Controlled Elemental Depth Profile in Sol–Gel-Derived PZT Films

Elemental depth profiles of PZT films prepared by two sol–gel formulations, differing in the zirconium precursor stabilization, were investigated by SIMS analysis. Early decomposition of the zirconium precursor yielded opposing gradients of zirconium and titanium, while simultaneous late decomposition of zirconium and titanium precursors provided profile uniformity. The gradients formed during initial crystallization are irreversible. Both types of films showed excellent hysteresis; however, uniform films exhibited a much higher dielectric constant, indicating superior piezoelectric properties. Non-uniform films displayed a complex CV pattern, consistent with an inhomogeneous structure. Finally, thermal decomposition of the individual metal precursors is crucial for controlling film uniformity.     

Superior Thermoelectric Performance of Textured Ca3Co4−xO9+δ Ceramic Nanoribbons

Calcium cobaltite Ca₃Co_4−xO_9+δ (CCO) is a promising p-type thermoelectric (TE) material for high-temperature applications in air. The grains of the material exhibit strong anisotropic properties, making texturing and nanostructuring mostly favored to improve thermoelectric performance. On the one hand multitude of interfaces are needed within the bulk material to create reflecting surfaces that can lower the thermal conductivity. On the other hand, low residual porosity is needed to improve the contact between grains and raise the electrical conductivity. In this study, CCO fibers with 100% flat cross sections in a stacked, compact form are electrospun. Then the grains within the nanoribbons in the plane of the fibers are grown. Finally, the nanoribbons are electrospun into a textured ceramic that features simultaneously a high electrical conductivity of 177 S cm⁻¹ and an immensely enhanced Seebeck coefficient of 200 µV K⁻¹ at 1073 K are assembled. The power factor of 4.68 µW cm⁻¹ K⁻² at 1073 K in air surpasses all previous CCO TE performances of nanofiber ceramics by a factor of two. Given the relatively high power factor combined with low thermal conductivity, a relatively large figure-of-merit of 0.3 at 873 K in the air for the textured nanoribbon ceramic is obtained.     

Corrosion of aluminium,stainless steels and AISI 680 nickel alloy in nitrogen‐based fuels

Nitrogen‐based compounds can potentially be used as alternative non‐carbon or low‐carbon fuels. Nevertheless, the corrosion of construction materials at high temperatures and pressures in the presence of such fuel has not been reported yet. This work is focused on the corrosion of AISI Al 6061, 1005 carbon steel (CS), 304, 316L, 310 austenitic stainless steels (SS) and 680 nickel alloy in highly concentrated water solution of ammonium nitrate and urea (ANU). The corrosion at 50 °C and ambient pressure and at 350 °C and 20 bar was investigated to simulate storage and working conditions. Sodium chloride was added to the fuel (0–5 wt%) to simulate industrial fertilizers and accelerated corrosion environment. Heavy corrosion of CS was observed in ANU solution at 50 °C, while Al 6061, 304 and 316L SS showed high resistance both to uniform and pitting corrosion in ANU containing 1% of sodium chloride. Addition of 5% sodium chloride caused pitting of Al 6061 but had no influence on the corrosion of SS. Tests in ANU at 350 °C and 20 bar showed pitting on SS 304 and 316L and 680 nickel alloy. The highest corrosion resistance was found for SS 310 due to formation of stable oxide film on its surface.     

Deformation Control During Thermal Treatment of Electrospun PbZr0.52Ti0.48O3 Nanofiber Mats

This paper focuses on the deformation origin of PbZr_0.52Ti_0.48O₃ (PZT) fiber mats obtained by electrospinning. The main cause of deformation of the green mats during heating was found to be a nonuniform relaxation of the stretched PVP polymer, due to nonuniform thermal decomposition of the Pb‐hexanoate in the fibers. This relaxation starts under 100°C, well below the polymer decomposition temperature. The shrinkage was found to accelerate above the polymer glass transition point, giving rise to an overall linear change of almost 50%. The “green” PZT mats were easily separated from the collector by first depositing a pure PVP sublayer on the collector. An optimal fabrication and slow multistep thermal treatment process that provides fiber mats with desired PZT phase and overcomes the nonuniform deformation is described.     

