Ionic conductivity of chitosan membranes

Chitosan membranes with various degrees of deacetylation and different molecular weights (MW) were prepared by film casting with aqueous solutions of chitosan and acetic acid. Ultraviolet (UV) spectrometry and infrared (IR) spectrometry were used to determine the degree of deacetylation (DDA) of chitosan. The viscosity-average MW of chitosan was measured in an aqueous solvent system of 0.25 M CH₃COOH/0.25 M CH₃COONa. The intrinsic ionic conductivities of the hydrated chitosan membranes were investigated using impedance spectroscopy. It was found that the intrinsic ionic conductivity was as high as 10⁻⁴ S cm⁻¹ after hydration for 1 h. The tensile strength and breaking elongation of the membranes were evaluated according to standard ASTM methods. The crystallinity and swelling ratio of the membranes were examined. A tentative mechanism for the ionic conductivity of chitosan membranes is also suggested.     

Properties of hydrophilic chitosan network membranes by introducing binary crosslink agents

Summary In this investigation chitosan (CS) was crosslinked using mixtures of sulfosuccinic acid (SSA) and glutaraldehyde (GA) as the binary crosslinking agents to form hydrophilic chitosan network membranes. GA and SSA improve the tensile strength and contribute to hydrophilicity of the membranes, respectively. The membranes prepared by varying the crosslinking agent ratios are also characterized using FT-IR, X-ray diffraction, and tensile testing, and their swelling ratio and thermal properties were measured. Experimental results reveal that the contact angle of the membrane decreases from 84.54° to 69.83° and the maximum stress rises from 39.62 MPa to 133.66 MPa as the increase of the binary crosslinking agent content. These resultant membranes not only maintain its hydrophilicity and but also enhance the mechanical strength.     

Dehydration of ethanol through blend membranes of chitosan and sodium alginate by pervaporation

Polyion complex membranes made by blending 84% deacetylated chitosan and sodium alginate biopolymers followed by crosslinking with glutaraldehyde were tested for the separation of ethanol–water mixtures. The membranes were characterized by FTIR to verify the formation of the polyion complex, X-ray diffraction (XRD) to observe the effects of blending on crystallinity, DSC, and TGA to investigate the thermal stability, and tensile testing to assess their mechanical stability. The effect of experimental parameters such as feed composition, membrane thickness and permeate pressure on separation performance of the crosslinked membranes was determined. Sorption studies were carried out to evaluate the extent of interaction and degree of swelling of the blend membranes, in pure as well as mixtures of the two liquids. Crosslinked blend membranes were found to have good potential for breaking the azeotrope of 0.135 mol fraction of water and a high selectivity of 436 was observed at a reasonable flux of 0.22 kg/(m² 10 μm h). Membrane selectivities were found to improve with decreasing membrane pressure but remained relatively constant for variable membrane thickness. Increasing membrane thickness decreased the flux and higher permeate pressure caused a reduction in both flux and selectivity.     

Propranolol hydrochloride release behaviour of crosslinked chitosan membranes

Chitosan membranes of 20 μm thickness were prepared by a solvent evaporation technique and crosslinked with different concentrations of glutaraldehyde to obtain membranes of various degrees of crosslinking. These membranes were characterized by thermogravimetric (TG) analysis, differential scanning calorimetry (DSC) and tensile strength studies. The effect of crosslinking on the permeability of membranes to propranolol hydrochloride was evaluated by permeation studies conducted in static glass diffusion cells. A decrease in the thermal stability of chitosan membranes due to crosslinking was observed. The tensile strength of the membranes was improved by crosslinking. The introduction of crosslink points within the membrane reduced its permeability to propranolol hydrochloride as evidenced by decreased permeability and diffusion coefficients. Permeability studies revealed the operation of a pore mechanism in the transport of hydrophilic agents such as propranolol hydrochloride through chitosan and crosslinked chitosan membranes.     

