Thickness-Dependent Segmental Dynamics in Supported Thin Films: Insights from a Dynamically Correlated Network Model.

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.

Thickness Dependence of Segmental Dynamics in Free-Standing Thin Films Predicted by a Dynamically Correlated Network Model.

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.

A Dynamically Correlated Network Model for the Collective Dynamics in Glass-Forming Molecular Liquids and Polymers.

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.