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Morphological transformations of diblock copolymers in binary solvents: A simulation study

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Abstract

Morphological transformations of amphiphilic AB diblock copolymers in mixtures of a common solvent (S1) and a selective solvent (S2) for the B block are studied using the simulated annealing method. We focus on the morphological transformation depending on the fraction of the selective solvent C S2, the concentration of the polymer C p , and the polymer–solvent interactions ε ij (i = A, B; j = S1, S2). Morphology diagrams are constructed as functions of C p , C S2, and/or ε AS2. The copolymer morphological sequence from dissolved → sphere → rod → ring/cage → vesicle is obtained upon increasing C S2 at a fixed C p . This morphology sequence is consistent with previous experimental observations. It is found that the selectivity of the selective solvent affects the self-assembled microstructure significantly. In particular, when the interaction ε BS2 is negative, aggregates of stacked lamellae dominate the diagram. The mechanisms of aggregate transformation and the formation of stacked lamellar aggregates are discussed by analyzing variations of the average contact numbers of the A or B monomers with monomers and with molecules of the two types of solvent, as well as the mean square end-to-end distances of chains. It is found that the basic morphological sequence of spheres to rods to vesicles and the stacked lamellar aggregates result from competition between the interfacial energy and the chain conformational entropy. Analysis of the vesicle structure reveals that the vesicle size increases with increasing C p or with decreasing C S2, but remains almost unchanged with variations in ε AS2.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant Nos. 21204040, 20904027, 21574071, 21528401, 20925414, and 91227121), the Program for Changjiang Scholars and Innovative Research Team in University of China (PCSIRT) (Grant No. IRT1257), and the 111 Project (Grant No. B16027).

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Authors and Affiliations

  1. School of Physics, Key Laboratory of Functional Polymer Materials of Ministry of Education, Nankai University, and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin, 300071, China

    Zheng Wang, Yuhua Yin, Run Jiang & Baohui Li

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  1. Zheng Wang
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  2. Yuhua Yin
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  3. Run Jiang
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  4. Baohui Li
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Correspondence to Baohui Li.

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arXiv: 1703.08913.

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Wang, Z., Yin, Y., Jiang, R. et al. Morphological transformations of diblock copolymers in binary solvents: A simulation study. Front. Phys. 12, 128201 (2017). https://doi.org/10.1007/s11467-017-0678-6

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