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Dynamical studies of confined fluids and polymers.

机译:密闭流体和聚合物的动力学研究。

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摘要

Soft matter, a class of materials including polymers, colloids, and surfactant molecules, are ubiquitous in our everyday lives. Plastics, soaps, foods and living organisms are mostly comprised of soft materials. Research conducted to understand soft matter behavior at the molecular level is essential to create new materials with unique properties. Self-healing plastics, targeted drug delivery, and nanowire assemblies have all been further advanced by soft matter research. The author of this dissertation investigates fundamental soft matter systems, including polymer solutions and melts, colloid dispersions in polymer melts, and interfacial fluids.;The dynamics of polymers and confined fluids were studied using the single-molecule sensitive technique of fluorescence correlation spectroscopy (FCS). Here, fluorescent dyes are attached to polymer coils or by introducing free dyes directly into the solution/film. Complementary experiments were also performed, utilizing atomic force microscopy (AFM) and ellipsometry.;FCS and AFM experiments demonstrated the significant difference in properties of thin fluid films of the nearly spherical, nonpolar molecule TEHOS (tetrakis(2-ethylhexoxy)silane) when compared to its bulk counterpart. AFM experiments confirmed TEHOS orders in layers near a solid substrate. FCS experiments show that free dyes introduced in these thin films do not have a single diffusion coefficient, indicating that these films have heterogeneity at the molecular level.;FCS experiments have been applied to study the diffusion of gold colloids. The diffusion of gold colloids in polymer melts was found to dramatically depart from the Stokes-Einstein prediction when colloid size was smaller than the surrounding polymer mesh size. This effect is explained by noting the viscosity experienced by the colloid is not equivalent to the overall bulk viscosity of the polymer melt.;The conformational change of polymers immersed in a binary solvent was measured via FCS. This experiment was conducted to test a theory proposed by Brochard and de Gennes, who postulated a polymer chain undergoes a collapse and a dramatic re-swelling as the critical point of the binary mixture is approached. Measuring polymer chain diffusion as a function of temperature, this theory was confirmed. To my knowledge, this was the first experimental evidence of contraction/re-swelling for polymers in critical binary solvents.
机译:软物质是一类包括聚合物,胶体和表面活性剂分子的材料,在我们的日常生活中无处不在。塑料,肥皂,食品和生物有机体主要由柔软的材料组成。进行研究以了解分子水平的软物质行为对于创建具有独特性能的新材料至关重要。自愈塑料,靶向药物递送和纳米线组件都已经通过软物质研究得到了进一步发展。本文的作者研究了基本的软物质系统,包括聚合物溶液和熔体,聚合物熔体中的胶体分散体以及界面流体。;使用单分子敏感性荧光相关光谱技术(FCS)研究了聚合物和密闭流体的动力学。 )。在这里,荧光染料附着在聚合物线圈上,或通过将游离染料直接引入溶液/薄膜中而附着。还利用原子力显微镜(AFM)和椭偏仪进行了补充实验; FCS和AFM实验表明,与近球形非极性分子TEHOS(四(2-乙基己氧基)硅烷)相比,流体薄膜的性能存在显着差异到它的大部分。 AFM实验证实了固体基材附近各层的TEHOS顺序。 FCS实验表明,引入这些薄膜的游离染料没有单一的扩散系数,表明这些薄膜在分子水平上具有异质性。FCS实验已用于研究金胶体的扩散。当胶体尺寸小于周围的聚合物筛孔尺寸时,发现金胶体在聚合物熔体中的扩散明显偏离了斯托克斯-爱因斯坦的预测。通过指出胶体所经历的粘度不等于聚合物熔体的总体积粘度来解释这种效果。通过FCS测量浸渍在二元溶剂中的聚合物的构象变化。进行该实验以测试由Brochard和de Gennes提出的理论,他们假设聚合物链发生崩溃,并且随着接近二元混合物的临界点而急剧膨胀。测量聚合物链扩散随温度的变化,这一理论得到了证实。据我所知,这是关键二元溶剂中聚合物收缩/再溶胀的第一个实验证据。

著录项

  • 作者

    Grabowski, Christopher A.;

  • 作者单位

    Wayne State University.;

  • 授予单位 Wayne State University.;
  • 学科 Physics Condensed Matter.;Physics Optics.
  • 学位 Ph.D.
  • 年度 2009
  • 页码 190 p.
  • 总页数 190
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 光学;
  • 关键词

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