Oxygen permeation of various archetypes of oxygen membranes based on BSCF

Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3‐δ tubes, capillaries, capillary modules, and asymmetric membranes were prepared and tested for oxygen permeation in a dead‐end vacuum operation mode at temperatures up to 850^°C. The capillary module was built up by reactive air brazing using seven capillaries and a supply tube. Two machined discs were used as an end cap and as a connector plate. The oxygen permeation behaves according to Wagner at small driving forces, but significant negative deviations were observed for asymmetric membranes and single capillaries at higher ones. This is caused by pressure drops at the vacuum side for single capillaries. The highest oxygen flux was revealed for the capillary module with 175.5 mL(STP)/min at a low‐vacuum pressure of 0.042 bar at 850^°C, but the asymmetric membrane showing a little bit higher flux at moderate vacuum pressures above 0.07 bar. © 2012 American Institute of Chemical Engineers AIChE J, 58: 3195–3202, 2012     

Pulse-modulation eddy current probes for imaging of external corrosion in nonmagnetic pipes

Since the nonmagnetic pipe is normally utilized in corrosive and hostile environment, it is prone to the external corrosion which occurs on the outer surface of the pipe and severely undermines the structural integrity and safety. Although Pulsed Eddy Current technique (PEC) is currently preferred for detection and evaluation of subsurface defects in tubular conductors, it is subject to technical drawbacks. In light of this, Pulse-modulation Eddy Current technique (PMEC) is intensively investigated in the paper for enhancement of the evaluation sensitivity to external corrosion and accuracy of corrosion imaging. Closed-form expressions of the PMEC response and its sensitivity to external corrosion in tubular conductors are formulated via the Extended Truncated Region Eigenfunction Expansion (ETREE) modeling. Following simulations for analysis and comparison of field signals and evaluation sensitivities of PMEC and PEC, experiments of PMEC for evaluation and imaging of external corrosion are carried out. Through theoretical and experimental investigation, it has been found that regarding the evaluation and imaging of external corrosion in nonmagnetic pipes, the PMEC-based probe have higher sensitivity and imaging accuracy than that based on PEC. The superiority of PMEC to PEC in inspection of tubular conductors is further identified.     

Effect of synthesis atmosphere on the proton conductivity of Y-doped barium zirconate solid electrolytes

Yttrium-doped barium zirconate ceramic powders were synthesized by the oxidant peroxide method in air and under controlled atmosphere of nitrogen inside a glove box. The powders were characterized by thermogravimetry, X-ray diffraction, scanning electron microscopy and transmission electron microscopy. After uniaxial cold isostatic pressing, green pellets were sintered at 1600 °C for 4 h. The electrical conductivity behavior was accessed by electrochemical impedance spectroscopy. The results show that specimens synthesized under controlled atmosphere achieved higher electrical conductivity, two orders of magnitude higher than specimens prepared in laboratory air. The enhancement in electrochemical properties and increase in sintering ability is attributed to the less carbonate contamination as a result lower grain boundary density in the samples prepared under controlled atmosphere.     

Theoretical study of the zero-gap organic conductor α-(BEDT-TTF)2I3

Abstract

The quasi-two-dimensional molecular conductor α-(BEDT-TTF)₂I₃ exhibits anomalous transport phenomena where the temperature dependence of resistivity is weak but the ratio of the Hall coefficient at 10 K to that at room temperature is of the order of 10⁴. These puzzling phenomena were solved by predicting massless Dirac fermions, whose motions are described using the tilted Weyl equation with anisotropic velocity. α-(BEDT-TTF)₂I₃ is a unique material among several materials with Dirac fermions, i.e. graphene, bismuth, and quantum wells such as HgTe, from the view-points of both the structure and electronic states described as follows. α-(BEDT-TTF)₂I₃ has the layered structure with highly two-dimensional massless Dirac fermions. The anisotropic velocity and incommensurate momenta of the contact points, ±k₀, originate from the inequivalency of the BEDT-TTF sites in the unit cell, where ±k₀ moves in the first Brillouin zone with increasing pressure. The massless Dirac fermions exist in the presence of the charge disproportionation and are robust against the increase in pressure. The electron densities on those inequivalent BEDT-TTF sites exhibit anomalous momentum distributions, reflecting the angular dependences of the wave functions around the contact points. Those unique electronic properties affect the spatial oscillations of the electron densities in the vicinity of an impurity. A marked behavior of the Hall coefficient, where the sign of the Hall coefficient reverses sharply but continuously at low temperatures around 5 K, is investigated by treating the interband effects of the magnetic field exactly. It is shown that such behavior is possible by assuming the existence of the extremely small amount of electron doping. The enhancement of the orbital diamagnetism is also expected. The results of the present research shed light on a new aspect of Dirac fermion physics, i.e. the emergence of unique electronic properties owing to the structure of the material.     

