Crystallization and Phase Behavior in Block Copolymer Solution: An <italic style="font-style: italic">in Situ</italic> Small Angle X-ray Scattering Study

Hong-Yan Zhu; Feng Tian; Xiu-Hong Li; Hui-Bin Qiu; Jie Wang

doi:10.1007/s10118-019-2258-4

Your Location：

Home >

Browse articles >

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

ARTICLE | Updated：2021-02-18

- Crystallization and Phase Behavior in Block Copolymer Solution: An in Situ Small Angle X-ray Scattering Study
- Crystallization and Phase Behavior in Block Copolymer Solution: An in Situ Small Angle X-ray Scattering Study
- Chinese Journal of Polymer Science 2019年37卷第11期页码：1162-1168
- Affiliations：
  
  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
- Author bio：
  
  hbqiu@sjtu.edu.cn (H.B.Q)
  wangjie@sinap.ac.cn (J.W.)
- Funds：
  
  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.
- DOI：10.1007/s10118-019-2258-4
  中图分类号：
- 收稿：2019-02-26，
  
  修回：2019-3-19，
  
  录用：2019-3-21，
  
  网络首发：2019-04-25，
  
  纸质出版：2019-11
- Accepted：
Scan QR Code
Zhu, H. Y.; Tian, F.; Li, X. H.; Qiu, H. B.; Wang, J. Crystallization and phase behavior in block copolymer solution: An in situ small angle X-ray scattering study. Chinese J. Polym. Sci. 2019, 37, 1162–1168.

Hong-Yan Zhu, Feng Tian, Xiu-Hong Li, et al. 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.
Zhu, H. Y.; Tian, F.; Li, X. H.; Qiu, H. B.; Wang, J. Crystallization and phase behavior in block copolymer solution: An in situ small angle X-ray scattering study. Chinese J. Polym. Sci. 2019, 37, 1162–1168. DOI： 10.1007/s10118-019-2258-4.

Hong-Yan Zhu, Feng Tian, Xiu-Hong Li, et al. 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. DOI：

摘要

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-

-poly(2-vinylpyridine) (PI-

-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.

关键词

Keywords

references

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 http://doi.org/10.1021/ma900939u .

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 http://doi.org/10.1021/acsmacrolett.6b00685 .

Mai, Y.; Eisenberg, A . Self-assembly of block copolymers . Chem. Soc. Rev. , 2012 . 41 5969 - 5985 . DOI: 10.1039/c2cs35115c http://doi.org/10.1039/c2cs35115c .

Tritschler, U.; Pearce, S.; Gwyther, J.; Whittell, G. R.; Manners, I . 50 th Anniversary perspective: Functional nanoparticles from the solution self-assembly of block copolymers . Macromolecules , 2017 . 50 3439 - 3463 . DOI: 10.1021/acs.macromol.6b02767 http://doi.org/10.1021/acs.macromol.6b02767 .

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. , 2014 . 111 17723 - 17731 . DOI: 10.1073/pnas.1408678111 http://doi.org/10.1073/pnas.1408678111 .

Noolandi, J.; Hong, K. M . Theory of block copolymer micelles in solution . Macromolecules , 1983 . 16 1443 - 1448 . DOI: 10.1021/ma00243a007 http://doi.org/10.1021/ma00243a007 .

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 http://doi.org/10.1021/ma5016819 .

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 http://doi.org/10.1021/am900555f .

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 http://doi.org/10.1103/PhysRevLett.71.2102 .

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 http://doi.org/10.1021/acs.macromol.5b00162 .

Takagi, H.; Hashimoto, R.; Igarashi, N.; Kishimoto, S.; Yamamoto, K . Frank-Kasper sigma phase in polybutadiene-poly( ε -caprolactone) diblock copolymer/polybutadiene blends . J. Phys. Condens. Matter , 2017 . 29 204002 DOI: 10.1088/1361-648X/aa6908 http://doi.org/10.1088/1361-648X/aa6908 .

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 http://doi.org/10.1039/c1sm05771e .

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 http://doi.org/10.1021/ma900483n .

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 http://doi.org/10.1021/mz300100b .

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 http://doi.org/10.1126/science.aam7212 .

Chen, L.; Lee, H. S.; Lee, S . Close-packed block copolymer micelles induced by temperature quenching . Proc. Natl. Acad. Sci. , 2018 . 115 7218 - 7223 . DOI: 10.1073/pnas.1801682115 http://doi.org/10.1073/pnas.1801682115 .

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 http://doi.org/10.1021/acs.macromol.8b01570 .

Gillard, T. M.; Lee, S.; Bates, F. S . Dodecagonal quasicrystalline order in a diblock copolymer melt . Proc. Natl. Acad. Sci. , 2016 . 113 5167 - 5172 . DOI: 10.1073/pnas.1601692113 http://doi.org/10.1073/pnas.1601692113 .

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 http://doi.org/10.1103/PhysRevLett.121.208002 .

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. , 2011 . 108 1810 - 1814 . DOI: 10.1073/pnas.1008695108 http://doi.org/10.1073/pnas.1008695108 .

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. , 2018 . 115 847 - 854 . DOI: 10.1073/pnas.1717850115 http://doi.org/10.1073/pnas.1717850115 .

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 http://doi.org/10.1002/(ISSN)1099-0518 .

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 http://doi.org/10.1007/BF00343058 .

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 .

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 http://doi.org/10.1107/S1600577516019135 .

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 http://doi.org/10.1107/S160057671601195X .

浏览量

124

Downloads

CSCD

文章被引用时，请邮件提醒。

Submit

工具集

关联资源

Achieving Complete Photonic Band Gaps in a Low-symmetric Rectangular Cross-sectional Columnar Phase Self-assembled from Block Copolymers

Homopolypeptide Vesicles Triggered by Side-Chain Hydration

Block Copolymer Colloidal Particles with Unique Structures through Three-dimensional Confined Assembly and Disassembly

Functionally Oriented Tumor Microenvironment Responsive Polymeric Nanoassembly: Engineering and Applications

Silk Sericin-inspired Poly-β-homoserine for Protein Protection

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

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

DOI：10.1007/s10118-019-2258-4

摘要

Abstract

关键词

Keywords

references