Nanocellular polymers (i.e., cellular polymers with cells and walls in the nanometric range) were first produced in the early 2000s, with the works of

The production of open‐cell (OC) nanostructures in polymer foams without non‐foamed solid skins by gas dissolution foaming has been developed in this work. First, several grades of MAM block copolymer (methyl methacrylate‐b‐butyl acrylate‐b‐methyl methacrylate) at high content are employed as heterogeneous phase in poly(methyl methacrylate) for producing OC structures. Atomic force microscopy and extensional rheology are used as methods to understand the main features to obtain OC nanocellular structures. Second, the gas diffusion barrier approach is employed for the first time in polymer blends to avoid the appearance of the solid skins in the borders, which typically appears when the cellular polymer is produced by gas dissolution foaming. The influence of the poly(vinyl alcohol) gas diffusion barrier is analyzed, together with the effect of heterogeneous nucleation provided by MAM copolymer, on the solid skins’ formation. The synergy between both approaches allows obtaining porous nanocellular polymeric films with an OC structure non‐constrained by the presence of outer solid skins.

Blends of poly(methyl methacrylate) (PMMA) and a triblock copolymer poly(methyl methacrylate)-b-poly(butyl acrylate)-b-poly(methyl methacrylate) (MAM) have been obtained following both out-of-equilibrium (extrusion) and near-equilibrium (solvent casting) production routes. The self-assembly capability and the achievable nanostructures of these blends are analyzed by transmission electron microscopy (TEM) regarding their production route and potential for the achievement of nanocellular foams by CO₂ gas dissolution foaming. The influence of the initial nanostructure of the solids on the obtained cellular structure of bulk and film samples is determined by high-resolution scanning electron microscopy (HRSEM) for diverse foaming conditions (saturation pressure, saturation temperature, and post-foaming stage), taking into account the required use of a foaming mold to achieve foams from films. Moreover, the influence of the nanostructuration on the presence of solid outer layers, typical of the selected foaming process, is addressed. Finally, consideration of a qualitative model and the obtained results in terms of nanostructuration, cellular structure, and foaming behavior, allow proposing a detailed cell nucleation, growth, and stabilization scheme for these materials, providing the first direct evidence of the cell nucleation happening inside the poly(butyl acrylate) phase in the PMMA/MAM blends.

The use of metal-organic frameworks (MOF) nanoparticles as nucleating agents in gas dissolution foaming processes is presented. In this work, MOF nanoparticles with three different particle sizes were synthetized and introduced in film composites based on polystyrene at 1 wt.%. The addition of nanoparticles with high affinity to CO₂, which is the gas used as a physical blowing agent, can contribute to increase the nucleation efficiency in comparison with the classical heterogeneous route using non CO₂-philic particles. Nanoparticles dispersion in solids and cellular structure in foams were studied as a function of the particle size and foaming parameters, studying for first time the impact of MOF nanoparticles on the nucleation by gas dissolution foaming. Nucleation efficiencies in the order of 10⁻² were achieved for PS/MOF composites. In addition, the thermal stability of the cellular structure in the composites was enhanced regarding to PS matrix, preserving the cellular structure regardless the foaming temperature. Therefore, MOF nanoparticles have emerged as promising nucleating agents in foaming procedures.