Preparation and characterization of chitosan-boehmite nanocomposite membranes for pervaporative ethanol dehydration

Abstract

Pervaporative ethanol dehydration was studied using some chitosan-boehmite nanocomposite membranes. Nanocomposite membranes were prepared by incorporation of 1 and 2?Wt. % loading of the boehmite nanoparticles synthesized by the low temperature sol-gel process. The prepared samples were characterized by FTIR, FESEM and XRD analysis. The results showed the filler particles uniform distribution within the chitosan matrix. Pervaporation performance of the prepared pristine and the nanocomposite membranes were evaluated for ethanol dehydration. The 2?Wt. % loaded boehmite nanocomposite membrane exhibited highest ethanol dehydration performance for 20?Wt. % water content feed at 50?°C as 0.513?kg/m² h and 676 as permeation flux and separation factor revealed ～50% and 2 times increments, respectively.     

Synthesis and characterization of asymmetric polyethersulfone membranes: effects of concentration and polarity of nonsolvent additives on morphology and performance of the membranes

In this study, effects of methanol, ethanol and 1‐propanol as variable nonsolvent additives (NSAs) on the morphology and performance of flat sheet asymmetric polyethersulfone (PES) membranes were investigated. The membranes were prepared from PES/Polyvinylpyrrolidone (PVP)/N‐methyl‐2‐pyrrolidone (NMP) system via phase inversion. The obtained results indicate that with the addition of NSAs to the casting solution, the membrane morphology changes slowly from macrovoids to an asymmetric structure with finger‐like pores. By increasing the NSAs concentrations in the casting solution and decreasing their polarities, the membrane structure changes from finger‐like pores to sponge. The AFM and SEM images reveal that addition of NSA to the casting solution decreases the pore size of the prepared membranes and reduces the pure water flux and BSA solution flux, while increasing the protein rejection. Surface analysis of the membranes showed that mean pore size and surface porosity of the prepared membranes with NSAs in the casting solution are smaller compared with those of the membrane prepared with no NSA. Pure water flux and BSA solution flux through the membranes decrease and BSA rejection increases with increase in the concentration of NSAs and decrease in their polarity. Finally, it can be concluded that the T_g values of the PES membranes increase by addition of NSAs to the casting solution. Copyright © 2009 John Wiley & Sons, Ltd.     

Blend membranes from cellulose/konjac glucomannan cuprammonium solution

The blend membranes were prepared from cellulose/konjac glucomannan (KGM) cuprammonium solution by coagulating with aqueous 10 wt% NaOH solution, 20°C and 40°C water, respectively. Miscibility, pore morphology, structure, water permeability and mechanical properties of the blend membranes were investigated. The complex forms of cellulose/KGM in the mixed solutions, the effect of various coagulants and the percent content of KGM (w_KGM) on the structure and properties of the blend membrane are discussed. SEM and mechanical relaxation analysis indicate that the blend membranes are miscible in the range of 0–30 wt% of w_KGM. When w_KGM was smaller than 20 wt%, the tensil strength of the blend membrane coagulated by alkali aqueous solution was enhanced, corresponding to homogeneous structure and small pore size. However, blend membranes having a larger pore size (366 nm by SEM) and water permeability (560 ml/m² h mmHg) were obtained by coagulating the cellulose/KGM (70:30) cuprammonium solution with 40°C water, where ca. 20% of KGM as pore former were removed from the membrane.     

Fabrication of cellulose triacetate/graphene oxide porous membrane

Cellulose triacetate (AC)/graphene oxide (GO) porous membranes were successfully fabricated by combining ultrasonication and phase inversion method. The structures and morphologies of the resultant composite membranes were investigated by X‐ray diffraction (XRD), scanning electron microscopy, and transmission electron microscopy, respectively. Microscopic and X‐ray diffraction measurements revealed that GO sheets were uniformly dispersed within the AC matrix. The pore size and structure were modulated by changing GO concentration from 0.25 to 1 wt%. Membrane thermal properties were also studied. Among all tested membranes, the most favorable GO amount was 1 wt%, giving Td_3% of 274°C, which represents a 22°C enhancement compared with AC. Conversely, the membranes showed improved barrier properties against water and ethanol. The decrease of both ethanol and water fluxes was assigned to the stabilization of composite membrane structure, as a result of GO progressive addition. Bovine serum albumin rejection assay indicated an increasing from 78% in the case of CA membrane to 99% in the case of CA/GO 1 wt% of the rejection degree after 90 min. Copyright © 2015 John Wiley & Sons, Ltd.     