Testing of an inductive current-limiting device based on high-Tc superconductors

An inductive current-limiting device (CLD) based on transition of a superconductor to the normal state is investigated. The device has low impedance under normal conditions of the circuit to be protected, and a high impedance developed rapidly in a self-switching mode under fault conditions. A model of the device consisting of a copper coil and a high-temperature superconducting ring, coupled magnetically, was tested. It is shown that the transition of the ring to the normal state and its return to the superconducting state take place in a relatively smooth manner, and do not lead to overvoltages across circuit elements. On the other hand, the rate of impedance rise is sufficient to limit both the steady-state and transient components of fault current. The influence of thermal processes in the ring on transient responses in the circuit with the CLD is discussed. Some considerations for a full a size design are also presented     

High Performance Core/Shell Ni/Ni(OH)2 Electrospun Nanofiber Anodes for Decoupled Water Splitting

Decoupled water splitting is a promising new path for renewable hydrogen production, offering many potential advantages such as stable operation under partial-load conditions, high-pressure hydrogen production, overall system robustness, and higher safety levels. Here, the performance of electrospun core/shell nickel/nickel hydroxide anodes is demonstrated in an electrochemical-thermally activated chemical decoupled water splitting process. The high surface area of the hierarchical porous electrode structure improves the utilization efficiency, charge capacity, and current density of the redox anode while maintaining high process efficiency. The anodes reach average current densities as high as 113 mA cm⁻² at a working potential of 1.48 V_RHE and 64 mA cm⁻² at 1.43 V_RHE, with a Faradaic efficiency of nearly 100% and no H₂/O₂ intermixing in a membrane-free cell.     

Organically Doped Metals—A New Approach to Metal Catalysis: Enhanced Ag‐Catalyzed Oxidation of Methanol

We report here a new approach for the modification of the performance of metal catalysts: organic doping of the metal. Specifically, we report that the doping of Ag with Congo Red (CR@Ag) significantly improves the performance of Ag as a catalyst for methanol oxidation to formaldehyde, outperforming both pure Ag and CR‐coated Ag (CR/Ag) in terms of lowering the temperature needed for maximal conversion by 100 °C, lowering the temperature by 200 °C to reach the maximal selectivity (aldehyde formation), and increasing the maximal space velocity by a factor of two. We were led to this discovery by a detailed investigation of the thermal behavior (thermogravimetric and differential thermal analysis and mass spectroscopy) of CR@Ag under an oxidative atmosphere, which has indicated that the metal is strongly catalyzing the CR oxidation, and which pointed to the relevant temperature for activation of the catalyst.     

Critical Current Densities in Thin Ceramic Tapes of Superconducting Ba2YCu3O7

Tape-cast slurries of Ba₂YCu₃O₇ powders offer a convenient means of preparing sintered ceramic samples for critical current density (J_c) measurements where the transport cross section is small and the current electrode areas are large. Samples were sintered from 900° to 1000°C and characterized for bulk density, grain size, phase composition, T_c, and J_c. Bulk density and grain size both increase with sintering temperature while all samples were single-phase perovskite except for those sintered at 900°C. The onset temperature for superconductivity is constant at about 93 K while the transition sharpens to R=0 at about 92 K for the densest samples. J_c rises with sintering temperature to a maximum of ∼10³ A/cm². A linear relationship between J_c and bulk density is predicted from microstructural considerations.     

YBCO Oxalate Coprecipitation in Alcoholic Solutions

A process for synthesis of ultrafine YBa₂Cu₃O_7–x powder by oxalate coprecipitation from nearly saturated solutions of the metal acetates and a 2-propanol solution of oxalic acid was developed. The coprecipitation was complete within 5 min in an ice bath at 0–2°C. The final stoichiometry was Y:Ba:Cu = 1:1.994:2.991, while the particle size and surface area in the homogeneous coprecipitated powder were 0.1–0.2 pm and 24.9 m².g⁻¹, respectively. Because of the uniformity and particle size of the coprecipitated material, reactive YBCO powder with a surface area of 1.7 m².g⁻¹ can be obtained at 780°C in about 12 h.