RESUMEN
A large body of experimental studies shows that the local dynamics in supercooled liquids are significantly altered by spatial nanoconfinement. In a previous study, we proposed a concept of a dynamically correlated network (DCN) model, which assumes that segments in a supercooled liquid undergo cooperative rearrangements within a network-like cluster. We further demonstrated that a model modified for freestanding thin films can predict for the glass transition dynamics in atactic polystyrene (PS) films consistent with experimental results. In this study, we adapted the model to apply it to supported thin films by introducing a layer of virtual vacant segments at the free surface and virtual anchoring segments at the liquid/substrate interface. The latter segments, carrying a finite number of virtual segments, reduce mobility at the interface. We evaluated the cooperative cluster size and distribution with respect to temperature and film thickness, along with the average relaxation time and glass transition temperature Tg for supported thin films of PS. The model predicted that the thickness dependence of Tg for PS becomes stronger with increasing time scale, and this result agreed well with experimental data across different timescales from pseudothermodynamic and dynamic measurements. The results provide insights into the origin of the dynamical decoupling between pseudothermodynamic and dynamic glass transition behaviors.
RESUMEN
The anomalous dynamics and glass transition behaviors of supercooled liquids under nanoconfinement, such as ultrathin polymer films, have attracted much attention in recent decades. However, a complete elucidation of this mechanism has not yet been achieved. For the dynamics of bulk materials without confinement, we previously proposed a dynamically correlated network (DCN) model, which was found to agree well with the experimental data. The model assumes that segments with thermal fluctuations are dynamically correlated to their neighbors to form string-like clusters, which eventually grow into networks as temperature decreases. In this study, we applied the DCN model to nanoconfined free-standing films by using a simple cubic lattice sandwiched between two free surface layers consisting of virtual "uncorrelated" segments. The average size of DCNs at lower temperatures decreased with decreasing thickness because of confinement. This trend was associated with a decrease in the percolation temperature at which the size of DCN diverges. It was also revealed that the fractal dimension of the generated DCNs exhibits a peak with respect to temperature. The segmental relaxation time for free-standing polystyrene films was evaluated, and the predicted thickness dependence of the glass transition temperature qualitatively agreed with the experimental data. The results suggest that the concept of DCN is compatible with the dynamics of free-standing thin films.
RESUMEN
The non-Arrhenius behavior of segmental dynamics in glass-forming liquids is one of the most profound mysteries in soft matter physics. In this article, we propose a dynamically correlated network (DCN) model to understand the growing behavior of dynamically correlated regions during cooling, which leads to the viscous slowdown of supercooled liquids. The fundamental concept of the model is that the cooperative region of collective motions has a network structure that consists of string-like parts, and networks of various sizes interpenetrate each other. Each segment undergoes dynamical coupling with its neighboring segments via a finite binding energy. Monte Carlo simulations showed that the fractal dimension of the DCNs generated at different temperatures increased and their size distribution became broader with decreasing temperature. The segmental relaxation time was evaluated based on a power law with four different exponents for the activation energy of rearrangement with respect to the DCN size. The results of the present DCN model are consistent with the experimental results for various materials of molecular and polymeric liquids.