Water vapor sorption and transport in dense polyimide membranes

The sorption and transport of water vapor in five dense polyimide membranes were studied by thermogravimetry. The sorption isotherms of water vapor in the polyimides could be successfully interpreted by both the dual‐mode sorption model and the Guggenheim–Anderson–de Boer equation. The water vapor diffusion behavior was found to be nearly Fickian at higher water vapor activities, whereas non‐Fickian diffusion was observed at lower water activities. The phenomena could be well described by the mechanism of combined Fickian and time‐dependent diffusion. The diffusion coefficient and water vapor uptake in the polyimides were strongly dependent on the polymer molecular structure. Except for the polyimide prepared from 3,3′,4,4′‐diphenylsulfone tetracarboxylic dianhydride and 1,3‐bis(4‐aminophenoxy) benzene, the permeability of water vapor in the dense polyimide membranes predicted from the sorption measurement at 30°C corresponded well with the water vapor permeability measured at 85°C. Among the polyimides studied, pyromellitic dianhydride–4,4′‐diaminophenylsulfone (50 mol%)/4,4′‐oxydianiline (50 mol%) showed both high water sorption and diffusion and, therefore, high water vapor permeability, which for vapor permeation membranes is necessary for the separation of water vapor from gas streams. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2306–2317, 2003     

Hindered diffusion of residue narrow cuts through polycarbonate membranes

Hindered diffusion plays an important role in catalytic processing of residue and heavy oil because of large size molecules in these feedstocks. Vacuum residue of Athabasca oil sand bitumen was fractionated into 13 narrow fractions and an end‐cut by supercritical fluid extraction and fractionation (SFEF). Diffusion transport of five SFEF cuts through four polycarbonate membranes was investigated using a diaphragm cell at 308 K. The results showed that diffusion coefficients of the five SFEF cuts decreased as the experiment proceeded, which illustrates that these cuts are polydisperse in size. The effective diffusion coefficients varied with molecular size and pore size. Hindered diffusion of the five SFEF cuts is significant in the membranes with nominal pore diameter of 15 nm, which is around the average pore size of typical hydrotreating catalyst. Comparisons between experimental data and theoretical prediction revealed that the actual hindered degree for diffusion of the five SFEF cuts is higher than that calculated by the Renkin equation. There were slight differences in diffusivity among saturate, aromatic, and resin constituents. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

Concentration dependence of the diffusion coefficient in polymer solution and molecular weight distribution determined by the diffusion method

The effects of the concentration dependence of the diffusion coefficient of a polymer solution (polystyrene in benzene and cyclohexane) in determining molecular weight distribution by the diffusion method are briefly discussed. The value of the ratio D_m0/D_A0 in a good solvent was found to be close to 1.0 for a polydisperse polymer and less than 1.0 for monodisperse polymers. Molecular weight distribution curves of the polydisperse sample were obtained by the diffusion method in cyclohexane and benzene, respectively. The molecular weight distribution curve obtained for the polymer used in benzene solution looked as if the polymer had a narrow molecular weight distribution. The phenomena cited above were interpreted in the light of the concentration dependence of the diffusion coefficient of polymer solutions.     

Polyamide‐imide nanofiltration hollow fiber membranes with elongation‐induced nano‐pore evolution

The molecular design of nanoporous membranes with desired morphology and selectivity has attracted significant interest over the past few decades. A major problem in their applications is the trade‐off between sieving property and permeability. Here, we report the discovery of elongation‐induced nano‐pore evolution during the external stretching of a novel polyamide‐imide nanofiltration hollow fiber membrane in a dry‐jet wet‐spinning process that simultaneously leads to a decreased pore size but increased pure water permeability. The molecular weight cutoff, pore size, and pore size distribution were finely tuned using this approach. AFM and polarized FTIR verified the nano‐pore morphological evolution and an enhanced molecular orientation in the surface skin layer. The resultant nanofiltration membranes exhibit highly effective fractionation of the monovalent and divalent ions of NaCl/Na₂SO₄ binary salt solutions. More than 99.5% glutathione can be rejected by the nanofiltration membranes at neutral pH, offering the feasibility of recovering this tripeptide. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Permeabilities of coagulated cellulose acetate dialysis membranes

