Synthesis and characterization of proton conducting polymer electrolyte based on poly(N‐vinyl pyrrolidone)

This work aims at developing and characterizing a proton conducting polymer electrolyte based on Poly(N‐vinyl pyrrolidone) (PVP) doped with ammonium bromide (NH₄Br). Proton conducting polymer electrolytes based on PVP doped NH₄Br in different molar ratios have been prepared by solution casting technique using distilled water as solvent. The XRD pattern confirms the dissociation of salt. The FTIR analysis confirms the complex formation between the polymer and the salt. The conductivity analysis shows that the polymer electrolyte with 25 mol % NH₄Br has the highest conductivity equal to 1.06 × 10^?3 S cm^?1 at room temperature. Also it has been observed that the activation energy evaluated from the Arrhenius plot is low (0.50 eV) for 25 mol % NH₄Br doped polymer electrolyte. The influence of salt concentration on dc conductivity and activation energy of the polymer electrolyte has been discussed. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Transport properties and density of NaI in N-methyl propionamide solutions in the temperature range 25–80°C

The density, viscosity and electrical conductivity of concentrated NaI in N-methyl propionamide solutions have been measured in the temperature range 25–80°C. The plots of the partial molar volumes vs the salt concentration show a minimum at ～1.2 m where a value close to the molecular volume of the pure salt is found. The experimental conductivity and viscosity data have been analyzed with the correct Arrhenius equation used in the treatment of transport in glass-forming liquids. At each concentration the glass-transition temperatures deduced from conductivity and viscosity are close value. Viscosity data were also treated following a model derived for the viscosity of suspensions of rigid spheres. The results show a solvation number of the cations in the concentrated solutions equal to 1.6.     

Enhanced conductivity of bacterial cellulose films reinforced with NH4I-doped graphene oxide

ABSTRACT

Bacterial cellulose (BC) films reinforced with reduced graphene oxide (RGO) platelets were investigated to assess their potential application as solid polymeric electrolytes. BC-RGO composites were further doped with NH₄I at different concentrations to evaluate the effect of NH₄I doping on the conductivity. Scanning electron microscopy images confirmed that GO addition did not alter BC coherent three-dimensional morphology. Electrochemical impedance spectroscopy studies revealed that the ionic conductivity increased with the ammonium iodide salt concentration. The highest conductivity found was 1.32 × 10^?4 S/cm for the samples doped with 5% NH₄I, suggesting that BC-RGO can be a promising candidate for electrochemical applications.     

Micellar association in simultaneous presence of organic salts/additives

Viscosity measurements under Newtonian flow conditions had been performed on cetyltrimethylammonium bromide (CTAB) aqueous solutions in the combined presence of sodium salts of aromatic acids (sodium salicylate, NaSal; sodium benzoate, NaBen; sodium anthranilate, NaAn) and organic additives (1-hexanol, C₆OH; n-hexylamine, C₆NH₂) at 30°C. On addition of C₆OH or C₆NH₂, the viscosity of 25 mM CTAB solution remained nearly constant without salt as well as with a lower salt concentration. This is due to low CTAB concentration which is not sufficient to produce structural changes in this concentration range of salts. However, as the salt concentration was increased further, the effect of C₆OH/C₆NH₂ addition was different with different salts: The viscosity first increased; then a decrease was observed with the former while with C₆NH₂ a decrease followed by constancy appeared in plots of relative viscosities (η _r ) vs. organic additive concentrations. At further higher salt concentration, the magnitude of η _r was much higher. The viscosity increase is explained in terms of micellar growth and the decrease in terms of swollen micelle formation (due to interior solubilization of organic additive) or micellar disintegration (due to formation of water + additive pseudophase).     

