Interaction of CO2 gas with silicone elastomer at high ambient pressures

Interaction of high-pressure CO₂ gas with a silicone elastomer, and to a lesser extent, with a nitrile rubber and a PTFE have been investigated. Sorptive dilations of the polymers were measured with the help of custom-made piezoelectric ultrasonic transducers under gas pressures of up to ca. 22 MPa at 42°C. The gas mass sorption was determined by a vibrating reed probe. For the silicone elastomer system the dilation isotherm mimics the sorption isotherm. The partial molar volume (PMV) of the absorbed CO₂ gas in the silicone elastomer has been computed. A significant drop in the PMV value is observed when the CO₂ gas becomes supercritical. In the transition region, the transmission of ultrasonic signals through the specimen indicated the formation of discrete small (estimated as about 60 μm in diameter) high density zones of CO₂ in the rubber matrix. The plasticization effects of the absorbed high pressure CO₂ gas have been identified from the interpretation of the changes in the acoustic longitudinal modulus obtained from ultrasonic transmission measurements. The effects of rapid gas decompression on the structural integrity of the various polymers have also been determined. Significant inflation of certain specimens occur toward the latter stages of the decompression cycle. The initiation and development of internal cracks or bubbles was followed by monitoring the ultrasonic signal attenuation.     

Sorption and partial molar volumes of gases in poly(ethylene-co-vinyl acetate)

Sorption and dilation properties of polymer-gas systems involving poly(ethylene-co-vinyl acetate) and N₂, CH₄, or CO₂, have been investigated at pressures up to 50 atm at temperatures of 10–40°C. Sorption isotherms for low-solubility gases (i.e., CH₄ and N₂) can be described by Henry's law, and those for high-solubility gas (i.e., CO₂) by Flory-Huggins dissolution equation. Dilation isotherms are similar in contour to the corresponding sorption isotherms. From the obtained sorption and dilation data, partial molar volumes of the gases in the polymer were determined as a function of temperature. Thermal expansivity of dissolved CO₂ molecules was estimated at ca. 2.4 × 10^?3°C^?1 from the temperature dependence of partial molar volume. The expansivity is smaller than that of liquid CO₂ and larger than those of the polymer and organic liquids. © 1994 John Wiley & Sons, Inc.     

The effect of lattice compressibility on the thermodynamics of gas sorption in polymers

A compressible lattice model with holes, the glassy polymer lattice sorption model (GPLSM), was used to model the sorption of carbon dioxide, methane, and ethylene in glassy polycarbonate and carbon dioxide in glassy tetramethyl polycarbonate. For glassy polymers, an incompressible lattice model, such as the Flory–Huggins theory, requires concentration-dependent and physically unrealistic values for the lattice site volumes in order to satisfy lattice incompressibility. Rather than forcing lattice incompressibility, GPLSM was used and reasonable parameter values were obtained. The effect of conditioning on gas sorption in glassy polymers was analyzed quantitatively with GPLSM. The Henry's law constant decreases significantly upon gas conditioning, reflecting changes in the polymer matrix at infinite dilution. Treating the Henry's law constant as a hypothetical vapor pressure at infinite dilution, gas molecules in the conditioned polymer are less “volatile” than those in the unconditioned polymer. Flory–Huggins theory was used to model the sorption of carbon dioxide, methane, and ethylene in silicone rubber. Above the glass transition temperature, the criterion of lattice incompressibility for Flory-Huggins theory was satisfied with physically realistic and constant values for the lattice site volumes. © 1992 John Wiley & Sons, Inc.     

Implementation of low temperature physical changes on silicone elastomers to achieve sensitivity gains through CPMAS NMR

Nuclear Magnetic Resonance Spectroscopy (NMR) has been used on several occasions to investigate the biodurability of silicone elastomers used in silicone breast implants. In all of these cases conclusions have been convoluted by lack of sensitivity. We have improved the sensitivity of solid state NMR characterizations of silicone elastomers used in silicone breast implants by changing the physical state of the elastomer. This was achieved by cooling the sample to −90 ^∘C, below its crystalline transition temperatures, and acquiring ²⁹Si Cross Polarization MAS (CPMAS) NMR. This approach yielded signal to noise enhancements as high as 8.5 fold for the elastomer backbone and modest improvements for (CH₃)₂RSiO_1/2 and silica filler signals.     

