Phthalonitrile end-capped sulfonated polyarylene ether nitriles for low-swelling proton exchange membranes

A series of phthalonitrile end-capped sulfonated polyarylene ether nitriles are synthesized via K₂CO₃ mediated nucleophilic aromatic substitution reaction at various molar ratios. The as-prepared polymer structures are confirmed by ¹H NMR and FTIR spectroscopy. The properties of membranes cast from the corresponding polymers are investigated with respect to their structures. The membranes exhibit good thermal and mechanical properties, low methanol permeability (0.01?×?10^?6–0.58?×?10^?6 cm²·s^?1 at 20 °C), and high proton conductivity (0.021–0.088 S·cm^?1 at 20 °C). The introduction of phthalonitrile is proved to increase intermolecular interaction, mainly contributing to the reduction in water uptake, swelling ratio, and methanol permeability. More importantly, its introduction does not decrease the proton conductivity, but there is a slight increase. Furthermore, the selectivity of SPEN-CN-50 can reach 4.11?×?10⁵ S·s·cm^?3, which is about nine times higher than that of Nafion 117. All the data show that the as-prepared membranes may be potential proton exchange membrane for DMFCs applications.     

Supported Liquid Membrane Extraction Study of (MoO4)2- Ions using Tri-n-octylamine as Carrier

Abstract

The transport of (MoO₄)^2- ions across a tri-n-octylamine (TOA) xylene-based supported liquid membrane has been studied at various HCl concentrations in the feed, TOA concentrations in the membrane, and NaOH concentrations in the strip solution. The distribution coefficient and flux of the Mo(VI) ion species vary with the HCl concentration, indicating that different polymeric species of this metal ion are present in the aqueous solution. A TOA concentration increase of up to 1.308 mol/dm³ enhances flux and permeability of this metal ion, which beyond this concentration is reduced due to an increase in carrier liquid viscosity. An increase in NaOH solution concentration has been found to increase flux and permeability values. The continuous increase in pH of the feed with the transport of metal ions indicates that the (MoO₄)^2- transport does not involve a decrease or increase in concentration as a result of association of lower to higher or decomposition of higher to lower metal ions polymeric species. The optimum conditions of transport of Mo(VI) metal ions across these membranes have been found to be HCl = 0.01, [NaOH] = 1, and [TOA] = 1.308, furnishing flux and permeability values of the order of 2.49 × 10^?4 mol·m^?2·s^?1 and 2.32 × 10^?10 m²·s^?1, respectively.     

Behavior of sulfonated poly(ether ether ketone) in ethanol–water systems

The behavior of sulfonated poly(ether ether ketone) (sPEEK) membranes in ethanol–water systems was studied for possible application in direct ethanol fuel cells (DEFCs). Polymer membranes with different degrees of sulfonation were tested by means of uptake, swelling, and ethanol transport with dynamic measurements (liquid–liquid and liquid–gas systems). Ethanol permeability was determined in an liquid–liquid diffusion cell. For membranes with an ion‐exchange capacity (IEC) between 1.15 and 1.75 mmol/g, the ethanol permeability varied between 5 × 10^?8 and 1 × 10^?6 cm²/s, being dependent on the measuring temperature. Ethanol and water transport in liquid–gas systems was tested with pervaporation as a function of IEC and temperature. Higher IEC accounted for higher fluxes and lower water/ethanol selectivity. The temperature had a large effect on the fluxes, but the selectivity remained constant. Furthermore, the membranes were characterized with proton conductivity measurements. The proton diffusion coefficient was calculated, and a transition in the proton transfer mechanism was found at a water number of 12. Membranes with high IEC (>1.6 mmol/g) exhibited larger proton diffusion coefficients in ethanol–water systems than in water systems. The membrane with the lowest IEC exhibited the best proton transport to ethanol permeability selectivity. The use of sPEEK membranes in DEFC systems depends on possible modifications to stabilize the membranes in the higher conductive region rather than on modifications to increase the proton conductivity in the stable region. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Poly(vinyl alcohol)/Cu(II) complex anion exchange membranes prepared using chemical fiber for direct methanol fuel cells

