Advertisement

Confinement and localization effects revealed for thin films of the miscible blend poly(vinyl methyl ether)/polystyrene with a composition of 25/75 wt%

  • Paulina Szymoniak
  • Marcel Gawek
  • Sherif Madkour
  • Andreas SchönhalsEmail author
Regular Article
  • 34 Downloads
Part of the following topical collections:
  1. Dielectric Spectroscopy Applied to Soft Matter

Abstract.

Thin films (200-7nm) of the asymmetric polymer blend poly(vinyl methyl ether) (PVME)/polystyrene (PS) (25/75wt%) were investigated by broadband dielectric spectroscopy (BDS). Thicker samples (\( \ge\)37 nm) were measured by crossed electrode capacitors (CEC), where the film is capped between Al-electrodes. For thinner films (\( \le\)37 nm) nanostructured capacitors (NSC) were employed, allowing one free surface in the film. The dielectric spectra of the thick films showed three relaxation processes ( \( \alpha_{{2}}^{}\) -, \( \alpha_{{1}}^{}\) - and \( \alpha^{{\prime}}_{}\) -relaxation), like the bulk, related to PVME fluctuations in local spatial regions with different PS concentrations. The thickness dependence of the \( \alpha_{{2}}^{}\) -process for films measured by CECs proved a spatially heterogeneous structure across the film with a PS-adsorption at the Al-electrodes. On the contrary, for the films measured by NSCs a PVME segregation at the free surface was found, resulting in faster dynamics, compared to the CECs. Moreover, for the thinnest films (\( \le\)26 nm) an additional relaxation process was detected. It was assigned to restricted fluctuations of PVME segments within the loosely bounded part of the adsorbed layer, proving that for NSCs a PVME enrichment takes place also at the polymer/substrate interface.

