Influence of density and temperature on the microscopic structure and the segmental relaxation of polybutadiene.

We investigate the influence of temperature and density on the local structure and the dynamics of polybutadiene by controlling both hydrostatic pressure and temperature in polarized neutron diffraction experiments on deuterated polybutadiene and in inelastic incoherent scattering experiments on protonated polybutadiene. We observe that the static structure factor S(Q) does not change along macroscopic isochores. This behavior is contrary to the relaxations observed on the nanosecond and picosecond time scales and viewed by the dynamic incoherent scattering law S(Q,omega), which differ strongly along the same thermodynamic path. We conclude that the static behavior, i.e., S(Q), is dominated by macroscopic density changes, similar to the vibrational excitations in the meV range. However, the relaxation dynamics is more sensitive to thermal energy changes. This is confirmed by the finding that lines of identical relaxation behavior (in time, shape, and Q dependence), isochrones on the 10(-9) sec time scale, clearly cross the constant density lines in the (P,T) plane. Concerning S(Q), we can reasonably relate the variation of the main-peak position to the average neighbor chain distance and deduce crude microscopic thermal expansion and compressibility coefficients. In the low-Q regime, the observed pressure and temperature variation of S(Q) exceeds the compressibility contribution and suggests the existence of additional scattering, which might originate from structural correlations arising at higher temperature and low pressure.