We prepared microporous aramid films through a simple, inexpensive and green way, using ionic liquids (IL) as porosity promoters. Commercial poly(m-phenylene isophthalamide) (MPIA) films with different IL proportions were prepared, and then microporous films were obtained by removing the IL in distilled water. Microporous films presented density values between 0.34 and 0.71 g⋅cm−3 (around five times lower to commercial MPIA), with a homogeneous and controlled cellular morphology dependent on the proportion of the IL, showing cell sizes in the microcellular range (radii between 1 and 8 µm). Thermal, mechanical and electrical properties (specifically ionic conductivity) of the aramid films were analyzed to evaluate the influence of the IL proportion. Finally, it was observed that the MPIA/IL system presented a reversible thermally induced phase-separation process around 60 °C, which was characterized through AFM-Raman images and spectra, together with the variation of the ionic conductivity.
