Description:
<jats:title>Abstract</jats:title><jats:p>The radiation‐initiated graft polymerization of 4‐vinylpyridine to high‐density polyethylene was studied over a wide range of reaction conditions of radiation intensity <jats:italic>I</jats:italic>, monomer concentration <jats:italic>M</jats:italic><jats:sub>1</jats:sub>, and polymer film thickness <jats:italic>L</jats:italic>. The conditions included both diffusion‐free and diffusion‐controlled graft polymerizations. The results corroborate our previous theoretical predictions on the effect of <jats:italic>I</jats:italic>, <jats:italic>M</jats:italic><jats:sub>1</jats:sub>, and <jats:italic>L</jats:italic> on the experimental grafting rate. The grafting rate is inverse first order in <jats:italic>L</jats:italic> for diffusion‐controlled reaction and independent of <jats:italic>L</jats:italic> for diffusion‐free reaction. The dependence of grafting rate on radiation intensity decreases from 1/2 to 1/4 order for diffusion‐controlled reaction. Diffusion control results in a decrease in the dependence of rate on monomer concentration. The observed decrease is somewhat greater than theoretically predicted.</jats:p>