Homotopy continuation enhanced branch and bound algorithms for strongly nonconvex mixed-integer nonlinear optimization

Large-scale strongly nonlinear and nonconvex mixed-integer nonlinear programming (MINLP) models frequently appear in optimization-based process synthesis, integration, intensification, and process control. However, they are usually difficult to solve by existing algorithms within acceptable time. In this study, we propose two robust homotopy continuation enhanced branch and bound (HCBB) algorithms (denoted as HCBB-FP and HCBB-RB) where the homotopy continuation method is employed to gradually approach the optimum of the NLP subproblem at a node from the solution at its parent node. A variable step length is adapted to effectively balance feasibility and computational efficiency. The computational results from solving four existing process synthesis problems demonstrate that the proposed HCBB algorithms can find the same optimal solution from different initial points, while the existing MINLP algorithms fail or find much worse solutions. In addition, HCBB-RB is superior to HCBB-FP due to much lower computational effort required for the same locally optimal solution.     

Combining molybdenum carbide with ceria overlayers to boost Mo/CeO2 catalyzed ammonia synthesis

The design of an efficient non-noble metal catalyst is of burgeoning interest for ammonia synthesis. Herein, we report a Mo₂C/CeO₂ catalyst that is superior in ammonia synthesis activity. In this catalyst, molybdenum carbide coexisted with the ceria overlayers which is from the ceria support as the strong metal–support interaction. There is a high proportion of low-valent Mo species, as well as high concentration of Ce³⁺ and surface oxygen species. The presence of Mo₂C and CeO₂ overlayers not only leads to enhancement of hydrogen and nitrogen adsorption, but also facilitates the desorption and exchange of adsorbed species with the gaseous reagents. Compared with the Mo/CeO₂ catalyst prepared without carbonization, the Mo₂C/CeO₂ catalyst is more than sevenfold higher in ammonia synthesis rate. This work not only presents an explicit example of designing Mo-based catalyst that is highly efficient for ammonia synthesis by tuning the adsorption and desorption properties of the reactant gases, but opens a perspective for other elements in ammonia synthesis.     

Various density light field image coding based on distortion minimization interpolation

In recent years, the light field (LF) as a new imaging modality has attracted wide interest. The large data volume of LF images poses great challenge to LF image coding, and the LF images captured by different devices show significant differences in angular domain. In this paper we propose a view prediction framework to handle LF image coding with various sampling density. All LF images are represented as view arrays. We first partition the views into reference view (RV) set and intermediate view (IV) set. The RVs are rearranged into a pseudo sequence and directly compressed by a video encoder. Other views are then predicted by the RVs. To exploit the four dimensional signal structure, we propose the linear approximation prior (LAP) to reveal the correlation among LF views and efficiently remove the LF data redundancy. Based on the LAP, a distortion minimization interpolation (DMI) method is used to predict IVs. To robustly handle the LF images with different sampling density, we propose an Iteratively Updating depth image based rendering (IU-DIBR) method to extend our DMI. Some auxiliary views are generated to cover the target region and then the DMI calculates reconstruction coefficients for the IVs. Different view partition patterns are also explored. Extensive experiments on different types LF images also valid the efficiency of the proposed method.     

Layered ceramics based on InGaO3(ZnO)2: Preparation and experimental investigation of high-temperature heat capacity and thermal conductivity

This paper reports on a method for producing ceramics from a high-purity, submicron InGaO₃(ZnO)₂ powder synthesised using a PVA-assisted gel combustion method, as well as an experimental study of the thermophysical properties of the ceramic materials obtained. The platelet-like crystallites of the InGaO₃(ZnO)₂ obtained were several microns long and up to several hundred nanometres thick. Layered ceramics obtained by sintering compacted InGaO₃(ZnO)₂ powders at temperatures of 1373–1773 K had a bulk density that was 68–96 % of the theoretical density. The temperature dependence of heat capacity in the range 306–1346 K was studied experimentally for InGaO₃(ZnO)₂ using the DSC method. It was found that, in the range 323–1173 K, layered InGaO₃(ZnO)₂ ceramics had a low thermal conductivity, which decreased from 2.0–1.3 W/(m K. The results obtained make it possible to consider this material as a promising thermal barrier coating.     