Atomistic packing models for experimentally investigated swelling states induced by CO2 in glassy polysulfone and poly(ether sulfone)

Atomistic packing models have been created, which help to better understand the experimentally observed swelling behavior of glassy polysulfone and poly (ether sulfone), under CO₂ gas pressures up to 50 bar at 308 K. The experimental characterization includes the measurement of the time‐dependent volume dilation of the polymer samples after a pressure step and the determination of the corresponding gas concentrations by gravimetric gas‐sorption measurements. The models obtained by force‐field‐based molecular mechanics and molecular dynamics methods allow a detailed atomistic analysis of representative swelling states of polymer/gas systems, with respect to the dilation of the matrix. Also, changes of free volume distribution and backbone mobility are accessible. The behavior of gas molecules in unswollen and swollen polymer matrices is characterized in terms of sorption, diffusion, and plasticization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1874–1897, 2006     

Polymer modification using difluoromethane (HFC 32) and carbon dioxide

The infusion of difluoromethane (HFC 32) and CO₂ into polystyrene and polyethylene has been characterized using a quartz crystal microbalance technique over a range of temperatures and pressures. The results were adequately modeled by Flory‐Huggins theory. Significant plasticization was observed in the polymeric materials and it is shown that manipulation of the experimental temperature, pressure, and rate of depressurisation can cause significant changes in the morphology of the samples. It is demonstrated for the first time how rate constant data for the kinetics of gas sorption can be extracted quickly and easily from in situ quartz crystal microbalance measurements. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1072–1083, 2006     

Permeation of binary gas mixture through glassy polymer membranes with concentration-dependent diffusivities

An analytical solution has been obtained for the modified dual-mode mobility model for a single gas proposed by Zhou and Stern and extended to a binary gas mixture to describe the pressure dependence of mean permeability coefficients for CO₂ and CH₄ mixtures in homogeneous cellulose triacetate membranes. The permeabilities calculated from the model fitted the corresponding experimental results quite well. Permeation experiments for equimolar CO₂ and CH₄ mixture in a homogeneous membrane of methyl methacrylate and n-sbutyl acrylate copolymer were performed along with sorption experiments for pure CO₂ and CH₄ to test the applicability of the model. The experimental permeabilities were close to those calculated from the model.     

Gas sorption-induced dilation of poly(4-methyl-1-pentene)

Sorption and volume dilation isotherms of semicrystalline poly(4-methyl-1-pentene) (PMP) were measured using CO₂ and C₃H₈ as penetrants, which have sieving diameters of 3.3 and 4.3 Å, respectively. On the other hand, the PMP crystal has a void width of approximately 4 Å as estimated by X-ray diffraction, so it was anticipated that CO₂ would be able to sorb into the PMP crystal while C₃H₈ would not. The data show that C₃H₈ has a constant partial molar volume of approximately 87 cc/mol, just above the value reported in other rubbery polymers, and are consistent with the hypothesis that the C₃H₈ molecules are too large to sorb into the PMP crystals. The partial molar volume of CO₂ was found to be 39 cc/mol for CO₂ weight fractions of up to 0.03. Since the typical partial molar volume of CO₂ in rubbery materials is 46 cc/mol, the lower values in this study were attributed to CO₂ sorption into crystalline regions of the polymer, which provided no dilation. Application of a two-phase model using the assumption of Henry's law sorption showed that apparently all C₃H₈ sorption was occurring in the amorphous region but approximately 16% of CO₂ sorption occurred in the crystalline regions. © 1996 John Wiley & Sons, Inc.     

