Comparative studies on the effects of casting solvent on physico‐chemical and gas transport properties of dense polysulfone membrane used for CO2/CH4 separation

The effects of casting solvents on the physico–chemical and transport properties of polysulfone membranes were investigated. Comparative analysis of the properties of membranes prepared from a new solvent (diethylene glycol dimethyether, DEG) and other commonly used solvents (1‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, dimethyl sulfoxide and N,N‐dimethylformamide) were performed using gas permeation, X‐ray diffraction, scanning electron microscopy, thermogravimetric, and Fourier transform infrared spectroscopy analyses. The degree of polymer–solvent interaction was evaluated using the solvent molar volume, and Hansen and Flory–Huggins parameters. Membrane prepared from DEG displayed a relatively higher permeability of 29.08 barrer and CO₂/CH₄ selectivity of 23.12 compared to membranes prepared from other solvents. This improved performance was attributed to the better interaction between the DEG solvent and polysulfone than other solvents that were considered. DEG has the highest molar volume of 142.280 cm³/mol and the lowest Flory–Huggins parameter of 0.129. Thus a thorough evaluation of polymer–solvent interaction is very crucial in preparing membranes with optimum performance. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42205.     

Use of inverse gas chromatography to quantify interactions in amine cured epoxy resins

Flory–Huggins interaction parameters, λ, were determined for a series of probes in an amine cured epoxy resin matrix (433–493 K) and its precursors (324–363 K) by inverse gas chromatography (IGC). Hildebrand–Scatchard theory was combined with Flory–Huggins theory in order to estimate infinte dilution solubility parameters (δ₂) for the matrix and its precursors at 298 K. It was shown that the value of the solubility parameter for the cured resin matrix lies between those of its precursors. Compared to the majority of published work, an unusual aspect of this application of IGC is that solubility parameters have been determined when the stationery phases are (i) small molecules and (ii) a highly crosslinked polymer. Moreover, all possible attempts have been made to ensure equilibrium conditions between probe and stationary phase, and compensation for asymmetry of peak profile has been applied in determining δ₂. The solubility parameters estimated by IGC are in good agreement with those calculated by other methods.     

Modeling solubility of gases in semicrystalline polyethylene

An absorption model of gases in semicrystalline polymer was built that was based on the activity coefficient theory in polymer solution and associated with crystallinity dependent on temperature. The solubility of ethylene, isopentane, and n‐hexane in three types of polyethylene (PE) were obtained by the use of a pressure‐decay method at temperatures of 333–363 K and pressures of up to 2 MPa, 80–300 KPa, and 19–100 KPa, respectively. Experimental data from three gases in each PE sample were used for the single‐parameter fitting, and fitting error was within about 12%. It was found that a single parameter was merely dependent on the properties of PE used. It was shown that, unlike with the Flory–Huggins model and the UNIFAC–M‐H method, correlation between the crystallinity of the semicrystalline polymer and temperature had to be taken into account in order for the solubility data of alkane, olefin, and aromatic hydrocarbons in polyethylene to fit well, especially in the temperature range near the melting point of the polymer. The four free‐energy contributions to the total gas activity were experimentally determined to be about 47%–60% combined, the free‐volume contribution about 12%–25%, and the elastic effect about 22%–35%, but the interactional contribution was zero. The contributions changed with the size of the gas molecules. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1737–1744, 2007     

Dissolution of waste plastics in biodiesel

The dissolution behavior of polystyrene (PS) and low‐density polyethylene (LDPE) in biodiesel was investigated with an eye towards developing methods to dispose waste plastics by burning them with fuel. To complement and guide the experimental investigations, molecular dynamics simulations were performed to calculate solubility parameters, cohesive energy densities, Flory‐Huggins χ parameters and phase diagrams of the target systems. Dissolution kinetics of PS and LDPE in methyl esters was monitored by gravimetry, from which parameters such as dissolution rates, activation energies, and scaling indices were estimated. The shear viscosity of the polymer solutions was measured to ascertain their suitability as fuel mixtures. The dissolution of PS in biodiesel appears to be controlled by the diffusion of polymer chains through a boundary layer adjacent to the polymer/solvent interface. Taken together, the experimental and modeling studies provide a predictive toolbox to design biodiesels of different compositions that will dissolve commodity polymers such as PS and LDPE to be used as fuels in engines. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Bulk polymer/solvent interactions for polyethylene and EVA copolymers,below their melting temperatures

