Hydrogen production through dry reforming of biogas using a porous electrochemical cell: Effects of a cobalt catalyst in the electrode and mixing of air with biogas

This paper reports the performance of porous Gd-doped ceria (GDC) electrochemical cells with Co metal in both electrodes (cell No. 1) and with Ni metal in the cathode and Co metal in the anode (cell No. 2) for CO₂ decomposition, CH₄ decomposition, and the dry reforming reaction of a biogas with CO₂ gas (CH₄ + CO₂ → 2H₂ + 2CO) or with O₂ gas in air (3CH₄ +?1.875CO₂ +?1.314O₂ → 6H₂ +?4.875CO +?0.7515O₂). GDC cell No. 1 produced H₂ gas at formation rates of 0.055 and 0.33?mL-H₂/(min?m²-electrode) per 1?mL-supplied gas/(min?m²-electrode) at 600?°C and 800?°C, respectively, by the reforming of the biogas with CO₂ gas. Similarly, cell No. 2 produced H₂ gas at formation rates of 0.40?mL-H₂/(min?m²) per 1?mL-supplied gas/(min?m²) at 800?°C from a mixture of biogas and CO₂ gas. The dry reforming of a real biogas with CO₂ or O₂ gas at 800?°C proceeded thermodynamically over the Co or Ni metal catalyst in the cathode of the porous GDC cell. Faraday's law controlled the dry reforming rate of the biogas at 600?°C in cell No. 2. This paper also clarifies the influence of carbon deposition, which originates from CH₄ pyrolysis (CH₄ → C + 2H₂) and disproportionation of CO gas (2CO → C + CO₂), on the cell performance during dry reforming. The dry reforming of a biogas with O₂ molecules from air exhibits high durability because of the oxidation of the deposited carbon by supplied air.     

Preparation of nanocrystalline MoSi2 with enhanced lithium storage by sol–gel and carbonthermal reduction method

Herein nanocrystalline MoSi₂ with enhanced lithium storage was successfully synthesized via a sol-gel and carbonthermal reduction method. Reduction of the gel mixture of Mo precursor and Si precursor by carbon at a desired temperature resulted in the formation of MoSi₂ nanoparticles. The gel mixture was obtained through the hydrolysis of TEOS and ammonium molybdate and the polymerization of hydrolysis products of TEOS. The reducing agent carbon was produced via decarburition of sucrose's hydrolysis products, which have been wrapped in the gel during its formation process. Addition of HCl to the mixed solution controlled the hydrolysis and polymerization rate, and enabled the formation of a gel mixture with homogeneously distributed hydrolysis products of ammonium molybdate, TEOS and sucrose. This achievement likely generates a novel route to synthesize non-oxide compounds such as silicide, carbide through the sol–gel and carbonthermal reduction process. In addition, the as-received MoSi₂ nanoparticles showed considerable activities in the reversible lithiation and delithiation process. When using as an anode for Li-ion batteries, MoSi₂ nanoparticles delivered a specific capacity of 325 mAh g^?1 at C/12 and showed an increasing capacity with cycling.     

CO2 laser-assisted preparation of transparent Eu2Ti2O7 thin films

We present a laser-assisted preparation of transparent europium-titanate Eu₂Ti₂O₇ thin films with tailored structural and optical properties. We have evaluated the effects of the irradiation time on the structural and the optical properties of the films. This approach allows the preparation of nanocrystalline crack-free films and micro patterns. The amorphous thin films were prepared by a sol-gel method. The films were annealed by a CO₂ laser beam for various time intervals. The laser irradiation induced a crystallization process that resulted in the formation of Eu₂Ti₂O₇ nanocrystals. The nanocrystals regularly grew with increasing irradiation time reaching the size from 25?nm to 45?nm. A film of a thickness 480?nm exhibited an optical transmission of 91.9% that is close to the maximal theoretical limit. The film's refractive index at 632?nm was 2.26. A micrometric pattern was prepared by a direct laser writing followed by a wet chemical etching. Feasibility of the demonstrated approach, together with the high film's quality, and europium-titanate chemical resistivity open up many opportunities for advanced applications. The approach can be used for a preparation of protective coatings and integrated photonic devices such as planar optical waveguides and couplers.     

