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.     

高分子混合物薄膜的相分离行为

从高分子混合物薄膜的相分离行为的机理，相分离后期粗化动力微区尺寸与时间的标度关系，影响高分子混合物薄膜表面形态形成的因素等几个方面对近年来高分子混合物薄膜相行为的研究进展进行总结，概述了今后可能的发展趋势。     

聚甲基丙烯酸甲酯/聚醋酸乙烯酯共混分相过程结构函数的标度分析和相凝聚

高分子共混体系相分离动力学研究已取得了很大的进展。Cahn理论可很好地描述相分离初期过程,de Gennes的蛇行理论可较好地描述相分离初期大分子扩散。在相分离后期,人们已经发现动力学参量的标度行为,但实验结果不一,标度成因尚不十分清楚。本文研究了聚甲基丙烯酸甲酯(PMMA)/聚醋酸乙烯酯(PVAc)共混体系相分离后期过程。分析了结构函数的标度行为,初步讨论了相凝聚特征。     

相分离高分子共混薄膜退火和准淬火的原位原子力显微镜研究

近年来,高分子共混薄膜在选择性渗透膜、生物材料、润滑剂、粘结剂、光敏电阻平板印刷、光电器件及纳米尺寸表面图案化等方面的研究日益受到重视,应用前景也十分可观,然而,由于其相容性较差,高分子共混物常发生相分离,相对于本体,表面的分子链具有更大的自由度,因此表面高分子链的热运动状态与本体有很大差别,为控制因相分离而导致的相区尺寸,人们必须同时对相分离热力学及动力学行为进行研究。     

SiO2粒子对PMMA/SAN共混体系相分离行为的影响

采用小角激光光散射(SALLS)并结合动态流变学方法,考察了气相法二氧化硅(SiO2)粒子的加入对聚甲基丙烯酸甲酯/苯乙烯-丙烯腈无规共聚物(PMMA/SAN)共混体系相行为的影响,得到了添加SiO2粒子前后的相图,发现SiO2粒子对基体相行为的影响与基体的组成有关.对PMMA/SAN(60/40)体系,加入SiO2粒子后相分离温度上升,但并未改变相分离机理,仍为亚稳单相分解过程(spinodal decomposition,SD);而对于PMMA/SAN(30/70)体系,加入SiO2粒子后却降低了体系的相分离温度.该现象可能是SiO2粒子和基体组分界面间组成与PMMA/SAN共混物基体组成的差异造成的.     

混合高聚物分相过程标度、分形与Monte Carlo模拟

基于光散射、Monte Carlo模拟标度理论和分形(Fractal)概念研究和分析了高分子混合体系不稳相分离过程结构函数的标度行为和成因, 结果表明相分离的形态是一种分形结构, 其分形维数不随时间变化. 结构函数的标度行为起源于相态的分形结构. 相态的分形结构是不稳相分离特征之一.     

圆柱表面上高分子共混刷微相分离的自洽场理论研究

我们运用高分子自洽场理论方法,结合“masking”技术,研究了高分子共混刷接枝到无限长圆柱表面上的微相分离行为. 理论预言了柱面上高分子共混刷的两种典型相分离形态：平行条纹相和环状相. 我们考察了圆柱半径、接枝密度以及相互作用参数对二者的影响,给出了体系在不同参数下相分离形态的相图,并且从相分离程度的角度对平行条纹相和环状相之间的转变作了解释. 我们还研究了平行条纹相相区数目以及环状相交替周期随圆柱半径的变化. 理论所预言的平行条纹相和环状相的存在以及体系参数对其稳定性的影响将有助于实验上合理设计、制备这类新颖的高分子刷材料.     

高分子浓溶液相分离动力学的Monte Carlo模拟

运用链动力学MonteCarlo方法模拟了高分子浓溶液的spinodal相分离动力学过程 .结果表明 :分相早期 ,散射峰的位置向左移动 ,不符合经典的Cahn Hilliard线性理论 ;分相后期 ,聚合物相形态处于逾渗状态 ,结构因子可以被标度化 ,且基本符合相应的Furukawa标度律 .模拟结果与相关实验相符 .揭示了线团尺寸在深度淬冷过程中先急剧收缩、然后随相分离的进行而逐步上升的复杂变化 ,表明链动力学MonteCarlo方法能同时考察高分子链的构象变化和多链体系的分相过程以及两者的关联     