In this work, the Flory–Huggins parameters corresponding to the amorphous phase of a polyethylene (PE) and two ethylene–vinyl acetate (EVA) copolymers (with 18 and 33 % vinyl acetate content, respectively) samples, with different solvents have been determined below the melting temperature of the polymers, in order to quantify the bulk interactions of these polymer/solvent systems. The employed solvents were a dispersion solvent (cyclohexane), a polar solvent (vinyl acetate) and an association solvent (methanol). Initially, the inverse gas chromatography measurements allowed obtaining the retention volumes, activity coefficients and overall Flory–Huggins parameters of every polymer/solvent system. According to these parameters, in all cases, the more compatible solvent was cyclohexane, so it was selected as the probe to calculate the percentages of crystallinity at room temperature, whose results were in agreement the literature data (35 % for PE, 29 % for EVA18, and 12 % for EVA33). The percentage of crystallinity allowed determining the amorphous Flory–Huggins parameters which are the ones which take into account just the bulk interactions in a polymer/solvent mixture. The Flory–Huggins parameter results show that, to accurately study the vapor–liquid equilibrium between a polymer and a solvent (bulk interactions), when the range of studied temperatures is below the melting point of the polymer, it is crucial to calculate the amorphous contribution (χ _amorphous) on the overall Flory–Huggins parameter. In the case of this study, the lower the vinyl acetate content (higher crystallinity), the higher the difference between the overall and amorphous Flory–Huggins parameters is. Analyzing the interactions between the three polymeric materials and the solvents it can be noticed that, for the most compatible solvent (cyclohexane), χ _amorphous represents the less contribution, or the highest correction, to the overall Flory–Huggins parameter (around 50 % for PE and EVA18, and 79 % for EVA33, the less crystalline polymer).     

Solubility of 1‐hexene in LLDPE synthesized by (2‐MeInd)2ZrCl2/MAO and by Mg(OEt)2/DIBP/TiCl4–TEA

The solubility of 1‐hexene was measured for linear low‐density polyethylenes (LLDPEs) produced over a heterogeneous Ziegler–Natta catalyst, Mg(OEt)₂/DIBP/TiCl₄–TEA (ZN), and over a homogeneous metallocene catalyst, (2‐MeInd)_zZrCl₂–MAO (MT). The 1‐hexene solubility in LLDPEs was well represented by the Flory–Huggins equation with a constant value of χ. ZN–LLDPEs dissolved a larger amount of 1‐hexene and thus showed a lower value of χ compared to MT–LLDPEs. The Flory–Huggins interaction parameter χ, or the solubility of 1‐hexene at a given temperature and pressure, was suggested as a sensitive measure for the composition distribution of LLDPEs. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1566–1571, 2002; DOI 10.1002/app.10418     

MesoDyn modeling study of the phase morphologies of miktoarm poly(ethylene oxide)‐b‐poly(methyl methacrylate) copolymers doped with nanoparticles

Earlier studies have shown that poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blocks are compatible at 270 and 298 K, and that their Flory–Huggins interaction parameters have the same blending ratio dependence at both temperatures. At a much higher temperature (400 K), the behavior of PEO/PMMA blends is strikingly different as both components become incompatible, while the Flory–Huggins parameters are low. Here we investigate the effect of doping with nanoparticles on the degree of incompatibility of twelve miktoarm PEO‐b‐PMMA copolymers at 400 K. Since PEO tends to be semicrystalline and long chains aggregate easily, PEO‐rich and long‐chain copolymer blends feature the highest degree of incompatibility for all nanoparticle arrangements and present cubic phase morphologies. In addition, the largest nanoparticles can reinforce the microscopic phase separation of all PEO‐b‐PMMA copolymers. This shows that the main factor affecting the phase morphology is the size of the nanoparticles. Also, only the asymmetric Da3‐type PEO‐rich copolymers show a hexagonal cylindrical phase morphology, which illustrates the effect induced by the nanoparticles on the microscopic phase separation changes of the PEO‐b‐PMMA copolymers. These induced effects are also related to the composition and molecular architecture of the copolymers. © 2013 Society of Chemical Industry     