Preparation and characterization of alginate hydrogel membranes crosslinked using a water‐soluble carbodiimide

The preparation of alginate hydrogel membranes by the film immersion method was optimized for maximum crosslinking using swelling measurements as an indicator of the degree of crosslinking. The variables investigated were the concentration of the nonsolvent (ethanol) for sodium alginate, water‐soluble carbodiimide (WSC) concentration, and pH of the crosslinking medium. Optimum conditions resulted when the crosslinking medium contained 60 vol % ethanol and 100 mM WSC at pH 4. Membranes prepared using different ethanol concentrations (100 mM WSC, pH 4) and different WSC concentrations (60 vol % ethanol, pH 4) were investigated using infrared spectroscopy. The spectra showed the characteristic ester linkage (crosslinking) band at 1698 cm^?1 in cases where swelling measurements indicated that crosslinking had occurred. Differential scanning calorimetry of noncrosslinked and crosslinked membranes indicated that crosslinking increased the crystallinity of the membrane. Durability trials showed that membranes crosslinked using the optimum conditions determined in this work retained all weight when immersed in water for 32 days. Membranes prepared using these conditions possessed the characteristics required for use in the pervaporation separation of ethanol–water mixtures. These membranes also have potential as protective coatings for hydrophobic, microporous membranes in the membrane distillation and osmotic distillation concentration of feeds containing surface active components. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 747–753, 2003     

壳聚糖膜的制备及其性能测试

以天然高分子材料壳聚糖为原料,采用流延法制备了壳聚糖膜。研究了N-乙酰化和交联壳聚糖膜的制备方法及性能特性等。通过FTIR、XRD和SEM方法表征结构,并测试了力学性能。试验结果表明交联和乙酰化可以增加壳聚糖膜的拉伸强度提高膜的性能。     

Poly(vinyl alcohol)‐based polymeric membrane: Preparation and tensile properties

A series of poly(vinyl alcohol) (PVA)‐based single‐layer organic polymeric membranes were prepared via the crosslinking of PVA with different amounts of formaldehyde. Meanwhile, for comparison, both a three‐layer organic polymeric membrane and a hybrid composite membrane were also prepared by the layer‐upon‐layer method. Their thermal stability and tensile properties were investigated to examine the effect of crosslinking on the membrane performances. Thermogravimetric analysis and differential scanning calorimetry thermal analyses showed that the thermal degradation temperature of the single‐layer crosslinked membrane C reached up to 325°C. Tensile testing indicated that the three‐layer organic polymeric membrane E had excellent tensile strength among these single‐layer and three‐layer membranes. The swelling properties revealed that the swelling degree value of these membranes decreased with an increase in methanol concentration; this suggests that they were not easily swollen by the methanol solution, which is meaningful for the separation of organic mixtures. Field emission scanning electron microscopy images exhibited that the crosslinking of functional groups impacted their structures and confirmed that their mechanical properties were related to their structures. These findings suggest that the crosslinking of functional groups is an effective method for adjusting the tensile strength of PVA‐based organic polymeric membranes and related hybrid composite membranes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Structure and ionic conductivity of a series of di‐o‐butyrylchitosan membranes

Di‐o‐butyrylchitosan was prepared by reacting chitosan with butyric acid anhydride in the presence of perchloric acid as a catalyst. ¹³C‐NMR and IR spectra of the modified chitosan suggested that both hydroxyl groups, at the C‐6 and C‐3 positions, in the chitosan molecules were substituted. The maximum degree of substitution was found to be less than 28%. The results of X‐ray diffractograms revealed that, in comparison with the unmodified chitosan membrane, the crystallinity of di‐o‐butyrylchitosan membranes was remarkably decreased. Meanwhile, it was also observed that the swelling indices of modified membranes were increased significantly in direct proportion to the degree of substitution. Thermogravimetric analysis indicated that the modified membranes exhibited a slightly increased thermal stability compared to the unmodified membrane. The ionic conductivity of di‐o‐butyrylchitosan membranes after hydration was investigated using impedance spectroscopy. Compared to the unmodified chitosan membrane, the hydrated di‐o‐butyrylchitosan membrane with a relatively high degree of the substitution showed an increased ionic conductivity of more than one order of magnitude. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2309–2323, 2004     

