Extremely asymmetric phase diagram of homopolymer-monotethered nanoparticles: Competition between chain conformational entropy and particle steric interaction.
The phase behaviors of homopolymer-monotethered nanoparticles (HMNs) in melt are investigated via a theoretical method combining self-consistent field theory for polymers and density functional theory for hard spheres. An extremely asymmetric phase diagram is observed: (i) microphases are only possible for the volume fraction of the tethered polymer fA> 0.35; (ii) in addition to lamellar phase, the system can only self-assemble into various morphologies with a polymer-rich matrix, including gyroid phase, cylindrical phase, and spherical phase. In the frame of this theory, the critical point for HMNs' microphase separation is significantly lower than that of linear diblock copolymers. Furthermore, the characteristic length of microphase-separated structures of HMNs is much smaller than that of linear diblock copolymers with the same molecular weight. Our calculation results on morphologies and characteristic length agree well with recent simulations and experimental observations.
The State Key Laboratory of Molecular Engineering of Polymers, Key Laboratory of Computational Physical Sciences, Department of Macromolecular Science, Fudan University, Shanghai 200433, China.
Tiancai
0000000324999472
T
Zhang
The State Key Laboratory of Molecular Engineering of Polymers, Key Laboratory of Computational Physical Sciences, Department of Macromolecular Science, Fudan University, Shanghai 200433, China.
Chao
C
Fu
The State Key Laboratory of Molecular Engineering of Polymers, Key Laboratory of Computational Physical Sciences, Department of Macromolecular Science, Fudan University, Shanghai 200433, China.
Yingzi
0000000285148228
Y
Yang
The State Key Laboratory of Molecular Engineering of Polymers, Key Laboratory of Computational Physical Sciences, Department of Macromolecular Science, Fudan University, Shanghai 200433, China.
Feng
F
Qiu