Green preparation of in situ Cr3C2 nano-coatings on graphite surface and their water-wettability and rheological properties

Cr₃C₂ coatings were successfully prepared on the surface of graphite flakes via a molten salt route by mixing Cr powders with natural graphite flakes in a binary LiCl-KCl salt at 450–950?°C for 4–12?h. The phases and microstructures of the coatings were verified by its XRD/XPS spectra and SEM/AFM observations, respectively. Together with the dissolution/dispersion evidence of chromium powders after interaction with the salt, and the slightly increased particle sizes due to the formation of Cr₃C₂ coatings on graphite flakes, a ‘template-growth’ kinetic process was therefore proposed on the formation of such coatings in the molten salt. The resultant coatings decreased the contact angle between water and graphite from 101° to ~ 75° and lowered the apparent viscosities of graphite water slurry by two orders of magnitude accordingly, suggesting that the coatings will afford graphite with good processing abilities for carbon-water based materials.     

Microwave and conventional treatment of low-cement high-alumina castables with different water-to-cement ratio; Part II. Dehydration

Modern refractory castables contain between 3.5 and 5?wt.-% water that is necessary for sufficient flow during emplacement and for the formation of hydrate phases, necessary for the green strength of the material. Prior to the high temperature use of this material, it must be dried very carefully to avoid explosive spalling.This paper will demonstrate that beside conventional drying of pre-shaped materials in resistance furnaces microwave radiation is an energy saving and rapid method to remove pore water as well as hydrate bond water from the castable. In comparison to resistance furnaces, the use of microwave radiation does not affect the castable properties as there are mechanical strength (MOR, CCS), open porosity and pore size distribution. This study proved microwave radiation as valuable alternative with a series of tabular alumina based low cement castables (LLC) in which the water-to-cement-ratio (wcr = 0.64, 0.75, 0.82 and 1.13) was systematically altered by changing the cement concentration at constant mixing water concentration of 4.5%.     

Liquid phase sintering and characterization of SiC ceramics

The present study focuses on the sintering of silicon carbide-based ceramics (SiC) by liquid phase sintering (LPS) followed by characterization of the produced ceramics. AlN/Re₂O₃ mixtures were used as additives in the LPS process. In the first step, the LPS-SiC materials were produced in a graphite resistance furnace in the form of discs at different temperatures. The conditions with the best results regarding real density and relative density were taken as reference for sintering in the form of prismatic bars. In the second step, these samples were evaluated regarding fracture toughness (K_IC), by the Single Edge V Notch Beam – SEVNB – method, and flexural strength. K_IC behavior was evaluated according to the depth and curvature radius of the notches. Reliable K_IC values were presented when the ceramic displayed a small curvature radius at the notch tip. When the radius was large, it did not maintain the square root singularity of the notch tip. Tests were carried out to determine K_IC values in atmospheric air and water. K_IC results were lower in water than air, with a decrease ranging between 2.56% and 11.26%. The observations indicated a direct grain size correlation between K_IC values and fracture strength of the SiC ceramics.     

Fabrication and piezoelectric properties of BaTiO3/BaTiO3-Bi(Mg1/2Ti1/2)O3-BiFeO3 composites

We fabricated xBaTiO₃ (BT)/(1-x)[BaTiO₃-Bi(Mg_1/2Ti_1/2)O₃-BiFeO₃] (BT-BMT-BF)?+?0.1?wt%MnCO₃ composites by spark plasma sintering and investigated the effect of BT content x, BT powder size, and BT-BMT-BF composition on piezoelectric properties. For xBT/(1-x)(0.3BT-0.1BMT-0.6BF) +?0.1?wt%MnCO₃ (x?=?0–0.75) composites with a 0.5-µm BT powder, the dielectric constant was increased with x, and the relative density was decreased at x?=?0.67 and 0.75, creating optimum BT content of x?=?0.50 with a piezoelectric constant d₃₃ of 107?pC/N. When a larger 1.5-µm BT powder was utilized for the composite with x?=?0.50, the d₃₃ value increased to 150?pC/N due to the grain size effect of the BT grains. To compensate for a compositional change from the optimum 0.3BT-0.1BMT-0.6BF due to partial diffusion between the BT and 0.3BT-0.1BMT-0.6BF grains, a 0.5BT/0.5(0.275BT-0.1BMT-0.625BF)?+?0.1?wt%MnCO₃ composite with the 1.5-µm BT powder was fabricated. We obtained an increased d₃₃ value of 166?pC/N. These results provided a useful composite design to enhance the piezoelectric properties.     

