Electrochemical determination of niobium cathode as an efficient electrocatalyst for hydrogen generation in acidic media

Hydrogen gas (H₂) is notified as a renewable energy carrier. It is wanted to discover a low-cost electrocatalyst for the hydrogen evolution reaction (HER) to substitute the high-cost Pt in electrolysis cell. Niobium electrocatalyst nominated to substitute noble materials for electrocatalytic H₂ production and its electrochemical manner was estimated in H₂SO₄ acid of various concentrations utilizing a steady-state polarization and electrochemical impedance spectroscopy (EIS). The influences of acid concentration, cathodic potential and temperature on the H₂ creation were examined. The outcomes display that HER on Nb electrode proceeds by the Volmer-Heyrovsky mechanism. EIS tests, under open circuit and under cathodic polarization, were performed and the fitting has been done utilizing a suggested model for the electrode/electrolyte interface. Apparent activation energies (E_a) were estimated to be ca. 10.5 kJ mol^?1 for the HER on Nb. Thus, Nb is a good electrocatalyst for the cathodic H₂ manufacturing.     

高压下CL-20拉曼光谱和红外光谱相变研究

为了更好地认识和了解CL-20晶体结构演变规律和相变行为,利用金刚石对顶砧超高压实验技术,在0~50GPa下,研究了高压下ε-CL-20的原位拉曼光谱和红外光谱。结果表明,CL-20晶体在整个加压过程中存在两个相变,第一个相变发生在4.2~7.5GPa,认为是ε相到对称性更低的γ相转变,相变产生的原因是在压强的作用下,笼环外的硝基方向发生改变,电子云密度重置导致的分子构型转变;第二个相变发生在14.2~18.9GPa,属于γ相到ζ相的晶体结构转变;卸压后,拉曼和红外光谱恢复常压状态,表明CL-20晶体在研究压强范围内的相变过程是可逆的。     

Effect of moisture and filler content on the structural,thermal and dielectric properties of polyamide‐6/boehmite alumina nanocomposites

Polyamide‐6 (PA‐6)/boehmite alumina (BA) nanocomposites were prepared via direct melt compounding. Structural, thermal and dielectric properties of ‘as‐received’ (including moisture) and ‘dried’ (thermally treated) specimens were examined. The BA nanofiller was homogeneously dispersed in the PA‐6 matrix. XRD and FTIR revealed that crystallization of PA‐6 in the γ phase was favoured over α phase with increasing BA content. The crystallinity index (CI) and the percentage of α and γ phases were also evaluated. Dried specimens exhibited a lower CI than as‐received specimens while the CI decreased with the addition of filler. Broadband dielectric spectroscopy revealed the presence of γ, β and α relaxations, the Maxwell–Wagner–Sillars effect and the contribution of conductivity relaxation in the as‐received samples. The drying procedure unmasked a double feature of both β and α modes. The results of the complementary techniques were analysed and the effects of moisture and/or the incorporation of BA nanofiller on the microstructure of the PA‐6 matrix are disclosed. © 2019 Society of Chemical Industry     

Study of spatial and temporal evolution of Ar and F atoms in SF6/Ar microsecond pulsed discharge by optical emission spectroscopy

The study of sulfur hexafluoride (SF₆) discharge is vital for its application in gas-insulated equipment. Direct current partial discharge (PD) may cause SF₆ decomposition, and the decomposed products of SF₆, such as F atoms, play a dominant role in the breakdown of insulation systems. In this study, the PD caused by metal protrusion defects is simulated by a needle-plate electrode using pulsed high voltage in SF₆/Ar mixtures. The spatial and temporal characteristics of SF6/Ar plasma are analyzed by measuring the emission spectra of F and Ar atoms, which are important for understanding the characteristics of PD. The spatial resolved results show that both F and Ar atom spectral intensities increase first from the plate anode to the needle and then decrease under the conditions of a background pressure of 400 Pa, peak voltage of −1000 V, frequency of 2 kHz, pulse width of 60 μs, and electrode gap of 5–9 mm. However, the distribution characteristics of F and Ar are significantly different. The temporal distribution results show that the spectral intensity of Ar decreases first and then increases slowly, while the spectral intensity of F increases slowly for the duration of the pulsed discharge at the electrode gap of 5 mm and the pulse width of 40–80 μs.     

Combination of nuclear magnetic resonance spectroscopy and nonlinear methods to analyze the copolymerization of phosphonic acid derivatives

We demonstrate in this study that the combination of modern inline monitoring methods [here: inline nuclear magnetic resonance (NMR)] with simulations gains more exact and profound kinetic results than previously used methods like linearization without that combination. The ¹H-NMR spectroscopic data (more than 100 data points) are used to construct the copolymerization diagram. The reactivity ratios are obtained applying the van Herks nonlinear least square method. The examination of the radical copolymerization of 2-hydroxyethyl methacrylate (HEMA) with (2-{[2-(ethoxycarbonyl)prop-2-en-1-yl]oxy}ethyl) phosphonic acid (ECPPA) as important adhesive monomer used in dentistry yields reactivity ratios of r_HEMA = 1.83; r_ECPPA = 0.42. The copolymerization diagram reflects nonideal, non-azeotropic copolymerization. The sequence distribution of the obtained by Monte Carlo simulation indicates the generation of statistical copolymers. As an important finding, it is demonstrated that the repeating units responsible for etching and adhesion are arranged over the whole polymer chain, which is necessary to achieve proper functionality. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48256.     

