Preparation and Characterization of Iron Oxides – Polymer Composite Membranes

Composite membranes of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) or ethyl cellulose filled with magnetic nanoparticles, that is, ferroferric oxides (Fe₃O₄) were prepared. These membranes were examined for nitrogen and oxygen permeability. In the case of ethylcellulose membranes the gas flow was too high, since the macropore were formed. In further permeation measurements PPO membranes with 1 to 10 w/w% magnetic particles content were investigated. For the higher concentration of magnetite (more than 20%) in PPO polymer solution sedimentation phenomenon was observed. Mass transport coefficients (permeation and selectivity) were evaluated. Selectivity of the investigated membranes changed with the weight fraction of magnetic particles from oxygen (plain) towards nitrogen (2 and more w/w%).     

Characteristics of permeation and separation of aqueous alcoholic solutions with chitosan derivative membranes

Permeation and separation characteristics for the feed vapours from aqueous alcoholic solutions through chitosan derivative membranes such as chitosan acetate (GA-ChitoA), chitosan (GA-Chito), and carboxymethyl chitosan acetate (GA-CM-ChitoA) membrane crosslinked with glutaraldehyde were investigated by evapomeation. The GA-Chito and GA-CM-ChitoA membranes prepared from casting solutions containing an optimum amount of glutaraldehyde showed a high permeation rate and high water permselectivity for an azeotropic composition in an aqueous ethanol solution. The permselectivity for water through the GA-CM-ChitoA membrane in evapomeation was in the order of aqueous solutions of methanol < ethanol < 1-propanol. The effect of the chemical and physical structure of these hydrophilic membranes on the permeation and separation characteristics is discussed.     

Separation of Water/Ethanol Vapor Mixtures through Chitosan and Crosslinked Chitosan Membranes

Abstract

The separation of water/ethanol vapor mixtures through chitosan membranes and crosslinked chitosan membranes was studied by means of the vapor permeation technique. The permeation performance was discussed in terms of separation factor and permeation flux. Crosslinking the chitosan membrane by glutaraldehyde enhanced the selectivity. The highest separation factor obtained was 6000 for a crosslinked chitosan membrane with a degree of deacetylation of 100%.     

Separation of aqueous organic liquid solutions through polymer membranes

Characteristics of permeation and separation for aqueous dimethyl sulfoxide, acetic acid and ethanol solutions through some polymer membranes such as chitosan, poly(vinyl chloride) and poly(dimethyl siloxane) membrane were studied by evapomeation. In temperature difference controlling evapomeation (TDEV), when the temperature of the feed solution was kept constant and the temperature of the membrane surroundings was changed, permselectivity for water increased in the chitosan and poly(vinyl chloride) membranes; in the poly(dimethyl siloxane) membrane the perm-selectivity for ethanol increased while decreasing the temperature of the membrane surroundings. Permeation and separation mechanisms for aqueous organic liquid solutions through the above polymer membranes by the TDEV method are discussed.     

Controlled release of riboflavin and insulin through crosslinked poly(vinyl alcohol)/chitosan blend membrane

The permeation of riboflavin and insulin through poly(vinyl alcohol) (PVA) and chitosan blend membrane was conducted. The permeability coefficients of both solutes through the crosslinked PVA and chitosan blend membrane were in the order of 10^?6?10^?7 cm³ cm/cm²s and showed a pH dependence. The pH-dependent permeation behavior was discussed in terms of water content and water structure inside of the swollen membrane. Riboflavin and insulin were presumed to permeate through the free water region in the swollen blend membrane. The DSC thermograms of these membranes indicated that the content of free water and the amount of freezing bound water increased with the water content in the membrane. The greater permeation rate of solutes in acidic solution rather than in neutral solution was due to an increase in both water content and the amount of free water and freezing bound water.     

The influence of metal oxides on the separation properties of hybrid alginate membranes

ABSTRACT

Alginate membranes filled with different metal oxide particles were prepared and the influence of the presence of different amounts of Fe₃O₄, ZnO, and Ag₂O particles on ethanol and water permeation was discussed. Ethanol and water vapour permeation rates were determined using the measuring cell method, and the mass transport coefficients were evaluated. It was found that the highest transport parameters were obtained for membranes with the highest metal oxide content. Furthermore, the highest flux, equal 8.49 kg·m^?2·h^?1, was obtained for the alginate membrane filled with 15 wt% of silver oxide particles, while the greatest selectivity coefficients were noted for membranes containing magnetite. In this case, for the alginate membrane with 15 wt% of magnetite content, the selectivity coefficient reached the best value of 108.15.     

