Glass transition temperature molecular structure

Material properties can be further classified into fundamental properties and derived properties. Fundamental properties are a direct consequence of the molecular structure, such as van der Waals volume, cohesive energy, and heat capacity. Derived properties are not readily identified with a certain aspect of molecular structure. Glass transition temperature, density, solubility, and bulk modulus would be considered derived properties. The way in which fundamental properties are obtained from a simulation is often readily apparent. The way in which derived properties are computed is often an empirically determined combination of fundamental properties. Such empirical methods can give more erratic results, reliable for one class of compounds but not for another. 

As the temperature is decreased, free-volume is lost. If the molecular shape or cross-linking prevent crystallisation, then the liquid structure is retained, and free-volume is not all lost immediately (Fig. 22.8c). As with the melt, flow can still occur, though naturally it is more difficult, so the viscosity increases. As the polymer is cooled further, more free volume is lost. There comes a point at which the volume, though sufficient to contain the molecules, is too small to allow them to move and rearrange. All the free volume is gone, and the curve of specific volume flattens out (Fig. 22.8c). This is the glass transition temperature, T . Below this temperature the polymer is a glass. 

There are a number of structural features which have a bearing on the value of the glass transition temperature. Since this temperature is that at which molecular rotation about single bonds becomes restricted, it is obvious that these features are ones which influence the ease of rotation. These can be divided into two groups ... 

Features of chemical structure that affect the degree of molecular freedom influence both the crystalline melting point and the glass transition temperature. Moreover, such features have roughly similar effects on both properties, so that the empirical rule has been found that for many polymers ... 

Diamantane-based polymers are synthesized to take advantage of their stiffness, chemical and thermal stability, high glass transition temperature, improved solubility in organic solvents, and retention of their physical properties at high temperatures. All these special properties result from their diamantane-based molecular structure [90]. Polyamides are high-temperature polymers with a broad range of applications in different scientific and industrial fields. However, their process is very difficult because of poor solubility and lack of adequate thermal stability retention [90]. Incorporation of 1,6- or... 

The glass transition temperatures (Tgs) of polyarylates derived from substituted HQs and substituted PECs are shown above in Table 19.1. Polyarylates containing bulky substituents, such as / Ifu, on the HQ units exhibit above high glass transitions due to the high rigidity of their molecular structures. Thus, fBu-HQ/PEC shows a high Tg of 146 °C when compared to that of Me-HQ/PEC (104 °C). 

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