Gas permeability in rubbery polyphosphazene membranes

The synthesis, characterization, and gas permeability of 10 new polyphosphazenes has been studied. Additionally, the first gas permeation data has been collected on hydrolytically unstable poly[bis-(chloro)phosphazene]. Gases used in this study include CO₂, CH₄, O₂, N₂, H₂, and Ar. CO₂ was the most permeable gas through any of the phosphazenes and a direct correlation between the T_g of the polymer and CO₂ transport was noted with permeability increasing with decreasing polymer T_g. To a lesser degree, permeability of all the other gases studied also yielded increases with decreasing polymer T_g. The trend observed for these new polymers was further supported by published data for other phosphazenes. Furthermore, permeability data for all gases were found to correlate to the gas condensability and the gas critical pressures, except for hydrogen, suggesting that the nature of the gas is also a significant factor for permeation through rubbery phosphazene membranes. Ideal separation factors () for the CO₂/H₂ and CO₂/CH₄ gas pairs were calculated. For CO₂/CH₄, no increase in was observed with decreasing T_g, however increases in were noted for the CO₂/H₂ pair.     

Thermodynamic interactions in rubbery polymer/gas systems

The Flory–Huggins interaction parameters χ for 23 gases (He, Ne, Ar, Kr, Xe, H₂, N₂, O₂, N₂O, CO₂, CH₄, C₂H₄, C₂H₆, C₃H₆, C₃H₈, 1,3-C₄H₆, four C₄H₈'s, n-C₄H₁₀, iso-C₄H₁₀, and n-C₅H₁₂) in five rubbery polymers (1,2-polybutadiene (PB), poly(ethylene-co-vinyl acetate)) (EVAc), polyethylene (PE), polypropylene (PP), and poly(dimethyl siloxane) (PDMS) were determined from either literature data on Henry's law coefficient and partial molar volume or those on sorptive dilation for each polymer/gas system. Values of χ for the gases increased in the order of PDMS < PP ≡ PB < EVAc ≡ PE. Among the gases except He and H₂ whose χ values are not reliable, Ne and Xe have respectively the highest and the lowest values of χ for the polyolefins. The χ values of the hydrocarbons were compared together with previously reported χ values of n-alkanes C₃-C₁₀. The dependencies of χ upon concentration and temperature were discussed on the basis of the literature data. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1049–1053, 1997     

Characterization of substructure resistance in asymmetric gas separation membranes

Gas permeation through a typical state-of-the-art membrane can be described by defining three morphological features: namely skin thickness, skin integrity, and substructure resistance. Traditional gas permeation measurements tend to characterize skin thickness and skin integrity, but not substructure resistance. This presents a serious obstacle to the optimization of advanced hollow fiber membranes, since as skin thicknesses are reduced, substructure resistance becomes an increasingly significant contribution to the overall permeation rate. This paper illustrates how substructure resistance can affect permeation properties and demonstrates a new technique for characterizing this frequently important morphological feature. The technique involves applying a constant transmembrane pressure while varying the average gas pressure within the membrane. Thus, the mean free path of gas molecules permeating through the substructure can be altered while maintaining a constant driving force for permeation. Such experiments characterize the magnitude of the substructure resistance, as well as provide insight into the governing transport mechanism. These constant driving force/variable pressure permeation measurements can estimate the average pressure or mean free path at the transition where substructure resistance becomes negligible. This can then be used to compare the morphological features of different membranes. This technique is demonstrated on well-defined coated ceramic membranes, asymmetric polymeric flat sheet membranes, and asymmetric polymeric hollow fiber membranes.     

The separation of tritiated water using supported polyphosphazene membranes

Carboxylated poly(diaryloxy)phosphazene was examined as the active constituent of the composite membranes to separate tritiated water (HTO) from light water. These membranes were tested with water containing 10 800 pCi/l and 3 μCi/l of tritiated water, respectively, under cross-flow filtration conditions. Reductions in the permeate of nearly 30% HTO were observed with these tritium concentrations. Low temperature (5°C), low pressure (137.9–551.6 kPa), and high pH (near 10 or above) were required to obtain such reductions (rejection). Salt species (Na₂SO₄, CaCl₂ and CaSO₄) at various concentrations and pressures, within a 137.9–551.6 kPa range, did not appear to affect the HTO separation efficiency. Mass balances performed during these experiments indicate an unaccounted small amount of tritium (0.5–2.2%). Sorption experiments with the polyphosphazene suggest that the membrane does not operate by an ion exchange mechanism; that is, tritium accumulation within the membrane.     

