Search results for "Solution theory"
showing 10 items of 90 documents
Pullulan and dextran: uncommon composition dependent Flory-Huggins interaction parameters of their aqueous solutions.
2008
Vapor pressure measurements were performed for aqueous solutions of pullulan ( M w 280 kg/mol) and dextran ( M w 60 and 2100 kg/mol, respectively) at 25, 37.5, and 50 degrees C. The Flory-Huggins interaction parameters obtained from these measurements, plus information on dilute solutions taken from the literature, show that water is a better solvent for pullulan than for dextran. Furthermore, they evince uncommon composition dependencies, including the concurrent appearance of two extrema, a minimum at moderate polymer concentration and a maximum at high polymer concentration. To model these findings, a previously established approach, subdividing the mixing process into two clearly separa…
Modelling the influence of nanoparticles in the phase behaviour of an epoxy/polystyrene mixture
2007
Abstract The cloud point temperatures of four series of epoxy/polystyrene blends have been experimentally determined as a function of polymer mass and system composition. The phase diagrams show an UCST behaviour, increasing incompatibility as the molar mass increases. The Flory–Huggins theory with a concentration-dependent interaction parameter has been developed to study the compatibility of two polymers in presence of spherical nanoparticles. This theory has been first compared with the experimental cloud point curve in absence of nanoparticles, and secondly it has been used to predict the thermodynamic behaviour in presence of different volume fraction of nanoparticles. Nanoparticles co…
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…
Pressure Effects on the Thermodynamics oftrans-Decahydronaphthalene/Polystyrene Polymer Solutions: Application of the Sanchez-Lacombe Lattice Fluid T…
2003
The cloud-point temperatures (T-cl's) of trans-decahydronaphthalene(TD)/polystyrene (PS, (M) over bar (w) = 270 000) solutions were determined by light scattering measurements over a range of temperatures (1-16degreesC), pressures (100-900 bar), and compositions (4.2-21.6 vol.-% polymer). The system phase separates upon cooling and T-cl was found to increase with rising pressure for constant composition. In the absence of special effects, this finding indicates positive excess volume for the mixing. Special attention was paid to the demixing temperatures as a function of pressure for different polymer solutions and the plots in the T-phi plane (where phi signifies volume fractions). The clo…
Making Floryr–Huggins Practical: Thermodynamics of Polymer-Containing Mixtures
2010
The theoretical part of this article demonstrates how the original Flory–Huggins theory can be extended to describe the thermodynamic behavior of polymer-containing mixtures quantitatively. This progress is achieved by accounting for two features of macromolecules that the original approach ignores: the effects of chain connectivity in the case of dilute solutions, and the ability of polymer coils to change their spatial extension in response to alterations in their molecular environment. In the general case, this approach leads to composition-dependent interaction parameters, which can for most binary systems be described by means of two physically meaningful parameters; systems involving …
Synthesis, crystal structure and magnetic properties of the spin crossover system [Fe(pq)3]2+
2008
Abstract Three new compounds formulated (ClO4)2[Fe(pq)3] (1), (BF4)2[Fe(pq)3] · EtOH (2) and {(ClO4)[MnCr(C2O4)3][Fe(pq)2(H2O)2]} (3), where pq is 2,2′-pyridylquinoline, have been synthesised and characterised. Despite the different crystal packing exhibited by 1 and 2, the cationic species [Fe(pq)3]2+ are structurally quite similar. At 293 K, the Fe–N bond lengths are characteristic of the iron(II) in the high-spin state. In contrast to 1, 2 undergoes a continuous spin transition. Indeed, at 95 K its structure experiences a noticeable change in the Fe–N bonds and angles, i.e. the Fe–N bonds shorten by 0.194 A on the average. The magnetic behaviour confirms that 1 is fully high-spin in the …
Thermodynamics of transfer of polar additives from the aqueous to the dodecylsurfactant micellar phases
1990
The enthalpies of transfer from water to aqueous surfactant solutions, ΔH(W→W+S), of polar additives have been determined as a function of the surfactant concentration at fixed additive concentration. The surfactants used are sodium dodecylsulfate (NaDS), dodecyltrimethylammonium bromide and dodecyldimethylamine oxide (DDAO). The additives used are iso-butanol t-butanol, butoxyethanol, phenol, benzene, tributylphosphine oxide (TBPO), octyldimethylphosphine oxide (ODPO), octydimethylamine oxide (ODAO), DDAO and NaDS. A maximum was observed in the plots of ΔH(W→W+S) vs. fsms curves for ODPO and ODAO in NaDS while a small minimum was observed for TBPO. The experimental data are rationalized on…
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…
Grafted polymer layers under shear: A Monte Carlo simulation
1993
Endgrafted polymers at surfaces exposed to a shear flow are modeled by a nonequilibrium Monte Carlo method where the jump rate of effective monomers to neighboring lattice sites against the flow direction is smaller than in the flow direction, assuming that this difference in jump rates is proportional to the local velocity of the flowing fluid. In the dilute case of isolated chains, the velocity profile is assumed linearly increasing with the distance from the surface, while for the case of polymer brushes the screening of the velocity field is calculated using a parabolic density profile for the brush whose height is determined self‐consistently. Linear dimensions of isolated chains are o…
Thermodynamics of Phase Behavior in PEO/P(EO-b-DMS) Homopolymer and Block Co-Oligomer Mixtures under Pressure
2003
The cloud-point temperatures (T-cl's) of poly(ethylene oxide) (PEO) and poly(ethylene oxide)-block-polydimethylsiloxane (P(EO-b-DMS)) homopolymer and block-oligomer mixtures were determined by turbidity measurements over a range of temperatures (105 to 130degrees), pressures (1 to 800 bar), and compositions (10-40 wt.-% PEO). The system phase separates upon cooling and T-cl was found to decrease with an increase in pressure for a constant composition. In the absence of special effects, this finding indicates negative excess volumes. Special attention was paid to the demixing temperatures as a function of the pressure for the different polymer mixtures and the plots in the T-phi plane (where…