Formation of Chlorotriophenoxy Radicals from Complete Series Reactions of Chlorotriophenols with H and OH Radicals

The chlorothiophenoxy radicals (CTPRs) are key intermediate species in the formation of polychlorinated dibenzothiophenes/thianthrenes (PCDT/TAs). In this work, the formation of CTPRs from the complete series reactions of 19 chlorothiophenol (CTP) congeners with H and OH radicals were investigated theoretically by using the density functional theory (DFT) method. The profiles of the potential energy surface were constructed at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The rate constants were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) contribution at 600–1200 K. The present study indicates that the structural parameters, thermal data, and rate constants as well as the formation potential of CTPRs from CTPs are strongly dominated by the chlorine substitution at the ortho-position of CTPs. Comparison with the study of formation of chlorophenoxy radicals (CPRs) from chlorophenols (CPs) clearly shows that the thiophenoxyl-hydrogen abstraction from CTPs by H is more efficient than the phenoxyl-hydrogen abstraction from CPs by H, whereas the thiophenoxyl-hydrogen abstraction from CTPs by OH is less impactful than the phenoxyl-hydrogen abstraction from CPs by OH. Reactions of CTPs with H can occur more readily than that of CTPs with OH, which is opposite to the reactivity comparison of CPs with H and OH.     

Optimal filtering and control for wireless networked closed-loop control systems

This article studies the optimal filtering and control for wireless networked control systems (WNCSs). In WNCSs, packets may be lost in both control and feedback channels and user datagram protocol is usually used to improve the performance of the real-time control. Relevant literature indicates that the conventional optimal filtering for such a system cannot be applied in practice due to the complex calculation with Gaussian mixtures. This paper proposes a novel scheme to realize the optimal filtering and the linear quadratic Gaussian control for WNCSs, in which the controlled node performs a local estimation and the remote-control node performs the final estimation and control, and a synchronization of two estimators is guaranteed by a communication mechanism. An optimal filtering algorithm is developed, the stability condition of the filtering error covariance is obtained, optimal finite-horizon and infinite-horizon control are derived, and the stability of the closed-loop control system is proved. Numerical simulations show the validity and feasibility of the theoretical results.     

Preparation of nanocrystalline nickel oxide from nickel hydroxide using spark plasma sintering and inverse Hall-Petch related densification

Nanocrystalline nickel oxide (NiO) was prepared from nickel hydroxide by Spark plasma sintering (SPS) and the mechanisms involved in the densification of NiO were studied. Reverse precipitated nickel hydroxide powders were SPS processed at 400, 600 and 700?°C with 70?MPa pressure. Pure NiO with 12?nm crystallite size formed after 400?°C sintering process. However NiO grains had grown to 18 and 38?nm after 600 and 700?°C sintering respectively. NiO pellets prepared using 600 and 700?°C SPS sintering schedules had relative densities of 83% and 94% respectively. Two displacement rate regimes were observed during densification of NiO in both 600 and 700?°C sintering processes. Decomposition of nickel hydroxide and particle sliding of NiO led to first displacement rate maximum while inverse Hall-Petch based plastic deformation facilitated densification during the constant second displacement rate regime. No densification occurred during sintering holding times indicating the limited role that diffusion played during densification.     

A mixed collector system for phosphate flotation

Flotation has been used in industry for more than a half century as the primary technique for upgrading phosphate. While the flotation of phosphate was inefficient when oleic acid was used alone as a collector, therefore a mixed collector of oleic acid (HOl), linoleic acid (LA) and linolenic acid (LNA) was employed to improve the recovery of phosphate flotation. The batch flotation results showed that the optimal composition of the mixed collector was 54 wt.% HOl, 36 wt.% LA and 10 wt.% LNA. Additionally, the effect of pH on the mixed collector application was studied while considering the surface tension, contact angle and micro-flotation. The results showed that the mixed collector should be used at a pH of 9.5. Above a pH of 9.5, the adsorption of fatty acids dimers on the apatite surface hindered phosphate flotation. The influence of the mixed collector assembly on apatite flotation was also investigated. It was demonstrated that due to its low critical micelle concentration, a sufficiently hydrophobic apatite surface could be generated at a collector concentration of 60 mg/L. In addition, zeta potential experiments suggested that collector adsorption was governed by chemisorption. FTIR and XPS spectra studies further indicated that the chemical reaction involved the carboxyl groups of fatty acids and Ca species at the apatite surface for each fatty acid in the mixed collector.     