PVA/Cu (II) complex anion exchange membranes (AEMs) were prepared for direct methanol fuel cells. The complex was for the first time used as membrane material of AEMs. Glutaraldehyde as a crosslinking agent was introduced to control water uptake and swelling of the membranes. The membranes with thickness of 1 μm were fabricated using chemical fibers based on the solution surface tension. The complex membranes show good ionic conductivity and low methanol permeability in the magnitude of 10^?2 S · cm^?1 and 10^?7 cm^?2 · S^?1, respectively. This is a facile, efficient, green, and fast way to prepare new AEMs for direct methanol fuel cells. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1172‐1178, 2013     

Determination of Ozonation Rate Constants for Lincomycin and Spectinomycin

Recent occurrences of pharmaceutical antibiotics in surface water, drinking water, and wastewater systems have gained significant attention due to their potential threats to human health. This study determined the absolute second-order rate constants of ozone with two amine-based antibiotics, namely, lincomycin and spectinomycin, using the stopped-flow technique under controlled ionic strength, buffer, and temperature. Results indicate that ozone reacts quickly with the selected antibiotics, and the reaction rate significantly depends on solution pH. For lincomycin, ozone attacks its free amine group and sulfur group with absolute rate constants of 2.76 × 10⁶ M^?1·s^?1 (for neutral form) and 3.26 × 10⁵ M^?1·s^?1 (for monoprotonated form), respectively. For spectinomycin, ozone attacks two free amine groups with absolute rate constants of 1.27 × 10⁶ M^?1·s^?1 (for neutral form) and 3.30 × 10⁵ M^?1·s^?1 (for monoprotonated form), respectively. These rate constants have been corrected to zero ionic strength. Protonated amine is nonreactive toward ozone. Model prediction indicates that lincomycin and spectinomycin can be effectively transformed by ozonation processes around neutral pH.     

A quaternized poly(vinyl alcohol)/chitosan composite alkaline polymer electrolyte: preparation and characterization of the membrane

Quaternized poly(vinyl alcohol)/chitosan (QPVA/CS) composite membranes were prepared by solution casting method with AlCl₃·6H₂O aqueous solution as solvent for CS and glutaraldehyde as a crosslinker. The crystalline, thermal and mechanical properties of the QPVA/CS composite membranes were studied by Fourier transform infrared spectroscopy, X-ray diffractometry, differential scanning calorimetry, thermogravimetry and tensile test measurements, respectively. The composite membranes were immersed in potassium hydroxide aqueous solution to form polymer electrolyte membranes. The alkaline uptake, swelling ratio, ion conductivity and methanol permeability of the electrolyte membranes were studied. The experimental results indicated that aluminum chloride hexahydrate (AlCl₃·6H₂O) had a positive effect on the mechanical properties of the QPVA/CS composite membrane. The elongation-at-break of this membrane reached the maximum of 401.0%. The alkaline uptake and swelling ratio of the composite membranes decreased. With the addition of 30 wt% AlCl₃·6H₂O, the composite membrane showed the ion conductivity and methanol permeability of 1.82 × 10^?2 S cm^?1 and 2.17 × 10^?6 cm² s^?1, respectively. These values were higher than those of the membrane with acetic acid as the solvent for CS. The selectivity of the QPVA/CS membrane could reach 8.39 × 10³ S s cm^?3. This study showed that with AlCl₃·6H₂O as the solution for CS, the high performance QPVA/CS composite alkaline polymer electrolyte membrane could be prepared.     