Influence of magnetic casting on the permeability and anti-fouling properties of a novel iron oxide/alumina/polysulfone mixed matrix membrane

Novel mixed matrix membranes (MMMs) were fabricated using Fe₃O₄, and Al₂O₃ nanoparticles (NPs) were added to the polysulfone (PSf) and N-methylpyrrolidone (NMP) solution. The nanocomposite membranes were fabricated using the NIPS (non-solvent induced phase separation) method. In order to create preferential permeation pathways for water across the MMMs, membrane formation is accomplished with an external magnetic field. Using magnetic casting cause the targeted placement of NPs in the best location and orientation. The performance of the prepared membranes was examined in terms of pure water flux and fouling parameters. Magnetic casting considerably increased pure water flux and decreased the total resistance of the optimum mixed matrix membrane, which contains 0.2% wt. of Fe₃O₄ NPs to 1175 L/m²h and 13.4 * 10¹¹ (m⁻¹), respectively. This is explained by the ordering of magnetic nanoparticles on the membrane sub-layer cast under the magnetic field of 500 mT, which changed the sub-layer structure. Less rough membrane surface of the mixed matrix membranes offered preferable anti-fouling properties against fouling by BSA proteins. The characterization of fabricated membranes was carried out using field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), energy dispersive X-ray (EDX), and water contact angle measurement methods.     

PVA/PEG/TEOS杂化膜制备及性能研究

以聚乙烯醇(PVA)与聚乙二醇(PEG)共混,并与正硅酸乙酯(TEOS)进行交联反应制备杂化膜。FTIR证实杂化溶胶液发生交联反应形成共价键Si—O—C,WXRD观察表明加入TEOS改变了膜结晶度,加入PEG提高了PVA膜对乙醇/水溶液的渗透通量,但分离因子下降,随着TEOS的加入,膜的分离因子提高。在TEOS质量分数为10%时,杂化膜的分离因子达到最大。提高退火温度可以提高膜的分离因子,但通量下降。在100℃下退火12 h的杂化膜对乙醇质量分数为85%的乙醇/水溶液的分离性能最佳。     

Selective permeabilities of chitosan-acetic acid complex membrane and chitosan-polymer complex membranes for oxygen and carbon dioxide

Summary Chitosan-acetic acid complex membrane and several chitosan-polymer complex membranes have been prepared and the gas permeabilities of these membranes have been examined. It has been found that chitosan-acetic acid complex membrane shows high permselectivities for oxygen and carbon dioxide, and synthetic polymers can modify the permeation behavior of chitosan membrane for oxygen and carbon dioxide. The separation factor CO₂/O₂ of these membranes were much smaller than unity, indicating possible applications for the preservations of fruits and vegetables. It has been noticed that the permeation behaviors of these membranes are markedly influenced by metal ions added into the membranes and the membranes have good mechanical strength.     

Permeation and separation characteristics of acetic acid/water mixtures through poly(vinyl alcohol‐g‐itaconic acid) membranes by pervaporation,evapomeation, and temperature‐difference evapomeation

In this study, itaconic acid (IA) was grafted onto poly(vinyl alcohol) (PVA) with cerium(IV) ammonium nitrate as an initiator at 45°C. The grafted PVA was characterized with Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, and differential scanning calorimetry. IA‐grafted PVA membranes were prepared with a casting method, and the permeation and separation characteristics of acetic acid/water mixtures were investigated with pervaporation (PV), evapomeation (EV) and temperature‐difference evapomeation (TDEV) methods. The effects of the feed composition, operating temperature, and temperature of the membrane surroundings on the permeation rate and separation factor for the acetic acid/water mixtures were studied. The permeation rates in EV were lower than those in PV, whereas the separation factors were higher. With the TDEV method, the permeation rates decreased and the separation factors increased as the temperature of the membrane surroundings decreased. The prepared membranes were also tested in PV, EV, and TDEV to separate the various compositions of the acetic acid/water mixtures (20–90 wt % acetic acid) at 40°C. The highest separation factor, 686, was obtained in TDEV with a 90 wt % acetic acid concentration in the feed. The activation energies of permeation in PV and EV were calculated to be 8.5 and 10.2 kcal/mol, respectively, for a 20 wt % acetic acid solution. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2322–2333, 2004     

Permeation and Separation Characteristics of Acetic Acid‐Water Mixtures by Pervaporation through Acrylonitrile and Hydroxy Ethyl Methacrylate Grafted Poly(vinyl alcohol) Membrane

Abstract

In this study, acrylonitrile (AN) and hydroxyl ethyl methacrylate (HEMA) were grafted onto poly(vinyl alcohol) (PVA) using cerium (IV) ammonium nitrate as initiator at 30°C. The graft copolymer was characterized using the Fourier transform infrared spectroscopy (FTIR) and elemental analysis. The grafted PVA membranes (PVA‐g‐AN/HEMA) were prepared by a casting method, and used in the separation of acetic acid‐water mixtures by pervaporation. The effects of the membrane thickness, operating temperature, and feed composition on the permeation rate and separation factor for acetic acid‐water mixtures were studied. Depending on the membrane thickness, the temperature and feed composition PVA‐g‐AN/HEMA membranes gave separation factors 2.26–14.60 and permeation rates of 0.18–2.07 kg/m²h. It was also determined that grafted membranes gave lower permeation rates and greater separation factors than PVA membranes. Diffusion coefficients of acetic acid‐water mixtures were calculated from permeation rate values. The Arrhenius activation parameters were calculated for the 20 wt.% acetic acid content in the feed using the permeation rate and the diffusion data obtained at between 25–50°C.     

