Spatial distribution of stabilizer-derived nitroxide radicals during thermal degradation of poly(acrylonitrile-butadiene-styrene) copolymers: a unified picture from pulsed ELDOR and ESR imaging

Double Electron-Electron Resonance (DEER) provides information on the spatial distribution of radicals on the length scale of a few nanometres, while Electron Spin Resonance Imaging (ESRI) provides information on a length scale of millimetres with a resolution of about 100 micrometres. Despite the gap between these length scales, results from the two techniques are found to complement and support each other in the characterization of the identity and distribution of nitroxide radicals derived from the Hindered Amine Stabilizer (HAS) Tinuvin 770 in poly(acrylonitrile-butadiene-styrene) (ABS) copolymers. DEER measurements demonstrate that there is no significant formation of biradicals from the bifunctional HAS, and provide the distributions of local radical concentrations. These distributions are poorly resolved for model-free analysis of the DEER data by the Tikhonov regularization; the resolution was significantly improved by utilizing information obtained by ESRI. DEER data can be fitted with only one adjustable parameter, namely the average radical concentration, if 1D and 2D spectral--spatial ESRI results on both the spatial distribution of nitroxides and their distribution between the acrylonitrile--styrene-rich (SAN) and butadiene-rich (B) microphases are considered.