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Crystallization and Phase Behavior in Block Copolymer Solution: An in Situ Small Angle X-ray Scattering Study

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Abstract

Amphiphilic diblock copolymers self-assemble into a variety of micellar structures with diverse shapes in selective solvents. Here, we study the concentration and temperature dependence of the packing structure of spherical micelles of a polyisoprene-b-poly(2-vinylpyridine) (PI-b-P2VP) diblock copolymer in toluene using synchrotron radiation small angle X-ray scattering (SR-SAXS) and atomic force microscopy (AFM) techniques. Randomly packed spherical micelles are detected in dilute solutions, while in concentrated solutions, face-centered cubic (FCC), body-centered cubic (BCC) mixed crystal structures, and pure BCC crystal structures are observed with an increase in concentration. In situ SAXS experiments on the FCC/BCC mixed crystal structures reveal a novel FCC/BCC → BCC → Disorder → BCC phase behavior during the thermal annealing process. These results demonstrated that the BCC phase is apparently more stable than the FCC phase in the current sphere-packing system and FCC/BCC is a metastable state. The incompatibility of the PI and P2VP blocks decreases at a higher temperature and renders the variation of domain spacing.

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Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (No. U1632117), the Shanghai Education Development Foundation, and the Shanghai Municipal Education Commission (No. 16SG54). The experiment was conducted on Shanghai Synchrotron Radiation Facility (SSRF) at BL16B and BL19U2.

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Authors and Affiliations

  1. Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201800, China

    Hong-Yan Zhu, Feng Tian, Xiu-Hong Li & Jie Wang

  2. University of Chinese Academy of Sciences, Beijing, 100049, China

    Hong-Yan Zhu

  3. Shanghai Advanced Research Institute, Zhangjiang Lab, Chinese Academy of Science, Shanghai, 201204, China

    Feng Tian, Xiu-Hong Li & Jie Wang

  4. School of Chemistry and Chemical Engineering, State Key Lab of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai, 200240, China

    Hui-Bin Qiu

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  1. Hong-Yan Zhu
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  2. Feng Tian
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  3. Xiu-Hong Li
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  4. Hui-Bin Qiu
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  5. Jie Wang
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Correspondence to Hui-Bin Qiu or Jie Wang.

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Zhu, HY., Tian, F., Li, XH. et al. Crystallization and Phase Behavior in Block Copolymer Solution: An in Situ Small Angle X-ray Scattering Study. Chin J Polym Sci 37, 1162–1168 (2019). https://doi.org/10.1007/s10118-019-2258-4

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  • DOI: https://doi.org/10.1007/s10118-019-2258-4

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