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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 116 (2002), S. 3925-3934 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The dynamic fragilities of six polymeric materials have been compared for isobaric (constant pressure) and isochoric (constant volume) conditions. Data were taken from the published literature for dynamic experiments performed at elevated pressures. Published pressure–volume–temperature (PVT) data were then used to determine the dynamic response as a function of temperature for both the isochoric and isobaric conditions. It is found that the pressure and volume dependences of the dynamic fragility vary greatly among the polymers for which data were available. For poly(vinyl acetate) (PVAc) and poly(ethyl acrylate) (PEA), the dynamic fragility is independent of the pressure and specific volume and the isochoric and isobaric fragilities are almost the same. On the other hand for poly(vinylchloride) (PVC), polystyrene (PS) and poly(methyl acrylate) (PMA), the dynamic fragility is sensitive to changes of pressure and volume and the isobaric behavior is more fragile than the isochoric behavior when referenced to the same glass formation points (Pg,Vg,Tg). It is also remarked that the signature Vogel–Fulcher temperature dependence of the isobaric dynamics is lost for the isochoric behavior of both PMA and PVC. © 2002 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1561-1573 
    ISSN: 0887-6266
    Keywords: glass transition ; isobaric ; isochoric ; polymer ; poly(carbonate) ; PVT behavior ; free volume theory ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Pressure-volume-temperature (PVT) studies were performed on a glass-forming polymer, poly(carbonate) (PC), under both isobaric and isochoric (constant volume) conditions. An isochoric glass transition was observed and the formation points were found to be consistent with those obtained isobarically. Although the isobaric and isochoric responses were, as expected, the same in the rubbery state, the glassy state values were found to be different and dependent upon the glass formation history. The isobaric data exhibited larger changes in going from the rubber to the glass, hence a “stronger” glass transition, than did the isochoric data. Inserting the experimental values for the thermal expansion coefficient α and isothermal compressibility β, into appropriate thermodynamic relations, measures of the strength of each transition are defined. Strength estimates based on literature values of α and β are compared to the experimental measures of the isochoric and isobaric transitions. In addition, both the isobaric and isochoric PVT results were analyzed in terms of the Fox and Flory free volume theory which assumes that the glass transition is an iso-free volume state. While the isobaric results were consistent with the Fox and Flory theory, the isochoric results were not consistent with the idea of an iso-free volume glass transition. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1561-1573, 1997
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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