Density fluctuations glass transition theory

The only currently existing theory for the glass transition is the mode coupling theory (MCT) (see, e.g. [95, 96, 106]). MCT is an approach based on a rather microscopic description of the dynamics of density fluctuations and correlations among them. Although the theory was only formulated originally for simple (monatomic) fluids, it is believed to be of much wider applicability. In this review we will only briefly summarize the main basis and predictions of this theory, focusing on those that can be directly checked by NSE measurements. 

The use of photon correlation spectroscopy to study the dynamics of concentration fluctuations in polymer solutions and gels is now well established. In bulk polymers near the glass transition there will be slowly relaxing fluctuations in density and optical anisotropy which can also be studied by this technique. In this article we review the development of the field of photon correlation spectroscopy from bulk polymers. The theory of dynamic light scattering from pure liquids is presented and applied to polymers. The important experimented considerations involved in the collection and analysis of this type of data are discussed. Most of the article focuses on the dynamics of fluctuations near the glass transition in polymers. All the published work in this area is reviewed and the results are critically discussed. The current state of the field is summarized and many suggestions for further work are presented. 

Leutheusser 1984 Bentzelius et al. 1984), has stirred both excitement and controversy (Mezei et al. 1987 Richter et al. 1991 Retry et al. 1991 Schonhals et al. 1993 Mezei 1991 Kim and Mazenko 1992). While the details of the mode-coupling theory are beyond the scope of this chapter, the main idea is that at high fluid densities there is a nonlinear feedback mechanism by which fluctuations in the structure (or local density) of the fluid become arrested and cannot relax to equilibrium. The point at which this occurs is then a purely dynamic glass transition. 

There are rival theories of the glass transition the Gibbs Dimarzio theory assumes that the configurational entropy of the chains approaches zero at Tg. Other researchers prefer a mode coupling theory (MCT), based on the dynamics of density fluctuations. However, it is difficult to extract a simple physical meaning from the complex equations that describe correlations between density fluctuations. Neither theory, at its current state of development, is particularly useful in understanding the properties of glassy polymers. 

When an atomic system is cooled below its glass temperature, it vitrifies, that is, it forms an amorphous solid [1]. Upon decreasing the temperature, the viscosity of the fluid increases dramatically, as well as the time scale for structural relaxation, until the solid forms concomitantly, the diffusion coefficient vanishes. This process is observed in atomic or molecular systems and is widely used in material processing. Several theories have been developed to rationalize this behavior, in particular, the mode coupling theory (MCT) that describes the fluid-to-glass transition kinetically, as the arrest of the local dynamics of particles. This becomes manifest in (metastable) nondecaying amplitudes in the correlation functions of density fluctuations, which are due to a feedback mechanism that has been called cage effect [2],... 

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