The refocused discrimination induced by variable amplitude minipulses (DIVAM) experiment — Improved domain selection in semicrystalline fluoropolymers by ~(19)F solid state nuclear magnetic resonance spectroscopy

摘要

The discrimination induced by variable amplitude minipulses (DIVAM) filter can be tuned to select for signals from a particular domain, therefore it is possible to obtain signals specific to different domains using only one experiment. An early description of the DIVAM sequence, where the filter terminates with cross-polarization, explains this tune ability using a simple one-spin-relaxation model, thereby limiting the selection mechanism to incoherent processes. Recently, a more complete description of the selection behaviour was offered for the DIVAM filter, when it was directly applied to the observed nucleus (direct DIVAM), taking into account both the incoherent and coherent terms. Direct DIVAM experiments on poly(vinylidenefluoride) (PVDF) show significant phase distortions when large excitation angles were used. The signal from the amorphous domain is seen to nutate in a normal fashion with respect to the excitation angle, while those from the crystalline and defect units did not. The refocused DIVAM sequence is introduced to restore normal nutation for all signals. The selection behaviour is investigated using SIMPSON (simulation program for solid-state nuclear magnetic resonance (NMR) spectroscopy) simulations. These illustrate that the isotropic shift terms have been effectively removed and the dipolar term attenuated, such that the chemical shift anisotropy (CSA) leads to domain selection; however, in a different manner than seen in direct DIVAM. Therefore, this sequence provides a method to select on the basis of the CSA term in the presence of both strong dipolar couplings and a large range of isotropic shifts.