Dispersion and self-assembly of nanospheres and nanorods in polymer nanocomposites.

摘要

Polymer nanocomposites are hybrid nanomaterials in which electrical, opto-electronic, magnetic, mechanical and other properties can be precisely tuned by choosing an appropriate combination of nanoparticle (NP) and polymer. This dissertation explores in-situ and ex-situ routes to disperse metal NP in polymers as well as the fundamental thermodynamic and dynamic principles underlying the NP dispersion in polymers. "In-situ" silver NP are prepared by the thermal decomposition of an organometallic precursor (1,1,1,5,5,5-hexafluoroacetylacetonato)silver(I) or (AgHFA) in homopolymer poly(methyl methactyalate), PMMA and block copolymer poly(MMA-b-styrene), PS-b-PMMA films. A range of complementary characterization techniques including Rutherford backscattering spectrometry (RBS), scanning force microscopy (SFM), transmission electron microscopy (TEM), and UV-visible spectroscopy are used to characterize the polymer nanocomposites. The in-situ formed "spherical" silver NP are observed to segregate to the surface and the substrate regions in PMMA and PS-b-PMMA films. By showing that the precursor organizes into aggregates in as-cast films, our experiments uncover the mechanism of NP segregation. Upon annealing, diffusion of the precursor to the surface and substrate occurs concurrently with NP formation resulting in enrichment of Ag at both interfaces. In PS-b-PMMA films, the Ag NP form during the self-assembly of the block copolymer. At the surface, NP organize into well-defined arrays that are guided by the PMMA domains. For the first time, our experiments also show that the kinetics of block copolymer reorganization is slowed down by the incorporation of NP. This dissertation also explores the self-assembly of "ex-situ" synthesized NP with aspect ratio > 1, namely gold nanorods functionalized with poly(ethylene glycol), PEG. After solvent annealing PS-b-PMMA with 5-vol% Au, the nanorods are selectively located and confined in the "lamellar" PMMA domains due to favorable PEG-PMMA interaction. Due to confinement, the majority of the nanorods orient with their long axis parallel to lamellae orientation. To further understand the nature of NP at surfaces, spherical gold NP are deposited on a PS melt surface and their embedding is followed by TEM. Before being completely embedded in PS, NP protruding from the surface are covered by a thin (∼ 1.5 nm) wetting layer, that produces a capillary pressure responsible for complete NP embedding.