Optimization study of polyethylene glycol and solvent system for gas permeation membranes

Cellulose acetate (CA) membranes blended with Polyethylene glycol (PEG) in acetone–water solvent system were synthesized by using solution-casting method that resulted in the formation of flexible, white membranes. Different molecular weight (MW) grades of PEG (including MW 1000, 10,000 and 20,000?g/mol) were used. Cast membranes were tested for tensile strength and permeability at different loading of PEG MW 10,000 and 20,000?g/mol. Excellent flexible membranes were produced in acetone–water solvent system in the presence of PEG, which were otherwise brittle. Surface structure and morphology were analysed using scanning electron microscopy. The presence of different functional groups was confirmed using Fourier transform infra-red spectroscopy and the mechanical characteristics were studied by tensile testing. The introduction of PEG caused an increase in permeability of the membranes. The increase in permeability is due to the opening up of pores as the membrane becomes more flexible, when the plasticizer is added. The permeability continues to increase with the addition of PEG. Moreover, the resulting membranes are not only more flexible, but also have largely improved tensile strength as compared to the CA membranes without PEG. This improved tensile strength can also be attributed to the improved flexibility of the membrane. A trade-off is reached between tensile strength and permeability as increasing amount of PEG improves tensile strength but the resulting membrane becomes too permeable to be used for gas separation. Moreover, using PEG of higher MW resulted in porous membranes, even at low amounts of PEG. Therefore, we concluded that CA membrane with less amount of low-MW PEG (i.e. 5% PEG of MW 1000?g/mol) must be used to optimize both permeability and tensile strength of the membrane.     

Membrane structure and its correlation with membrane permeability

Methods for the investigation of pore and molecular structure of synthetic membranes are reviewed. Membranes are classified as coarse-porous, fine-porous, and solution-diffusion membranes, on one hand; and homogeneous, asymmetric, and composite on the other, Pore structure of synthetic membranes can be elucidated in detail only by electron and raster electron microscopic investigations. Inspection of molecular structure requires diversely specific test probes such as low-energy neutron scattering and/or diffraction, and gas sorption and permeability measurements, as well as thermodynamic and thermomechanical analysis. Other methods used to elucidate pore and molecular structure of synthetic membranes are discussed and, concurrently, membrane structure is correlated with membrane permeability.     

Turbulent flow technique for the estimation of oxygen diffusive permeability of membranes for the oxygenation of blood and other cell suspensions

When transport-efficient membrane modules (such as those where the liquid flows outside hollow fibre membranes) or membranes with prolonged resistance to wetting are used for the oxygenation of blood or other cell suspensions, membrane contribution to the overall oxygen transfer resistance into the liquid may become significant. Thus, estimation of membrane diffusive permeability towards relevant gases (e.g., oxygen) is important to develop new membranes and to ensure reproducible commercial membrane performance.

In this paper, we report on a turbulent flow technique for the estimation of the oxygen diffusive permeability of membranes used in outside-flow oxygenators. Water is re-circulated under turbulent flow conditions in a closed-loop from a reservoir to the shell of lab-scale membrane modules. The overall oxygen transfer to water coefficient is estimated at increasing water flow rates from the time the change of dissolved oxygen tension in the stream leaving the water reservoir occurs. Oxygen diffusive permeability is estimated as the reciprocal overall transfer resistance at infinitely high water flow rates, for negligible gas-side oxygen transport resistance. The technique was used to estimate oxygen diffusive permeability of commercial Oxyphan^® polypropylene membranes for blood oxygenation and of two laboratory polypropylene membranes, the one featuring a microporous wall structure with smaller-than-standard pore size, the other featuring an outer thin, dense layer supported by a thick spongy layer. The turbulent flow technique yields oxygen diffusive permeability estimates consistent both with membrane hydraulic permeability towards gaseous nitrogen, membrane wall structure, and with values in literature obtained using a liquid reactive with oxygen, but without the complications associated with reaction and physical transport kinetic characterisation. We conclude that the turbulent flow technique is a useful tool in the development and quality control of membranes for the oxygenation of blood and other cell suspensions.     

