Measurement of sorption and diffusion in nonporous membranes by transient permeation experiments

The knowledge of sorption and diffusion of liquids or vapors and their mixtures in nonporous membranes facilitates systematic membrane selection and process design. A novel experimental technique for the measurement of sorption and diffusion in nonporous membranes is described. An experimental apparatus has been designed for carrying out the transient permeation experiments. A general time-lag analysis procedure has also been developed in order to obtain the sorption and diffusion parameters from the transient permeation data. The effects of concentration dependent diffusivities, polymer swelling and a thermodynamic correction factor have been included in the analysis. Transient permeation experiments have been carried out to determine the sorption and diffusion of acetone in polydimethylsiloxane (PDMS). The results obtained are in good agreement with data from the literature, indicating that the proposed technique is suitable for the measurement of sorption and diffusion in nonporous membranes.     

A new sorption model with a dynamic correction for the determination of diffusion coefficients

This paper describes an improvement to the method used for the calculation of diffusion coefficients from data obtained by the measurement of vapor sorption kinetics in a flat, non-porous polymeric membrane. The advantage of our corrected model is that it can be applied to systems displaying both fast and slow sorption kinetics, as is demonstrated using cellulose myristate – hexane and cellulose acetovalerate – ethanol systems at a temperature of 298 K. Experiments were conducted on a specially developed sorption apparatus equipped with McBain’s spiral quartz balances. Sorption kinetics are generally described by the solution of Fick’s second law, the solution of which assumes relative pressure in the form of the unit step function. Our correction involves modifying this solution so that a more realistic relative pressure increase is assumed in terms of the Laplace transform.     

Water and methanol permeation through short-side-chain perfluorosulphonic acid ionomeric membranes

The water and methanol transport into a short-side-chain perfluorosulphonic acid ionomeric (PFSI) membrane suitable for application in proton exchange membrane fuel cells (PEMFC), namely Hyflon^® Ion, was studied between 35 and 65 °C. In particular, the permeabilities of pure water, pure methanol and their mixtures at different temperatures were measured through pervaporation experiments, at various values of feed composition. Due to the presence of mutual interactions between permeants as well as among penetrants and polymeric matrix, the composition of the feed solution affects the membrane permeability in a way which cannot be predicted on the basis of permeability data of the pure liquid components alone. It has been found in particular that the presence of the water in the mixture enhances the methanol permeability, due to the positive effects of matrix plasticization and favourable energetic interactions. In turn, by considering water permeability data in the presence of a poorly permeating component such as glycol, it can be concluded that also water permeation is enhanced by the presence of methanol, although to a lower extent.     

Probing supported model and native membranes using AFM

Atomic Force Microscopy (AFM) has gained lots of interest since its ability to get high resolution imaging in liquid environment. In the last years, this technique was particularly successful in probing the surface of membrane model systems of biological interest and spectacular results have been obtained with native specialized membranes. In this review, we aim at highlighting the recent developments that illustrate the unique powerfulness of AFM in determining the nanoscale organization of membranes and their local physical properties. An important part will focus on AFM high resolution imaging of transmembrane proteins in model and native membranes and on the study of few applications such as biosensors. An overview of main recent developments of AFM as well as new possibilities gained by combination with other techniques will also be addressed.     

Ion-transport and diffusion coefficients of non-plasticised methacrylic-acrylic ion-selective membranes

The ion-transport behaviour of methacrylic-acrylic-based polymers for ion-selective electrode (ISE) membranes was investigated by a spectrophotometric method to determine the apparent diffusion coefficient. By observing the degree of deprotonation of the chromoionophore or chromogenic ionophore, the extent of penetration of cations into the polymer films was determined. The transport of the cations into the optode films depended on the stoichiometry of complexation by the ionophores. The apparent diffusion coefficients, estimated from the deprotonation data were of the order of 10⁻¹² to 10⁻¹¹ cm² s⁻¹. These values indicate that the apparent ion mobility in the methacrylic-acrylic ISE membranes is approximately a thousand times lower than that in plasticised PVC ISE membranes. For some ionophores, the value of the apparent diffusion coefficient could be modulated according to the ionophore content in the membrane and the data obtained for a calixarene containing membrane were tested against a model for facilitated diffusion with chained carriers. The data did not fit a model where intramolecular diffusion was limiting, but were consistent with a first-order rate-limiting mechanism involving an intermediate 1:2 complex between ion and ionophore. In this instance, the lowest values for D_app were thus not necessarily obtained for lowest ionophore loading and in the range examined, a trend of decreasing D_app with increasing ionophore was noted.     

