Time-resolved GISAXS and cryo-microscopy characterization of block copolymer membrane formation

Time-resolved grazing-incidence small-angle X-ray scattering (GISAXS) and cryo-microscopy were used for the first time to understand the pore evolution by copolymer assembly, leading to the formation of isoporous membranes with exceptional porosity and regularity. The formation of copolymer micelle strings in solution (in DMF/DOX/THF and DMF/DOX) was confirmed by cryo field emission scanning electron microscopy (cryo-FESEM) with a distance of 72 nm between centers of micelles placed in different strings. SAXS measurement of block copolymer solutions in DMF/DOX indicated hexagonal assembly with micelle-to-micelle distance of 84–87 nm for 14–20 wt% copolymer solutions. GISAXS in-plane peaks were detected, revealing order close to hexagonal. The d-spacing corresponding to the first peak in this case was 100–130 nm (lattice constant 115–150 nm) for 17 wt% copolymer solutions evaporating up to 100 s. Time-resolved cryo-FESEM showed the formation of incipient pores on the film surface after 4 s copolymer solution casting with distances between void centers of 125 nm.     

Polystyrene-poly(2-ethylhexylmethacrylate) block copolymers: Synthesis,bulk phase behavior,and thin film structure

Anionic polymerization was employed to synthesize well-defined diblock copolymers of polystyrene and poly(2-ethylhexylmethacrylate), PS-PEHMA. Diblock morphologies in bulk and in substrate-supported thin films were characterized by small-angle X-ray scattering (SAXS) and atomic force microscopy (AFM), respectively. PS-PEHMA diblocks exhibited thermotropic order-disorder transitions; one diblock showed a thermoreversible transition between lamellae and a higher-temperature morphology assigned as perforated lamellae. Unlike PS-poly(alkylmethacrylate) diblocks where the alkyl group is n-butyl or n-pentyl, PS-PEHMA diblocks showed a typical decreasing Flory interaction parameter with increasing temperature. Thin films of PS-cylinder-forming PS-PEHMA diblocks showed a strong preference for the cylinders to lie in the plane of the film; films of incommensurate thickness readily formed terraces. Films of commensurate thickness were easily aligned over macroscopic areas through the application of mechanical shear.     

Morphological and mechanical study of nanostructured epoxy systems modified with amphiphilic poly(ethylene oxide-b-propylene oxide-b-ethylene oxide)triblock copolymer

Thermosetting systems based on DGEBA epoxy resin and poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (EPE) triblock copolymer were prepared and investigated. Different mixtures were obtained by using different contents of EPE block copolymer in order to study the influence of the modifier on the properties of the final materials. All thermosetting systems were prepared without using any solvent and were cured at ambient temperature, taking into account the lower critical solution temperature (LCST) behavior of the block copolymer. DSC results indicated that the addition of block copolymer affected to the curing reaction time and to the glass transition temperature of the mixtures and also the miscibility of EPE triblock copolymer in the epoxy resin was proved. The morphologies studied by AFM and TEM showed clear nanostructuration up to 25 wt % EPE content. The addition of 5 and 15 wt % of EPE block copolymer led to a considerable improvement in the toughness of the materials. When EPE block copolymer was added to the epoxy resin, the surface became more hydrophilic and the UV–vis transmittance decreased slightly maintaining a high level of transparency.     

Waterborne redox-active helix–coil–helix triblock metallopolymers: Synthesis,disassembly and electrochemical behaviors

Metallopolymers are emerging as a class of promising materials due to versatile properties and functionalities with a broad range of applications in high-performance devices. In this paper, a series of new helix–coil–helix poly(γ-benzyl-L-glutamate)-b-poly(ethylene glycol)-b-poly(γ-benzyl-L-glutamate) triblock copolymers selectively decorated with cyanoferrate complex (BEB-Fe) was successfully synthesized by combining ring-opening polymerization of γ-benzyl-L-glutamate carboxyanhydride using a primary amine terminated poly(ethylene glycol) as macromolecular initiator with a post-functionalization procedure. The polymers were characterized using GPC, NMR, UV–vis, FT-IR, CD, XRD, DLS, TEM, DSC and CV. Microstructural and morphological analysis revealed that incorporation of a proper amount of ferrate complex (≥19 wt%) in BEB led to disassembly of hexagonally packed structures of EBE. This afforded hybrid nanostructures with a size of approximately 18 nm. Glass transition temperature of BEB-Fe increased gradually with increasing ferrate fractions. BEB-Fe hybrid nanomaterials were electrochemically active. The apparent diffusion coefficient of BEB-Fe was increased with increasing ferrate fractions.     

