In free-standing polymer thin films,
the glass-transition temperature
decreases as the film thickness is reduced. This behavior is ascribed
to the formation of mobile layers near the two film/air interfaces
(“free surfaces”). Here, we propose to describe this
phenomenon using our recently developed “SL-TS2” mean-field
theory, in which the phenomenological “two-state, two-(time)scale”
(TS2) approach for the relaxation time is coupled to the Sanchez–Lacombe
equation of state (SL-EoS). Here, we first recap our SL-TS2 approach
for bulk materials and demonstrate that the model correctly describes
both pressure–volume–temperature (PVT) and relaxation
time data for polystyrene (PS) and poly(methyl methacrylate) (PMMA)
polymers both above and below their glass-transition temperatures
(T
g). Next, we formulate a simple density-gradient
version of SL-TS2 to describe the density and relaxation time dependence
of the spatial position in the film near the free surface. By minimizing
the free-energy functional, we obtain a simple partial differential
equation for the equilibrium density profile and the relaxation time
profile. Solving this equation and utilizing a simple logarithmic
mixing rule, we can compute the relaxation time dependence on temperature
as a function of film thickness. The results are compared with experimental
data for free-standing films of PS and PMMA, and a good semiquantitative
agreement is found. The approach can be generalized in a straightforward
fashion to supported (instead of free-standing) thin films.