Microporous 3D aluminum MOF doped into chitosan‐based mixed matrix membranes for ethanol/water separation

An aluminum metal–organic framework (Al‐MOF), [Al(OH)(BPDC)] (DUT‐5; BPDC = Biphenyl‐4,4′‐dicarboxylate), was synthesized using solvothermal reactions. The high surface area and micropores (approximately 1.2 nm) of DUT‐5 were characterized using N₂ gas sorption measurements. The thermal stability of DUT‐5 and its phase purity were also investigated. The different amounts of DUT‐5 (0.1, 0.15, and 0.2 wt%) were successfully incorporated into the chitosan (CS) polymer to prepare a mixed matrix membrane (MMM) for the pervaporation of water/ethanol at 25°C. In particular, when 0.15 wt% of DUT‐5 was loaded, the DUT‐5@CS MMMs displayed excellent permeability and selectivity in ethanol/water separation. The results indicated that compared with pristine chitosan membranes, the flux of DUT‐5@CS membranes with 0.15 wt% loading significantly increased from 315 to 378 (g/m² h^?1) and the separation factor from 347 to 3,429. These promising results of the microporous Al‐MOF doped into chitosan MMMs reveal its good application potential for the bio‐ethanol separation processes.     

The effect of sodium dodecyl sulfate solutions as gelation media on the formation of PES membranes

Sodium dodecyl sulfate (SDS) aqueous solutions were used as gelation media in the preparation of polyethersulfone (PES) membranes. The casting solution composition was the same for all the tested membranes. The temperatures of gelation media were 4 and 20°C. The concentration of SDS was changed from 0 to 3.0 g/l at 4°C and 0 to 1.6 g/l at 20°C.The surface tension of the gelation media was measured by drop weight method and the electrical conductivities were also determined. The membranes were characterized by transport parameters obtained from separation experiments and roughness parameters, obtained by the atomic force microscopic (AFM) technique.The molecular weight cut-off (MWCO) values of the studied membranes were found to be between 9 000 and 88 000 Da for membranes gelled at 4°C, and between 28 000 and 85 000 Da for membranes gelled at 20°C. The pore sizes were found to be between 3.04 and 10.73 nm for the membranes gelled at 4°C and between 4.48 and 10.74 nm for membranes gelled at 20°C, respectively. In general, both MWCO and pore size decreased with an increase of SDS concentration in gelation media when the concentration was below critical micelle concentration (CMC) and increased with an increase with SDS concentration when the concentration was above CMC. Images of membrane surfaces, taken by AFM, showed that the size of nodules and depressions decreased with a decrease in pore size. The roughness of membranes increased with an increase in pore size and MWCO.     

Phase separation and polymer crystallization in a poly(4‐methyl‐1‐pentene)–dioctylsebacate–dimethylphthalate system via thermally induced phase separation

The effects of the polymer concentration and quenching temperature on the phase separation, the membrane morphology and polymer crystallization behavior in a poly(4‐methyl‐1‐pentene) (TPX)‐dioctylsebacate (DOS)‐dimethylphthalate (DMP) system via thermally induced phase separation were studied with a pseudobinary phase diagram, with the weight ratio of DOS:DMP = 1:1. SEM was used to observe the membrane morphology and structure, whereas the TPX crystallization behavior was studied with DSC and WAXD. Liquid‐liquid phase separation occurred, although quenching under the crystallization temperature. As the quenching temperature decreased, the pore size decreased, with better connected pore structure formed. The membranes quenched at 333 and 363 K showed good cellular structures, with an average pore size of about 2.3μm, whereas the pores of the membranes quenched at 393 and 423 K were not well formed, with some lamellar crystals on the inner side. The diluent assisted the mobility of the polymer chain, which improved the polymer crystallization. Dual‐melting‐peak behavior occurred for all the samples studied here. As the quenching temperature increased, the first peak of the melting trace moved to a higher temperature, whereas the second one stayed almost the same. The flexibility of the TPX main chain was restricted by the side groups, which allowed liquid‐liquid phase separation to occur first when quenched below the equilibrium crystallization temperature. This allowed primary and secondary crystallization, which was responsible for the dual‐melting‐peak behavior. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 153–161, 2007     

