Journal of Chemical Physics, Vol.106, No.5, 1950-1960, 1997
The Ordering of Symmetrical Diblock Copolymers - A Comparison of Self-Consistent-Field and Density-Functional Approaches
Polymer reference interaction site model (PRISM) based density functional (DF) theory is used to evaluate the structure and thermodynamics of structurally symmetric, freely jointed, diblock chains with 0.50 volume fraction. These results are compared to the results of self-consistent-held (SCF) theory. Agreement between the predictions of the SCF and DF theories is found for the lamella spacing well above the order-disorder transition (ODT) and for the qualitative behavior of the interfacial thickness as a function of both chain length and Flory-Huggins chi parameter. Disagreement is found for the magnitude of the interfacial thickness where DF theory indicates that the thickness is 1.7 +/- 0.2 times larger than that predicted by SCF theory. It appears that behavior on the monomer length scale is sensitive to system specific details which are neglected by SCF theory.
Keywords:INTEGRAL-EQUATION THEORY;NONUNIFORM POLYATOMIC SYSTEMS;MOLECULAR-WEIGHT DEPENDENCE;POLYMER-POLYMER INTERFACES;STRONG-SEGREGATION LIMIT;STATE ALKANE MELT;MICROPHASE SEPARATION;BLOCK COPOLYMERS;INHOMOGENEOUS POLYMERS;IMMISCIBLE POLYMERS