Polydiacetylenes crystal defect

It is important not to lose perspective when considering the defect sensitive properties of polydiacetylene and (SN) crystals. Although (SN) produced by solid-state reaction is not well ordered the crystalline perfection of this polymer is much higher than for conventional organic polymers. Polydiacetylene crystals are obtainable... 

Polydiacetylenes (2) come closest to the model one-dimensional organic semiconductor and can be readily obtained in form of large, nearly defect-free single crystals so that a large number of experiments and measurements have been carried out on these materials. Their structure is shown in Figure 3 where also some typical side-groups R are indicated. On table I we summarize some measured va-... 

Here we outline a dynamical description (42) of the polymerisation of the polydiacetylenes. The approach relies much on the one used (43,44) in the theory of non radiative transitions in crystals and the soliton description of the defects in the lD-or-ganic semiconductors. 

Some important aspects of topochemical polymerizations can be understood by inspection of Eq. (1), All reactivity comes about by very specific rotations of the monomers and by 1,4-addition of adjacent units and an extended, fully conjugated polymer chain is formed. The unique feature of the topochemical polymerization of diacetylenes is the fact that in many cases the reaction can be carried out as a single phase process. This leads to macroscopic, defect-free polymer single crystals which cannot be obtained, in principle, by crystallization of ready-made polymers by conventional methods. Thus, polydiacetylenes are ideal models for the investigation of the behaviour of macromolecules in their perfect three dimensional crystal lattice. 

Various techniques have been used to prepare single crystals of polydiacetylene. Bulk crystals obtained by conventional crystallization procedures (e.g., slow cooling or evaporation from solution) tend to be riddled with defects such as grain boundaries or stacking faults, and are not suitable for optical applications. The LB technique, on the other hand, has been... 

Creep. One of the most remarkable aspects of the deformation of polydiacetylenes is that it is not possible to measure any time-dependent deformation or creep when crystals are deformed in tension parallel to the chain direction (14,24). This behviour is demonstrated in Figure 3 for a polyDCHD crystal held at constant stress at room temperature and the indications are that creep does not take place at temperatures of up to at least 100 C (24). Creep and time-dependent deformation are normally a serious draw-back in the use of conventional high-modulus polymer fibres such as polyethylenes (28). Defects such as loops and chain-ends allow the translation of molecules parallel to the chain direction in polyethylene fibres. In contrast since polydiacetylene single crystal fibres contain perfectly-aligned long polymer molecules (cf Figure lb) there is no mechanism whereby creep can take place even at high temperatures. 

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