Superconducting Quantum Metamaterials from High Pressure Melt Infiltration of Metals into Block Copolymer Double Gyroid Derived Ceramic Templates

Mesoscale order can lead to emergent properties including phononic bandgaps or topologically protected states. Block copolymers offer a route to mesoscale periodic architectures, but their use as structure directing agents for metallic materials has not been fully realized. A versatile approach to mesostructured metals via bulk block copolymer self-assembly derived ceramic templates, is demonstrated. Molten indium is infiltrated into mesoporous, double gyroidal silicon nitride templates under high pressure to yield bulk, 3D periodic nanocomposites as free-standing monoliths which exhibit emergent quantum-scale phenomena. Vortices are artificially introduced when double gyroidal indium metal behaves as a type II superconductor, with evidence of strong pinning centers arrayed on the order of the double gyroid lattice size. Sample behavior is reproducible over months, showing high stability. High pressure infiltration of bulk block copolymer self-assembly based ceramic templates is an enabling tool for studying high-quality metals with previously inaccessible architectures, and paves the way for the emerging field of block-copolymer derived quantum metamaterials.     

Synthesis and characterization of poly(ethylene oxide)‐based glycopolymers and their biocompatibility with osteoblast cells

Poly(ethylene oxide)‐block‐poly(methacryl‐d ‐glucopyranoside) (PEO‐GP) and poly(methacryl‐d ‐glucopyranoside) (H‐GP) glycopolymers were synthesized by deacetylation of acetylated polymers which were synthesized via atom transfer radical polymerization. The synthesized glycopolymers were characterized using ¹H NMR, ¹³C NMR and Fourier transform infrared (FTIR) spectroscopies, gel permeation chromatography (GPC), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The deacetylated polymers exhibited onset decomposition temperatures about 60 °C lower compared to the polymers having acetyl pendants. The glass transition temperature (T_g) of the acetylated homopolymer was 133 °C and that of the PEO‐based block copolymer was 124 °C. The deacetylated polymers H‐GP and PEO‐GP exhibited T_g values of about ?30 °C. Biocompatibility of the H‐GP and PEO‐GP glycopolymers was obtained by studying osteoblast cell adhesion, viability and proliferation in vitro. The cell viability showed an increase with increasing concentration of H‐GP from 0.1 to 1 µmol L^?1 and then decreased with further increase in its concentration (10–1000 µmol L^?1). PEO‐GP did not show a significant variation in cell viability on variation of its concentration from 0.1 to 1000 µmol L^?1. The significant improvement in biocompatibility with osteoblast cells in the presence of PEO‐GP was considered as due to the covalently bonded PEO segment of the methacrylate glycopolymer block. © 2014 Society of Chemical Industry     

Synthesis and characterization of copolymers with the same proportions of polystyrene and poly(ethylene oxide) compositions but different connection sequence by the efficient Williamson reaction

The AB type diblock PS‐b‐PEO and ABA type triblock PS‐b‐PEO‐b‐PS copolymers containing the same proportions of polystyrene (PS) and poly(ethylene oxide) (PEO) but different connection sequence were synthesized and investigated. Using the sequential living anionic polymerization and ring‐opening polymerization mechanisms, diblock PS‐b‐PEO copolymers with one hydroxyl group at the PEO end were obtained. Then, using the classic and efficient Williamson reaction (realized in a ‘click’ style), triblock PS‐b‐PEO‐b‐PS copolymers were achieved by a coupling reaction between hydroxyl groups at the PEO end of PS‐b‐PEO. The PS‐b‐PEO and PS‐b‐PEO‐b‐PS copolymers were well characterized by ¹H NMR spectra and SEC measurements. The critical micelle concentration (CMC) and thermal behaviors were also investigated by steady‐state fluorescence spectra and DSC, respectively. The results showed that, because the PEO segment in triblock PS‐b‐PEO‐b‐PS was more restricted than that in diblock PS‐b‐PEO copolymer, the former PS‐b‐PEO‐b‐PS copolymer always gave higher CMC values and lower crystallization temperature (T_c), melting temperature (T_m) and degree of crystallinity (X_c) parameters. © 2015 Society of Chemical Industry     

增容高抗冲聚苯乙烯/高乙烯基聚丁二烯橡胶热塑性硫化胶的Mullins效应及其可逆性

采用动态硫化法制备了苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)增容高抗冲聚苯乙烯(HIPS)/高乙烯基聚丁二烯橡胶(HVPBR)热塑性硫化胶(TPV),考察了SBS用量对TPV物理机械性能的影响,表征了TPV的微观形貌,并研究了TPV的Mullins效应及其可逆性。结果表明,SBS可显著改善HIPS/HVPBR体系的相容性,其用量为12份时,TPV的物理机械性能较好;SBS增容TPV的断面平整、结构致密,界面相互作用明显增强;SBS增容TPV在循环单轴拉伸过程中出现明显的Mullins效应,提高应变速率时,TPV的最大应力和内耗呈增大趋势,瞬时残余形变则减小;当拉伸比相同时,TPV经第1次拉伸热处理后,第2次单轴拉伸中TPV的最大应力和内耗均增大,瞬时残余形变则减小。     

