The behaviour in supercritical CO2 of block copolymers containing styrenic, butadiene, and methacrylic or perfluroalkyl blocks is studied in view of a specific swelling and foaming by a gas dissolution process. These block copolymers are considered as neat materials or as additives in blends e.g in polystyrene (PS) or polymethylmethacrylate (PMMA) matrices. In both cases (neat or blend) the copolymers may exhibit a structuration at a micro or nano level. The phase separated (nano) structures depend on the block type and the concentration of copolymers in the polymer matrix, so that micelles, vesicles, lamellas, or warm-like structures are generated. Furthermore when one block is chosen as a highly CO2-philic moiety, the nanostructures are able to act as CO2 reservoirs. The result is the possibility to control microcellular foaming, or sometimes nanocellular foaming, of commodity amorphous polymers such as PMMA and PS. Besides, at room temperature, the blocks can be either glassy or rubbery in order to freeze the growth and coalescence of cells during foaming. Different cellular polymers were elaborated by varying either the copolymer type or the foaming conditions (saturation pressure, temperature, depressurization rate). Cell sizes are accessible in a range from 0.2 to 200 μm, and densities from 0.40 to 1 g/cm3. It is also shown that nanostructuring polymers are also efficient to produce polymer foams with oriented / structured voids. This new approach could be used to produce nanocellular or ultra microcellular polymer foams in a simple process, using blending and extrusion.

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The effect of the catalyst concentration on the synthesis and textural properties of polyisocyanurate-polyurethane aerogels is analyzed. The use of different catalyst amounts allows obtaining low-density aerogels (0.10−0.16 g/cm 3 ) with high porosities (85−91%). Their porous structures were analyzed by scanning electron microscopy and nitrogen adsorption−desorption isotherm. A noticeable decrease in the size of the scattering centers, particles and pores, was achieved when reducing the catalyst amount. In some samples, the small size of these features, much smaller than the wavelength of visible light, causes a bare light dispersion, leading to the first transparent polyisocyanurate-polyurethane aerogels. Light transmittance measurements at 532 nm have been made showing high values (ca. 76% for 1 mm thick samples) for the formulations with the smallest particle and pore sizes. These aerogels presenting optical transparency have many potential applications such as solar collectors, glazing systems for insulating windows, and sensors, among others.

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