Semicrystalline polymers glass transition temperatures

Fig. 2.18. Schematic DSC thermogram of a semicrystalline polymer = glass transition temperature = crystallization temperature = melting temperature = decomposition temperature...

In a semicrystalline polymer, the crystals are embedded in a matrix of amorphous polymer whose properties depend on the ambient temperature relative to its glass transition temperature. Thus, the overall elastic properties of the semicrystalline polymer can be predicted by treating the polymer as a composite material... 

The polymers can either be amorphous or semicrystalline, witli increased glass transition temperatures by increasing the phenyl units in the backbone. 

In contrast to the mature instrumental techniques discussed above, a hitherto nonexistent class of techniques will require substantial development effort. The new instruments will be capable of measuring the thermal (e.g., glass transition temperatures for amorphous or semicrystalline polymers and melting temperatures for materials in the crystalline phase), chemical, and mechanical (e.g., viscoelastic) properties of nanoscale films in confined geometries, and their creation will require rethinking of conventional methods that are used for bulk measurements. 

Although polymers exhibit both viscous and elastic responses at all temperatures, the elastic response is particularly strong at temperatures less than 50°C above the glass transition temperature, particularly for polymers well above their critical molecular weight. Polymers are often considered to have dominant viscous rheological responses if they are stressed at temperatures over 100 °C above the glass transition temperature for amorphous polymers or 100°C above the crystalline melting point for semicrystalline resins. 

Composite-based PTC thermistors are potentially more economical. These devices are based on a combination of a conductor in a semicrystalline polymer—for example, carbon black in polyethylene. Other fillers include copper, iron, and silver. Important filler parameters in addition to conductivity include particle size, distribution, morphology, surface energy, oxidation state, and thermal expansion coefficient. Important polymer matrix characteristics in addition to conductivity include the glass transition temperature, Tg, and thermal expansion coefficient. Interfacial effects are extremely important in these materials and can influence the ultimate electrical properties of the composite. 

Amorphous polymers characteristically possess excellent optical properties. Unlike all the other commercially available fluoropolymers, which are semicrystalline, Teflon AF is quite clear and has optical transmission greater than 90% throughout most of the UV, visible, and near-IR spectrum. A spectrum of a 2.77-mm-thick slab of AF-1600 is shown in Figure 2.5. Note the absence of any absorption peak. Thin films of Teflon AF have UV transmission greater Ilian 95% at 200 mm and are unaffected by radiation from UV lasers. The refractive indexes of Teflon AF copolymers are shown in Figure 2.6 and decrease with increasing FDD content. These are the lowest refractive indexes of any polymer family. It should be noted that the abscissa could also be labeled as glass transition temperature, Tg, since Tg is a function of the FDD content of the AF copolymer. Abbe numbers are low 92 and 113 for AF-1600 and AF-2400. 

Most addition polymers are thermoplastics that is, they are hard at room temperature but soften and eventually melt as they are heated. At low temperatures there is very little motion of the molecules and the polymer is glasslike and brittle. As the temperature of the polymer is raised, it passes through its glass transition temperature (Tg). Above J , more motion of the chains is possible and the polymer is a rubbery solid. Eventually, the polymer passes through its crystalline melting point (Tm) and melts to form a viscous liquid. Many semicrystalline polymers are most useful at temperatures between Tg and Tm. Both Tg and Tm increase as the crystallinity of the polymer increases and as the strength of the intermolecular forces between the polymer chains increases. The total intermolecular force increases as the length of the polymer chains increases. 

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