Structural defects, polymers

The extent of head-to-head units in PVC and their effect on stability of the polymer is yet to be conclusively demonstrated, although it would seem that as compared to other structural defects their contribution to polymer instability is a minor one. 

Tacticity or stereochemical arrangement of atoms in three-dimensional space in relation to each other along the polymer chain cannot really be termed a structural defect. But researchers have shown that tacticity has an important bearing on the reactivity and thermal stability of PVC. For this reason tacticity is being discussed under this section. 

Recent research has conclusively demonstrated the presence of extremely low levels of tertiary and allylic chlorines in PVC as structural defects [118]. Such chlorines, which are extremely labile, when present in areas of like-charge concentration in the polymer matrix would be more susceptible to breaking from the chain than the ordinary secondary chlorines. 

The resulting ladder polymer LPPP 12 possesses a number average molecular weight of 25000, which corresponds to the incorporation of 65 phenylene units. No structure defects could be detected using NMR spectroscopy. LPPP 12 is... 

Another definition, taking into account polymerization conversion, has been more recently proposed.192 Perfect dendrimers present only terminal- and dendritic-type units and therefore have DB = 1, while linear polymers have DB = 0. Linear units do not contribute to branching and can be considered as structural defects present in hyperbranched polymers but not in dendrimers. For most hyperbranched polymers, nuclear magnetic resonance (NMR) spectroscopy determinations lead to DB values close to 0.5, that is, close to the theoretical value for randomly branched polymers. Slow monomer addition193 194 or polycondensations with nonequal reactivity of functional groups195 have been reported to yield polymers with higher DBs (0.6-0.66 range). 

The ordinary monomer units of PVC are not expected to absorb any terrestrial solar radiation (1>.2>.3 A) Thus, under the usual ambient conditions, photodegradation of the polymer must be initiated by chromophoric impurities. These impurities may simply be structural defects in the PVC itself, or they may be extraneous substances that have been incorporated into the polymer. Several of these potential photosensitizers are discussed in the following sections. 

In the field of polymer chemistry the regio- and stereoselectivity of the Diels-Alder reaction is used for the concerted synthesis of structurally homogeneous double-stranded ladder polymers [39], which are useful materials with nonlinear optical properties and high electrical conductivity. It has turned out that the repeated Diels-Alder method is superior to an alternative two-step process, in which first an open chain precursor is formed followed by polymer ring closure as structural defects can occur [40]. 

N.H.S. Lee, Z.-K. Chen, W. Huang, Y.-S. Xu, and Y. Cao, Synthesis and characterization of naphthyl-substituted polyfp-phenylene vinylene)s with few structural defects for polymer light-emitting diodes, J. Polym. Sci., Part A Polym. Chem., 42 1647-1657, 2004. 

However, defects and distortions are present in crystals of polymers and they play an important role in the Crystal Structures of polymers, X-ray diffraction data provides a lot of information... 

These novel carbon nanostructures can also be modified by (a) doping, that is the addition of foreign atoms into the carbon nanostructure, (b) by the introduction of structural defects that modify the arrangement of the carbon atoms and (c) by functionalization involving covalent or noncovalent bonding with other molecules. These modifications opened up new perspectives in developing novel composite materials with different matrices (ceramic, polymer and metals). For example, polymer composites containing carbon nanostructures have attracted considerable attention due to... 

Defects in carbon nanostructures can be classified into (a) structural defects, (b) topological defects, (c) high curvature and (d) non-sp2 carbon defects. Even slight changes within the carbon nanostructure can modify the chemical and physical properties. Some defects in carbon systems results in high chemical reactivity, mainly due to the accumulation of electrons in the vicinity of the dopant. These defects can be used as anchoring sites in order to make the carbon nanostructures more compatible with ceramic or polymer matrices, thus enhancing interactions between carbon structures (filler) and the host matrices. 

To the best of our knowledge, the supercoil conformation of the monoden-dron jacketed polystyrene is one of the first observations of a defined tertiary structure in synthetic polymers. The plectoneme conformation could be caused by underwinding or overwinding of a backbone from its equilibrium state [168]. Quick evaporation of the solvent certainly can cause a residual torsion in the molecule as it contracted in itself. Unlike macroconformations of biomolecules, where the tertiary structures are often stabilized by specific interactions between side groups, the supercoil of the monodendron jacketed polymers is metastable. Eventually, annealing offered a path for the stress relaxation and allowed the structural defects to heal [86]. 

In contrast to metals and semiconductors, the valence electrons in polymers are localized in covalent bonds.The small current that flows through polymers upon the application of an electric field arises mainly from structural defects and impurities. Additives, such as fillers, antioxidants, plasticizers, and processing aids of flame retardants, cause an increase of charge carriers, which results in a decrease of their volume resistivity. In radiation cross-linking electrons may produce radiation defects in the material the higher the absorbed dose, the greater the number of defects. As a result, the resistivity of a radiation cross-linked polymer may decrease. Volume resistivities and dielectric constants of some polymers used as insulations are in Table 8.3. It can be seen that the values of dielectric constants of cross-linked polymers are slightly lower than those of polymers not cross-linked. 

As well known, the crystalline structure of polymers is generally characterized by a comparatively high proportion of defects compared with the case of low molecular weight substances these defects may be due either to chemical faults or may be simply attributed to the mechanism of crystallization. As a consequence, this means that most polymers can contain a small proportion of extraneous units in the crystal state. However, we will not consider as real cases of macromolecular isomorphism those having a concentration of either component below 5%. 

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