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.
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References
M.L. Robenson, Polym. Eng. Sci. 24, 8 (1984)
X. Lu, R.A. Weiss, Macromolecules 25, 3242 (1992)
J. Mijović, H. Lee, J. Kenny, J. Mays, Macromolecules 39, 2172 (2006)
A. Schönhals, F. Kremer, Theory of Dielectric Relaxation, in Broadband Dielectric Spectroscopy, edited by F. Kremer, A. Schönhals (Springer, Berlin, 2002)
F. Kremer, A. Schönhals, Broadband Dielectric Measurement Techniques, in Broadband Dielectric Spectroscopy, edited by F. Kremer, A. Schönhals (Springer, Berlin, 2002)
D. Labahn, R. Mix, A. Schönhals, Phys. Rev. E. 79, 011801 (2009)
H. Huth, A. Minakov, C. Schick, J. Polym. Sci., Part B: Polym. Phys. 44, 2996 (2006)
H. Yin, A. Schönhals, Soft Matter 8, 9132 (2012)
J. Colmenero, A. Arbe, Soft Matter 3, 1474 (2007)
T.P. Lodge, T.C.B. McLeish, Macromolecules 33, 5278 (2000)
G.-C. Chung, J.A. Kornfield, S.D. Smith, Macromolecules 27, 5729 (1994)
G. Katana, E.W. Fischer, T. Hack, V. Abetz, F. Kremer, Macromolecules 28, 2714 (1995)
S. Salaniwal, R. Kant, R.H. Colby, S.K. Kumar, Macromolecules 35, 9211 (2002)
A. Arbe, A. Alegria, J. Colmenero, S. Hoffmann, L. Willner, D. Richter, Macromolecules 32, 7572 (1999)
R.E. Wetton, W.J. MacKnight, J.R. Fried, F.E. Karasz, Macromolecules 11, 158 (1978)
P. Szymoniak, S. Madkour, A. Schönhals, A. Macromolecules 52, 1620 (2019)
I. Cendoya, A. Alegria, J.M. Alberdi, J. Colmenero, H. Grimm, D. Richter, B. Frick, Macromolecules 32, 4065 (1999)
C.M. Roland, K.L. Ngai, Macromolecules 24, 2261 (1991)
H. Yang, P.F. Green, Macromolecules 46, 9390 (2013)
R.P. Sharma, P.F. Green, Macromolecules 50, 6617 (2017)
P.G. Debenedetti, F.H. Stillinger, Nature 410, 259 (2001)
C.A. Angell, Science 267, 1924 (1995)
H. Yin, S. Madkour, A. Schönhals, in Dynamics in Geometrical Confinement, Vol. 2: Progress in Dielectrics, edited by F. Kremer (Springer, Cham, 2014)
M. Ediger, J.A. Forrest, Macromolecules 47, 471 (2014)
J.A. Forrest, K. Dalnoki-Veress, Adv. Colloid Interface Sci. 94, 167 (2001)
Z. Fakhraai, J.A. Forrest, Phys. Rev. Lett. 95, 025701 (2005)
S. Madkour, P. Szymoniak, A. Hertwig, M. Heidari, R. von Klitzing, S. Napolitano, M. Sferazza, A. Schönhals, ACS Macro Lett. 6, 1156 (2017)
M. Santore, Curr. Opin. Colloid Interface Sci. 10, 176 (2005)
S. Granick, Eur. Phys. J. E 9, 421 (2002)
C. Housmans, M. Sferrazza, S. Napolitano, Macromolecules 47, 3390 (2014)
K. Paeng, S.F. Swallen, M.D. Ediger, J. Am. Chem. Soc. 133, 8444 (2011)
H. Yin, S. Madkour, A. Schönhals, Macromolecules 48, 4936 (2015)
S. Madkour, P. Szymoniak, M. Heidari, R. von Klitzing, A. Schönhals, ACS Appl. Mater. Interfaces 9, 7535 (2017)
V.M. Boucher, D. Cangialosi, H. Yin, A. Schönhals, A. Alegria, J. Colmenero, Soft Matter 8, 5119 (2012)
H. Yin, D. Cangialosi, A. Schönhals, Thermochim. Acta 566, 186 (2013)
R.A.L. Jones, E.J. Kramer, Polymer 34, 115 (1993)
Q.S. Bhatia, D.P. Pan, J.T. Koberstein, Macromolecules 21, 2166 (1988)
K.R. Thomas, N. Clarke, R. Poetes, M. Morariu, U. Steiner, Soft Matter 15, 3517 (2010)
S. Madkour, P. Szymoniak, C. Schick, A. Schönhals, J. Chem. Phys. 146, 203321 (2017)
S. Madkour, P. Szymoniak, J. Radnik, A. Schönhals, ACS Appl. Mater. Interfaces 9, 37289 (2017)
G. Reiter, M. Hamieh, P. Damman, S. Sclavons, S. Gabriele, T. Vilmin, E. Raphael, Nat. Mater. 4, 754 (2005)
N. Gotzen, H. Huth, C. Schick, G. Van Assche, C. Neus, B. Mele, Polymer 51, 647 (2010)
H. Yin, S. Napolitano, A. Schönhals, Macromolecules 45, 1652 (2012)
A. Serghei, F. Kremer, Rev. Sci. Instrum. 79, 026101 (2008)
M. Tress, E. Mapesa, W. Kossack, W. Kipnusu, M. Reiche, F. Kremer, Science 341, 1371 (2013)
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)
H.Z. Vogel, Phys. Chem. 22, 645 (1921)
G.S. Fulcher, J. Am. Ceram. Soc. 8, 339 (1925)
G. Tammann, W.Z. Hessez, Anorg. Allg. Chem. 156, 245 (1926)
J.S. Higgins, J.E.G. Lipson, R.P. White, Philos. Trans. R. Soc. 368, 1009 (2010)
N. Jiang, J. Shang, X. Di, M.K. Endoh, T. Koga, Macromolecules 47, 2682 (2014)
N. Jiang, M. Sen, M.K. Endoh, T. Koga, E. Langhammer, P. Bjöörn, Langmuir 34, 4199 (2018)
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Szymoniak, P., Gawek, M., Madkour, S. et al. Confinement and localization effects revealed for thin films of the miscible blend poly(vinyl methyl ether)/polystyrene with a composition of 25/75 wt%⋆. Eur. Phys. J. E 42, 101 (2019). https://doi.org/10.1140/epje/i2019-11870-3
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DOI: https://doi.org/10.1140/epje/i2019-11870-3