Liquid-liquid phase equilibria in polymer solutions and polymer mixtures

The pressure dependence of liquid-liquid equilibria in weakly interacting binary macromolecular systems (homopolymer solutions and blends) will be discussed. The common origin of the separate high-temperature/low-temperature and high-pressure/low-pressure branches of demixing curves will be demonstrated by extending the study into the region of metastable liquid states including the undercooled, overheated and stretched states (i.e. states at negative pressures). The seemingly different response of the UCST-branch of solutions and blends when pressurized (pressure induced mixing for most polymer solutions, pressure induced demixing for most blends) will be explained in terms of the location of a hypercritical point found either at positive (most solutions) or negative pressure (most blends). Further, it is shown that the pressure dependence of demixing of homopolymer solutions and blends may be described using a ‘master-curve’ which, however, is sometimes partly masked by degradation or by vapour-liquid and/or solid-liquid phase transitions. Experimental results demonstrating the extension of liquid-liquid phase boundary curves into the metastable regions will be presented, and the existence of solubility islands in the vicinity of the hypercritical points discussed.     

Influence of solid surface on the compatibility in polymer blends produced in situ

Blends of linear polyurethane and poly(methyl methacrylate) were obtained in situ in the course of simultaneously proceeding reactions of polymerization and polyaddition. The effect of filler nanoparticles on the thermodynamic properties of the systems was investigated. Introduction of filler into the monomer mixture before curing increases the compatibility of final systems, as follows from diminishing thermodynamic interaction parameters. The reverse correlation has been established between the interaction parameter and the fraction of an interfacial region between two phases, its origin being the result of incomplete phase separation. Introducing filler into the reaction system determines simultaneously the increasing compatibility and increasing fraction of an interfacial region, i.e., prevents phase separation. Both effects are due to increasing of the interaction between two polymeric components at the interface with solid and changing conditions of incomplete phase separation in the course of reaction.     

Influence of fibrous and solid fillers on the rheological and surface properties of polymer compositions

The influence of fibrous and solid granulated fillers on the rheological and surface properties of polymer compositions on the basis of poly(vinyl alcohol) and carboxymethyl cellulose is demonstrated. The effect of the concentration of initial polymer solutions and the time of complex formation on the properties of polymer complexes upon the addition of various fillers is revealed.     

Effect of deuterium substitution on the surface interactions in binary polymer mixtures

We have examined the effect of deuterium labeling on surface interactions in mixtures of random olefinic copolymers [C₄H₈]_1−x[C₂H₃(C₂H₅)]_x. Based on surface segregation data we have determined a surface energy difference χ_s between pure blend constituents. In each binary mixture components have different fractions x₁, x₂ of the group C₂H₃(C₂H₅), and one component is labeled by deuterium (dx) while the other is hydrogenous (hx). The mixtures are grouped in four pairs of structurally identical blends with swapped labeled constituent (dx₁/hx₂, hx₁/dx₂). For each pair the surface energy parameter χ_s increases when the component with higher fraction x is deuterated, i.e., χ_s(dx₁/hx₂) > χ_s(hx₁/dx₂) for x₁ > x₂. A similar pattern has been found previously for the bulk interaction parameter χ. This is explained by the solubility parameter formalism aided by the lattice theory relating the surface excess to missing-neighbor effect. χ_s has also an additional contribution, insensitive to deuterium swapping effect, and related to entropically driven surface enrichment in a more stiff blend component with a lower fraction x. Both enthalpic and entropic contributions to χ_s seem to depend on the extent of chemical mismatch between blend components. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2691–2702, 1998     

Managing polymer surface structure using surface active block copolymers in block copolymer mixtures

Surface coatings were prepared from semifluorinated monodendron surface‐active block copolymers (SABC) and a thermoplastic elastomer (TPE) [poly(styrene‐b‐ethylene butylene‐b‐styrene)] by either spin‐casting a bilayer structure or by blending. The surface of these coatings was characterized by contact angle measurements, scanning force microscopy (SFM) and near‐edge X‐ray absorption fine structure (NEXAFS) methods. Both bilayers and blends resulted in very low energy surfaces under the right processing conditions and the liquid crystallinity of the semifluorinated monodendrons gave rise to temporally stable, non‐reconstructing surfaces in water. However for small thicknesses of the SABC top layer or for low SABC content blends, SFM shows islands of the fluorinated block of the SABC and incomplete surface coverage of the TPE, an observation confirmed by NEXAFS analysis. Very high water contact angles were produced by even modest amounts of SABC in either case but to achieve low contact angle hysteresis, it was necessary to produce uniform surface coverage by the SABC. Such uniform coverage can be accomplished by spin casting a top layer of SABC as thin as 60 nm in the bilayer case but at least 10 wt% SABC in TPE combined with drop casting of a hot solutions is needed for the blends to achieve equivalent surface structure and properties. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 411–420, 2004     

Phase equilibria in polymer solutions

A theoretical study of phase equilibria in multicomponent polymer solutions is presented. The treatment is based on the virial expansion of the osmotic pressure. A program for the numerical determination of phase diagrams is worked out and applied to the polystyrene-cyclohexane system. The present approach is compared with the Flory-Huggins theory of polymer solutions, which is shown to represent a special class of approximations in the present treatment.     

