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Design, synthesis, and film formation of fluorine containing colloidal dispersions.

机译：含氟胶体分散体的设计，合成和成膜。

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Fluoropolymers (FPs) have been subject of interest for many years, however due to extreme synthetic and processing conditions their applications have been limited. This dissertation focuses on design and synthesis of fluorine containing colloidal dispersions to advance limited knowledge and to gain further understanding of fluorine containing colloidal dispersions. Fluoroacrylates and fluoro methacrylates consisting of varying chain length of perfluoroalkyl side chain were copolymerized with methylmethacrylate (MMA) and n-butylacrylate (n-BA) under aqueous environment utilizing phospholipids (PLs) as dispersing agent. Morphologies of colloids, coalescence, and film formation processes after water evaporation was investigated using various microscopic probes such as transmission electron microscope (TEM), atomic force microscopy (AFM), nuclear magnetic resonance (NMR), infrared (IR), and internal reflection infrared imaging (IRIRI). These studies showed that FPs exist as phase-separated domains within colloidal particles leading to unique non-spherical morphologies where blocky phase of FPs exists on the p-MMA/nBA core. Upon coalescence FPs migrates to the film-air (F-A) interface, generating highly hydrophobic and ultra low coefficient of friction surfaces. Further studies focused on utilization of pentafluorostyrene (PFS) as fluorinated component incorporated into p-MMA/nBA colloids, which upon copolymerization with polyethyleneglycol (PEG) molecules leads to surfaces that repel proteins. Copolymerizing PFS in two step synthetic processes, resulted in unique acorn-shaped colloids that consist of two phases p-MMA/nBA and p-nBA/PFS. These acorn-shaped colloids are able to self-assemble which is driven by the surface energies of substrates. For high surface energy substrates, such as glass, fluorinated phase is observed at the F-A interface, but for low surface energy substrates, such as polytetrafluoroethylene (PTFE), hydrogenated phase is exposed at the F-A interface. Using a number of spectroscopic and morphological analytical approaches combined with contact angle analysis as well as thermodynamic modeling aspects of acorn-shaped particles, morphologies and film formations were examined and confirmed the self-assembly of acorn-shaped colloidal particles.
机译：含氟聚合物（FPs）多年来一直是人们关注的主题，但是由于极端的合成和加工条件，其应用受到了限制。本文主要研究含氟胶态分散体的设计与合成，以提高有限的认识，并进一步理解含氟胶态分散体。在水性环境下，使用磷脂（PLs）作为分散剂，将由变化的全氟烷基侧链链长组成的氟丙烯酸酯和氟甲基丙烯酸酯与甲基丙烯酸甲酯（MMA）和丙烯酸正丁酯（n-BA）共聚。使用各种显微镜探针，如透射电子显微镜（TEM），原子力显微镜（AFM），核磁共振（NMR），红外（IR）和内部反射，研究了水蒸发后的胶体形态，聚结和成膜过程。红外成像（IRIRI）。这些研究表明，FPs作为胶体颗粒内的相分离域存在，从而导致独特的非球形形态，其中FPs的嵌段相存在于p-MMA / nBA核心上。聚结后，FPs迁移至薄膜-空气（F-A）界面，从而产生高度疏水和超低摩擦系数的表面。进一步的研究集中于利用五氟苯乙烯（PFS）作为掺入p-MMA / nBA胶体中的氟化成分，该物质在与聚乙二醇（PEG）分子共聚后形成排斥蛋白质的表面。在两步合成过程中共聚PFS，得到独特的橡子状胶体，该胶体由p-MMA / nBA和p-nBA / PFS两相组成。这些橡子状胶体能够自组装，这是由基质的表面能驱动的。对于玻璃等高表面能基材，在F-A界面处观察到氟化相，而对于低表面能的基材，如聚四氟乙烯（PTFE），则在F-A界面处暴露了氢化相。使用多种光谱学和形态学分析方法，结合接触角分析以及橡子形颗粒的热力学建模方面，检查了形态和膜形成，并确认了橡子形胶体颗粒的自组装。

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