The crystal structure of phase IV of poly(vinylidene fluoride)

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Abstract
The crystal structure of phase IV (polar α or δ phase) poly(vinylidene fluoride) was studied by x-ray diffraction. Oriented phase IV was obtained by orienting phase II (α phase) and then corona poling at approximately 2 MV/cm. The resulting material is a mixture of phases I, II, and IV. Infrared spectra indicate that phase IV has the same chain conformation (TGTG′) as phase II. The reflections of phase IV can be indexed to an orthorhombic unit cell with lattice constants similar to the phase II lattice constants, a=0.496 nm, b=0.964 nm, and c (chain axis)=0.462 nm. There are two chains in this unit cell. The two chains pack with the chain dipole moments parallel. Three different ways of packing the chains were investigated: both chains up, one up and one down, and a statistical up-down packing. It was found that to within a 97% confidence level, the chains pack with a statistical up-down packing.