Phase Separation, Wetting and Dewetting in PS/PVME Blend Thin Films: Dependence on Film Thickness and Composition Ratio

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Abstract

The effects of film thickness and composition ratio on the morphology evolution of polystyrene (PS)/poly(vinyl methyl ether) (PVME) blend thin films were investigated. Diverse morphology evolutions including droplet-matrix structure, hole emergence, bicontinuous structure formation, percolation-to-droplet transition could be observed under annealing in two-phase region, depending on film thickness and composition ratio. The mechanism for these morphology variations was related to the complex effects of phase separation, dewetting and preferential wetting. The comparison between the thickness of bottom PVME layer and the twice of gyration radius 2Rg(PVME) played a dominant role in morphology control. Only when the PS/PVME film had specific film thickness and compositional symmetry, phase separation and dewetting could happen in sequence.

Keywords

Phase separation Dewetting Wetting 

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (No. 51403026).

References

  1. 1.
    Reiter, G. Dewetting as a probe of polymer mobility in thin films. Macromolecules 1994, 27(11), 3046–3052CrossRefGoogle Scholar
  2. 2.
    Reiter, G. Unstable thin polymer films: rupture and dewetting processes. Langmuir 1993, 9(5), 1344–1351CrossRefGoogle Scholar
  3. 3.
    Radoev, B. P.; Scheludko, A. D.; Manev, E. D. Critical thickness of thin liquid films: theory and experiment. J. Colloid Interface Sci. 1983, 95(1), 254–265CrossRefGoogle Scholar
  4. 4.
    Reiter, G. Dewetting of thin polymer films. Phys. Rev. Lett. 1992, 68(1), 75–78CrossRefGoogle Scholar
  5. 5.
    Morariu, M. D., "Pattern formation by capillary instabilities in thin films", University Library Groningen. 2004Google Scholar
  6. 6.
    Vrij, A. Possible mechanism for the spontaneous rupture of thin, free liquid films. Discuss. Faraday Soc. 1966, 42, 23–33CrossRefGoogle Scholar
  7. 7.
    Xie, R.; Karim, A.; Douglas, J.; Han, C.; Weiss, R. Spinodal dewetting of thin polymer films. Phys. Rev. Lett. 1998, 81(6), 1251–1254CrossRefGoogle Scholar
  8. 8.
    Sferrazza, M.; Heppenstall-Butler, M.; Cubitt, R.; Bucknall, D.; Webster, J.; Jones, R. Interfacial instability driven by dispersive forces: the early stages of spinodal dewetting of a thin polymer film on a polymer substrate. Phys. Rev. Lett. 1998, 81(23), 5173–5176CrossRefGoogle Scholar
  9. 9.
    Xue, L.; Han, Y. Pattern formation by dewetting of polymer thin film. Prog. Polym. Sci. 2011, 36(2), 269–293CrossRefGoogle Scholar
  10. 10.
    Mitlin, V. S. Dewetting of solid surface: analogy with spinodal decomposition. J. Colloid Interface Sci. 1993, 156(2), 491–497CrossRefGoogle Scholar
  11. 11.
    Mitlin, V. S. On dewetting conditions. Colloids Surf.Physicochem. Eng. Aspects 1994, 89(2-3), 97–101CrossRefGoogle Scholar
  12. 12.
    Liu, Y.; Rafailovich, M.; Sokolov, J.; Schwarz, S.; Zhong, X.; Eisenberg, A.; Kramer, E.; Sauer, B.; Satija, S. Wetting behavior of homopolymer films on chemically similar block copolymer surfaces. Phys. Rev. Lett. 1994, 73(3), 440CrossRefGoogle Scholar
  13. 13.
    Wensink, K.; Jérôme, B. Dewetting induced by density fluctuations. Langmuir 2002, 18(2), 413–416CrossRefGoogle Scholar
  14. 14.
    Yerushalmi-Rozen, R.; Kerle, T.; Klein, J. Alternative dewetting pathways of thin liquid films. Science 1999, 285(5431), 1254–1256CrossRefGoogle Scholar
  15. 15.
    Geoghegan, M.; Krausch, G. Wetting at polymer surfaces and interfaces. Prog. Polym. Sci. 2003, 28(2), 261–302CrossRefGoogle Scholar
