Tailoring Spontaneous Pillar Structure Using Phase-Separating Organosiloxane Sol-Gel Systems in Micro-Fabricated Grooves

A sharp transition to pillar structure has been observed in simple sol-gel systems accompanying phase separation inside rectangular-sectioned open grooves which were fabricated on a silica glass chip. The structural variation was investigated using two contrastive systems; one with a rapid sol-gel reaction and the other with a sluggish reaction. In the slower system, transition from web-like bicontinuous structure to pillar structure, we call it as “web-to-pillar transition”, occurred when the bulk characteristic length Λ_m exceeded the width of the groove D. On the other hand, the transition did not occur in the same condition in the faster system; it occurred when Λ_m became much longer than D. A consistent formation mechanism model was also proposed using a relation between interfacial curvatures and pressure.     

受限空间下的烯烃聚合研究

近些年来,随着纳米技术的发展,出现了很多微纳米反应器,该反应器能够提供具有纳米尺寸的反应环境,使得在该环境下进行的反应受到纳米空间的影响,生成具有纳米效应或特殊结构的产物。在聚烯烃催化聚合中,也出现很多具有受限空间的微纳米反应器载体,这些载体不仅能够负载烯烃催化剂,还能为烯烃聚合反应提供受限空间环境。在纳米尺度效应的影响下,催化烯烃聚合进程发生变化,可以得到一些具有特殊结构与性能(比如高熔点、超高分子量、纤维状)的聚烯烃产物。本文总结现阶段受限空间下烯烃聚合研究的最新成果,主要根据聚合物的不同结构进行分类,分别介绍了受限空间对聚烯烃产物的形貌、反应动力学及活性、初级结构、二级结构和凝聚态结构及性能的影响,并对受限聚合研究的发展趋势进行了展望。     

Phase Separation in Sol-Gel System Containing Mixture of 3- and 4-Functional Alkoxysilanes

The phase separation behavior of gelling systems containing the mixture of 3-functional and 4-functional alkoxysilanes has been investigated. The relation between the starting composition and resultant macroporous morphology was examined using tetramethoxysilane (TMOS) and vinyltrimethoxysilane (VTMS) as starting alkoxysilanes, formamide (FA) as an additive, under an acidic condition. Up to TMOS:VTMS molar ratio of 0.5:0.5, the phase relation remained almost unchanged from that of pure TMOS system which exhibits morphology with well-defined co-continuous macropores in a very limited concentration region. On the VTMS-rich side typically TMOS:VTMS = 0.2:0.8, however, the co-continuous macroporous morphology was obtained in a broader composition range than those of either pure TMOS or VTMS system. A dome-like pseudo binary region was obtained with the two-phase region extending toward FA-rich direction. The domain size and pore volume of the gels with macroporous morphology could be controlled by alkoxide:water ratio and total solvent fraction, respectively.     

受限空间内聚苯乙烯微粒的制备

以(N,N-二甲氨基-4-吡啶)五氰合铁(II)封端的聚氧丙烯聚氧乙烯共聚物(EPE-Fe)与苯乙烯在水中自组装形成纳米体系(EPE-Fe-St), 在纳米尺度受限空间内进行了苯乙烯自由基聚合, 制备了聚苯乙烯微球(EPE-Fe-PS). 用Fe³⁺对自组装体系的纳米球壳进行固化后形成Fe-EPE-Fe-St 体系, 聚合后也制备了聚苯乙烯微球(Fe-EPE-Fe-PS). 研究结果表明,制备了粒径为60～200 nm 的不同粒径单分散聚苯乙烯微球, 聚合温度对纳米Fe-EPE-Fe-St 体系粒径影响较小, 而对EPE-Fe-St 体系较大. 在受限空间内苯乙烯的自由基聚合可得到数均分子量超过70 万的聚苯乙烯; 自组装体系中引发剂量增多使聚苯乙烯分子量下降, 聚合温度上升也使分子量下降, 而增加自组装的EPE-Fe 用量可增加聚苯乙烯的分子量. 两种受限条件下的聚苯乙烯微球的玻璃化转变温度(T_g)在90～135 ℃之间, 纳米反应器壳层的硬化提高了聚苯乙烯微球的T_g.     

