Study of the diffusion in polymers of molecules comparable in size and structure to the segments of the chain molecules is suggested as a means of securing information on structure and molecular friction forces in polymers. A convenient method for measuring the diffusivity in polymers of such compounds tagged with C‐14 was devised and used to study the diffusivity of octadecane, octadecanol, stearic acid, and octadecyl stearate for a range of temperatures in polymers including natural rubber, GR‐S, polybutadiene, polyisoprene, and polyisobutylene. Diffusivities were independent of concentration for the range used. The diffusivities of straight chain hydrocarbons in natural rubber appear to vary inversely as the molecular weight of the diffusing compound. Evidence was found for association effects in the diffusion of stearic acid in natural rubber. Activation energies for diffusion of the compounds were quite similar in any one polymer and of the same order as reported for low molecular weight hydrocarbons and for viscous flow. Larger differences in activation energies were observed for diffusion in the different polymers. Correlations were observed for the diffusivities of octadecane in a series of polymers with their densities and thermal expansivities, especially the latter. Some study was given to the effect on the diffusivity of octadecane of such parameters as polymer unsaturation, solution viscosity, molecular weight, and crosslink density. The diffusivity of octadecane in natural rubber had a pronounced maximum as a function of crosslink density, coinciding with the maximum in tensile strength. Possible implications of this are discussed. The diffusivities of octadecane in a series of elastomers were studied in relation to the internal frictional losses observed for 60 cps vibrations over a range of temperatures. It was concluded that frictional forces deduced from the diffusivity measurements have some correspondence to high frequency viscoelastic phenomena which involve small units of structure comparable in size to the segments of the polymer molecules.

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