Coupled Transport of Zr(IV) through Tri-n-butylphosphate-Xylene-Based Supported Liquid Membranes

Abstract

The transport of Zr(IV) through tri-n-butylphosphate-xylene-based liquid membranes, supported in a polypropylene hydrophobic microporous film, has been studied. The concentration of HNO₃ in the feed solution and tri-n-butylphosphate (TBP) carrier in the membrane were varied, and the flux and permeability coefficients were determined. The optimum conditions found for maximum flux were determined to be 10 mol/dm³ HNO₃ and 2.93 mol/dm³ TBP with a flux value of 12.9 × 10^?6 mol · m^?2 · s^?1. The solvent extraction study revealed that 1.25 to 3.5 protons are involved in zirconium transport, and that two molecules of TBP are involved in the complex formation. The value of protons involved varies with acid concentration. The zirconium ion transport is coupled with nitrate ions transport.     

Transport of Co(II) Ions through Di(2-ethylhexyl) Phosphoric Acid-CCl4 Supported Liquid Membranes

Abstract

A liquid membrane transport study of Co(II) using di(2-ethylhexyl) phosphoric acid (D2EPHA) as carrier and CCl₄, as diluent supported on polypropylene microporous film has been carried out. The carrier concentration in the membrane and HCl concentration in the stripping phase have been varied to see the effect on transport of Co(II) ions across the membrane. Maximum flux and permeability values of 1.23 × 10^?5 mol · m^?2 · s^?1 and 7.66 × 10^?11 m²/s, respectively, at a 0.87 mol/dm³ carrier concentration in the membrane have been found. At 1 mol/dm³ HCl concentration in the stripping phase the flux and permeability have maximum values of 1.4 mol · m^?2 · s^?1 and 5.27 × 10^?11 m²/s, respectively. The distribution coefficient of Co(II) ions into organic phase has been found to increase with increasing carrier concentration. The diffusion coefficient determined varies from 13.73 × 10^?11 to 0.83 × 10^?11 m²/s, which is the reverse order of the values of the distribution coefficient and explains the permeability of the Co(II) D2EPHA complex through the membrane.     

Isobaric measurement of gas permeability of polymers

The principles and design of a gas permeability measuring instrument based on thermal conductivity measurement are described. Since the thermal conductivity of a gas mixture is dependent upon the partial pressure fraction rather than absolute partial pressure of sample gas, and the permeation rate of reference and sample gases through polymer films differe considerably, a pressure-equalizing device is necessary for the accurate measurement of gas permeability. The three types of measurements—integral, differential (flow method), and decay rate measurements—can be used with the instrument. The results of permeability constants and diffusion constants obtained with the methods showed good agreement with the conventional vacuum-type method. With proper selection of methods, the instrument can measure the gas flux through the range of 10^?10 to 10^?3 cm³ (STP)/cm² sec cm Hg. Some advantages of the methods are discussed.     

Application of Electroless Deposited Thin-Film Palladium Composite Membrane in Hydrogen Separation

Abstract

In recent years, there has been increased interest in developing inorganic and composite membranes for in-situ separation of hydrogen to achieve an equilibrium shift in catalytic membrane reactors. The productivity of these membrane reactors, however, is severely limited by the poor permeability and selectivity of available membranes. To develop a new class of permselective inorganic membranes, electroless plating has been used to deposit palladium thin-films on a microporous ceramic substrate. A palladium thin-film coating was deposited on a microporous ceramic disk (α-alumina, φ 39 mm × 2 mm thickness, nominal pore size 150 nm and open porosity ≈ 42%) by electroless deposition. The film was evaluated by SEM and EDX analysis. A steady-state counter-diffusion method, using gas chromatographic analysis, was used to evaluate the permeability and selectivity of the composite palladium membrane for hydrogen separation at temperatures from 373 to 573 K. The pressure on the high pressure side of the membrane ranged from 170 to 240 kPa and the low pressure side was maintained at 136 kPa. The measured hydrogen permeabilities at 573 K were found to be 1.462×10^?9 mol·m/m²·s·Pa^0.778, and 3.87×10^?8 mol · m/m² · s · Pa^0.501 for palladium film thicknesses of 8.5 and 12 μm, respectively. The results indicate that the membrane has both high permeability and selectivity for hydrogen and may find applications in high temperature hydrogen separation and membrane reactors.     

