Poly(vinyl alcohol)/chitosan oligosaccharide blend submicrometer fibers prepared from aqueous solutions by the electrospinning method

Submicrometer fibers of poly(vinyl alcohol) (PVA) and chitosan oligosaccharide [COS; i.e., (1→4)‐2‐amino‐2‐deoxy‐β‐D ‐glucose] were prepared by an electrospinning method with aqueous solutions with polymer concentrations of 7.5–15 wt %. Scanning electron microscopy, Fourier transform infrared, X‐ray diffraction, differential scanning calorimetry, and thermogravimetric analysis were used to characterize the morphology and properties of the PVA/COS fibers. The PVA/COS mass ratio, the total polymer concentration, and processing parameters such as the applied voltage and capillary‐to‐collector distance played important roles in controlling the fiber morphology. Fourier transform infrared and X‐ray diffraction data demonstrated that there were possibly hydrogen bonds between COS and PVA molecules that weakened the interactions in COS and improved the electrospinnability of PVA/COS. Moreover, with a higher percentage of COS in the PVA/COS blend fibers, superior thermal stability could be obtained. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Extraction of 1-butanol from aqueous solutions by pervaporation

The extraction of 1-butanol from fermentation broths by pervaporation offers potential for use in biotechnology. Various membrane materials have been screened for their suitability for this process. Polydimethylsiloxane (PDMS) membranes gave the best results in terms of flux and selectivity, with large variations depending on their nature and preparation. Selectivity was further increased by including either organophilic adorbents (cyclodextrins, zeolites), or oleyl alcohol in dense PDMS membranes. The predominance of driving force (i.e. activity gradient) on pervaporation extraction performances was shown by a comparative study on different binary aqueous solutions of alcohols. Water flux remained practically constant while the alcohol flux was linearly related to its feed concentration. The conclusions obtained with binary mixtures were consistent with those obtained with two model ternary solutions; the influence of salt on 1-butanol permeability was negligible, whereas ethanol had a strong effect.     

Crosslinked poly(vinyl alcohol)/carboxymethyl chitosan hydrogels for removal of metal ions and dyestuff from aqueous solutions

Hydrogels composed of poly(vinyl alcohol) (PVA) and carboxymethyl chitosan (CMCh) were synthesized via ultraviolet (UV) irradiation that can be used in several industrial fields. Several analysis tools were used to characterize the physical and thermal properties of CMCh/PVA hydrogels namely FT‐IR, scanning electron microscope (SEM), XRD, thermogravimetric analysis (TGA), and differential scanning calorimetery (DSC). TGA results showed that CMCh/PVA hydrogels are thermally more stable than CMCh and their thermal stability increases as PVA content increases in the hydrogel. Also, DSC results showed that CMCh/PVA hydrogels are at least partial miscible blends. Moreover, the swelling behavior of the CMCh/PVA hydrogels was studied in different buffered solutions and in different salt solutions at various concentrations. CMCh/PVA hydrogels swell much more than CMCh especially at alkaline pH. Both metal and dye uptake were studied for CMCh/PVA hydrogels. The hydrogels adsorb much more dyestuff and metal ions like Cu²⁺, Cd²⁺, and Co²⁺ than CMCh itself. Much dyestuff and metal ions are adsorbed by the hydrogels as PVA content increases in the hydrogel. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Electrospinning of chitosan/poly(vinyl alcohol)/acrylic acid aqueous solutions

Chitosan bicomponent fibers were prepared via the electrospinning of chitosan/poly(vinyl alcohol)/acrylic acid aqueous solutions with different concentrations. With a 4% acrylic acid aqueous solution, when the chitosan/poly(vinyl alcohol) mass ratios were lower than 80/20, electrospinning nanofibers could be obtained. With a 90% acrylic acid aqueous solution, when the chitosan/poly(vinyl alcohol) mass ratios were less than 95/5, good nanofibers could be electrospun. The average diameter of the nanofibers gradually decreased, and its distribution became narrower as the poly(vinyl alcohol) concentration increased. Chitosan/poly(vinyl alcohol)/acrylic acid aqueous solutions could be electrospun at various concentrations by the adjustment of the chitosan and poly(vinyl alcohol) concentrations. The effects of the viscosity and conductivity of the blend solution on the morphologies of the fiber mats were also investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5692–5697, 2006     

