Organic polymers can be made porous via continuous or discontinuous expansion processes in scCO₂. The resulting foams properties are controlled by the interplay of three groups of parameters: (i) Chemical, (ii) physico-chemical, and (iii) technological/process that are explained in this paper. The advantages and drawbacks of continuous (extrusion, injection foaming) or discontinuous (batch foaming) foaming processes in scCO₂, will be discussed in this article; especially for micro or nano cellular polymers. Indeed, a challenge is to reduce both specific mass (e.g., ρ < 100 kg·m⁻³) and cell size (e.g., average pore diameter ϕ_average^pores < 100 nm). Then a particular system where small “objects” (coreshells CS, block copolymer MAM) are perfectly dispersed at a micrometric to nanometric scale in poly(methyl methacrylate) (PMMA) will be presented. Such “additives”, considered as foaming aids, are aimed at “regulating” the foaming and lowering the pore size and/or density of PMMA based foams. Differences between these additives will be shown. Finally, in a PMMA/20 wt% MAM blend, via a quasi one-step batch foaming, a “porous to nonporous” transition is observed in thick samples. A lower limit of pore size (around 50 nm) seems to arise.

The two-step batch foaming process of solid-state assisted by supercritical CO₂ is a versatile technique for the foaming of polymers. In this work, it was assisted by an out-of-autoclave technology: either using lasers or ultrasound (US). Laser-aided foaming was only tested in the preliminary experiments; most of the work involved US. Foaming was carried out on bulk thick samples (PMMA). The effect of ultrasound on the cellular morphology was a function of the foaming temperature. Thanks to US, cell size was slightly decreased, cell density was increased, and interestingly, thermal conductivity was shown to decrease. The effect on the porosity was more remarkable at high temperatures. Both techniques provided micro porosity. This first investigation of these two potential methods for the assistance of supercritical CO₂ batch foaming opens the door to new investigations. The different properties of the ultrasound method and its effects will be studied in an upcoming publication.

This work addresses the structural quantification of multiphase materials, here nanostructured polymer solid precursors and their micro/nano sized foamed counterparts. It is based on a strategy of contrast/edge enhancement, locally adaptive to image data in digital images of materials. The method allows to binarize straightforwardly the structures (the phases) in TEM and SEM images after edge identification, edge choice, and image virtual reconstruction. A detailed insight is brought into one‐step batch supercritical CO₂ foaming of acrylic amorphous PMMA (polymethyl methacrylate) polymers, aided by the nanostructuration of block copolymers (BCP), here MAM (butyl acrylate center block methyl acrylate side blocks). The foaming conditions, i.e., pressure drop rate (PDR) and saturation temperature required for an actual one‐step procedure are specified and clarified, whereas previous works, dealing with “one‐step procedures”, are probably incurring in a two‐step procedure. The roles of the BCP content (and size) and saturation temperature are carefully analyzed and further clarified, more comprehensively than in previous literature. Thanks to the analysis of size distributions of foams and foam blend precursors (0.25, 0.5, 10 wt% MAM), bi modality of 10 wt% foams is for example revealed. A discussion of kinetics effects, i.e., evolutions of the effective sample temperature T_ef(t), and the effective glass transition temperature T_g, ef(t). provides a new insight of “pseudo” one‐step VS “real” one‐step batch foaming.