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Showing papers by "James A. Forrest published in 1996"


Journal ArticleDOI
TL;DR: The concept of cooperative rearrangement was introduced in an attempt to unify these two views of the glass transition by demonstrating that such cooperativity, coupled with a thermodynamic glass transition, resulted naturally insystem dynamics such as those described by the WLFequation for temperatures near freezing.
Abstract: We report the first measurements of the glass transition temperature ${T}_{g}$ for thin freely standing polystyrene (PS) films. We have used Brillouin light scattering to measure ${T}_{g}$ for freely standing films of different thicknesses. We find that ${T}_{g}$ decreases linearly with film thickness $h$ for $h\ensuremath{\le}700\AA{}$, with a reduction of 70 K for a film with $h\phantom{\rule{0ex}{0ex}}=\phantom{\rule{0ex}{0ex}}290\AA{}$. These measurements characterize unambiguously the effects of the free surface on ${T}_{g}$ of thin polymer films. Results are compared to similar results for supported PS films [Keddie et al., Europhys. Lett. 27, 59 (1994)], and we find that their measured values are influenced strongly by the substrate.

1,052 citations


Journal ArticleDOI
TL;DR: In this article, the morphology of phase separation in a thin film blend of polystyrene (PS) and polyisoprene (PI) in a common solvent of toluene was studied.
Abstract: We present the results of a study of the morphology of phase separation in a thin film blend of polystyrene (PS) and polyisoprene (PI) in a common solvent of toluene. The blend is quenched by rapid solvent evaporation using a spincoating technique rather than a temperature quench. The mass fraction of polystyrene is varied to determine the effect of the substrate on thin film phase separation morphology. We compare the phase separation morphology for very thin films of the PS/PI blend cast onto three different substrates: Si(001) with a native oxide layer (Si (SINGLEBOND) SiOx), Si(001) etched in hydrofluoric acid (Si-H), and a Au/Pd alloy sputtered onto Si(001). We observe large differences between the morphologies of 1000 A thick blend films on the Si(SINGLEBOND) SiOx and Si-H substrates as the mass fraction is varied due to the difference in the wetting properties of PS on the two substrates. Smaller differences are observed between the films on the Si(SINGLEBOND) SiOx and Au/Pd substrates only for film thicknesses h < 600 A. © 1996 John Wiley & Sons, Inc.

47 citations


Journal ArticleDOI
TL;DR: In this paper, Brillouin light scattering (BLS) was used to investigate the mechanical properties of thin polystyrene (PS) and polyisoprene (PI) films incorporated in a multilayer geometry consisting of alternating layers of the two polymers.
Abstract: We have used Brillouin light scattering (BLS) to investigate the mechanical properties of thin polystyrene (PS) and polyisoprene (PI) films incorporated in a multilayer geometry consisting of alternating layers of the two polymers. All samples had a total thickness h ∼1600 A, and consisted of between 2 and 10 individual polymer films ; individual layer thicknesses were as small as 160 A. Ellipsometry was used to determine the thickness of the PS and PI layers. The velocities of several high-frequency film-guided mechanical waves were measured using BLS and the results are compared with values calculated using an effective medium approach. The effective elastic constants of the multilayered films were obtained from those determined for thick films of PS and PI. Remarkable agreement was obtained between the measured and calculated velocities even for samples in which the individual layer thicknesses were much less than the unperturbed size of the polymer molecules. These results suggest that the mechanical properties of polymers change very little even when the molecules are forced into highly confined geometries.

31 citations