Separation of Lactic Acid through Polymer Inclusion Membranes Containing Ionic Liquids

Optically pure lactic acid that can be prepared by fermentation is one of the important raw materials for biodegradable polymer. Since an economical technique is desired that separates lactic acid from the fermentation broth, we proposed lactate permeation through a poly(vinyl chloride)(PVC)-based membrane containing ionic liquids as a carrier. Lactate was successfully permeated through polymer inclusion membranes (PIMs) containing Aliquat 336, Cyphos IL -101, and -102 as ionic liquids. From the viewpoints of permeation rates and the pH drop of the feed phase, Aliquat 336 was the best ionic liquid. Based on the experimental results, we calculated the overall mass transfer coefficients and evaluated the contribution of membrane resistance to the overall permeation resistance. Furthermore, permeation behavior was explained by the solution-diffusion model. The superior stability of PIMs over the supported ionic liquid membranes was observed for membranes containing Aliquat 336 as a carrier. The PVC-based membrane process containing Aliquat 336 was found to be promising for lactate separation on an industrial scale.     

Pervaporation separation of water/isopropanol mixtures through crosslinked carboxymethyl chitosan/polysulfone hollow‐fiber composite membranes

Carboxymethyl chitosan (CMCS)/polysulfone (PS) hollow‐fiber composite membranes were prepared through glutaraldehyde (GA) as the crosslinking agent and PS hollow‐fiber ultrafiltration membrane as the support. The permeation and separation characteristics for dehydration of isopropanol were investigated by the pervaporation method. Pure chitosan, carboxymethyl chitosan, and crosslinked carboxymethyl chitosan membranes were characterized by Fourier transform infrared (FT‐IR) spectroscopy and X‐ray diffraction (XRD) to study the crosslinking reaction mechanism and degree of crystallinity, respectively. The effects of feed composition, crosslinking agent, membrane thickness, and feed temperature on membrane performance were investigated. The results show that the crosslinked CMCS/PS hollow‐fiber composite membranes possess high selectivity and promising permeability. The permeation flux and separation factor for isopropanol/water is 38.6 g/m²h and 3238.5, using 87.5 wt % isopropanol concentration at 45°C, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1959–1965, 2007     

Synthesis of graft copolymeric membranes of poly(vinyl alcohol) and polyacrylamide for the pervaporation separation of water/acetic acid mixtures

Graft copolymers of poly(vinyl alcohol) (PVA) with polyacrylamide were prepared and membranes were fabricated at 48 and 93% grafting of acrylamide onto PVA. These membranes were used in the pervaporation separation of water/acetic acid mixtures at 25, 35, and 45°C. The permeation flux, separation selectivity, diffusion coefficient, and permeate concentration were determined. The highest separation selectivity of 23 for neat PVA at 25°C and the lowest value of 2.2 for 93% acrylamide‐grafted PVA membranes were observed. A permeation flux of 1.94 kg m^?2 h^?1 was found for the 93% grafted membrane at 90 mass % of water in the feed mixture. The diffusion coefficients in a water/acetic acid mixture had an effect on the membrane permselectivity. The Arrhenius equation was used to calculate the activation parameters for permeation as well as for the diffusion of water and of acetic acid. The activation energy values for the permeation flux varied from 97 to 28 kJ/mol. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 244–258, 2002     

Preparation and testing of polyvinyl alcohol composite membranes for reverse osmosis

Thin film composite membranes were prepared by coating porous polysulfone membranes with a polyvinyl alcohol layer and further cross-linking its surface. The thin layer of cross-linked polyvinyl alcohol served as a selective membrane. The membranes were prepared under various conditions and tested for sodium chloride separation. A high sodium chloride separation was achieved but the permeation rate was low compared with commercially available thin film composite membranes. Resistance against the flow of solvent water and sodium chloride solute were determined for individual component barrier layers.     