Dissociation et hydratation de nitrates alcalins dans le carbonate de propylene aqueux

Dissociation of lithium, sodium, potassium and tetraethylammonium nitrates and perchlorates in propylene carbonate has been studied by conductometry. Dissociation constants of alkali nitrates are 3·14 × 10^?3 (LiNO₃), 8·35 × 10^?3 (NaNO₃ and 1·92 × 10^?2 (KNO₃) at 25°C. The perchlorates and tetraethylammonium nitrate are strong electrolytes. The solubility products are 4·1 × 10^?4 (LiNO₃), 1·2 × 10^?5 (NaNO₃ and 2·5 × 10^?5 (KNO₃). The conductivity of saturated solutions of nitrates in the aqueous solvent has been determined up to 0·6 M water. Results are used to calculate the equilibrium constants for the reaction I^± + H₂O = I^± H₂O; Li⁺ 6·5, Na⁺ 2·5, K⁺ 0·5 and NO^?₃ 2·4. Dissociation constants, solubility products and hydration constants are compared with values reported for other solvents.     

Acides forts dans le dimethylsulfoxide

Dissociation of acids in dimethylsulfoxide has been studied by conductometry. Trifluoromethanesulphonic acid is completely dissociated. Dissociation constants of the other acids are: picric acid 10^+0·3, methanesulphonic acid 10^?1·76, hydrochloric acid 10^?2·01, trifluoroacetic acid 10^?3·45 and sulphuric acid ? 10^?1·41. The proton ionic conductivity is “normal”. The acids dissociation is compared in dimethylsulfoxide and other solvents.     

Mixed Matrix Silicone and Fluorosilicone/Zeolite 4A Membranes for Ethanol Dehydration by Pervaporation

The ability of homogeneous and mixed matrix membranes prepared using standard silicone rubber, poly(dimethylsiloxane) (PDMS), and fluorosilicone rubber, poly(trifluoropropylmethylsiloxane) (PTFPMS), to dehydrate ethanol by pervaporation was evaluated. Although PDMS is generally considered to be the benchmark hydrophobic membrane material in pervaporation, water/ethanol molar permselectivity of a pure PDMS membrane was found to be 0.89 for a feed containing 80/20 w/w ethanol/water at 50°C, indicating a slight selectivity for water. Fluorinated groups in PTFPMS improved the water-ethanol permselectivity to 1.85, but decreased the water permeability from 9.7 × 10^?12 kmol · m/m² · s · kPa in PDMS to 5.1 × 10^?12 kmol · m/m² · s · kPa (29,000 and 15,200 Barrer, respectively). These water permeabilities are attractive, particularly since the rubbery materials should not experience the steep declines in water permeability observed with most standard dehydration membranes as water concentration in the feed decreases. However, the water selectivity is lower than desired for most applications. Particles of hydrophilic zeolite 4A were loaded into both PDMS and PTFPMS matrices in an effort to boost water selectivity and further improve water permeability. Water-ethanol permselectivities as high as 11.5 and water permeabilities as high as 23.2 × 10^?12 kmol · m/m² · s · kPa were observed for the PTFPMS/zeolite 4A mixed matrix membranes?6 times higher than for the unfilled PTFPMS membrane.     

