Carbon-13 NMR of polyethylenes: Correlation of the crystalline component T1 with structure

The carbon-13 spin-lattice relaxation times T₁ of the crystalline portion of a set of polyethylenes have been studied. Chain structure and crystallization conditions have been varied over the widest possible extremes so that large differences are developed in the level of crystallinity, the supermolecular structure, and the crystallite thickness. Concomitantly, the observed crystalline T₁ values cover the extraordinarily wide range of about 40–4500 s. They bear a one-to-one relation with the crystallite thickness, which is found to be the key structural variable determining this property. A correlation with the temperature for the α-transition can be established, which implies a similar type of segmental motions for the two phenomena. Major changes in the interfacial structure can also have a drastic influence on the value for the crystalline T₁. Analysis of the magnetization decay curve also allows for a quantitative determination of the degree of crystallinity, which is found to be in excellent agreement with the corresponding value found from Raman spectroscopy.