant effect on the flow structure. While the dead zones are created in both corners of the distributors, the perforated distributor generates more startup bubbles, heterogeneous flow field, and better gas–solid interaction above the entrance region due to jet formation.     

Mg0.5NixZn0.5-xFe2O4 spinel as a sustainable magnetic nano-photocatalyst with dopant driven band shifting and reduced recombination for visible and solar degradation of Reactive Blue-19

Focussing on visible light active ferrites for high performance removal of noxious pollutants, we report the synthesis of Mg_0.5Ni_xZn_0.5-xFe₂O₄ (x = 0.1, 0.2, 0.3, 0.4, & 0.5) ferrite nanoparticle for degradation of reactive blue-19 (RB-19). Lattice parameters calculated using intense X-ray diffraction (XRD) peaks and Nelson-Riley plots (N-R plot) are in well agreement with each other. The sample Mg_0.5Ni_0.4Zn_0.1Fe₂O₄ (M5N4) exhibits best performance with 99.5% RB-19 degradation in 90 min under visible light. Photoluminescence (PL) results confirm that recombination of charge carriers is highly reduced in the photocatalyst. Scavenging experiments suggest that O₂⁻ radicals were the dominant species responsible for photocatalytic performance. The photocatalytic mechanism was explained in terms of dopant driven shifting of conduction bands and valence bands (calculated by Mott-Schottky plots). The thermodynamic probability of radical generation along with role of redox cycles of metal ions has been discussed in the mechanism. The dye degradation was ascertained by detection of intermediates via mass spectrometry analysis and a possible degradation route was also predicted. The findings in this work provide intriguing opportunities to modify the electronic band structure of spinel ferrites for visible and solar light photocatalytic activity for environmental detoxification.     

Triphenylphosphonium (TPP)-Based Antioxidants: A New Perspective on Antioxidant Design

Mitochondrial oxidative damage and dysfunction contribute to a wide range of human diseases. Considering the limitation of conventional antioxidants and that mitochondria are the main source of reactive oxygen species (ROS) which induce oxidative damage, mitochondria-targeted antioxidants which can selectively block mitochondrial oxidative damage and prevent various types of cell death have been widely developed. As a lipophilic cation, triphenylphosphonium (TPP) has been commonly used in designing mitochondria-targeted antioxidants. Conjugated with the TPP moiety, antioxidants can achieve more than 1000-fold higher mitochondrial concentration depending on cell membrane potentials and mitochondrial membrane potentials. Herein we discuss the deficiencies of conventional antioxidants and the advantages of mitochondrial targeting, and review various types of TPP-based mitochondria-targeted antioxidants. These provide theoretical and background support for the design of new anti-oxidant.     

中子平衡节块离散纵标法及CMFD加速技术研究

本文基于横向积分离散纵标方程,解析得到横向积分通量中出射通量与入射通量的关系,并根据类似于扩散方程节块展开法的输运节块中子平衡方程形式,得到了一种高效的节块离散纵标法数值迭代策略。数值结果表明,本文提出的方法可行且数值结果正确。此外,粗网有限差分(CMFD)加速技术在节块离散纵标法中也取得了非常好的应用效果。     

Chemically modified organic/inorganic nanoporous composite particles for the adsorption of reactive black 5 from aqueous solution

In the present work, we report a chemically modified polyacrylamide/silica nanoporous composite adsorbent for the removal of reactive black 5 (RB5) azo dye from aqueous solutions. The composite adsorbent was synthesized in a packed bed and modified by ethylenediamine (EDA). The adsorbent was characterized by Fourier transformation infrared (FT-IR), thermogravimetric analysis (TGA), thermoporometry, Brunauer, Emmett and Teller (BET) method and scanning electron microscopy (SEM). Mechanical stability of the adsorbent was examined in a packed bed by following the back-pressure of the column. Pore diameter of the composite adsorbent in dry and wet states was estimated to be about 18.71 nm and 12.61 nm, respectively. Adsorption experiments were performed in batch mode and effect of various operational parameters on the adsorption capability of the adsorbent was studied systematically. The maximum adsorption capacity of the modified composites was found to be 454.5 mg RB5/g of adsorbent. The equilibrium data were analyzed by Langmuir, Freundlich, Sips, BET and Redlich–Peterson isotherm models and found to fit well to the BET isotherm. The data kinetically followed the pseudo-second-order model. High adsorption capacity, fast removal mechanism, and good mechanical stability are three advantages of the presented composite for the removal of RB5.     

A novel Ag–CuAlO2 sealant for reactive air brazing of 3YSZ and AISI 310S

Based on reactive air brazing (RAB), we designed a new type of sealant (Ag–xCuAlO₂) for joining 3 mol.% yttria-stabilized zirconia (YSZ) ceramics and AISI 310S stainless steel. The CuAlO₂ content affected the wettability of the sealant on the YSZ surface, and the joints had a high shear strength when Ag–2 wt.%CuAlO₂, which had a small contact angle on the YSZ substrate, was used as the sealant. In addition, the thickness of the oxide layer was reduced compared to that for the Ag–CuO sealant. The effects of the processing parameters on the microstructure and shear strength of the joints were investigated, and the as-brazed joints reached their highest shear strength (93.7 MPa) when brazed at 1040 °C for 30 min. After high-temperature oxidation at 800 °C for 200 h, the shear strength of the joints remained at 50 MPa, and no apparent change in the microstructure was observed, proving that the joints possessed excellent oxidation resistance.