Synthesis and Characterization of ß-Myrcene-Styrene and ß-Ocimene-Styrene Copolymers.

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 ß-myrcene- and ß-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. A new class of terpene-based hybrid systems, holding promise for applications in surface coating technologies, is identified.

Monolithic nanoporous crystalline aerogels.

Monolithic 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. Their outstanding guest transport properties combined with low material cost, robustness, durability, and ease of handling and recycle make these aerogels suitable for applications in chemical separations, purification, and storage as well as in biomedicine. Scientific, technological, and industrial perspectives for monolithic nanoporous-crystalline polymeric aerogels are also discussed.

Time-resolving analysis of cryotropic gelation of water/poly(vinyl alcohol) solutions via small-angle neutron scattering.

The 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. However, solvent crystallization is incomplete, and an unfrozen liquid microphase more concentrated in PVA than the initial solution is also formed. Crystallization of PVA takes place inside the unfrozen liquid microphase and is slowed down because of formation of a microgel fraction. Water crystallization takes place in the early 10 min of the treatment of the solution at subzero temperatures, and although below 0 degrees C the PVA solutions used for preparation of cryogels should be below the spinodal curve, occurrence of liquid-liquid phase separation could not be detected in our experiments. Upon thawing, ice crystals melt, and transparent gels are obtained that become opaque in approximately 200 min, due to a slow and progressive increase of the size of microheterogeneities (dilute and dense regions) imprinted during the fast freezing by the crystallization of water. During the permanence of these gels at room temperature (for hours), the presence of a high content of water (higher than 85% by mass) prevents further crystallization of PVA. Crystallization of PVA, in turn, is resumed by freezing the gels at subzero temperatures, after water crystallization and consequent formation of an unfrozen microphase. The kinetic parameters of PVA crystallization during the permanence of these gels at subzero temperatures are the same shown by PVA during the first freezing step of the solutions.

Mesoscopic and microscopic investigation on poly(vinyl alcohol) hydrogels in the presence of sodium decylsulfate.

The 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. The structural organization of freeze/thaw PVA hydrogel membranes does not change either after rehydration of dried gels or in the presence of a tensile force. Finally, addition of surfactant micelles inside the gel provides a formulation with both hydrophobic and hydrophilic regions, which demonstrates the potential of the system for drug delivery. Both SANS and EPR measurements show that sodium decylsulfate (C10OS) micelles do not significantly interact with the PVA gel. Variation of the gel structure by the number of freeze/thaw cycles should modulate the rate of release of an active constituent, for example, in a dermal patch.

A study of the microstructural and diffusion properties of poly(vinyl alcohol) cryogels containing surfactant supramolecular aggregates.

Surfactant-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. The surfactant concentration within the cryogel, measured by ion chromatography, is the same as that in the rehydrating surfactant solution. Electron paramagnetic resonance (EPR) spin-probe and small-angle neutron scattering (SANS) measurements show that surfactant self-aggregation in the gel is similar to that in water, occurring at the same critical concentration and resulting in the formation of micellar aggregates whose structure is not affected by the cryogel polymeric scaffold. However, both the micelle intradiffusion coefficients, measured by PGSE-NMR, and the spin-probe correlation times, measured by EPR, indicate that dynamic processes in the hydrogel are much slower than in bulk water. A quantitative analysis of these results suggests that the cryogel polymer-poor domains, in which surfactant molecules are solubilized, have an average dimension of approximately 0.1 microm. Interestingly the experimental data also show that the polymer-poor phase contains more polymer than expected, suggesting that the spinodal decomposition, which occurs during the freezing step of cryogel preparation, is not complete or prevented by ice formation.