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。     

基板界面对PS/PMMA溶液共混物溶剂挥发成膜相结构的影响

研究了PS PMMA的共混物溶液溶剂蒸发成膜时的基板界面效应 .利用扫描电子显微镜 (SEM)研究了PS PMMA(5 5 ) (W W) THF高分子共混物溶液在不同基板上通过溶剂挥发成膜的相形态结构 .通过FTIR及ATR FTIR检测了共混物薄膜及其表面的共混组成 .研究结果表明 ,成膜基板对高分子共混物溶液成膜后的相形态有很重要的影响 .控制共混物溶液体系成膜过程中的动力学因素 ,可以调控出所设想的各种复杂的相结构形态     

溶剂对SEBS/PMMA共混物薄膜形态的影响

采用原子力显微镜研究了聚（苯乙烯嵌-乙烯／丁烯嵌-苯乙烯）（SEBS）和聚甲基丙烯酸甲酯（PMMA）共混物不同溶剂旋转涂膜的表面形态和相分离行为。结果表明,用共混物的氯仿溶液旋转涂膜,可见明显的共混物的宏观相分离和SEBS的微观相分离形态。改变选择性溶剂可使旋涂膜具有不同的均匀度和形态结构,其相区的尺寸和形状相差甚大,有海岛型、网状、双连续状结构。AFM显示用环己烷／丁酮混合溶剂旋转涂膜,共混物的相分离最为彻底;用选择性溶剂氯仿时次之,但有明显的相分离;对SEBS和PMMA均无选择性的单一溶剂或混合溶剂则无明显相分离。     

SiO_2纳米粒子对PMMA/PS共混物共连续相结构退火粗化过程的影响

考察了亲水性纳米SiO2粒子的加入对聚甲基丙烯酸甲酯/聚苯乙烯(PMMA/PS)共混体系的共连续相结构在静态高温退火时形态稳定性的影响,发现静态高温退火条件下,填充体系共连续组成范围变窄幅度较小、特征结构尺寸的粗化速率减慢.流变测试表明纳米SiO2粒子加入之后PMMA/PS共混体系的黏弹性显著提高,从而能减缓破坏构成共连续相结构的纤维断裂或回缩等松弛过程的速率,有效地抑制PMMA/PS共混体系的共连续相结构粗化进程,提高相结构的稳定性.根据现有的两种粗化理论的定性分析表明,在高填充量的共混体系中,加入纳米SiO2粒子导致共混体系的黏弹性的显著改变是影响PMMA/PS共混体系在静态高温退火时共连续相结构粗化速率的主要因素,相对而言界面张力的变化对共连续相结构在静态高温退火时的粗化速率影响则应该较小.     

界面张力对高分子共混物梯度相形态形成的影响研究

研究了界面张力对ＰＰ／ＥＶＡ共混体系梯度相形态形成的影响。首先将ＥＶＡｃ进行皂化反应得到一系列－ＯＨ基含量不同即极性不同的ＥＶＡ，然后将这些ＥＶＡ分别与ＰＰ共混从而得到一系列相界面张力不同的共混物。说明通过对共混物相界面张力的调整，可以达到随意控制梯度相形态形成速度的目的。     

玻璃基板作用下高分子共混物薄膜相形态发展过程

研究了玻璃基板作用下极性高聚物为低组分的共混物薄膜在退火条件下相形态的发展过程 .选用聚苯乙烯 (PS) 聚甲基丙烯酸甲酯 (PMMA)与聚苯乙烯 (PS) 聚ε 己内酯 (PCL)两个体系 ,在玻璃基板上Spin Coating成膜后退火 .由于共混物薄膜中极性相对较大的高聚物组分 (PMMA和PCL)相对于极性较小的PS组分对玻璃基板具有更好的润湿性 ,所以在上述的两个共混薄膜体系中其相形态分别显示PMMA和PCL在低组分比例下最终发展成为连续相 .利用扫描电镜以及元素分析很好地验证了以上的结论 ,并且对其机理进行了解释 .此外 ,改变PS的分子量与PCL共混 ,研究了组分粘度对薄膜相形态发展的影响 .结果表明 ,PS组分粘度越大 ,共混物薄膜相结构发展速度越慢     

SEBS/PMMA共混物膜的表面和本体形态结构

用扫描电镜(SEM)和原子力显微镜(AFM)研究了两种不同共混比的聚(苯乙烯-嵌-乙烯/丁烯-嵌-苯乙烯)(SEBS)和聚甲基丙烯酸甲酯(PMMA)共混膜的表面形态和相分离行为。结果表明,当膜厚为25μm时,两种共混膜表面均未见明显的相分离形貌,而在膜体相中可见宏观相分离结构。当膜厚为120 nm时,质量比为30/70的共混膜表面可见明显的“海-岛”状宏观相分离;而质量比为60/40的共混膜表面未见明显宏观相分离,仅有少量PMMA小颗粒嵌于SEBS基体中,形成SEBS趋于包裹PMMA微区的稳定“笼型”结构,其尺度属于介观相分离。退火后,两样品膜的体相形态与表面形貌趋于一致,均呈现宏观的相分离结构。     

PMMA/PS共混物薄膜中Voronoi结构的形成

Vomnoi结构与一些自然结构十分相象,早在17世纪,Descartes就在他的著作中采用了类似Vomnoi结构的图形来表示太阳系及其环境中的物质分布．Vomnoi图（如图1所示）的概念来自于计算几何,设有平面空间点集合A={a1,a2,……an},其中ai=（xi,yi）,对于任意一个ai,满足｜P-ai｜≤min ｜P-aj｜（j=1,2,……,n;j≠i）的点P=（x,y）的轨迹称为点集A的vomnoi图．     

