Kinetic modeling of novel solid desiccant based on PVA-LiCl electrospun nanofibrous membrane

A new polymer-based composite desiccant, Polyvinyl alcohol-LiCl nanofibrous membrane (PVA-LiCl NFM), has been prepared by the electrospinning technique. The newly-developed desiccant membrane not only has large moisture adsorption capacity, fast moisture adsorption rate and favorable stability, but also is featured by its low regeneration temperature. In this work, adsorption and desorption kinetic models are explored for PVA-LiCl NFMs, which include the pseudo-first and the pseudo-second order model based on the rate law and a diffusion model based on the Fick's law. The results indicate that the moisture adsorption and desorption kinetics of the PVA-LiCl NFMs follow the pseudo-second-order law very well. As the key parameters in the diffusion model, the equilibrium adsorption capacity and the diffusion coefficient are focused on, and they can be well determined by the Brunauer–Emmett–Teller (BET) model and the radial-basis-functions artificial neural network (RBFANN) model, respectively. Finally, the adsorption and desorption activation energy of the PVA-LiCl NFM with a 0.15 mass ratio of LiCl to PVA are recognized as 24.36 and 26.52 kJ/mol, respectively. The work is of great importance to the better application of the newly-developed desiccant material (PVA-LiCl NFM).     

Preparation and characterization of composite membranes with Brønsted acidic ionic liquid

Poly-(vinyl alcohol) (PVA) proton-conducting composite membranes were prepared using succinic acid (SA) as a cross-linking agent and Brønsted acidic ionic liquid (BAIL) as a proton source. The incorporated BAILs resulted in a relatively high proton conductivity compared with PVA/SA membrane without BAILs. The proton conductivities of PVA/SA/BAIL composite membranes increased versus the BAIL content. In addition, the optimal resultant proton conductivity of PVA/SA/BAIL composite membrane under dry condition could reach 0.4 mS/cm at 140 °C, which was higher than that of PVA/sulfosuccinic acid (SSA) composite membrane (0.032 mS/cm), PVA/SSA/5-aminotetrazole membrane (0.022 mS/cm at 130 °C), and PVA/chlorosulfonic acid/glutaraldehyde membrane (0.0585 mS/cm at 90 °C) measured at the same condition. It was notable that the PVA/SA/BAIL composite membranes could reach high thermal stability up to 150 °C, which was higher than that of traditional PVA membranes (below 80 °C).     

Natural and synthetic solid polymer hybrid dual network membranes as electrolytes for direct methanol fuel cells

Hybrid dual-network membranes comprising chitosan (CS)–polyvinyl alcohol (PVA) networks crosslinked with sulfosuccinic acid (SSA) and glutaraldehyde (GA) and modified with stabilized silicotungstic acid (SWA) are reported for their application in direct methanol fuel cells (DMFCs). Physico-chemical properties of these membranes are evaluated using thermo-gravimetric analysis and scanning electron microscopy in conjunction with their mechanical properties. Based on water sorption and proton conductivity measurements for the membranes, the optimum content of 10 wt.% SWA in the membrane is established. The methanol crossover for these membranes are studied by measuring the mass balance of methanol using density meter and are found to be lower compared to Nafion-117 membrane. The membrane–electrode assembly with 10 wt.% stabilized SWA–CS–PVA hybrid membrane with SSA and GA as crosslinking agent delivers a peak power density of 156 mW cm⁻² at a load current density of 400 mA cm⁻² and 88 mW cm⁻² at a load current density of 300 mA cm⁻², respectively, in DMFC at 70 °C.     

