Theoretical investigation of intrinsic point defects and the oxygen migration behavior in rare earth hafnates

In this work, the composition-dependent point defect types and formation energies of RE₂Hf₂O₇ (RE = La, Ce, Pr, Nd, Pm, Sm, Eu and Gd) as well as the oxygen diffusion behavior are systematically investigated by first-principles calculations. The possible defect reactions and dominant defect complexes under stoichiometric and non-stoichiometric conditions are revealed. It is found that O Frenkel pairs are the predominant defect in stoichiometric pyrochlore hafnates. Hf-RE cation anti-site defects, accompanied by RE vacancies and/or oxygen interstitials, are stable in the non-stoichiometric case of HfO₂ excess. On the other hand, RE-Hf anti-site defects together with oxygen vacancies and/or RE interstitials are preferable in the case of RE₂O₃ excess. The energy barriers for the migration along the V_O48f - V_O48f pathway of pyrochlore hafnates were calculated to be between 0.81 eV and 0.89 eV. Based on these results, a defect engineering strategy is proposed and the pyrochlore hafnates investigated here are predicted to exhibit potential oxygen ionic conductivity.     

Photophysical investigation of the formation of defect levels in P doped ZnO thin films

Zinc oxide (ZnO) offers a major disadvantage of asymmetry doping in terms of reliability, stability, and reproducibility of p-type doping, which is the main hindrance in realization of optoelectronic devices. The problem is even more complicated due to formation of various native defects in unintentionally doped n-type ZnO. The realization of p-type conductivity in doped ZnO requires an in-depth understanding of the formation of an effective shallow acceptor, as well as donor-acceptor compensation. Photophysical properties such as photoconductivity along with photoluminescence (PL) studies have unprecedentedly and effectively been utilized in this work to monitor the evolution of various in-gap defects. Phosphorus (P) doped ZnO thin films have been grown by RF magnetron sputtering under various Ar to O₂ gas ratios to investigate the effect of O₂ on the donor-acceptor compensation by comprehensive photoconductivity measurements supported by the PL studies. Initial elemental analyses indicate presence of abundant zinc vacancies (V_Zn) in O-rich ambience. The results predict that P sits in the zinc (Zn) site rather than the oxygen (O) site causing the formation of P_Zn–2V_Zn acceptor-like defects, which compensates the donor defects in P doped ZnO films. Photocurrent spectra uniquely reveal presence of more oxygen vacancies (V_O) defects states in lower O₂ flow, which gets compensated with an increase in the O₂ flow. Successive photocurrent transients indicate probable presence of more V_O in the films grown with lower O₂ flow and more V_Zn in higher O₂ flow. Overall the photosensitivity measurements clearly present that O-rich ambience expedites the formation of acceptor defects which are compensated, thereby lowering the dark current and enhancing the ultraviolet photosensitivity.     

NiFe layered double hydroxide as an efficient bifunctional catalyst for electrosynthesis of hydrogen peroxide and oxygen

Two electron oxygen reduction reaction to produce hydrogen peroxide (H₂O₂) is a promising alternative technique to the multistep and high energy consumption anthraquinone process. Herein, Ni–Fe layered double hydroxide (NiFe-LDH) has been firstly demonstrated as an efficient bifunctional catalyst to prepare H₂O₂ by electrochemical oxygen reduction (2e^? ORR) and oxygen evolution reaction (OER). Significantly, the NiFe-LDH catalyst possesses a high faraday efficiency of 88.75% for H₂O₂ preparation in alkaline media. Moreover, the NiFe-LDH catalyst exhibits excellent OER electrocatalytic property with small overpotential of 210 mV at 10 mA cm^?2 and high stability in 1 M KOH solution. On this basis, a new reactor has been designed to electrolyze oxygen and generate hydrogen peroxide. Under the ultra-low cell voltage of 1 V, the H₂O₂ yield reaches to 47.62 mmol g_cat^?1 h^?1. In order to evaluate the application potential of the bifunctional NiFe-LDH catalyst for H₂O₂ preparation, a 1.5 V dry battery has been used as the power supply, and the output of H₂O₂ reaches to 83.90 mmol g_cat^?1 h^?1. The excellent electrocatalytic properties of 2e^? ORR and OER make NiFe-LDH a promising bifunctional electrocatalyst for future commercialization. Moreover, the well-designed 2e^? ORR-OER reactor provides a new strategy for portable production of H₂O₂.     

