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Pressure-composition phase diagram of diblock copolymers
H Degaki1,2, I Taniguchi2,3, S Deguchi2
1Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.
Abstract:
Phase diagrams of diblock copolymers as functions of pressure and composition, essential for the molecular design of energy-efficient polymeric materials with pressure processability, are presented. While pressure-dependent modifications of temperature-composition phase diagrams have been investigated in relation to temperature-induced transitions, diagrams explicitly displayed on the pressure-composition plane remain largely underexplored. To establish a fundamental understanding of pressure-induced phase transitions, we construct pressure-composition phase diagrams using compressible random phase approximation theory and self-consistent field theory. The contrast in block compressibility is shown to govern pressure-responsive phase behavior: a large contrast enhances miscibility under pressure, whereas a small contrast reduces it. In highly asymmetric systems with more compressible soft segments, voids preferentially accumulate in soft domains, stabilizing ordered phases and skewing phase boundaries. These results provide a theoretical basis for the rational design of pressure-responsive polymeric systems.
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