Preparation and pervaporation performance of surface crosslinked PVA/PES composite membrane

This study describes the facile preparation of poly(vinyl alcohol) (PVA)/polyethersulfone (PES) composite membranes by interfacial reaction technique, aiming at acquiring the improved structural and operational stability of the resulting membranes. The effect of interfacial crosslinking agent and hydrophilicity of support layer on the interfacial adhesive strength and pervaporation performance of composite membranes were investigated. The optimal recipe for PVA/PES composite membrane preparation was as follows: PES support layer was treated with 0.1 wt.% borax aqueous solution, fully dried and then immersed into 2 wt.% PVA aqueous solution. The resulting PVA active layer was 1–1.5 μm thick after twice dip-coating. The as-prepared PVA/PES composite membrane exhibited high separation factor of over 438, high permeation flux of 427 g m⁻² h⁻¹ for 80 wt.% EG in the feed at 70 °C and desirable structural stability. It could be derived that adoption of interfacial reaction would be an effective method for preparing the composite membranes suitable for large-scale dehydration of ethylene glycol/water mixture.     

Dehydration of acetic acid by pervaporation using SPEK-C/PVA blend membranes

Sulfonated cardo polyetherketone (SPEK-C) and poly(vinyl alcohol) (PVA) blend membranes were prepared by solution casting method and used in pervaporation (PV) dehydration of acetic acid. The membranes were characterized by Fourier transform infrared (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and contact angle meter. The results show that thermal crosslinking occurred to the membrane under high temperature annealing. The effective d-spacing (inter-segmental spacing) decreased with PVA content decreasing. The hydrophilicity of the blend membrane increased with SPEK-C content increasing. Swelling and sorption experiments show that the swelling degree of the blend membrane increased, however both the sorption and diffusion selectivities decreased with increasing PVA content. The diffusion selectivity is higher than the sorption selectivity. This suggests that PV dehydration of acetic acid is dominated by the diffusion process. The pervaporation separation index (PSI) of the membrane increases with increasing PVA content and arrives at a maximum when the SPEK-C/PVA ratio is 3/2, then decreases with further addition of PVA. The membrane has an encouraging separation performance with a flux of 492 g m⁻² h⁻¹ and separation factor of 59.3 at 50 °C at the feed water content 10 wt%.     

Thin‐film composite membranes incorporated with large‐area graphene oxide sheets and adjustable surface charges

In this research, composite membranes were prepared by cross‐linking of poly(vinyl alcohol) (PVA) and glutaraldehyde (GA) on amidoximated ultrafiltration membrane. During this procedure, it was taken advantage of large‐area graphene oxide sheets as graphitic nets in the active layer. These membranes were used to remove an industrial textile dye (Chrysophenine GX) from wastewater. Optimum condition for membrane preparation was 1.5% wt. of PVA, 1.5% wt. of GA, and 0.3% wt. of graphene oxide sheets. Permeation results showed that electrostatic charges on membrane surface have easily converted from positive into negative ones. Contact angle was significantly decreased (63.5° to 28.8°). Final nanofiltration membrane showed lowest fouling rate during removing the industrial direct dye (flux recovery ratio: 96.60%, reversible fouling ratio: 23.82%, and irreversible fouling ratio: 3.39%). Pore size of this membrane was <8 nm, and Chrysophenine GX was eliminated by 98.5% with water permeability of 12.23 L/m².h.bar.     

A Study of cryostructuring of polymer systems. 41. Complex and composite poly(vinyl alcohol) cryogels containing soluble and insoluble forms of chitosan,respectively

Complex macroporous poly(vinyl alcohol) (PVA) cryogels have been obtained by cryogenic treatment (freezing at–20°C for 12 h followed by defrosting at a rate of 0.03°C/min) of PVA–chitosan hydrochloride mixed solutions. The subsequent alkaline treatment of the cryogels has resulted in the transformation of the water-soluble salt form of chitosan into its insoluble basic form, which coagulates inside the bulk of the continuous phase of PVA cryogel into small particles with sizes of 2–5 µm. In the resulting composite cryogels, these particles play the role of an “active” filler, which increases the rigidity and heat endurance of the gel material. It has been shown that the sorption capacity of such chitosan particles entrapped into the bulk of composite cryogels with respect of bivalent copper ions is noticeably higher than the sorption capacity of ground chitosan particles incorporated as a discrete filler into the continuous phase PVA cryogels. The study of the properties of PVA–chitosan hydrochloride mixed solutions revealed that these polymers are, to a large extent, compatible with one another in a common solvent at a low ionic strength. Therefore, liquidliquid phase separation of these systems due to the thermodynamic incompatibility of macromolecules of different natures is observed only upon increasing the ionic strength by adding a low-molecular-mass salt (NaCl, 0.15 mol/L) to the solution.     

