Heterogeneous dynamics at the glass transition in van der Waals liquids, in the bulk and in thin films
- Cite this article as:
- Long, D. & Lequeux, F. Eur. Phys. J. E (2001) 4: 371. doi:10.1007/s101890170120
It has been shown over the last few years that the dynamics close to the glass transition is strongly heterogeneous, both by measuring the diffusion coefficient of tagged particles or by NMR studies. Recent experiments have also demonstrated that the glass transition temperature of thin polymer films can be shifted as compared to the same polymer in the bulk. We propose here first a thermodynamical model for van der Waals liquids, which accounts for experimental results regarding the bulk modulus of polymer melts and the evolution of the density with temperature. This model allows us to describe the density fluctuations in such van der Waals liquids. Then, by considering the thermally induced density fluctuations in the bulk, we propose that the 3D glass transition is controlled by the percolation of small domains of slow dynamics, which allows to explain the heterogeneous dynamics close to Tg. We show then that these domains percolate at a lower temperature in the quasi-2D case of thin suspended polymer films and we calculate the corresponding glass transition temperature reduction, in quantitative agreement with experimental results of Jones and co-workers. In the case of strongly adsorbed films, we show that the strong adsorption amounts to enhance the slow domains percolation. This effect leads to 1) a broadening of the glass transition and 2) an increase of Tg in quantitative agreement with experimental results. For both strongly and weakly adsorbed films, the shift in Tg is given by a power law, the exponent being the inverse of that of the correlation length of 3D percolation.