The solvent dependence of the sorptive abilities of tetracyanocomplexes

The two different types of tetracyanocomplexes [ZnNi(CN)₄·nH₂O] and [Cd(en)Pd(CN)₄·2C₆H₆] have been examined as sorptive materials in a simple contact with benzene, after their modification with auxiliary solvents and their use in gas chromatographic experiments. All forms of sorption experiments show identical characteristics from the view of the sorption of aromatic compounds as exemplified by benzene. The tetracyanocomplexes exhibit a permanent capability of sorption, even when heated to a temperature of 260°C and show a separation ability towards sorbed materials depending on the solvent used and on the degree of thermal degradation of the tetracyanocomplex. The prducts of the modification and sorption (in static and dynamic) experiments have been characterized by IR spectroscopy, X-ray patterns and by thermal analysis.     

Sorption and partial molar volume of gases in poly (dimethyl siloxane)

Sorption of N₂, O₂, Ar, CH₄, CO₂, C₂H₄, and C₂H₆ in poly (dimethyl siloxane) liquid and rubber and the dilation of the polymers due to sorption of the gases are studied at 25°C under pressures up to 50 atm. In the liquid, the sorption isotherms for low-solubility and high-solubility gases are described by Henry's law and the Flory–Huggins equation, respectively. Gas sorption in the rubber, which contains a 29 wt % silica filler, follows the dual-mode sorption model, though marked hysteresis is observed in the sorption of O₂ and CH₄. The dilation isotherms increase linearly or exponentially in both polymers with increasing pressure. Considering that gas molecules adsorbed into micropores of the filler particles do not participate in the dilation, partial molar volumes of the dissolved gases in the rubber are determined from data of sorption and dilation. The values are nearly equal to the partial molar volumes in the liquid (48–60 cm³/mol).     

On pressure dependence of the parameters of the dual-mode sorption model

Sensitivity of the parameters of the dual-mode sorption (DMS) model on the pressure range, in which sorption of gases in polymers have been studied, was analyzed. Different “gas-polymer” systems were considered but the most detailed analysis was performed for sorption of argon and nitrogen in poly[5,5-difluoro-6,6-bis(trifluoromethyl)] norbornene and polysulfone. It was shown that the model parameters depend upon the range of gas pressure studied. Expanding of the pressure range (0-p_i) results in an increase in the Langmuir adsorption capacity C′_H and in reduction of Henry's law solubility coefficient k_D and Langmuir affinity parameter b. These behaviors does not depend on a choice of an experimental apparatus or software and procedure of nonlinear least squares treatment of the data. As statistical analysis indicated, a systematic error of the measurement cannot call forth the observed dependencies of the model parameters. Different physical reasons of these behaviors were considered, among them: the pressure dependence of the affinity parameter, and the dilation of a polymer. The results obtained showed that although the DMS model, as a rule, gives an excellent fit of the experimental curves, and, hence, can be used as a form of compact storage of information on gas sorption in polymers, one should be careful in using it outside the pressure range in which its parameters have been determined. © 1996 John Wiley & Sons, Inc.     

Simulation of experimentally observed dilation phenomena during integral gas sorption in glassy polymers

A molecular modeling investigation of dilation effects induced by sorbed gas molecules in two glassy polymers is presented. As experimental reference, integral sorption of CO₂ and CH₄ was measured for polysulfone (PSU) and a polyimide (6FDA‐TrMPD, PI4) at 308 K and a pressure of 10 bar. Simultaneously, the gas induced swelling effect was measured with a dilatometer based on a capacitive distance sensor recorded. The experimental evidence of the (on the observed time scale and concentration levels) elastic nature of the gas induced dilation is supported by the dilation and contraction behavior observed in molecular dynamics (MD) simulations of respective detailed atomistic packing models. These models were constructed in accordance with gas concentration levels obtained from the experimental sorption results. Quantitative deviations between simulated and measured dilations are discussed as a consequence of an anelastic response of the polymer matrix which is too fast to be resolved in the experiments whose kinetics is dominated by diffusional processes. In the simulation, the initial insertion of penetrant molecules into equilibrated packing models “circumvents” the slow diffusional process of the experiment and allows a reasonable representation of the dilation process as well as a closer investigation. Our simulation approach reveals a different behavior for PSU and PI4 on the corresponding time scale. Most likely, the different chain mobility of the two polymers is responsible for the respective response to the inserted amount of gas molecules which is discussed in terms of the different chain mobilities of the two polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 59–71, 2008     