Liquid–liquid phase separation in polysulfone/polyethersulfone/N‐methyl‐2‐ pyrrolidone/water quaternary system

To construct a phase diagram of the polysulfone (PSF)/polyethersulfone (PES)/N‐methyl‐2‐pyrrolidone (NMP)/water quaternary system, cloud point measurements were carried out by a titration method. The miscible region in the PSF/PES/NMP/water quaternary system was narrow compared to the PSF/NMP/water and PES/NMP/water ternary systems. The binary interaction parameters between PSF and PES were estimated by water sorption experiments. The calculated phase diagram based on the Flory–Huggins theory fit the experimental cloud points well. In addition to the usual polymer–liquid phase separation, polymer–polymer phase separation, which resulted in a PSF‐rich phase and a PES‐rich phase, was observed with the addition of a small amount of nonsolvent. The boundary separating these two modes of phase separation could be well described and predicted from the calculated phase diagrams with the estimated binary interaction parameters of the components. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2113–2123, 1999     

Compatibility between Drugs and Polymer in Nanoparticles Produced by the Miniemulsion-Solvent Evaporation Technique

Encapsulation of poorly soluble drugs in polymer nanoparticles is a common strategy to increase bioavailability of drugs. The miniemulsion-solvent evaporation technique is widely used for encapsulating drugs in polymer nanoparticles because it is a versatile process, allowing many drug–polymer pair combinations. However, above a critical concentration of drug, which depends on the drug and polymer, nanoparticles tend to precipitate. Herein, the importance of drug solubility and miscibility in the polymer phase for selecting the optimal polymer matrix is investigated. Ibuprofen, naproxen methyl ester, and naproxen, as models for poorly soluble drugs, are encapsulated with various loadings in polycaprolactone nanoparticles by the miniemulsion-solvent evaporation method. The miscibility between drug and polymer is estimated by calculating Flory–Huggins interaction parameters (χ) from differential scanning calorimetry measurements and calculating the difference in Hansen solubility parameter of drugs and polymer. Both values can be used for determining the feasibility of the drug encapsulation in polymer nanoparticles.     

Computer simulation of phase separation in binary polymer mixtures

Phase separation of binary polymer mixtures was numerically simulated by solving the time-dependent Langevin equation with Flory–Huggins free energy in two dimensions by using a finite difference method. Spinodal decomposition following structure coarsening was calculated. Simulation results were verified by evaluating the evolution of the wave number obtained from the calculated phase structure by Fourier transformation. Then, computer experiments were carried out to investigate effects of volume fraction and polymer characters, the number of segments, and solubility parameter on morphology. The phase separation time, when the phase began to separate, decreased with deviating volume fraction from 0.5 and with decreasing number of segments and difference between solubility parameters. The difference between solubility parameters had the largest influence on the phase separation time among them and had two effects, the acceleration of phase separation and the restriction of structure coarsening. © 1995 John Wiley & Sons, Inc.     

Turbidimetric and intrinsic viscosity study of EVA copolymer–solvent systems

Both Hansen solubility parameter and Flory–Huggins interaction parameter of two EVA [Poly(ethylene-co-vinyl acetate)] copolymers with different vinyl acetate content have been obtained by means of intrinsic viscosity measurements. To calculate this last parameter it was also necessary to determine the theta solvent at different temperatures of the two EVA copolymers with turbidimetric measurements. The results indicate that the vinyl acetate content is a variable which influences the composition of the theta solvent and Flory–Huggins parameter (the higher the vinyl acetate content, the lower the Flory–Huggins parameter), although its influence over the Hansen solubility parameter is almost negligible.     

Multiparameter solution model and evaluation of polymer–polymer miscibility using inverse gas chromatography data

Inverse gas chromatography (IGC) has been widely used to determine the Flory–Huggins parameters, χ, between solutes (probes) and polymers. This study correlated the Flory–Huggins parameter data using a multiparameter model, which included dispersion, polarity, acidity, and basicity components. The parameters of poly(ε‐caprolactone) (PCL) and polyepichlorohydrin (PECH) were calculated from IGC data using a series of probes. The parameters of the polymers were used to evaluate mutual miscibility between PCL and PECH. The results predicted miscibility in agreement with the conclusion of an IGC study using blends of PCL and PECH. A method to estimate the confidence interval of polymer parameters was proposed. The anomalous solubility parameter of polymer mixtures previously reported was also explained using this model. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermodynamic interactions of solvents with styrene–butadiene–styrene triblock copolymers