基板界面对ＰＳ／ＰＭＭＡ共涨物薄膜相逆转组成比的影响

近年来高分子共混体系中的界面,表面效应逐渐引起了越来越多研究者的兴越,人们发现,当共混物薄膜厚度减至一定程度时,聚合物共混物薄膜中的相形态,相容性和相分离动力学与本体中有较大的不同^[1~3].基板界面作用对共混薄膜体的热力学,动力学行为产生很大的影响,我们以往的研究^[4,5]也发现,ＰＰ／ＥＶＡc(70/3０）共混体系退火过程中,基板界面（如玻璃）作用可大大加速分散相（ＥＶＡc)粒子的粗化凝聚过程,本研究用聚甲基丙烯酸甲酯和聚苯乙烯共混物押氢呋喃深液在不同在板介质（如玻璃基板,ＰＰ基板）上成膜,用相产左显微镜观测了膜的相形态变化并确定共混和的的相逆转区域,用界面张力和共混物薄膜上下表面的ＡＴＲ－ＦＴＩＲ实验结果探讨了成膜过程中的基板界面效应对相逆转区域的影响。     

介观模拟方法研究高分子表面活性剂在水介质中的聚集行为

高分子表面活性剂已广泛应用于许多领域, 其构型复杂、分子量大等特点使其聚集行为不同于小分子表面活性剂. 从微观上认识其聚集行为可为应用提供指导, 因而此方面的研究倍受关注. 计算机模拟技术的发展使我们能成功地在微观或介观水平上获得高分子表面活性剂聚集行为的信息. 本文综述了耗散粒子动力学(DPD)和介观动力学(MesoDyn)在高分子表面活性剂聚集行为研究中的应用. 着重介绍了这两种介观模拟方法研究单一高分子表面活性剂溶液的相行为及其与低分子表面活性剂之间的相互作用, 揭示了实验中难以观测的微观相分离及聚集体结构形态的变化规律. 这些信息可以为实验研究提供指导和补充.     

聚甲基丙烯酸甲酯/苯乙烯-丙烯腈无规共聚物薄膜表面原位原子力显微镜相图

采用原位原子力显微镜在线跟踪方法,研究了聚甲基丙烯酸甲酯/苯乙烯 丙烯腈无规共聚物共混体系表面相分离行为,得到了具有下临界共溶温度（临界温度约为175 ℃）原位相图。 与文献报道的用离位方法所得结果的主要差别是原位的临界相分离温度稍有提高,以及离位结果中存在的组成对称性。 这些差别主要来源于离位和原位实验方法上的差别,薄膜厚度减小导致的相容性,热力学历史的变化以及基底效应的加剧。     

Effect of Nanoclay on the Phase Separation Behavior of Poly（methyl methacrylate）/Poly（vinyl acetate） Binary Polymer Blends

The effect of nanoclay on the phase-separation behavior of poly（methyl methacrylate）/poly（vinyl acetate）（PMMA/PVAc） blends has been mainly investigated by small-angle laser light scattering. It is found that the effect of clay on the thermodynamics and kinetics of phase-separation for PMMA/PVAc blends seems inconsistent. The kinetics phaseseparation rate decreases, while the thermodynamics parameters, cloud points Tc and delay time tD of isothermal phaseseparation also decrease, and the variation amplitude depends on the matrix composition. The affinity of clay to PMMA results in the composition difference between the border layer and the polymer matrix and further causes the concentration fluctuation at the early stage of phase separation to reduce Tc and tD. On the other hand, the decrease of phase-separation rate is caused by the mechanical barrier effect of clay on the macromolecular diffusion of blend matrix. Hence, such seemingly counterintuitive results on the thermodynamics and kinetics of phase-separation are attributed to different dominant factors.     

Influence of Poly (methyl metacrylate) Addition on Resistive Switching Performance of P3HT/P(VDF-TrFE) Blend Films

Organic semiconducting/ferroelectric blend films attracted much attention due to their elec-trical bistability and rectification properties and thereof the potential in resistive memory devices. Blend films were usually deposited from solution, during which phase separation oc-curred, resulting in discrete semiconducting phase whose electrical property was modulated by surrounding ferroelectric phase. However, phase separation resulted in rough surface and thus large leakage current. To further improve electrical properties of such blend films, poly(methyl metacrylate) (PMMA) was introduced as additive into P3HT/P(VDF-TrFE) semiconducting/ferroelectric blend films in this work. It indicated that small amount of PMMA addition could effectively enhance the electrical stability to both large electrical stress and electrical fatigue and further improve retention performance. Overmuch PMMA addition tended to result in the loss of resistive switching property. A model on the con-figuration of three components was also put forward to well understand our experimental observations.     

聚甲基丙烯酸甲酯与聚醋酸乙烯酯共混的红外光谱研究

用红外光谱(FTIR)研究了聚甲基丙烯酸甲酯(PMMA)与聚醋酸乙烯酯(PVAc)共混体系相容性,在160℃以上共混体系发生相分离;分相体系与非分相体系的FTIR谱明显不同;共混体系的FTIR谱不能从两统组分红外光谱简单加和得到;结果表明大分子构象发生了变化,PMMA/PVAc体系相容可能是大分子构象熵变所致。     

3D FT-IR imaging spectroscopy of phase-separation in a poly(3-hydroxybutyrate)/poly(l-lactic acid) blend

In the present study, 3D FT-IR spectroscopic imaging measurements were applied to study the phase separation of a poly(3-hydroxybutyrate) (PHB)/poly(l-lactic acid) (PLA) (50:50 wt.%) polymer blend film. While in 2D projection imaging the z-dependent information is overlapped, thereby complicating the analysis, FT-IR spectro-micro-tomography, obtained from computed tomographic back projection calculations, results in distinct 3D chemical images that provide detailed information of phase separation of the two polymer components that are well separated.     

