Sorption and transport of inert gases in PVF2/PMMA blends

Sorption and transport of several inert gases (He, Ar, N₂, and CH₄) in miscible blends of PMMA and PVF₂ are reported as a function of pressure at 35°C. For each gas, the permeabilities are independent of pressure for all blend compositions. Sorption isotherms are linear for rubbery compositions (PVF₂-rich) and nonlinear for glassy compositions (PMMA-rich) as expected. In contrast to CO₂, these gases do not plasticize any of these materials. The data are analyzed using appropriate models for sorption and transport, and the parameters are correlated in terms of blend composition and molecular characteristics of the gases. Effects of crystallinity are discussed. Sorption behavior is compared with poly(methyl acrylate) and poly(vinyl acetate).     

Gas sorption in poly(butylene terephthalate). II. Influence of crystallinity and molecular orientation

Sorption measurements of CO₂, Ne, and Ar in poly(butylene terephthalate) (PBTP) films were studied by the gravimetric method with a recording microbalance at 298 K in the pressure range of 1–22 bar. The semicrystalline samples were annealed and oriented at 373 K. The sorption isotherms for CO₂ in PBTP films in the glassy state can be well described by the dual-sorption theory. The nonlinear sorption behavior of Ne and Ar can be satisfactorily analyzed using the sorption model developed for noble gases in PBTP. For the undrawn annealed films, it has been found that the increment of crystallinity leads to the reduction of the equilibrium gas concentration. For the oriented films, the gas concentration rises with increasing draw ratio. It appears that the sorption behavior for all tested gases in the oriented PBTP films does not depend on the changes of crystallinity and crystalline morphology under extension. The difference of the critical pressure p^* indicates the change in the size of the frozen microvoids existing in the noncrystalline phase, which was altered by annealing and drawing. © 1993 John Wiley & Sons, Inc.     

Gas transport in polymer membrane at temperatures above and below glass transition point

The processes of gas sorption and permeation in a polymer membrane at temperatures above and below the glass-transition point were examined using poly-4-methylpentene-1 (glass-transition temperature reported to be 40°C) as a membrane material. The permeabilities to O₂ and N₂ were independent of applied gas pressure at every temperature; the mean permeability coefficient to CO₂ increased with increasing gas pressure. The logarithm of the mean permeability coefficient to CO₂ increased linearly with gas pressure due to the plasticization effect induced by sorbed CO₂. From the sorption isotherms for CO₂ at 20 and 30°C it was judged that the glass transition was brought about by sorbed CO₂ at temperatures below the glass-transition point of the pure polymer. © 1994 John Wiley & Sons, Inc.     

Sorption of CO2/CH4 mixtures in poly(phenylene oxide) and a carboxylated derivative

The sorption of CO₂ and CH₄ and their binary mixtures in poly(phenlene oxide) (PPO) and its carboxylated derivative (CPPO) is reported. All mixed gas data are accurately described by the dual model sorption model, which predicts mixed gas sorption on the basis of pure gas sorption parameters. The present paper extends the mixed gas sorption data base to include polymers having a wide range of permeabilities and chemical structures. The confirmed accuracy of the model for these systems provides strong support for applying the mixed gas dual mode sorption model to any gas/polymer system. A numerical simulation of the mixed gas sorption experiment is also presented which greatly simplifies the experimental procedures used to maintain the partial pressure of one of the gas components at a constant value over the course of a sorption isotherm measurement. By establishing the appropriate amounts of each gas component which are added to the polymer sample chamber of the sorption cell, the mixed gas apparatus simulator (MIGAS) can be used to maintain the partial pressure of one of the components to within 1% of the desired value.     

