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Confinement-induced vitrification in polyethylene terephthalate

AutorBaltá Calleja, Francisco José ; Marco, G. di; Flores, Araceli ; Pieruccini, M.
Fecha de publicación4-jun-2007
EditorAmerican Institute of Physics
CitaciónPhysical Review B - Condensed Matter and Materials Physics 75: 224201 (2007)
ResumenDynamic mechanical thermal analysis performed on cold-drawn polyethylene terephthalate (PET), cold crystallized (annealed) in the temperature interval 100-140°C, reveals the presence of marginally glassy domains above the annealing temperature Ta. This suggests that the thermodynamic force driving crystallization causes the structural arrest of some noncrystalline domains. The latter thus need a temperature higher than Ta to completely defreeze. Differential scanning calorimetry supports this point of view. Analogous investigations on unoriented PET, cold crystallized in the same conditions, do not show the same peculiarities; thus, chain orientation is relevant to vitrification. This phenomenology is first cast in the language of thermodynamics by introducing an excess chemical potential δμ describing the presence of structural constraints in the amorphous domains and the effect of chain orientation. For a first test of this picture, the orientation contribution to δμ is calculated by means of the Gaussian chain model (this implicitly assumes that δμ is related to the density fluctuations). The resulting expression is then used to discuss the structural differences between cold-drawn and unoriented PET samples reported in the literature. © 2007 The American Physical Society.
Descripción9 págs.; 5 figs.; 1 app; PACS number s : 61.82.Pv, 61.82.Rx, 64.70.Pf, 05.20. y; Erratum Phys. Rev. B 79, 019903 (2009)
Versión del editorhttps://doi.org/10.1103/PhysRevB.75.224201
Identificadoresdoi: 10.1103/PhysRevB.75.224201
issn: 1098-0121
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