Recovery of 1-butanol from a model pharmaceutical aqueous waste by pervaporation

Pervaporation experiments were conducted to recover 1-butanol from model pharmaceutical aqueous waste using a surface modified poly(vinylidene difluoride) membrane. The surface modification of the membrane was made using silicone grease as an ultra-thin layer on the surface to improve the pervaporation performance of the membrane. The effect of operating variables such as feed composition, feed temperature and feed flow rate on permeation fluxes, separation factor and pervaporative separation index were studied in order to optimize the operating variables. The experimental results showed that surface modified poly(vinylidene difluoride) membrane was 1-butanol permselective, especially for low feed compositions. 1-Butanol separation factor of 6.4 and a total flux of have been obtained at a feed composition of 7.5 wt%, feed temperature of , feed flow rate of and permeate pressure of 50 mmHg. The total flux of the surface modified membrane increased with increasing the feed composition, feed temperature, feed flow rate of the mixture whereas the separation factor follows a reversed order except for flow rate. The influence of operating variables such as feed composition and temperature on partial flux and permeate composition was modelled based on Fick's first law to understand the process behaviour and it will be very useful for design purpose. These models will be used to predict the required membrane surface area for recovery of 1-butanol for the range of experimental feed compositions.     

Polyelectrolyte multilayer modified nanofiltration membranes for the recovery of ionic liquid from dilute aqueous solutions

The feasibility of nanofiltration membranes fabricated by static polyelectrolyte layer‐by‐layer deposition of poly(styrene sulfonate) and poly(allylamine hydrochloride) on poly(ether sulfone) ultrafiltration and alumina microfiltration membranes for the recovery of ionic liquid from low molecular weight sugar was investigated. The surface properties of these modified membranes were correlated with their performances. The selectivity for 1‐butyl‐3‐methylimidazolium chloride over cellobiose and glucose was found to be as high as 50.5/2.3 for modified alumina and 32.3/3.5 for modified poly(ether sulfone) membranes with optimized number of bilayers. The values for membrane permeance were 4.8 and 2.5 L m^?1 h² bar^?1, respectively. For low depositions, the separation mechanism was predominantly governed by size‐exclusion. For higher depositions, the enhanced negative zeta potential of the modified membranes suggested preferred dominating electrostatic interactions, resulting in high selectivity of ionic liquids over low molecular weight sugars. At very high depositions, the molecular weight cut‐off of the membrane becomes constricting for size‐exclusion effect. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45349.     

Nanofibrous scaffold prepared by electrospinning of poly(vinyl alcohol)/gelatin aqueous solutions

A series of nanofibrous scaffolds were prepared by electrospinning of poly(vinyl alcohol) (PVA)/gelatin aqueous solution. PVA and gelatin was dissolved in pure water and blended in full range, then being electrospun to prepared nanofibers, followed by being crosslinked with glutaraldehyde vapor and heat treatment to form nanofibrous scaffold. Field emission scanning electron microscope (FESEM) images of the nanofibers manifested that the fiber average diameters decreased from 290 to 90 nm with the increasing of gelatin. In vitro degradation rates of the nanofibers were also correlated with the composition and physical properties of electrospinning solutions. Cytocompatibility of the scaffolds was evaluated by cells morphology and MTT assay. The FESEM images revealed that NIH 3T3 fibroblasts spread and elongated actively on the scaffolds with spindle‐like and star‐type shape. The results of cell attachment and proliferation on the nanofibrous scaffolds suggested that the cytotoxicity of all samples are grade 1 or grade 0, indicating that the material had sound biosafety as biomaterials. Compared with pure PVA and gelatin scaffolds, the hybrid ones possess improved biocompatibility and controllability. These results indicate that the PVA/gelatin nanofibrous have potential as skin scaffolds or wound dressing. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Comparison between supported gas membrane process and supported liquid membrane process for the separation of NH3 from aqueous media containing NH3 and CO2

A comparison between the hollow fibre supported gas membrane (SGM) process and the hollow fibre supported liquid membrane (SLM) process for the separation of NH₃ from aqueous solutions containing NH₃ and CO₂ was performed. The experimental data as well as the model simulation demonstrate that the SLM process can remove NH₃ from aqueous solutions of NH₃ and CO₂ at a higher rate than the SGM process when the NH₃ loading is low or the ratio of NH₃ to CO₂ is low. This study suggests that the proper combination of the SGM process and the SLM process can strip NH₃ more effectively from aqueous solutions containing NH₃ and CO₂.     

A supported liquid membrane system for the selective recovery of rare earth elements from neodymium-based permanent magnets

The rare earth elements (REEs) play a vital role in the development of green energy and high-tech industries. In order to meet the fast-growing demand and to ensure sufficient supply of the REEs, it is essential to develop an efficient REE recovery process from post-consumer REE-containing products. In this research effort, we have developed a supported liquid membrane system utilizing polymeric hollow fiber modules to extract REEs from neodymium-based magnets with neutral extractants such as tetraoctyl digylcol amide (TODGA). The effect of process variables such as REE concentration, molar concentration of acid, and membrane area on REE recovery was investigated. We have demonstrated the selective extraction and recovery of REEs such as Nd, Pr, and Dy without co-extraction of non-REEs from permanent NdFeB magnets through the supported liquid membrane system. The extracted REEs were then recovered by precipitation followed by the annealing step to obtain crystalline REE powders in nearly pure form. The recovered REE oxides were characterized by X-ray diffraction, scanning electron microscope coupled with energy-dispersive X-ray spectroscopy, and inductively coupled plasma–optical emission spectroscopy.     