Structure and electrical properties of Ca2+-doped (Na0.47Bi0.47Ba0.06)TiO3 lead-free piezoelectric ceramics

The lead-free piezoelectric ceramics (Na_.47Bi_.47Ba_.06)_1-xCa_xTiO₃ (x?=?0, 0.01, 0.02, 0.03, 0.05, and 0.08, abbreviated as BNBTC/0, BNBTC/1, BNBTC/2, BNBTC/3, BNBTC/5, and BNBTC/8, respectively) were obtained using the solid-state reaction method. The structure, electric conductivity, and dielectric, ferroelectric, and piezoelectric properties of the Ca²⁺-doped (Na_.47Bi_.47Ba_.06)TiO₃ ceramics were thoroughly investigated. The ceramics sintered at 1200?°C exhibit dense microstructures, having relative densities higher than 96%. The X-ray diffraction results demonstrate that all ceramics have a pure perovskite structure. The mean grain sizes of the ceramics are related to the Ca²⁺ quantity. A small quantity of Ca²⁺ ions (x?≤?0.03) improves the piezoelectric and ferroelectric properties of the samples. The dielectric behavior of the samples is sensitive to the Ca²⁺ content and electric poling. The results demonstrate that the electrical properties of the (Na_.47Bi_.47Ba_.06)TiO₃ lead-free ceramics can be well tuned by varying the Ca²⁺ quantity.     

Methodology for dependence-based integrated constitutive modelling: An illustrative application to SiCp/Al composites

In industrial forming and machining process, the large plastic deformation of material takes place in wide loading ranges of strain-rate and forming temperature. A satisfactory modelling of quasi-static and dynamic material behaviors is of great importance for understanding physical process and processes optimization. A dependence-based integrated methodology, together with an improved weighted multi-objective parameter identification strategy is presented for the development of phenomenological constitutive model and the parameter identification using experimental data from quasi-static and dynamic tests with instantaneous strain rate variations and plastic strain-related temperature changes. The improved multi-objective parameter identification model is reformulated by introducing three weighting factors for valuing different measure errors and fit standard errors in individual objective function corresponding to each test, considering the sampling point number and active material parameter number under different loading conditions, and balancing optimization opportunity of quasi-static and dynamic sub-objective functions. The methodology is verified for feasibility through illustrative constitutive identification for SiC_p/Al composites. This may provide a methodology of constitutive modelling for predicting material behaviors in quasi-static and dynamic modes equally well.     

Ultrasonic vibration-assisted laser engineering net shaping of ZrO2-Al2O3 bulk parts: Effects on crack suppression,microstructure, and mechanical properties

Laser additive manufactured zirconia-alumina ceramic (ZrO₂-Al₂O₃) parts demonstrate severe problems resulting from cracking and inhomogeneous material dispersion. To reduce these problems, we propose a novel ultrasonic vibration-assisted laser engineered net shaping (LENS) process for fabrication of bulk ZrO₂-Al₂O₃ parts. Results showed that the initiation of cracks and the crack propagation were suppressed in the parts fabricated by LENS process with ultrasonic vibration. For the parts fabricated without ultrasonic vibration, the sizes of cracks decreased with the increase of laser power. Scanning electron microscope analyses proved that the introduction of ultrasonic vibration was beneficial for grain refinement and uniform material dispersion. Due to the suppressed cracking, refined grains, and homogenized material dispersion, the parts fabricated with ultrasonic vibration demonstrated better mechanical properties (including higher microhardness, higher wear resistance, and better compressive properties), compared with the parts fabricated without ultrasonic vibration.