Microstructure and mechanical properties of bacterial cellulose/chitosan porous scaffold

A family of polysaccharide based scaffold materials, bacterial cellulose/chitosan (BC/CTS) porous scaffolds with various weight ratios (from 20/80 to 60/40 w/w%) were prepared by freezing (−30 and −80 °C) and lyophilization of a mixture of microfibrillated BC suspension and chitosan solution. The microfibrillated BC (MFC) was subjected to 2,2,6,6-tetramethylpyperidine-1-oxyl radical (TEMPO)-mediated oxidation to introduce surface carboxyl groups before mixing. The integration of MFC within chitosan matrix was performed by 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (EDC)-mediated cross-linking. The covalent amide bond formation was determined by ATR-FTIR. Because of this covalent coupling, the scaffolds retain their original shapes during autoclave sterilization. The composite scaffolds are three-dimensional open pore microstructure with pore size ranging from 120 to 280 μm. The freezing temperature and mean pore size take less effect on scaffold mechanical properties. The compressive modulus and strength increased with increase in MFC content. The results show that the scaffolds of higher MFC content contribute to overall better mechanical properties.     

The effect of heat treatment of PES and PVDF ultrafiltration membranes on morphology and performance for milk filtration

The flat sheet polyethersulfone (PES) and poly(vinylidene fluoride) (PVDF) membranes were prepared by immersion precipitation technique. The influence of hot air and water treatment on morphology and performance of membranes were investigated. The membranes were characterized by AFM, SEM, cross-flow filtration of milk and fouling analysis. The PES membrane turns to a denser structure with thick skin layer by air treatment at various temperatures during different times. This diminishes the pure water flux (PWF). However the milk permeation flux (MPF) was considerably improved at 100 °C air treatment for 20 min with no change in protein rejection. The smooth surface and slight decrease in surface pore size for air treated PES membrane at 100 °C compared to untreated membrane may cause this behavior for the membrane. The water treatment of PES membranes at 55 and 75 °C declines the PWF and MPF and increases the protein rejection. This is due to slight decrease in membrane surface pore size. The treatment of PES membrane with water at higher temperature results in a porous structure with superior performance. The fouling analysis of 20 min treated membrane indicates that the surface properties of 100 °C air treated and 95 °C water treated PES membranes are improved compared to untreated membrane. The SEM observation depicts that the morphology of air and water treated PVDF membranes was denser and smoother with increasing the heat treatment temperature. The 20 min air treated PVDF membranes at 100 °C and water treated at 95 °C exhibited the highest performance and antifouling properties.     

Pervaporation dehydration of ethanol–water mixtures with chitosan/hydroxyethylcellulose (CS/HEC) composite membranes: I. Effect of operating conditions

Composite hydrophilic pervaporation membranes were prepared from chitosan blended with hydroxyethylcellulose using cellulose acetate as a porous support. The membranes were tested for dehydration performance of ethanol–water mixtures of ethanol concentrations 70–95 wt.% in the laminar flow region, at temperatures 50–70°C and at permeate pressures of 3–30 mmHg. The composite membrane showed an improved dehydration performance compared with dense CS/HEC membrane developed earlier. The effects of operating conditions also revealed that pervaporation of low water content feed carried out at high feed flow rate and at low temperature and permeate pressure was an advantage.     