Poly(Vinylidene fluoride-co-hexa fluoropropylene)/Poly vinyl alcohol porous membranes for the application of fuel cells

Composite polymer electrolyte membranes PVdF-HFP/PVA were prepared by phase inversion technique. The prepared membranes were soaked in DI water and 6 M sulfuric acid in order to attain the porosity and functionality. The extended porosity was determined by scanning electron microscopy (SEM). Amorphous phase was enhanced by the inclusion of acid. Amorphous state provides a free path which causes the movement of ions leading to an increase in the conductivity. The infra-red spectroscopic measurements revealed the presence of acid moieties in the composite membranes and confirmed its functionality. Thermal gravimetric analysis showed high thermal stability of the membrane. The polymer membrane prepared with extended porosity [PVdF-HFP (7 wt.%)/PVA (4.6 wt.%)] exhibited maximum protonic conductivity due to the effect of high porous nature and the entrapment of acid moieties.     

Selective recovery of palladium from used aqua regia by hollow fiber supported with liquid membrane

This research study was aimed at recovering palladium from used aqua regia by means of a hollow fiber thoroughly supported with liquid membrane. The liquid membrane, consisting of two extractants—thioridazine HCl and oleic acid-solubilized in chloroform—was used to coat the rmcroporous hollow fiber throughout. Sodium nitrite, a stripping agent, which was fed through the shell side, flowed counter-currently with the feed solution fed via the tube side. The following factors were investigated: the concentrations of the two extractants and of sodium nitrite, the pH of used aqua regia, the flow rates of both the feed and stripping solution, and the number of runs in the hollow fiber module. It was found that after a 30-mmute operation, 29.10% of palladium ion was optimally recovered at 0.0005-M thioridazine and 0.05-M oleic acid. With reference to the precious metals recovered, the following order was recorded: Pd(II)>Pt(IV)>Cu(II)>Au(III). It was observed that synergistic extraction could be gained at the concentration level of the extradants, regulated in the experiment. The liquid membrane system had long-term stability and even after the third run, it could still recover palladium up to 65%.     

Poly(vinyl alcohol) hydrogels. Formation by electron beam irradiation of aqueous solutions and subsequent crystallization

Aqueous solutions of poly(vinyl alcohol) were submitted to varying doses of electron beam irradiation. By modification of the classical Flory-Huggins equations appropriate to the initial state of solution of the polymer, the molecular weight between crosslinks, M_c, was calculated as a function of radiation dose, initial polymer concentration, and temperature. Following crosslinking in the solution state, crystallization was induced by dehydrating the network at temperatures above 90°C. Following dehydration, the polymer network was reequilibrated with water and its tensile properties compared with identically prepared hydrogels not subjected to crystallization by dehydration. Greatly enhanced values of ultimate tensile strength and resistance to tear result from the treatment producing crystallization, compared with those of the crosslinked but not previously dehydrated gels.     

Hollow fiber supported liquid membrane process for the separation of NH3 from aqueous media containing NH3 and CO2

A hollow fiber supported liquid membrane (SLM) process was investigated experimentally and theoretically for the separation of NH₃ from aqueous solutions containing NH₃ and CO₂. DTPA and D2EHPA were used as carriers and n-decanol was used as a diluent in this process. The membrane stripping experiments, as well as the extractive equilibrium experiments, indicate that DTPA is a better carrier than D2EHPA in relation to the increase in the NH₃ stripping rate. The influence of operating conditions, such as flow rate, the ratio of NH₃ to CO₂, and carrier concentration, on the membrane stripping rate were examined. The experimental data demonstrate that the NH₃ stripping rate by an SLM process is not significantly influenced by the amount of CO₂ present, as is that by the supported gas membrane. To predict the stripping of NH₃ from solutions containing NH₃ and CO₂, a mathematical model incorporating chemical equilibria and Nernst–Planck diffusion was developed to describe the mass transport. The experimental data suggested that the SLM process can effectively strip NH₃ from aqueous solutions containing NH₃ and CO₂.     

