Search results for "Numeral system"

1988

The unperturbed dimensions parameter KΘ is one of the most important characteristics of a polymer chain. For binary systems (polymer/solvent) and mostly for ternary systems (polymer/solvent(1)/solvent(2)) the KΘ values show large discrepancies with respect to those under thetaconditions in a single solvent. These discrepancies can be explained by considering that the interaction parameter χ (and consequently the coil dimensions or the number of intramolecular contacts between polymer segments) changes with molecular weight M. Assuming this dependency, a modified Stockmayer-Fixman equation is proposed from which a unique value of KΘ for a given polymer, independent of M, is obtained. The use…

On the thermodynamic treatment of poly(vinylidene fluoride)/polystyrene blend under liquid—liquid phase separation conditions

1995

Abstract This paper deals with experimental and theoretical investigations on the compatibility of binary of polymer blends in solution. The experimental phase boundary of a crystalline polymer such as poly(vinylidene fluoride) with polystyrene (an amorphous polymer) in dimethylformamide as solvent has been determined by size-exclusion chromatography at 25°C. The composition of the coexisting phases has been used to calculate interaction parameters by means of the Flory—Huggins-type function for the free energy of mixing, including composition dependence of the polymer-polymer interaction parameter and a first correction term denoted as ternary interaction parameter. The calculation of thes…

Phase Behavior of the System Linear Polyglycerol + Methanol + Carbon Dioxide

2011

To compare the phase behavior of linear and hyperbranched polymers, the phase envelopes of the ternary system linear polyglycerol + methanol + carbon dioxide were determined for polymers of varying molar mass. Phase changes were detected by a static synthetic method using the Cailletet setup for temperatures between 331 K and 421 K and pressures up to 13.1 MPa. Besides the vapor–liquid and liquid–liquid equilibria, also the vapor–liquid to vapor–liquid–liquid and vapor–liquid–liquid to liquid–liquid phase boundaries are reported. The experimental results are similar to systems with hyperbranched polymers (rather than linear polymers). For the systems with linear polymers, however, the bubbl…

A thermodynamic analysis on the coincidence of extrema conditions in the sorption equilibrium for ternary polymer systems

1993

Flory-Huggins theory of polymer solutions has been used to express the condition of extrema values in the total sorption, as well as the inversion point in the preferential adsorption parameters for termary polymer systems. Two approaches have been followed, the first considers the binary and ternary interaction parameters independent of polymer concentration and solvent composition. In the second one, this dependence has been introduced. Our attention is focused on the volume fraction of solvent mixture dependence of the above parameters, in order to confirm or not the coincidence between the extrema values and the inversion point. Several cosolvent and cononsolvent ternary polymer systems…

Prediction of maxima and minima in the curve of total sorption parameter in ternary polymer systems. Influence of ternary interaction parameter

1993

Flory-Huggins theory modified by Pouchly has been applied to predict maxima and minima in the curve of total sorption in ternary polymer systems formed by a polymer and two liquids. In this work, different diagrams based on experimental magnitudes easily obtained such as the difference in affinities of liquids, solvents and non solvents, and the solvent molar volume ratio. Total sorption parameter has been considered to be the decisive magnitude to define extrema conditions in both cosolvent and cononsolvent ternary polymer systems. The theoretical prediction is not altered by the inclusion of ternary interactions. Different examples of ternary systems dealing with vinyl polymers and polydi…

A comparative study between cosolvent and cononsolvent ternary polymer systems through the preferential adsorption coefficient

1993

Sorption equilibrium of polystyrene and poly (dimethyl siloxane) in mixed solvents has been monitored by means of the preferential adsorption coefficient experimentally determined from intensity light scattering measurements. The pairs of solvents used to dissolve each polymer sample have been selected for the purpose to perform cosolvent and cononsolvent ternary polymer systems. Flory-Huggins formalism including ternary interactions has been used to predict the sorption equilibrium for the cosolvent system and, for the first time, for cononsolvent ones. Moreover, the proportionality between binary and ternary interactions, recognized by Pouchly, is also corroborated for both ternary polyme…

On the calculation of free energy of mixing for aqueous polymer solutions with group-contribution models

2010

Abstract Liquid–liquid phase separation processes are currently used as a route to prepare polymeric porous structures for various applications (membranes and scaffolds for tissue engineering). In membrane and foam fabrication technologies, binary and mainly ternary polymer solutions are used. Membrane morphology is strongly affected by phase equilibria of processing solution. In order to achieve a better control of membrane morphology and to explore a wide quantity of solvents, a predictive tool addressing experimentals would be strongly advisable. In this paper, group contribution models were chosen to test the applicability on a PLLA–dioxane–water ternary polymer solution, whose experime…

On The Incompatibility of Dextran and Pullulan in Aqueous Solutions and Its Modeling

2012

Joint aqueous solutions of branched dextran and linear pullulan are investigated with respect to their phase separation. The experiments demonstrate that the polymers are – depending on the molar mass of dextran – incompatible in aqueous solutions despite their chemical similarity. This finding can be modeled on the basis of an approach accounting for chain connectivity and conformational relaxation of the components. According to these calculations, the polymers exhibit a miscibility gap in joint solutions despite the favorable interactions between them. Using information on the subsystems H2O/dextran and H2O/pullulan, the assumption of complete miscibility of the polysaccharides is requir…

Review: Solution equilibria of ternary complexes formed from copper(II), aliphatic amines, and bioligands

2014

This review provides a summary of the coordination chemistry of ligands in the ternary system: copper(II)–aliphatic amine–bioligand, where amine = ethylenediamine – En, diethylenetriamine – Dien, or N, N, N′, N″, N″-pentamethyldiethylenetriamine – Me5dien, and bioligand = selected amino acid, aminohydroxamic acid, or aminophosphonic acid, in aqueous solution. We would like to show the specific interactions of copper(II) in ternary systems in the context of complex equilibria chemistry.

Heat capacities of butanol and pentanol in aqueous dodecyltrimethylammonium bromide solutions

1987

Heat capacities of the ternary systems water-dodecyltrimethylammonium bromide (DTAB)-butanol and water-DTAB-pentanol were measured at 25°C. The standard partial molar heat capacities of pentanol in micellar solutions show a maximum at about 0.35 mol-kg−1 DTAB that has been attributed to a micellar structural transition. This maximum tends to vanish by increasing the alcohol concentration and by decreasing the alcohol alkyl chain length; in the case of butanol it was not detected. The behavior of the standard partial molar heat capacities of alcohols in micellar solutions in the region above the cmc and below the structural transition was explained using a previously reported mass-action mod…