Chapter 12 Polymer Glass Transitions.pptVIP

* Crystallization is the process by which, upon cooling, an ordered (i.e., crystalline) solid phase is produced from a liquid melt having a highly random molecular structure. The melting transformation is the reverse process that occurs when a polymer is heated. The glass-transition phenomenon occurs with amorphous or noncrystallizable polymers that, when cooled from a liquid melt, become rigid solids yet retain the disordered molecular structure that is characteristic of the liquid state. Three phenomena that are important with respect to the design and processing of polymeric materials are crystallization, melting, and the glass transition. 12.1、CRYSTALLIZATION The time dependence of crystallization is the same as for many solid-state transformations—Figure 10.10; that is, a sigmoidal-shaped curve results when fraction transformation (i.e., fraction crystallized) is plotted versus the logarithm of time (at constant temperature). Mathematically, fraction crystallized y is a function of time t according to the Avrami equation, where k and n are time-independent constants, whose values depend on the crystallizing system. Figure 12.1 Plot of normalized fraction crystallized versus the logarithm of time for polypropylene(聚丙烯) at constant temperatures of 140, 150 and160oC. Rate of crystallization may be specified in the same manner as for the transformations discussed in Section 10.3; that is, rate is equal to the reciprocal of time required for crystallization to proceed to 50% completion.This rate is dependent on crystallization temperature and also on the molecular weight of the polymer; rate decreases with increasing molecular weight. For polypropylene (as well as any polymer), the attainment of 100% crystallinity is not possible. Therefore, in Figure 12.1, the vertical axis is scaled as “normalized fraction crystallized.” A value of 1.0 for this parameter corresponds to the highest level of crystallization that is achieved during the tests, which, in reality, is le