Abstract.
Confinement effects in polystyrene and poly(methyl methacrylate) films and nanocomposites are studied by fluorescence. The ability to employ an intensive measurable, the excited-state fluorescence lifetime, in defining the glass transition temperature, Tg, of polymers is demonstrated and compared to the use of an extensive measurable, fluorescence intensity. In addition, intrinsic fluorescence from the phenyl groups in polystyrene is used to determine the Tg-confinement effect in films as thin as ~15 nm. The decrease in Tg with decreasing film thickness (below ∼60 nm) agrees well with results obtained by extrinsic pyrene fluorescence. Dye label fluorescence is used to quantify the enhancement in Tg observed with decreasing thickness (below ~90 nm) in poly(methyl methacrylate) films; addition of 2–4 wt% dioctyl phthalate plasticizer reduces or eliminates the Tg-confinement effect in films down to 20 nm thickness. Intrinsic polystyrene fluorescence, which is sensitive to local conformation, is used to quantify the time scales (some tens of minutes) associated with stress relaxation in thin and ultrathin spin-coated films at Tg + 10 K. Finally, the shape of the fluorescence spectrum of pyrene doped at trace levels in polystyrene films and polystyrene-silica nanocomposites is used to determine effects of confinement on microenvironment polarity.
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References
C.L. Jackson, G.B. McKenna, J. Non-Cryst. Solids 131, 221–224 (1991)
G. Reiter, Europhys. Lett. 23, 579–584 (1993)
J.L. Keddie, R.A.L. Jones, R. Cory, Europhys. Lett. 27, 59–64 (1994)
J.H. van Zanten, W.E. Wallace, W.-L. Wu, Phys. Rev. E 53, R2053–R2056 (1996)
J.A. Forrest, K. Dalnoki-Veress, J.R. Stevens, J.R. Dutcher, Phys. Rev. Lett. 77, 2002–2005 (1996)
B.J. Ash, L.S. Schadler, R.W. Siegel, Mater. Lett. 55, 83–87 (2002)
S. Merabia, P. Sotta, D. Long, Eur. Phys. J. E 15, 189–210 (2004)
M. Alcoutlabi, G.B. McKenna, J. Phys.: Condens. Matter 17, R461–R524 (2005)
C.B. Roth, J.R. Dutcher, J. Electroanal. Chem. 584, 13–22 (2005)
D.B. Hall, J.C. Hooker, J.M. Torkelson, Macromolecules 30, 667–669 (1997)
F. Xie, H.F. Zhang, F.K. Lee, B. Du, O.K.C. Tsui, Y. Yokoe, K. Tanaka, A. Takahara, T. Kajiyama, T. He, Macromolecules 35, 1491–1492 (2002)
T.A. Tran, S. Said, Y. Grohens, Composites A 36, 461–465 (2005)
T. Miyazaki, K. Nishida, T. Kanaya, Phys. Rev. E 69, 061803 (2004)
A. Serghei, Y. Mikhailova, H. Huth, C. Schick, K.J. Eichhorn, B. Voit, F. Kremer, Eur. Phys. J. E 17, 199–202 (2005)
M. Wubbenhorst, C.A. Murray, J.R. Dutcher, Eur. Phys. J. E 12, S109–S112 (2003)
K. Fukao, Y. Miyamoto, Phys. Rev. E 61, 1743–1754 (2000)
J.A. Forrest, C. Svanberg, K. Revesz, M. Rodahl, L.M. Torell, B. Kasemo, Phys. Rev. E 58, R1226–R1229 (1998)
K. Akabori, K. Tanaka, T. Nagamura, A. Takahara, T. Kajiyama, Macromolecules 38, 9735–9741 (2005)
C.J. Ellison, S.D. Kim, D.B. Hall, J.M. Torkelson, Eur. Phys. J. E 8, 155–166 (2002)
C.J. Ellison, J.M. Torkelson, J. Polym. Sci. B: Polym. Phys. 40, 2745–2758 (2002)
C.J. Ellison, J.M. Torkelson, Nat. Mater. 2, 695–700 (2003)
C.J. Ellison, R.L. Ruszkowski, N.J. Fredin, J.M. Torkelson, Phys. Rev. Lett. 92, 095702 (2004)
C.J. Ellison, M.K. Mundra, J.M. Torkelson, Macromolecules 38, 1767–1778 (2005)
P. Rittigstein, J.M. Torkelson, J. Polym. Sci. B: Polym. Phys. (accepted)
J.S. Royal, J.M. Torkelson, Macromolecules 25, 1705–1710 (1992)
J.S. Royal, J.M. Torkelson, Macromolecules 26, 5331–5335 (1993)
R.D. Priestley, L.J. Broadbelt, J.M. Torkelson, Macromolecules 38, 654–657 (2005)
R.D. Priestley, C.J. Ellison, L.J. Broadbelt, J.M. Torkelson, Science 309, 456–459 (2005)
D.B. Hall, J.M. Torkelson, Macromolecules 31, 8817–8825 (1998)
A. Dhinojwala, J.M. Torkelson, Macromolecules 27, 4817–4824 (1994)
S.D. Kim, J.M. Torkelson, Macromolecules 35, 5943–5952 (2002)
D.D. Deppe, A. Dhinojwala, J.M. Torkelson, Macromolecules 29, 3898–3908 (1996)
D.D. Deppe, R.D. Miller, J.M. Torkelson, J. Polym. Sci. Part B: Polym. Phys. 34, 2987–2997 (1996)
D.B. Hall, P. Underhill, J.M. Torkelson, Polym. Eng. Sci. 38, 2039–2045 (1998)
G. Beaucage, R. Composto, R.S. Stein, J. Polym. Sci. Part B: Polym. Phys. 31, 319–326 (1993)
C.J. Ellison, Ph.D. thesis, Northwestern University, 2005 p. 111
W.F. Jager, O. van den Berg, S. Picken, J. Macromol. Symp. 230, 11–19 (2005)
J.M. Torkelson, S. Lipsky, M. Tirrell, Macromolecules 14, 1601–1603 (1981)
J.C. Hooker, J.M. Torkelson, Macromolecules 28, 7683–7692 (1995)
J.L. Keddie, R.A.L. Jones, R.A. Cory, Faraday Discuss 98, 219–230 (1994)
L. Hartmann, W. Gorbatschow, J. Hauwede, F. Kremer, Eur. Phys. J. E 8, 145–154 (2002)
L.L. Kosbar, S.W.J. Kuan, C.W. Frank, R.F.W. Pease, ACS Symp. Ser. 381, 95–111 (1989)
K. Kalyanasundaram, J.K. Thomas, J. Am. Chem. Soc. 10, 133–138 (1977)
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Mundra, M., Ellison, C., Rittigstein, P. et al. Fluorescence studies of confinement in polymer films and nanocomposites: Glass transition temperature, plasticizer effects, and sensitivity to stress relaxation and local polarity. Eur. Phys. J. Spec. Top. 141, 143–151 (2007). https://doi.org/10.1140/epjst/e2007-00032-0
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DOI: https://doi.org/10.1140/epjst/e2007-00032-0