界面张力在基板诱导共混物分散相粒子粗化生长加速现象中的作用

通过相差显微镜和计算机图像处理来研究两相聚合物体系的粗化过程 .将具有不同聚比的乙烯 聚醋酸乙烯酯 (EVAc)共聚物与聚丙烯 (PP)共混 ,制备不同相界面张力的系列共混物薄膜 .观察了在玻璃基板的作用下 ,不同界面张力体系的分散相粒子粗化行为 ,发现界面张力在约 0 4 8·1 0 - 5N cm以上的体系中分散相粒子的粗化有明显的加速现象 ,粒子体积生长与时间关系的指数大于 1 0 ;而两相界面张力较低的情况下 ,选择具有不同表面极性的基板对同一体系试验 ,我们均未发现有粗化加速现象产生 ,且采用不同基板之间的试验结果差异很小 ,亦即当高分子共混物的相界面张力大于一定值时 ,仅与基板存在有关 ,粒子的粗化行为被加速     

相形态对聚合物反应共混过程的影响

通过采用典型的热力学不相容共混体系聚烯烃弹性体/聚苯乙烯(POE/PS),利用流变学和形态研究的方法,考察了不同相形态(海岛结构和双连续结构)对聚合物反应共混过程的影响.研究发现相形态对聚合物原位增容共混反应有显著的影响,界面反应的进程与界面形态的变化能力直接相关.对于双连续结构的共混物,其形态稳定性最差,因而最有利于界面反应的发生;而在海岛结构的共混体系中,界面反应的进程则取决于界面变形的难易程度,黏度比小的体系更容易发生界面反应。     

高分子共混物薄膜表面形貌形成过程中的溶剂效应

采用原子力显微镜观测了由四氢呋喃和2-丁酮分别作为共溶剂制备得到的聚苯乙烯/聚甲基丙烯酸甲酯(PS/PMMA)共混物薄膜的表面形貌.研究发现,溶剂效应对共混物薄膜的表面形貌有较大影响,表面形貌中凸起与凹坑的组分分布是由溶剂效应决定的,与组分比无关.溶剂对不同组分的溶解能力不同还可以导致薄膜表面相逆转点的偏移.     

Large impact in electrical properties of polypropylene by improving the filler-matrix interface effect in PP/PS blends

Inorganic nanoparticles are widely used to improve space charge behavior, DC breakdown strength and other electrical properties of polymer insulating materials, but the uniform distribution of inorganic nanofillers in matrix is difficult due to their agglomeration and bad compatibility with the polymeric matrix. In this paper, polypropylene (PP)/polystyrene (PS) blends were prepared to suppress space charge accumulation and improve DC breakdown strength. Polypropylene-g-polystyrene (PP-g-PS) graft copolymer was used as compatibilizer to improve the compatibility of PP matrix and PS filler. The evolution of microstructure of PP/PS blends were investigated by scanning electron microscope (SEM), the space charge distributions were measured by a pulsed electro-acoustic (PEA) system, and DC breakdown strength was also tested. The morphologies show that the size of PS particles reduced to 310 nm when the content of PP-g-PS graft copolymer increased to 24 wt%, and the interaction between PP matrix and PS particles enhanced. The presence of PS particles in all PP/PS blends suppressed the space charge accumulation compared to neat PP, but the DC breakdown strength in uncompatibilized blend was lower than neat PP. The increasing of content of PP-g-PS improved the DC breakdown strength with the maximum value of 408.9 kV/mm was obtained. This may attribute to excellent interface structure formed between PP matrix and PS particles.     

DC Electrical Study of Modified PMMA,PVC and their Blend

Summary: Thin films of high molecular weight PMMA, PVC and their blend were prepared with solution cast method. Further they were modified by adding Camphor Sulphonic Acid (CSA) to them. DSC studies indicate single glass transition temperature (Tg) for unmodified as well as modified blends indicating the miscibility of polymers. FTIR studies show the interaction between CSA-PVC, CSA-PMMA, CSA-(PVC+PMMA) blend. The D.C. electrical study was carried out at various temperatures from room temperature (307 K) to 373 K. After modification the variation of DC conductivity (σ) is found to decrease in PVC and the PVC-PMMA blend whereas it is found to increase in PMMA with rise in temperature.     

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.     

振荡剪切流场下PS/PVME/SiO2复合物的相行为

利用光学显微镜-剪切台联用系统研究了振荡剪切流场下聚苯乙烯（PS）/聚甲基乙烯基醚（PVME）/二氧化硅（SiO₂）纳米粒子复合物的热力学稳定性. 结果表明,小振幅振荡剪切可导致PS/PVME共混物出现类似在稳态流场下的剪切诱导相容及剪切诱导相分离现象. 共混体系存在临界振荡频率ω_c,当振荡频率低于ω_c时,发生剪切诱导相分离（SID）行为,反之发生剪切诱导相容（SIM）行为. SiO₂纳米粒子的加入使复合体系的相容性提高. 存在一个临界SiO₂纳米粒子含量φ_c,当SiO₂纳米粒子含量高于φ_c时,复合体系中不存在临界振荡频率ω_c,低振荡频率下的剪切诱导相分离得到抑制. 此外,复合体系的上述行为与升温速率和共混物组成密切相关.