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
1. [1]
  Suo, T.; Yan, D.; Yang, S.; Shi, A. C. A theoretical study of phase behaviors for diblock copolymers in selective solvents. Macromolecules 2009, 42, 6791-6798. doi: 10.1021/ma900939u
2. [2]
  Liu, M.; Qiang, Y.; Li, W.; Qiu, F.; Shi, A. C. Stabilizing the frank-kasper phases via binary blends of ab diblock copolymers. ACS Macro Lett. 2016, 5, 1167-1171. doi: 10.1021/acsmacrolett.6b00685
3. [3]
  Mai, Y.; Eisenberg, A. Self-assembly of block copolymers. Chem. Soc. Rev. 2012, 41, 5969-5985. doi: 10.1039/c2cs35115c
4. [4]
  Tritschler, U.; Pearce, S.; Gwyther, J.; Whittell, G. R.; Manners, I. 50th anniversary perspective: Functional nanoparticles from the solution self-assembly of block copolymers. Macromolecules 2017, 50, 3439-3463. doi: 10.1021/acs.macromol.6b02767
5. [5]
  Lee, S.; Leighton, C.; Bates, F. S. Sphericity and symmetry breaking in the formation of frank-kasper phases from one component materials. Proc. Natl. Acad. Sci. U.S.A. 2014, 111, 17723-17731. doi: 10.1073/pnas.1408678111
6. [6]
  Noolandi, J.; Hong, K. M. Theory of block copolymer micelles in solution. Macromolecules 1983, 16, 1443-1448. doi: 10.1021/ma00243a007
7. [7]
  Choi, S.-H.; Bates, F. S.; Lodge, T. P. Small-angle x-ray scattering of concentration dependent structures in block copolymer solutions. Macromolecules 2014, 47, 7978-7986. doi: 10.1021/ma5016819
8. [8]
  Simone, P. M.; Lodge, T. P. Phase behavior and ionic conductivity of concentrated solutions of polystyrene-poly(ethylene oxide) diblock copolymers in an ionic liquid. ACS Appl. Mater. Interfaces 2009, 1, 2812-2820. doi: 10.1021/am900555f
9. [9]
  McConnell, G. A.; Gast, A. P.; Huang, J. S.; Smith, S. D. Disorder-order transitions in soft sphere polymer micelles. Phys. Rev. Lett. 1993, 71, 2102-2105. doi: 10.1103/PhysRevLett.71.2102
10. [10]
  Ito, M. M. M.; Ito, K.; Shibayama, M.; Sugiyama, K.; Yokoyama, H. Phase behavior of block copolymers in selective supercritical solvent. Macromolecules 2015, 48, 3590-3597. doi: 10.1021/acs.macromol.5b00162
11. [11]
  Takagi, H.; Hashimoto, R.; Igarashi, N.; Kishimoto, S.; Yamamoto, K. Frank-kasper sigma phase in polybutadiene-poly(epsilon-caprolactone) diblock copolymer/polybutadiene blends. J. Phys. Condens. Matter 2017, 29, 204002. doi: 10.1088/1361-648X/aa6908
12. [12]
  Blanazs, A.; Warren, N. J.; Lewis, A. L.; Armes, S. P.; Ryan, A. J. Self-assembly of double hydrophilic block copolymers in concentrated aqueous solution. Soft Matter 2011, 7, 6399-6403. doi: 10.1039/c1sm05771e
13. [13]
  Virgili, J. M.; Hexemer, A.; Pople, J. A.; Balsara, N. P.; Segalman, R. A. Phase behavior of polystyrene-block-poly(2-vinylpyridine) copolymers in a selective ionic liquid solvent. Macromolecules 2009, 42, 4604-4613. doi: 10.1021/ma900483n
14. [14]
  Dorin, R. M.; Marques, D. S.; Sai, H.; Vainio, U.; Phillip, W. A.; Peinemann, K.-V.; Nunes, S. P.; Wiesner, U. Solution small-angle x-ray scattering as a screening and predictive tool in the fabrication of asymmetric block copolymer membranes. ACS Macro Lett. 2012, 1, 614-617. doi: 10.1021/mz300100b
