Cooling Flexible chains

One method of classifying plastics is by their response to heat. Thermoplasts, also known as thermoplastic polymers, soften and liquefy on heating and harden again when cooled. The process is reversible and can be repeated. On heating, the weak secondary bonds between polymer chains are broken, which facilitates relative movement between the chains. If the molten polymer is further heated until the primary covalent bonds also break, degradation of the thermoplast follows. Thermoplastic polymers are linear or exhibit branching with flexible chains and include polyethylene, polystyrene and polypropylene (Figure 4.10). 

Fig. 3. Specific volume against temperature obtained [1] during stepwise cooling for x == 10. The open circles are for chains subject to full torsional potential, whereas tte filled circles are for flexible chains with their torsional potential switched off...

Further cooling of the smectic phase may lead to crystallization or perhaps to the formation of a smectic glass. The semicrystalline state of the rigid-rod polymers is different from that of the flexible-chain polymers described in Chapter 7. The low segmental flexibility of the former prevents chain folding and the crystals should be of the fringed micelle type. 

Thermoplastics soften when heated (and eventually liquefy) and harden when cooled — processes that are totally reversible and may be repeated. On a molecular level, as the temperature is raised, secondary bonding forces are diminished (by increased molecular motion) so that the relative movement of adjacent chains is facilitated when a stress is applied. Irreversible degradation results when a molten thermoplastic polymer is raised to too high a temperature. In addition, thermoplastics are relatively soft. Most linear polymers and those having some branched structures with flexible chains are thermoplastic. These materials are normally fabricated by the simultaneous application of heat and pressure (see Section 15.22). Examples of common thermoplastic polymers include polyethylene, polystyrene, poly(ethylene terephthalate), and poly(vinyl chloride). 

Thermal Properties. Before considering conventional thermal properties such as conductivity it is appropriate to consi r briefly the effect of temperature on the mechanical properties of plastics. It was stated earlier that the properties of plastics are markedly temperature dependent. This is as a result of their molecular structure. Consider first an amorphous plastic in which the molecular chains have a random configuration. Inside the material, even though it is not possible to view them, we loiow that the molecules are in a state of continual motion. As the material is heated up the molecules receive more energy and there is an increase in their relative movement. This makes the material more flexible. Conversely if the material is cooled down then molecular mobility decreases and the material becomes stiffer. 

Optical and electro-optical behavior of side-chain liquid crystalline polymers are described 350-351>. The effect of flexible siloxane spacers on the phase properties and electric field effects were determined. Rheological properties of siloxane containing liquid crystalline side-chain polymers were studied as a function of shear rate and temperature 352). The effect of cooling rate on the alignment of a siloxane based side-chain liquid crystalline copolymer was investigated 353). It was shown that the dielectric relaxation behavior of the polymers varied in a systematic manner with the rate at which the material was cooled from its isotropic phase. 

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