Influence of binary surfactant mixtures on the rheology of associative polymer solutions

Hydrophobically modified alkali-soluble emulsion polymers (HASE) are a class of comblike associative polymers that can impart high viscosities to aqueous solutions. The rheology of HASE solutions can be tuned by the addition of surfactants, such as nonylphenol ethoxylates (NP e), where e is the length of the hydrophilic (ethoxylate) chain. While previous studies have considered individual surfactants, our focus here is on binary surfactant mixtures. We find that equimolar NP4-NP12 mixtures significantly enhance the zero-shear viscosities of HASE solutions as compared to equivalent amounts of NP8, especially at high overall surfactant concentrations. Dynamic rheological measurements suggest that the higher viscosities are due to increases in the lifetime of hydrophobic junctions in the polymer-surfactant network. In contrast to the above results, equimolar NP4-NP8 mixtures are rheologically identical to equivalent solutions of NP6. The differences between the two sets of mixtures are further correlated with cloud point measurements and thereby with the overall hydrophilic-lipophilic balance (HLB) of the surfactant system.     

Phase equilibria in chemical reactive fluid mixtures

Downstream processing is a major part of nearly all processes in the chemical industries. Most separation processes in the chemical (and related) industries for fluid mixtures are based on phase equilibrium phenomena. The majority of separation processes can be modelled assuming that chemical reactions are of no (or very minor) importance, i.e., assuming that the overall speciation remains unchanged during a separation process. However, there are also a large number of industrially important processes where the thermodynamic properties are influenced by chemical reactions. The phase equilibrium of chemical reactive mixtures has been a major research area of the author’s group over nearly 40 years. In this contribution, three examples from that research are discussed. The first example deals with the vapour phase dimerisation of carboxylic acids and its consequences on phase equilibrium phenomena and phase equilibrium predictions. The second example deals with the solubility of sour gases (e.g., carbon dioxide and sulfur dioxide) in aqueous solutions of ammonia. That topic has been of interest for many years, e.g., in relation with the gasification and liquefaction of coal and, more recently, with the removal of carbon dioxide from flue gas in the “chilled ammonia process”. The third example deals with phase equilibrium phenomena in aqueous solutions of polyelectrolytes. It deals with the phenomenon of “counter ion condensation” and methods to model the Gibbs free energy of such solutions.     

Membrane equilibria in concentrated polymer solutions

Membrane equilibria in concentrated polymer solutions are investigated. A three-component system (solvent, a polymer and an arbitrary solute) is considered. Starting with the virial expansion of the osmotic pressure, the Gibbs-Duhem equation for the system is integrated and the chemical potentials of the different components are evaluated. From the latter the equilibrium conditions are derived for a variety of experimental situations. The treatment is extended to the study of partition equilibria in gels, using a concentrated polymer solution as a model for the gel.     

Phase equilibria in ternary polymer blends

The phase states and rheological properties of blends of three polymers??polystyrene, poly(methyl methacrylate), and the styrene-acrylonitrile copolymer??in the common solvent chloroform are studied. The phase diagrams are constructed and the positions of spinodals are determined via the method of turbidity points. The effect of the third polymer on the compatibility of the binary blend obeys Prigogine??s rule; that is, it is determined by the solubility of the added polymer in the first two components. The extremum composition dependence of rheological properties of ternary polymer systems in the vicinity of the separation point (the metastable region) is found. Through the method of convex-shell construction, the phase diagrams are calculated.     

Phase equilibria in binary mixtures with monoethyl succinate

Monoethyl succinate was produced by partial esterification of succinic anhydride with ethanol using Amberlyst 15^® as catalyst. After separation and purification, the purity of monoethyl succinate was confirmed by nuclear magnetic resonance (NMR). Vapor pressure of monoethyl succinate was measured and correlated with Antoine equation. Vapor-liquid equilibria at constant temperature were measured for the binary systems ethyl acetate + monoethyl succinate, acetic acid + monoethyl succinate, and water + monoethyl succinate at 323.15 K, and ethanol + monoethyl succinate at 313.15 K. Binary parameters for the NRTL equations were obtained by fitting experimental data using the regression tool in ASPEN Plus^® using the Hayden-O’Connell method for vapor phase fugacities. The model agrees reasonably well with the experimental data.     