Fundamental thermodynamic interaction data for various solvents with two styrene–butadiene–styrene triblock copolymers (Kraton D-1101 and Kraton D-1300X) have been collected by the use of inverse gas chromatography at infinite dilution. Experimental results are presented for nine D-1101/solvent systems and nine D-1300X/solvent systems at 308, 328. and 348 K. Weight-fraction activity coefficients and Flory–Huggins χ interaction parameters have been calculated from the retention volumes. The χ parameter is used as a measure of the strength of interaction and therefore as a guide in the prediction of polymer–solvent compatibility. In addition, partial molar heats of mixing, ΔH_m^∞, and heats of solution, ΔH_s, were determined. The Hildebrand–Scatchard solubility theory was combined with the Flory theory in order to estimate the solubility parameter of the thermoplastic rubbers at the three different temperatures.     

Thermodynamic interactions of EVA copolymer‐solvent systems by inverse gas chromatography measurements

The solubility parameter and the Flory–Huggins interaction parameter of two EVA (ethylene–vinyl acetate) copolymers, each one with different vinyl acetate content, are calculated by using inverse gas chromatography technique. The influence of the vinyl acetate percentage is analyzed and indicates that the polymer–solvent interactions are stronger in the case of the copolymer with the highest vinyl acetate percentage. The results also point to the fact that the most favorable solvents for the studied materials are the aromatic‐type ones. Finally, from the calculated values of the polymer solubility parameter (16.3 MPa^0.5 for EVA 460 and 15.1 MPa^0.5 for EVA410, at 50°C), it can be noticed that the solubility parameter of the EVA copolymer with the largest vinyl acetate content is the closest to the solubility parameter of pure vinyl acetate. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Ternary phase equilibria of polystyrene with a second polymer and a solvent

Phase diagrams including tie lines for nine ternary solvent–polymer–polymer systems have been obtained using size exclusion chromatography. The systems studied were toluene–polystyrene (PS)–isoprene rubber (IR), toluene–PS–butadiene rubber (BR), cyclohexane–PS–BR, tetrahydrofuran(THF)–PS–poly(methyl methacrylate) (PMMA), and THF–PS–poly(butyl methacrylate) (PBMA) at temperatures between 30 and 75°C. The results indicate PS-PMMA is less compatible than PS-PBMA in the presence of THF. Also, the combination of trans- and 3,4–IR-PS is less compatible than cis–IR-PS in the presence of toluene. The original Flory–Huggins model for ternary systems has been modified to account for the concentration dependence of the interaction parameters. The modified Flory–Huggins model consists of two interaction parameters per binary. Using this model, six parameters have been regressed for each of the experimental systems studied. Although the parameters are not physically meaningful, the model and the parameters obtained using it are useful for correlating the experimental phase diagrams. The results obtained using the modified six parameter model are shown to be superior to those obtained using the original three parameter model. © 1993 John Wiley & Sons, Inc.     

A study of some equation‐of‐state parameters of poly(methylhydrosiloxane‐co‐dimethylsiloxane) with some solvents by gas chromatography

Trace amount of methyl acetate, ethyl acetate, tert‐butyl acetate, pentane, hexane, and heptane were passed through the chromatographic column loaded with poly(methylhydrosiloxane‐co‐dimethylsiloxane) coated on Chromosorb W. The retention diagrams of the solvents on the copolymer were plotted by means of specific retention volumes at temperatures between 40 and 80°C by inverse gas chromatography technique. In this study, some thermodynamic interaction parameters such as Flory–Huggins polymer–solvent interaction parameter, equation‐of‐state polymer–solvent interaction parameter, effective exchange energy parameter, and weight fraction activity coefficients at infinite dilution of the solvent were determined. Then, the exchange enthalpy parameter and entropy parameter were determined by using a relation for the enthalpy interaction parameter of the equation‐of‐state theory, which is arranged for the inverse gas chromatography conditions. Later, the partial molar heat of sorption and the partial molar heat of mixing were obtained. The solubility parameter of this copolymer was determined as 6.64 (cal/cm³)^1/2 at room temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1627–1631, 2007     