The diffusive flux of NaCl and the hydraulic flux of pure water through coagulated cellulose acetate membranes are examined. Coagulated cellulose acetate membranes (without densification by heat treatment or drying) possess higher permeability than what may be expected from the permeabilities of the dry polymer. Their overall hydraulic permeability (ultrafiltration rate of water) is greatly dependent upon the membrane casting conditions and the resulting asymmetry of the membrane. On the other hand, the asymmetry of a membrane does not play as great a role in the diffusive permeability of a solute. With homogeneous membranes, higher diffusive flux is always accompanied by higher hydraulic permeability. With asymmetric membranes, this is not always true. The diffusive permeability of NaCl and the hydraulic permeability of water through coagulated cellulose acetate membranes can be controlled nearly independently. Consequently, high diffusive (NaCl) permeability with low hydraulic water permeability and vice versa can be obtained by varying the casting conditions and also by partially saponifying the denser portion of the membrane.     

Hindered diffusion of asphaltenes through microporous membranes

The relationship between the diffusion coefficient of asphaltenes and pore size was studied experimentally using track-etched mica membranes. The asphaltenes were extracted from Kuwait atmospheric bottoms using criteria of n-pentane insolubility and tetrahydrofuran solubility at 25°C. Data were obtained for asphaltene fractions of narrow size range by using gel permeation chromatography to analyze the diffusion samples. The results show a very strong pore size effect on diffusion coefficient in the range 70–500 Å pore radius for asphaltenes whose GPC-equivalent polystyrene molecular weight is 3000 or greater. By properly accounting for the molecular size of the asphaltene fractions, we are able to obtain good agreement between the measured diffusion coefficients and those predicted from a hydrodynamic theory of hindered diffusion.     

Zeolite filled P84 co-polyimide membranes for dehydration of isopropanol through pervaporation process

We have developed zeolite 5A and 13X embedded P84 co-polyimide membranes with enhanced permeability and selectivity for the pervaporation dehydration of isopropanol (IPA). It is found that a higher annealing temperature, i.e., is more favorable to improve adhesion between zeolite and polymer phase, and to enhance charge transfer complexes (CTCs) formation. FESEM, DSC and gas permeation results show that zeolite 13X has better compatibility with the matrix polymer than zeolite 5A because of stronger interactions between Na cations in zeolite 13X framework and electron acceptor groups of P84 polyimide. The addition of zeolite into the P84 dense membrane improves water sorption capacity and pervaporation separation performance significantly. Owing to the bigger pore size, larger pore volume, higher sorption capacity and better adhesion, the zeolite 13X incorporated P84 membranes has a much higher permeability than zeolite 5A filled membranes. Interestingly, both have comparably high selectivity possibly because of the effects of chain rigidification and partial pore blockage. The addition of zeolite 13X reduces activation energy for water permeation through the membrane but increases that for IPA permeation. However, the addition of zeolite 5A increases activation energy for both water and IPA permeation. Pervaporation permeability increases with zeolite 13X loading, while the selectivity achieves the maximum at 30 wt% zeolite 13X loading. When the zeolite 13X loading approaches 40 wt%, the adhesion between zeolite and polymer becomes poor and the membrane selectivity declines. A comparison between pervaporation and gas separation results reveals that pervaporation membranes can tolerate a higher degree of interstitial defects than gas separation membranes because of stronger molecular interactions between the feed and the polymer, and the larger molecular size difference between penetrants in the former.     