Structural,electrical and electrochemical properties of polyacrylonitrile-ammonium hexaflurophosphate polymer electrolyte system

Polyacrylonitrile (PAN) based polymer electrolyte membranes complexed with Ammonium hexafluorophosphate (NH₄PF₆) with different molar concentration are prepared by solution casting method. Increase in the amorphous nature by the addition of Ammonium salt and the formation of polymer-salt complex are confirmed by X ray diffraction studies and infrared spectroscopy respectively. The glass transition temperature is measured for all membranes and it showed a lowest value for the PAN complexed with 20 mol% of NH₄PF₆. Electrical properties are studied by AC impedance spectroscopy. An ionic conductivity of the order of 10^?3 Scm^?1 is obtained for the 80 PAN / 20 NH₄PF₆ polymer electrolyte. Conductivity, dielectric and modulus spectra from the impedance data are analysed to understand the ionic transport mechanism. Transference number measurement is done to study the ionic contribution to the charge transport. A proton battery with the configuration, Zn+ ZnSO₄. 7H₂O /80 PAN / 20 NH₄PF₆ / PbO₂ +V₂O₅ has been constructed and its discharge characteristics are studied.     

Physico-chemical properties of concentrated solutions of some tetraalkylammonium salts in formamide in the temperature range 25–80°

In this work density and viscosity measurements for concentrated solutions in formamide of Bu₄NJ, Bu₄NBr, Bu₄NCl, Pr₄NJ salts in the temperature range 25–80° are reported. The apparent molar volumes φν are square root linear functions of the salt concentration. The values of the partial molar volumes $\text{V}$₂ decrease when the concentration increases and more over are almost constant at the last concentration used. Viscosity data have been analysed using Vand—Einstein model on viscosity of rigid sphere suspensions. In the diluted solution range a different behaviour between tetraalkylammonium salt solutions and alkaline-earth metal ones is shown. This difference is interpreted by supposing that the size of alkaline, alkaline-earth metal solvated cation varies with concentration, while the size of tetraalkylammonium solvated cation is unchangeable.     

Density,viscosity and electrical conductivity of LiCl and some uni-bivalent electrolytes in formamide solutions at 25°C

Density, viscosity and equivalent conductivity in formamide at 25°C are reported for LiCl, Mg(ClO₄)₂, CaCl₂, CaBr₂, Ca(NO₃)₂, ZnCl₂, ZnBr₂ and ZnI₂ salts. The linear dependence of the density of the investigated salts on the concentration is interpreted assuming that the structural configuration of the solvent formamide remains unchanged in the concentration range experienced. Viscosity and conductivity data have been treated following a proposal of Angell. A least-squares program used to linearise the lg Λ and the lg η functions against 1/(N₀ ? N) gives N₀ values, the glass-transition concentration at 25°C, acceptably low and sufficiently close in most cases.     

A study on polymer blend electrolyte based on PVA/PVP with proton salt

Proton-conducting polymer blend electrolytes based on PVA–PVP–NH₄NO₃ were prepared for different compositions by solution cast technique. The prepared films are investigated by different techniques. The XRD study reveals the amorphous nature of the polymer electrolyte. The FTIR and laser Raman studies confirm the complex formation between the polymer and salt. DSC measurements show decrease in T _g with increasing salt concentration. The ionic conductivity of the prepared polymer electrolyte was found by ac impedance spectroscopy analysis. The maximum ionic conductivity was found to be 1.41 × 10^?3 S cm^?1 at ambient temperature for the composition of 50PVA:50PVP:30 wt% NH₄NO₃ with low-activation energy 0.29 eV. The conductivity temperature plots are found to follow an Arrhenius nature. The dielectric behavior was analyzed using dielectric permittivity (ε*) and the relaxation frequency (τ) was calculated from the loss tangent spectra (tan δ). Using this maximum ionic conducting polymer blend electrolyte, the primary proton battery with configuration Zn + ZnSO₄·7H₂O/50PVA:50PVP:30 wt% NH₄NO₃/PbO₂ + V₂O₅ was fabricated and their discharge characteristics studied.     