In situ crosslinking of chitosan and formation of chitosan-silica hybrid membranes with using γ-glycidoxypropyltrimethoxysilane as a crosslinking agent

Crosslinking on chitosan was conducted with γ-glycidoxypropyltrimethoxysilane (GPTMS) with in situ formation of chitosan-silica hybrid membranes. The formed silica structure was observed with ²⁹Si NMR, scanning, and transmission electronic microphotograghy. Energy dispersive X-ray Si-mapping analysis demonstrated the homogeneous dispersion of silica in chitosan polymer domains. The formed chitosan-silica hybrid materials exhibited improved thermal stability and low degree of swelling in water. The hydrophilicity of chitosan membranes was maintained after the crosslinking reaction. This approach provided a convenient way to prepare crosslinked chitosan and chitosan-silica hybrid materials and the materials were potentially applied in biomaterials and separation membranes.     

Dehydration of 1,4-dioxane by pervaporation using crosslinked calcium alginate-chitosan blend membranes

Summary  Sodium alginate (SA) and chitosan (CS) blended membranes were crosslinked with maleic anhydride (MA) for the separation of 1,4-dioxane/water mixtures at 30 °C by pervaporation (PV). The membranes were characterized by Fourier transform infrared (FTIR) analysis and Ion Exchange Capacity (IEC) to verify the crosslinking. Thermogravimetric analysis (TGA) and X-ray diffraction (XRD) pattern were used to observe the thermal degradation and crystalline nature of the membrane respectively. The membrane performance was studied by calculating flux, selectivity, and pervaporation separation index. Sorption studies were carried out to evaluate the extent of interaction and degree of swelling of the membranes in pure liquids as well as in binary mixtures. The effects of experimental parameters such as feed composition, membrane thickness, and permeate pressure on separation performance of the crosslinked membranes were determined. The experimental result suggested that the membrane has a good potential for breaking the aqueous azeotrope 1,4-dioxane.     

Water state in chemically and physically crosslinked chitosan membranes

Chemically and physically crosslinked chitosan membranes were prepared by treating chitosan (Ch) with glutaraldehyde (GA) and sulfuric acid (SA). FTIR and XRD results were employed to confirm the formation of covalent and ionic crosslinks between Ch, GA, and SA. The states of water in non‐crosslinked and covalently and ionically crosslinked chitosan membranes containing different amount of water were investigated by low temperature differential scanning calorimetry measurements. The equilibrium swelling in water was examined gravimetrically. Two types of water were found in the polymer samples, i.e., freezing water and non‐freezing water. The effect of crosslinking process on water state and water uptake was analyzed. The water uptake decreased after chitosan crosslinking with GA, but significantly increased after later crosslinking with SA. The amount of non‐freezing water was generally smaller in crosslinked membranes. An impact of molecular and supermolecular structure on water uptake and state of water in non‐crosslinked and crosslinked chitosan membranes was discussed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1707–1715, 2013     

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     

Novel pH,ion sensitive polyampholyte gels based on carboxymethyl chitosan and gelatin

Natural pH and ion sensitive polyampholyte gels were successfully prepared by blending carboxymethyl chitosan (CM‐chitosan) and gelatin using glutaraldehyde as crosslinking agent. Their swelling behaviour under the influence of pH and ionic strength of the solution has been studied, and molecular interaction and, morphology of the gels were investigated by infrared spectroscopy and scanning electron microscopy. At the isoelectric point (IEP) the blend gels shrunk most, and when pH deviated from the IEP they behaved as polycations or polyanions. A decrease in swelling degree (D_s) with rising NaCl concentration up to 0.15 M was observed for all gels, while addition of Ca²⁺ made them shrink due to formation of Ca²⁺ crosslinked bridges. The blended gels showed increasing sensitivity to pH and ionic strength as the weight fraction of CM‐chitosan increased. Two essential components seem to regulate the swelling behaviour of blended gel: the first is related to osmotic pressure difference caused by the redistribution of mobile ions; the second is related to the possible formation of interactions corresponding to hydrogen bonding and hydrophobic interactions. © 2003 Society of Chemical Industry     

