Chain stiffness glass transition temperature

In discussing the influence of steric features on mechanical properties, it is convenient to consider the side chains and the main chain separately. The effects of flexible side chains differ completely from those of stiff side chains. Long, flexible side chains reduce the glass transition temperature, while stiff side chains increase it. Long, flexible side chains increase the free volume and ease the steric hindrance from neighboring chains and as such facilitate the movement of the main chain. Figure 13.28 illustrates... 

The glass transition temperature of a random copolymer usually falls between those of the corresponding homopolymers since the copolymers will tend to have intermediate chain stiffness and interchain attraction. Where these are the only important factors to be considered a linear relationship between Tg and copolymer composition is both reasonable to postulate and experimentally verifiable. One form of this relationship is given by the equation... 

Stretching denotes a monoaxial or biaxial mechanical stress of a molded article close to the glass transition temperature. This leads to a controlled orientation of the molecular chains in the direction of stretching and thus to a substantial change in some physical properties. Fibers and foils made of synthetic polymers gain their optimal properties only by this mechanical post-treatment. Stability, stiffness, and dimensional stability of fibers, for example, increase nearly proportionally with the stretch ratio, whereas stretchability decreases. In practice, the stretch ratio is between 1 2 and 1 6, depending on the polymer material and the desired properties. 

Permeation is dependent on the segmental motion of the polymer chains and the free volume of chain segments. The free volume decreases, whereas the chain stiffness increases, as the temperature of the polymeric membrane is lowered toward the glass transition temperature Tf. The free volume is similar for all polymers at the Tf. 

Against this background of infusible conducting polymers, the development of the soluble polythiophenes is most interesting. Glass transition temperatures have been reported as 48 °C for poly(3-butylthiophene) and 145 °C for poly(3-methyl-thiophene) 261). These polymers also show crystallinity in films and can be crystallized from solution. Solution studies indicate that there are two chain conformations 262) and the availability of a non-conjugated conformation may be a key to the low transition temperatures and solubility, when compared to the stiff-chain conjugated polymers. 

Those which do crystallise invariably do not form perfectly crystalline materials but instead are semi-crystalline with both crystalline and amorphous regions. The crystalline phases of such polymers are characterised by their melting temperature (TJ. Many thermoplastics are, however, completely amorphous and incapable of crystallisation, even upon annealing. Amorphous polymers (and amorphous phases of semi-crystalline polymers) are characterised by their glass transition temperature (T), the temperature at which they transform abruptly from the glassy state (hard) to the rubbery state (soft). This transition corresponds to the onset of chain motion below T the polymer chains are unable to move and are frozen in position. Both T and T increase with increasing chain stiffness and increasing forces of intermolecular attraction. 

A great number of initiators and monomers are now available, allowing almost perfect control over most of the important parameters of LCPs main chain stiffness tacticity glass transition temperatures processabiUty from solution or melt mesogen density along the main chain combination with... 

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