液膜萃取本地产烟叶中烟碱的研究

采用液膜萃取技术对本地产烟叶的烟碱进行了分析,膜载体使用0.45 μm的PVC油膜和定性滤纸,浸泡膜载体的溶剂分别使用十一烷,十六烷和CHCl3.液膜萃取后的样品经GC/MS分析表明,滤纸作为膜载体的萃取效率明显高于PVC油膜;相同膜载体的情况下,以CHCl3浸泡的膜载体的萃取效果比较好.文中还对两种膜载体在不同溶剂浸泡下的烟碱的萃取效率以及最佳萃取时间进行了研究.     

Silicalite-filled poly(siloxane imide) membranes for removal of VOCs from water by pervaporation

Silicalite-filled poly(siloxane imide) (PSI) membranes were prepared for the separation of volatile organic compounds (VOCs) from water via pervaporation. PSI copolymer was synthesized by polycondensation of 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) with a siloxane-containing diamine, e.g., poly(dimethylsiloxane), bis(3-aminopropyl) terminated (PSX), added with 3,3-diaminodiphenyl sulfone (DDS). 2,4,6-Triamine pyrimidine (TAP) was added into the casting solution in order to enhance the compatibility between the polymeric matrix and the filler, silicalite. The PSI membranes were characterized by SEM. The surface morphology for the membrane with the addition of TAP differs from that without TAP. The latter seems to be consisting of particles in the membrane surface. The sorption selectivity of the PSI membranes for chloroform/water solutions was investigated, and there was a highest value for it around 50 wt.% of PSX content. The pervaporation performance of the membranes was studied with the separation of chloroform/water mixture. The silicalite-filled membrane with 120 μm thickness exhibit a high total permeation flux of 280 g m⁻² h⁻¹ with separation factor of 52.2 for 1.2 wt.% of the chloroform/water mixture.     

Water sorption and diffusion coefficients of protons and water in PVDF-g-PSSA polymer electrolyte membranes

Water sorption properties, proton NMR spectra, and diffusion of water and protons in poly(vinylidene fluoride)-graft-polystyrene sulfonic acid (PVDF-g-PSSA) polymer electrolyte membranes were studied. Sorption curves for the membranes with different degrees of grafting in protonated and Na⁺ form were measured by equilibrating the membranes over saturated salt solutions. The membrane water content was found to be sensitive to changes in relative humidity (RH). The water/sulfonic acid ratio λ for the protonated samples was around 2 at 20% RH and increased to λ ∼ 30 at 100%. Proton NMR, pulsed field gradient proton NMR (PFG-NMR), and impedance measurements were made on membranes with different λ. In the proton NMR spectra only one peak was found, originating from the water in the membrane. The chemical shift of the peak was found to be dependent on the counterion and the water content. The water self-diffusion coefficients D_H2O, measured by PFG-NMR, increased with degree of grafting and water content of the membranes. The proton conductivity and the calculated proton mobility decreased more steeply than the D_H2O with decreasing water content. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2893–2900, 1999     

Self-assembly of inner skin hollow fiber polyelectrolyte multilayer membranes by a dynamic negative pressure layer-by-layer technique