多相高分子体系中的粘弹相分离行为

相分离广泛存在于各种凝聚态物质中.根据局部浓度的变化形式,可将相分离分为固体模型(model B)和流体模型(model H),这两种模型适用于动力学对称的体系.近年来,Tanaka发现在一些动力学不对称的多组分高分子体系里存在一种新的相分离模式,其相分离过程分为动力学过程可用一个普适的粘弹模型来进行描述.动力学不对称可由体系中两组分间大的尺寸差异或玻璃化温度差异引起.本文介绍了多相高分子体系中产生粘弹相分离的原理及其基本特征,并讨论了模量、粘度、填料等因素对粘弹相分离动力学过程及多相体系微观结构的影响.     

高分子相分离的分子动力学模拟

用粗粒化分子动力学(MD)模拟方法从分子层次研究两组分聚合物共混体系相分离过程中的动力学. 在相分离初期, 相区尺寸不随时间增加而变化; 在相分离中期, 相区尺寸与时间有很好的标度关系, 标度指数(α=1/3)符合Lifshiz-Slyozov提出的以扩散为主导的蒸发-凝聚机理的标度预测; 在相分离后期, 体系实现宏观相分离, 相区尺寸不再随时间改变而变化. 体积分数小的高分子链尺寸在相分离过程中先收缩再扩张, 在实现宏观相分离后, 高分子链尺寸又回到本体状态尺寸.     

Thermodynamic Analysis of Phase Separation of a Thermoplastic in the Precursors of Different Epoxy-Amine Systems

The miscibility of a thermoplastic, polystyrene (PS), with the precursors of several epoxy-amine systems has been studied thermodynamically and experimentally. The epoxy-amine systems were different only in the origin of amino groups, which were provided by a monoamine (MA) and a diamine (DA) in different proportions. Cloud-point curves (CPC) at conversion zero were reported for five modified systems with different MA-DA proportion. All CPCs showed an UCST behaviour. CPC shifted to lower temperatures when the ratio of MA/DA in the system increased, meaning that the MA produces an increase in the miscibility of the system. A model based on the Flory-Huggins theory was used for the thermodynamic analysis, in which the dependence of interaction parameter on temperature and composition, χ(T,ϕ), and the polydispersity of components were considered. A general equation for χ(T,ϕ) also depending on the MA-DA proportion was reached and used to obtain the phase diagram of the different systems. A high level of agreement between theoretical and experimental CPCs was obtained.     

Phase Separation of Polyethylene Glycol/Salt Aqueous Two-Phase Systems

Abstract

Salt in polyethylene glycol (PEG)/salt aqueous two-phase systems was excluded by PEG and concentrated in the solvent volume available for dissolution of salt (PEG-free solvent). The concentration of salt in the PEG-free solvent of the PEG-rich phase was the same as that at the critical point regardless of the compositions of the PEG/salt two-phase systems. This explained that the phase separation of PEG/salt two-phase systems occurs when the concentration of salt in the PEG-free solvent reaches its solubility limit. The concentration of salt required in the PEG-free solvent for the phase separation was lower with higher molecular weight of PEG. The solubility of salt in the PEG-free solvent decreased with increases in the molal surface tension increment of salt. The solubility limit of salt in the PEG-free solvent was 0.93 M for ammonium sulfate, 0.77 M for potassium phosphate, 0.75 M for sodium tartrate, 0.67 M for sodium phosphate, and 0.53 M for potassium citrate.     

用SEC柱和胶束流动相分离小分子的模型

 使用体积排阻色谱 (SEC)柱和胶束流动相成功地分离了一些小分子化合物 ,给出了分离模型。这种分离方式是基于胶束和水相在色谱过程中的不同迁移以及溶质在胶束和水相间的不同分配而实现的 ,其分离的机制与胶束电动色谱 (micellar electrokinetic chromatography,MEKC)十分相似。理论处理的结果表明 ,溶质的保留体积与胶束浓度有关 ;通过溶质的保留体积可得到溶质在胶束和水相间的分配系数。还采用了两种不同的 SEC柱分离了一些脂肪醇 ,验证了这一理论模型 ,测定了它们的分配系数 ,结果表明两种柱测得的小分子醇在胶束和水相中的分配系数具有较好的一致。     

