Synthesis of thermoresponsive copolymer/silica-coated magnetite nanoparticle composite and its application for heavy metal ion recovery

To enhance chemical stability and suppress of aggregation of magnetite nanoparticles (MNPs), which are used as a support for thermoresponsive copolymer immobilization, silica coating of the MNPs is applied via the electrooxidation method. Although the resulting silica coated-MNPs also formed aggregates, the size distribution of the aggregate shifted to smaller size range. Because of that, the surface area available for copolymer immobilization increased approximately 6.7 times at maximum as compared with that of the uncoated MNPs. It contributed to the increase of the amount of the immobilized copolymer on the silica-coated MNPs, which is approximately four times larger than that on the uncoated MNPs. Fe₃O₄ dissolution test confirmed enhancement of chemical stability of MNPs. The thermoresponsive copolymer immobilized on the silica-coated MNPs shows the ability to recycle Cu(II) ion from Cu(II) containing solution by changing temperature with significantly shorter time than those in other thermoresponsive adsorbents in gel form.     

Synthesis of succinic acid-based polyamide through direct solid-state polymerization method: Avoiding cyclization of succinic acid

Succinic acid is an important synthetic monomer but it is difficult to use it as a precursor for synthesizing high molecular weight polyamide, due to its tendency to perform intra-cyclization reaction at high temperature. In order to solve this problem, in this paper, the direct solid-state polymerization (DSSP) method with the initial reactant, nylon salt which was composed of 1, 5-diaminopentane, succinic acid, and terephthalic acid, was applied to synthesize the bio-based copolyamide PA 5T/54. In comparison with the conventional melting polymerization method, the DSSP method can prevent the cyclization reaction of succinic acid effectively due to the lower reacting temperature as well as the restriction effect of the nylon salt. As a result, the product fabricated by DSSP method has higher molecular weight and much lighter color from red to white. Therefore, the DSSP method is advantageous for the synthesis of the polymers or copolymers composed of the succinic acid as the monomer. Furthermore, the polymerization mechanism proposed in this work can serve as a guidance for the design of the molecular structure and control of the polymerization process.     

Investigation the correlation between chemical structure and swelling,thermal and flocculation properties of carboxymethylcellulose hydrogels

Hydrophilic polymer networks (hydrogels) based on sodium carboxymethylcellulose (NaCMC) and polycarboxylic acids (oxalic, succinic, citric and adipic) as cross-linking agents are synthesized by esterification reaction; one series of NaCMC hydrogels cross-linked with citric acid is prepared with acrylamide and acrylic acid (Aam/Aac) copolymers using the design of semi-interpenetrating polymer networks (semi-IPN), in order to increase their potential application for flocculation purposes. The Infrared spectroscopy (FTIR) of hydrogels confirms the esterification reaction between NaCMC and cross-linking agents. Results of swelling measurements show that citric acid in the amount of 15 wt% gives the hydrogels with the best absorption capacity. The results of Differential scanning calorimetry (DSC) and Thermal gravimetric analysis (TGA) show no significant difference in thermal properties of neat and semi-interpenetrating NaCMC hydrogels. The amorphous nature of hydrogels is confirmed by X-ray diffraction analysis (XRD). The results of flocculation study show that combination of NaCMC network and Aam/Aac copolymer with initial mass ratio of 10/90 creates a theoretical platform for the production of flocculant which could show high efficacy in purifying of water dominated by positively charged particles.     

Polymer electrets and their applications

Polymer electrets have revealed great potential application in electromechanical devices because of the low weight, large quasi-piezoelectric sensitivity, and excellent flexibility. For an electret, a permanent and macroscopic electric field exists on the surface, principally led by a macroscopic electrostatic charge on the surface or a net orientation of polar groups inside the object. Here, progress in the development of polymer electrets is reviewed. After a brief retrospect of the research courses and those typical polymer electrets that are classified into fluorine polymer and nonfluorine polymer, we present a survey on the charging methods, including corona, soft X-ray, contact, thermal and monoenergetic particle beams. The latest representative applications (i.e., power harvesting, sensors, field effect transistors, and biomedicine) based on polymer electrets are also summarized. Finally, we complete this review with a discussion on perspectives and challenges in this field.     

Understanding δ-Bi2O3 fluorite degradation mechanism and related solutions for promising applications in distributed multigeneration

Oxygen selective membrane on the base of cermet δ-Bi₂O₃/Ag with an interpenetrating structure has the maximum potential efficiency of air separation. However, the degradation processes, including the phase degradation of fluorite δ-Bi₂O₃, do not make it possible to create a membrane with the required perfection and durability. In this work, the ordering of oxygen vacancies with the transformation of fluorite into the rhombohedral phase (S.G. R-3) was studied by powder HT XRD in situ at 600 °C on dense Bi_0.78Er_0.2Hf_0.02O_1.51 ceramics. Fast regeneration of disordered fluorite occurs at T = 640–700 °C. The phase degradation of fluorite due to the segregation of dopants at the second stage leads into stable phases - sillenite, tetragonal or rhombohedral phase (S.G. R-3m), depending on the composition of δ-Bi₂O₃. Fast regeneration of fluorite occurs when heated to 820 °C, which is unacceptable for membranes. Analysis of all available data allows us to propose approaches to optimize the composition of δ-Bi₂O₃ and technical solutions for creating durable oxygen selective membranes with promising use in distributed multigeneration. As a result of the analysis, a new solid electrolyte with better parameters was obtained.     