Resonance Assignments of Lowly Populated and Unstable Enzyme Intermediate Complex under Real-Time Conditions

Unstable and low-abundance protein complexes represent a large family of transient protein complexes that are difficult to characterize, even by means of high-resolution NMR spectroscopy. A method to assign the NMR signals of these unstable complexes through a combination of selective isotope labeling of amino acids in a protein and site-specific labeling the protein with a paramagnetic tag is presented herein. By using this method, the resonances of unstable thioester intermediate complex (lifetime <5 h and highest concentration ≈20 μm ) generated by Staphylococcus aureus sortase A and its peptide substrate under a real-time reaction have been assigned.     

Corrosion behaviour of Al1.3CrFeNi chemically complex alloy

In this study, corrosion behaviour of double-phase Al_1.3CrFeNi chemically complex alloy was investigated, including hot corrosion and electrochemical corrosion. Hot corrosion behaviour of Al_1.3CrFeNi alloy was explored in molten 75 wt-% Na₂SO₄?+?25 wt-% NaCl salt. The result revealed that the corrosion kinetic curve of Al_1.3CrFeNi alloy followed the exponential rate rule through mass loss measurement. In addition, it prevented that the formed corrosion layer had obvious stratification including external granular Al₂O₃ and inner porous Cr₂O₃ when corrosion time was up to 100?h. Besides, it should be noted that the Al_1.3CrFeNi alloy was sensitive to the molten salt containing chlorine, which makes the alloy surface leave voids and bring about acceleration of corrosion. Meanwhile, electrochemical corrosion resistance of Al_1.3CrFeNi alloy in NaCl solution with different concentrations (0.6, 1.0 and 2.0?mol?L^?1) was investigated at room temperature. The results revealed that Al_1.3CrFeNi alloy showed superior corrosion resistance in NaCl solution due to the existence of Al and Cr which aid the formation of protective oxide layer.     

Investigation of the relationship between intergranular corrosion and retrogression and reaging in the AA6063

AA6063 was heat treated with different retrogression temperatures and durations, and the effect of heat treatment conditions on the microstructure, hardness, electrical conductivity, intergranular corrosion (IGC) and electrochemical corrosion behaviours of the AA6063 was determined compared with the T6 condition. The IGC test was applied according to the BS EN ISO 11846: 2008 standard. Moreover, potentiodynamic polarization tests were applied to determine the electrochemical corrosion behaviour of the heat‐treated samples. Electrochemical corrosion tests were carried out by using a Ivium Compactstat potentiostat in 3.5 wt.%. NaCl solution at 24°C with a scanning rate of 0.5 mV/s. The corrosion test cell consisted of the reference electrode (Ag/AgCl), working electrode (test sample) and a reference electrode (platinum). The effect of IGC on the microstructure of AA6063 and corrosion depth values was investigated by using a stereo optical microscope and a light metal microscope, respectively. Corrosion depth examinations were performed on microstructures taken from the cross‐sections of the samples. The chemistry of the precipitates formed at grain boundaries and distribution of the precipitates in the microstructure were investigated by scanning electron microscope, energy dispersive X‐ray and transmission electron microscope analyses. The results showed that retrogression and reaging heat treatment improves both the corrosion resistance and the mechanical properties of AA6063. After 50°C/15 min RRA heat treatment, the highest corrosion resistance and a higher hardness value than the T6 level were obtained.     

磁场环境下铝电解熔融铝液成分激光诱导击穿光谱原位测量分析

铝电解车间具有高温、强磁、多粉尘等环境特点,当前生产过程中熔融原铝的成分检测主要是人工取样然后离线分析,化验过程及结果具有较大的滞后性,故将激光诱导击穿光谱(LIBS)技术应用于铝电解车间铝液成分原位、实时测量具有重要意义。实验采用Nd:YAG脉冲激光器,多通道光纤光谱仪和电感耦合器件(CCD)探测器组成的激光诱导击穿光谱测量系统对电流为400kA电解槽中熔融铝液的主要成分铁、硅进行了探测,对原铝中部分元素的特征谱线进行了归属分析。考察了激光能量在磁场环境下的衰减变化及谱线梯度变迁规律,结果表明,距离电解槽边缘约2m处激光能量衰减达最大。分析了磁场对测试系统的影响,并建立了定标曲线,铁和硅两种元素按照内标法建立的定标曲线拟合度分别为93.50%和97.10%,采用该模型进行了测试实验,并用国标GB/T 7999—2015中光电直读发射光谱(OES)测试的相关指标验证测试结果的重复性与允许差。实验证明,LIBS技术在电解铝行业在线检测方面具有较好的应用前景,但是测试的稳定性与重复性也是面临的一个重要问题。