Polysulfone Membranes via Thermally Induced Phase Separation

Polysulfone (PSF) membranes have gained great attention in the fields of ultrafiltration,microfiltration,and thin film composite membranes for nanofiltration or reverse osmosis.For the first time,it is proposed to fabricate PSF membranes via thermally induced phase separation (TIPS) process using diphenyl sulfone (DPSO2) and polyethylene glycol (PEG) as mixed diluent.DPSO2 is chosen as a crystallizable diluent,while PEG is considered in terms of molecular weight (Mw) and dosage.We systematically investigate the interactions between PSF,DPSO2 and PEG based on the simulation calculations and solubility parameter theory.It is inferred that DPSO2 has an excellent compatibility with PSF,and the addition of PEG results in the ternary system thermodynamically less stable and then facilitates its liquid-liquid (L-L) phase separation.SEM images indicate that cellular-like pores are obvious throughout the membrane when the PEG content in the mixed diluent is 25 wt％-35 wt％.We can facilely manipulate the pore size,water flux and mechanical properties of PSF membranes with the dosage of PEG-200,the Mw of PEG or the cooling rate.The successful application of TIPS can provide a new approach for structure manipulation and performance enhancement of PSF membranes.     

A Discrete,Space Variation Model for Studying the Kinetics of Shape Deformation of Vesicles Coupled with Phase Separation

Summary: The evolution dynamics of phase separation, coupled with shape deformation of vesicles is described by using dissipative dynamic equations, specifically the time‐dependent Ginzburg‐Landau (TDGL) equations. In order to improve the numerical stability and thus to efficiently deal with a large deformation of vesicles, a new algorithm, namely the discrete space variation model (DSVM) has been developed for the first time. The algorithm is based on the variation of the discretized free‐energy functional, which is constructed in discrete membrane space, in contrast to the commonly used continuous free‐energy functional. For the sake of numerical tractability, only the cylindrical vesicles (2D), with two components, are taken into consideration to illustrate the efficiency and validity of new algorithm. The simulation results, based on the DSVM algorithm have been compared with those from both linear analysis and strong segregation theory using the continuous space free‐energy functional. It is found that the DSVM algorithm can correctly describe the coupling between the lateral phase‐separation on the vesicle membrane and the vesicle shape deformation, both for early and late stages.

A flower‐like vesicle obtained by DSVM simulation.     

相分离免疫分析的研究进展

相分离免疫分析通过开展快速的均相反应和简单的异相分离而兼具了均相免疫与异相免疫的优点,方法易于实现自动化.本文介绍了相分离免疫分析的基本原理,对相分离免疫分析载体、固定化方式、标记物、应用及发展方向进行了评述.引用文献60篇.     

甲基睾酮的控温相分离免疫分析

建立了一种新的甲基睾酮（ＭＴ）测定的免疫分析方法。通过将ＭＴ与牛血清白蛋白（ＢＳＡ）偶联制得了ＭＴ全抗原ＭＴ－３－ＢＳＡ（Ａｇｍｔ）。将Ａｇｍｔ经兔子免疫获得了针对ＭＴ的多克隆抗体（Ａｂｍｔ）。与温度敏感性水凝胶偶联的抗原（ＰＮＴＰ－Ａｇｍｔ）和游离半抗原ＭＴ竞争性地与有限量的Ａｂｍｔ和辣根过氧化物酶（ＨＲＰ）的偶联物（ＡＢｍｔ－ＨＲＰ）反应。根据临界析相温度以上免疫复合物沉淀的特性进行分离,根据     

Theoretical Modeling of the Phase Separation Dynamics in Blends of Reactive Monomers

Summary: Experimental observations of the dynamics of phase behavior for blends of reactive constituents, i.e. diglycidyl ether of bisphenol A (DGEBA), curing agent methylene dianiline (MDA), and a reactive liquid rubber (R45EPI), have been theoretically modeled by coupling system thermodynamics governed by a summation of the free energies of mixing and network elasticity with reaction kinetics and diffusion equations. Snap‐shots of the temporal evolution of ternary phase diagrams have been established based on the self‐condensation reactions of DGEBA‐MDA and R45EPI as well as a cross‐reaction between the two constituents forming a copolymer. Numerical solution of the proposed mean‐field model provides good qualitative agreement with experimental results, namely, the observance of phase separation followed by a phase dissolution and subsequent secondary segregation in a 50/25.4/50 DGEBA/MDA/R45EPI mixture, as well as a single gradual phase separation in a 70/25.4/30 mixture. The phase separation dynamics are explained by a competition between the growth in molecular weights of the reactive species rendering the systems towards instability, and the formation of copolymer acting to compatibilize the mixtures.

Theoretical phase diagram for a DGEBA/MDA/R45EPI system.     