Nafion膜在直接甲醇燃料电池中的应用及改进

Nafion质子交换膜性能优越,广泛应用于固体聚合物燃料电池中,但因存在甲醇渗透问题,使其在直接甲醇燃料电池中的应用受限制。本文讨论了Nafion质子交换膜的物质传输机理,侧重介绍甲醇分子的渗透机理,综述了基于降低甲醇渗透率而对Nafion膜所做的改进性研究和几种具有应用前景的替代膜。     

Membrane permeation of water—alcohol binary mixtures

The permeability and selectivity of nylon-6, cellophane, and cellulose 2.5-acetate membranes toward binary mixtures of aliphatic alcohols and water were studied at 60°C. Commercial membranes made of the above materials were used with and without preswelling. The cellophane membranes swelled considerably more than the other types of membranes in both water and in aqueous isopropanol mixtures containing over 40 mole% H₂O. Therefore, the effects of swelling on membrane permeability were examined in some detail with cellophane membranes. The permeability characteristics of cellophane membranes could be altered significantly by suitable pretreatment. The effects of pretreatment are negligible in the case of cellulose 2.5-acetate and nylon-6 membranes.     

过渡金属有机络合物添加剂对聚酰亚胺气体分离膜性能的影响

采用具有庞大取代基团的过渡金属有机络合物作为添加剂制备了聚酰亚胺气体分离膜,研究了过渡金属盐、有机配体和金属络合物对聚酰亚胺均质膜和非对称膜氢、氮气体透过性能的影响,结果表明过渡金属盐添加剂提高了分离系数,但降低了气体透过速率;有机配体添加剂增大了气体透过速率却降低了分离系数;以络合物作添加剂时,可在不降低分离系数的情况下使气体透过速率得到提高,是一种改进气体分离膜性能的有效方法。     

Quantum mechanical scattering cross sections and permeability coefficients for ions crossing the human red cell and resting squid axon membranes

Quantum mechanical calculations of elastic scattering cross sections for some permeant ions crossing the human red blood cell and resting axolemma squid axon membranes have been carried out using the three-dimensional spherically symmetric square potential well. Making the assumption that the permeability coefficient is inversely proportional to scattering cross section, we obtain the order of membrane selectivity for the ions as well as values for the permeability coefficients. Despite the relatively simple method used, good agreement between calculated permeability coefficients and data available in the literature is obtained. We suggest that elastic scattering cross section measurements for ions in various membranes would be valuable not only because they give a precise idea about the permeability ratios between ions but they also determine the form of the potential the ions are moving in.     

Conventional processes and membrane technology for carbon dioxide removal from natural gas:A review

Membrane technology is becoming more important for CO 2 separation from natural gas in the new era due to its process simplicity,relative ease of operation and control,compact,and easy to scale up as compared with conventional processes.Conventional processes such as absorption and adsorption for CO 2 separation from natural gas are generally more energy demanding and costly for both operation and maintenance.Polymeric membranes are the current commercial membranes used for CO 2 separation from natural gas.However,polymeric membranes possess drawbacks such as low permeability and selectivity,plasticization at high temperatures,as well as insufficient thermal and chemical stability.The shortcomings of commercial polymeric membranes have motivated researchers to opt for other alternatives,especially inorganic membranes due to their higher thermal stability,good chemical resistance to solvents,high mechanical strength and long lifetime.Surface modifications can be utilized in inorganic membranes to further enhance the selectivity,permeability or catalytic activities of the membrane.This paper is to provide a comprehensive review on gas separation,comparing membrane technology with other conventional methods of recovering CO 2 from natural gas,challenges of current commercial polymeric membranes and inorganic membranes for CO 2 removal and membrane surface modification for improved selectivity.     