In the past studies, electrostatic layer-by-layer (LbL) adsorption of oppositely charged polyelectrolytes has proven to be a promising method for the preparation of polyelectrolyte multilayer membranes (PEMMs). Till now, this method was mainly used to assemble flat sheet and tubular membranes. Since hollow fiber membrane has some advantages such as high-packing density, self-contained mechanical support and hence the consequent economical superiority, this study therefore seeked to assemble inner skin hollow fiber PEMMs by using a dynamic LbL adsorption technique. The assembly process was successfully accomplished by alternatively dynamically filtrating polyacrylic acid (PAA) and polyethyleneimine (PEI) on a hydrolyzed hollow fiber polyacrylonitrile (PAN) membrane under a negative pressure condition. In the case of pervaporation separation of 95 wt.% ethanol–water mixture (50 °C), the membrane obtained with only 4.5 and 6.5 bilayers had separation factor of 245 and 1338 while the permeate fluxes were 290 and 120 g/(m² h), respectively. The pervaporation separation behavior of various alcohol/water mixtures with the alcohols being t-butanol, 2-propanol and ethanol were also investigated. Finally, scanning electron microscopy and atomic force microscopy clearly confirms a uniform and defect-free layer formed on the inner surface of hollow fiber support. Since different polyelectrolyte pairs could be used to assemble PEMMs for different uses, it was expected that the dynamic negative pressure LbL adsorption technique could also potentially be used to prepare many types of PEMMs in other fields.     

New methods for the determination of the parameters of a concentration‐dependent diffusion law for molecular penetrants from transient permeation or sorption data

New methods were developed for the determination of the plasticization parameters and the limit diffusion coefficient of a penetrant whose diffusivity varies exponentially with its concentration. No specific computer softwares is required for their use and they are user friendly. The method using differential permeation data is based on the correlations between the slope of the reduced permeation flux versus time plot at the inflexion point, and the two key parameters of the concentration‐dependent diffusivity laws. For the transient sorption method, the slope of the penetrant mass uptake versus square‐root of time curve leads to the same parameters of the diffusion law via similar correlations.     

Differential permeation — Part I: A method for the study of solvent diffusion through membranes

We describe the differential permeation method for the study of the diffusion of solvents from a liquid (or liquid mixture) through flat or tubular membranes. This method consists of measuring the transient permeation rates through the membrane when one of its faces is suddenly put into contact with the liquid medium. The change in the transient rate with time is analyzed by numerical best fitting methods to determine the Fickian diffusion coefficient. A simplified equation is proposed for the fitting of the response of a tubular membrane. Deviations from the Fickian transport mechanism with concentration-independent diffusion coefficient can be evidenced and eventually analyzed by using other mechanistic models.     

Diffusion of glycosylphosphatidylinositol (GPI)-anchored bovine prion protein (PrP) in supported lipid membranes studied by single-molecule and complementary ensemble methods

In this work cellular bovine prion protein (PrP^c) was incorporated in supported lipid membranes and its lateral diffusion was studied by single-dye tracking (SDT) and a complementary ensemble method, fluorescence recovery after photobleaching (FRAP). PrP^c was purified from calf brain with its native glycosylphosphatidylinositol (GPI) anchor and reconstituted into DMPC lipid vesicles. Homogeneous spreading on solid supports over macroscopic areas was confirmed with fluorescence microscopy. FRAP results demonstrated very high mobile fractions of up to 94%, confirming that most of the GPI-anchored PrP^c are freely diffusive in the fluid supported membrane matrix. Moreover, the lateral diffusivity of PrP^c significantly depends on the pH of the buffer, suggesting that the conformation of PrP^c and thus the frictional drag exerted to the protein molecule (and thus the effective hydrodynamic radius) is influenced by the effective net charge. To complement the ensemble results obtained by FRAP, the statistical variation of lateral diffusion coefficients of individual PrP^c molecules in the supported membranes were measured with SDT. Simulation-based statistical analysis indicated that in addition to the expected statistical scatter there is a significant spread of diffusion coefficients, while the average of the diffusion coefficients of individual proteins obtained by SDT is in excellent agreement with those measured by ensemble FRAP. In further experiments, PrP^c was laterally concentrated in the membrane by the application of tangential electric fields (membrane electrophoresis). However, the equilibrium concentration profile reached after 20 min was different from an exponential gradient. This finding suggests that PrP^c purified from bovine brain possesses non-uniform net charges. As the lateral diffusion coefficient of proteins in two-dimensional lipid membranes sensitively depends upon the frictional drag, the combination of SDT, ensemble FRAP, and membrane electrophoresis can be used as a powerful tool to gain insights into protein–protein binding and oligomer formation that would play a crucial role in infectious protein transmitted diseases such as BSE.     

