Search results for "THERMODYNAMICS"

Liquid/Gas and Liquid/Liquid Phase Equilibria of the System Water/Bovine Serum Albumin

2013

The thermodynamic behavior of the system H2O/BSA was studied at 25 °C within the entire composition range: vapor pressure measurements via head space sampling gas chromatography demonstrate that the attainment of equilibria takes more than one week. A miscibility gap was detected via turbidity and the coexisting phases were analyzed. At 6 °C the two phase region extends from ca. 34 to 40 wt % BSA; it shrinks upon heating. The polymer rich phase is locally ordered, as can be seen under the optical microscope using crossed polarizers. The Flory-Huggins theory turns out to be inappropriate for the modeling of experimental results. A phenomenological expression is employed which uses three adju…

1988

An apparatus for turbidimetric measurements of demixing temperatures under shear flow is presented, and the results of experiments with trans-decahydronaphthalene/polystyrene (TD/PS) solutions, investigating molecular weights ranging from 100 kg/mol to 1770 kg/mol, are compared with viscometric data. It is found that the sign and magnitude of shear effects depend on molecular weight (Mw), polymer concentration (c2), and shear rate (). For the first time, it was possible to study a solution which exhibits shear dissolution at low shear rates but shear demixing at high shear rates.

Solvent quality as reflected in concentration- and temperature-dependent Flory-Huggins interaction parameters

2001

Flory-Huggins interaction parameters (χ) between poly(dimethylsiloxane) (weight-average molecular weight = 152 kg/mol) and various solvents (methyl ethyl ketone, toluene and n-octane) were determined as a function of composition and temperature with vapor-pressure measurements. These data, complemented by independent information for dilute and very concentrated solutions, serve as the basis for a discussion of solvent quality via different theoretical relations. Regardless of polymer concentration, the χ values fall from methyl ethyl ketone via toluene to n-octane, the ketone being the worst solvent and the hydrocarbon being the best solvent. The variation of χ with composition and temperat…

Interfacial tension between polymer-containing liquids - Predictability and influences of additives

1999

The first part of the contribution deals with the interfacial tension, σ, of phase-separated polymer solutions in single or mixed solvents and of binary polymer blends as a function of the relative distance to the critical temperature of the system, special attention being paid to the possibilities of theoretical prediction. Two methods are discussed in more detail. One is based on a realistic description of the Gibbs energy of mixing as a function of composition, the second correlates σ with the length of the measured tie line. The second part is devoted to another aspect, namely the effects of additives on the interfacial tension between the coexisting phases of demixed polymer solutions …

Phase behavior of the system hyperbranched polyglycerol+methanol+carbon dioxide

2010

Abstract Phase equilibrium data have been measured for the ternary system hyperbranched polyglycerol + methanol + carbon dioxide at temperatures of 313–450 K and pressures up to 13.5 MPa. Phase changes were determined according to a synthetic method using the Cailletet setup. At elevated temperatures the system shows a liquid–liquid–vapor region with lower solution temperatures. Besides the vapor–liquid and liquid–liquid equilibria, the vapor–liquid to vapor–liquid–liquid and vapor–liquid–liquid to liquid–liquid phase boundaries are reported at different polymer molar masses and can serve as test sets for thermodynamic models. A distinct influence of the polymer molar mass on the vapor–liqu…

Lattice fluid model generalized for specific interactions: An application to ternary polymer solutions

2011

Abstract The phase diagram of the Poly- l -Lactic-Acid (PLLA), dioxane and water system was derived by using the lattice fluid model generalized for specific interactions. A qualitative analysis of Hansen solubility parameters together with empirical observations were adopted to reduce the number of adjustable parameters. The as-selected model parameters were derived by fitting a set of cloud point curves; consequently, the complete phase diagram of the system was computed. The use of specific interactions between species gave out a quantitative agreement with a set of experimental data, whereas changing the polymer polydispersity the agreement is only qualitative. In principle, the present…

The effect of pressure on the liquid–liquid phase equilibrium of two polydisperse polyalkylsiloxane blends

2002

The effect of pressure-induced immiscibility in polymer blends is investigated by experimental and theoretical methods. Experimental data of cloud point curves and critical points are obtained by turbidity measurements. The chosen system is a mixture of polydimethylsiloxane and polyhexylmethylsiloxane which is one of the very few polymer blends exhibiting pressure-induced immiscibility. This unusual behaviour is related to a critical temperature minimum of the critical curve and cloud point isopleths at positive pressure in the temperature–pressure diagram. The effect of the chain length on the critical temperature minimum is investigated here based on theoretical models. The effect of diff…

Shear Effects on the Phase Diagrams of Solutions of Highly Incompatible Polymers in a Common Solvent. 2. Experiment and Theory

1997

Cloud point temperatures (Tcp) were measured at different constant shear rates for three representatives of the ternary system cyclohexanone/polystyrene/poly(n-butyl methacrylate) (CHO/PS/PBMA) by means of a newly constructed rheo-optical apparatus that can be operated in the temperature range from 0 to 100 °C up to maximum shear rates of 1440 s-1 and maximum stresses of 384 Pa. In all cases one observes an extension of the homogeneous region as the shear rate γ is raised. With the system CHO/PS 196w/PBMA 2050 (the figures denote the molar masses of the polymers in kilograms/mole) the effects become maximum for high concentrations of PBMA, where the demixing temperatures increase by more th…

Shear Effects on the Phase Diagrams of Solutions of Highly Incompatible Polymers in a Common Solvent. 1. Equilibrium Behavior and Rheological Propert…

1997

Phase diagrams (cloud points, tie lines, critical compositions) and viscosities of homogeneous solutions were determined at temperatures ranging from 20 to 100 °C for three representatives of the ternary system cyclohexanone/polystyrene/poly(n-butyl methacrylate) [CHO/PS/PBMA] in preparation of a study on shear influences. An only moderate increase of the two-phase region observed upon heating (LCST behavior) witnesses little heat effects upon mixing. Tie lines which are nearly parallel to the PS/PBMA edge of the Gibbs phase triangle indicate comparable solvent quality of CHO for both polymers. The quantitative mathematical description of the equilibrium behavior-required for a theoretical …

Ternary Polymer Solutions with Hydrogen Bonds, 2

2007

Experimental ternary phase diagrams for ternary systems CHL/PS-MAA/PVPy with diverse MAA contents have been determined by GPC. The presence of MAA in the copolymers gives rise to specific interactions, by hydrogen bond formation between both polymeric components, so strong that the isotherm for the system with the highest MAA content so far studied, CHL/PS-MAA(8%)/PVPy, is representative of a complex coacervation situation. By applying the theoretical background deduced by coupling the Flory-Huggins lattice model to the AET developed for ternary polymeric systems SPP with specific intermolecular interactions (via hydrogen bonds), free energy surfaces for the CHL/PS-MAA/PVPy systems are cons…