pH‐responsive permeability of PE‐g‐PMAA membranes

Poly(methacrylic acid) (PMAA) grafted porous PE membranes (PE‐g‐PMAA) were studied. It was found that (1) a wide range of graft yields can be achieved by varying irradiation time (20–240 min) and monomer concentration (0.22M–0.66M), (2) the grafted membrane exhibits reversible permeability response, (3) the membrane shows a maximum permeability response at an intermediate permeant molecular weight due to size exclusion effect, and (4) depending on the graft yield, two types of permeability response can be obtained. These observations are consistent with our earlier study on poly(N‐isopropylacrylamide) (PNIPAAm)–grafted porous polyethylene membranes. In addition, it was observed that the solvent used during grafting may influence the graft location—presumably due to variations in pore wetting. Specifically, compared to water solvent, methanol can increase grafting inside membrane pores, an observation inferred from membrane swelling, thickness measurement, and SEM characterization. Moreover, preferential grafting inside the membrane pores, as affected by increasing methanol content in the grafting solvent, results in lower membrane permeability and a greater pore graft‐controlled type of permeability response. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 778–786, 2000     

Ionic salt permeability through phase‐separated membranes composed of amphoteric polymers

Amphoteric copolymers composed of hydrophilic poly(dimethyl acrylamide) and hydrophobic poly(dimethyl siloxane) formed phase‐separated membranes. The hydrophilic and hydrophobic components formed continuous phase‐separated domains in the membranes. The hydrated poly(dimethyl acrylamide) domains formed membrane‐spanning pathways, which permitted an ionic salt to permeate the membranes. The permeability of the ionic salt through the amphoteric copolymer membranes was studied. On the basis of the results, the mechanism of salt transport could be explained by the free‐volume theory, which was used for the analysis of diffusive transport in the hydrated, homogeneous membranes. The diffusion coefficient of the ionic salt increased exponentially as the volume ratio of the hydrophilic polymer to water [(1 − H)/H, where H is the degree of hydration] decreased in the membrane. It was possible to postulate that the diffusion of the ionic salt through the membranes was dependent on the free‐volume fractions of water and hydrophilic poly(dimethyl acrylamide) domains in the membranes. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Analysis of compaction and life‐time prediction of porous polymer membranes: influence of morphology,diffusion and creep behaviour

In membrane applications, large values of permeability and selectivity are generally desired during the whole period of application. The permeability of porous polymer membranes often is reduced by the effect of compaction. Compaction of polymer membranes is a time‐dependent process which is strongly determined by the viscoelastic properties of the polymer and its plasticisation caused by the feed medium (e.g. a liquid medium or a process gas in the case of porous support structures). In this study, the time‐dependent compaction of porous polymer membranes under pressure is modelled. The influence of viscoelastic and diffusion properties of the polymer material on the permeability of the membrane is analysed for different types of membrane morphologies. The life‐time of a porous polymer membrane is associated with the time at which the glass transition is achieved in a creep experiment. Equations are derived in order to estimate the maximum life‐time of polymer membranes based on compaction. The analysis reveals that the diffusion coefficient, the average retardation time in creep, the magnitude of creep compliance and the time–temperature–pressure shift factor strongly influence compaction of microporous membranes. Generally, a larger tortuosity at constant porosity yields a lower life‐time of the membrane. Buckling of cell struts is the dominant failure mechanism in porous membranes with a very high porosity and allows an estimation of life‐time. © 2016 Society of Chemical Industry     

Diffusion of poly(vinylpyrrolidone) through cellulose ester membranes

Diffusion coefficients of poly(vinylpyrrolidone) in aqueous solutions were ascertained by the diaphragm method as a function of molecular weight and temperature using mixed cellulose ester (Millipore) membranes. The results agree satisfactorily with diffusion coefficients obtained by other methods. Separation of polymer according to molecular size takes place on diffusion as a function of membrane pore diameter. Also, interaction between the polymer and membrane has been observed resulting in a distribution coefficient between solution and membrane larger than 1. The energy and entropy of activation, repectively, increase with polymer chain length, and their magnitudes are in agreement with the view that segment mobility is operative for the diffusion process.     

