Pressure and Temperature Effects in Homopolymer Blends and Diblock Copolymers

Thermal composition fluctuations in a homogeneous binary polymer blend and in a diblock copolymer were measured by small-angle neutron scattering as a function of temperature and pressure. The experimental data were analyzed with theoretical expressions, including the important effect of thermal fluctuations. Phase boundaries, the Flory-Huggins interaction parameter and the Ginzburg number were obtained. The packing of the molecules changes with pressure. Therefore, the degree of thermal fluctuation as a function of packing and temperature was studied. While in polymer blends packing leads, in some respects, to a universal behaviour, such behaviour is not found in diblock copolymers. It is shown that the Ginzburg number decreases with pressure sensitively in blends, while it is constant in diblock copolymers. The Ginzburg number is an estimation of the transition between the universality classes of the `mean-field' approximation and the three-dimensional Ising model. The phase boundaries in blends increase with pressure, while the phase boundary of the studied block copolymer shows an unusual shape: with increasing pressure it first decreases and then increases. Its origin is an increase of the entropic and of the enthalpic parts, respectively, of the Flory-Huggins interaction parameter.