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.     

Optical and electrical properties of ITO film on flexible fluorphlogopite substrate

Indium Tin Oxide (ITO) films were prepared, at room temperature, on a fluorphlogopite substrate using magnetron sputtering technology. At various temperatures of 500 °C, 600 °C, 700 °C, 800 °C, and 900 °C, the samples were (had) annealed for 2 h (a 2-h duration). The results showed improvement in the crystalline performance of ITO film at selected annealing temperatures, with a significant reduction in resistivity at 800 °C. The lowest resistivity is 4.08 × 10^?4 Ω-cm, which is nearly an order of magnitude lower than the unannealed sample. All samples have an average light transmittance above 85% in the visible light range (400–800 nm), and with increasing annealing temperature, the average light transmittance tends to decrease. Besides, at the sensitive wavelength of 550 nm, the light transmittance is as high as 93.74%. The sheet resistance testing of the sample was through the number of bending times, which revealed that with the increase of the number of bending, the sheet resistance increases. However, after 1200 bending times, the change rate of the sheet resistance remains below 5%. Thus, the ITO film prepared on the flexible fluorphlogopite substrate revealed excellent optical and electrical properties, good flexibility, and improved stability after high-temperature annealing, which guarantees successful application in flexible electronic devices.     

Sputtered Fe1·5CoNi0.5 coating: An improved protective coating for SOFC interconnect applications

In an attempt to optimize the properties of FeCoNi coating for planar solid oxide fuel cell (SOFC) interconnect application, the coating composition is modified by increasing the ratio of Fe/Ni. An Fe_1·5CoNi_0.5 (Fe:Co:Ni = 1.5:1:0.5, atomic ratio) metallic coating is fabricated on SUS 430 stainless steel by magnetron sputtering, followed by oxidation in air at 800°C. The Fe_1·5CoNi_0.5 coating is thermally converted to (Fe,Co,Ni)₃O₄ and (Fe,Co,Mn,Ni)₃O₄ without (Ni,Co)O particles. After oxidation for 1680 h, no further migration of Cr is detected in the thermally converted coating region. A low oxidation rate of 5.9 × 10^?14 g² cm^?4 s^?1 and area specific resistance of 12.64 mΩ·cm² is obtained for Fe_1·5CoNi_0.5 coated steels.     

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.     

Morphology-controlled fabrication of nanostructured WO3 thin films by magnetron sputtering with glancing angle deposition for enhanced efficiency photo-electrochemical water splitting

Herein, the tungsten trioxide (WO₃) nanostructure thin films with different morphologies are firstly fabricated by magnetron sputtering with glancing angle deposition technique (MS-GLAD), followed by the post annealed treatment process in air ambient for 2 h. It is demonstrated that the geometry of MS-GLAD setup, mainly substrate position, played a crucial role in determining the morphology, crystallinity, optical transmittance, and photo-electrochemical (PEC) performance of the WO₃ nanostructured thin film. With the different substrate positions in the MS-GLAD system, the WO₃ nanorod film layer could be precisely changed to combine an underlying dense layer with a nanorod layer and then nanocolumnar film. Moreover, the prepared samples' chemical composition and work function are studied by X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS), respectively. The combining WO₃ nanostructure produced high PEC efficiency compared to the single layer of the WO₃ nanorods sample and the dense WO₃ thin film sample. Thus, morphology-controlled nanostructure film based on the MS-GLAD technique in our study provides a simple approach to enhance the photo-anode for PEC water splitting application.     

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.     

Complex study of protective Cr3C2–NiAl coatings deposited by vacuum electro-spark alloying,pulsed cathodic arc evaporation,magnetron sputtering,and hybrid technology

Coatings were obtained by vacuum electro-spark alloying (VESA), pulsed cathodic arc evaporation (PCAE), magnetron sputtering (MS) techniques and VESA-PCAE-MS hybrid technology using Cr₃C₂–NiAl electrodes. The structure of the coatings was analyzed using scanning and transmission electron microscopy, X-ray diffraction and energy-dispersive spectroscopy. Mechanical properties were determined by nanoindentation, while tribological properties were assessed using pin-on-disk tribometer. Corrosion resistance was estimated by voltammetry in 1 N H₂SO₄ and 3.5%NaCl solutions. Oxidation resistance tests were performed at 800°С in air. The VESA coating had the highest thickness, low friction coefficient and high wear resistance. PCAE coating demonstrated the highest hardness (24 GPa) and elastic recovery (59%), oxidation resistance and superior corrosion resistance both in 1 N H₂SO₄ (i_corr = 70 μА/cm²) and 3.5%NaCl (i_corr = 0.74 μА/cm²) solutions. The MS coating had average mechanical properties and low corrosion current density (71 μА/cm²) in 1 N H₂SO₄. Deposition of coatings using VESA-PCAE-MS hybrid technology led to an increase in corrosion and oxidation resistance at least by 1.5 times in comparison with the VESA coating.     

Sputtered Ir–Ru based catalysts for oxygen evolution reaction: Study of iridium effect on stability

Magnetron sputtered low-loading iridium-ruthenium thin films are investigated as catalysts for the Oxygen Evolution Reaction at the anode of the Proton Exchange Membrane Water Electrolyzer. Electrochemical performance of 50 nm thin catalysts (Ir pure, Ir–Ru 1:1, Ir–Ru 1:3, Ru pure) is tested in a Rotating Disk Electrode. Corresponding Tafel slopes are measured before and after the CV-based procedure to compare the activity and stability of prepared compounds. Calculated activities prior to the procedure confirm higher activity of ruthenium-containing catalysts (Ru pure > Ir–Ru 1:3 > Ir–Ru 1:1 > Ir pure). However, after the procedure a higher activity and less degradation of Ir–Ru 1:3 is observed, compared to Ir–Ru 1:1, i.e. the sample with a higher amount of unstable ruthenium performs better. This contradicts the expected behavior of the catalyst. The comprehensive chemical and structural analysis unravels that the stability of Ir–Ru 1:3 sample is connected to RuO₂ chemical state and hcp structure. Obtained results are confirmed by measuring current densities in a single cell.     

Fabrication,structural and vibrational properties,and physical and optical properties tailoring of nanocrystalline MoS2 films

The modification and tuning features of nanostructured films are of great interest because of controllable and distinctive inherent properties in these materials. Here, nanocrystalline MoS₂ films were fabricated on the stainless steels by a radio frequency magnetron sputtering at ambient temperature. X-ray photoelectron spectroscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction and Raman scattering spectroscopy were used to study the chemical state, chemical composition, crystal structure and vibrational properties of the fabricated MoS₂ films. The bias voltage dependent structural evolution and its influence on the optical properties of MoS₂ nanocrystalline films were systematically investigated. Besides, the residual stresses of MoS₂ nanocrystalline films were explored by employing sin²ψ approach. X-ray diffraction demonstrates that the nanocrystalline MoS₂ films have single-phase hexagonal crystal structure. All MoS₂ films are polycrystalline in nature. The bandgap values are found to be intensively dependent on bias voltage. Our findings show that the nanocrystalline MoS₂ films with different physical properties and intense quantum confinement effect can be realized through adjusting bias voltages. This work may provide deep insight for realizing transitional metal dichalcogenide-based nanostructured film optoelectronic devices with tunable physical properties through a traditional, very cost-effective, and large-scale fabrication method.