减压渣油超临界流体萃取馏分在多孔有机膜中的扩散规律

利用超临界流体萃取分馏技术将大港减渣分离成16个窄馏分和1个萃余残渣,选择第3#、6#、9#、12#、15#窄馏分和残渣作为研究对象,运用隔膜池分别测定了308 K下各个油样通过额定孔径为15、50、80和1000 nm 4种聚碳酸酯膜有效扩散系数和平均有效扩散系数。结果显示,大港减渣窄馏分及萃余残渣在膜孔中的有效扩散系数随着实验的进行逐渐降低,表明它们是由一定尺寸分布的组分构成的复杂混合物。随着馏分变重和膜孔直径的降低,各馏分的有效扩散系数均逐渐降低。受阻扩散因子的计算结果表明窄馏分和萃余残渣在15、50和80 nm 3种膜片中的扩散均受到不同程度的阻碍。窄馏分在50和80 nm膜孔中的受阻程度较小,而在15 nm膜孔中的受阻程度相对较大。萃余残渣在这3种膜孔中均存在较为明显的扩散阻力,在15 nm膜孔中的受阻程度尤其严重。受阻扩散因子关联结果表明,在重油分子尺寸和孔径比值相同的条件下,窄馏分和萃余残渣的扩散受阻程度并不相同,分析认为这可能是两者分子构型的差异造成的。     

In-solution structure formation of poly(vinylidene fluoride) building units influencing on the final membrane characteristics

A systematic study was carried out on the initial casting solutions of asymmetric PVDF ultrafiltration membranes to observe the aggregate structure of polymer building units in solution and the properties of the membranes in terms of microstructure morphology, crystallinity, average pore size, pore-size distribution, total porosity, hydrophobicity, wetting energy, molecular weight cut-off, and permeability. Hydrophobic membrane of higher porosity exhibiting higher flux was obtained from the solution of bigger polymer structural units while the membrane obtained from solution of smaller polymer structural units exhibited relatively rougher and hydrophilic surface and smaller uniform pores with lesser flux.     

Mesoporous carbon membranes from polyimide blended with poly(ethylene glycol)

The control of the mesoporous structure in a carbon membrane from a poly(ethylene glycol)/polyimide‐blended polymer was investigated. The size of the pores tends to become large with increase of the content of poly(ethylene glycol) against polyimide, that is, the mesoporous structure could be controlled by the composition of the blended polymers. On the other hand, the average molecular weight of poly(ethylene glycol) has little effect from the viewpoint of the control of the pore structure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 836–841, 2001     

Effect of membrane morphology on rising properties of filtration resistance in microfiltration of dilute colloids

The effect of membrane morphology on the flux decline behaviors in dead‐end unstirred microfiltration of very dilute colloids of polystyrene latex was examined using mixed cellulose ester and cellulose acetate membranes with interconnected tortuous pores and track‐etched polycarbonate membranes with uniform straight cylindrical pores. The plots of reciprocal filtration rate against the filtrate volume per unit membrane area for the former two membranes exhibit concave downward curves in the initial period when the membrane pore blocking is significant, whereas the plot for the latter shows a concave upward curve in that period. The former results were described by a serial resistance model consisting of the initial membrane pore blocking followed by filter cake growth, and the latter was represented by a parallel resistance model in which the pore blocking and cake growth develop simultaneously from the beginning of filtration. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3511–3522, 2017     

Acrylonitrile-based copolymers: Synthesis,characterization, and formation of ultrafiltration membranes utilized for the immobilization of proteins

Various high molecular weight copolymers of acrylonitrile and a vinyl comonomer containing an aryl amine, a pyridine, or an aliphatic hydroxyl group were synthesized via slurry polymerization techniques so as to contain from 1 to 15 mol % functional comonomer. The comonomer content was quantitated by ultraviolet absorbance, base titration of acid polymer salts, and/or relative chemical reactivity with trichloro-s-triazine. Thin films were cast from copolymer solutions, coagulated into unsupported ultrafiltration membrances, and characterized with respect to both water permeability and pore size distribution. Analysis by size exclusion chromatography of the membrane permeate of a pool of dextran fractions yielded a continuous distribution curve for membrane pore size over the range 1.5 to 70 nm. The ultrafiltration membranes were used for protein immobilization after appropriate chemical activation. The three distinct types of functional copolymers gave comparable results for α-chymotrypsin, with protein weight loadings of 6–12% and 40–65% retention of enzymatic specific activity.     