Predicting the Solubility of Solid Phenanthrene: A Combined Molecular Simulation and Group Contribution Approach

A simple correction to the infinite dilution activity coefficient computed via molecular simulation for a nonelectrolyte solid solute in solution is proposed. The methodology adopts the concept that the activity coefficient may be fundamentally interpreted as a product of a residual and combinatorial term. The residual contribution is assumed to be insensitive to concentration, and the combinatorial term is modeled using the athermal Flory–Huggins theory. The proposed method uses only properties for the solute computed at infinite dilution to estimate solution‐phase properties at finite concentrations. Properties of the pure solid solute are estimated using the group contribution method of Gani and coworkers, allowing for efficient blind solubility predictions to be made. The method is applied to predict the solubility of solid phenanthrene in 17 different solvents. For all cases, the combinatorial correction lowers the predicted solubility relative to the infinite dilution approximation, and in general, improves agreement with experiment. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2647–2661, 2013     

Thermodynamic interactions of a copolyester of bisphenol A with terephthalic acid and isophthalic acid with some solvents

The retention diagrams of n‐octane, n‐nonane, n‐decane, n‐butyl acetate, isobutyl acetate, and isoamyl acetate on the polyarylate Ardel D‐100, a copolyester of bisphenol A with terephthalic acid and isophthalic acid, were plotted at temperatures between 120 and 260°C by an inverse gas chromatography technique. The glass‐transition temperature of the copolymer was determined to be 190°C from the discontinuity of these diagrams. The retention diagrams of benzene, ethyl benzene, n‐propyl benzene, isopropyl benzene, and chlorobenzene were also plotted between 200 and 260°C. The specific retention volume, weight fraction activity coefficient, Flory–Huggins polymer–solvent interaction parameter, hard‐core polymer–solvent interaction parameter, and effective exchange energy parameter were determined for the studied solvents. The parameters suggest that the studied aromatic hydrocarbons and aliphatic esters are moderately good solvents and chlorobenzene is a very good solvent for this copolyester, but the n‐alkanes are very poor solvents. The solubility parameter of this copolymer was determined to be 11.6 (cal/cm³)^1/2 at room temperature by extrapolation of the values of the solubility parameters from the studied temperatures to 25°C. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2365–2368, 2005     

Vapor–liquid equilibria for benzene/polybutadiene and cyclohexane/polybutadiene systems at 333, 355, and 373 K using gas chromatography

A perturbation chromatography apparatus has been designed and constructed for determining the vapor–liquid equilibrium between a two-component (solvent/helium) vapor phase and a two-component (polymer/solvent) liquid phase. The apparatus performed very well, giving reproducible and reliable results that agree with independent, previously reported studies. All tests of the equipment indicated that it was successful in meeting the conditions of low column pressure drop, small perturbations, and slow flow rate that are required for perturbation chromatography. Binary polymer/solvent data were obtained for polybutadiene (PBD)/benzene or polybutadiene/cyclohexane systems at solvent partial pressures to 40 kPa and for n-hexane at infinite dilution, all at the three temperatures of 333.15, 355.00, and 373.15 K. The experimental data for each system can be represented within experimental error by the Flory–Huggins polymer solution theory using a single binary interaction parameter that is independent of temperature and concentration.     

Determination of the Flory-Huggins interaction parameter of polystyrene—polybutadiene blends by thermal analysis

Blends of polystyrene (PS) and polybutadiene (PBD) were investigated by differential scanning calorimetry. From the phase composition diagram of the blends, it appears that PBD dissolves more in the PS-rich phase than does PS in the PBD-rich phase. This result is consistent with the behavior of the specific heat increment at the glass transition temperature of PBD in the PS-PBD blends. From the measured glass transition temperature and apparent weight fractions of PS and PBD dissolved in each phase, values of the Flory—Huggins polymer—polymer interaction parameter (χ₁₂) were determined to be 0.0040–0.0102 depending on the composition and molecular weights of the PS and the PBD. No significant difference in χ₁₂ was observed among the blending methods. The composition-dependent value of the Flory—Huggins polymer—polymer interaction parameter was found to be similar to the value of χ₁₂. The polymer—polymer interaction parameter appears to depend on the degree of polymerization of the polymers as well as on the apparent volume fraction of the polymers dissolved in each phase. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1301–1308, 1997