Citation: Hong-Yan Zhu, Feng Tian, Xiu-Hong Li, Hui-Bin Qiu, Jie Wang. Crystallization and Phase Behavior in Block Copolymer Solution: An in Situ Small Angle X-ray Scattering Study[J]. Chinese Journal of Polymer Science, ;2019, 37(11): 1162-1168. doi: 10.1007/s10118-019-2258-4 shu

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

Hong-Yan Zhu ^a,b ,
Feng Tian ^a,c ,
Xiu-Hong Li ^a,c ,
Hui-Bin Qiu ^d,, ,
Jie Wang ^a,c,,

a.
Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, China
b.
University of Chinese Academy of Sciences, Beijing 100049, China
c.
Shanghai Advanced Research Institute, Zhangjiang Lab, Chinese Academy of Science, Shanghai 201204, China
d.
School of Chemistry and Chemical Engineering, State Key Lab of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240, China

Corresponding author: Hui-Bin Qiu, hbqiu@sjtu.edu.cn Jie Wang, wangjie@sinap.ac.cn
Received Date: 26 February 2019
Revised Date: 19 March 2019
Available Online: 25 April 2019

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.
- In situ SAXS,
- Block copolymers,
- Self-assembly,
- Micelle,
- Phase transition
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