High Ethene/Ethane Selectivity in 2,2′‐Bipyridine‐Based Silver(I) Complexes by Removal of Coordinated Solvent

Following removal of coordinated CH₃CN, the resulting complexes [Ag^I(2,2′‐bipyridine)][BF₄] ( 1 ) and [Ag^I(6,6′‐dimethyl‐2,2′‐bipyridine)][OTf] ( 2 ) show ethene/ethane sorption selectivities of 390 and 340, respectively, and corresponding ethene sorption capacities of 2.38 and 2.18 mmol g^?1 when tested at an applied gas pressure of 90 kPa and a temperature of (20±1) °C. These ethene/ethane selectivities are 13 times higher than those reported for known solid sorbents for ethene/ethane separation. For 2 , ethene sorption reached 90 % of equilibrium capacity within 15 minutes, and this equilibrium capacity was maintained over the three sorption/desorption cycles tested. The rates of ethene sorption were also measured. To our knowledge, these are the first complexes, designed for olefin/paraffin separations, which have open silver(I) sites. The high selectivities arise from these open silver(I) sites and the relatively low molecular surface areas of the complexes.     

Investigation of Sr uptake by birnessite-type sorbents from seawater

Sorption of micro- and microamounts of Sr from seawater has been studied using granulated Na-birnessite. Distribution coefficients of ⁹⁰Sr in the natural seawater are 0.8–1.2?×?10³ ml g^?1, in the model seawater they are 1.6–1.8?×?10³ ml g^?1. Application of Na-birnessite was shown to be prospective in sorption–desorption–regeneration regime. In dynamic sorption conditions, over 150 bed volumes of seawater can be purified till 5% breakthrough occurs at feed rate 10 BV h^?1. Na-birnessite can be used for ⁹⁰Sr radionuclide removal from liquid radioactive wastes containing seawater.

     

Energy material - the role of silicotungstic acid and fly ash in sulfonated poly (ether sulfone) composites for PEMFC applications

The composite polymer electrolyte membranes were prepared from sulfonated poly (ether sulfone) (SPES), silicotungstic acid (STA) and fly ash (FA). Post sulfonation process was adopted to synthesize SPES using sulphuric and chlorosulfonic acid. The prepared electrolyte membranes were examined by water uptake capacity, swelling ratio, ion-exchange ability, proton conductivity, thermal stability and electrochemical performance for evaluating the pertinence of these membranes in fuel cell applications. As such the pristine membrane restricts with the proton conductivity of 0.042?S cm^?1 at 30?°C and 0.060?S cm^?1 at 90?°C while the polymer composite membrane, SP-STA-FA-10 reveals the maximum conductivity of 0.054?S cm^?1 at 30?°C and 0.073?S cm^?1 at 90?°C. It also exhibits good thermal stability than that of the pure membrane. The membrane electrode assemblies (MEAs) have been successfully developed from SPES as well as SP-STA-FA-10 membranes and their electrochemical performance were studied the wide range of current density. Herein, the composite membranes derived from SPES, STA and FA can be viable candidates for fuel cell applications.     

Electrochemical performance of LiVPO<Subscript>4</Subscript>F/C composite cathode prepared through amorphous vanadium phosphorus oxide intermediate

