Self-diffusion of linear and cyclic alkanes, measured with pulsed-gradient spin-echo nuclear magnetic resonance

Abstract

Self-diffusion coefficients of linear and cyclic alkanes in melt, in blends with equivalent linear alkanes, and dissolved in linear polyethylene, were measured by pulsed-gradient spin-echo nuclear magnetic resonance at various temperatures. The results indicate the following: (i) at the same carbon number, cyclic alkanes diffuse more slowly than linear alkanes in their respective melts, but linears and cyclics share a similar rapid rate of decrease with increasing carbon number; (ii) in blends of linear and cyclic alkanes at the same carbon number the single average diffusion coefficient observed varies monotonically as a function of composition; and (iii) two distinct diffusion coefficients are observed in the cycloalkane/linear polyethylene blends, with the extrapolated trace cycloalkane diffusion consistent with Rouse behavior. The results are compared with recent numerical simulations and with experiments in other polymer systems, forming a consistent picture of the effects of diffusant mass, molecular shape and flexibility, and the dynamic attributes of the host material.