A selective organosilica membrane for ethyl acetate dehydration by pervaporation

Organosilica bis(triethoxysilyl) ethane (BTESE) membranes were explored for pervaporation dehydration of binary and ternary mixtures of ethyl acetate (EA) by undiluted sol coating combined with flash firing. Three BTESE membranes (M1, M2, and M3) were fabricated on macroporous supports by varying BTESE concentrations (0.5, 2.5, and 5 wt% BTESE, respectively) in polymer sols. The membranes were characterized by DLS, SEM, FTIR, XRD, contact angle, AFM, and pervaporation performance to discuss the effect of the BTESE contents in the polymer sol on the formation and dehydration performance of resulting organosilica membranes. It was found that 5 wt% loading of BTESE led to a highly selective membrane for dehydration of EA/H₂O mixture. Among the synthesized membranes, M3 delivered flux of 0.84 ± 0.05 kg.m⁻².h⁻¹ with a selectivity of >10,000 for EA/H₂O mixture (98/2 wt%) at 60°C. The time course of pervaporation dehydration for the EA/H₂O mixture (95/5 wt%) confirms the stability of BTESE membrane in the investigated time period of 120 h. Further, the membrane exhibited excellent selectivity larger than 10,000 for separation of ternary mixtures (90/2/8 wt%) of ethyl acetate/ethanol/water and n-propyl acetate/isopropanol/water respectively, the composition of which is similar to the top product of the distillation column used in the industrial esterification process. The best separation performance and excellent acid stability of BTESE membranes in this study suggest that the simple synthesis protocol of undiluted sol coating and flash firing will provide a cost-effective, quick, and efficient synthesis route for practical membrane based applications.     

西汉徐地鲁恭王宫苑园林——鲁灵光殿研究

汉代是中国园林的形成阶段,不仅园林建筑物有所增加,成为住宅的延伸与扩展,而且人工造景比重也增大,造园要素趋于完备。园林的内容与功能随着社会生活的改变而逐步多样和完善,不仅是射猎、走狗、跑马的场所,还可以是游船、宴乐、赏鱼虫走兽、观看百戏的地方。造园在布局上也采用灵活多变的手法,按功能的需要,穿插安置不同形式的厅堂、楼阁、亭榭等。通过对鲁灵光殿时代背景及汉代园林、建筑营造形式的深入研究,结合文献的相关记述,梳理出鲁灵光殿的沿革,并以此为依据,对鲁灵光殿进行复原。     

Application of bio-based dimer acid diglycidyl ester in paper-based copper clad laminate

Using dimer acid (DA) as raw material, DA diglycidyl ester (DADGE) was synthesized and used as reactive toughening agent to prepare paper-based copper clad laminate (p-CCL). The factors affecting the epoxy value of DADGE and the effect of the resin on the gelation time were studied. The effects of the epoxy value and the addition amount of DADGE on the solderleaching resistance, flammability, water absorption, bending strength, and impact strength of the p-CCL were discussed. The results showed when the molar ratio of DA to ECH was 1:8 and the molar ratio of DA to sodium hydroxide was 1:1.6, the epoxy value of DADGE reached the maximum value of 0.23 mol/100 g. The DADGE can shorten the gelation time of the glue. The p-CCL meets the performance of the IPC-TM-650 standard. And when the addition amount of DADGE is less than 12 wt %, the flammability of the p-CCL reaches UL94V-0 level. The p-CCL prepared by adding 6 wt % of DADGE with 0.08 mol/100 g epoxy value has the best comprehensive performance, its toughness and rigid are comparable to those of p-CCL with 12 wt % of commercially available high performance toughening agents and it has higher solderleaching resistance. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47508.     

矿山深部卸压技术研究现状及展望

随着国内外矿山进入深部开采阶段，高应力特征显现，岩爆、冲击地压等地质灾害频发，增加了深部矿产资源开采的难度。卸压技术能够有效解决矿山深部局部高应力集中并防治矿山动力地质灾害，因而受到国内外学者的广泛关注。通过梳理国内外卸压技术研究现状，归纳总结了主要卸压技术（包括水力卸压、钻孔卸压、卸压槽/卸压巷道和爆破卸压等）及常用的研究手段（相似材料模拟和数值模拟），对比分析了各类卸压技术的优缺点。结合当前金属矿山深部开采的实际需求，提出未来卸压技术理论研究的若干重要方向：（1）深化理论研究，通过经验公式来确定合理的卸压参数，从而指导生产实践；（2）相比其他卸压技术，爆破卸压的应用前景广阔，同时多种卸压方法相结合是未来深部矿山开采的有效措施；（3）数值模拟在卸压技术及参数确定方面的优势显著，未来卸压技术研究应充分了解现场复杂地质条件，结合相似模拟、数值模拟与现场试验，提出一套适用于金属矿山深部开采实际的卸压技术方案。     

Effects of phenylenediamines and alkoxysilanes on gas transport properties of polyimide - silica hybrid membranes

Gas transport properties of polyimides (PIs) and their silica hybrids were investigated. The PIs synthesized with several methyl-substituted phenylenediamines were hybridized with silica via a sol–gel process with different alkoxysilanes. The prepared hybrid membranes showed controlled gas permselectivity, depending on the selected phenylenediamines and alkoxysilanes. It was worth noting that the hybrids prepared with tetraethoxysilane possessed improved CO₂ permselectivity with increasing silica content, which tended to exceed the upper-bound trade-off line. This fact suggested the additional formation of free volume holes especially favorable for the CO₂/CH₄ separation around the polymer/silica interfacial area.