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.     

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。     

旧城文脉的延续与空间的完善--以珠海市莲花路街区立体化改造为例

珠海市莲花路街区存在商业空间不成系统、商业集聚力缺乏、公共空间缺乏活力、步行街过大的人流量影响地面环境等问题,需对其进行城市空间的立体化改造.规划保留旧的城市轴线以延续城市文脉,开辟新的城市轴线以发展和完善城市空间,并力图使新的休闲娱乐轴线与莲花路历史文化轴线实现有机结合.     

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。     

Nonlinear state feedback controller design for underactuated mechanical system: A modified block backstepping approach

This paper presents the formulation of a novel block-backstepping based control algorithm to address the stabilization problem for a generalized nonlinear underactuated mechanical system. For the convenience of compact design, first, the state model of the underactuated system has been converted into the block-strict feedback form. Next, we have incorporated backstepping control action to derive the expression of the control input for the generic nonlinear underactuated system. The proposed block backstepping technique has further been enriched by incorporating an integral action additionally for enhancing the steady state performance of the overall system. Asymptotic stability of the overall system has been analyzed using Lyapunov stability criteria. Subsequently, the stability of the zero dynamics has also been analyzed to ensure the global asymptotic stability of the entire nonlinear system at its desired equilibrium point. The proposed control algorithm has been applied for the stabilization of a benchmarked underactuated mechanical system to verify the effectiveness of the proposed control law in real-time environment.     

自然崩落法放矿排产品位连续预测模型

简单介绍了自然崩落法的放矿原理,阐述了劳伯斯特品位估值法的原理,针对目前该方法不能计算任意放矿阶段出矿品位的缺点,提出了连续品位预测模型,并采用VB语言和Access数据库技术实现了排产品位预测软件。     

Shell-core-corona aggregates formed from poly(styrene)-poly(4-vinylpyridine) block copolymer induced by added homopolymer via interpolymer hydrogen-bonding

The solution behavior of poly(styrene)-poly(4-vinylpyridine) (PS-b-P4VP) block copolymer with added poly(4,4′-oxydiphenylenepyromellitamic acid) (POAA) homopolymer in DMF is studied by dynamic light scattering (DLS), nuclear magnetic resonance (NMR), and transmission electron microscopy (TEM). It is found that coaggregation takes place when mixing PS-b-P4VP block copolymer and POAA homopolymer in DMF due to the strong interpolymer hydrogen-bonding between POAA chains and P4VP blocks. The coaggregation is a diffusion-controlled process and the complexation-induced aggregates are very stable. NMR measurements demonstrate that the resultant aggregates are much more swollen compared with typical amphiphilic block copolymer core-shell micelles. DLS measurements with Eu³⁺ as a probe combined with TEM observation, are employed to study the structure of the aggregates. Results reveal that the formed aggregates are core-shell spheres with the P4VP/POAA complexes as core and the PS blocks as shell when the weight ratio of POAA to PS-b-P4VP is lower. However, a core-shell-corona structure forms with a thin layer of POAA chains adsorbed on the initial core-shell aggregates with increasing weight content of POAA to 60%. Finally, possible mechanisms of the structural transitions are proposed.