Gas permeation of polymer blends. IV. Poly(vinyl chloride) (PVC)/acrylonitrile–butadiene–styrene (ABS) terpolymer

The transport behavior of He, O₂, N₂, and CO₂ in membranes of poly(vinyl chloride) (PVC)/acrylonitrile–butadiene–styrene (ABS) blends has been studied at 25°C. The blends were further characterized by dynamic mechanical measurements, differential thermal analysis (DTA), density measurements, and x-ray diffraction. The equilibrium sorption of CO₂ and N₂ was measured directly at atmospheric pressure using an electromicrobalance and compared with sorption values obtained as P/D ratios from permeation measurements. The rates of permeation (P) and diffusion (D) increase with increasing ABS content in the blends. The P and D values are not additive, and only slight indications of phase inversion in the blends are observed at 5–10 wt-% ABS in the blends. Experimental densities of the blends are higher than calculated densities assuming volume additivity. The data are interpreted to mean that the PVC/ABS blends form a two-phase system composed of a soft polybutadiene (rubber) phase and a rigid PVC/styrene–acrylonitrile copolymer (SAN) phase of mutually compatible components. DTA and dynamic mechanical measurements also show a two-phase system. Sorption values of CO₂ and N₂ by equilibrium sorption measurements increase with increasing ABS content in the blends without the large fluctuations which have been observed for the sorption values obtained from the time lag method. Comparison of the two types of sorption values (from direct measurements and from P/D ratios) show larger deviations for CO₂ than for N₂. This suggests that the time lag method is not valid for permeants with polar character in heterogeneous two-phase systems where chemical immobilizing effect on the permeant molecules occurs.     

Sorption and interactions of gases in polyaniline powders of different doping levels

Sorption of different gases (N₂, O₂, CH₄, and CO₂) were performed on as-synthesized polyemeraldine base, on HCl 4M doped, on NH₄OH 1M undoped, and on HCl 10^?2M redoped powders. In the pressure range examined (100–700 torr), linear sorption isotherms were observed for N₂ and correspond to an ordinary dissolution in Henry's law state. Concerning O₂, CH₄, and CO₂, nonlinear isotherms were evidenced and could be described by the dualmode sorption mechanism proposed for glassy polymers, which consists of the combination of a Henry's type dissolution with a Langmuir sorption in unrelaxed gaps between macromolecular chains. Specific interactions between polyaniline (PANi) and O₂, CH₄, and CO₂, were studied. Gas permeation experiments were performed by using different upstream pressures, P₁, and have confirmed the dissolution of Henry's type for N₂ and the dualmode mechanism for O₂ and CO₂. From the fits of the sorption isotherms, gas solubilities of N₂, O₂, CH₄, and CO₂ were calculated for three different gas pressures and analyzed in terms of gas separation for permeation experiments. © 1995 John Wiley & Sons, Inc.     

Sorption and transport of CO2 in PVF2/PMMA Blends

The sorption and transport of CO₂ in miscible PVF₂/PMMA blends are reported at 35°C as a function of pressure from 1 to 25 atm. Significant plasticization by CO₂ is evident for all blend compositions. This effect induced further crystallization of PVF₂ for some blends, altered the shape of sorption isotherms for blends with a glassy amorphous phase, and resulted in permeabilities which increased with pressure for all compositions. Modified sorption and transport models to account for plasticization are used to analyze the data. The effect of crystallinity on observed behavior has been accounted for using approximate models to allow comparison of responses of sorption and transport with blend composition.     

CO2, N2 gas sorption and permeation behavior of chitosan membrane

The sorption equilibria for CO₂ and N₂ in dry chitosan membrane at 20 and 30 ‡C were measured by a pressure decay method. The steady-state permeation rates for CO₂ and N₂ in dry and wet (swollen with water vapor) chitosan membranes at 20 and 30 ‡C were measured by a variable volume method. The sorption equilibrium for N₂ obeyed Henry’s law, whereas that for CO₂ was described apparently by a dual-mode sorption model. This non-linear sorption equilibrium for CO₂ could be interpreted by the interaction of sorbed CO₂ with the chitosan matrix expressed as a reversible reaction. The logarithm of the mean permeability coefficient for CO₂ in dry chitosan membrane increased linearly with upstream gas pressure. A linear increase of the logarithmic mean permeability coefficient for CO₂ with the pressure could be interpreted in terms of a modified free-volume model. The mean per-meability coefficient for N₂ in dry chitosan membrane only slightly increased with upstream gas pressure. The per-meabilities for CO₂ and N₂ in wet chitosan membrane increased by 15 to 17 times and 11 to 15 times, respectively, as compared to those in the dry membrane.     

