Radicals spherulites

Figure 5.7. Optical microscope image of a thin film (thickness 2 p.m) of a-p-NPNN grown on a glass substrate (1.6 x 1.0 mm, crossed polarizers). Reprinted from Journal of Crystal Growth, Vol. 209, J. Caro, J. Fraxedas and A. Figueras, Thickness-dependent spherulitic growth observed in thin films of the molecular organic radical p-nitrophenyl nitronyl nitroxide, 146-158, Copyright (2000), with permission from Elsevier.

PVDF is mainly obtained by radical polymerisation of 1,1-difluoroethylene head to tail is the preferred mode of linking between the monomer units, but according to the polymerisation conditions, head to head or tail to tail links may appear. The inversion percentage, which depends upon the polymerisation temperature (3.5% at 20°C, around 6% at 140°C), can be quantified by F or C NMR spectroscopy [30] or FTIR spectroscopy [31], and affects the crystallinity of the polymer and its physical properties. The latter have been extensively summarised by Lovinger [30]. Upon recrystallisation from the melted state, PVDF features a spherulitic structure with a crystalline phase representing 50% of the whole material [32]. Four different crystalline phases (a, jS, y, S) may be identified, but the a phase is the most common as it is the most stable from a thermodynamic point of view. Its helical structure is composed of two antiparallel chains. The other phases may be obtained, as shown by the conversion diagram (Fig. 7), by applying a mechanical or thermal stress or an electrical polarisation. The / phase owns ferroelectric, piezoelectric and pyroelectric properties. 

The strong performance of fracture parameter, found in the iPPMA composites, is probably due to a stronger chemical interfacial adhesion owing to the presence of reactive radicals of maleic anhydride, but also its nucleating action producing a smaller size of spherulites and consequently a more pronounced presence of amorphous phases allows it to absorb more energy during the fracture test. 

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