LiVPO₄F/C composites with better electrochemical performance were prepared by calcination of LiF and amorphous vanadium phosphorus oxide (VPO) intermediate synthesized by a sol–gel method using H₃PO₄, V₂O₅ and citric acid as raw materials. The properties of LiVPO₄F/C composites were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical tests. The analysis of XRD patterns and Fourier transform infrared spectra (FTIR) reveal that VPO intermediate prepared by sol–gel method is amorphous and VPO₄ may exist in VPO intermediate. The compositions of LiVPO₄F/C composites are related to the calcination temperature for preparation of amorphous VPO/C intermediate and LiVPO₄F/C composite prepared by VPO/C synthesized at 700°C consists of a single crystal phase of LiVPO₄F. The electrochemical tests show that LiVPO₄F/C composite prepared by VPO/C synthesized at 700°C exhibits higher discharge capacity and excellent cycle performance. This LiVPO₄F/C composite displays discharge capacity of 133 mAh g⁻¹ at 0.5 C (78 mA g⁻¹) and remains capacity retention of 96.8% after 30 cycles, even at a high rate of 5 C, the composite exhibits high discharge capacity of 115 mAh g⁻¹ and capacity retention of 97% after 100 cycles.     

Pervaporation separation of water–acetic acid mixtures through poly(vinyl alcohol)-silicone based hybrid membranes

Hybrid membranes were prepared using poly(vinyl alcohol) (PVA) and tetraethylorthosilicate (TEOS) via hydrolysis followed by condensation. The obtained membranes were characterized by Fourier transform infrared spectroscopy, wide-angle X-ray diffraction and differential scanning calorimetry. The remarkable decrease in degree of swelling was observed with increasing TEOS content in membranes and is attributed to the formation of hydrogen and covalent bonds in the membrane matrix. The pervaporation performance of these membranes for the separation of water–acetic acid mixtures was investigated in terms of feed concentration and the content of TEOS used as crosslinking agent. The membrane containing 1:2 mass ratio of PVA and TEOS gave the highest separation selectivity of 1116 with a flux of 3.33 × 10⁻² kg/m² h at 30 °C for 10 mass% of water in the feed. Except for membrane M-1, the observed values of water flux are close to the values of total flux in the investigated composition range, signifying that the developed membranes are highly water selective. From the temperature dependence of diffusion and permeation values, the Arrhenius apparent activation parameters have been estimated. The resulting activation energy values, obtained for water permeation being lower than those of acetic acid permeation values, suggest that the membranes have higher separation efficiency. The activation energy values calculated for total permeation and water permeation are close to each other for all the membranes except membrane M-1, signifying that coupled-transport is minimal as due to higher selective nature of membranes. Further, the activation energy values for permeation of water and diffusion of water are almost equivalent, suggesting that both diffusion and permeation contribute almost equally to the pervaporation process. The negative heat of sorption values (ΔH_s) for water in all the membranes suggests the Langmuir's mode of sorption.     

Effect of fulvic acid on the sorption and desorption of 90Sr2+ on red earth

Summary Sorption and desorption of radiostrontium on the red earth and its solid components in the presence and absence of fulvic acid were investigated by a batch technique under ambient conditions at pH 5.3±0.1 and T = 25±2 °C. The organic matter in the red earth is a significant trap of ⁹⁰Sr²⁺ and the presence of fulvic acid enhances the sorption of ⁹⁰Sr²⁺ on the red earth at pH 5.3. It was found that all the sorption and desorption isotherms are linear and the sorption of ⁹⁰Sr²⁺ on the red earth can be described by a reversible sorption process and the sorption mechanism is mainly ion-exchange. The effect of ionic strength on ⁹⁰Sr²⁺ sorption was also investigated.     

Thermal stability and lifetime of [AMIM]Cl-PFSA composite membranes

1-Allyl-3-methylimidazolium chloride [AMIM]Cl hybrid perfluorosulfonic acid (PFSA) composite electrolyte membrane was prepared and characterized by TG and FTIR technique. The conductivity was measured using AC impedance method. The results showed that when raised from 20 to 90 °C, the conductivity of composite membrane was increased from 4.50 × 10⁻⁶ to 1.34 × 10⁻⁵ S cm⁻¹, before and after the modification of triethylamine, the thermal stability of composite membrane was not changed, but the TEA-PFSA with [AMIM]Cl reactivity was a little difference. However, the heat resistance of composite membrane was significantly enhanced compared with that of PFSA membrane, the peak temperature of composite membrane almost disappeared in first stage, and offset to the high-temperature zone. When heated at 350 °C, the decomposition rate of PFSA, 10%[AMIM]Cl-PFSA and 10%[AMIM]Cl-TEA-PFSA membrane was 13.71, 3.67 and 1.26%, respectively. If the decomposition process follows isothermal first-order reaction and the conversion rate α is 10%, the activation energy E _α of the composite membrane is 97.4 kJ mol⁻¹. Besides, the isothermal lifetime of composite membrane was also measured.