Preparation of PVA membranes containing β-cyclodextrin oligomer (PVA/CD membrane) and their pervaporation characteristics for ethanol/water mixtures

Poly(vinyl alcohol) (PVA) membranes were modified by introducing β-cyclodextrin (β-CD) oligomer, which has an inclusion ability sensitive to size, structure, and hydrophilicity of the guest molecule. The modified membranes (PVA/CD membrane) were prepared by casting of the aqueous solutions of PVA and β-CD oligomer. The CD oligomer was immobilized in the membranes by cross-linking with glutaraldehyde. The cross-linking times were 1 and 8 h. The content of CD in the membranes was 33 wt %. The effects of CD on the pervaporation characteristics for water/ethanol were investigated by comparisons with those of the cross-linked PVA membranes. For the 1 h cross-linked membranes, CD increased both the water permeation rate and selectivity at lower ethanol concentrations in the feed. At higher ethanol concentrations, CD increased the water selectivity, but it decreased the water permeation rate. For the 8 h cross-linked membranes, at lower ethanol concentrations, CD increased the water permeation rate, but the water selectivity through the PVA/CD membrane was almost equal to that of the PVA membrane. At higher ethanol concentrations, CD increased the water selectivity and decreased the water permeation rate. These effects of CD can be interpreted in terms of the inclusion strength in the cavity and the reduction of the cross-linking density of the PVA phase in the membranes. © 1994 John Wiley & Sons, Inc.     

Magnetic Mixed Matrix Membranes Consisting of PPO Matrix and Magnetic Filler in Gas Separation

Poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and magnetic neodymium powder particles MQP-14-12 have been used for the preparation of magnetic mixed matrix membranes. Permeability diffusion and sorption coefficients of O₂, N₂, and synthetic air components were estimated for homogeneous and heterogeneous membranes using the Time Lag method based on dynamic experiments in a constant pressure system. The influence of magnetic field and magnetic powder particles on the gas transport properties of MMMs was studied. The results showed that the membrane permeation properties were improved with the magnetic neodymium particle filling. It was observed that the magnetic ethylcellulose and poly(2,6-dimethyl-1,4-phenylene oxide) membranes showed higher gas permeability, while their permselectivity and solubility were rather maintained or slightly increased. The results also showed that the magnetic powder addition enhanced gas diffusivity significantly in EC and PPO membranes.     

Influence of Various Parameters on the Air Separation Process by Magnetic Membranes

Polymer membranes filled with magnetic powder and magnetized, used for an air enrichment, are investigated. Various polymer matrix with different types and granulation of dispersed magnetic powder were used for the preparation of the membranes. All membranes were examined for N₂, O₂, and air permeability. Mass transport coefficients were evaluated basing on Time Lag methods and D1-D8 system. Structure and morphology of the obtained membranes were investigated using fractal analysis. Box counting method for calculating generalized fractal dimension was applied. Obtained results allowed to optimize the preparation procedure of magnetic membranes with the best permeation properties.     

Blend membranes from carboxymethylated chitosan/alginate in aqueous solution

The blend membranes were satisfactorily prepared by coagulating a mixture of O‐carboxymethylated chitosan (CM‐chitosan) and alginate in aqueous solution with 5 wt % CaCl₂, and then by treating with 1 wt % HCl aqueous solution. Their structure and miscibility were characterized by scanning electron micrograph, X‐ray diffraction, infrared spectra, differential thermal analysis, and atomic absorption spectrophotometer. The results indicated that the blends were miscible, when the weight ratio of CM‐chitosan to alginate was in the range from 1 : 1 to 1 : 5. The polymers interpenetration including a Ca²⁺ crosslinked bridge occurred in the blend membrane, and leads to high separation factor for pervaporation separation of alcohol/water and low permeation. The tensile strength in the wet state (σ_b = 192 kg cm⁻² for CM‐chitosan/alginate 1 : 1) and thermostability of the blend membranes were significantly superior to that of alginic acid membrane, and cellulose/alginate blend membranes, owing to a strong electrostatic interaction caused by —NH₂ groups of CM‐chitosan with —COOH groups of algic acid. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 610–616, 2000     

聚醚砜酮基炭膜的制备及其气体分离性能

采用浸渍涂膜法,以商用聚醚砜酮(PPESK)为前驱体制备了管式复合炭膜,考察了涂膜次数、改性剂及其加入量对所制备炭膜的气体分离性能的影响.结果表明,随着涂膜次数增多,气体分子的渗透速率逐渐减小而选择性呈增大趋势;加入改性剂后的复合炭膜渗透速率和分离系数均有不同程度的提高,表明改性剂不仅改善了涂膜液与支撑体之间的复合效果、减少涂膜次数,同时也促进了气体渗透速率的提高.利用扫描电镜对复合炭膜的微观形貌进行观测,可以看出,复合炭膜由支撑体和分离膜层2部分组成.膜表面很致密均匀,无明显缺陷,分离层薄而均一,厚度在5μm左右,且与支撑体结合紧密.