In situ FTIR measurement of carbon dioxide sorption into poly(ethylene terephthalate) at elevated pressures

Knowledge of the sorption rate and solubility of CO₂ in polymers are of great importance for developing technologies utilizing high‐pressure and supercritical CO₂‐assisted processes. Many conventional techniques for measuring gas sorption have inherent complications when used at elevated pressures. In this work, we demonstrate the use of near‐IR spectroscopy as an accurate method to measure CO₂ sorption kinetics and solubility in PET at elevated pressures. Sorption kinetics and solubility are measured at 0, 28, and 50°C between pressures of 57.1 and 175.2 atm. Both initially amorphous and initially partially crystalline samples of PET are studied, and the effects of the initial crystallinity are determined. In addition, the effects of CO₂ processing on the final crystallinities of our samples are measured. Crystallization was induced in PET at 28 and 50°C over the range of pressures studied. However, at 0°C, no detectable crystallization occurred in PET, even in the presence of high pressures of CO₂. The method demonstrated in this work could easily be extended to directly measure CO₂ sorption in other polymers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 764–775, 2000     

Low-pressure CO2 sorption in poly(vinyl benzoate) conditioned to high-pressure CO2

Sorption of CO₂ in poly(vinyl benzoate) was gravimetrically measured at pressures up to 1 atm. Sorption isotherms were determined above and below the glass transition temperature T_g from 5 to 85°C. The isotherms were analyzed by the dual-mode sorption model assuming that the plasticizing effect of sorbed CO₂ is negligible at this pressure range. The solubilities and Henry's law dissolution parameters were compared with those obtained by the high-pressure sorption and permeation measurements. Henry's law dissolution parameters were in good agreement with one another. However, the solubilities first determined here were smaller than those determined by the high-pressure sorption experiment at the same temperature. It was clear that the Langmuir capacity of the present specimen was smaller in spite of similar high-pressure CO₂ exposure. Relaxation of the polymer was expected to be one of the reasons. This expectation was confirmed from the observation and analysis of sorption isotherms after two kinds of treatments. After annealing above T_g, the Langmuir capacity was shown to be decreased to 1/2 or even to 1/3 from the sorption isotherms below 45°C. This means that the conditioning to the high-pressure CO₂ surely has a large effect on the nature of glassy polymer. Just after high-pressure CO₂ exposure at 25°C, increased solubility was observed. Furthermore, the slow decrease of solubility, that is, the decrease of conditioning effect, was also followed from the continual measurements at 25°C. This result reflects not only the characteristic of sorption capacity after high-pressure CO₂ exposure, but also the relaxation of polymer in glassy state.     

Effect of ultraviolet light irradiation on gas permeability in polyimide membranes. II. Irradiation of membranes with high-pressure mercury lamp

A photocrosslinkable polyimide membrane was prepared and investigated with regard to the effect of ultraviolet light irradiation (UV-irradiation) using a high-pressure mercury lamp on their gas permeabilities and permselectivities. Permeability and diffusion coefficients for O₂, N₂, H₂, and CO₂ were determined using the vacuum-pressure and time-lag methods. Sorption properties for carbon dioxide were determined to evaluate the changes in the free volume in the membranes by the irradiation. The apparent gas permeabilities decreased and permselectivity, particularly for H₂ over N₂, increased with increasing UV-irradiation time without a significant decrease in the flux of H₂. They depended on the membrane thickness, suggesting asymmetrical changes in the membrane due to UV-irradiation. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 49–60, 1998     

Gas permeation in miscible homopolymer-copolymer blends: II. Tetramethyl bisphenol-A polycarbonate and a styrene/acrylonitrile copolymer

