高压结晶PET/PC共混体系中生长在伸直链晶体内部球晶形态的观察

自从Wundedich等报道聚乙烯（PE）在高压结晶时可以生成伸直链晶体以来,相继很多有关聚合物体系的高压结晶行为方面的研究已见报道．研究结果表明,聚合物在高压下经历相转变时可产生非常丰富的微观结构,而球晶及伸直链晶体是其中最常见的两种结晶形态．但是,所观察到的这两种聚合物晶体都是分别存在,且独立生长的．到目前为止,尚未见到关于高压下球晶可以在伸直链晶体内部存在的报道．     

拉伸外场作用下热定型工艺对湿法隔膜微观结构及性能影响关系研究

在湿法隔膜制备过程中,热定型工艺与常规热定型工艺有所不同,在高温处理同时还需要对隔膜进行拉伸回缩,即湿法隔膜在热定型过程中存在拉伸外场和温度场耦合作用.本文通过设计不同拉伸比与回缩比,研究了热定型工艺中拉伸外场(拉伸比、回缩比)对隔膜微观结构及宏观热收缩性能的影响关系.结果 发现,小的拉伸比(≤1.3)仅作用于聚乙烯的...     

利用原位X射线散射研究神经酰胺E与海藻糖的相互作用

海藻糖和神经酰胺在皮肤保湿中具有重要作用。 利用原位X射线散射设备,研究了在干燥和升降温过程中海藻糖与神经酰胺之间的分子相互作用。 结果表明,在海藻糖的存在下,神经酰胺E与细胞膜脂分子一样难以失水而延缓了结晶过程。 反之,神经酰胺也抑制了海藻糖在干燥过程中结晶,从而延缓了水分挥发。 此外,在海藻糖的存在下,冷冻干燥的神经酰胺乳液样品加热至105 ℃再降至室温,形成了皮肤中广泛存在的正交晶相和液晶相共存的结构,很好地模拟了皮肤细胞间脂层的相结构。 发现海藻糖代替了角质层中的其它成分,保护神经酰胺分子以真实皮肤中的方式排列。     

The spatial correlation between crystalline and amorphous orientations of isotactic polypropylene during plastic deformation: An in situ observation with FTIR imaging

On the basis of research method in FTIR imaging, we made a heterogeneous thin film of isotactic polypropylene(i PP) that contains a few large spherulites(~150 μm) which are surrounded by small spherulites(~15 μm) for tensile testing. The evolution processes of crystalline and amorphous orientations of i PP are monitored with its characteristic peaks at 998 and 973 cm-1, respectively. By introducing the correlation images, the analysis demonstrates the relationships between the orientation evolutions of crystalline and amorphous phases in a space of 250 μm× 250 μm detecting area. During the plastic deformation, crystalline orientation is higher than amorphous orientation outside the large spherulite, while that is opposite inside the region. In addition, the evolutions of crystalline and amorphous orientations almost keep a positive correlation.     

原位小角X射线散射研究热拉工艺对熔融拉伸法制备的聚丙烯微孔膜结构的影响

采用原位小角X射线散射和扫描电子显微镜研究了热拉过程中,拉伸比和拉伸温度对熔融拉伸法制备的聚丙烯微孔膜晶体和孔洞结构的影响.研究结果表明,冷拉、热定型过程中片晶簇被分离开,其内部结构在热拉过程中不发生分离等变形;随着热拉拉伸比的增加,片晶簇间架桥长度不断增大;与冷拉、热定型样品相比,热拉后的微孔膜架桥沿垂直于拉伸方向具有较好的周期性.不同的拉伸温度结果表明,架桥长度随拉伸温度升高而增加;温度过高时架桥会发生熔融.     

同步辐射显微技术在高分子材料结构研究中的应用

高分子材料以其优异的性能广泛应用于人类生活的每个角落,但其发展受限于研究手段.基于同步辐射先进光源的研究方法(如散射、吸收和成像等)具有高的空间、时间和能量分辨的优势,是揭示高分子材料多尺度结构形成和演化动力学最有效的工具之一.文章结合作者和国内外同行的工作,以具体案例的形式介绍了同步辐射技术在高分子材料结构研究中的应用.希望能起到抛砖引玉的作用,吸引更多的从事高分子材料结构研究的同行利用同步辐射开展科学研究,同时希望更多的进行物理学研究的同行来帮助回答高分子物理的一些基本科学问题.     

