Thermal desorption and pyrolysis direct analysis in real time mass spectrometry of Nafion membrane

Perfluorosulfonic acid ionomer membranes have been widely used as proton conducting membranes in various electrochemical processes such as polymer electrolyte fuel cells and water electrolysis. While their thermal stability has been studied by thermogravimetry and analysis of low molecular weight products, their decomposition mechanism is little understood. In this study a newly developed methodology of thermal desorption and pyrolysis in combination with direct analysis in real time mass spectrometry is applied for Nafion membrane. An ambient ionization source and a high-resolution time-of-flight mass spectrometer enabled unambiguous assignment of gaseous products. Thermal decomposition is initiated by side chain detachment above 350°C, which leaves carbonyls on the main chain at the locations of the side chains. Perfluoroalkanes are released above 400°C by main chain scission and their further decomposition products dominate above 500 °C. DFT calculation of reaction energies and barrier heights of model compounds support proposed decomposition reactions.     

Authenticity green coffee bean species and geographical origin using near-infrared spectroscopy combined with chemometrics

To prevent the adulteration of agricultural resources and provide a solution to enhance the green coffee bean supply chain, authentication using the near-infrared spectroscopy (NIRS) technique was investigated. Partial least square with discrimination analysis (PLS-DA) models combined with various preprocessing methods were built from NIR spectra of 153 Vietnamese green coffee samples. The model combined with the standard normal variate and the first order of derivative yielded excellent performance in predicting coffee species with the error cross-validation of 0.0261. PLS-DA model of mean centre and first-order derivative spectra also yielded good performance in verifying geographical indication of green coffee with the error of 0.0656. By contrast, the predicting abilities of post-harvest methods were poor. The overall results showed a high potential of the NIRS in online authentication practices.     

Enhanced electrochemical performance of LiNi0.8Co0.1Mn0.1O2 via titanium and boron co-doping

Titanium and boron are simultaneously introduced into LiNi_0.8Co_0.1Mn_0.1O₂ to improve the structural stability and electrochemical performance of the material. X-ray diffraction studies reveal that Ti⁴⁺ ion replaces Li⁺ ion and reduces the cation mixing; B³⁺ ion enters the tetrahedron of the transition metal layers and enlarges the distance of the [LiO₆] layers. The co-doped sample has spherical secondary particles with elongated and enlarged primary particles, in which Ti and B elements distribute uniformly. Electrochemical studies reveal the co-doped sample has improved rate performance (183.1 mAh·g^-1 at 1 C and 155.5 mAh·g^-1 at 10 C) and cycle stability (capacity retention of 94.7% after 100 cycles at 1 C). EIS and CV disclose that Ti and B co-doping reduces charge transfer impedance and suppresses phase change of LiNi_0.8Co_0.1Mn_0.1O_2.     

Colossal dielectric response and relaxation behavior in novel system of Zr4+ and Nb5+ co-substituted CaCu3Ti4O12 ceramics

In this work, we developed a novel system of isovalent Zr⁴⁺ and donor Nb⁵⁺ co-doped CaCu₃Ti₄O₁₂ (CCTO) ceramics to enhance dielectric response. The influences of Zr⁴⁺ and Nb⁵⁺ co-substituting on the colossal dielectric response and relaxation behavior of the CCTO ceramics fabricated by a conventional solid-phase synthesis method were investigated methodically. Co-doping of Zr⁴⁺ and Nb⁵⁺ ions leads to a significant reduction in grain size for the CCTO ceramics sintered at 1060 °C for 10 h. XRD and Raman results of the CaCu₃Ti_3.8-xZr_xNb_0.2O₁₂ (CCTZNO) ceramics show a cubic perovskite structure with space group Im-3. The first principle calculation result exhibits a better thermodynamic stability of the CCTO structure co-doped with Zr⁴⁺ and Nb⁵⁺ ions than that of single-doped with Zr⁴⁺ or Nb⁵⁺ ion. Interestingly, the CCTZNO ceramics exhibit greatly improved dielectric constant (~10⁵) at a frequency range of 10²–10⁵ Hz and at a temperature range of 20–210 °C, indicating a giant dielectric response within broader frequency and temperature ranges. The dielectric properties of CCTZNO ceramics were analyzed from the viewpoints of defect-dipole effect and internal barrier layer capacitance (IBLC) model. Accordingly, the immensely enhanced dielectric response is primarily ascribed to the complex defect dipoles associated with oxygen vacancies by co-doping Zr⁴⁺ and Nb⁵⁺ ions into CCTO structure. In addition, the obvious dielectric relaxation behavior has been found in CCTZNO ceramics, and the relaxation process in middle frequency regions is attributed to the grain boundary response confirmed by complex impedance spectroscopy and electric modulus.     