高密度聚乙烯电子束辐射交联的研究

用高能电子束辐射技术研究了添加敏化剂季戊四醇三丙烯酸酯(PETA)和抗氧剂300的高密度聚乙烯(HDPE)体系的辐射交联效应.通过测定试样辐射后交联度、拉伸强度、直角撕裂强度等性能,考察了辐射剂量、w(PETA)和 w(300)对 HDPE辐射交联的影响;并用差示扫描量热法和热重分析研究了HDPE辐射后的结晶性和热稳定...     

Preparation of ion exchange membranes by preirradiation induced grafting of styrene/divinylbenzene into crosslinked PTFE films and successive sulfonation

Ion exchange membranes (IEMs) were prepared by preirradiation induced grafting of styrene with or without divinylbenzene (DVB) into crosslinked polytetrafluoroethylene (RX‐PTFE) films and successively sulfonated by chlorosulfonic acid. The effects of the DVB concentration and solvent on the kinetic of the graft polymerization were studied. The ion exchange capacity (IEC) values of the prepared membranes ranging from 1.5 to 2.8 mequiv/g were obtained. The degree of swelling increased with the increase in the degree of grafting, while higher crosslinking density of both the RX‐PTFE matrices and the grafts suppressed the degree of swelling. The chemical stabilities of the IEMs were tested by recording the weight of the membranes being soaked in hot H₂O₂ solutions. The weight‐time curves of the prepared membranes showed one‐step quick decrease due to the decomposition of the poly(styrene‐sulfonic acid) (PSSA) grafts. Higher crosslinking density in both the RX‐PTFE matrices and the grafts improved the chemical stability of the IEMs. The ionic conductivity of the IEMs increases with the increase in the IEC values. The IEMs with IEC values higher than 2.2 mequiv/g hold the higher ionic conductivity than that of Nafion® 112 membrane. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3587–3599, 2006     

Tensile,Swelling, and Oxidative Degradation Properties of Crosslinked Polyvinyl Alcohol/Chitosan/Halloysite Nanotube Composites

Glutaraldehyde (GA) crosslinked polyvinyl alcohol (PVA)/chitosan (CS)/halloysite nanotube (HNT) composite films were prepared using a wet casting method. The tensile, morphology, thermal degradation, swelling, moisture, and oxidative degradation properties of crosslinked composite films were carried out. The presences of crosslinking in the composite films were confirmed by FTIR result. The tensile strength of the crosslinked composite films increased up to 0.5 wt% of HNTs loading. Increasing HNTs reduced the thermal degradation, swelling, and moisture properties of crosslinked composite films reduced with the increase of HNTs content. Results also indicated that the crosslinked composite films were degraded using Fenton reagent.     

Preparation and permeability of solutes through acrylic acid-g-methylcellulose copolymer membranes

Graft copolymer membranes from the methylcellulose and the acrylic acid were prepared and their properties and the permeability of four solutes were estimated. Acrylic acid-g-methylcellulose (AA-g-MC) copolymer dissolved in aqueous acetone solvent was cast to prepare membranes followed by the subsequent crosslinking either with aluminium potassium sulfate or by the thermal-curing method. The equilibrium water content in the membrane increased with the volume fraction of acetone in the aqueous acetone solvent system. Membrane, the ionically crosslinked with the aluminum potassium sulfate, showed the water content in the range of 38.5 and 58.4% and 0.25–0.33 kg/mm² of the tensile strength in the wet state. Compared with ionically crosslinked membranes, thermally dried membranes exhibited a more dense structure, resulting in lower water contents and higher mechanical strength. Experimental results on the permeation of four small and midsize solutes through the graft copolymer membranes revealed the molecular weight dependence of the permeability coefficient. The higher the degree of swelling, the greater the permeability coefficient. Ionically crosslinked membranes had higher solute permeability than the commercial Cuprophane membrane had. © 1993 John Wiley & Sons, Inc.     

