Enhanced relative permittivity in niobium and europium co-doped TiO2 ceramics

The appearance of colossal permittivity materials broadened the choice of materials for energy-storage applications. In this work, colossal permittivity in ceramics of TiO₂ co-doped with niobium and europium ions ((Eu_0.5Nb_0.5)_xTi_1-xO₂ ceramics) was reported. A large permittivity (ε_r ～ 2.01?×?10⁵) and a low dielectric loss (tanδ ～ 0.095) were observed for (Eu_0.5Nb_0.5)_xTi_1-xO₂ (x?=?1%) ceramics at 1?kHz. Moreover, two significant relaxations were observed in the temperature dependence of dielectric properties for (Eu, Nb) co-doped TiO₂ ceramics, which originated from defect dipoles and electron hopping, respectively. The low dielectric loss and high relative permittivity were ascribed to the electron-pinned defect-dipoles and electrons hopping. The (Eu_0.5Nb_0.5)_xTi_1-xO₂ ceramic with great colossal permittivity is one of the most promising candidates for high-energy density storage applications.     

Yttrium doping of Ba0.5Sr0.5Co0.8Fe0.2O3-δ part II: Influence on oxygen transport and phase stability

Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ (BSCF) in its cubic perovskite phase has attracted much interest for potential use as oxygen transport membrane (OTM) due to its very high oxygen permeability at high temperatures. However, performance degradation due to a sluggish phase decomposition occurs when BSCF is operated below 840?°C. Partial B-site substitution of the transition metal cations in BSCF by larger and redox-stable cations has emerged as a potential strategy to improve the structural stability of cubic BSCF. In this study, the influence of yttrium doping (0…10?mol-%) on oxygen transport properties and stability of the cubic BSCF phase is assessed by in situ electrical conductivity relaxation (ECR) and electrical conductivity measurements during long-term thermal annealing both at 700?°C and 800?°C. Detailed phase analysis is performed by scanning electron microscopy (SEM) after long-term annealing of the samples in air at different temperatures.     

十二烷基硫酸钠（SDS）对铜电沉积行为的影响

在酸性体系中采用阴极扫描伏安和计时电流等电化学测试方法，研究添加十二烷基硫酸钠（SDS）对铜电沉积过程的影响机理。结果表明：SDS的添加使沉积电位正移，降低了阴极极化。SDS浓度低于临界胶束浓度1g/L时，铜的成核弛豫时间延长，形核速率降低。SDS浓度高于临界胶束浓度时，形成SDS球状胶束，铜的成核弛豫时间减少，形核速率加快。铜晶核形成过程符合Scharitker?Hill 三维成核/生长机制，当SDS为1g/L时，在-0.2V的低过电位区，铜结晶按渐进成核方式进行，在-0.23--0.28V的高过电位区，铜结晶按瞬时成核方式进行。而当SDS为0.5g/L时，铜在-0.2V--0.25V的低电位区和在-0.28V的高电位区均符合渐进成核。     

Alkyl Tail Segments Mobility as a Marker for Omega-3 Polyunsaturated Fatty Acid-Rich Linseed Oil Oxidative Aging