Solid Polymer Electrolyte Complexes of Polyoxyethylene-Containing Star-Shaped Block Copolymers and Copolymers with Uniform Grafts

Ionic conductivities of salt complexes of polyoxyethylene (PEO)-containing star-shaped block copolymers and copolymers with uniform grafts were measured. The results were compared with the thermal characteristics and crystallinity of the complexes obtained from DSC and WAXD analysis. The conductivity increases with PEO content of the copolymers, more noticeably at PEO contents over 50%. For the complexes of the star-shaped block copolymers of styrene (S) and ethylene oxide (EO), conductivity decreases in the following order of salts: KCNS > NH₄CNS > NaCNS. The room temperature conductivity of the KCNS complex with EO/K ratio = 20 can reach a value of 2 × 10^?5 S cm^?1 at 57% PEO content of the copolymer. The complex with FeCl₂ displays a conductivity even higher than that of the NaCNS complex. Addition of γ-butyrolactone reduces the crystallinity and enhances markedly the ionic conductivity. For complexes of the copolymers with uniform PEO grafts the conductivity decreases in the following order of salts: KCNS > LiClO₄ > FeCl₂. Complexes with LiClO₄ exhibit a maximum conductivity at EO/Li = 20. For different kinds of copolymers with uniform PEO grafts, conductivity of the complexes increases in the order: PS-g-PEO < PMMA-g-PEO < polymethyl acrylate-g-PEO.     

Shape-controlled fabrication of polypyrrole microstructures by replicating organic crystals through electrostatic interactions

Polypyrrole (PPy) microstructures with diverse shapes were synthesized in an aqueous inorganic salt medium including organic crystals and pyrrole (Py). A series of sulfobenzoic acid salt forms with various cations (K⁺, Na⁺, Li⁺, NH₄⁺) in different positions (para, meta, ortho) of the sulfonate group on the benzene ring were used to form organic crystals as sacrificial templates. Using these crystals, we produced five different shapes of PPy microstructures (hexagonal microplates, curled nanofibers, lozenge-shaped microplates, rigid rods, parallelogram microplates), which replicated the shapes of the organic crystal templates through electrostatic interaction between the anionic crystal surfaces and the cationic PPy chains. In contrast, PPy that was polymerized without crystals showed bulky agglomerates of 200-500 nm size. The electrical properties were dictated by the molecular structures of the organic salt molecules used. While the highest conductivity (200.3 Scm⁻¹) was observed in PPy using crystals of para-linked 4-sulfobenzoic acid monopotassium salt, the lowest conductivity (0.8 Scm⁻¹) was observed in PPy prepared in the presence of crystals of ortho-linked 2-sulfobenzoic acid monoammonium salt.     

Preparation and Characterization of Energetic Nanocomposites of Organic Gel – Inorganic Oxidizers

Two types of polymeric sols, resorcinol‐formaldehyde (RF) and resorcinol‐furfural (RFur), were mixed in a water‐containing medium with aqueous solutions of inorganic salts: NH₄ClO₄, Mg(ClO₄)₂, and NH₄NO₃. After gelation and an ambient pressure drying, hybrid nanocomposites with properties of energetic materials were obtained. It was stated that salt concentration and addition of a second solvent (e.g., methanol or N,N‐dimethylformamide) to the mixture of reagents have crucial meaning for gel formation. In the case when only water was used, the mixture of organic sol/inorganic salt did not transfer from sol to gel, and precipitates were formed. Conventional drying of wet gelled composites leads to rigid material called xerogels. The RF xerogels are red and RFur xerogels are black. Typically, xerogels are transparent at low salt concentration (below 30%). The microstructure, morphology, and some other properties of chosen composites were studied by means of HR SEM, AFM, XRD, DTA/TG, and N₂ adsorption isotherm techniques. SEM observation revealed that sizes of the oxidizer particles vary from less than 100 nm to ca. 1000 nm. XRD analyses also confirmed the presence of nanometer‐sized crystals of oxidizers in some formulations. The specific surface area of polymeric matrix/oxidizer composites was found to be in the range from 0.002 to 0.3 m² g⁻¹. After removing the salt from the composites (by extraction with boiling water), the specific surface area grows even up to 210 m² g⁻¹. TG/DTA analyses showed that the tested composites decompose as typical energetic materials. If pre‐heated and exposed to flame, some of them (especially RF/Mg(ClO₄)₂ composites) undergo violent deflagration with loud sound and flash effect.     