Preparation and characterization of PVDF microporous membrane with highly hydrophobic surface

Using the mixture of triethyl phosphate (TEP) and N,N‐dimethylacetamide (DMAc) as solvent, PVDF microporous membranes with highly hydrophobic surface were prepared by a modified NIPS method with a dual coagulation process. The effects of the exposure time on these membranes before being immersed into the coagulation bath and the composition in the coagulation bath on precipitation rate, membrane morphology, membrane hydrophobicity, membrane mechanical property, and membrane performance were studied. The morphologies and hydrophobicities of PVDF microporous membranes were investigated by scanning electron microscopy (SEM) and contact angle (CA) measurement. The precipitation processes were observed by light transmittance measurement. The pore size distribution was determined by liquid permeation technique. PVDF microporous membrane obtained by passing evaporation period of 60 min before being immersed into the water bath showed a high water CA of 122.1°. Using ethanol (EtOH) as coagulation bath, the water CAs of the top surface and bottom surface of the membrane increased to 125.9 and 132.6°, respectively. To further improve PVDF membrane hydrophobicity, a dual coagulation process was used and the mixed solvent (TEP–DMAc) was added into the first coagulation bath for 30 sec. Increase in the TEP–DMAc content led to the change in the morphology type of the membrane, that is, from an asymmetric structure with a dense top surface to a symmetric structure with a skinless top surface, and the pore size distribution widened greatly. By increasing the mass ratio of TEP to DMAc, the denseness of the membrane surface decreased significantly. Adding 60 wt% of TEP–DMAc to the first coagulation bath and the mass ratio of TEP to DMAc was 60:40, the CA reached to a maximum as high as 136.6°, and PVDF microporous membrane showed a high porosity of 80% and an excellent mechanical property of 3.14 MPa tensile strength and 61.79% elongation ratio. Copyright © 2009 John Wiley & Sons, Ltd.     

Preparation of porous nanocomposite scaffolds with honeycomb monolith structure by one phase solution freezedrying method

Biodegradable porous nanocomposite scaffolds of poly（lactide-co-glycolide）（PLGA） and L-lactic acid（LAc） oligomer surface-grafted hydroxyapatite nanoparticles（op-HA） with a honeycomb monolith structure were fabricated with the single-phase solution freeze-drying method.The effects of different freezing temperatures on the properties of the scaffolds,such as microstructures,compressive strength,cell penetration and cell proliferation were studied.The highly porous and well interconnected scaffolds with a tunable pore structure were obtained.The effect of different freezing temperature（4℃,-20℃,-80℃and -196℃） was investigated in relation to the scaffold morphology,the porosity varied from 91.2%to 83.0%and the average pore diameter varied from（167.2±62.6）μm to（11.9±4.2）μm while theσ₁₀ increased significantly.The cell proliferation were decreased and associated with the above-mentioned properties.Uniform distribution of op-HA particles and homogeneous roughness of pore wall surfaces were found in the 4℃frozen scaffold.The 4℃frozen scaffold exhibited better cell penetration and increased cell proliferation because of its larger pore size,higher porosity and interconnection.The microstructures described here provide a new approach for the design and fabrication of op-HA/PLGA based scaffold materials with potentially broad applicability for replacement of bone defects.     

Effect of neutralization and cross-linking on the thermal degradation of chitosan electrospun membranes

Thermal degradation of as-electrospun chitosan membranes and samples subsequently treated with ethanol and cross-linked with glutaraldehyde has been studied by thermogravimetry (TG) coupled with an infrared spectrometer. The influence of the electrospinning process and cross-linking in the electrospun chitosan thermal stability was evaluated. Up to three degradation steps were observed in the TG data, corresponding to water dehydration reaction at temperatures below 100 °C, loss of side groups formed between the amine groups of chitosan and trifluoroacetic acid between 150 and 270 °C and chitosan thermal degradation that starts around 250 °C and goes up to 400 °C. The Kissinger model was employed to evaluate the activation energies of the electrospun membranes during isothermal experiments and revealed that thermal degradation activation energy increases for the samples processed by electrospinning and subsequent neutralization and cross-linking treatments with respect to the neat chitosan powder.     