Kinetics and modeling of the diffusion‐controlled diallyl terephthalate polymerization

Free radical polymerization kinetics of diallyl terephthalate in bulk was investigated in a wide temperature range from 50°C to 150°C with four different peroxide initiators. Conversion points were measured using Fourier Transform Infrared (FTIR) measurements. The initiator efficiencies and the initiator decomposition rate constants were evaluated from special experiments, applying the theory of dead end polymerization. In addition, the ratios between the degradative and the effective kinetic rate constants to propagation rate constants were obtained from molecular weight measurements at various initiator concentrations. The ratio of chemically controlled termination and propagation rate constant k/k_tc of the polymerization system was obtained using the initial rates of polymerization and the number average molecular weight data between 0.25 · 10^?3 and 15.7 · 10^?3 L mol^?1 s^?1. The glass transition temperature of the polymer, 191°C, was measured by the Alternating Differential Scanning Calorimetry (ADSC) technique. Computed conversions from the developed kinetic model were in good agreement with the conversion and molecular weight measured data. The values of diffusion controlled propagation and termination rate constants k_td0 and k_pd0 with clear and physical meaning were the only two parameters obtained from the developed kinetic model fitting. Polym. Eng. Sci. 44:2005–2018, 2004. © 2004 Society of Plastics Engineers.     

New high permeable polysulfone/ionic liquid membrane for gas separation

In this study, the effects of 1-Ethyl-3-methylimidazolium tetrafluoroborate ionic liquid on CO₂/CH₄ separation performance of symmetric polysulfone membranes are investigated. Pure polysulfone membrane and ionic liquid-containing membranes are characterized. Field emission scanning electron microscopy (FE-SEM) is used to analyze surface morphology and thickness of the fabricated membranes. Energy dispersive spectroscopy (EDS) and elemental mapping, Fourier transform infrared (FTIR), thermal gravimetric (TGA), X-ray diffraction (XRD) and Tensile strength analyses are also conducted to characterize the prepared membranes. CO₂/CH₄ separation performance of the membranes are measured twice at 0.3 MPa and room temperature (25 °C). Permeability measurements confirm that increasing ionic liquid content in polymer-ionic liquid membranes leads to a growth in CO₂ permeation and CO₂/CH₄ selectivity due to high affinity of the ionic liquid to carbon dioxide. CO₂ permeation significantly increases from 4.3 Barrer (1 Barrer=10^-10 cm³(STP)·cm·cm^-2·s^-1·cmHg^-1, 1cmHg=1.333kPa) for the pure polymer membrane to 601.9 Barrer for the 30 wt% ionic liquid membrane. Also, selectivity of this membrane is improved from 8.2 to 25.8. mixed gas tests are implemented to investigate gases interaction. The results showed, the disruptive effect of CH₄ molecules for CO₂ permeation lead to selectivity decrement compare to pure gas test. The fabricated membranes with high ionic liquid content in this study are promising materials for industrial CO₂/CH₄ separation membranes.     

Characterization of pressure-sensitive adhesives. II. Water vapor permeation studies

The permeability of water vapor in a composite film [a Mylar (trademark of DuPont, Inc.) film coated with a pressure sensitive adhesive on both sides] and a Mylar film (type D) have been determined at 23°C. The water vapor permeability in the pressure sensitive adhesive, Flexbond 150 (a trademark of Air Products and Chemicals), and the Mylar film have been found to be 3.23 × 10^?7 and 2.30 × 10^?8 cm³ (STP) cm · cm^?2 · s^?1 · (cm Hg)^?1, respectively, at 23°C.     

