SYNTHESIS AND CHARACTERIZATION OF MACROMOLECULAR LAYERS GRAFTED TO POLYMER SURFACES

The composition and behavior of surfaces and interfaces play a pivotal role in dictating the overall efficiency of the majority of polymeric materials and devices. Surface properties of the materials can be altered using surface modification techniques. It is necessary to highlight that successful methods of surface modification should affect only the upper layer of the polymer material without changing bulk properties. The processes must introduce new functionalities to the surface, optimize surface roughness, lubrication, hydrophobicity, hydrophilicity, adhesion, conductivity, and/or biocompatibility. Research presented in this dissertation is dedicated to the synthesis, characterization, and application of thin macromolecular layers anchored to polymer substrates. Specifically, attachment of functional polymers via a \u27grafting to\u27 approach has been extensively studied using PET and nylon model substrates. First, poly(glycidyl methacrylate) was used to introduce permanent functionalities to the model substrates by anchoring it to model films. Then, three different functional polymers were grafted on top of the previous layer. As one part of this study, the temperature and time dependence of grafting functional layers were studied. The surface coverage by hydrophobic polymer was determined from experimental data and predicted by a model. In general, the model has a high degree of predictive capability. Next, surface modification of polymeric fibers and membranes is presented as an important application of the polymer thin layers targeted in the study. Specifically, the procedures developed for surface modification of model substrates was employed for modification of PET, nylon, and cotton fabrics as well as PET track-etched membranes. Since epoxy groups are highly reactive in various chemical reactions, the approach becomes virtually universal, allowing both various surfaces and end-functionalized macromolecules to be used in the grafted layer synthesis. PET membranes modified with a reactive anchoring layer can be successfully used to build membrane assemblies by incorporating silica, aluminum, or titanium oxide microparticles as spacers. It is expected that the proposed approaches for the surface modification of the membranes and for the generation of multilayered membrane assemblies can be employed straightforwardly to provide an efficient platform for fabrication of breathable protective materials. Characterization of modified membranes with a cantilever-based method, which can be used for prediction of properties and behavior of thin grafted films, is reported. This technique can be used as a method for fast screening of modified membranes. The method is very robust and capable of detecting very small quantities of substance adsorbed; kinetics of the process can be tracked, as well. This approach can be further developed as a handheld sensor for early warning of the presence of chemical vapors and nerve agents