Simona Longo

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.

Monolithic nanoporous–crystalline aerogels based on PPO

Monolithic and robust aerogels exhibiting nanoporous–crystalline modifications of an industrially relevant polymer (poly(2,6-dimethyl-1,4-phenylene)oxide, generally known as polyphenyleneoxide, PPO), have been obtained from thermoreversible gels, by sudden solvent extraction with supercritical carbon dioxide. The aerogel formation occurs only in the presence of semicrystalline nanofibrils of syndiotactic polystyrene, a polymer presenting molecular miscibility with PPO in the amorphous phase. These mixed monolithic aerogels can present nanoporous–crystalline phases of both polymers and hence are very promising for water and air purification. For instance, the carbon tetrachloride uptake from 10 ppm aqueous solutions can be as high as 19 wt%.

Clay exfoliation and polymer/clay aerogels by supercritical carbon dioxide

Supercritical carbon dioxide (scCO2) treatments of a montmorillonite (MMT) intercalated with ammonium cations bearing two long hydrocarbon tails (organo-modified MMT, OMMT) led to OMMT exfoliation, with loss of the long-range order in the packing of the hydrocarbon tails and maintenance of the long-range order in the clay layers. The intercalated and the derived exfoliated OMMT have been deeply characterized, mainly by X-ray diffraction analyses. Monolithic composite aerogels, with large amounts of both intercalated and exfoliated OMMT and including the nanoporous-crystalline δ form of syndiotactic polystyrene (s-PS), have been prepared, by scCO2 extractions of s-PS-based gels. Also for high OMMT content, the gel and aerogel preparation procedures occur without re-aggregation of the exfoliated clay, which is instead observed for other kinds of polymer processing. Aerogels with the exfoliated OMMT have more even dispersion of the clay layers, higher elastic modulus and larger surface area than aerogels with the intercalated OMMT. Extremely light materials with relevant transport properties could be prepared. Moreover, s-PS-based aerogels with exfoliated OMMT could be helpful for the handling of exfoliated clay minerals.

Monolithic Aerogels Based on Poly(2,6-diphenyl-1,4-phenylene oxide) and Syndiotactic Polystyrene

Molecular sorption behavior of amorphous and semicrystalline samples based on poly(2,6-diphenyl-1,4-phenylene oxide) (PPPO) has been compared. Fully amorphous PPPO powders, as obtained by supercritical carbon dioxide (scCO2) extraction of concentrated solutions, present uptake of pollutants much higher than for commercial sorbent materials based on semicrystalline PPPO (Tenax TA). Robust monolithic aerogels with good handling characteristics can be easily obtained by solvent extraction by scCO2 from gels including PPPO blends with syndiotactic polystyrene (s-PS). These monolithic PPPO/s-PS aerogels present many advantages as sorbent materials with respect to both amorphous and semicrystalline PPPO powders. In fact, besides the obvious advantages in terms of easier and safer handling, the new monolithic aerogels present higher surface areas and equilibrium guest uptakes.