We studied film formation of composites of surfactant-free polystyrene (PS) nanoparticles and modified Na-activated bentonite (MLB), by steady state fluorescence (SSF) technique. The films were prepared from a mixture of pyrene (P)-labeled PS particles and MLB at various compositions at room temperature. These films were annealed at elevated temperatures above the glass transition (T(g)) temperature of polystyrene for 10 min. Scattered light (I(S)) and fluorescence intensities (I(P)) from P were measured after each annealing step to monitor the stages of film formation. Evolution of transparency of the composite films was monitored by using photon transmission intensity, I(tr) Atomic force microscopy (AFM) was used to detect the variation in physical structure of annealed composite films. The nanocomposite films exhibited a percolation threshold at 20 wt.% MLB content. Below this fraction two distinct film formation stages were observed which are known as void closure and interdiffusion and above this fraction no film formation was detected. At 0-20 wt.% MLB, minimum film formation, T(0), void closure, T(v) and healing, T(h) temperatures were determined. Void closure and interdiffusion stages were modeled and related activation energies were determined. Void closure activation energies decreased as the percent of MLB increased, no variation was observed in backbone activation energies. (c) 2008 Elsevier B.V. All rights reserved.