Polymorphism of poly(vinylidene fluoride). PVDF, in the presence of Lucentite STN organically modified silicate (OMS) is investigated for PVDF nanocomposites melt-crystallized at high supercooling temperatures where neat PVDF crystallizes exclusively in the alpha crystalline phase Nanocomposites were prepared from solution with 0-10 wt% OMS composition Here we observed that clay addition promotes gamma phase formation in nanocomposites melt-crystallized at high supercooling (i e. at low crystallization temperature), whereas previously we showed that even small amount of nanosilicates resulted in beta phase formation in cold-crystallized PVDF nanocomposites [1]. Wide-angle X-ray scattering (WAXS), Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) studies showed that alpha- and gamma-phases co-existed in nanocomposites containing up to 0 1 wt% OMS. and the amount of alpha-crystals substantially diminished for higher OMS content Formation of gamma-crystal phase was confirmed with morphologic observation of spherulites of low-birefringence using polarizing optical and atomic force microscopies, and their crystalline structures were verified by FTIR and Raman microscopic spectroscopy We also address in this work the ambiguities in assessing PVDF crystallographic phases, and correct the phase identification errors which have persisted up to this point in the literature based on melting point confusion The crystal phase identification for PVDF nanocomposites is discussed and clarified, based on X-ray scattering, vibrational spectra, and thermal analysis. For reference, we provide a vibrational band list, indicating the close, or overlapping bands, of the three phases of PVDF alpha, beta and gamma (C) 2010 Elsevier Ltd All rights reserved