We report a study of the impact of cold crystallization on the structure of nanocomposites comprising poly(vinylidene fluoride) (PVDF) and Lucentite STN (TM) organically modified silicate (OMS). Nanocomposites were prepared from solution over a very wide composition range, from 0.01 to 20% OMS by weight. Thermal preparation involved cold crystallization at 145 degrees C of quenched, compression-molded plaques. Static and real-time wide and small angle X-ray scattering (WAXS, SAXS), Fourier transform infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC) were used to investigate the crystalline phase of PVDF. For OMS content greater than 0.50 wt%, WAXS studies show that that the silicate gallery spacing increases modestly in the nanocomposites compared to neat OMS film, indicating a level of polymer intercalation. Using Gaussian peak fitting of WAXS profiles, we determine that the composition range can be divided into three parts. First, for OMS greater than 0.5 wt%, alpha phase fraction, phi(alpha), is insignificant (phi(alpha) similar to 0-0.01). Second, at the intermediate range, for OMS between 0.5 wt% down to 0.025 wt%, beta phase dominates and the beta fraction, phi(beta), is related to alpha by phi(beta) > phi(alpha). Third, below 0.025 wt% OMS, alpha dominates and phi(alpha) > phi(beta). The ability ol'small amounts of OMS (>= 0.025 wt%) to cause beta crystal domination is remarkable. Overall, crystallinity index (from the ratio of WAXS crystal peak area to total area) ranges from about 0.36 to 0.51 after cold crystallization. Real-time WAXS studies during heating of initially cold crystallized nanocomposites show that there is no inter-con version between the alpha and beta phase PVDF crystals, where these crystals coexist at room temperature. While all samples showed a strong SAXS Bragg peak, indicating existence of two-phase lamellar stacks, the sample containing predominantly beta phase had poorly correlated lamellar stacks, compared to samples containing predominantly alpha phase. (c) 2006 Elsevier Ltd. All rights reserved.