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Thickness dependence of the glass transition temperature in thin polymer films

Cited 151 time in Web of Science Cited 154 time in Scopus
Authors
Kim, Jae Hyun; Jang, Jyongsik; Zin, Wang-Cheol
Issue Date
2001
Publisher
American Chemical Society
Citation
Langmuir, 2001, 17, 2703
Abstract
In this paper the glass transition temperature (Tg) in thin polymer films has been studied. Ellipsometry
has been used to measure Tg of poly(R-methylstyrene) (PAMS) thin films as a function of the film thickness
for two molecular weights. When the films were thinner than a few hundred angstroms, substantial
reduction in Tg was apparent. The Tg depression pattern did not show the difference between molecular
weights. The Michaelis-Menten equation was adapted and used to fit the experimentally obtained Tg
data. From this analogized Michaelis-Menten function fitting, the fitting parameters Tg,¥ and ê could be
obtained. The obtained Tg,¥ corresponded with the bulk Tg, and the parameter ê was correlated with the
statistical segment length. A continuous multilayer model was proposed and derived to describe the effect
of surface on the observed Tg reduction in thin films, and the depth-dependent Tg profile was obtained.
These results showed that Tg at the top surface was much lower than the bulk Tg and gradually approached
the bulk Tg with increasing distance from the edge of the film. The model and equation were modified to
apply for the polymer coated on the strongly favorable substrate and the freely standing film.
ISSN
0743-7463
Language
English
URI
https://hdl.handle.net/10371/49115
DOI
https://doi.org/10.1021/la001125k
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