Glass transitions of freely suspended polymer films

We introduce a minimal theory of glass formation based on the ideas of molecular crowding and resultant string-like cooperative rearrangement, and address the effects of free interfaces. In the bulk case, we obtain a scaling expression for the number of particles taking part in cooperative strings, and we recover the Adam-Gibbs description of glassy dynamics. Then, by including thermal dilatation, the Vogel-Fulcher-Tammann relation is derived. Moreover, the random and string-...

Confining glassy polymer into films can substantially modify their local and film-averaged properties. We present a lattice model of film geometry with void-mediated facilitation behaviors but free from any elasticity effect. We analyze the spatially varying viscosity to delineate the transport property of glassy films. The film mobility measurements reported by [Yang et. al., Science, 2010, 328, 1676] are successfully reproduced. The flow exhibits a crossover from simple vis...

Thin liquid films on surfaces are part of our everyday life, they serve e.g. as coatings or lubricants. The stability of a thin layer is governed by interfacial forces, described by the effective interface potential, and has been subject of many studies in the last decades. In recent years, the dynamics of thin liquid films came into focus since results on the reduction of the glass transition temperature raised new questions on the behavior of especially polymeric liquids in...

The Monte Carlo carbyne model is modified to investigate the glass transition of the semi-flexible entangled polymer chains. The stochastic bombardment between monomers are monitored by Metropolis algorithm with help of the consideration of hard potential while the mobility of monomers is governed by its mass, scattering rate and temperature. Our model is capable to show that the glass transition temperature reduces with decreasing film thickness and the formation of critical...

Using molecular dynamics simulation of a polymer glass model we investigate free-standing polymer films focusing on the in-plane shear modulus $\mu$ and the corresponding shear-stress relaxation modulus $G(t)$ as functions of temperature $T$, film thickness $H$ (tuned by means of the lateral box size $L$) and sampling time $\Delta t$. Various observables are seen to vary linearly with $1/H$ demonstrating thus the (to leading order) linear superposition of bulk and surface pro...

We describe a series of surface levelling experiments in glassy polystyrene (PS) of varying molecular weight. The evolution through a mobile surface layer is described by the glassy thin film equation that was introduced and used in a previous work. Excellent agreement with the data is achieved, with surface mobility as the single free parameter. Different molecular-weight dependencies in mobility are then observed above and below the glass transition. The results are discuss...

A derivation is given for the Vogel-Fulcher-Tammann thermal activation law for the glassy state of a bulk polymer. Our microscopic considerations involve the entropy of closed polymer molecular chains (i.e. polymer closed strings). For thin film polymer glasses, one obtains open polymer strings in that the boundary surfaces serve as possible string endpoint locations. The Vogel-Fulcher-Tammann thermal activation law thereby holds true for a bulk polymer glass but is modified ...

We study long polymer chains in a poor solvent, confined to the space between two parallel hard walls. The walls are energetically neutral and pose only a geometric constraint which changes the properties of the coil-globule (or "$\theta$-") transition. We find that the $\theta$ temperature increases monotonically with the width $D$ between the walls, in contrast to recent claims in the literature. Put in a wider context, the problem can be seen as a dimensional cross over in...

Searching for the ideal glass transition, we exploit the ability of glassy polymer films to explore low energy states in remarkably short time scales. We use 30 nm thick polystyrene (PS) films, which in the supercooled state basically display the bulk polymer equilibrium thermodynamics and dynamics. We show that in the glassy state, this system exhibits two mechanisms of equilibrium recovery. The faster one, active well below the kinetic glass transition temperature ($T_g$), ...

We review recent results from computer simulation studies of polymer glasses, from chain dynamics around the glass transition temperature Tg to the mechanical behaviour below Tg. These results clearly show that modern computer simulations are able to address and give clear answers to some important issues in the field, in spite of the obvious limitations in terms of length and time scales. In the present review we discuss the cooling rate effects, and dynamic slowing down of ...