Amorphous thermal history

Some representative backbone stmctures of PQs and PPQs and their T data are given in Table 1. As in other amorphous polymers, the Ts of PQs and PPQs are controlled essentially by the chemical stmcture, molecular weight, and thermal history. Several synthetic routes have been investigated to increase the T and also to improve the processibiUty of PPQ (71). Some properties of PPQ based on 2,3-di(3,4-diaminophenyl)quinoxaline and those of l,l-dichloro-2,2-bis(3,4-diaminophenyl)ethylene are summarized in Table 2. 

An important subdivision within the thermoplastic group of materials is related to whether they have a crystalline (ordered) or an amorphous (random) structure. In practice, of course, it is not possible for a moulded plastic to have a completely crystalline structure due to the complex physical nature of the molecular chains (see Appendix A). Some plastics, such as polyethylene and nylon, can achieve a high degree of crystallinity but they are probably more accurately described as partially crystalline or semi-crystalline. Other plastics such as acrylic and polystyrene are always amorphous. The presence of crystallinity in those plastics capable of crystallising is very dependent on their thermal history and hence on the processing conditions used to produce the moulded article. In turn, the mechanical properties of the moulding are very sensitive to whether or not the plastic possesses crystallinity. 

From the preceding discussion it is clear that ageing does substantially affect the glass-rubber transition. The effect of ageing on secondary transitions has been the subject of many studies (see, e.g. Howard and Young, 1997). From Struik s observations on a large number of amorphous polymers it has become clear that thermal history does not affect the secondary transitions (Struik, 1987). 

Struik showed furthermore that for amorphous and semi-crystalline polymers the ageing effect after complicated thermal histories is strikingly similar. In both cases high stresses can erase previous ageing and "rejuvenate" the material. 

The second condition to validate the scheme B is that embrittlement must correspond to a critical morphological state that is the only approach to explain its sudden character. The extensive and careful work of Kennedy et al. (//) on relationships between fracture behavior, molar mass and lamellar morphology, shows that this condition is fulfilled in the case of PE. Comparing various samples of different molar masses with different thermal histories, they found that the thickness of the amorphous layer (la) separating two adjacent lamellae is the key parameter (Fig. 6). As a matter of fact, there is a critical value lac of the order of 6-7 nm. For la > lac the samples are always ductile whatever their molar mass, whereas for U < laC the samples are consistently brittle. As a result, lac appears to be independent of the molar mass. Indeed, there is a specific molar mass, probably close to 70 kg.mof for PE below which crystallization is so fast that it is impossible to have la values higher than lac whatever the processing conditions. 

Thermal history such as annealing or quenching significantly affects the mechanical behavior of thermoplastics. As a typical example in amorphous glassy thermoplastics. 

---