Structure and Chemical Interactions at Model Polymer Interfaces

小行星9310151 将为两种类型的材料系统生成分子和聚合物界面处的结构和化学的相关性： 1)柔性链分子和聚合物作为薄膜吸附在固体表面上，和2）无机膜，特别是金属，沉积（在真空中）在分子和聚合物表面上。 所有相关性将通过使用由具有精确控制的选定官能团阵列的自组装单层制备的定义明确的基质，以及通过应用对单层-亚单层水平的分子特征敏感的先进定量表征工具，尽可能定量。 钉扎晶格的关键概念被定义为当形成界面时发生吸附或成核的特定位点阵列，将上述两个系统的实验相互关联，并将指导这项工作的过程。 在柔性链分子吸附的情况下，将开发相关性，其将平面内排列（由钉扎晶格决定）与化学键合（势阱深度）和吸附（钉扎）位点的移动性的相关动力学与在吸附（自组装）链组装相中开发的平面外结构相关联。 这些相关性将统一的发展一个简单的理论框架，将集中在试图描述的自由体积（缺陷配置）的分布。 在金属原子沉积（真空）的情况下，将开发相关的成核（钉扎）网站（官能团）的分布和它们的化学（金属有机）的金属膜的形态。 这项特别的工作将集中在真空沉积实验研究，监测原位红外光谱，X射线光电子能谱和光谱椭圆偏振，但也将包括有限的理论研究与他人合作。 上述努力的预期成果是一个连贯的框架，理论和实验的发展，用于设计广泛变化，精确定义的功能化单分子膜和理解的吸附/化学吸附性能在很宽的范围内的吸附物从近平衡的分子吸附高度放热的金属原子化学吸附。 该研究将被设计为有效地将这些结果与涉及聚合物表面和界面特性（如粘附力和润湿性）的实际材料科学问题以及聚合物的金属化问题联系起来。 ***

9310151 Allara Correlations of structure and chemistry at molecular and polymer interfaces will be generated for two types of materials systems: 1) flexible chain molecules and polymers adsorbed as thin films at solid surfaces and 2) inorganic films, specifically metals, deposited (in vacuo) onto molecular and polymer surfaces. All correlations will be driven to be as quantitative as possible by the use of well-defined substrates prepared from self-assembled monolayers with precisely controlled arrays of selected functional groups and by the application of advanced, quantitative characterization tools, sensitive to molecular features at the monolayer-submonolayer level. The key concept of a pinning lattice, defined as the specific array of sites upon which adsorption or nucleation takes place when an interface is formed, interrelates the experiments with the above two systems and will guide the course of this work. In the case of flexible chain molecule adsorption, correlations will be developed which relate the in-plane arrangements, dictated by the pinning lattice, with the chemical bonding (potential well depth) and the associated dynamics of mobility of the adsorption (pinning) sites with the out-of-plane structures which develop in the adsorbed (self- assembled) chain assembly phases. These correlations will be unified by the development of a simple theoretical framework which will focus on attempts to describe the distribution of free volume (defect configurations). In the case of the metal atom deposition (in-vacuo), correlations will be developed which relate the nucleation (pinning) site (functional groups) distributions and their chemistry (metal-organic) to the morphology of the metal films. This particular effort will focus on experimental in-vacuo deposition studies, monitored by insitu infrared spectroscopy, x- ray photoemission and spectroscopic ellipsometry, but also will include limited theoretical studies in collaboration with others. The expected outcome of the above efforts is the development of a coherent framework, both theoretical and experimental, for designing widely varying, precisely defined functionalized monolayers and for understanding the adsorption/chemisorption properties over a wide range of adsorbates from near-equilibrium molecular adsorption to highly exothermic metal atom chemisorption. The research will be designed to efficiently relate these results to practical materials science issues involving polymer surface and interface properties such as adhesion and wetting and to metallization of polymers. ***