Lactones in the Synthesis of Prostaglandins and Prostaglandin Analogs

In the total stereo-controlled synthesis of natural prostaglandins (PGs) and their structural analogs, a vast class of compounds and drugs, known as the lactones, are encountered in a few key steps to build the final molecule, as: δ-lactones, γ-lactones, and 1,9-, 1,11-, and 1,15-macrolactones. After the synthesis of 1,9-PGF_2α and 1,15-PGF_2α lactones, many 1,15-lactones of E₂, E₃, F₂, F₃, A₂, and A₃ were found in the marine mollusc Tethys fimbria and the quest for understanding their biological role stimulated the research on their synthesis. Then 1,9-, 1,11-, and 1,15-PG lactones of the drugs were synthesized as an alternative to the corresponding esters, and the first part of the paper describes the methods used for their synthesis. The efficient Corey procedure for the synthesis of prostaglandins uses the key δ-lactone and γ-lactone intermediates with three or four stereocenters on the cyclopentane fragment to link the PG side chains. The paper describes the most used procedures for the synthesis of the milestone δ-Corey-lactones and γ-Corey-lactones, their improvements, and some new promising methods, such as interesting, new stereo-controlled and catalyzed enantioselective reactions, and methods based on the chemical/enzymatic resolution of the compounds in different steps of the sequences. The many uses of δ-lactones not only for the synthesis of γ-lactones, but also for obtaining 9β-halogen-PGs and halogen-substituted cyclopentane intermediates, as synthons for new 9β-PG analogs and future applications, are also discussed.     

Sol-gel auto-combustion synthesis of Ba–Sr hexaferrite ceramic powders

We report the mechanism involved in sol-gel auto-combustion synthesis of Ba–Sr-hexaferrite (Ba_1-xSr_xFe₁₂O₁₉; x = 0, 0.25, 0.5, 0.75 and 1, BSFO) ceramic powders through the analysis of the phases evolved during annealing of the as-synthesized powders, along with their structure and morphological studies. The XRD patterns of the as-synthesized samples indicate the formation of barium/strontium monoferrite ((Ba/Sr)Fe₂O₄) and maghemite (γ-Fe₂O₃) phases along with a minute amount of hematite (α-Fe₂O₃) phase. Annealing of these samples facilitates formation of BSFO phase through the solid state reaction between BaFe₂O₄ and γ-Fe₂O₃ phase. Interestingly, after annealing the samples with x = 0, 0.5 and 1, at 1000 °C for 2 h, we observed that phase pure Ba–Sr hexaferrite structure forms, but for samples with x = 0.25 and 0.75, high amount of hematite (α-Fe₂O₃) phase is observed, especially for x = 0.75. The reason associated with this could be the large difference between the ionic radii of Ba²⁺ and Sr²⁺ ions occupying the oxygen site. Furthermore, our study on annealing dependent phase evolution confirms that, this difference in ionic radii forbids the formation of a single phase Ba–Sr hexaferrite. The growth of clear hexagonal-shaped plate-like particles with varied particle sizes was observed for all the samples. The particle size variation may be due to the influence of the ionic radii difference on the sinterability of the samples. Our study provides a better understanding of synthesis mechanism of Ba–Sr hexaferrite samples.     

Sintering behavior of Ni–Zn ferrite powders prepared by molten-salt synthesis

Ni_0.5Zn_0.5Fe₂O₄ powders were prepared by a novel molten-salt synthesis method. The effects of calcination processes of the powders on their sintering behaviors were investigated. Compared with the synthesis by traditional solid-state reaction, the proposed molten-salt method can significantly reduce the synthesis temperature of Ni_0.5Zn_0.5Fe₂O₄ from 800 to 550°C below, and the prepared powders have relatively high sintering activity at low temperature, which can thus decrease the sintering temperature. However, the abnormal growth of grains is easy to occur during sintering, thus resulting in uneven grain size. In particular, during the molten-salt synthesis, the holding time for calcination is a dominant factor affecting the activity and crystallization degree of the resultant powders. From the point of view of increasing the density of sintered bodies, the optimal conditions for synthesizing Ni_0.5Zn_0.5Fe₂O₄ powder by the proposed molten-salt synthesis is 400°C for 6 h. In addition, the saturate magnetization of the finally obtained ferrite ceramics has nothing to do with the preparation processes, while their coercivity depends on their densification and grain size caused by their different processing routes.     

