Selective NMR pulse sequences for the study of solid fluoropolymers

Fluorine-19 NMR spectra of solids have some special features, which are discussed in this article. In particular, they generally contain two abundant spin baths (protons and fluorine nuclei). This situation throws up some special operational requirements, as does the study of heterogeneous samples. The relaxation characteristics of heterogeneous systems, which are briefly described herein, frequently permit the use of specific pulse sequences to obtain subspectra for individual components. Various possible selective sequences for use in fluorinated heterogeneous organic solids are listed and their actions rationalized on the basis of molecular mobility. Semicrystalline hydrogen-containing fluoropolymers form especially suitable systems for such operations, and in order to understand their domain structures it is essential to obtain subspectra of the amorphous and crystalline domains. Examples are given of the use of selective pulse sequences for studying fluoropolymers, especially for poly(vinylidene fluoride) (PVDF) and the copolymer P(VDF75/TrFE25) (TrFE = trifluoroethylene).