Gas sorption and transport properties for He, H₂, O₂, N₂, Ar, CH₄, and CO₂ at 35°C near atmospheric pressure have been obtained for miscible blends of tetramethyl bisphenol-A polycarbonate (TMPC) and a random copolymer of styrene with acrylonitrile (SAN) containing 9.5% by weight of acrylonitrile. All gas permeability, diffusion, and solubility coefficients obtained are lower than that calculated from the semilogarithmic additivity rule. These results are qualitatively interpreted by ternary solution theory and activated state theory which have been proposed to describe gas sorption and diffusion in miscible blends. The negative deviation of gas permeabilities for the blends from this rule can be explained semiquantitatively by free volume theory which takes volume contraction on mixing into account. The negative deviation increases with gas molecular size which results in larger ideal gas separation factors than that calculated from the additivity rule. For He/CH₄ and H₂/CH₄ pairs, the permselectivities for the blends are higher than that for either pure TMPC or SAN. The deviation from additivity for gas transport properties of TMPC/SAN blends is the opposite of that observed in the first paper of this series for PMMA/SAN blends. This can be attributed to the stronger interactions in TMPC/SAN blends than in PMMA/SAN blends.     

Diffusion and sorption for carbon dioxide in Kapton at extremely low pressure

Pressure-dependent solubility and diffusion coefficients for carbon dioxide in glassy polymers have been well described using the “dual sorption and transport model.” However, the plastisization effect by high-pressure carbon dioxide seems to promote the pressure dependence of the sorption and transport coefficients. To avoid the relaxation process by the plastization which is superimposed on the diffusion process, the diffusion and sorption of carbon dioxide were measured at extremely low pressure (below 1 cmHg). Linear isotherms observed for CO₂ sorption into Kapton were interpreted in terms of the dual model equation at extremely low pressure. From the permeation curve of the Kapton/CO₂ system, the diffusion and permeation coefficients were obtained according to the usual manner, and both coefficients were independent of pressure. Sorption and transport parameters were obtained from sorption isotherms and average values of the permeation coefficients. The parameters thus obtained were substituted in an approximated dual sorption and transport equations at extremely low pressure and the pressure independence of the diffusion and permeation coefficients were sufficiently reproduced. It is a good technique to experiment at such extremely low pressure when the validity of the dual model is evaluated. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1013–1017, 1998     

Carbon dioxide sorption and diffusion in poly(3‐hydroxybutyrate) and poly(3‐hydroxybutyrate‐CO‐3‐hydroxyvalerate)

CO₂ sorption and diffusion in poly(3‐hydroxybutyrate) and three poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) copolymers were investigated gravimetrically at temperatures from 25° to 50°C and pressures up to 1 atm. The sorption behavior proved to be linear for all the copolymers studied. An additional set of measurements performed in a pressure decay apparatus at 35°C showed that the linearity could be extrapolated to pressures up to 25 atm. The sorption results obtained from both techniques were in good agreement. The poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) sorption kinetics were increasingly non‐Fickian at the higher temperatures, thus preventing the calculation of diffusion coefficients above 35°C. Interestingly, this was not the case for poly(3‐hydroxybutyrate), and diffusion coefficients and permeabilities could be calculated at all of the investigated temperatures. The 35°C permeabilities were fairly low, which is attributed to the high degree of crystallinity of this polyester family. Finally, the poly(3‐hydroxybutyrate) barrier properties against CO₂ are successfully compared with those of some selected common thermoplastics. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2391–2399, 1999     

Residual porosity in polymeric latex films

Solubility and diffusivity measurements of a probe gas (CO₂), which has an inherently low solubility in the polymer, have been used to characterize residual porosity in polymeric latex films. Sorption isotherms resembling those of a glassy polymer were obtained, even though the glass transition temperature of the polymer was 1°C, about 30°C below the experimental temperature. Solvent cast films of the same polymer exhibited much lower solubilities, and followed the expected Henry's law behavior. CO₂ solubility and diffusivity were found to decrease with aging time for the latex films, but did not quite reach the values of the solvent cast films, even after 75 days at room temperature. The sorption data could be described by the dual-mode sorption model, which is commonly employed in the analysis of glassy polymer sorption isotherms. Estimates of the amount of porosity were made from the sorption data, and values ranging from 0.6–0.03% were obtained for latex films aged from 62 h to 75 days, respectively. Our results suggest that permeability differences noted by others for latex and solvent cast films of the same polymer are due to the substantial solubility differences for low-solubility penetrants in these two types of films.     

