Selected methods of surface engineering applied to materials science
Öztürk, Gözde İpek (2004) Selected methods of surface engineering applied to materials science. [Thesis]
Two approaches were developed to surface-functionalize commercially available injection molded isotactic polypropylene tubes: Non-reactive method: A novel technique, in which organosiloxane films were fabricated and anchored on low-surface-energy polymer without invoking chemical pretreatment of the surface, was developed to surface-functionalize injection molded polypropylene tubes. In envisaging a non-reactive approach, polypropylene tubes were incubated in solutions that encouraged inter-molecular chain separation of surfacepositioned polymeric chains and entry of small, monomeric silane precursors into the sub-layers. During precursor activation, the reaction conditions encouraged activated silane species potentially in and above the plastic matrix to crosslink, in principle affording a thin coating whose bulk was partially submerged and entangled within the plastic matrix. The binary network afforded, for example, polyaminopropylsiloxane entangled within polypropylene, described a system in which two interconnected polymers shared no formal covalent bonds but nevertheless were inseparable. Reactive method: In surface-engineering of injection-molded polypropylene tubes by oxidative activation, native, mesoscopically flat tubes were oxidized using aqueous ammonium peroxydisulfate. When evaluated in the context of the conditions employed for oxidation, FTIR-ATR spectral analysis indicated that the activated plastics predominantly bore carboxyl, ketone and possibly hydroxyl groups as major surface products and an approximate uniform increase of matrix-bound oxidation products up to 16 hours reaction time. Scanning electron microscopy analyses showed insignificant changes of mesoscale topology up to 8 hours reaction time, sparsely distributed bulges of approximate 400nm diameter developed by 12 hours reaction time, and a sudden and marked transformation thereafter to give the sponge-like mesoscale topology. The main mechanisms envisaged to rationalize the topology included organized pitting of the surface, oxidation-mediated phase separation, or a combination of the two. While degradative loss of polymer chains clearly pointed to the former mechanism, it by itself could not rationalize the topology, as pitting would have been anticipated gradually in time. In fact, the dramatic change of topology, which suddenly developed late in the oxidation process, could only be consistent with a phase separation. This deduction was corroborated in conducting the parallel experiment with gradually oxidized melt-blown fibers. Mesopatterning induced by oxidation described an alternative to current methods based on lithography, self-organization and solvent casting.
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