Synthesis of industrial scale NaY zeolite membranes and ethanol permeating performance in pervaporation and vapor permeation up to 130 °C and 570 kPa

NaY zeolite tubular membranes in an industrial scale of 80 cm long were synthesized on monolayer and asymmetric porous supports. The quality of synthesized membranes were evaluated by pervaporation (PV) experiments in 80 cm long at 75 °C in a mixture of water (10 wt.%)/ethanol (90 wt.%), resulting in higher permeation fluxes of 5.1 kg m⁻² h⁻¹ in the monolayer type membrane and of 9.1–10.1 kg m⁻² h⁻¹ in the asymmetric-type membranes, respectively. The uniformity with small performance fluctuation in longitudinal direction of the membranes were observed by PV for 10–12 cm long samples at 50 °C in a mixture of methanol (10 wt.%)/MTBE (90 wt.%). The ethanol single component permeation experiments in PV and vapor permeation (VP) up to 130 °C and 570 kPa were performed to determine the relations between the ethanol flux and the ethanol pressure difference across the membrane which is represented by permeance (Π, mol m⁻² s⁻¹ Pa⁻¹) for estimate of potential of ethanol extraction through the present NaY zeolite membranes applying feasible studies. Results indicate that (1) the permeation fluxes are linearly proportional to the driving force of vapor pressure for each sample in VP and PV. The permeances through an asymmetric support type membrane were rather constant of 0.6–1.2 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ in the wide temperature range of 90–130 °C in PV and VP, indicating that the ethanol permeances have weak temperature dependency with the feed at the saturated vapor pressure.

The results of superheating VP experiments showed that ethanol permeation fluxes are increased with increasing of the degree of superheating at a given constant feed vapor pressure. The ethanol permeances are increased with increasing of temperature at a given feed vapor pressure. The superheating VP could be a feasible process in industry.     

Comparison between the pervaporation and vapor permeation performances of polycarbonate membranes

The pervaporation and vapor permeation performance of symmetrical and asymmetrical polycarbonate membranes, prepared via a dry-phase inversion and wet-phase inversion methods, respectively, were studied by measuring the permeation rate and separation factor. It was found that the polymer concentration effect on the pervaporation performance for the symmetrical polycarbonate membrane was lower than that for the asymmetrical polycarbonate membrane. Compared with pervaporation, vapor permeation has a significantly increased separation factor with a decreased permeation rate for the symmetrical polycarbonate membrane. Water molecules preferentially dissolve into the symmetrical polycarbonate membrane and diffuse easily through the membrane.     

A fundamental study of organofunctionalised PDMS membranes for the pervaporative recovery of phenolic compounds from aqueous streams

Modified polydimethylsiloxane (PDMS) composite membranes in which a known mol% of the SiMe groups were replaced by a short methylene spacer group terminated by one of the four side-arm functional groups, acetate, ---CO₂Me; ethylether, OEt; dimethylamino, ---NMe₂; and pyridyl, ---py; were fabricated and tested in short term trials for the pervaporative recovery of cresols from aqueous solution. The influences of functional group type, functional group loading, pH, temperature and purity of the feed solution were investigated. Three commercially available hydrophobic membranes were also examined for comparison. It was found that significant performance enhancements, compared with an unfunctionalised PDMS membrane, were realised for all functionalised PDMS membranes, with dimethylamino and ethylether functionalities proving the most effective. A functional group loading level close to 20% was found to be optimal for this application, The influence of feed pH in the range of 5–8.5 was small on total flux but significant on selectivity for amine loaded membranes. By contrast, the effect of feed temperature was significant on total flux but negligible on selectivity. Low levels of phenolic impurities in a p-cresol feed solution were found to have negligible effect on the separation. Compared with commercially available zeolite filled PDMS and PEBA membranes, the functionalised PDMS membranes showed a better overall performance. The PV performance of all new membranes followed the trend: o-cresol>p-cresol>phenol.     

A SEM–EDX study of highly stable supported liquid membranes based on ionic liquids

This work evaluates the operational stability of six different supported liquid membranes (SLMs) based on ionic liquids (ILs). [bmim⁺][PF₆⁻]_, [bmim⁺][BF₄⁻] and [bmim⁺][NTf₂⁻] were used as supporting phase in Nylon^® and Mitex^® membranes. Scanning electron microscopy (SEM) combined with energy dispersive X-ray (EDX) analysis was used to characterize the membrane surface morphologically and examine the global chemical composition of the membranes and the distribution of the ILs within them.

