The structure-properties relationships of sustainable materials derived from biomass-based monomers are investigated, focusing on hybrid styrene/terpene-based copolymers with blocky microstructures, such as β-myrcene- and β-ocimene-styrene copolymers. The samples show complex glass transition dynamics, as evidenced by the physical aging experienced by the amorphous phase in styrene-rich copolymers. The tendency of styrene- and terpene-rich sequences to give heterogeneous morphologies with correlation strength extending over 10-40 nm is outlined, through small-angle X-ray scattering analysis.
View Article and Find Full Text PDFMonolithic aerogels can be easily obtained by drying physical gels formed by linear uncross-linked polymers. Preparation methods, structure, and properties of these physically cross-linked polymeric aerogels are reviewed, with particular emphasis to those whose cross-linking knots are crystallites and, more in particular, crystallites exhibiting nanoporous-crystalline forms. The latter aerogels present beside disordered amorphous micropores (typical of all aerogels) also all identical nanopores of the crystalline phases.
View Article and Find Full Text PDFThe structural transformations occurring in initially homogeneous aqueous solutions of poly(vinyl alcohol) (PVA) through application of freezing (-13 degrees C) and thawing (20 degrees C) cycles is investigated by time resolving small-angle neutron scattering (SANS). These measurements indicate that formation of gels of complex hierarchical structure arises from occurrence of different elementary processes, involving different length and time scales. The fastest process that could be detected by our measurements during the first cryotropic treatment consists of the crystallization of the solvent.
View Article and Find Full Text PDFThe structure of poly(vinyl alcohol) (PVA) hydrogels formed as a result of freeze/thaw treatments of aqueous solutions of the polymer (11 wt % PVA) in the freshly prepared state is analyzed through the combined use of small (SANS) and ultrasmall (USANS) angle neutron scattering techniques. The structure of these hydrogels may be described in terms of polymer rich regions, with dimensions of the order of 1-2 microm, dispersed in a water rich phase, forming two bicontinuous phases. The PVA chains in the polymer rich phase form a network where the cross-linking points are mainly crystalline aggregates of PVA having average dimensions of approximately 45 A.
View Article and Find Full Text PDFSurfactant-containing poly(vinyl alcohol) (PVA) cryogels have been prepared by drying and reswelling hydrogel patches, previously obtained by the freeze/thaw procedure, in decyltrimethylammonium bromide (C10TAB) aqueous solutions. The microstructural and diffusive properties of the resulting material have been characterized by a combined experimental strategy. Gravimetric measurements show that the cryogel maximum swelling is not affected by the surfactant.
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