Spinodal equation for polydisperse polymer solutions
- 8 July 1986
- journal article
- Published by The Royal Society in Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences
- Vol. 406 (1830) , 63-73
- https://doi.org/10.1098/rspa.1986.0064
Abstract
In this paper polydisperse polymer solutions are considered to be described by a class of free-energy functions generalizing the classical Flory-Huggins relation by replacing Huggins’ X -term by a function which is assumed to depend on a finite number of moments of the molar mass distribution. Most free-energy functions used in practice obey this condition. For this class of free-energy functions a spinodal theorem is proved; if the phase considered lies on the spinodal, then a matrix Q is positive semidefinite and its determinant, det Q , equals zero. The calculation of the matrix Q is relatively simple. M. Gordon, P. Irvine & J. W. Kennedy ( J. Polymer Sci . 61, 199 (1977)) and P. Irvine & M. Gordon ( Proc. R. Soc. Lond. A 375, 397 (1981)) showed that the spinodal problem considered may be simplified by replacing the given distribution by a spinodal equivalent distribution consisting of a number of discrete polymer species. For this reason a finite moment problem has to be solved. The theorem proved in this paper results in avoiding the solution of this moment problem and, furthermore, guarantees the stability matrix to possess the minimal order.Keywords
This publication has 10 references indexed in Scilit:
- Liquid-Liquid Equilibrium of Polydisperse Copolymer Solutions. Multivariate Distribution Functions in Continuous ThermodynamicsJournal of Macromolecular Science: Part A - Chemistry, 1985
- Continuous Thermodynamics of Polymer Solutions: The Effect of Polydispersity on the Liquid-Liquid EquilibriumJournal of Macromolecular Science: Part A - Chemistry, 1985
- Continuous thermodynamics of complex mixturesFluid Phase Equilibria, 1983
- Truncation theorems for spinodals and critical points of mean-field models for polydisperse polymer solutionsProceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1981
- Phase diagrams and pulse‐induced critical scatteringJournal of Polymer Science: Polymer Symposia, 1977
- Liquid-liquid phase separation in multicomponent polymer systems, 12. Molecular weight dependence of the pair-interaction parameter in the system polystyrene/cyclohexaneDie Makromolekulare Chemie, 1975
- Generalization of the flory‐huggins treatment of polymer solutionsJournal of Polymer Science Part C: Polymer Symposia, 1972
- Liquid-Liquid Phase Separation in Multicomponent Polymer Systems. X. Concentration Dependence of the Pair-Interaction Parameter in the System Cyclohexane-PolystyreneMacromolecules, 1971
- Liquid–liquid phase separation in multicomponent polymer solutions. II. The critical stateJournal of Polymer Science Part A-2: Polymer Physics, 1968
- THERMODYNAMIC PROPERTIES OF SOLUTIONS OF LONG‐CHAIN COMPOUNDSAnnals of the New York Academy of Sciences, 1942