Single-ion-conducting nanocomposite polymer electrolytes based on PEG400 and anionic nanoparticles: Part 2. Electrical characterization

Molecular relaxation and polarization phenomena of twelve single-ion-conducting nanocomposite polymer electrolytes (nCPEs) are studied using Broadband Electrical Spectroscopy (BES). The electrolytes are obtained by combining PEG400 oligomers with increasing amounts of anionic nanofiller comprised of fluorinated-TiO₂ associated with Li⁺ cations (LiFT^®), resulting in [PEG400/(LiFT)_y] systems with 0 ≤ y ≤ 26.4. This new class of [PEG400/(LiFT)_y] electrolytes allows us to achieve a significant single-ion conductivity (1.1·10⁻⁵ S cm⁻¹ at 30 °C for n_Li/n_O = 0.113) without the addition of lithium salts. To the best of our knowledge, this is the highest conductivity value reported for this class of electrolytes. This study, in conjunction with the results reported in Part 1, leads us to hypothesize a conduction mechanism in terms of two types of long-range charge-transfer processes. The first charge-transfer occurs at the interface between the filler nanoparticles and filler-PEG domains, while the second occurs through the PEG400 matrix with the assistance of polymer segmental motion. The measured Li⁺ transference numbers confirm that the studied materials are single-ion conductors.     

Influence of oxygen partial pressure on the oxygen diffusion and surface exchange coefficients in mixed conductors

The performances of mixed ionic and electronic conductors is used in many applications, such as oxygen transport membranes or electrodes in solid oxide fuel cells. The performances of these systems depend mainly on two fundamental parameters including oxygen diffusion (D_O) and the oxygen exchange coefficient (k). This work focuses on the impact of the oxygen partial pressure on oxygen diffusion and surface exchange coefficients of mixed conducting materials, as reported studies are scarce in the literature. In this way, two different mixed conducting materials are studied, namely, La_0.6Sr_0.4Fe_0.6Ga_0.4O_3-δ, a perovskite-type material, and the nickelate La₂NiO_4+δ. The D_O and k coefficients are determined by a specific oxygen permeation measurement and by the isotopic exchange depth profile method.     

Fabrication of BSCF-based mixed oxide ionic-electronic conducting multi-layered membrane by sequential electrophoretic deposition process

The Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ (BSCF)-based multi-layered oxygen separation membrane was fabricated by the sequential electrophoretic deposition (EPD) process. A thin porous/dense bi-layer of BSCF was formed on a thick porous support of BSCF. The porous support prepared by a sacrificial template method using BSCF powder mixed with wheat starch (30 wt%) as a pore-forming agent, followed by uniaxial pressing and low-temperature sintering, was directly used as an EPD electrode. A thin BSCF layer was first formed on the porous support, and then a thin BSCF + PMMA (polymethyl methacrylate) layer was sequentially formed on the thin BSCF layer using a bimodal suspension of BSCF and PMMA. A 30-μm thin porous/dense bi-layer of BSCF of which the total thickness was obtained by optimizing the processes of EPD and subsequent co-sintering. The oxygen separation performance of 3.7 ml (STP) min^?1 cm^?2 at 860 °C was achieved for the BSCF-based multi-layered oxygen separation membrane.     

Fabrication and thermo stability of the SnO2/Ag/SnO2 tri-layer transparent conductor deposited by magnetic sputtering

Using the magnetic sputtering technique, the SnO₂/Ag/SnO₂ tri-layer transparent films were fabricated on float glasses successfully. Compared with the commercial FTO (F-doped SnO₂) film, the SnO₂/Ag/SnO₂ tri-layer films have higher visible-light transmittance and better conductivity. The total thickness of the SnO₂/Ag/SnO₂ films is one third of the commercial FTO film leading to the high visible-light transmittance. The high carrier concentration of the SnO₂/Ag/SnO₂ films contributes to the tri-layer films’ low resistivity. In addition, to further improve the performance of the SnO₂/Ag/SnO₂ tri-layer films, samples were annealed under different temperatures. The results illustrate that the lowest sheet resistance (5.92 Ω/sq) and the highest visible-light transmittance (87.0%) were obtained after annealing at 200 °C. Furthermore, the thermal stability of the films could be enhanced by a multi-step annealing process due to the recrystallization effect.     

Preparation and properties of lithium sulfonated polyoxadiazoles electrolyte

以硫酸肼（HS）、对苯二甲酸（TPA）、4，4'-联苯醚二甲酸（DPE）为单体，发烟硫酸做溶剂和脱水剂一步合成了一系列不同TPA和DPE单体配比的磺化聚芳噁二唑（SPOD），再通过氢氧化锂中和得到聚芳噁二唑磺酸锂（Li-SPOD）聚合物电解质，采用浇铸成膜法制得Li-SPOD电解质膜，研究改变TPA和DPE两种单体配比对Li-SPOD结构及性能的影响。结果表明，几种不同单体配比均能实现在聚合过程中一步得到SPOD，磺酸基团接枝在DPE结构的苯环上，并且可以达到理论接枝量；同时Li-SPOD电解质膜的聚集态结构差异很小；热性能的表现均非常优异，初始热分解温度都在450 ℃以上；力学性能随DPE单体含量的增加稍有下降但依然保持在较高的水平；电导率约为10^-5S/cm级别，随DPE含量增加而逐渐降低；Li-SPOD固态电解质电化学稳定性较好，对锂稳定电化学窗口均在4.0 V以上。     

Impedance spectroscopy analysis of CeNbO4.25

Monoclinic CeNbO4.25 was prepared by solid state reaction. Complex impedance analysis indicated the presence of grain interior effect along with the grain boundary contribution. The values of ionic tra...