Sorption of light gases in glassy poly(ethyl methacrylate)

Although gas sorption in glassy polymers is a well‐studied phenomenon, no general microscopical model is developed which is able to describe the gas sorption in a wide temperature range using only characteristics of polymer and gas molecule. In this work, sorption isotherms and desorption kinetics of O₂, Ar, and N₂ for glassy poly(ethyl methacrylate) have been measured in the temperature range from 160 to 308 K. To describe both the phenomena, the model is developed which postulates that, in the frozen structure of glassy polymer, any cavities between macromolecules are the sorption sites for small molecules. The cavities of small size can expand elastically to accommodate a gas molecule. The sorption sites are considered to be the potential wells and their depths are distributed according to Gaussian law. The concentration of sorption sites, their mean depth and depths dispersion, and the frequency of molecules oscillations in the sorption sites are the only parameters which determine both the gas transport and sorption. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 288–296     

Sorption of carbon dioxide in fluorinated poyimides

Sorption isotherms of CO₂ for ten fluorinated polyimides measured at 35°C and up to about 25 atm are analyzed according to the dual-mode sorption model. Sorption properties for these polyimides are compared with those for other glassy Polymers including unfluorinated polyimides. The glassy polymers with higher glass transition temperatures T_g tend to show greater CO₂ sorption. Introduction of a ? C (CF₃)₂? linkage into the repeat unit of the main chain increases the sorption by 20–80%. For glassy polymers, including the fluorinated and unfluorinated polyimides, the Langmuir affinity constant b and Henry's law solubility constant k_D are correlated with the content of functional (carbonyl or sulfonyl) groups [FG], and composite parameter reflecting the magnitude of both [FG] and free-space fraction V_F, respectively, with some exceptions. The Langmuir capacity constant C′_H is correlated with T_g, but there are two correlation lines; one for unfluorinated polyimides and a different one for other glassy polymers including fluorinated polyimides. The slope of the former group is smaller probably because of smaller differences in thermal probably because of smaller differences in thermal expansion coefficients in rubbery and glassy states. Most fluorinated polyimides show greater solubility of CO₂ than unfluorinated polyimides and other glassy polymers, because of their larger C′_H and k_D. © 1993 John Wiley & Sons, Inc.     

A steady‐state mass balance model of the polycarbonate–CO2 system reveals a self‐regulating cell growth mechanism in the solid‐state microcellular process

A simple mechanism regulating polymer mobility is demonstrated to determine initial and final growth states of solid‐state microcellular foams. This mechanism, governed by the extent of plasticization of the polymer by the dissolved gases, is examined with a mass balance model and results from foam growth experiments. Polycarbonate was exposed to CO₂, which acted as both a plasticizing gas and a physical blowing agent driving foam growth. The polycarbonate specimens were saturated to the equilibrium gas concentration at 25 °C for CO₂ pressures of 1–6 MPa in 1‐MPa increments. Equilibrated specimens were heated in a glycerin bath until thermal equilibrium was reached, and a steady foam structure was attained. Glycerin bath temperatures of 30–150 °C in 10 °C increments were examined. Using knowledge of gas solubility, the equation of state for CO₂, the effective glass‐transition temperature as a function of gas concentration, and a model for mass balance within a solid‐state foam, we demonstrate that foam growth terminates when sufficient gas is driven from the polycarbonate matrix into the foam cells. The foam cell walls freeze at the elevated bath temperature because of gas transport from the polycarbonate matrix and the associated rise in the polymer glass‐transition temperature to that of the heated bath. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 868–880, 2001     

Evaluation of gas sorption parameters and prediction of sorption isotherms in glassy polymers