基于门控联合池化自编码器的通用性文本表征

为了学习文本的语义表征,以往的研究者主要依赖于复杂的循环神经网络(recurrent neural networks, RNNs)和监督式学习方法。该文提出了一种门控联合池化自编码器(gated mean-max AAE)用于学习中英文的文本语义表征。该文的自编码器完全通过多头自注意力机制(multi-head self-attention mechanism)来构建编码器和解码器网络。在编码阶段,提出了均值—最大化(mean-max)联合表征策略,即同时运用平均池化(mean pooling)和最大池化(max pooling)操作来捕获输入文本中多样性的语义信息。为促使联合池化表征可以全面地指导重构过程,解码器采用门控操作进行动态关注。通过在大规模中英文未标注语料上训练模型,获得了高质量的句子编码器。在重构文本段落的实验中,该文模型在实验效果和计算效率上均超越了传统的RNNs模型。将公开训练好的文本编码器,使其可以方便地运用于后续的研究。     

古建筑木结构透榫节点力学模型研究

为研究古建筑木结构透榫节点的M-θ力学模型，在分析透榫节点构造特征与受力机理的基础上，建立其数值模型，用透榫节点的试验数据验证了该数值模型的正确性，并分析了节点缝隙、木材横纹弹性模量和大榫头长度对透榫节点受弯承载力的影响。根据受力分析结果，建立以弹性点、屈服点与极限点为特征点的三折线多参数M-θ力学模型，其结果与多数的试验结果基本吻合，并将该力学模型应用于木构架的受力分析。研究结果表明：透榫节点的滞回耗能能力强，节点的变形主要集中在榫头处。当榫头与卯口之间的缝隙增大时，节点的受弯承载力降低。随木材横纹弹性模量的提高和大榫头长度的增加，节点的受弯承载力有一定提高。文章建立的M-θ力学模型能较好反映透榫节点的受力过程，适用于木构架的受力分析，其荷载 位移骨架曲线与试验结果基本吻合。研究成果可为古建筑木结构的维修与保护提供参考。     

叠合盆地凸起区多期复杂断裂特征及形成机制——以准噶尔盆地车排子凸起为例

以高精度三维地震资料为基础,结合构造演化恢复和区域构造背景,系统研究了准噶尔盆地车排子凸起断裂分布和形成机制。结果表明,车排子凸起发育深部和浅部2套断裂体系,深部断裂体系和浅部断裂体系分别发育3种断裂样式。车排子凸起共经历5个构造演化阶段,其中,晚二叠世挤压-逆冲控制了深部断裂体系的初始形成,晚侏罗世逆冲-走滑控制了深部断裂体系的最终定型,新近纪叠加掀斜、局部伸展控制了浅部断裂体系的形成。不同断裂体系在油气成藏过程中均起到了重要作用。其中:深部断裂体系的红车断裂是重要的油源断裂,低序级断层控制形成了石炭系火山岩优质储集体;浅部断裂体系使得油气向浅部层系运移调整,同时形成了断块圈闭、断鼻圈闭和断层-岩性圈闭等丰富的圈闭类型。     

Size-controlled synthesis of Mo powders via hydrogen reduction of MoO2 powders with the assistance of Mo nuclei

The size-controlled preparation of Mo powders is always a challenge and important task in the molybdenum metallurgy. In the current study, Mo powders with controllable sizes are synthesized by hydrogen reduction of MoO₂ powders with the assistance of Mo nuclei in the range of 900–1100 °C. The influences of the particle sizes of Mo nuclei, the additive amount as well as reaction temperature on the morphology and particle sizes of the final products are studied. For the hydrogen reduction of MoO₂ without any additive, the obtained Mo powders always have large particle sizes. However, the addition of small amounts of nuclei in MoO₂ can help Mo nucleate dispersedly, and the growth of Mo could be also controlled by adjusting the sizes of added nuclei, amount of addition and the reaction temperature. With the addition of Mo nuclei, the different sizes of Mo powders with the good dispersity can be prepared. As adding commercial Mo powders with the particle size of about 2.03 μm, the micron-sized Mo powders ranged from 2.11 μm to 3.25 μm could be prepared. While for the case of adding ultrafine Mo nuclei of about 170 nm, Mo powders from 0.28 μm to 0.88 μm can be obtained. Moreover, the more the amounts of nuclei added and the lower the reaction temperature (in the range of 900–1100 °C) is, the smaller the particle size of the prepared Mo powder will be. The current method is a facile and feasible method, and is potential to be used for industrial production of Mo powder with controllable particle sizes.     

Effect of microstructure on the fatigue crack growth behaviour of a near-α Ti alloy

Fatigue crack growth behaviour of Ti–6Al–2Zr–1.5Mo–1.5V (VT-20 a near-α Ti alloy) was studied in lamellar, bimodal and acicular microstructural conditions. Fatigue crack growth tests at both increasing and decreasing stress intensity factor range values were performed at ambient temperature and a loading ratio of 0.3 using compact tension samples. Lamellar and acicular microstructures showed lower fatigue crack growth rates as compared to the bimodal microstructure due to the tortuous nature of cracks in the former and the cleavage of primary α in the latter. The threshold stress intensity factor range was highest for acicular microstructure.