Omega-3 polyunsaturated fatty acid (PUFA)-rich linseed oil (LSO) is an important component in biological systems, foods, and many other industrial products. In recent years, LSO has attracted increased attention in the field of functional foods, which has highlighted its facile susceptibility to aging by autoxidation. Common colorimetric and a long list of spectral methodologies have been used to follow after and predict LSO shelf life's quality, especially in regards to aging by autoxidation. These standard methodologies are nevertheless limited, because of the complexity of the LSO's chemical and physical changes. The goal of the present study is to develop a sensorial ¹H LF-NMR energy relaxation time application based on monitoring primary chemical and structural changes occurring with time and temperature during oxidative thermal stress for better and rapid evaluation of LSO's aging process. Using ¹H low-field NMR, the different T₂ times of energy relaxations due to spin–spin coupling, and proton motion/mobility of LSO molecular segments were monitored. As previously reported, we characterized the chemical and structural changes in all phases of the autoxidation aging process. Starting from the initiation phase (abstraction of hydrogen radical, fatty acid chain rearrangement, and oxygen uptake yielding hydroperoxides products), through to the propagation phase (chain reactions resulting in tail cleavage to form alkoxy radicals, and alpha, beta-unsaturated aldehydes formation), and a termination phase (cross linking and production of polymerization end products). The ¹H LF NMR transverse relaxation approach, monitors both the covalent bond's strong forces (100–400 kJ mol⁻¹) in LSO oxidative aging decomposition, as well as secondary relatively weak interactive forces by hydrogen bonds (~70 kJ mol⁻¹), and electrostatic bonds (0–50 kJ mol⁻¹) contributing to secondary crosslinking interactions leading to a LSO viscous gel of polymerized products in the termination phase. In the present paper, we show that LSO tail segments mobility in terms of T₂ multi-exponential energy relaxation time decays, generated by data reconstruction of ¹H transverse relaxation components are providing a clear, sharp, and informative understanding of LSO sample's autoxidation aging processes. To support T₂ time domain data analysis, we used data from high-field band-selective ¹H NMR pulse excitation for quantification of hydroperoxides and aldehydes of the same LSO samples treated under the same thermal conditions (25, 40, 60, 80, 100, 120 °C) with pumped air for 168 hours. Peroxide value, viscosity, and self-diffusion analyses, as well as fatty acids profile and by-products determined by GC–MS on the same samples were carried out, and correlated with the LSO tail T₂ energy relaxation time results. From these results, it is postulated that selective determination of LSO tail T₂ time domain can be used as a rapid evaluation marker for following omega-3 PUFA-rich oils oxidative aging process within industrial and commercial products.     

Combining effects of TiO6 octahedron rotations and random electric fields on structural and properties in Na0.5Bi0.5TiO3

The structural and dielectric properties of Na_0.5Bi_0.5TiO₃ (NBT) ceramics and crystals have been investigated and are compared to that of Pb(Zr_0.55Ti_0.45)O₃ (PZT55/45) and Pb(Mg_1/3Nb_2/3)_0.72Ti_0.28O₃ (PMNT 72/28) ceramics. X-ray diffraction (XRD) profiles for (100), (110), (111), (200), (220), and (222) (referred to cubic structure) reveal that the monoclinic structure with Cc space group exists both in the NBT single crystal and ceramics. The diffraction profile obtained with high resolution laboratory XRD for the NBT single crystal can be well described, using Cc model instead of R3c model. The dielectric constant of NBT below T_hump shows some similarity to that of PZT45/55 ceramics below 50°C in which oxygen octahedron rotations cause the frequency dispersion of the dielectric constant. The temperature-dependent dielectric constant for NBT can be deconvolved into two independent processes. The lower temperature process shows a typical relaxor characteristic and follows the Vogel-Fulcher relationship. The other process at higher temperature shows less frequency-dependent behavior. Comparing the dielectric constant of NBT with that of PZT55/45 and PMNT72/28 reveals that both oxygen octahedral rotations and random electric fields play an important role in the frequency dispersion of the dielectric constant for NBT relaxor feroelectric.     

高分子聚合物松弛行为及模型的研究进展

高分子聚合物材料作为一种使用频率高且应用范围广的材料,其松弛行为对于其加工制品的精度具有重要的影响,且高分子化学合成的结果会最终影响高分子聚合物的松弛行为。由此总结了高分子聚合物松弛行为的特点,整理了其力学松弛及模型、松弛时间的研究进展。并由此提出现阶段高分子聚合物的松弛行为研究的局限性,并指出未来的研究方向。     

Effect of fatigue loading-confining stress unloading rate on marble mechanical behaviors: An insight into fracture evolution analyses