Study of the freshly impregnated membranes showed that, in all cases, the ILs were homogeneously distributed, mostly filling the pores of the membranes although, in some cases, a small amount of excess of IL was located on the external membrane surface. Stability tests were performed by keeping the respective impregnated membranes immersed for a week in a diffusion cell including two independent compartments and using n-hexane/n-hexane as the respective feed and receiving phases. The SEM–EDX study of membranes after continuous operation showed that the ILs were still retained within the membrane pores and only small losses of the IL initially located on the external surface were observed. These observations are in complete agreement with the ionic losses determined by mass balance.     

Sorption and transport behavior of gasoline components in polyethylene glycol membranes

Desulphurization mechanism of polyethylene glycol (PEG) membranes has been investigated by the study of solubility and diffusion behavior of typical gasoline components through PEG membranes with various crosslinking degrees. The sorption, diffusion and permeation coefficients were calculated by the systematic studies of dynamic sorption curves of gasoline components such as thiophene, n-heptane, cyclohexane, cyclohexene and toluene in PEG membranes. Furthermore, the temperature dependence of diffusion and solubility coefficients and the influence of crosslinking degree on sorption and diffusion behaviors were conducted to elucidate the mass-transfer mechanism. According to the discussions on dynamic sorption curves, transport mode, activation energy and thermodynamic parameters, thiophene species were the preferential permeation components. Crosslinking is an effective modification way to improve the overall performance of PEG membranes applied in gasoline desulphurization. The pervaporation (PV) and gas chromatography (GC) experiments results corresponded to the conclusions. All these investigations will provide helpful suggestions for the newly emerged membrane desulphurization technology and complex organic mixture separation by pervaporation.     

Prediction of the selectivity in the recovery of transesterification reaction products using supported liquid membranes based on ionic liquids

Previously, we reported the selective simultaneous separation of the substrates and products of a transesterification reaction (vinyl butyrate, 1-butanol, butyl butyrate and butyric acid) through supported liquid membranes (SLMs) based on ionic liquids (ILs) and concluded that transport of the compounds was mainly regulated by the affinity of the ionic liquid towards each solute.     

The use of moment theory to interpret diffusion and sieving measurements in terms of the pore size distribution in heteroporous membranes

Moment theory has been applied to model porous membranes to show that one can place reasonable bounds on the cumulative pore size distribution, the hindered diffusivity or the reflection coefficient of large solutes in a heteroporous membrane by measuring the diffusive permeability to a small solute, the hydraulic permeability and one or two additional transport characteristics. These additional measurements involve either the flux of a small solute at Pe1, the hindered diffusivity of a large solute or the reflection coefficient of a large solute at Peå1. Membrane heteroporosity is incroporated in the predicted bounds without requiring one to make any a priori assumptions about the nature of the pore size distribution. In this paper, the results from calculations performed with different model membranes containing log-normal pore size distributions are reported. A comparison of the results obtained with three different membranes shows that one can distinguish between membranes with the same average pore size but different pore size distributions by measuring either the hindered diffusion coefficient or the reflection coefficient of two different sized solutes. A comparison of the bounds on D and the bounds on σ predicted from different types of transport measurements shows that, under certain conditions, one can place tighter bounds on one transport characteristic by measuring a different one.     

Transport properties of PVA/PEI/PEG composite membranes: sorption and permeation characterizations

Poly(vinylalcohol)/poly(ethyleneglycol)/poly(ethyleneimine) blend membranes were prepared by solution casting followed by solvent evaporation. The chemical structure of the prepared membranes was analyzed by FTIR and DSC. The sorption behavior as well as the permeabilities of the membranes for pure CO₂ and N₂ were investigated. The results show that the PVA/PEI/PEG membranes possess a higher permeability of CO₂ and a lower permeability of N₂. The membrane displays a CO₂ permeability of 27 Barrer, and a N₂ permeability of 3 Barrer at 25°C and 1 bar. CO₂ sorption behavior of the composite membrane, which can be classified as a dual-mode sorption model, and N₂ sorption behavior of the copolymeric membrane is in agreement with the Fickian diffusion model.