Characterization and evaluation of commercial poly (vinylidene fluoride)‐g‐sulfonatedPolystyrene as proton exchange membrane

The possibility of developing low‐cost commercial grafted and sulfonated Poly(vinylidene fluoride) (PVDF‐g‐PSSA) membranes as proton exchange membranes for fuel cell applications have been investigated. PVDF‐g‐PSSA membranes were systematically prepared and examined with the focus of understanding how the polymer microstructure (degree of grafting and sulfonation, ion‐exchange capacity, etc) affects their methanol permeability, water uptake, and proton conductivity. Fourier transform infrared spectroscopy was used to characterize the changes of the membrane's microstructure after grafting and sulfonation. The results showed that the PVDF‐g‐PSSA membranes exhibited good thermal stability and lower methanol permeability. The proton conductivity of PVDF‐g‐PSSA membranes was also measured by the electrochemical impedance spectroscopy method. It was found that the proton conductivity of PVDF‐g‐PSSA membranes depends on the degree of sulfonation. All the sulfonated membranes show high proton conductivity at 92°C, in the range of 27 to 235 mScm⁻¹, which is much higher than that of Nafion212 (102 mScm⁻¹ at 80°C). The results indicated that the PVDF‐g‐PSSA membranes are particularly promising membranes to be used as polymer electrolyte membranes due to their excellent stability, low methanol permeability, and high proton conductivity.     

Amphiphile grafted membranes for the separation of oil-in-water dispersions

Perfluorinated end-capped polyethylene glycol surfactants were covalently attached to fritted glass membranes as a means to improve the separation of oil-in-water emulsions. Hexadecane was used as representative oil for the oil-in-water emulsions; membrane pore size was varied between 10 and 174 microm. Membranes were characterized with respect to contact angle, permeability of bulk fluids, and separation efficiency. Performance was compared to similar metrics applied to unmodified membranes. Modified membranes demonstrated static hexadecane contact angles which were higher than static water contact angles converse to their unmodified counterparts. The relative hydrophilicity and corresponding oleophobicity of the modified membranes resulted in greater water permeability as compared to hexadecane permeability. The presence of the perfluorinated constituent of the amphiphile retarded the flow of hexadecane. For modified membranes, suspended hexadecane coalesced at the membrane surface, was undercut by water, and floated to the surface such that only trace amounts of oil were present in the permeate. Therefore, modified membranes resisted fouling from oil due to the self-cleaning properties of the attached amphiphile.     

Some comments on the applicability of gas permeation methods to characterize porous membranes based on improved experimental accuracy and data handling

The measurement of the gas permeability coefficient as a function of the mean pressure across a membrane can be used to determine a mean pore radius of the membrane. This method has been applied by several authors to characterize microporous and asymmetric ultrafiltration or hyperfiltration membranes. This paper shows how the data acquisition and handling are improved. Experiments are performed on microporous Millipore membranes with a nominal pore radius of 50 nm and on ultrafiltration merebranes of poly(2,6-dimethyl-1,4-phenyleneoxide) with an expectedly sharp pore-size distribution around 2 nm. For the Millipore membrane an unexpected dependence of the calculated pore radius on the type of gas used in the experiment has been found. Measurements on the ultrafiltration membranes indicate that the viscous flow contribution to the permeability coefficient cannot be determined with sufficient accuracy. It is concluded that application of the gas permeation method has some limitations which were not previously recognized.     

Fabrication and characterization of single layer and multi-layer anodic alumina membranes

Porous alumina films containing parallel capillary pores of uniform size were fabricated by anodically oxidizing high purity aluminum films in phosphoric acid and sulfuric acid solutions. These films were formed into membranes by post-oxidation processing that removes unoxidized aluminum as well as a barrier layer of alumina from the base of the pores. Symmetric membranes were made by oxidizing at constant current density conditions. Two layer composite membranes were made by changing current density during the oxidation process. The thickness, pore density and porosity of each membrane were predicted from the relationships between structural characteristics and processing conditions that were developed in previously reported kinetic studies of anodic oxidation of aluminum.Each membrane was then characterized using permeability measurements. The hydraulic permeability of membranes formed in phosphoric acid and the diffusive permeability of membranes formed in sulfuric acid were measured. A comparison of the measured permeability values to those predicted using the structural characteristics calculated using relationships developed in the kinetic studies shows excellent agreement. These results illustrate that porous alumina membranes can be fabricated with transport characteristics that can be predicted from the processing conditions used during membrane formation.     

