Wednesday, February 8, 2012

Mesoscale spatial distribution of electron spins studied by time-resolved small-angle and ultrasmall-angle neutron scattering with dynamic nuclear polarization: A case of 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) doped in high-density polyethylene

Kumada, T., Y. Noda, S. Koizumi, and T. Hashimoto, J. Chem. Phys., 133, (2010)


We carried out time-resolved small-angle neutron scattering (SANS) and ultrasmall-angle neutron scattering (USANS) studies of dynamically polarized high-density polyethylene (HDPE) doped with 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) persistent free radicals. We observed a remarkable enhancement of the scattering intensity shortly after a switching of microwave frequency from positive (negative) to negative (positive) dynamic nuclear polarization (DNP). The enhancement was found to be due to spatially heterogeneous proton-spin polarization generated as a result of heterogeneously distributed TEMPO in the HDPE sample. The spatial fluctuation of the polarization ranged up to the length-scale of ≥ 100 nm. This result strongly suggests that the TEMPO free radicals are localized more in nonfibrils but less in fibrils of HDPE. In this way, we propose that the time-resolved DNP-SANS and DNP-USANS be general techniques to determine mesoscale spatial distribution of electron spins in dielectric materials.