NMR characterization of styrene-divinylbenzene gel beads using freezing point depression of benzene

Freezing processes of benzene in the presence of styrene-divinylbenzene gel beads were investigated by proton nuclear magnetic resonance spectroscopy. Some portion of benzene in the pore did not freeze below its freezing point, which was detected until ?80°C. Temperature dependence of the amount of unfrozen benzene was discussed in relation to the pore size and the cross-linking density of gel beads. The small pore size and high crosslinking density increased the amount of unfrozen benzene, whereas the polymer matrix concentration showed little effect on the freezing processes. © 1995 John Wiley & Sons, Inc.     

Microfiltration performance of regenerated cellulose membrane prepared at low temperature for wastewater treatment

A series of regenerated cellulose membranes with pore diameters ranging from 21 to 52 nm have been prepared by dissolving cellulose in 5 wt% LiOH/12 wt% urea aqueous solution re-cooled to −12 °C. The influences of cellulose concentration on the structure, pore size, and the mechanical properties of the membrane were studied by using Wide angle X-ray diffraction, scanning electron micrography and tensile testing. Their pore size, water permeability, equilibrium-swelling ratio and fouling behaviors of the cellulose membranes were characterized. The water-soluble synthetic and natural polymers as organic matter were used to evaluate the microfiltration performance of the regenerated cellulose membrane for wastewater treatment in aqueous system. The results revealed that the organic matter with molecular weight more than 20 kDa effected significantly on the membrane pore density, and reducing factor a _2, whereas that having molecular weight less than 20 kDa exhibited a little influence on the membrane pore size reducing factor a ₁. Furthermore, a simple model to illustrate of microfiltration process of the RC membrane for wastewater treatment was proposed.     

Temperature Responsive Shape‐Memory Scaffolds with Circumferentially Aligned Nanofibers for Guiding Smooth Muscle Cell Behavior

Structural simulation of the smooth muscle layer plays an important role in tissue engineering of blood vessels for the replacement of damaged arteries. However, it is difficult to construct small‐diameter tubular scaffolds to homogenously locate and align smooth muscle cells (SMCs). In this work, novel temperature responsive shape‐memory scaffolds are designed for SMC culturing. The scaffolds are composed of an outer layer of poly(lactide–glycolide–trimethylene carbonate) (PLGATMC) for programming the deformation from planar to small‐diameter tubular shape and an inner layer of aligned nanofibrous membrane of poly(lactide–glycolide)/chitosan (PLGA/CS) to regulate cell adhesion, proliferation, and morphology. The SMC behaviors and functions are dependent on the PLGA/CS ratios of membranes, and the scaffold with PLGA/CS 7:3 membrane exhibits the most suitable ability to regulate SMC behavior. The PLGA/CS@PLGATMC scaffold can be deformed into a temporary planar at 20 °C for convenient seeding and attachment of SMCs and then immediately self‐rolled into 3D tube at 37 °C. The proposed strategy offers a practical approach for the development of small‐diameter vascular scaffolds from 2D planar into 3D tubular shape by self‐rolling.     

Separation of small molecules using novel rolltruded membranes. I. Apparatus and preliminary results

A novel membrane production technique, rolltrusion, has been developed for the preparation of permselective polymeric membranes for both gas and vapor separations and pervaporation applications. Pinhole-free thin films with a regulated three-dimensional morphology comprising crystalline and amorphous regions have been produced with improved mechanical properties in three dimensions. Because rolltrusion is a solid-state processing technique, it is not restricted by solubility constraints inherent in the common solvent-based thinfilm production techniques. Consequently it can be extended to include commercially available engineering plastics that have not been used as membranes previously because of their limited solvent solubility. These polymers are interesting because of their applicability to temperatures in excess of 200 to 300°C in harsh chemical environments, compared with the ca. 150°C ceiling usually encountered in the most rugged of solvent-cast polymers. In the first part of this series we detail an automated experimental permeation apparatus that permits testing of both single-component and multicomponent gases and vapors over a temperature range of ?73 to 273°C. Currently, modifications to the permeation cell are underway to permit pervaporation studies in the apparatus. To illustrate the operation of the apparatus, and to some degree the effect of rolltrusion processing, experimental permeability, diffusivity, solubility, and actual gas separation factors (via gas chromatography) are detailed for several light gases in rolltruded isotactic poly(propylene) (iPP) and in the thermally and chemically resistant thermoplastic, poly(ether ether ketone) (PEEK). Permeation temperatures to at least 225°C have been studied using PEEK, representing the first published experimental permeability and gas-separation results for such engineering polymers at temperatures above 200 °C. © 1992 John Wiley & Sons, Inc.     

