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Assembling and properties of the polymer-particle nanostructured materials

Posted on:2011-08-10Degree:Ph.DType:Dissertation
University:Clarkson UniversityCandidate:Sheparovych, RomanFull Text:PDF
GTID:1441390002966616Subject:Chemistry
Abstract/Summary:
Complementary properties of the soft and hard matter explain its common encounter in many natural and manmade applications. A combination of flexible organic macromolecules and hard mineral clusters results in new materials far advantageous than its constituents alone. In this work we study assembling of colloidal nanocrystals and polymers into complex nanostructures. Magnetism, surface wettability and adhesion comprise properties of interest for the obtained nanocomposites.;Applying a magnetic field induces a reversible 1D ordering of the magnetically susceptible particles. This property was employed in the fabrication of the permanent chains of magnetite nanocrystals (d=15nm). In the assembling process the aligned particles were bound together using polyelectrolyte macromolecules. The basics of the binding process involved an electrostatic interaction between the positively charged polyelectrolyte and the negative surface of the particles (aqueous environment). Adsorption of the polymer molecules onto several adjacent particles in the aligned 1D aggregate results in the formation of the permanent particulate chains. Positive charges of the adsorbed polyelectrolyte molecules stabilize the dispersion of the obtained nanostructures in water. Magnetization measurements revealed that superparamagnetic nanoparticles, being assembled into 1D ordered structures, attain magnetic coercivity. This effect originates from the magnetostatic interaction between the neighboring magnetite nanocrystals. The preferable dipole alignment of the assembled nanoparticles is directed along the chain axis.;Another system studied in this project includes polymer-particle responsive surface coatings. Tethered polymer chains and particles bearing different functionalities change surface properties upon restructuring of the composite layer. When the environment favors polymer swelling (good solvent), the polymer chains segregate to the surface and cover the particles. In the opposite case, when polymer is in a dry state or in poor solvent its chains collapse and expose the particulate layer. The goal was to design responsive surface system possessing low adhesiveness in air and in aqueous environments. Two factors provide low adhesion: surface roughness induced by the particles monolayer and fast adapting of low surface/interfacial energy upon changing environmental properties. Surface roughness reduces the total area of the contacting asperities, while selective switching of the surface composition provides a low interfacial energy. In air the hydrophilic polymer chains collapse and uncover hydrophobic particles, while in water the polymer segregates on top of the particles thus lowering surface water interfacial energy.;Silica particles coated with mixed polymer brushes have been used for modification of surface wettability. In particular, aqueous dispersions of the modified silica produced superhydrophobic surface coatings. Hydrophobicity of the casted layers was achieved by modification of the particle surface with either polystyrene (PS) or polydimethylsiloxane (PDMS). Stable aqueous dispersions of these particles were obtained by co-grafting of the hydrophilic polymers. Selective segregation of the polymer chains upon changing environment from water to air rendered desired surface properties of colloids in dispersion and in dry state. To achieve superhydrophobic effect, roughness of the casted layers was increased by controlled aggregation of the original nano-sized particles. By depositing their flocks onto substrate surface we created uniformly distributed micro-sized asperities. Being composed of the nanosized particles, large asperities created multiscale surface roughness with a structure similar to the surface of lotus leaves.
Keywords/Search Tags:Surface, Polymer, Particles, Assembling
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