Polymer dynamics, mode-coupling theory

Kokorin YuK, Pokrovskii VN (1993) New approach to the relaxation phenomena theory of the amorphous linear entangled polymers. Int J Polym Mater 20(3-4) 223-237 Kostov KS, Freed KF (1997) Mode coupling theory for calculating the memory functions of flexible chain molecules influence on the long time dynamics of oligoglycines. J Chem Phys 106(2) 771-783... 

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. 

I. Non-crystalline polymers. J Appl Chem 2 493-500 Gotze W (2009) Complex dynamics of glass forming liquids a mode-coupling theory. Oxford University Press, Oxford... 

Another strong point of the simulation approach is its ability to selectively change parts of the model Hamiltonian. In this way one can compare a chemically realistic model of PB with a freely rotating chain version of the same polymer and does not have to switch to a completely different polymer with some of the same properties like is unavoidable in experiments [33]. With this approach we could establish that identical structure on the two-body correlation function level (single chain and liquid structure factors) does not imply identical dynamics which raises questions on the applicability of the mode-coupling theory of the glass transition to polymer melts. 

To what extent the schematic model systems A and B for a polymer melt show this typical relaxation behavior will be addressed in this subsection, by calculating various structural correlation functions that probe the dynamical changes of the melt on different length scales (Section 6.3.2.1). From these correlation functions it is possible to extract relaxation times the temperature dependence of which can be studied and compared to that of transport coefficients, such as the diffusion coefficient. This will be done in Section 6.3.2.2. The final paragraph of this subsection then deals with the calculation of the incoherent intermediate scattering function and its quantitative interpretation in the framework of the idealized mode coupling theory (MCT). " ... 

In a mode coupling approach, a microscopic theory describing the polymer motion in entangled melts has recently been developed. While these theories describe well the different time regimes for segmental motion, unfortunately as a consequence of the necessary approximations a dynamic structure factor has not yet been derived [67,68]. 

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