Characterization and quantification of amorphous content in some selected parenteral cephalosporins by calorimetric method

Summary Amorphous content of a crystalline drug affects its physical and chemical properties as well as its performance. Consequently it is important to assess the extent of amorphous contents in pharmaceuticals. The present study utilizes the technique of solution calorimetry to quantify the percentage of crystallinity in samples of varying amorphous content in cefazolin sodium monohydrate, ceftriaxone sodium, cefotaxime sodium and cefoperazone sodium. Enthalpy of solution of 100% crystalline and amorphous drugs as well as their physical mixtures over the range 0-100 mass/mass% amorphous content were determined. As expected it has been found that amorphous forms have significantly higher energy than the corresponding crystalline form for all the drugs. Enthalpy of solution (Δ_solH), an extensive thermodynamic property can provide a precise and unambiguous measure of the relative crystallinity provided amorphous and crystalline standards are appropriately chosen. A good correlation has been found between Δ_solH and the amorphous contents of the drugs.     

Characterization and transport properties of Nafion/polyaniline composite membranes

Nafion membranes were modified by chemical polymerization of aniline using ammonium peroxodisulfate as the oxidant. The Nafion-polyaniline composite membranes were extensively characterized using scanning electron microscopy (SEM), atomic force microscopy (AFM), infrared (FTIR-ATR) and X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and ion-exchange capacity measurements. The transport properties were also evaluated by conductivity and electrodialysis measurements. The data show that when a high oxidant concentration (1 M (NH4)2S2O8) is used, polyaniline is mostly formed at the surface of the Nafion membrane with a higher proportion of oligomers. On the contrary, when 0.1 M oxidant is used, polyaniline is mostly formed inside the ionic domains of Nafion, blocking the pathway to ion transport and thus reducing the transport of Zn2+ as well as the transport of H+. These data were also compared to the data obtained with poly(styrene sulfonate)-PANI composite membranes.     

Influence of the transport direction on gas permeation in two-layer ceramic membranes

Experimental and theoretical results of studying gas permeation through porous membranes are presented. In order to mimic an asymmetric membrane two porous ceramic disks with different pore radii were arranged in series. Besides the possibility to perform conventional permeation measurements, the applied experimental setup permits the determination of the pressure at the interface between the two discs. To predict the performance of the asymmetric structure, in preliminary experiments structure parameters were determined for both membranes separately. For the same total pressure difference across the two-disk arrangement, different interlayer pressures and fluxes were predicted and detected experimentally depending on the flow direction.     

Characterization of the pore area distribution in porous membranes using transport measurements

An approach originally proposed by Mason and coworkers has been applied to model porous membranes to show that transport measurements with small and large solutes can be used to distinguish between porous membranes with the same average pore size but different pore size distributions. In addtion, it is shown that such measurements can be used to account for membrane heteroporosity when predicting the sieving characteristics of a membrane. This is done by applying moment theory to results from flux measurements for a small solute at Pe ≈ 1 or to results from measurements of the reflection coefficient for a large solute at infinite Pe. No a priori assumptions about the nature of the distribution of pore areas are necessary.In this paper, the results from calculations performed with three different model membranes with log-normal pore size distribution are reported. These results show that one can begin to distinguish between membranes by measuring the hydraulic and diffusive permeability and performing at least one additional flux measurement — with either a small, non-hindered solute at Pe ≈ 1 or a large solute at infinite Pe. Results also show that a fairly narrow window can be placed on the sieving curve for a heteroporous membrane without performing any sieving measurements. This is an interesting and encouraging result because it means that many of the problems that arise from measuring and interpreting pore size distributions using more traditional techniques can be avoided by using small solute flux measurements to predict the separation characteristics of many porous membranes.     