Investigation of thermal residual stresses during laser ablation of tantalum carbide coated graphite substrates using micro-Raman spectroscopy and COMSOL multiphysics

Laser ablation of high-temperature ceramic coatings results in thermal residual stresses due to which the coatings fail by cracking and debonding. Hence, the measurement of such residual stresses during laser ablation process holds utmost importance from the view of performance of coatings in extreme conditions. The present research aims at investigating the effect of laser parameters such as laser pulse energy, scanning speed and line spacing on thermal residual stresses induced in tantalum carbide-coated graphite substrates. Residual stresses were measured using micro-Raman spectroscopy and correlated with Raman peak shifts. Transient thermal analysis was performed using COMSOL Multiphysics to model the single ablated track and residual stresses were reported at low, moderate and high pulse energy regimes. The results showed that the initial laser conditions caused higher tensile residual stresses. Moderate pulse energy regime comprised higher compressive residual stresses due to off centre overlapping of the laser pulses. Higher pulse energy (250 μJ), higher scanning speed (1000 mm/s) and moderate line spacing (20 μm) caused accumulation of tensile residual stresses during the final stage of laser ablation. The deviation of experimental residual stresses from COMSOL numerical model was attributed to unaccounted additional stresses induced during thermal spraying process and deformation potentials in the numerical model.     

Development of an SFMM/CGO composite electrode with stable electrochemical performance at different oxygen partial pressures

This paper carefully evaluates the electrocatalytic activity of Sr₂FeMo_0.5Mn_0.5O₆ (SFMM) double perovskite as a candidate to substitute the state-of-the-art Ni/YSZ fuel electrode. The electrochemical performance of a 40% SFMM/CGO composite electrode was studied in CO/CO₂ and H₂ with different oxygen partial pressure. Two different cell configurations are prepared at a relatively low temperature of 800 °C to increase the electrochemically active surface area. The cell was supported with a 150 μm 10Sc1CeSZ electrolyte in the first configuration. The cell in the second configuration was made by applying a 400 nm thin 8YSZ layer on 150 μm CGO electrolyte to improve the electrolyte ionic conductivity. Improving catalytic activity with increasing oxygen partial pressure is a key characteristic of the developed electrode. The polarization resistance of about 0.34 and 0.56 Ω cm² at 750 °C in 3%H₂O + H₂ and 60% CO/CO₂ makes this electrode a promising candidate for SOCs application.     

Influence of Al3+ doping for V5+ on the structural,optical, thermal and electrical properties of V2-xAlxO5-δ (x=0–0.20) ceramics

This paper reports an investigation on the structure-properties correlation of trivalent metal oxide (Al₂O₃)-doped V₂O₅ ceramics synthesized by the melt-quench technique. XRD patterns confirmed a single orthorhombic V₂O₅ phase formation with increasing strain on the doping of Al₂O₃ in place of V₂O₅ in the samples estimated by Williamson-Hall analysis. FTIR and Raman investigations revealed a structural change as [VO₅] polyhedra converts into [VO₄] polyhedra on the doping of Al₂O₃ into V₂O₅. The optical band gap was found in a wide semiconductor range as confirmed by UV–visible spectroscopy analysis. The thermal and conductivity behavior of the prepared samples were studied using thermal gravimetric analysis (TGA) and impedance analyzer, respectively. All the prepared ceramics exhibit good DC conductivity (0.22–0.36 Sm^-1) at 400 ?C. These materials can be considered for intermediate temperature solid oxide fuel cell (IT-SOFC)/battery applications due to their good conductivity and good thermal stability.     

超宽带大功率合成器设计北大核心CSCD

在80 MHz~1 GHz频段,单个功率管输出功率能达到100 W以上,为研制输出功率400 W的功率放大器,文中设计了四路功率合成器。该合成器需要实现功率容量大、工作频带宽、体积小的设计目标。在功率容量方面,文中采用悬置带状线结构,其功率容量远远大于微带线结构;在工作频带方面,采用切比雪夫九节阻抗变换器,将工作带宽拓宽为80 MHz~1 GHz;在体积方面,文中合成器的功率合成部分采用Y型节级联实现四路功率合成,阻抗变换部分采用切比雪夫阻抗变换器进行阻抗变换,该结构相较于磁环巴伦功率合成器,不但具有损耗小、平坦度高的优点,而且通过将阻抗变换器设计成曲折的形状,进一步缩小了合成器体积。仿真与实测结果显示该合成器在80 MHz~1 GHz范围内还具有较高的平坦度,合成效率可达90%以上。