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|Title:||PEO/CHCl3. Crystallinity of the Polymer and Vapor Pressure of the Solvent. Equilibrium and Nonequilibrium Phenomena|
|Authors:||Khasanova, A. Kh.|
Wolf, B. A.
|Publisher:||American Chemical Society (ACS)|
|Citation:||Khasanova A. Kh. PEO/CHCl3. Crystallinity of the Polymer and Vapor Pressure of the Solvent. Equilibrium and Nonequilibrium Phenomena / A. Kh. Khasanova, B. A. Wolf. — DOI 10.2495/SC210181 // Macromolecules. — 2003. — Vol. 36. — Iss. 17. — P. 6645-6652.|
|Abstract:||Vapor pressures were measured for the system CHCl3/PEO 1000 (PEO stands for poly(ethylene oxide) and 1000 for Mw in kg/mol) at 25°C as a function of the weight fraction w of the polymer by means of a combination of headspace sampling and gas chromatography. The establishment of thermodynamic equilibria was assisted by employing thin polymer films. The degrees of crystallinity α of the pure PEO and of the solid polymer contained in the mixtures were determined via DSC. An analogous degree of polymer insolubility β was calculated from the vapor pressures measured in this composition range. The experiments demonstrate that both quantities and their concentration dependence are markedly affected by the particular mode of film preparation. These nonequilibrium phenomena are discussed in terms of frozen local and temporal equilibria, where differences between α and β are attributed to the occlusion of amorphous material within crystalline domains. Equilibrium information was obtained from two sources, namely from the vapor pressures in the absence of crystalline material (gas/liquid) and from the saturation concentration PEO (liquid/solid). The thermodynamic consistency of these data is demonstrated using a new approach that enables the modeling of composition dependent interaction parameters by means of two adjustable parameters only.|
DIFFERENTIAL SCANNING CALORIMETRY
DEGREE OF POLYMER INSOLUBILITY
DEGREES OF CRYSTALLINITY
|metadata.dc.description.sponsorship:||The authors are grateful to the “Deutscher Akademischer Austauschdienst” and to the Civilian Research and Development Foundation (USA, REC-005.2001) for financial support.|
|Appears in Collections:||Научные публикации, проиндексированные в SCOPUS и WoS CC|
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