Amorphous reduced glass transition temperature

The glass transition temperature of amorphous PET is in the range of 65-75 °C, and this can increase to 125 C after being drawn and partially crystallized, reflecting the reduced rotational mobility of the chain segments. The crystallite... 

The flexibility of amorphous polymers is reduced drastically when they are cooled below a characteristic transition temperature called the glass transition temperature (Tg). At temperatures below Tg there is no ready segmental motion and any dimensional changes in the polymer chain are the result of temporary distortions of the primary covalent bonds. Amorphous plastics perform best below Tg but elastomers must be used above the brittle point, or they will act as a glass and be brittle and break when bent. 

The concept of polymer free volume is illustrated in Figure 2.22, which shows polymer specific volume (cm3/g) as a function of temperature. At high temperatures the polymer is in the rubbery state. Because the polymer chains do not pack perfectly, some unoccupied space—free volume—exists between the polymer chains. This free volume is over and above the space normally present between molecules in a crystal lattice free volume in a rubbery polymer results from its amorphous structure. Although this free volume is only a few percent of the total volume, it is sufficient to allow some rotation of segments of the polymer backbone at high temperatures. In this sense a rubbery polymer, although solid at the macroscopic level, has some of the characteristics of a liquid. As the temperature of the polymer decreases, the free volume also decreases. At the glass transition temperature, the free volume is reduced to a point at which the... 

The Polymer. Amorphous Polystyrene. All of the expandable polystyrene referred to above is the amorphous type that is obtained by free radical initiation. This polymer is completely noncrystalline, and in the absence of impurities such as monomer and blowing agent it exhibits a glass-transition temperature of about 100°C. Both the rate of expansion and the extent of expansion are enhanced by reducing molecular weight, but the foam becomes less resistant to collapse on further steaming (63). Other polymeric modifications are discussed below. 

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