Glass transition, relaxation

The kinetic character of the glass transition and the resulting non-equilibrium character of the glassy state are responsible for the phenomena of structural relaxation, glass transition hysteresis, and physical aging (Kovacs, 1963 Struik, 1978). 

Ta Main relaxation (glass transition or melting) temperature. 

Included in this section is a description of the various transformations taking place in amorphous alloys, such as structural relaxation, glass transition and amorphous-to-crystalline transition. The main techniques employed to study these transitions are described in more detail and further conclusions are given that can be drawn from the results of these studies. 

Due to the cooperative character of molecular movements associated with this relaxation, the linearity of the semilog plot v versus 1/T is not fulfilled (Fried 2007). The activation energy of a-relaxation (glass transition) can be determined by using the equation (10.5) only when it is ntilized in a limited frequency range. 

An alternative method to observe dielectric properties is termed thermal stimulated currents (TSC). This method involves polarization of a sample at high temperature (relative to Tg) and quenching to a temperature where depolarization is kineticaUy prevented in the time scale of the experiment. The temperature is then increased and the depolarization current is measured, yielding peak values associated with polymer transitions analogous to t", E" and tan S values obtained by conventional dielectric and dynamic mechanical measurements. The TSC spectra can reveal secondary relaxations, glass transitions and liquid or crystalline phase transitions and hquid crystalhne phase transitions. TSC has been applied to PBT/PC and PA6/ABS blends to study the intermixing of the components of the respective blends [58]. The TSC method is described in several references [59-61]. 

The relaxatioa temperature appears to iacrease with increa sing HFP coateat. Relaxatioa iavolves 5—13 of the chaia carboa atoms. Besides a and y relaxations, one other dielectric relaxation was observed below —150° C, which did not vary ia temperature or ia magnitude with comonomer content or copolymer density (55). The a relaxation (also called Glass 1) is a high temperature transition (157°C) andy relaxation (Glass 11) (internal friction maxima) occurs between —5 and 29°C. 

Determination of the glass-transition temperature, T, for HDPE is not straightforward due to its high crystallinity (16—18). The glass point is usually associated with one of the relaxation processes in HDPE, the y-relaxation, which occurs at a temperature between —100 and —140° C. The brittle point of HDPE is also close to its y-transition. 

The most desirable annealing temperatures for amorphous plastics, certain blends, and block copolymers is just above their glass transition temperature (Tg) where the relaxation of stress and orientation is the most rapid. However, the required temperatures may cause excessive distortion and warping. 

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