Infrared spectroscopic studies of CO2 sorbed in glassy and rubbery polymeric membranes

Infrared spectra of CO₂ sorbed in rubbery and glassy polymers were measured to examine the relationships between the spectroscopic data and physical properties of the polymeric membranes. The “V-shape” tendency in the plot of W₁ [i.e., half-width of CO₂ peak sorbed in the membranes] vs glass-transition temperature (T_g) is observed, and has exactly the same tendency that is widely known from the plot of log D (diffusion coefficient) vs T_g. It is suggested that the membranes having a wider W₁ give a faster diffusion coefficient, since W₁ is inversely related to the moment of inertia of CO₂ in the membranes. Two distinct peaks of CO₂ were not observed in the infrared spectra of CO₂ sorbed in the glassy polymers. This suggests that the states of CO₂ in the Henry mode and Langmuir mode in the glassy polymers are similar in the spectroscopic measurements. © 1994 John Wiley & Sons, Inc.     

Photoviscoelastic behavior of amorphous polymers during transition from the glassy to rubbery state

Tensile stress‐relaxation experiments with simultaneous measurements of Young's relaxation modulus, E, and the strain‐optical coefficient, C_?, were performed on two amorphous polymers—polystyrene (PS) and polycarbonate (PC)—over a wide range of temperatures and times. Master curves of these material functions were obtained via the time‐temperature superposition principle. The value of C_? of PS is positive in the glassy state at low temperature and time; then it relaxes and becomes negative and passes through a minimum in the transition zone from the glassy to rubbery state at an intermediate temperature and time and then monotonically increases with time, approaching zero at a large time. The stress‐optical coefficient of PS is calculated from the value of C_?. It is positive at low temperature and time, decreases, passes through zero, becomes negative with increasing temperature and time in the transition zone from the glassy to rubbery state, and finally reaches a constant large negative value in the rubbery state. In contrast, the value of C_? of PC is always positive being a constant in the glassy state and continuously relaxes to zero at high temperature and time. The value of C_σ of PC is also positive being a constant in the glassy state and increases to a constant value in the rubbery state. The obtained information on the photoelastic behavior of PS and PC is useful for calculating the residual birefringence and stresses in plastic products. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2252–2262, 2001     

Characterization of the transport properties of membranes of uncertain macroscopic structural homogeneity

The present paper confirms and extends previous applications of an original method of time-lag analysis to (concentration-independent) gas permeation through porous pellets produced by uniaxial compaction of fine graphite powder. It is shown that this approach to the study of membrane permeability enables one to (i) detect unambiguously a macroscopic structural inhomogeneity affecting transport across the membrane (often present as an unsuspected artifact of the membrane fabrication process); (ii) determine appropriate average values of the resulting space-dependent diffusion, D(x), and sorption, S(x), coefficients (without recourse to equililibrium sorption measurements); (iii) secure substantial information about the functional form, as well as the degree, of variability of D(x) and S(x); and ultimately (iv) link this information to the underlying membrane structural inhomogeneity. In the present context, the salient underlying structural feature is nonuniform porosity across the membrane, represented by (x), and the link between D(x), S(x) and (x) is provided by the simple dual-mode (intrapore gas-phase + adsorbed-phase) model of sorption and transport in porous media. The effect of increasing overall pellet porosity (_obs) by reducing applied compacting pressure, was specifically studied and found to entail marked enhancement of the degree of structural inhomogeneity without material changes in the functional form of D(x), S(x) and hence of (x). The conclusions drawn from time-lag analysis were shown to be consistent with the observed behavior of apparent diffusion coefficients derived from transient-state sorption or permeation measurements and with the results of dual-mode steady-state permeation analysis. The latter results showed additionally that, for a more complete interpretation of observed transport behavior, the variability across the pellet of the orientation of graphite particles should also be taken into account.     

The gas transport properties of amine-containing polyurethane and poly(urethane-urea) membranes

A series of amine-containing polyurethanes and poly(urethane-urea)s based on 4,4′-diphenylmethane diisocyanate and either poly(ethylene glycol) of molecular weights 400 or 600 were prepared as gas separation membranes. The amine functional groups of N-methyldiethanolamine (MDEA) and/or tetraethylenepentamine (TEPA) were introduced into the hard segment as a chain extender. The gas transport data of He, H₂, O₂, N₂, CH₄ and CO₂ in these polymer membranes were determined by using the Barrer's high-vacuum technique and the time-lag method. The restriction of chain mobility has been shown by the formation of hydrogen bonding in the soft segment and hard-segment domains, resulting in the increase in the density, glass transition temperature of soft segments (T_gs). The separation mechanism of various gas pairs used in industrial processes is also discussed. Effect of pressure on permeability of the gases above and below T_gs was studied. It was found that the gas permeability increased or decreased with upstream pressure above T_gs, and should be described by a modified free-volume model. On the other hand, the condensable CO₂ exhibits a minimum permeability at a certain upstream pressure below T_gs. The permeability of He and H₂ were pressure independent above and below the T_gs.     