One-pot synthesis of poly(methacrylic acid)-b-poly(2,2,2-trifluoroethyl methacrylate) diblock copolymers via RAFT polymerization

In this work, the reversible addition-fragmentation chain transfer (RAFT) polymerization was utilized to synthesize the amphiphilic diblock copolymers of poly(methacrylic acid)-b-poly(2,2,2-trifluoroethyl methacrylate) (PMAA-b-PTFEMA) via one-pot two-step reaction protocol. The controlled radical polymerization of MAA monomer was first carried out in pure water by using 4-cyanopentanoic acid dithiobenzoate (CADB) as chain transfer agent. Subsequently, the as-synthesized PMAA homopolymers with dithiobenzoate end-groups were employed as macro-CTA and chain-extended in situ with the hydrophobic TFEMA monomer. The reactions were carried out in 1,4-dioxane/water medium. Both the polymerization of PMAA and PTFEMA blocks showed the well controllability on the molecular weighs and distributions. It was found that the amphiphilic diblock copolymers formed the stable spherical particles via the polymerization-induced self-assembly. Meanwhile, the effect of various parameters, such as the concentration ratio of TFEMA monomer over PMAA macro-CTA, the solvent condition (different ratio of 1,4-dixane/water), and the pH, on the RAFT polymerization of TFEMA monomer were investigated in detail. Their kinetic results suggested that the propagation of TFEMA monomer on the macro-CTA was performed at the particle/water interfaces. The concentration of chain transfer agents at the interfaces determined the polymerization rate. Finally, the stability of the fluorinated polymer dispersions was also evaluated in this work.     

Polymer brush coatings for combating marine biofouling

A variety of functional polymer brushes and coatings have been developed for combating marine biofouling and biocorrosion with much less environmental impact than traditional biocides. This review summarizes recent developments in marine antifouling polymer brushes and coatings that are tethered to material surfaces and do not actively release biocides. Polymer brush coatings have been designed to inhibit molecular fouling, microfouling and macrofouling through incorporation or inclusion of multiple functionalities. Hydrophilic polymers, such as poly(ethylene glycol), hydrogels, zwitterionic polymers and polysaccharides, resist attachment of marine organisms effectively due to extensive hydration. Fouling release polymer coatings, based on fluoropolymers and poly(dimethylsiloxane) elastomers, minimize adhesion between marine organisms and material surfaces, leading to easy removal of biofoulants. Polycationic coatings are effective in reducing marine biofouling partly because of their good bactericidal properties. Recent advances in controlled radical polymerization and click chemistry have also allowed better molecular design and engineering of multifunctional brush coatings for improved antifouling efficacies.     

刺激响应性聚合物纳米胶束在药物控释中的应用研究

聚合物纳米胶束不仅可以提高药物的溶解度、生物利用度,延长药物在人体内的循环时间,还可以有效控制药物的释放而实现靶向治疗效果,极大地减少药物对人体的副作用。通过嵌段共聚物的纳米工程,可制备出具有细胞或组织靶向性且对物理或化学刺激敏感的高分子药物载体。本文综述了对pH值、温度、超声波和光具有响应性的聚合物纳米胶束的制备及其在药物控制释放领域的应用。     

三角平衡轮廓轮胎滚动阻力的仿真研究

三角平衡轮廓轮胎是一种新型的轮胎结构,以低扁平率的传统轮廓轮胎255/30R22为基础,在其胎肩处和胎侧处增加高强度的支撑块来提高轮胎的性能。支撑块起到支撑胎面的作用,提高了胎侧的刚度。本文以滚动阻力计算公式和材料内耗机理为基础,用ABAQUS软件分别模拟2种轮胎的滚动阻力来验证三角平衡轮廓轮胎是否具有较低的滚动阻力。首先建立三角平衡轮廓轮胎和255/30R22轮胎的三维模型,施加相同载荷,对其进行以60km/h滚动工况的力学分析,算出单元积分点的生热率,提取每个单元的体积,最后计算每一种胶料的滚动阻力及轮胎总滚动阻力。通过两者的对比,三角平衡轮廓轮胎的滚动阻力仅18.7N,低于255/30R22轮胎滚动阻力的二分之一。     

综采工作面过辅助运输联络斜巷关键技术研究

为了提高综采工作面安全高效生产,以东滩煤矿143下04综采工作面回采过程中过142运输巷2号辅助运输联络斜巷为背景,在工程实践中主要采用了加强顶板管理、加强截割层位控制以及加强设备管理等关键技术,工作面在生产过程中未出现顶板冒落、掉顶现象,安全稳定的通过辅助运输联络斜巷穿层区域,为综采工作面安全高效的生产积累了经验。