Effect of hydroxyl and nitrate ions on the sorption of ammonium ions by sulphonic cation exchangers

The sorption of ammonium ions and ammonia by the H+ form of sulphonic acid cation exchangers Amberlite 252, Lewatit 2629 and Relite C 360 from a solution containing NH₄NO₃ in the range of 0 to 0.214 equ/L and NH₃ in the range of 0.353 to 0 equ/L was investigated to establish the possibility of their application for the recovery of ammonium from caustic condensate generated in nitrogen fertilizer production. Breakthrough and elution curves were obtained, determining the concentration of ammonium with Nessler's reagent. The sorption of ammonium and ammonia depends on the concentration ratio of ammonia to ammonium nitrate [NH₃]/[NH₄NO₃]. On decreasing [NH₃]/[NH₄NO₃], the concentration ratio of hydroxyl to nitrate ions [OH⁻]/[NO⁻₃] and the effluent pH prior to NH⁺₄ breakthrough also decrease. This results in a decrease in the NH⁺₄ sorption because of a deficiency in the neutralization of hydrogen ions released (ordinary cation-exchange process). Thus, adverse circumstances create an unfavorable medium for NH⁺₄ removal from the caustic condensate. Maximum sorption of NH⁺₄ is attained at [NH₃]/[NH₄NO₃] ∼1.2. A further decrease in [NH₃]/[NH₄NO₃] is followed by a significant decrease in the effluent pH, which leads to an increase in the concentration of protonated sulphonic acid groups (-SO₃H), resulting in a decrease in the ion-exchange ability of the cation exchangers under investigation with respect to NH⁺₄ removal. The concentration (g/L) of NH₄NO₃ in the eluate from the cation-exchanger regeneration, carried out using 0.7 bed volumes (BV) of 20% HNO₃, amounts to 136.7 for Relite C 360, 119.5 for Lewatit K 2629 and 96.7 for Amberlite 252. The content of undamaged beads after 100 cycles (each cycle comprises saturation with caustic condensate, containing ammonia and ammonium, successive regeneration with 20% nitric acid and washing) is from 97 to 99.8%. Resistance to boiling in 20% HNO₃ solution is from 97 to 99.8%. These are applicable for the recovery of NH₄NO₃ from the caustic condensate in the nitrogen fertilizers production, preventing economic damage and environmental contamination from nitrogen compounds.     

Effect of propylene carbonate on the ionic conductivity of polyacrylonitrile‐based solid polymer electrolytes

Solid polymer electrolyte membranes consisting of polyacrylonitrile (PAN) as a host polymer, ammonium nitrate (NH₄NO₃) as a complexing salt, and propylene carbonate (PC) as a plasticizer were prepared by a solution casting technique. An increase in the amorphous nature of the polymer electrolytes was confirmed by X‐ray diffraction analysis. A shift in the glass‐transition temperature of the PAN/NH₄NO₃/PC electrolytes was observed in the differential scanning calorimetry thermograms; this indicated interactions between the polymer and the salt. The impedance spectroscopy technique was used to study the mode of ion conduction in the plasticized polymer electrolyte. The highest ionic conductivity was found to be 7.48 × 10^?3 S/cm at 303 K for 80 mol % PAN, 20 mol % NH₄NO₃, and 0.02 mol % PC. The activation energy of the plasticized polymer electrolyte (80 mol % PAN/20 mol % NH₄NO₃/0.02 mol % PC) was found to be 0.08 eV; this was considerably lower than that of the film without the plasticizers. The dielectric behavior of the electrolyte is discussed in this article. A literature survey indicated that the synthesis and characterization of ammonium‐salt‐doped, proton‐conducting polymer electrolytes based on PAN has been rare. The use of the best composition membrane (80 mol % PAN/20 mol % NH₄NO₃/0.02 mol % PC) proton battery was constructed and evaluated. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41743.     

