Structural models, glass transition temperature

As a consequence, the overall penetrant uptake cannot be used to get direct informations on the degree of plasticization, due to the multiplicity of the polymer-diluent interactions. The same amount of sorbed water may differently depress the glass transition temperature of systems having different thermal expansion coefficients, hydrogen bond capacity or characterized by a nodular structure that can be easily crazed in presence of sorbed water. The sorption modes, the models used to describe them and the mechanisms of plasticization are presented in the following discussion. 

A simple algorithm [17] makes it possible to find the probability of any fragment of macromolecules of Gordonian polymers. Comparison of these probabilities with the data obtained by NMR spectroscopy provides the possibility to evaluate the adequacy of a chosen kinetic model of a synthesis process of a particular polymer specimen. The above-mentioned probabilities are also involved in the expressions for the glass transition temperature and some structure-additive properties of branched polymers [18,19]. 

In view of the development of the continuous chain model for the tensile deformation of polymer fibres, we consider the assumptions on which the Coleman model is based as too simple. For example, we have shown that the resolved shear stress governs the tensile deformation of the fibre, and that the initial orientation distribution of the chains is the most important structural characteristic determining the tensile extension below the glass transition temperature. These elements have to be incorporated in a new model. 

Plasticized Polymers. As mentioned above the glass transition temperature Tg is lowered by adding certain organic liquids, the so called plasticizers. The illustration of polymers above T0 by means of a model remains valid also for plasticized systems. The configuration that is built up at the transition from the melt to the glass, in this case, remains below the glass temperature, too. Thus, we have an extended structure containing holes. ... 

With these three different examples it has been demonstrated that the systematics observed for the polymorphism of m-l.c. s is also valid for the side chain polymers, provided that a flexible spacer connects the rigid mesogenic moieties to the polymer main chain. Deviations from this behavior are observed, when the mesogenic moieties are directly linked to the backbone. Under these conditions, normally no liquid crystalline behavior is to be expected, according to the model considerations mentioned in Chap. 2.1. Some examples, however, proved l.c. properties for such systems, which are characterized by two striking properties Very high glass transition temperatures and only smectic structures even in case of short substituents... 

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