     

Mordenite-incorporated PVA–PSSA membranes as electrolytes for DMFCs

Composite membranes with mordenite (MOR) incorporated in poly vinyl alcohol (PVA)–polystyrene sulfonic acid (PSSA) blend tailored with varying degree of sulfonation are reported. Such a membrane comprises a dispersed phase of mordenite and a continuous phase of the polymer that help tuning the flow of methanol and water across it. The membranes on prolonged testing in a direct methanol fuel cell (DMFC) exhibit mitigated methanol cross-over from anode to the cathode. The membranes have been tested for their sorption behaviour, ion-exchange capacity, electrochemical selectivity and mechanical strength as also characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis. Water release kinetics has been measured by magnetic resonance imaging (NMR imaging) and is found to be in agreement with the sorption data. Similarly, methanol release kinetics studied by volume-localized NMR spectroscopy (point resolved spectroscopy, PRESS) clearly demonstrates that the dispersion of mordenite in PVA–PSSA retards the methanol release kinetics considerably. A peak power-density of 74 mW/cm² is achieved for the DMFC using a PVA–PSSA membrane electrolyte with 50% degree of sulfonation and 10 wt.% dispersed mordenite phase. A methanol cross-over current as low as 7.5 mA/cm² with 2 M methanol feed at the DMFC anode is observed while using the optimized composite membrane as electrolyte in the DMFC, which is about 60% and 46% lower than Nafion-117 and PVA–PSSA membranes, respectively, when tested under identical conditions.     

Biosorption of Cr(VI) from Water Using Biomass of <Emphasis Type="Italic">Aeromonas hydrophila</Emphasis>: Central Composite Design for Optimization of Process Variables

The potential use of biomass of Aeromonas hydrophila for biosorption of chromium from aqueous solution was investigated. The variables (pH, initial Cr(VI) concentration, biomass dose, and temperature) affecting process were optimized by performing minimum number of experimental runs with the help of central composite design. The results predicted by design were found to be in good agreement (R ² = 99.1%) with those obtained by performing experiments. Multiple regression analysis shows that uptake decreases with increase in pH and biomass dose, whereas it increases with increase in temperature and concentration. The maximum removal of Cr(VI) predicted by contour and optimization plots was 184.943 mg/g at pH 1.5, initial Cr(VI) concentration 311.97 mg/L, temperature 60 °C, and biomass dose 1.0 g. The removal of Cr(VI) was governed by adsorption of Cr(VI) as well as its reduction into Cr(III), which further gets adsorbed. The sorption capacity of biomass was calculated from experimental data using Langmuir sorption model and was found to be 151.50 mg/g at 40 °C and pH 1.5, which is comparable to other biosorbents. In addition to this, Dubinin–Radushkevich model was applied, and it was found that nature of sorption was chemisorption.     

Chemically modified proton‐conducting membranes based on sulfonated polyimides: Improved water stability and fuel‐cell performance

A series of branched/crosslinked sulfonated polyimide (B/C‐SPI) membranes were prepared and evaluated as proton‐conducting ionomers based on the new concept of in situ crosslinking from sulfonated polyimide (SPI) oligomers and triamine monomers. Chemical branching and crosslinking in SPI oligomers with 1,3,5‐tris(4‐aminophenoxy)benzene as a crosslinker gave the polymer membranes very good water stability and mechanical properties under an accelerated aging treatment in water at 130 °C, despite their high ion‐exchange capacity (2.2–2.6 mequiv g^?1). The resulting polymer electrolytes displayed high proton conductivities of 0.2–0.3 S cm^?1 at 120 °C in water and reasonably high conductivities of 0.02–0.03 S cm^?1 at 50% relative humidity. In a single H₂/O₂ fuel‐cell system at 90 °C, they exhibited high fuel‐cell performances comparable to those of Nafion 112. The B/C‐SPI membranes also displayed good performances in a direct methanol fuel cell with methanol concentrations as high as 50 wt % that were superior to those of Nafion 112. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3751–3762, 2006     

