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.     

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.     

Charge source and the charging mechanism of the contact electrification of polymer powder

The charge sources, as well as the charging mechanism of the contact electrification (CE) of polymers, are still debatable. Since CE is accompanied by destruction, it is considered that “hard contacting” via ball milling can induce covalent bond scission and produce naked-activated-charge sources. Regarding “soft contacting” via nano-scale sliding, which does not induce covalent bond scission, a frontier-electron, “f-electron,” of the naked-activated-charge source is crucial to electron transfer among the naked-activated-charge sources. Here, we configure naked-activated-charge-source models, naked-activated-mechano-anion, and naked-activated-mechano-cation, which are produced by mechanical energy induced heterogeneous covalent bond scission, as well as naked-activated-mechano-radicals that are produced by homogeneous covalent bond scission. Regarding “soft contacting” among naked-activated-charge sources in a vacuum, f-electron can be transferred from a donor to an acceptor if the energy level of the donor is higher than that of the acceptor. The net amount of the normalized transferred-f-electrons is obtained by adopting settings in which the average energy level of the naked-activated-charge sources (as the donors) is higher than that of the sources employed as acceptors. Thus, the surfaces comprising the donors and acceptors will exhibit positive and negative net surface charges, respectively. We conclude that net surface charges depend on the average energy level of naked-activated-charge sources. Further, we observe that the alignment of polyethylene (PE)-polyvinyl chloride (PVC)-polytetrafluoroethylene (PTFE) to the average energy level is identical to that of the triboelectric series.     

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.     

基于深度信念网络的列车故障音频诊断方法

铁路在交通运输行业有着举足轻重的地位，一旦列车发生故障将会导致严重的生命财产损失。由于列车发生故障的概率相对较低，因此难以捕获列车的故障样本。针对上述问题，提出了一种无监督学习的列车故障识别方法，通过检测列车音频信号来识别列车故障。该方法基于深度信念网络(DBN)，利用小波包分解提取检测信号的特征向量并将其作为DBN的输入，待网络充分训练后，由训练好的DBN识别当前列车的运行状况。现场监测实验结果表明，该方法能够在无监督的条件下有效识别列车故障，保障了列车的运行安全。     

基于深度学习的秀丽隐杆线虫显微图像分割方法

利用计算机实现自动、准确的秀丽隐杆线虫(C.elegans)的各项形态学参数分析,至关重要的是从显微图像上分割出线虫体态,但由于显微镜下的图像噪声较多,线虫边缘像素与周围环境相似,而且线虫的体态具有鞭毛和其他附着物需要分离,多方面因素导致设计一个鲁棒性的C.elegans分割算法仍然面临着挑战。针对这些问题,提出了一种基于深度学习的线虫分割方法,通过训练掩模区域卷积神经网络(Mask R-CNN)学习线虫形态特征实现自动分割。首先,通过改进多级特征池化将高级语义特征与低级边缘特征融合,结合大幅度软最大损失(LMSL)损失算法改进损失计算;然后,改进非极大值抑制;最后,引入全连接融合分支等方法对分割结果进行进一步优化。实验结果表明,相比原始的Mask R-CNN,该方法平均精确率(AP)提升了4.3个百分点,平均交并比(mIOU)提升了4个百分点。表明所提出的深度学习分割方法能够有效提高分割准确率,在显微图像中更加精确地分割出线虫体。     

Annealing temperature dependent structural and optical properties of electrodeposited CdSe thin films

Cadmium selenide films were synthesized using simple electrodeposition method on indium tin oxide coated glass substrates. The synthesized films were post annealed at 200 °C, 300 °C and 400 °C. X-ray diffraction of the films showed the hexagonal structure with crystallite size <3 nm for as deposited films and 3–25 nm for annealed films. The surface morphology of films using field emission scanning electron microscopy showed granular surface. The high resolution transmission electron microscopy of a crystallite of the film revealed lattice fringes which measured lattice spacing of 3.13 Å corresponding to (002) plane, indicating the lattice contraction effect, due to small size of CdSe nanocrystallite. The calculation of optical band gap using UV–visible absorption spectrum showed strong red-shift with increase in crystallite size, indicating to the charge confinement in CdSe nanocrystallite.