Probing Liquid-Liquid Phase Separation of a Polyethylene Blend with Thermal Analysis

Summary: A series of polyethylene (PE) blends consisting of a high density polyethylene (HDPE) and a linear low density polyethylene (LLDPE) with a butene-chain branch density of 77/1000 carbon was prepared at different concentrations. The LLDPE only crystallized below 50 °C, therefore, above 80 °C and below the melting temperature of HDPE, only HDPE crystallized in the PE blends. A specifically designed multi-step experimental procedure based on thermal analysis technique was utilized to monitor the liquid–liquid phase separation (LLPS) of this set of PE blends. The main step was first to quench the system from the homogeneous temperatures and isothermally anneal them at a prescribed temperature higher than the equilibrium melting temperature of the HDPE for the purpose of allowing the phase morphology to develop from LLPS, and then cool the system at constant rate to record the non-isothermal crystallization. The crystallization peak temperature (T_p) was used to character the crystallization rate. Because LLPS results in HDPE-rich domains where the crystallization rates are increased, this technique provided an experimental measure to identify the binodal curve of the LLPS for the system indicated by increased T_p. The result showed that the LLPS boundary of the blend measured by this method was close to that obtained by phase contrast optical microscopy method. Therefore, we considered that the thermal analysis technique based on the non-isothermal crystallization could be effective to investigate the LLPS of PE blends.     

聚合物共混物的相容性及相分离

综述了聚合物共混物相容性和相分离的研究现状。介绍了聚合物共混物的相容性理论,影响相容性的因素及改善和相容性的方法和表征相容性的手段。聚合物共混物的相分离机理制约着材料的性能,旋节分离和成核－增长相分离分别形成不同的形态结构。旋节分离和成核－增长相分离所对应的动力学过程是不同的,散射光强与相分离时间分别满足指数和幂指数关系。     

Electronic Communication in Confined Space Coronas of Shell-by-Shell Structured Al2O3 Nanoparticle Hybrids Containing Two Layers of Functional Organic Ligands

A first series of examples for confined space interactions of electron-rich and electron-poor molecules organized in an internal corona of shell-by-shell (SbS)-structured Al₂O₃ nanoparticle (NP) hybrids is reported. The assembly concept of the corresponding hierarchical architectures relies on both covalent grafting of phosphonic acids on the NPs surface (SAMs formation; SAM=self-assembled monolayer) and exohedral interdigitation of orthogonal amphiphiles as the second ligand layer driven by solvophobic interactions. The electronic communication between the chromophores of different electron demand, such as pyrenes, perylenediimides (PDIs; with and without pyridinium bromide headgroups) and fullerenes was promoted at the layer interface. In this work, it is demonstrated that the efficient construction principle of the bilayer hybrids assembled around the electronically “innocent” Al₂O₃ core is robust enough to achieve control over electronic communication between electron-donors and -acceptors in the interlayer region. The electronic interactions between the electron-accepting and electron-donating moieties approaching each other at the layer interface were monitored by fluorescence measurements.     

巯基聚甲基丙烯酸甲酯纳米球在水溶液中的相分离研究

采用无皂乳液聚合法制备了单分散、直径为140 nm左右的巯基聚甲基丙烯酸甲酯纳米球(mercapto polymethylmethacrylate,PMMA-SH),并且利用荧光光谱法对其水分散液进行了相分离研究.实验结果表明所制备的PMMA-SH纳米球具有温敏性,当体系从0℃向30℃变化时,体系由低温热力学平衡态转变成高温非热力学平衡态,出现相分离现象,其相分离温度约为14~16℃.     

Poly(methyl methacrylate) Membrane: Dynamic Measurement of Concentrations During Water-Induced Phase Separation

The properties of membranes produced by nonsolvent-induced phase separation (NIPS) depend on the rate of mass transfer of mobile components. This paper reports the use of Fourier transform infrared-attenuated total reflectance (FTIR-ATR) using principle component regression (PCR) analysis to study the compositional change of polymer solution immersed into the water prior to the phase demixing. To correlate the compositional change with the macroscopic structure, the observation on the dynamics of NIPS is made by a low magnification optical microscope equipped with a video camera. The morphology of the films was also examined by scanning electron microscope. Acetone and N, N-dimethylformamide were chosen as solvents to present different behavior of poly (methyl methacrylate) (PMMA) solutions during the NIPS process. The ratio of solvent and nonsolvent exchange, flux ratio shows the mass transfer in the homogeneous polymer solution after immersion in a nonsolvent bath. The results show that the flux ratio ( ) is affected by solvents which probably affects the ultimate structures of the precipitated polymer.