Crystallized state,thickening process,and crystal transformation of single crystal of trans-1,4-polybutadiene

The effect of heat treatment of trans-1,4-polybutadiene single crystals prepared from dilute benzene solution was studied by dilatometry, X-ray diffraction, and dynamic viscoelastic measurement. The crystal transformation temperature of the single crystal is 55.5ddot]C, 20ddot]C lower than that of the bulk crystallized sample. After heat treatment of the single crystal above 55.5ddot]C, their crystal transformation temperature increases to 69.5ddot]C. At the same time, thickening of the lamellae suddenly occurs and the viscoelastic primary absorption observed in the single crystal mat disappears. It is suggested that this means that the amorphous region attached to the single crystal rapidly crystallized above this temperature, in particular the loose loops attached to the end surface of the crystal are dragged into the crystalline phase to form tight loops as a result of the sliding diffusion of molecules along their axes. This is accompanied by the sudden thickening of the lamellae at the crystal transformation temperature. These observations confirmed more thoroughly our previous prediction that the single crystal of trans-1, 4-polybutadiene, as formed, contains loose loops. The thickening phenomena and the change in the crystal transformation temperature of the trans-1,4-polybutadiene single crystal by heat treatment are also discussed from the thermodynamic viewpoint.