Investigation of gas transport through porous membranes based on nonlinear frequency response analysis

Theoretical development of a new experimental method for investigation of mass transport in porous membranes, based on the principle of the modified Wicke-Kallenbach diffusion cell and the nonlinear frequency response analysis is presented. The method is developed to analyze the transport of a binary gas mixture in a porous membrane. The mixture is assumed to consist of one adsorbable and one inert component. Complex mass transfer mechanism in the membrane, where bulk or transition diffusion in the pore volume and surface diffusion take place in parallel, is assumed. Starting from the basic mathematical model equations and following a rather standardized procedure, the frequency response functions (FRFs) up to the second order are derived. Based on the derived FRFs, correlations between some characteristic features of these functions on one side, and the whole set of equilibrium and transport parameters of the system, on the other, are established. As the FRFs can be estimated directly from different harmonics of the measured outputs, these correlations give a complete theoretical basis for the proposed experimental method. The method is illustrated by quantifying the transport of helium (inert gas) and C₃H₈ and CO₂ (adsorbable gases) through a porous Vycor glass membrane.     

Simulations of gas transport in membranes based on polynorbornenes functionalized with substituted imide side groups

This paper studies the diffusive and sorption steps of several gases across membranes cast from poly(N-phenyl-exo,endo-norbornene-5,6-dicarboximide) chloroform solutions. Chains packing effects on gas transport was investigated by conducting a parallel study on the permeation characteristics of membranes cast from hydrogenated poly(N-phenyl-exo,endo-norbornene-5,6-dicarboximide) chloroform solutions. The permeability coefficients of several gases in the two membranes were measured finding that hydrogenation of the norbornene moieties decreases gas permeability. The transition states approach was used to determine the trajectories of the gases in the two types of membranes from which the diffusion coefficients were obtained. Monte Carlo techniques based on the Widom method were used to simulate gas sorption process as a function of pressure. The values of the solubility coefficients thus obtained undergo a relatively sharp drop at low pressures approaching to a constant value as pressure increases. With the exception of carbon dioxide, pretty good agreement between the experimental and simulated values of the permeability coefficient is found for the gases studied.     

Effect of mild solvent post-treatments on the gas transport properties of glassy polymer membranes

This study examines the effect of treatment of defective glassy polymer membranes with a variety of vapors and liquids which have varying solvency power for the polymer. The pure-gas oxygen/nitrogen selectivities of defective, asymmetric membranes are shown to be permanently increased, in special cases, by treatment with certain solvents which have adequate solvency power to cause a critical level of swelling in the membrane skin layer. Three distinct types of membranes have been treated; asymmetric polysulfone membranes formed by dry/wet phase inversion, spin-coated poly(phenylene oxide)-ceramic composite membranes and solution-deposited polyimide-ceramic composite membranes. While the detailed fundamental processes controlling the elimination of surface defects are complex, our results suggest that plasticization of the selective skin layer, coupled with surface-tension driven cohesive forces are likely to be the key factors at play.     

Characterization of amorphous silica surface

A short survey is presented of results on the dehydration, dehydroxylation and rehydroxylation of the surface of amorphous silica.     

Mechanisms of lithium transport in amorphous polyethylene oxide

We report calculations using a previously reported model of lithium perchlorate in polyethylene oxide in order to understand the mechanism of lithium transport in these systems. Using an algorithm suggested by Voter, we find results for the diffusion rate which are quite close to experimental values. By analysis of the individual events in which large lithium motions occur during short times, we find that no single type of rearrangement of the lithium environment characterizes these events. We estimate the free energies of the lithium ion as a function of position during these events by calculation of potentials of mean force and thus derive an approximate map of the free energy as a function of lithium position during these events. The results are consistent with a Marcus-like picture in which the system slowly climbs a free energy barrier dominated by rearrangement of the polymer around the lithium ions, after which the lithium moves very quickly to a new position. Reducing the torsion forces in the model causes the diffusion rates to increase.