聚酰亚胺膜气体渗透性的改性进展

聚酰亚胺分离膜(PI)是由芳香二酐和二胺单体缩聚而成的,它是主链含有酰亚胺环的一类高聚物。因其具有良好的气体分离性能、热稳定性、耐溶剂性等特性而受到人们的广泛关注。但是,其气体渗透-选择性的平衡问题限制了其在气体分离领域的广泛应用。因此,研究者们将目光转向了聚酰亚胺膜气体渗透性的改性方面,使其具有良好的气体渗透性,用于混合气体的高效分离。文章综述了近年来研究者对聚酰亚胺气体渗透性的研究进展,详细介绍了共混改性、交联改性和分子结构改性方面的最新研究成果,并总结展望了聚酰亚胺膜今后的研究趋势。为未来高效分离膜的研发提供了参考。     

Acrylonitrile copolymers: Synthesis,characterization, and formation of ultrafiltration membranes

A variety of poly(acrylonitrile‐co‐acrylamide) polymers of different compositions were synthesized by free radical copolymerization. Thin films were cast from polymer solutions, and coagulated into ultrafiltration membranes. The effect of preparative parameters on membrane gel structure was investigated. For nonsupported membranes, concentrated polymer solutions produce fine pore membranes with a lower flux; extending the drying time causes a diminution in membrane thickness, swelling index, and fluxes; the membrane thickness, swelling index, and permeate flux all increased with increasing coagulation bath temperature. For supported membranes, dilute polymer casting solutions, small casting gate opening, and added polyvinylpyrrolidone to the casting solution all increased the permeate flux. The membranes containing acrylamide were more hydrophilic, and had a smaller dispersion force component of the surface free energy than those prepared from the polyacrylonitrile homopolymer. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1271–1277, 1999     

Preparation and characterization of porous poly(vinylidene fluoride) membranes for dehumidification with poly(ethylene glycol) as an additive

Porous poly(vinylidene fluoride) (PVDF) membranes for dehumidification were prepared from a PVDF/dimethylformamide/water system by phase inversion with poly(ethylene glycol) (PEG) as an additive at various concentrations (1.2, 1.8, and 2.4%) and with various molecular weights (1000, 2000, and 6000). The surface morphologies of the resultant membranes were characterized with scanning electron microscopy and atomic force microscopy, and the pore diameter, porosity, and pore size distribution of the membranes were also determined by a gas‐sorption method. The influence of the concentration and molecular weight of PEG on water‐vapor transport through the membranes was evaluated. The moisture‐transport property of the membranes was improved significantly with increases in the concentration and molecular weight of PEG, and a membrane with good moisture permeability was obtained with 2.4% PEG‐6000 as an additive. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Immobilization of polymers on cellulose acetate membranes

Using models of dead-end filtration theory, the kinetics of forming dynamic layers of sulfate lignin (SL) and sodium carboxy-methylcellulose (Na-CMC) onto CA membranes during cross-flow filtration of dilute solutions of polymers was studied. It was found for both polymers (compact SL and linear Na-CMC), that the polymer layer with the least hydraulic resistance, which yields a small reduction in membrane water permeability (10–20%), but a significant increase in salt rejection, is formed, if the process kinetics corresponds to J-V linear dependence predicted by the model of 'blocking a pore by a single particle's. The results obtained may be used to define the optimum conditions for immobilizing the available catalytic active polymers on regular semipermeable membranes during the membrane filtration process.