以水作相分离造孔剂制备P(VDF-HFP)/PMMA聚合物电解质膜

介绍了一种以水代替常用的有机物质作为相分离造孔剂制备混合型聚合物电解质的新方法.所研究的混合型聚合物为聚(偏二氟乙烯-六氟丙烯)和聚甲基丙烯酸甲酯的混合物.扫描电镜SEM图表明这种混合型聚合物膜具有蜂窝状结构,有利于膜电导率的增加.利用FTIR,XRD和DSC等方法研究了混合型聚合物电解质中两种聚合物间的相互作用.用电化学交流阻抗方法测得在30℃下P(VDF-HFP)/PMMA摩尔比为1:1的混合型聚合物电解质的离子电导率为0.804×10^-3S/cm.对照其它方法,本方法具有制备容易、成本较低和有利于环境保护等优点.     

Phase separation in semi-interpenetrating polymer networks based on crosslinked poly(urethane) and linear poly(methyl methacrylate) containing iron,copper, and chromium chelates

Phase separation that occurs during formation of semi-interpenetrating polymer networks of various compositions based on crosslinked poly(urethane) and linear poly(methyl methacrylate) containing 1 wt % iron, copper, and chromium chelates has been studied by the methods of DSC and DMA. It has been shown that, in contrast to chromium chelates, the incorporation of iron and copper β-diketonates into the semi-interpenetrating polymer networks (PU : PMMA = 50 : 50) causes retardation of phase separation owing to high rates of poly(urethane) and poly(methyl methacrylate) formation and the appearance of chelate complexes with both blend components at the interface. A more complete phase separation in metal-containing semi-interpenetrating polymer networks (PU : PMMA = 70 : 30) is associated with the fact that chemical kinetics and complexation processes act in opposite directions. The latter processes prevail, and the influence of the type of metal ion in a chelate that predominantly interacts with PU in the blend is diminished.     

聚氯乙烯-聚氧乙烯共混物的反相色谱研究

用反相色谱研究了聚氯乙烯与聚氧乙烯的相容性,发现其共混物的比保留体积V_g23具有重量加和性,表明共混物可能发生了相分离。导出了相分离体系聚合物相互作用参数X₂₃的近似关系式:X₂₃=(X₁₂-X₁₃)²/2,由此式可以解释X₂₃对探针种类的依赖性。聚氯乙烯和聚氧乙烯共混体系的反相色谱实验结果基本符合这一关系式。     

Poly(ethylene-co-vinyl alcohol) and poly(methyl methacrylate) blends: Phase behavior and morphology

In this work blends of poly(ethylene-co-vinyl alcohol) (EVOH) with different ethylene contents (27, 32, 38 and 44 mol%) and poly(methyl methacrylate) (PMMA) were prepared by mechanical mixing in the melted state. The miscibility and melting behavior as a function of blend composition and the ethylene content in EVOH copolymers were investigated by means of differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). The morphology of the cryofractured surfaces was examined by scanning electron microscopy (SEM). DSC and DMTA data show that EVOH/PMMA blends are immiscible, independent of EVOH and blend composition. The SEM analysis in agreement with DMTA analysis indicates that the morphology of phases depends on the blend composition, with phase inversion occurring as the concentration of one or other polymer component increases. However, the copolymer composition apparently does not affect the domain size distribution for blends containing 20 wt% of EVOH or 20 wt% of PMMA. A better phase adhesion is observed mainly for blends with 50 wt% of each polymer component.     

Binary versus ternary interactions in a completely miscible three‐polymer blend system: Poly(ϵ‐caprolactone) with two different methacrylic polymers

A truly miscible ternary miscible blend consisting of poly(?‐caprolactone) (PCL), poly(phenyl methacrylate), and poly(benzyl methacrylate) (PBzMA) was discovered. The three‐polymer blend system was completely miscible within the entire composition range at ambient temperature up to about 150 °C, and ternary phase diagrams at increasing temperatures were characterized and interpreted. A ternary‐interaction model based on the modified Flory–Huggins expression was used to describe the phase diagrams with the individual binary interaction strengths. The model fitted well with the experimental‐phase diagram for the ternary blend system at T = 250 °C, where the binary PCL‐PBzMA blend system is on the critical points of phase separation. Interpretation of discrepancy between the model and experimental at other temperatures was handled with an empirical approach. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 747–754, 2002