New understanding on the memory effect of crystallized iPP

In this study, recovery processes of isotactic polypropylene(iPP) melted spherulites at 135 °C after melting at higher temperatures(170 °C–176 °C) were investigated with polarized optical microscopy and Fourier transform infrared spectroscopy. The recovery temperature was fixed to exclude the interference from heterogeneous nuclei. After melting at temperatures between 170 °C and 174 °C, the melted spherulite could recover back to the origin spherulite at low temperatures. Interestingly, a distinct infrared spectrum from iPP melt and crystal was observed in the early stage of recovery process after melting at low temperatures, where only IR bands resulting from short helices with 12 monomers or less can be seen, which indicates that the presence of crystal residues is not the necessary condition for the polymer memory effect. Avrami analysis further indicated that crystallization mainly took place in melted lamellae. After melting at higher temperatures, melted spherulite cannot recover. Based on above findings, it is proposed that the memory effect can be mainly ascribed to melted lamellae, during which crystalline order is lost but conformational order still exists. These conformational ordered segments formed aggregates, which can play as nucleation precursors at low temperatures.     

溶液结晶制备聚乙烯/碳纳米管串晶结构

通过等温以及非等温溶液结晶法制备了聚乙烯/碳纳米管复合串晶(shish-kebab)结构.电镜结果显示,等温结晶1 h得到的聚乙烯/碳纳米管串晶(shish-kebab)结构kebab长度为30~140 nm,kebab间间距为35~80 nm.使用非等温结晶法得到的产物kebab长度为40~180 nm,kebab间距与等温结晶过程得到的相同.此外实验发现聚乙烯/碳纳米管shish-kebab结构生长过程中,kebab的生长与新的kebab形成是同步发生,直至结晶结束.将得到的聚乙烯/碳纳米管shish-kebab结构在对二甲苯中静置3个月,光学图像显示仍能保持良好的分散性.使用沸腾对二甲苯冲洗聚乙烯/碳纳米管shish-kebab结构以验证其稳定性,发现冲洗过程中虽然部分聚乙烯链溶解,但仍有部分聚乙烯链吸附于碳纳米管上,并在降温过程中重新生成shish-kebab结构.     

A theoretical interpretation of free volume at glass transition

We device a relaxed lattice model (RLM) to study the mechanism of glass transition,which unifies the cageeffects from particle-particle interaction and entropy.By analyzing entropy in RLM with considering the influence of interactions on equilibrium,we demonstrate that glass transition is a second-order phase transition.For a perfect onedimensional linked particle system like linear polymer under normal pressure,the free volume at glass transition is rigorously deduced out to be 2.6％,which provides a theoretical basis for the iso-free volume of 2.5％ given by Willian,Landel and Ferry (WLF) equation.Extending to system with dead particles linked with higher dimensions like branched or cross-linked chains under positive or negative pressure,free volume at glass transition is varied,based on which we construct a phase diagram of glass transition in the space of free volume-dead particle-pressure.This demonstrates that free volume is not the single parameter determining glass transition,while either dead particles like cross-linked points or external force fields like pressure can vary free volume at the glass transition.     

新型显示偏光片光学膜的加工-结构-性能关系

偏光片是薄膜晶体管液晶显示器(TFT-LCD)和有机发光二极管显示(OLED)中最重要的组成部分之一,是一种是由偏光膜、支撑膜、相位差膜等光学膜组合成的多层高分子复合膜.每个组成膜所用材料不同,在偏光片中也发挥不同的作用.随着新型显示的发展,偏振片的产业规模和需求呈井喷之势.然而,目前国内偏光片主要依赖进口,其原因是对偏光片中的各层高分子薄膜加工机制并不明晰,基础研究较为薄弱.本文介绍了本课题组在聚乙烯醇(PVA)偏光膜、三醋酸纤维素(CTA)相位差膜、聚对苯二甲酸乙二醇酯(PET)支撑膜的相关研究进展.通过高时间分辨同步辐射X射线散射与多种原位拉伸装置联用的实验手段,模拟真实复杂的工业生产环境,在线采集偏光片三张光学膜的结构演化规律,并建立其与光学等性能的关系,为光学膜高端制造提供基础原理指导.最后,我们展望了新型显示偏光片光学膜今后的发展方向.