Rocks in underground works usually experience rather complex stress disturbance. For this, their fracture mechanism is significantly different from rocks subjected to conventional triaxial compression conditions. The effects of stress disturbances on rock geomechanical behaviors under fatigue loading conditions and triaxial unloading conditions have been reported in previous studies. However, little is known about the dependence of the unloading rate on fatigue loading and confining stress unloading (FL-CSU) conditions that influence rock failure. In this paper, we aimed at investigating the fracture behaviors of marble under FL-CSU conditions using the post-test X-ray computed tomography (CT) scanning technique and the GCTS RTR 2000 rock mechanics system. Results show that damage accumulation at the fatigue stage can influence the final fracture behaviors of marble. The stored elastic energy for rock samples under FL-CSU tests is relatively larger compared to those under conventional triaxial tests, and the dissipated energy used to drive damage evolution and crack propagation is larger for FL-CSU tests. In FL-CSU tests, as the unloading rate increases, the dissipated energy grows and elastic energy reduces. CT scanning after the test reveals the impacts of the unloading rate on the crack pattern and a fracture degree index is therein defined in this context to represent the crack dimension. It shows that the crack pattern after FL-CSU tests depends on the unloading rate, and the fracture degree is in agreement with the analysis of both the energy dissipation and the amount of energy released. The effect of unloading rate on fracture evolution characteristics of marble is revealed by a series of FL-CSU tests.     

电流驰豫法测试氧化镧掺杂的氧化铈中氧离子迁移

采用甘氨酸-硝酸盐法(GNP)合成了Ce0.65La0.35O1.825(LDC)粉末,在1400℃下烧结10 h得到陶瓷试样,用XRD和SEM表征了样品的物相和表面形貌。用直流电场测试了试样在不同温度下的电流驰豫现象,并计算了不同温度下试样中迁移氧离子数目和材料直流电导率。结果表明,在固态电解质材料中突然施加强电场,可迁移离子基本都发生了位置偏移,但极少部分可以产生长程迁移。随着温度的升高,样品中发生迁移的氧离子数目增加,但都远小于氧空位总量。迁移氧离子数目与温度之间满足阿累尼乌斯公式,其迁移活化能为0.83 eV。     

Hydrostatic pressure influence on electric relaxation response of bismuth manganite ceramics

Electrical impedance of bismuth manganite ceramics was studied under ambient and high hydrostatic pressure. Local disorder of crystal lattice was confirmed using XRD and DSC. Two relaxation processes were discerned. One was attributed to small polarons, which showed a changeover from variable range hopping features related to Fermi glass and structural disorder to the nearest neighbor hopping behavior in higher temperature range related to uniform distribution of energy levels. Hydrostatic pressure shortened relaxation times that would be interesting for applications. The second process, which was assigned to the nearest neighbor hopping of polarons, also exhibited a changeover to glassy features in a high-temperature range.     

Electrocatalytic activity of perovskite-based cathodes for solid oxide fuel cells

A very active cathode material for intermediate temperature - solid oxide fuel cells (IT-SOFCs) is obtained by mixing La_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ (LSCF) and Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ (BSCF) powders. Three different volume ratios are considered: BSCF-LSCF 50-50 v/v% (BL50), BSCF-LSCF 70-30 v/v% (BL70) and 30–70 v/v% (BL30).The electrodes are slurry coated on Ce_0.8Sm_0.2O_2-δ electrolyte and sintered at 1100 °C. After the sintering step XRD-analyses highlight relevant cation inter-diffusion within the mixed powders. As a result, an enhanced activity of BL30-BL70 electrodes towards oxygen reduction reaction is detected in comparison to LSCF or BSCF pure powders. A polarization resistance of 0.021 Ω cm2 at 650 °C for BL70 is obtained, one of the lowest value reported in literature for SOFC cathodes. Furthermore, all the electrodes show lower activation energy than the two reference materials in the considered temperature range (500–650 °C) and two different kinetic regimes are identified at the extremes of this range. Effect of the applied overpotential (0–0.3 V) on the electrode kinetic is also investigated.After a preliminary ageing, performed at 650 °C for 200 h by applying a current density of 200 mA cm-2, the electrodes preserve a remarkable performance as IT-SOFC cathodes, despite an initial degradation. A stable value of 0.048 Ω cm2 of polarization resistance for the sample richer in BSCF is recorded.