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• W2039219259 abstract "An analysis of the behavior of polymer systems in the condensed amorphous state shows that they may resemble both gases (e.g., high elasticity) and liquids (high density, ability to flow and crystallize, etc.). Moreover, polymer systems, analogously to gases, exhibit distribution according to their thermodynamic potentials, which for polymers is connected with the distribution according to end-to-end distances, while for gases it is related to the distribution according to velocities (in both cases we have a Maxwell distribution). The similarity between gases and macromolecules is also suggested by the low proper density of the latter (∼0.05 for the θ-dimensions). The preceding facts allow us to formulate the concept of phase dualism, according to which each segment of the polymer system in the condensed state possesses at the same time features both gas-like and liquid-like. The occurrence of one or the other of the likenesses or their simultaneous occurrence depends on the direction and scale of the segment's reaction towards external effects (field of force, temperature, etc.). Keeping in mind the existence of phase dualism one may describe, at least in a thermodynamically formal way, virtually all the peculiar features of the behavior of polymer systems in various transitions. In particular, a quantitative and qualitative interpretation is possible of a nontrivial transition from crystallization with chain folding to crystallization with chain extension for when a system containing randomly coiled macromolecules is compressed on all sides. In this case the compression will affect the dual phase system in two ways. First, the segment liquid will be compressed while the internal energy will be reduced by ΔUt and second, the interaction between the segments will be strengthened. The thermodynamic characteristics of the “segment gas” under compression on all sides must be altered, losing some gas-like qualities, towards the transition of the whole system into a “real liquid.” Such a transition is feasible if the statistical coil forms a compact globule, or if it becomes straightened and forms nematic structures, while the internal energy changes by ΔUg. An analysis of the thermodynamic losses caused by such transitions shows that a transition of the latter type, i.e., with unfolding of the macromolecular chains, is the more likely one. Earlier investigations carried out by us indicate that on reaching some critical degree of unfolding, a transition must occur from crystallization with folding to crystallization with extension, which, together with the conclusion mentioned above, explains the specificity of crystallization under hydrostatic compression. Quantitative evaluations of pressure at which the transition from one manner of crystallization to another should occur give P > 2500 atm, in good accord with the experimental data." @default.
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• W2039219259 date "2007-03-08" @default.
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• W2039219259 title "Gas- and liquid-like phase dualism in polymers" @default.
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• W2039219259 doi "https://doi.org/10.1002/polc.5070610133" @default.
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