Synthesis of thermoresponsive block and graft copolymers via the combination of living cationic polymerization and RAFT polymerization using a vinyl ether-type RAFT agent

A novel vinyl ether-type RAFT agent, benzyl 2-(vinyloxy)ethyl carbonotrithioate (BVCT) was synthesized for various block copolymers via the combination of living cationic polymerization of vinyl ethers and reversible addition−fragmentation chain transfer (RAFT) polymerization. The novel BVCT–trifluoroacetic acid adduct play an important role to produce well-defined block copolymers, which is both as a cationogen under EtAlCl₂ initiation system in the presence of ethyl acetate for living cationic polymerization and a RAFT agent for blocks by RAFT polymerization. The resulting polymer, poly(vinyl ether)s, by living cationic polymerization had a high number average α-end functionality (≥0.9) as determined by both ¹H NMR and MALDI-TOF-MS spectrometry. In addition, this poly(vinyl ether)s worked well as a macromolecular chain transfer agent for RAFT polymerization. The RAFT polymerization of radically polymerizable monomers was conducted in toluene using 2,2′-azobis(isobutyronitrile) at 70 °C. For example, a double thermoresponsive block copolymer (MOVE₆₁-b-NIPAM₁₅₀) consisting of 2-methoxyethyl vinyl ether (MOVE) and N-isopropylacrylamide (NIPAM) was prepared via the combination of living cationic polymerization and RAFT polymerization. The block copolymer reversibly formed and deformed micellar assemblies above the phase separation temperature (T_ps) of poly(NIPAM) block in water. This BVCT is not only functioned as an initiator, but also acted as a monomer. When BVCT was copolymerized with MOVE by living cationic polymerization, followed by graft copolymerization with NIPAM via RAFT polymerization, well-defined graft copolymers (MOVE_n-co-BVCT_m)-g-NIPAM_x (n = 62–73, m = 1–9, x = 19–214) were successfully obtained. However, no micelle formed in water above T_ps of poly(NIPAM) graft chain unlike the case of block copolymers.     

Effect of nanoparticle surface functionality on microdomain orientation in block copolymer thin films under electric field

The electric field induced microdomain orientations has been an interesting research topic. In this article, the effect of nanoparticle surface functionality on microdomain alignments in block copolymer/nanoparticle hybrid thin films was investigated with transmission electron microscopy experiments. The presence of gold nanoparticles influenced the microdomain orientation behaviors of block copolymer/nanoparticle thin films. The possibility for complete alignment normal to the substrate was illustrated by controlling electric field strength, concentration, and surface ligands of nanoparticles. This work provides basic and essential data to understand the properties and behaviors of emerging block copolymer/nanoparticle hybrid thin films.     

The theoretical BER performance analysis of a cooperative diversity scheme in frequency selective fading channel

A novel cooperative diversity scheme based on Distributed Space-Time Block Coding and Multi-Carrier Code Division Multiple Access (DSTBC-MC-CDMA) is proposed which works well in frequency selective fading channels with multiple single-antenna users. And an analytical error model is established to describe the symbol decoding errors between interusers, based on which a close form expression for theoretical Bit Error Rate (BER) performance of the scheme is derived to analyze the influence of the interuser decoding errors on the BER performance of the scheme. Then simulation is complimented to verify the analytic result above, which also shows that the BER performance of DSTBC-MC-CDMA outgoes that of non-cooperative MC-CDMA with considerable gains. Further- more, the simulations coincide with the theoretical results well.     

不同剂量 X射线全身照射对小鼠胸腺细胞周期进程的影响

本文采用细胞计量术研究了不同剂量Ｘ射线全身照射后小鼠胸腺细胞周期进程的变化。结果表明,７５ｍＧｙ Ｘ射线全身照射后２４～７２ｈ胸腺细胞周期各时相细胞数目发生明显变化,Ｇ０／Ｇ１期细胞数低于对照组,Ｓ期细胞数增多,说明其ＤＮＡ合成能力增强,至７ｄ时达到对照组水平;２．０Ｇｙ全身照射后４ｈ时胸腺细胞便开始出现明显的Ｇ２阻滞,１２ｈＧ２阻滞达最高点,７２ｈ其细胞周期进程明显加快,至７ｄ时达对照组水平。不     

浅层超稠油热采杜84-平28井设计与实钻技术

曙一区杜84块是辽河油田超稠油难采储量中规模较大的具有代表性的区块,开发中存在注汽困难、生产周期短、油井作业频繁热损失大、地层普遍出砂、综合成本高、开采难度大等一系列问题。根据油藏生产动态和综合分析油藏地质参数,结合油藏特征及原井网开发状况,通过对杜84-平28井优化设计和精心组织施工,重点对施工中产生的主要问题进行分析,采取科学合理的技术措施,取得显著的开发效果。     

高速铁路绝缘块耐环境能力的研究

铁路扣件系统是将钢轨固定在轨枕上,阻止钢轨相对于轨枕发生横纵向移动,保持轨距,在高速铁路运行过程中起到缓冲减震作用的系统。经过长期使用及列车的运行,有些尼龙产品扣件存在不同程度的损坏,产生松动现象,进而影响铁路运行安全。以扣件系统中的绝缘轨距块为研究对象,从环境及气候等多种因素研究其对轨距块性能的影响,找寻较为关键的影响因素。研究结果发现,室外环境放置的轨距块极限剪切性能下降更明显,耐冲击性更差。经过研究不同恶劣环境下轨距块性能的变化,发现高温高湿及高温环境下产品性能下降幅度较大,其中高温高湿影响最大。