Structural Aspects of P2-Type Na0.67Mn0.6Ni0.2Li0.2O2 (MNL) Stabilization by Lithium Defects as a Cathode Material for Sodium-Ion Batteries

A known strategy for improving the properties of layered oxide electrodes in sodium-ion batteries is the partial substitution of transition metals by Li. Herein, the role of Li as a defect and its impact on sodium storage in P2-Na_0.67Mn_0.6Ni_0.2Li_0.2O₂ is discussed. In tandem with electrochemical studies, the electronic and atomic structure are studied using solid-state NMR, operando XRD, and density functional theory (DFT). For the as-synthesized material, Li is located in comparable amounts within the sodium and the transition metal oxide (TMO) layers. Desodiation leads to a redistribution of Li ions within the crystal lattice. During charging, Li ions from the Na layer first migrate to the TMO layer before reversing their course at low Na contents. There is little change in the lattice parameters during charging/discharging, indicating stabilization of the P2 structure. This leads to a solid-solution type storage mechanism (sloping voltage profile) and hence excellent cycle life with a capacity of 110 mAh g^-1 after 100 cycles. In contrast, the Li-free compositions Na_0.67Mn_0.6Ni_0.4O₂ and Na_0.67Mn_0.8Ni_0.2O₂ show phase transitions and a stair-case voltage profile. The capacity is found to originate from mainly Ni³⁺/Ni⁴⁺ and O^2-/O^2-δ redox processes by DFT, although a small contribution from Mn⁴⁺/Mn⁵⁺ to the capacity cannot be excluded.     

Warm-white light performance of Dy3+, Eu3+: NaLa(WO4)2 phosphors excited with a 450-nm LED

Dy³⁺, Eu³⁺: NaLa(WO₄)₂ phosphors are successfully synthesized through the solid-state reaction technique. The phase-structure and morphology are measured via X-ray diffraction and energy dispersive spectrometry. The concentrations of Dy³⁺, Eu³⁺, La³⁺, and W⁶⁺ are measured via ICP. The absorption and excited spectra are presented, which indicate that a blue band ranging from 430 to 480 nm is suitable for excitation. Using a commercial blue LED with a wavelength of 450 nm as the excitation light source, emission spectra for samples with varying dopant concentration ratios of Dy³⁺ to Eu³⁺ are obtained, which show good tunable yellow and red emission. For the purpose of investigating white LED performance, CIE spectra and a white light photo are also presented. The results reveal that varying the dopant concentration ratio of Dy³⁺ to Eu³⁺ plays a key role in the warm-white performance. With increasing concentration of Eu³⁺, the correlated color temperature decreases from 4069 to 3172 K, which indicates good warm-white performance.     

Application of higher order spectral features and support vector machines for bearing faults classification

Condition monitoring and fault diagnosis of rolling element bearings timely and accurately are very important to ensure the reliability of rotating machinery. This paper presents a novel pattern classification approach for bearings diagnostics, which combines the higher order spectra analysis features and support vector machine classifier. The use of non-linear features motivated by the higher order spectra has been reported to be a promising approach to analyze the non-linear and non-Gaussian characteristics of the mechanical vibration signals. The vibration bi-spectrum (third order spectrum) patterns are extracted as the feature vectors presenting different bearing faults. The extracted bi-spectrum features are subjected to principal component analysis for dimensionality reduction. These principal components were fed to support vector machine to distinguish four kinds of bearing faults covering different levels of severity for each fault type, which were measured in the experimental test bench running under different working conditions. In order to find the optimal parameters for the multi-class support vector machine model, a grid-search method in combination with 10-fold cross-validation has been used. Based on the correct classification of bearing patterns in the test set, in each fold the performance measures are computed. The average of these performance measures is computed to report the overall performance of the support vector machine classifier. In addition, in fault detection problems, the performance of a detection algorithm usually depends on the trade-off between robustness and sensitivity. The sensitivity and robustness of the proposed method are explored by running a series of experiments. A receiver operating characteristic (ROC) curve made the results more convincing. The results indicated that the proposed method can reliably identify different fault patterns of rolling element bearings based on vibration signals.     

Three‐dimensional color prediction modeling of single‐ and double‐layered woven fabrics

In this research, the three‐dimensional structural and colorimetric modeling of three‐dimensional woven fabrics was conducted for accurate color predictions. One‐hundred forty single‐ and double‐layered woven samples in a wide range of colors were produced. With the consideration of their three‐dimensional structural parameters, three‐dimensional color prediction models, K/S‐, R‐, and L*a*b*‐based models, were developed through the optimization of previous two‐dimensional models which have been reported to be the three most accurate models for single‐layered woven structures. The accuracy of the new three‐dimensional models was evaluated by calculating the color differences ΔL*, ΔC*, Δh°, and ΔE_CMC(2:1) between the measured and the predicted colors of the samples, and then the error values were compared to those of the two‐dimensional models. As a result, there has been an overall improvement in color predictions of all models with a decrease in ΔE_CMC(2:1) from 10.30 to 5.25 units on average after the three‐dimensional modeling.     

基于可靠性评价的含缺陷核压力管道疲劳寿命预测方法

含缺陷压力管道经缺陷评定合乎使用后,其疲劳寿命的估计具有重要的工程意义。将整个含缺陷压力管道作为一个整体,分析了含缺陷压力管道的疲劳裂纹扩展特点,提出了相应的含缺陷压力管道疲劳寿命的计算过程,并在基于可靠性评价的基础上,给出了核压力管道的可接受失效概率,最终得到了含缺陷核压力管道疲劳寿命预测方法。