Calculation of the Liquid and Gas Permeability of Hydrophobic Low-Porosity Membranes of an Arbitrary Thickness

A method for calculating the liquid and gas permeability of hydrophobic low-porosity membranes of an arbitrary thickness is described. The calculation is based on the solution of a problem on percolation—the procedure of finding the distribution of liquid and gas over the membrane thickness. The dependence of the permeability for liquid on the share of pores that are potentially accessible to being filled with liquid is obtained for both thin and thick membranes. This dependence is of a universal nature and can easily be recalculated into a dependence of permeability on the pressure drop for membranes with any distribution of pores by size. Numerical estimates of principal characteristics for a membrane that possesses pores of three types are performed. The characteristics in question include permeabilities for liquid and gas; fluxes of the liquid; critical pressures, at which the permeability for liquid turns other than zero; and the working range of pressures, in which the membrane is capable of working normally. All these data permit the optimization of the operation of similar membranes, in particular, gas-delivering membranes that are used in hydrogen–oxygen fuel cells with a solid polymer electrolyte.     

Solvent-dependent permeability in asymmetric ceramic membranes with tortuous or non-tortuous mesopores

Solvent-dependent transport and the role of surface interactions were examined in commercial mesoporous ceramic membranes using permeability and thermoporometry measurements. The membranes chosen were titania (TiO₂) with tortuous interconnected pores (1, 5, and 50 kDa, corresponding to pore diameters of ca. 8.2, 18.3, and 33.2 nm, respectively) and alumina (Al₂O₃) with non-tortuous 20 nm cylindrical pores. A pre-water/solvent/post-water permeability cycle was employed to account for structural differences between membranes and to gauge the effect of residual solvent on water permeability at different temperatures. Our results suggest that in both types of membranes, restricted permeability of 1-butanol and cyclohexane was due to a combination of surface sorption and an increase in disjoining pressure due to solvation forces. Sorption and solvation forces were prevalent as their length scales were on the same order of magnitude as the pore radii. For 1-butanol, chemisorption changed the surfaces from hydrophilic to hydrophobic, and led to a significant decrease in post-water permeability. While Darcy's law could not describe 1-butanol and cyclohexane permeability, it did apply to water and 1,4-dioxane in the 20 nm alumina membranes. Thermoporometry, coupled with permeability, was further used to evaluate surface wetting within the mesopores.     

Metal oxides nanocomposite membrane for biofouling mitigation in wastewater treatment

These days our one of the major challenges is the treatment of polluted wastewater produced by the growing population and industrial activities. The conventional wastewater treatment methods are costly and need to be more advanced. For this reason, membrane technology has been used as an effective wastewater treatment method for many decades due to its high removal power, selectivity, and permeability properties. Biofouling causes a serious concern related to membrane permeability, shortens membrane life, and selectivity. Polymeric membranes are widely used in wastewater treatment due to their good pore-forming ability, higher flexibility, and relatively low costs but are limited to their hydrophobicity property and more susceptible to fouling. Metal oxides nanomaterials are widely used in the formation of polymer nanocomposite membranes because of their hydrophilicity, larger surface area, pore channels, and high toxicity towards pathogenic micro-organisms. In this review, we have discussed the factors affecting membrane biofouling and their conventional and current treatment methods with their limitations. We have also referred to the use of metal oxide nanomaterials, as an antibacterial agent, for the fabrication of polymer nanocomposite membranes and discuss their antibacterial activity with antibiofouling behavior.     

Evaluation of asymmetrical structure dialysis membrane by tortuous capillary pore diffusion model

The tortuous capillary pore diffusion model (TCPDM) has been used for estimating diffusive and pure water permeability from simple structure parameters such as pore diameter, surface porosity, wall thickness and tortuosity. The validity of this model for evaluation of homogeneous membrane has been already confirmed. Recently, there is a trend toward the use of asymmetrical dialysis membranes made of synthetic polymer such as poly(acrylonitrile) (PAN), polysulfone (PS) and a polyethersulfone polyarylate (PEPA) blend polymer. The purpose of the present study is to apply the TCPDM to evaluation of commercially available hollow-fiber dialysis membranes with asymmetrical structures by simplifying them to a double-layer membrane. The TCPDM is capable of estimating pore tortuosity of asymmetrical dialysis membranes having skin and supporting layers from data on membrane thickness, pore diameter, pure water permeability and water content. Values for diffusive permeability obtained by the TCPDM are in a good agreement with experimental data. This TCPDM model is useful for evaluation of not only homogeneous membrane but also asymmetrical membrane.     