Characterization and performance evaluations of sodium zeolite‐Y filled chitosan polymeric membrane: Effect of sodium zeolite‐Y concentration

Sodium zeolite‐Y (NaY zeolite) filled chitosan polymeric membranes were developed and characterized. The impact of adding different concentrations of NaY zeolite into the homogeneous chitosan membrane was investigated. The surface morphology, mechanical–physical properties, sorption, and pervaporation performance for the dehydration of isopropanol–water mixture separation by the pervaporation process were studied and evaluated. A homogeneous chitosan membrane showed preferential water sorption and permeation compared to isopropanol. The optimum concentration of NaY zeolite added to the homogeneous chitosan membrane was 0.4 wt %, which showed that the dispersion of the NaY zeolite was the most homogeneous and finely covered by the chitosan polymer in the zeolite–chitosan polymer interface. The tensile strength and percent strain at maximum of this membrane were 59.347 MPa and 27.5%, respectively. The sorption experiments showed that the degree of swelling was 6.54% with 1.01 wt % isopropanol sorbed in these membranes. The pervaporation separation tests demonstrated that the NaY zeolite filled chitosan membrane was capable for isopropanol–water mixture separation and improved the pervaporation separation index from 272 (homogeneous chitosan membrane) to 2687. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1740–1751, 2006     

Reinforcement of pH‐responsive γ‐poly(glutamic acid)/chitosan hydrogel for orally administrable colon‐targeted drug delivery

Orally administrable hydrogel was prepared by crosslinking chitosan (CS) with γ‐poly(glutamic acid) (γ‐PGA) for an excellent pH‐responsive colon‐targeted drug delivery system. The stable crosslinked amide bond appeared in the shifted region of FTIR spectroscopy, and the tensile strength and elastic modulus were also reduced by crosslinking of CS and γ‐PGA. The surfaces of crosslinked hydrogel have a homogeneous pore array with pore size corresponding to the varied blending ratio. The swelling ratio was dramatically changed by increasing the pH from 3 to 6, and the responsiveness of swelling ratio to the reversible pH changes between 3 and 10 was reliable for 72 h. The drug diffusion rate was mainly dependent on the pH, and a water‐soluble tetrazolium (WST‐1) assay indicated that cytocompatibility of the hydrogel was in an acceptable range. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci. 2013     

Preparation of fructose‐mediated (polyethylene glycol/chitosan) membrane and adsorption of heavy metal ions

Chitosan is an efficient metal chelater, but its practical use is limited due to the stability in acid solutions, adsorption capacities. In this study, we attempt to find a new pH‐dependent adsorbent based on fructose‐mediated chitosan/PEG membrane and examines several experimental parameters relative to their formation and characteristics. The membrane was characterized in terms of their fourier transforms infrared spectroscopy‐attenuated total reflectance (FTIR‐ATR) spectra, X‐ray diffraction (XRD) analysis, surface morphologies, tensile strength, mediating degree analysis, and swelling behavior at pH 3 and 6 medium. To estimate the potential of these membranes as a biosorbent, the capability and behavior for the adsorption of heavy metal ions were investigated using Lead ions as a model compound. FTIR‐ATR result showed that the Schiff's base reaction was favor formed in high pH condition. Swelling study showed that the swelling degree of homogeneous mediated membrane decreases as the pH of the final fructose‐mediated chitosan/PEG gel increase, which was demonstrated by mediating degree analysis. Low crystallinity of fructose‐mediated membranes is responsible for its sorption efficiency. With increasing the amount of fructose in the chitosan/PEG there is a proportionality of the adsorption capacity except that the high fructose content (10 wt %). The pH 6 treated 5 wt % fructose‐mediated membrane has a maximum sorption capacity to about 185 mg/g. The adsorption isotherms could be well fitted by the Langmuir equation. The results showed the potential applicability of fructose‐mediated chitosan/PEG membrane as a biosorbent for metal recovery. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007