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.     

Numerical investigations on flashback dynamics of premixed methane-hydrogen-air laminar flames

Injecting hydrogen into the natural gas network to reduce CO₂ emissions in the EU residential sector is considered a critical element of the zero CO₂ emissions target for 2050. Burning natural gas and hydrogen mixtures has potential risks, the main one being the flame flashback phenomenon that could occur in home appliances using premixed laminar burners. In the present study, two-dimensional transient computations of laminar CH₄ + air and CH₄ + H₂ + air flames are performed with the open-source CFD code OpenFOAM. A finite rate chemistry based solver is used to compute reaction rates and the laminar reacting flow. Starting from a flame stabilized at the rim of a cylindrical tube burner, the inlet bulk velocity of the premixture is gradually reduced to observe flashback. The results of the present work concern the effects of wall temperature and hydrogen addition on the flashback propensity of laminar premixed methane-hydrogen-air flames. Complete sequences of flame dynamics with gradual increases of premixture velocity are investigated. At the flame flashback velocities, strong oscillations at the flame leading edge emerge, causing broken flame symmetry and finally flame flashback. The numerical results reveal that flashback tendency increase with increasing wall temperature and hydrogen addition rate.     

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.     

Spray pressure variation effect on the properties of CdS thin films for photodetector applications

Herein, we report the photosensing property of CdS thin films. CdS thin films were coated onto glass substrates via a spray pyrolysis method using different spray pressures. Prepared films were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), and optical and photoluminescence spectroscopy. XRD analysis demonstrated the growth of crystalline CdS films with crystallite sizes varying from 26 to 29 nm depending on the pressure. The SEM and EDAX analyses revealed nearly-stoichiometric CdS films with smooth surfaces and slight variation in grain morphology due to pressure changes. Optical measurements showed a direct bandgap varying from 2.37 eV to 2.42 eV due to pressure changes. A photodetector was also fabricated using the grown CdS films; the fabricated photodetector exhibited good performance depending on the spray pressure. A spray pressure of 1.5 GPa resulted in high photoresponsivity and external quantum efficiency.     

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.     

Spray coating process variable and property analysis of UV-curable polyurethane acrylate coating on polycarbonate substrate

A series of spray coating experiments were conducted on an UV-curable, polyurethane-modified, acrylate-based coating formulation with the aim to control defects, coating thickness, and thickness variation. Statistical approaches including design of experiment, residual examination, analysis of variance, and t-test were used in designing the experiments and analyzing data. Viscosity of formulation, atomizing pressure, liquid feeding pressure, distance between nozzle and substrate, and travel speed of substrate were the process variables studied. The ranges of process variables that gave defect-free coating were identified and used in the subsequent experiments to determine process variables and interactions that had significant contribution to the changes in coating thickness and thickness variation. All process variables studied were found to have contribution to the change in coating thickness, but they showed no significant contribution to the variation of coating thickness. No interaction displayed significant contribution. Confirmation tests performed on extra samples prepared with varying coating thicknesses indicated a good agreement with the experimental results. Additional samples were tested for total transmittance, transmission haze, adhesion, surface roughness, hardness, scratch hardness, abrasion resistance, and durability to attack of car wash chemicals. Spray coated samples showed slight improvement in the total transmittance over the uncoated samples, while maintaining the transmission haze and exhibiting rougher surfaces. Only samples with thin coatings were found to possess sufficient adhesion to the substrate. These thin coatings gave improved hardness, scratch hardness, and durability to car wash attack to the level comparable to commercial coated polycarbonate headlamp lenses, whilst giving better abrasion resistance.     

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.     

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.