Journal of Chemical Physics, Vol.119, No.18, 9894-9902, 2003
Influence of monomer sequence on microstructure of nonadditive hard chain copolymers: Simulation and equation of state
Influence of copolymer structure on self-assembly of the copolymer was investigated by introducing nonadditive size interactions among different type segments in copolymers composed of touching hard spheres. The copolymer structures investigated are diblock, alternating, multiblock, and random. The copolymers were simulated using discontinuous molecular dynamics simulation. Equations of state of the different model copolymers were developed using the TPT1 theory. Diblock copolymers were found to self assemble readily at high values of the nonadditivity parameter Delta and at high densities. Multiblock and random copolymers self assembled to a smaller extent and the alternating copolymer self-assembled only at very high Delta and densities. The TPT1 equation of state provided good prediction of the compressibilities of the different copolymer systems at negative and small positive values of Delta. Deviations between the model and simulation results were observed at high Delta and high densities. Deviations were associated with self-assembly of the copolymers. (C) 2003 American Institute of Physics.