15. [15]
  Kim, K.; Schulze, M. W.; Arora, A.; Lewis, R. M.; Hillmyer, M. A.; Dorfman, K. D.; Bates, F. S. Thermal processing of diblock copolymer melts mimics metallurgy. Science 2017, 356, 520-523. doi: 10.1126/science.aam7212
16. [16]
  Chen, L.; Lee, H. S.; Lee, S. Close-packed block copolymer micelles induced by temperature quenching. Proc. Natl. Acad. Sci. U.S.A. 2018, 115, 7218-7223. doi: 10.1073/pnas.1801682115
17. [17]
  Chu, C.-Y.; Pei, R.-Y.; Chen, H.-L. Order-order transition from ordered bicontinuous double diamond to hexagonally packed cylinders in stereoregular diblock copolymer/homopolymer blends. Macromolecules 2018, 51, 8493-8500. doi: 10.1021/acs.macromol.8b01570
18. [18]
  Gillard, T. M.; Lee, S.; Bates, F. S. Dodecagonal quasicrystalline order in a diblock copolymer melt. Proc. Natl. Acad. Sci. U.S.A. 2016, 113, 5167-5172. doi: 10.1073/pnas.1601692113
19. [19]
  Lewis, R. M.; Arora, A.; Beech, H. K.; Lee, B.; Lindsay, A. P.; Lodge, T. P.; Dorfman, K. D.; Bates, F. S. Role of chain length in the formation of frank-kasper phases in diblock copolymers. Phys. Rev. Lett. 2018, 121, 208002. doi: 10.1103/PhysRevLett.121.208002
20. [20]
  Fischer, S.; Exner, A.; Zielske, K.; Perlich, J.; Deloudi, S.; Steurer, W.; Lindner, P.; Forster, S. Colloidal quasicrystals with 12-fold and 18-fold diffraction symmetry. Proc. Natl. Acad. Sci. U.S.A. 2011, 108, 1810-1814. doi: 10.1073/pnas.1008695108
21. [21]
  Kim, K.; Arora, A.; Lewis, R. M., ; Liu, M.; Li, W.; Shi, A. C.; Dorfman, K. D.; Bates, F. S. Origins of low-symmetry phases in asymmetric diblock copolymer melts. Proc. Natl. Acad. Sci. U.S.A. 2018, 115, 847-854. doi: 10.1073/pnas.1717850115
22. [22]
  Hadjichristidis, N.; Iatrou, H.; Pispas, S.; Pitsikalis, M. Anionic polymerization: High vacuum techniques. J. Polym. Sci., Part A: Polym. Chem. 2000, 38, 3211-3234. doi: 10.1002/(ISSN)1099-0518
23. [23]
  Auschra, C.; Stadler, R. Synthesis of block copolymers with poly(methyl methacrylate)-p(B-B-MMA), p(EB-B-MMA), p(S-B-B-B-MMA) and p(S-B-EB-B-MMA). Polym. Bull. 1993, 30, 257-264. doi: 10.1007/BF00343058
24. [24]
  Tian, F.; Li, X. H.; Wang, Y. Z.; Yang, C. M.; Zhou, P.; Lin, J. Y.; Zeng, J. R.; Hong, C. X.; Hua, W. Q.; Li, X. Y. Small angle X-ray scattering beamline at ssrf. Nucl. Sci. Technol. 2015, 26, 030101.
25. [25]
  Zeng, J.; Bian, F.; Wang, J.; Li, X.; Wang, Y.; Tian, F.; Zhou, P. Performance on absolute scattering intensity calibration and protein molecular weight determination at bl16b1, a dedicated saxs beamline at ssrf. J. Synchrotron Rad. 2017, 24, 509-520. doi: 10.1107/S1600577516019135
26. [26]
  Li, N.; Li, X.; Wang, Y.; Liu, G.; Zhou, P.; Wu, H.; Hong, C.; Bian, F.; Zhang, R. The new ncpss bl19u2 beamline at the ssrf for small-angle X-ray scattering from biological macromolecules in solution. J. Appl. Cryst. 2016, 49, 1428-1432. doi: 10.1107/S160057671601195X
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