Search results for "Flory–Huggins solution theory"
showing 10 items of 88 documents
Influence of PVP/VA copolymer composition on drug–polymer solubility
2015
In this study, the influence of copolymer composition on drug-polymer solubility was investigated. The solubility of the model drug celecoxib (CCX) in various polyvinylpyrrolidone/vinyl acetate (PVP/VA) copolymer compositions (70/30, 60/40, 50/50 and 30/70 w/w) and the pure homopolymers polyvinylpyrrolidone (PVP) and polyvinyl acetate (PVA) was predicted at 25 °C using a thermal analysis method based on the recrystallization of a supersaturated amorphous dispersion (recrystallization method). These solubilities were compared with a prediction based on the solubility of CCX in the liquid monomeric precursors of PVP/VA, N-vinylpyrrolidone (NVP) and vinyl acetate (VA), using the Flory-Huggins …
Polymer-polymer interaction, in the presence of a solvent as measured by viscometry
2001
Dilute solution viscometry experiments have been carried out in five ternary polymer systems solvent(1)/polymer(2)/polymer(3). Values of the specific viscosity of polymer (3) in a ‘binary solvent’ formed by polymer(2) + solvent(1) have been used to determine the compatibility of the polymer blends. Krigbaum and Wall formalism has been used to predict compatibility which relies on an interaction parameter that depends on the concentration, weight fraction and molar mass of each polymer. To reduce the dependences and to clarify the criterion of compatibility, a parameter independent of polymer (3) composition and molar mass has been deduced. This parameter shows the same behaviour with polyme…
Liquid/Liquid Demixing in the System n-Hexane/Narrowly Distributed Linear Polyethylene
2004
Demixing conditions were measured visually for solutions of three narrowly distributed polyethylene samples (M ranging from 6.5 to 380 kg/mol) in n-hexane up to 500 K and 150 bar. This information yields the critical line for infinite molar mass; i.e., it specifies the pT area within which one is safe from phase separation irrespective of the molar mass of the polymer and of the composition of the mixture. The experimental findings are in good qualitative agreement with the predictions of the Sanchez−Lacombe theory applied without any adjustable parameters. The influences of molar masses are, however, underestimated, and the resulting critical compositions are too small. For a more quantita…
Solution properties of polyelectrolytes—V. Viscometric study of mixed polyanions in pure water
1990
Abstract A viscometric study of sodium polystyrene sulphonate (NaPSS) and sodium poly( l -glutamate) (NaPLG) in salt-free water has been carried out as a function of the total concentration, cm, and the concentration of one polyelectrolyte at fixed concentration of the other. The influences of the molecular weight and concentration are considered in order to establish the degree of compatibility. For the first time, an equation is proposed to define the reduced viscosity of the NaPSS + NaPLG mixture in water. The viscometric interaction parameter, Bm, taking into account the electrostatic and thermodynamic interactions between both polyions, is defined as a geometrical mean of the contribut…
Binding between (Ethylene Oxide)13−(Propylene Oxide)30−(Ethylene Oxide)13 and Sodium Decanoate. Volume, Enthalpy, and Heat Capacity Studies
2002
Volume, enthalpy, and heat capacity of transfer (ΔYt) of (ethylene oxide)13−(propylene oxide)30−(ethylene oxide)13 (L64), at some concentrations, from water to the aqueous sodium decanoate (NaDec) solutions as functions of the surfactant concentration (mS) were determined at 298 K. The copolymer was studied in both the unassociated and associated forms. For a given L64 concentration (mC), the ΔYt vs mS profiles for the volume and the enthalpy are equal but different from that of the heat capacity because the latter contains also the relaxation terms. The experimental data were analyzed by assuming the distribution of L64 between the aqueous and the micellar phases and the shift of micelliza…
Phase diagrams of the system tetrahydrofuran/γ-butyrolactone/poly(ether imide) and determination of interaction parameters
1998
Abstract The thermodynamic interactions in the ternary mixture tetrahydrofuran/γ-butyrolactone/poly(ether imide) (THF/γ-BL/PEI) are investigated from 30 to 50°C. This is a membrane-forming system with a high He-selectivity. Cloud point measurements show that the two binary polymer solutions THF/PEI and γ-BL/PEI exhibit miscibility gaps which close towards the centre of the ternary phase diagram where the mixtures become homogeneous (cosolvency). Vapour pressures were determined for the subsystem THF/γ-BL. For the theoretical calculations the Gibbs energy of mixing is formulated according to the Flory-Huggins theory and the interaction parameter χ THF γ-BL calculated from the vapour pressure…
Solution properties of polyelectrolytes XII. Semi-quantitative approach to mixed electrostatic and hydrophobic polymer-gel interactions
1996
Abstract Aqueous size-exclusion chromatography of polyanions, where secondary effects affect the total separation mechanism, was investigated. For elution of polyelectrolytes on inorganic silica-based supports, the electrostatic polymer-gel repulsive interactions were evaluated through the values for a hypothetical repulsion layer, X e , according to the model developed by other workers. Using a similar procedure, the existence of an effective barrier defined as X e − X h is proposed for those systems in which electrostatic repulsion and hydrophobic interactions take place simultaneously as secondary mechanisms. X h can be viewed as a measure of the “enlargement” of the geometrical pore rad…
Intermolecular structure factors of macromolecules in solution: Integral equation results
1999
The inter-molecular structure of semidilute polymer solutions is studied theoretically. The low density limit of a generalized Ornstein-Zernicke integral equation approach to polymeric liquids is considered. Scaling laws for the dilute-to-semidilute crossover of random phase (RPA) like structure are derived for the inter-molecular structure factor on large distances when inter-molecular excluded volume is incorporated at the microscopic level. This leads to a non-linear equation for the excluded volume interaction parameter. For macromolecular size-mass scaling exponents, $\nu$, above a spatial-dimension dependent value, $\nu_c=2/d$, mean field like density scaling is recovered, but for $\n…
Enthalpy and Entropy Contributions to Solvent Quality and Inversions of Heat Effects with Polymer Concentration
2006
Vapor pressures above the solutions of polystyrene in either cyclohexane (32-60 °C) or toluene (10-70 °C) have been measured by a combination of head space sampling and gas chromatography as a function of the volume fraction φ of the polymer. The thus obtained Flory-Huggins interaction parameters Χ (φ; T) were complemented by data for three other systems (tert-butyl acetate/polystyrene, cyclohexane/poly(vinyl methyl ether), 2-propanol/poly(butyl methacrylate)) reported in the literature and analyzed in terms of their enthalpy and entropy parts Χ H and Χ s . Furthermore these experimental findings were modeled by means of an approach splitting the mixing process conceptually into two parts a…
Quick and reliable routes to phase diagrams for polyethersulfone and polysulfone membrane formation
2000
Phase diagrams were measured and calculated for the ternary membrane forming systems DMF/water/polysulfone and DMF/water/polyethersulfone at different temperatures. Customary experiments yielded cloud point curves, tie lines, and critical compositions. The theoretical computation starts from the Flory-Huggins theory and employs binary interaction parameters g ij that vary with the composition. This information was mainly obtained by means of Headspace-Gas Chromatography (HSGC, yielding the partial pressures of the volatile components); these data were complemented by light scattering and swelling experiments. The calculation of binodals, spinodals, tie lines, and critical points avoids the …