Pervaporation dehydration of ethylene glycol with chitosan–poly(vinyl alcohol) blend membranes: Effect of CS–PVA blending ratios

Chitosan–poly(vinyl alcohol), CS–PVA, blended membranes were prepared by solution casting of varying proportions of CS and PVA. The blend membranes were then crosslinked interfacially with trimesoyl chloride (TMC)/hexane. The physiochemical properties of the blend membranes were determined using Attenuated Total Reflection-Fourier Transform Infrared Spectroscopy (ATR-FTIR), X-ray diffraction (XRD), differential scanning calorimetry (DSC), tensile test and contact angle measurements. Results from ATR-FTIR show that TMC has crosslinked the blend membranes successfully, and results of XRD and DSC show a corresponding decrease in crystallinity and increase in melting point, respectively. The crosslinked CS–PVA blend membranes also show improved mechanical strength but lower flexibility in tensile testing as compared to uncrosslinked membranes. Contact angle results show that crosslinking has decreased the surface hydrophilicity of the blend membranes. The blend membrane properties, including contact angle, melting point and tensile strength, change with a variation in the blending ratio. They appear to reach a maximum when the CS content is at 75 wt%. In general, the crosslinked blend membranes show excellent stability during the pervaporation (PV) dehydration of ethylene glycol–water mixtures (10–90 wt% EG) at different temperatures (25–70 °C). At 70 °C, for 90 wt% EG in the feed mixture, the crosslinked blend membrane with 75 wt% CS shows the highest total flux of 0.46 kg/(m² h) and best selectivity of 986. The blending ratio of 75 wt% CS is recommended as the optimized ratio in the preparation of CS–PVA blend membranes for pervaporation dehydration of ethylene glycol.     

Effect of separating layer in pervaporation composite membrane for MTBE/MeOH separation

The composite membranes with polyvinylalcohol (PVA) as separating layer material and polyacrylonitrile (PAN) or cellulose acetate (CA) as supporting layer material were prepared for separating methyl tert-butyl ether (MTBE)/MeOH mixture by pervaporation (PV). The results showed that PV performance of the composite membrane with PVA membrane as separating layer was superior to that with CA membrane as separating layer, and the PV performance of PVA/CA composite membrane with CA membrane as supporting layer was better. The parameters to prepare the composite membrane remarkably affected PV performance of the composite membrane. The permeate flux of both composite membranes of PVA/PAN and PVA/CA was over 400 g/m² h, and the concentration of MeOH in the permeate reached over 99.9 wt.% for separating MTBE/MeOH mixture.     

LiFePO<Subscript>4</Subscript>/CA cathode nanocomposite with 3D conductive network structure for Li-ion battery

A novel LiFePO₄/Carbon aerogel (LFP/CA) nanocomposite with 3D conductive network structure was synthesized by using carbon aerogels as both template and conductive framework, and subsequently wet impregnating LiFePO₄ precursor inside. The LFP/CA nanocomposite was characterized by X-ray diffraction (XRD), TG, SEM, TEM, nitrogen sorption, electrochemical impedance spectra and charge/discharge test. It was found that the LFP/CA featured a 3D conductive network structure with LiFePO₄ nanoparticles ca. 10–30 nm coated on the inside wall of the pore of CA. The LFP/CA electrodes delivered discharge capacity for LiFePO₄ of 157.4, 147.2, 139.7, 116.3 and 91.8 mA h g⁻¹ at 1 °C, 5 °C, 10 °C, 20 °C and 40 °C, respectively. In addition, the LFP/CA electrode exhibited good cycling performance, which lost less than 1% of discharge capacity over 100 cycles at a rate of 10 °C. The good high rate performances of LiFePO₄ were attributed to the unique 3D conductive network structure of the nanocomposite.