Graphical abstract

Keywords

Topical issue: Dielectric Spectroscopy Applied to Soft Matter 

Supplementary material

10189_2019_11870_MOESM1_ESM.pdf (413 kb)
Supplementary material

References

  1. 1.
    M.L. Robenson, Polym. Eng. Sci. 24, 8 (1984)Google Scholar
  2. 2.
    X. Lu, R.A. Weiss, Macromolecules 25, 3242 (1992)CrossRefADSGoogle Scholar
  3. 3.
    J. Mijović, H. Lee, J. Kenny, J. Mays, Macromolecules 39, 2172 (2006)CrossRefADSGoogle Scholar
  4. 4.
    A. Schönhals, F. Kremer, Theory of Dielectric Relaxation, in Broadband Dielectric Spectroscopy, edited by F. Kremer, A. Schönhals (Springer, Berlin, 2002)Google Scholar
  5. 5.
    F. Kremer, A. Schönhals, Broadband Dielectric Measurement Techniques, in Broadband Dielectric Spectroscopy, edited by F. Kremer, A. Schönhals (Springer, Berlin, 2002)Google Scholar
  6. 6.
    D. Labahn, R. Mix, A. Schönhals, Phys. Rev. E. 79, 011801 (2009)CrossRefADSGoogle Scholar
  7. 7.
    H. Huth, A. Minakov, C. Schick, J. Polym. Sci., Part B: Polym. Phys. 44, 2996 (2006)CrossRefADSGoogle Scholar
  8. 8.
    H. Yin, A. Schönhals, Soft Matter 8, 9132 (2012)CrossRefADSGoogle Scholar
  9. 9.
    J. Colmenero, A. Arbe, Soft Matter 3, 1474 (2007)CrossRefADSGoogle Scholar
  10. 10.
    T.P. Lodge, T.C.B. McLeish, Macromolecules 33, 5278 (2000)CrossRefADSGoogle Scholar
  11. 11.
    G.-C. Chung, J.A. Kornfield, S.D. Smith, Macromolecules 27, 5729 (1994)CrossRefADSGoogle Scholar
  12. 12.
    G. Katana, E.W. Fischer, T. Hack, V. Abetz, F. Kremer, Macromolecules 28, 2714 (1995)CrossRefADSGoogle Scholar
  13. 13.
    S. Salaniwal, R. Kant, R.H. Colby, S.K. Kumar, Macromolecules 35, 9211 (2002)CrossRefADSGoogle Scholar
  14. 14.
    A. Arbe, A. Alegria, J. Colmenero, S. Hoffmann, L. Willner, D. Richter, Macromolecules 32, 7572 (1999)CrossRefADSGoogle Scholar
  15. 15.
    R.E. Wetton, W.J. MacKnight, J.R. Fried, F.E. Karasz, Macromolecules 11, 158 (1978)CrossRefADSGoogle Scholar
  16. 16.
    P. Szymoniak, S. Madkour, A. Schönhals, A. Macromolecules 52, 1620 (2019)CrossRefADSGoogle Scholar
  17. 17.
    I. Cendoya, A. Alegria, J.M. Alberdi, J. Colmenero, H. Grimm, D. Richter, B. Frick, Macromolecules 32, 4065 (1999)CrossRefADSGoogle Scholar
  18. 18.
    C.M. Roland, K.L. Ngai, Macromolecules 24, 2261 (1991)CrossRefADSGoogle Scholar
  19. 19.
    H. Yang, P.F. Green, Macromolecules 46, 9390 (2013)CrossRefADSGoogle Scholar
  20. 20.
    R.P. Sharma, P.F. Green, Macromolecules 50, 6617 (2017)CrossRefADSGoogle Scholar
  21. 21.
    P.G. Debenedetti, F.H. Stillinger, Nature 410, 259 (2001)CrossRefADSGoogle Scholar
  22. 22.
    C.A. Angell, Science 267, 1924 (1995)CrossRefADSGoogle Scholar
  23. 23.
    H. Yin, S. Madkour, A. Schönhals, in Dynamics in Geometrical Confinement, Vol. 2: Progress in Dielectrics, edited by F. Kremer (Springer, Cham, 2014)Google Scholar
  24. 24.
    M. Ediger, J.A. Forrest, Macromolecules 47, 471 (2014)CrossRefADSGoogle Scholar
  25. 25.
    J.A. Forrest, K. Dalnoki-Veress, Adv. Colloid Interface Sci. 94, 167 (2001)CrossRefGoogle Scholar
  26. 26.
    Z. Fakhraai, J.A. Forrest, Phys. Rev. Lett. 95, 025701 (2005)CrossRefADSGoogle Scholar
  27. 27.
    S. Madkour, P. Szymoniak, A. Hertwig, M. Heidari, R. von Klitzing, S. Napolitano, M. Sferazza, A. Schönhals, ACS Macro Lett. 6, 1156 (2017)CrossRefGoogle Scholar
  28. 28.
    M. Santore, Curr. Opin. Colloid Interface Sci. 10, 176 (2005)CrossRefGoogle Scholar
  29. 29.
    S. Granick, Eur. Phys. J. E 9, 421 (2002)CrossRefGoogle Scholar
  30. 30.
    C. Housmans, M. Sferrazza, S. Napolitano, Macromolecules 47, 3390 (2014)CrossRefADSGoogle Scholar
  31. 31.
    K. Paeng, S.F. Swallen, M.D. Ediger, J. Am. Chem. Soc. 133, 8444 (2011)CrossRefGoogle Scholar
  32. 32.
    H. Yin, S. Madkour, A. Schönhals, Macromolecules 48, 4936 (2015)CrossRefADSGoogle Scholar
  33. 33.
    S. Madkour, P. Szymoniak, M. Heidari, R. von Klitzing, A. Schönhals, ACS Appl. Mater. Interfaces 9, 7535 (2017)CrossRefGoogle Scholar
  34. 34.
    V.M. Boucher, D. Cangialosi, H. Yin, A. Schönhals, A. Alegria, J. Colmenero, Soft Matter 8, 5119 (2012)CrossRefADSGoogle Scholar
  35. 35.
    H. Yin, D. Cangialosi, A. Schönhals, Thermochim. Acta 566, 186 (2013)CrossRefGoogle Scholar
  36. 36.
    R.A.L. Jones, E.J. Kramer, Polymer 34, 115 (1993)CrossRefGoogle Scholar
  37. 37.
    Q.S. Bhatia, D.P. Pan, J.T. Koberstein, Macromolecules 21, 2166 (1988)CrossRefADSGoogle Scholar
  38. 38.
    K.R. Thomas, N. Clarke, R. Poetes, M. Morariu, U. Steiner, Soft Matter 15, 3517 (2010)CrossRefADSGoogle Scholar
  39. 39.
    S. Madkour, P. Szymoniak, C. Schick, A. Schönhals, J. Chem. Phys. 146, 203321 (2017)CrossRefADSGoogle Scholar
  40. 40.
    S. Madkour, P. Szymoniak, J. Radnik, A. Schönhals, ACS Appl. Mater. Interfaces 9, 37289 (2017)CrossRefGoogle Scholar
  41. 41.
    G. Reiter, M. Hamieh, P. Damman, S. Sclavons, S. Gabriele, T. Vilmin, E. Raphael, Nat. Mater. 4, 754 (2005)CrossRefADSGoogle Scholar
  42. 42.
    N. Gotzen, H. Huth, C. Schick, G. Van Assche, C. Neus, B. Mele, Polymer 51, 647 (2010)CrossRefGoogle Scholar
  43. 43.
    H. Yin, S. Napolitano, A. Schönhals, Macromolecules 45, 1652 (2012)CrossRefADSGoogle Scholar
  44. 44.
    A. Serghei, F. Kremer, Rev. Sci. Instrum. 79, 026101 (2008)CrossRefADSGoogle Scholar
  45. 45.
    M. Tress, E. Mapesa, W. Kossack, W. Kipnusu, M. Reiche, F. Kremer, Science 341, 1371 (2013)CrossRefADSGoogle Scholar
  46. 46.
    A. Schönhals, F. Kremer, Analysis of Dielectric Spectra and The Scaling of the Dynamics of Glasses and Supercooled Liquids, in Broadband Dielectric Spectroscopy, edited by F. Kremer, A. Schönhals (Springer, Berlin, 2002)Google Scholar
  47. 47.
    H.Z. Vogel, Phys. Chem. 22, 645 (1921)Google Scholar
  48. 48.
    G.S. Fulcher, J. Am. Ceram. Soc. 8, 339 (1925)CrossRefGoogle Scholar
  49. 49.
    G. Tammann, W.Z. Hessez, Anorg. Allg. Chem. 156, 245 (1926)CrossRefGoogle Scholar
  50. 50.
    J.S. Higgins, J.E.G. Lipson, R.P. White, Philos. Trans. R. Soc. 368, 1009 (2010)CrossRefADSGoogle Scholar
  51. 51.
    N. Jiang, J. Shang, X. Di, M.K. Endoh, T. Koga, Macromolecules 47, 2682 (2014)CrossRefADSGoogle Scholar
  52. 52.
    N. Jiang, M. Sen, M.K. Endoh, T. Koga, E. Langhammer, P. Bjöörn, Langmuir 34, 4199 (2018)CrossRefGoogle Scholar

Copyright information

© EDP Sciences, Società Italiana di Fisica and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Paulina Szymoniak
    • 1
  • Marcel Gawek
    • 1
  • Sherif Madkour
    • 1
  • Andreas Schönhals
    • 1
    Email author
  1. 1.Bundesanstalt für Materialforschung und -prüfung (BAM)BerlinGermany

Personalised recommendations