Polymer processing structural changes

Hence, the performed above analysis has shown that different solvents using in low-temperature nonequilibriiun polycondensation process can result not only in symthesized polymer quantitative characteristics change, but also in reaction mechanism and polymer chain structure change. This effect is comparable with the observed one at the same polymer receiving by methods of equilibrium and nonequilibrium polycondensation. Let us note, that the fractal analysis and irreversible aggregation models allow in principle to predict symthesized polymer properties as a function of a solvent, used in synthesis process. The stated above results confirm Al-exandrowicz s conclusion [134] about the fact that kinetics of branched polymers formation effects on their topological structures distribution and macromolecules mean shape. 

Repeating unit isomerization is similar in several respects to isomerization polymerization (26,27). Isomerization polymerization may be defined as a process whereby a monomer of structure A is converted to a polymer of repeating unit structure B, wherein the conversion of A to B represents a structural change which is not a simple ring opening or double bond addition ... 

As in PP-based nanocomposite systems, the extended Trouton rule, 3r 0 (y t) = r E (so t), also does not hold for PLANC melts, in contrast to the melt of pure polymers. These results indicate that in the case of P LANC, the flow induced internal structural changes also occur in elongation flow [48], but the changes are quite different in shear flow. The strong rheopexy observed in the shear measurements for the PLA-based nanocomposite at very slow shear rate reflects the fact that the shear-induced structural change involved a process with an extremely long relaxation time. 

An important feature of filled elastomers is the stress softening whereby an elastomer exhibits lower tensile properties at extensions less than those previously applied. As a result of this effect, a hysteresis loop on the stress-strain curve is observed. This effect is irreversible it is not connected with relaxation processes but the internal structure changes during stress softening. The reinforcement results from the polymer-filler interaction which include both physical and chemical bonds. Thus, deforma-tional properties and strength of filled rubbers are closely connected with the polymer-particle interactions and the ability of these bonds to become reformed under stress. 

A three-dimensional network formed in the presence of the dispersed filler and therefore the process proceeded in the thin surface layer on the surface of the previously hardened resin (filler). The use of such a system enables the physical structure of the polymer to be changed without changing its chemical nature. At the same time, all the effects usually observed for filled polymers may be expected to be present. 

Interestingly, there have been repeated attempts to view such gradual structural changes due to chemical equilibria as phase transitions as well [262]. Instructive examples for such an analysis are living polymers — for example, in demixing solutions of polymers [263] and in sulfur [264], where the reversible polymerization process has been treated as a second-order phase transition. The experimental evidence for such an interpretation is, however, at best weak [265], and classical association models [266] describe the thermodynamic properties equally well. 

We should also mention an early work by Slonimsky and Askadsky 74 who were apparently the first to observe structural changes taking place in extension under condition s of constant force. Three characteristic sections (see Fig. 20) were identified on the curves of strain versus tension time at F = const. These sections correspond to polymer flow in the amorphous state, the process of molecular ordering and crystallization, and, finally, to polymer flow in the crystalline state. The presence of crystalline formations on the latter section was detected with the help of X-ray-structural and electron-microscopic investigation of extended samples. As the tensile stress was lifted, the sample amorphised again and contracted. The occurrence of a drastic increase in strain on the second section was accounted for 74) by exhaustion of the longevity of supramolecular structures. 

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