Orientation in uniaxially drawn polystyrene plasticized by CO2 sorption

Uniaxial drawing experiments of the polystyrene films plasticized by a sorption of compressed CO₂ gas at pressures up to about 18 MPa were carried out with strain rates ε of 0.0290 and 0.0079 s^?1. The drawing was performed successfully with draw ratio λ up to 4 at the temperatures of 308.15, 318.15, 328.15, and 338.15 K. The Hermans orientation function f of the drawn samples was determined from the dichroic ratio measured by an infrared spectrophotmeter. While f value increases with increasing ε or λ, it decreases with increasing CO₂ pressure or temperature. © 1995 John Wiley & Sons, Inc.     

Study of transport of pure and mixed CO2/N2 gases through polymeric membranes

The permeations of pure CO₂ and N₂ gases and a binary gas mixture of CO₂/N₂ (20/80) through poly(dimethylsiloxane) (PDMS) membrane were carried out by the new permeation apparatus. The permeation and separation behaviors were characterized in terms of transport parameters, namely, permeability, diffusion, and solubility coefficients which were precisely determined by the continuous‐flow technique. In the permeation of the pure gases, feed pressure and temperature affected the solubility coefficients of CO₂ and N₂ in opposite ways, respectively; increasing feed pressure positively affects CO₂ solubility coefficient and negatively affects N₂ solubility coefficient, whereas increasing temperature favors only N₂ sorption. In the permeation of the mixed gas, mass transport was observed to be affected mainly by the coupling in sorption, and the coupling was analyzed by a newly defined parameter permeation ratio. The coupling effects have been investigated on the permeation and separation behaviors in the permeation of the mixed gas varying temperature and feed pressure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 179–189, 2000     

Sorption and diffusion of supercritical carbon dioxide into polysulfone

Sorption and diffusion of supercritical carbon dioxide (SCCO₂) into polysulfone (PSF) from 313 K and 20 MPa to 333 K and 40 MPa were investigated in this study. A simple gravimetric method was used to measure the mass gain of SCCO₂ in PSF, and the Fick's diffusion model was applied to describe the desorption process. The sorption amount, the sorption diffusivity under supercritical states, and the desorption diffusivity at ambient conditions are presented. Comparisons of the sorption amounts and diffusivities of CO₂ for polymers of polycarbonate and PSF are discussed according to the interactions between gas and polymers. The morphology change and plasticization effect attributed to gas sorption in PSF were studied. Effects of glass‐transition temperature and yielding stress for PSF and other polymers were used to describe the difference in their diffusivities for the sorption and desorption processes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 474–482, 2004     

Mixed gas and pure gas transport properties of copolyimide membranes

Copolyimides were synthesized from dianhydride of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA) with various diamine contents of 4,4′‐oxydianiline (ODA) and 2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (TeMPD) by chemical imidization in a two‐step procedure. Polyimides (PIs) were characterized using thermogravimetric analysis, Fourier transform infrared spectroscopy, differential scanning calorimetry, as well as specific volume and free volume. The gas transport properties for pure gas and blends of CO₂ and CH₄ for the homopolymers and 6FDA‐ODA/TeMPD copolymers were investigated at 35°C and 150 psi pressure. In pure gas permeation, permeability of CO₂ and CH₄ increased with increasing TeMPD content in the diamine moiety, whereas the ideal selectivity decreased with increasing TeMPD content. In the mixed gas permeation, permeabilities and separation factor were measured as a function of CO₂ feed molar fraction for five PI membranes. The behavior of pure gas and mixed gas permeabilities and separation factor of CO₂/CH₄ mixtures as the chemical nature of the diamine and the CO₂ molar fraction in the feed gas were varied and are discussed in detail. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2013