In the present study, various diffusive processes have been investigated during foaming of powdered precursors of polyimide. A detailed analysis of the powdered precursor's characteristics allows for an enhanced morphological understanding of the resulting microstructures and foam unit cell. Parameters that are central to the foaming process such as particle morphology, volatile concentration and sorption-desorption processes are evaluated. Isothermal and non-isothermal desorption experiments have been carried out by thermogravimetric analysis (TGA), and specific diffusive processes have been correlated to thermodynamic and kinetic transitions by means of modulated differential scanning calorimetry (MDSC) of the corresponding materials. It was found that two primary fluxes of volatiles, one out of the external surface of the particles (responsible for volatile desorption) and the other into the growing bubble (responsible for vapor supersaturation inside the bubble) compete against each other creating a competitive scenario that becomes the controlling factor for potential inflation within the precursor particles. (c) 2005 Elsevier Ltd. All rights reserved.