FLUCTUATION PHENOMENA IN STRUCTURALLY SYMMETRICAL POLYMER BLENDS

Polymer reference interaction site model theory with the new molecular closures is employed to numerically and analytically study structurally and interaction potential symmetric binary blends. Both the compressibility and free energy routes to the thermodynamics are studied and the issue of thermodynamic consistency is addressed. A variety of non-Flory-Huggins effects, or "fluctuation phenomena," are found. These include nonuniversal renormalization of the critical temperature and effective chi-parameter from their mean field values, composition-dependent chi-parameters, and nonlinear dependence of the inverse osmotic compressibility on inverse temperature. All these fluctuation effects depend on degree of polymerization, N, chain length asymmetry, polymer density, range and precise form of the attractive tail potentials, chain stiffness, and proximity to the phase boundary. Some of the fluctuation effects are intrinsic, i.e., survive in the long chain N→∞ limit, while others are finite size effects which arise from chain-connectivity-induced coupled local density and long wavelength concentration fluctuations. Due to the multiple sources of the fluctuation effects, even asymptotic finite size effects can appear "intrinsic" over extended ranges of N. Comparison with lattice Monte Carlo simulations of Deutsch and Binder shows good agreement with the theoretical predictions. All the fluctuation effects can be understood in simple terms by examining the enthalpy of mixing and local interchain correlations. The key physical process is thermally driven local interchain rearrangements corresponding to the formation of diffuse interfaces and clusters or droplets. Analytic results are derived using the Gaussian thread model, which provides a simple physical understanding of the origin of the numerically determined fluctuation effects. In the long chain limit the predictions for the thread blend are shown to be exactly thermodynamically consistent which is a unique circumstance for liquid state theories. The relation of the blend fluctuation stabilization process to the corresponding diblock copolymer problem is briefly discussed. © 1995 American Institute of Physics.