Transport of chromium(VI) through a Cyanex 921‐supported liquid membrane from HCl solutions

The transport of chromium(VI) through a flat‐sheet supported liquid membrane containing Cyanex 921 as a carrier has been investigated. The permeation of the metal is investigated as a function of various experimental variables: hydrodynamic conditions, concentration of chromium(VI) and HCl in the feed phase, carrier concentration and diluent in the membrane and strippant concentration in the stripping phase. The mass transfer coefficient and the thickness of the aqueous boundary layer were calculated from the experimental data. Furthermore, the selectivity of Cyanex 921‐based flat‐sheet supported liquid membrane towards different metal ions and the behaviour of the system against other carriers are presented. Copyright © 2003 Society of Chemical Industry     

Preparation of poly(vinyl alcohol)/tetraethyl orthosilicate hybrid membranes modified with TMPTMS by sol-gel method for removal of lead from aqueous solutions

Poly(vinyl alcohol)/tetraethyl orthosilicate (PVA/TEOS) ion exchange hybrid membranes modified with 3-mercaptopropyltrimethoxysilane (TMPTMS) were prepared by the sol-gel method, and their applications for the removal of lead ions from aqueous solutions in a batch sorption process were studied. The functional groups of the hybrid membranes were characterized by FTIR. Batch adsorption studies such as TMPTMS content, pH, adsorbent dose, contact time, initial concentration and temperature were evaluated. The maximum adsorption capacity of lead ions was found to be 61.62mg g^?1, respectively. The kinetic data were analyzed by pseudo-first-order and pseudo-second-order kinetic models. The Freundlich and Langmuir isotherm models were applied to describe the equilibrium data. Thermodynamic parameters indicated that the lead adsorption onto the membrane is an endothermic and spontaneous process. The PVA/TEOS/TMPTMS hybrid membrane is regenerated by 0.5M HNO₃/0.1 M HCl in equal ratio solution and the adsorption capacity did not change remarkably after five sorption-desorption cycles.     

Selective recovery of acetone-butanol-ethanol from aqueous mixture by pervaporation using immobilized ionic liquid polydimethylsiloxane membrane

An effective in situ recovery of acetone, butanol and ethanol (ABE) from fermentation broth is requisite to overcome the low productivity of ABE production. Pervaporation has proven to be one of the best methods for recovering ABE from fermentation broth. We fabricated an immobilized ionic liquid-polydimethylsiloxane (PDMS) membrane in which a [Tf₂N]^? based ionic liquid covalently bound to the PDMS backbone polymer and used it to recover ABE from aqueous solution by pervaporation. Permeate flux of immobilized IL-PDMS membrane was 7.8 times higher than that of conventional supported IL-PDMS membrane (where ILs are physically absorbed on the supported membrane). Butanol enrichment factor of immobilized IL-PDMS membrane was three-times higher than that of PDMS membrane. In addition, high enrichment factor both to acetone and ethanol as well as high operational stability of immobilized IL-PDMS membrane can enhance the efficacy of ABE recovery by employing this membrane.     

聚乙烯醇/淀粉纳米晶复合膜的制备及表征

利用蜡质玉米淀粉通过硫酸酸解制备淀粉纳米晶（SN）,并采用溶液流延法制备聚乙烯醇（PVA）/SN复合膜,研究SN对复合膜结构和性能的影响。结果表明,制备的SN样品为盘状颗粒,平均直径为30～60 nm;随着SN含量的增加,PVA/SN复合膜的力学性能和阻隔性能均呈现先增后减的变化;在SN含量为10 %时,复合膜的拉伸和阻隔性能最好,拉伸强度由纯PVA膜的47 MPa提高至54 MPa,气体透过系数相对于纯PVA膜也降低了70 %。     

Preparation and Characterization of Poly (vinyl alcohol)/Antimony-Doped Tin Oxide Nanocomposites

Nanocomposites of poly (vinyl alcohol) and antimony-doped tin oxide (ATO) were prepared by solution blending. The PVA composites were characterized by FTIR, TGA, DSC, WXRD and stress-strain testing. It has been found that adding ATO to the matrix has great influence on the crystallization behavior and glass transition temperature of PVA. The mechanical properties of PVA changed with the filler content, exhibiting an initial increase in these properties due to polymer-filler interactions. After a maximum value, at about 5 wt%, the mechanical properties decreased. Thermal stability of the nanocomposites was found to be remarkably enhanced by the incorporation of ATO.     

聚乙烯醇/膨润土杂化水凝胶的力学性能和溶胀行为

利用冷冻-解冻法制备了聚乙烯醇/膨润土杂化水凝胶. X射线衍射结果表明,膨润土以剥离形式分布在水凝胶基体中. 研究结果表明,与纯PVA5水凝胶相比,经过5个冷冻-解冻循环制备的含2%(w)膨润土的杂化水凝胶的拉伸模量、拉伸强度和断裂伸长率分别增加了44.0%, 74.2%和25.2%,而溶胀行为与5个循环的纯水凝胶相近. 含0.5%(w)膨润土的杂化水凝胶的拉伸模量和拉伸强度高于基体水凝胶,其在溶胀400 min时的溶胀度高于所有的样品.