A model of continuous‐site distribution for gas sorption in glassy polymers is examined with sorption data of CO₂ and Ar in polycarbonate. A procedure is presented for determining from a measured isotherm the number of sorption sites in a polymer, an important parameter that previously had to be assumed. With this parameter value and solubility data obtained at zero pressure, the model can reasonably predict sorption isotherms of CO₂ in glassy polycarbonate for a wide temperature range. The number of sorption sites and the average site volume evaluated from CO₂ sorption isotherms are employed for the prediction of Ar sorption isotherms with zero‐pressure solubility data and the independently measured partial molar volume of Ar. A reasonable fit to the measured isotherms of Ar is achieved. With the proposed procedure, the continuous‐site model shows several advantages over the conventional dual‐mode sorption model. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 883–888, 2000     

Elaboration and characterisation of PDMS-HTiNbO5 nanocomposite membranes

Poly(dimethylsiloxane) (PDMS)-HTiNbO₅ nanocomposite membranes with various HTiNbO₅ nanofiller content were prepared by melt intercalation. WAXS diffraction measurements and TEM observations have suggested that the HTiNbO₅ mineral was exfoliated in the PDMS matrix. The influence of the filler in the membrane was evaluated by water diffusion, gas permeation (CO₂, N₂, O₂, ethane and ethylene), toluene pervaporation and by CO₂ sorption measurements.A filler content of only 2 wt.% in PDMS-HTiNbO₅ nanocomposite membranes slows down the water diffusion significantly, and a filler content of 5 wt.% reduces also the permeability of the films for toluene. The addition of a filler content up to 10 wt.% do not significantly influences the gas permeability (P) except for CO₂. The PDMS matrix appears to be highly permeable and, therefore, a decreasing effect on P is only marked for a very high HTiNbO₅ content. This effect is more pronounced for CO₂, the P value of which decreases by 80% when the amount of nanofiller is 40 wt.%. The sorption measurements show that the interaction between CO₂ and PDMS is weak (isotherms agree with Henry’s law). The filler decreases the solubility of CO₂ in the films (S = 7.94 × 10⁻³ and S = 5.44 × 10⁻³ cm³ STPcm⁻³ film cmHg⁻¹ for PDMS and PDMS-HTiNbO₅ 40 wt.%, respectively).     

Effect of penetrant-induced isothermal glass transition on sorption,dilation, and diffusion behavior of polybenzylmethacrylate/CO2

The effect of a penetrant-induced isothermal glass transition on sorption, dilation, and diffusion behavior was studied in a single experimental run for CO₂ in cast polybenzylmethacrylate films. The dual-mode type sorption isotherms below the glass transition temperature of the polymer changed to linear ones above a certain concentration. Meanwhile, partial molar volume of CO₂ determined from the dilation of the films above the concentration gave a value very close to the one reported for rubbery polymers, and diffusion coefficients became less concentration-dependent. The results were conformable to the concept of unrelaxed volume in glassy polymers. © 1996 John Wiley & Sons, Inc.     

Solubility and partial molar volume of carbon dioxide and ethane in crosslinked poly(ethylene oxide) copolymer

Experimental solubility and sorptive dilation data are reported for carbon dioxide and ethane in a crosslinked poly(ethylene oxide) (XLPEO) rubbery copolymer. Five different temperatures (253 ≤ T(K) ≤ 308) were considered, with a maximum gas pressure of 2.09 MPa (20.6 atm). The polymer was prepared by photopolymerization of a solution containing 70 wt % poly(ethylene glycol) methyl ether acrylate (PEGMEA) and 30 wt % poly(ethylene glycol) diacrylate (PEGDA). Sorption isotherms were described by the Flory‐Huggins model. For each gas, the Flory‐Huggins interaction parameter was a decreasing function of temperature and did not show a composition dependence. Dilation and sorption data were combined to calculate the partial molar volume (PMV) of the gases in the polymer, which was an increasing function of temperature. Based on a comparison with literature data for a XLPEO homopolymer prepared from pure PEGDA over the same range of operating conditions, an effect of the network composition on both gas solubility and PMV was found. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 456–468, 2010