Chain flexibility, of polymers

A criticism often aimed at the use of extrinsic fluorescent probes is the possible local perturbation induced by the probe itself on the microenvironment to be probed. There are indeed several cases of systems perturbed by fluorescent probes. However, it should be emphasized that many examples of results consistent with those obtained by other techniques can be found in the literature (transition temperature in lipid bilayer, flexibility of polymer chains, etc.). To minimize the perturbation, attention must be paid to the size and shape of the probe with respect to the probed region. 

This investigation shows that it is indeed possible to study the flexibility of polymer chains in polymer matrices by means of excimer-forming probes and that the rotational mobility of these probes reflect the glass transition relaxation phenomena of the polymer host matrix, in agreement with the appropriate WLF equation. 

Two conflicting theoretical views concerning the flexibility of polymer chains and the role of the volume effect and the draining effect on fry] are discussed in the literature polymer chains of typical flexibility such as vinyl polymer chains, and a large value of Ip] can be interpreted in terms of the excluded volume effect (view point A) polymer chains are semi- or inflexible and their large unperturbed chain dimension is mainly responsible for a large [ry] (view point B). The former has its foundation on the two parameter theory 110. Untill 1977 these inconsistencies constituted one of the most outstanding problems yet unsolved in the science of polymer solutions. 

For radiation grafting, the stabilization of radicals in the polymer films is very important. Due to the flexibility of polymer chains, rearrangements and chemical interactions are possible over longer distance, in particular above the glass transition temperature. To lower the probability of radical recombination, exposed polymer substrates can be stored at low temperatures to reduce the chain mobility inside the polymer. Temperatures of -80°C are usually sufficient to stabilize the radicals over weeks to months. 

Fluorescence anisotropy studies are popular in biological and biochemical research of lipid membranes [16-18], proteins [19-22], etc. and also in polymer science. They have been performed for monitoring the conformations and flexibility of polymer chains in dilute, semidilute and concentrated solutions [23-27], in polymer melts and blends [28-31], and also for studying polymer self-assembly [32-34]. Nowadays, steady-state and time-resolved fluorescence anisotropy are currently used methods in polymer chemistry. 

The semi-flexibility of polymer chains due to the hindered internal rotation is revealed by the correction from the contribution of the internal rotation in the mean-square end-to-end distance, as... 

However, the conformation statistics in Flory s treatment gives the conformational free energy, rather than the conformational entropy adapted in the Gibbs-DiMarzio theory. In addition, W was calculated with respect to the fully ordered state therefore. In W = 0 simply implies the return to the fully ordered state, rather than frozen in a disordered state. Furthermore, reflects the static semi-flexibility, while the glass transition should be related with the d3mamic semi-flexibility of polymer chains. Therefore, fundamental assumptions of the Gibbs-DiMarzio thermodynamic theory are misleading. 

An equation for gel fraction calculation which takes account on the thermal behavior (Tg in K) relates to the flexibility of polymer chains was reported [92Z1], where D is absorbed dose ... 

Ductile deformation requires an adequate flexibility of polymer chain segments in order to ensure plastic flow on the molecular level. It has been long known that macromoleculai- chain mobility is a crucial factor decisive for either brittle or ductile behavior of a polymer [93-95]. An increase in the yield stress of a polymer with a decrease of the temperature is caused by the decrease of macromoleculai chain mobility, and vice versa the yield stress can serve as a qualitative measure of macromolecular chain mobility. It was shown that the temperature and strain rate dependencies of the yield stress are described in terms of relaxation processes, similarly as in linear viscoelasticity. Also, the kinetic elements taking pai-t in yielding and in viscoelastic response of a polymer are similar segments of chains, part of crystallites, fragments of amorphous phase. However, in crystalline polymei-s above their glass transition temperature the yield stress is determined by the yield stress required for crystal deformation... 

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