  16. 16.
    Xia, T.; Qin, Y.; Huang, Y.; Huang, T.; Xu, J.; Li, Y. Sequence control of phase separation and dewetting in PS/PVME blend thin films by changing molecular weight of PS. J. Chem. Phys. 2016, 145(20), 204903CrossRefGoogle Scholar
  17. 17.
    Ogawa, H.; Kanaya, T.; Nishida, K.; Matsuba, G. Phase separation and dewetting in polystyrene/poly (vinyl methyl ether) blend thin films in a wide thickness range. Polymer 2008, 49(1), 254–262CrossRefGoogle Scholar
  18. 18.
    El-Mabrouk, K.; Belaiche, M.; Bousmina, M. Phase separation in PS/PVME thin and thick films. J. Colloid Interface Sci. 2007, 306(2), 354–367CrossRefGoogle Scholar
  19. 19.
    You, J.; Liao, Y.; Men, Y.; Shi, T.; An, L.; Li, X. Composition effect on interplay between phase separation and dewetting in PMMA/SAN blend ultrathin films. Macromolecules 2011, 44(13), 5318–5325CrossRefGoogle Scholar
  20. 20.
    You, J.; Hu, S.; Liao, Y.; Song, K.; Men, Y.; Shi, T.; An, L. Composition effect on dewetting of ultrathin films of miscible polymer blend. Polymer 2009, 50(19), 4745–4752CrossRefGoogle Scholar
  21. 21.
    Ermi, B. D.; Karim, A.; Douglas, J. F. Formation and dissolution of phase-separated structures in ultrathin blend films. J. Polym. Sci., Part B: Polym. Phys. 1998, 36(1), 191–200CrossRefGoogle Scholar
  22. 22.
    Sauer, B. B.; Walsh, D. J. Use of neutron reflection and spectroscopic ellipsometry for the study of the interface between miscible polymer films. Macromolecules 1991, 24(22), 5948–5955CrossRefGoogle Scholar
  23. 23.
    Azzam, R. M. A.; Bashara, N. M.; Ballard, S. S. Ellipsometry and polarized light. Phys. Today 1978, 31(11), 72–72CrossRefGoogle Scholar
  24. 24.
    Xia, T.; Ogawa, H.; Inoue, R.; Nishida, K.; Yamada, N. L.; Li, G.; Kanaya, T. Dewetting process of deuterated polystyrene and poly(vinyl methyl ether) blend thin films via phase separation. Macromolecules 2013, 46(11), 4540–4547CrossRefGoogle Scholar
  25. 25.
    Tanaka, K.; Yoon, J. S.; Takahara, A.; Kajiyama, T. Ultrathinning-induced surface phase separation of polystyrene/poly(vinyl methyl ether) blend film. Macromolecules 1995, 28(4), 934–938CrossRefGoogle Scholar
  26. 26.
    Polios, I.; Soliman, M.; Lee, C.; Gido, S.; Schmidt-Rohr, K.; Winter, H. Late stages of phase separation in a binary polymer blend studied by rheology, optical and electron microscopy, and solid state NMR. Macromolecules 1997, 30(15), 4470–4480CrossRefGoogle Scholar
  27. 27.
    Zhang, S.; Shi, T.; You, J.; Li, Y. Solvent annealing induced phase separation and dewetting in PMMA/SAN blend films: composition dependence. Polym. Chem. 2013, 4(14), 3943–3948CrossRefGoogle Scholar
  28. 28.
    Zhang, S.; Zhu, Y.; Shi, T.; Zhao, H.; You, J.; Li, Y. Selective solvent annealing induced phase separation and dewetting in PMMA/SAN blend ultrathin films. J. Polym. Sci., Part B: Polym. Phys. 2014, 52(19), 1243–1251CrossRefGoogle Scholar
  29. 29.
    Seemann, R.; Herminghaus, S.; Jacobs, K. Dewetting patterns and molecular forces: a reconciliation. Phys. Rev. Lett. 2001, 86(24), 5534–5537CrossRefGoogle Scholar
  30. 30.
    You, J.; Zhang, S.; Huang, G.; Shi, T.; Li, Y. Solvent annealing induced phase separation and dewetting in PMMA/SAN blend film: film thickness and solvent dependence. J. Chem. Phys. 2013, 138(24), 244907.CrossRefGoogle Scholar

Copyright information

© Chinese Chemical Society, Institute of Chemistry, Chinese Academy of Sciences and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.College of Material Science and EngineeringChongqing University of TechnologyChongqingChina

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