透氢钯复合膜的原理、制备及表征

钯及其合金膜由于具有透氢性好和耐高温的特点,除了用作氢气分离和纯化器外,还可以用作脱氢、制氢等反应的反应器,以实现反应和分离的一体化,并提高转化率和选择性。本文综述了钯基复合膜的原理、制备及表征,并重点介绍了本研究组的光催化镀膜工艺。     

A transient experiment to measure the diffusive permeability of hollow fiber membranes

A precise and rapid transient diffusion experiment has been developed to measure the diffusive permeability of hollow fibers. In this experiment a sealed hollow fiber containing a radioactive solute is exposed sequentially to several well-stirred solute-free reservoirs. This method was used to measure the diffusive permeability of collagen and Cuprophan hollow fibers in an isotonic saline solution for a spectrum of ¹⁴C labelled solutes: urea, sucrose and polyethylene glycol (PEG). To study the effect of environment on membrane permeability, collagen membranes were investigated with urea, sucrose and tritiated water in the following solutions with varying ionic strength and hydrogen ion concentration: pH2 HCl, distilled water and pH2 HCl with 0.8 M NaCl.In each environment, the membranes showed the expected decreases in diffusive permeaability with increasing molecular weight. Collagen membranes ranged from 4 (urea) to 40 (PEG) times the permeability of Cuprophan membranes. The Cuprophan data are consistent with results obtained elsewhere using scaled-down dialyzers. In response to environmental changes, the diffusive permeability of collagen membranes changed overall by a factor of 3 with the following rank: pH 2 HCl > distilled water > pH2 HCl and 0.8 M NaCl. The hydraulic permeability of these membranes changed by a factor of 2 but in a different order pH2 HCl > pH2 HCl and 0.8 M NaCl > distilled water. These permeability changes can be explained in terms of the known environmental dependence for the structure of collagen membranes and have been shown to be consistent with trends predicted by simple transport models.     

Hydraulic and osmotic permeabilities of water and water/sucrose solutions through cellophane membranes

Measurements were made of different transport phenomena in cellophane membranes, using a specially designed device. The aqueous, hydraulic permeability was studied over a range of temperatures between 30 and 50°C. The hydraulic permeability/temperature relationship was found to be linear. The use of sucrose solutions of equal concentration in the two phases on either side of the membrane produced a considerable variation in the hydraulic permeability when the solution concentrations were greater than 0.1 M. Osmotic flow experiments were carried out for sucrose/water solutions, and the coefficient of osmotic permeability was found to be independent of the solution concentrations separated by the membrane within the range of concentrations studied (up to 0.2 M). The equivalent pore radius was calculated for the membranes used; these values are higher than that of the molecular diameter of water. The reflection coefficient was calculated for one of the membranes used and a value of 0.077 was obtained.     

Specific binding structures of dendrimers on lipid bilayer membranes

Dissipative particle dynamics simulations are used to study the specific binding structures of polyamidoamine (PAMAM) dendrimers on amphiphilic membranes and the permeation mechanisms. Mutually consistent coarse-grained (CG) models both for PAMAM dendrimers and for dimyristoylphosphatidylcholine (DMPC) lipid molecules are constructed. The PAMAM CG model describes correctly the conformational behavior of the dendrimers, and the DMPC CG model can properly give the surface tension of the amphiphilic membrane. A series of systematic simulations is performed to investigate the binding structures of the dendrimers on membranes with varied length of the hydrophobic tails of amphiphiles. The permeability of dendrimers across membranes is enhanced upon increasing the dendrimer size (generation). The length of the hydrophobic tails of amphiphiles in turn affects the dendrimer conformation, as well as the binding structure of the dendrimer-membrane complexes. The negative curvature of the membrane formed in the dendrimer-membrane complexes is related to dendrimer concentration. Higher dendrimer concentration together with increased dendrimer generation is observed to enhance the permeability of dendrimers across the amphiphilic membranes.