Shadow curves polydisperse systems

Figure 15.5 Effect of molecular weight dispersity ( )) (formerly known as polydispersity) using schematic Gibbs triangle diagrams for polymer-solvent system, generation of cloud point curve and shadow curve in temperature-composition diagram.

The spinodal curve and the critical points (including multiple critical points) only depend on few moments of the molar-mass distribution of the polydisperse system while the cloud-point curve the shadow curve and the coexistence curves are strongly influenced by the whole curvature of the distribution function. The methods used that include the real molar-mass distribution or an assumed analytical distribution replaced by several hundred discrete components have been reviewed by Kamide. In the 1980s continuous thermodynamics was applied, for example, by Ratzsch and Kehlen to calculate the phase equilibrium of a solution of polyethene in supercritical ethene as a function of pressures at T= 403.15 K. The Flory s model was used with an equation of state to describe the poly-dispersity of polyethene with a a Wesslau distribution. Ratzsch and Wohlfarth applied continuous thermodynamics to the high-pressure phase equilibrium of ethene [ethylene]-I-poly(but-3-enoic acid ethene) [poly(ethylene-co-vinylace-tate)] and to the corresponding quasiternary system including ethenyl ethanoate [vinylacetate]. In addition to Flory s equation of state Ratzsch and Wohlfarth also tested the Schotte model as a suitable means to describe the phase equilibrium neglecting the polydispersity with respect to chemical composition of the... 

Due to the polydispersity, the demixing behavior becomes much more complicated for a polydisperse polymer in comparison with a monodisperse polymer, as shown in Fig. 1. The binodal curve in this system splits into three kinds of curves a cloud-point curve, a shadow curve, and an infinite number of coexistence curves. The meaning of these curves becomes clear if one considers the cooling process. 

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