Hydrogen bonding in polymer mixtures

The enthalpy–infrared frequency shift correlation for simple acids and bases is extended to study hydrogen bonding in polymer systems. The acidity of a polymer is calibrated by comparing the shifts in hydroxyl absorption frequency of the acidic polymer when mixed with a series of bases with the corresponding spectral shifts of known acids with the same bases. The basicity of a polymer is calibrated by measuring the hydroxyl frequency shifts of known acids when mixed with the basic polymer. For polymers containing carbonyl groups, the shift in carbonyl absorption is also a measure of basicity. The acidity and basicity constants obtained for polymers are in good agreement with the values for small-molecule analogs. The enthalpies of hydrogen bond formation in polymer mixtures are calculated from the acidity or basicity constants.     

Phase equilibria in binary mixtures of propane + acenaphthene

In the near-critical region of propane, phase equilibria of binary mixtures of propane + acenaphthene have been investigated experimentally. Apart from the three-phase equilibrium solid acenaphthene + liquid + vapour, two-phase boundaries liquid + vapour and solid acenaphthene + liquid have been investigated over the entire mole fraction range. The measurements were performed in the temperature region 350–420 K with pressures up to 10 MPa.     

Phase equilibria in binary mixtures of ethane and hexadecane

This paper reports experimental results of a study of the phase behaviour of binary mixtures of ethane + hexadecane. In the near-critical region of ethane liquid + vapour and solid hexadecane + liquid two-phase boundaries have been measured. Also the three-phase equilibrium solid hexadecane + liquid + vapour has been determined experimentally. The experimental data cover the complete mole fraction range. Pressures up to 18 MPa were applied and the investigation was performed in a temperature region from about 260 K up to 450 K.     

Influence of carbonates on the surface charge of a natural solid

Carbonates are the predominating species in natural chemical processes. Thus, understanding the reactions that occur on their surfaces is very important. The aim of this study was to determine the influence of carbonates on the surface charge of a natural soil sample. First, surface properties of a synthesized calcite were determined using a simplified surface speciation model correlated to potentiometric titrations, and then intrinsic acidity constants and pH(znpc) (pH where protonic surface charge is equal to 0) were studied for solids with different percentages of calcite. A strong influence on surface properties of the solids was evidenced even for small additional quantities of calcite.     

Gas-liquid equilibria in mixtures of hydrogen and 1-methylnaphthalene

The gas-liquid equilibria in hydrogen-1-methylnaphthalene mixtures were experimentally determined at four temperatures from 190 to 430°C and seven pressures from 20 to 250 atm. The Henry constant of hydrogen dissolved in 1-methylnaphthalene was evaluated from the data. A flow apparatus was used to produce the saturated equilibrium phases. The data were found to be consistent with the Gibbs-Duhem equation integrated by the method of orthogonal collocation. Vapor pressures of 1-methylnaphthalene required for the thermodynamic consistency calculations were determined with the same apparatus. Comparison of the new mixture equilibrium data is made with the correlations of Chao and Seader (1961) and Grayson and Streed (1963).     

Thermochemical characteristics of nicotinamide protolytic equilibria in water-dimethylsulfoxide mixtures

The heat effects of nicotinamide protonation in water-dimethylsulfoxide (DMSO) solutions over the concentration range 0–0.75 DMSO mole fractions were determined calorimetrically at 25.00 ± 0.01°C and ionic strength 0.25 (NaClO₄). Changes in the enthalpy of protonation as the content of DMSO increased were found to be described by an S-shaped curve. This curve shape was caused by the dynamics of reagent solvation contributions as the concentration of DMSO grew with the predominance of the nicotinamide solvation contribution.     

Adsorption equilibria of binary gas mixtures on graphitized carbon black

Adsorption equilibria for binary gas mixtures (methane-carbon dioxide, methane-ethane, and carbon dioxide-ethane) on the graphitized carbon black STH-2 were measured by the open flow method at 293.2 K. The experimental pressure range was (0 to 1.6) MPa. The extended Langmuir (EL) model and the ideal adsorption solution theory (IAST) have been adopted to predict the equilibria of binary gas mixtures. The results indicate that gas mixtures adsorbed on the homogeneous surface of STH-2 exhibit the nonideal behavior, which is mainly induced by adsorbate-adsorbate interactions. The real adsorption solution theory (RAST) has been used to analyze the property of the adsorbed mixtures. The activity coefficients have been correlated with the Wilson equation. The investigation demonstrates that the nonideality of adsorbed phase is completely dissimilar with the bulk liquid phase. The adsorption of the heavier component would benefit the adsorption of the lighter component.