Crystallization behavior and density functional theory study of solution combustion synthesized silicon doped calcium phosphates

The influence of heat-treatment temperatures (700 °C, 900°C, 1200 °C) on the phase, physical properties, crystallization rate, and in vitro properties of the solution combustion synthesized silicon-doped calcium phosphates (CaPs) were investigated. The thermodynamic aspects (enthalpy, entropy, and free energy) of the synthesis process and the crystallographic properties of the final samples were first predicted and then confirmed using density functional theory (DFT). Results demonstrated that the crystallization rate was controlled by the fuel(s) type (glycine, citric acid, and urea) and the amounts of Si⁴⁺ ions (0, 0.1, 0.4 mol). The highest calculated crystallization rate values of the un-doped, 0.1, and 0.4 mol Si-doped samples were 64%, 22%, 38%, respectively. The obtained results from the DFT simulation revealed that crystal growth in the direction of c-axis of hydroxyapatite (HAp) structure could change the stability of (001) surface of (HAp). Also, the computational data confirmed the adsorption of Si–OH groups on the (001) surface of HAp during the SCS process with an adsorption energy of 1.53 eV. AFM results in line with DFT simulation showed that the observed change in the surface roughness of Si-doped CaPs from 2 to 8 nm could be related to the doping of Si⁴⁺ ions onto the surface of CaPs. Besides, the theoretical and experimental investigation showed that crystal growth and doping of Si⁴⁺ ions could decrease the activation energy of oxygen reduction reaction (ORR). Furthermore, the results showed that the crystallized HAp structure could have great potential to efficiently reduce oxidative stress in human body.     

A review on direct synthesis of dimethoxymethane

Polyoxymethylene dimethyl ethers are recognized as the prospective diesel additive to decrease the pollutant emission from the light-duty vehicles, which can be polymerize form the monomer of dimethoxymethane (DMM). The industrial synthesis of DMM is mainly involved two-step process: methanol is oxidized to form the formaldehyde in fixed bed reactor and then reacted with the generated formaldehyde through acetalization in continuous stirred-tank reactor. Due to huge energy consumption, this typical synthesis route of DMM needs to be upgraded and more green routes should be determined. In this review, four state-of-the-art one-step direct synthetic routes, including two upgrading routes (methanol direct oxidation and direct dehydrogenation) and two green routes (methanol diethyl ether direct oxidation and carbon oxides direct hydrogenation), have been summarized and compared. Combination with the reaction mechanism and catalytic performance on the different catalysts, the challenges and opportunities for every synthetic route are proposed. The relationships between catalyst structure and property in different synthesis strategy are also investigated and then the suggestions of the design of catalyst are given about future research directions that efforts should be made in. Hopefully, this review can bridge the gap between newly developed catalysts and synthesis technology to realize their commercial applications in the near future.     

基于多边限定的室内定位方法设计与系统实现

随着基于位置服务（Location Based Services，LBS）的发展与智能移动设备的普及，室内定位算法与系统受到了广泛研究与关注。为提高室内定位精度、增强系统鲁棒性，提出了基于多边限定的fingerprint定位方法。基于Wi-Fi RSSI（Received Signal Strength Indication）信号处理建立离线fingerprint数据库；通过对拟合距离-RSSI函数分析，提出了多边限定的方法确定一个最佳参考点（Reference Point，RP）集合，缩小在线定位阶段的搜索范围。在此基础上，再利用fingerprint定位方法进行定位。此外，实现了基于提出方法的室内定位系统原型用于算法性能评估。通过大量真实场景实验分析、验证了相较于传统fingerprint方法，基于多边限定的fingerprint定位方法能有效提高室内定位精度，增强系统鲁棒性。