Highly hydrophobic microporous low‐density polyethylene hollow fiber membranes by melt‐extrusion coupled with salt‐leaching technique

Microporous and highly hydrophobic low‐density polyethylene (LDPE) hollow fiber membranes were successfully prepared via a solvent‐free method, combining melt‐extrusion, and salt‐leaching techniques. NaCl particles with particle size of 5–10 µm were mixed with LDPE pellets to produce a blend of 35, 40, 50, 60, 65 and 68 wt% of salt. A microporous structure was produced by leaching the salt particles from the hollow fiber matrix via immersion in water at 60°C. The fabricated membranes were then characterized in terms of morphology, porosity and pore size distribution, surface roughness, and hydrophobicity, as well as mechanical properties. The remarkable increase in the water contact angles from 98° for LDPE hollow fibers fabricated without the addition of salt (blank sample) to 130° for membranes fabricated with initial salt content of 68 wt% is mainly attributed to the rough surface structure, comprising a large number of micropapillas produced by removing the imbedded salt crystals. The increase in surface roughness and porosity of hollow fiber membranes with increasing initial salt content was confirmed by scanning electron microscope and atomic force microscopy. Copyright © 2013 John Wiley & Sons, Ltd.     

Surface‐initiated atom transfer radical polymerization from porous poly(tetrafluoroethylene) membranes using the C?F groups as initiators

This work reports the surface‐initiated atom transfer radical polymerization (ATRP) from hydrogen plasma‐treated porous poly(tetrafluoroethylene) (PTFE) membranes using the C? F groups as initiators. Hydrogen plasma treatment on PTFE membrane surfaces changes their chemical environment through defluorination and hydrogenation reactions. With the hydrogen plasma treatment, the C? F groups of the modified PTFE membrane surface become effective initiators of ATRP. Surface‐initiated ATRP of poly(ethylene glycol) methacrylate (PEGMA) is carried out to graft PPEGMA chains to PTFE membrane surfaces. The chain lengths of poly(PEGMA) (PPEGMA) grafted on PTFE surfaces increase with increasing the reaction time of ATRP. Furthermore, the chain ends of PPEGMA grown on PTFE membrane surfaces then serve as macroinitiators for the ATRP of N‐isopropylacrylamide (NIPAAm) to build up the PPEGMA‐b‐PNIPAAm block copolymer chains on the PTFE membrane surfaces. The chemical structures of the modified PTFE membranes are characterized using X‐ray photoelectron spectroscopy. The modification increases the surface hydrophilicity of the PTFE membranes with reductions in their water‐contact angles from 120° to 60°. The modified PTFE membranes also show temperature‐responsive properties and protein repulsion features owing to the presence of PNIPAAM and PPEGMA chains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2076–2083, 2010     

New morphological control for thick,porous membranes with a plasma graft‐filling polymerization

Morphological control of membranes with plasma graft‐filling polymerization was proposed for thick, porous membranes. The morphology depended closely on the plasma within the membrane pore, which was determined by the plasma‐discharge power (PDP) and the gas pressure. The membrane morphology was investigated in terms of solvent composition in monomer solution, PDP, Ar pressure, and pore size of a substrate. Morphologies of membranes prepared were evaluated by a microscopic Fourier transform infrared mapping method. This study demonstrates that it is possible to control the membrane morphology by manipulating the plasma power and Ar pressure instead of morphological control by solvent‐dependent monomer activity. Additionally, through indirect methods this study reveals that plasma exists even in sub‐micropores (ca. 0.4 μm in diameter). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1216–1224, 2003