Use of ultrasound in petroleum residue upgradation

Conventional processes for the upgradation of residual feedstocks, viz., thermal cracking and catalytic cracking are carried out in the temperature range of 400–520°C. Such high temperatures can in principle be substituted by acoustic cavitation. In the present work, two vacuum residues, namely, Arabian mix vacuum residue (AMVR) and Bombay high vacuum residue (BHVR) and one asphalt, viz., Haldia asphalt (HA) were subjected to acoustic cavitation for different reaction times from 15 min to 120 min at ambient temperature and pressure. An attempt has been made to seek a performance comparison of two devices of acoustic cavitation, namely, ultrasonic bath and ultrasonic horn with regard to their ability to upgrade the petroleum residues to lighter, more value‐added products mainly the hydrocarbons boiling in the range of gas oil fraction. Another attempt has been made to study the effect of ultrasound on the upgradation of the residue when it is emulsified in water with the help of different surfactants. For all the cases, a kinetic model has been developed based on the constituents of the residue so as to get an insight into the reaction mechanism. The study revealed that ultrasonic horn is more effective in bringing about the upgradation than ultrasonic bath and that the acoustic cavitation of the aqueous emulsified hydrocarbon mixture could reduce the asphaltenes content to a greater extent than the acoustic cavitation of non‐emulsified hydrocarbon mixture. The reduction in asphaltenes content of BHVR was found to be more followed by AMVR followed by HA. The variation in the rate constants was found to be feed specific and the rate constants for the conditions of maximum conversion of asphaltenes to gas oil for AMVR, BHVR and HA were found to be 0.29 × 10^?4 s^?1, 1.4 × 10^?4 s^?1 and 0.23 × 10^?4 s^?1, respectively.     

CuO‐filled aminomethylated polysulfone hybrid membranes for deep desulfurization

CuO‐filled aminomethylated polysulfone hybrid membranes were prepared for sulfur removal from gasoline. The as‐prepared membranes were characterized using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X‐ray diffraction (XRD). The separation performance of the hybrid membranes was evaluated by pervaporation (PV) separation of n‐heptane/thiophene binary mixture. CuO‐filling leads to a decrease in permeation flux. The sulfur‐enrichment factor increased first and then decreased with increasing CuO loading, and it is worth noting that there is a rebound in enrichment factor above 8 wt % CuO loading. Influencing factors such as nitrogen content, feed temperature, sulfur content, and various hydrocarbons on membrane PV performance were also evaluated. Permeation flux of 23.9 kg·μm·m^?2·h^?1 and sulfur‐enrichment factor of 3.9 can be achieved at 4 wt % CuO loading in PV of n‐heptane/thiophene binary mixture with 1500 μg·g^?1 sulfur content. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3718–3725, 2013     

Rapid pyrolysis and hydropyrolysis of Canadian coals

A range of Canadian coals were subjected to variable heating-rate conditions in a variety of atmospheres. Heating rate was found to have little effect on total weight loss of the coal, but a dramatic effect on the actual composition of products. High heating rates substantially increased the yield of light hydrocarbons. Operation in ≈100 KPa (1 atm) H₂ at high heating rate resulted in 5% conversion to light hydrocarbon gas and liquid products. Operation in ≈10 MPa (100 atm) H₂ at a heating rate of 600 Ks^?1 gave 10% coal conversion to light liquid products (benzene, xylene, toluene).     

Characterization of the Binding Interaction between Poly(Epicholorohydrin‐Diamine) and Reactive Dyes using a Multiple Linear Regression and Quartz Crystal Microbalance Methods

Abstract

The binding processes of Reactive Red K‐2BP (K‐2BP) and Reactive Violet K‐3R (K‐3R) onto poly(epicholorohydrin‐diamine)(PEPIDA) in solution and film were investigated by spectrophotometric and quartz crystal microbalance (QCM) methods, respectively. By using a multiple linear regression technique, the concentrations of the colored components in the mixtures of dye+PEPIDA were measured simultaneously from the absorbance spectra. The binding equilibrium constants for K‐3R and K‐2BP onto PEPIDA in solution were estimated to be 9.31×10⁶ and 1.86×10⁶ L · mol^?1, respectively. The difference in the color removal between K‐3R and K‐2BP by PEPIDA was discussed. The binding processes of K‐3R and K‐2BP onto PEPIDA film were followed by the QCM. The binding equilibrium constants were evaluated to be 1.27×10⁶ and 3.28 ×10⁵ L · mol^?1 for K‐3R and K‐2BP onto PEPIDA film, respectively. They are less than those determined in PEPIDA solutions. The binding rate constants for K‐3R and K‐2BP onto PEPIDA film were estimated to be 1.43×10⁵ and 1.72×10⁵ L · mol^?1 · s^?1, respectively.