Ion migration behavior and its interaction with sintering environment in cation conductor during flash sintering

Flash sintering has been reported in various ceramics. Nevertheless, anion and cation conductors exhibit different flash-sintering behaviors, and the interaction mechanism between the conductive species and the sintering environment has remained unclear. Herein, we report the flash-sintering phenomena of a typical cation conductor, Na₃Zr₂(SiO₄)₂(PO₄) with anode region surrounded by air and NaNO₃ environments. The results prove that the ionic behavior and joule heating distribution can be controlled by changing the electrode environment. Four possible scenarios describing the ion migration behavior and interaction with the environment are proposed for providing a guidance for controlling the ion interaction behavior during flash sintering.     

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.     

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.     

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.     

Irradiation-induced large bubble formation and grain growth in super nano-grained ceramic

In this work, 0.5TRPO•0.5Gd₂Zr₂O₇ ceramic with an average grain size of only ∼15 nm was prepared by a high pressure (5 GPa/520 °C) sintering method. Phase evolutions and microstructure changes of the as-fabricated super nano and micron-grained ceramics under a high-dose displacement damage induced by 300 keV Kr²⁺ ions were investigated. The results show that the super nano-grained ceramic has low degree of amorphization, obvious grain growth (2–3 times in grain size) and big Kr bubbles (10–68 nm) formation after irradiation. The micron-grained ceramic was severely amorphized after irradiation and many microcracks were formed parallel to its surface. The formation mechanism of Kr bubbles in the super nano-grained ceramic is on account of grain boundary diffusion and migration induced by the accumulation of the injecting Kr ions and irradiation defects. Nevertheless, microcracks formed in the micron-grained sample are caused by the accumulation of Kr atoms.     

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.     

High-resolution FIB-TEM-STEM structural characterization of grain boundaries in the high dielectric constant perovskite CaCu3Ti4O12

In this work, the grain boundaries composition of the polycrystalline CaCu₃Ti₄O₁₂ (CCTO) was investigated. A Focused Ion Beam (FIB)/lift-out technique was used to prepare site-specific thin samples of the grain boundaries interface of CCTO ceramics. Scanning transmission electron microscopy (STEM) coupled with energy dispersive X-ray spectrometry (EDXS) and Electron Energy Loss Spectroscopy (EELS) systems were used to characterize the composition and nanostructure of the grain and grain boundaries region. It is known that during conventional sintering, discontinuous grain growth occurs and a Cu-rich phase appears at grain boundaries. This Cu-rich phase may affect the final dielectric properties of CCTO but its structure and chemical composition remained unknown. For the first time, this high-resolution FIB-TEM-STEM study of CCTO interfacial region highlights the composition of the phases segregated at grain boundaries namely CuO, Cu₂O and the metastable phase Cu₃TiO_4.     

Ion beam induced evolution of surface morphology and optical properties of SnO2–ZnO nanocomposite thin films

SnO₂–ZnO nanocomposite thin films, prepared by a simple carbothermal reduction based vapor deposition method, were irradiated with 8 MeV Si³⁺ ions for engineering the morphological and optical properties. The surface morphology of the nanocomposites was studied by atomic force microscopy (AFM), while the optical properties were investigated by photoluminescence spectroscopy (PL) and Raman spectroscopy. AFM studies on the irradiated samples revealed growth of nanoparticles at lower fluence and a significant change in surface morphology leading to the formation of nanosheets and their aggregates at higher fluences. A tentative mechanism underlying the observed ion induced evolution of surface morphology of SnO₂–ZnO nanocomposite is proposed. PL studies revealed strong enhancement in the UV emissions from the nanocomposite thin film at lower fluence, while a drastic decrease in the UV emissions along with a significant enhancement in the defect emissions has been observed at higher fluences.