Electrical Conductivity,Viscosity and Density of NaI in Formamide Solutions in the Temperature Range 35–80°C

In this work the measurements of electrical conductivity, viscosity and density of NaI salt in formamide solutions in the composition range 0–21 mole % and in the temperature range 35–80°C are reported. The experimental data have been analyzed with equations utilized for transport in glass forming liquids. The glass-transition temperatures deduced from conductivity and viscosity data, reported in graph against the salt concentration, lie on the same straight line. Alternatively, the experimental conductivity and viscosity data have been analyzed with a three-parameter equation which describes the isothermal composition dependence of transport processes. At the four temperatures used the plots of 1gΛ and 1g against 1/(x₀?x), where x₀ is the glass transition concentration, were linearized by almost the same x₀ value. The values of the apparent and partial molar volumes of salt, deduced from density measurements,were found to be close to the value of the molecular volume of pure salt. This fact is interpreted in terms of equivalent energies of the ion-dipole and of the dipole-dipole interactions.     

The effect of EPIDA units on the conductivity of poly(ethylene glycol)-4,4′-diphenylmethane diisocyanate-EPIDA polyurethane electrolytes

Novel thermoplastic polyurethanes with chelating groups were synthesized from 4,4′-diphenylmethane diisocyanate (MDI), poly(ethylene glycol) (PEG), and EP-IDA. Differential scanning calorimetry (DSC), fourier transform infrared spectroscopy (FT-IR), and impedance spectroscopy (IS) were used to monitor changes in the morphology of these polyurethanes with the concentration of lithium perchlorate (LiClO₄) dopants. Adding the salt significantly changes the FTIR spectrum of the polyurethane, indicating an interaction between the lithium cation within the urethane group and the chelating group. The soft segment T_g increases with LiClO₄ concentration, as determined by DSC, indicating that solubility of the lithium cation in the host polyurethane increases with the chelating groups. IS shows that the bulk conductivity reaches a maximum as the salt concentration is increased. One of the investigated polyurethane electrolytes has an ionic conductivity as high as ∼10⁻⁶ S cm⁻¹ at room temperature.     

Development and Study of Solid Polymer Electrolyte Based on Polyvinyl Alcohol: Mg(ClO4)2

Magnesium ion-conducting solid polymer electrolytes consisting of polyvinyl alcohol with magnesium perchlorate (Mg(ClO₄)₂) as electrolytic salt have been developed and their experimental investigations are reported. The solid polymer electrolytes have been prepared by well-known solution casting method using double-distilled water as a solvent. The highest room temperature conductivity of the order of 10^?4 S cm^?1 was obtained for the solid polymer electrolyte with the composition 80?mol% polyvinyl alcohol:20?mol% Mg(ClO₄)₂. The pattern of the temperature-dependent conductivity shows Arrhenius behavior. The Fourier transform infrared spectroscopy analysis confirms the complex formation of the polymer with the salt. The X-ray diffraction results reveal that the crystalline phase of polymer host has completely changed on the addition of dopant. Differential scanning calorimetry studies show a decrease in melting temperature of the polyvinyl alcohol with the increasing dopant concentration. The real part of dielectric permittivity shows a strong dispersion at lower frequencies, which implies the space charge effects arising from the electrodes. The loss tangent spectrum reveals that the jumping probability per unit time decreases with the increasing salt concentration. The total ionic transference number measured has been found to be in the range of 0.92–0.94 for all the polymer electrolyte systems. The result reveals that the conducting species are predominantly ions. The solid polymer electrolyte with highest conductivity showed an electrochemical stability of 2?V. The results obtained by cyclic voltammetry on stainless steel/solid polymer electrolyte/stainless steel, Mg/solid polymer electrolyte/Mg symmetrical cells show evidence for reversibility.     

Apparent and partial molar volumes of concentrated solutions of some uni-univalent electrolytes in formamide

The density of solutions of NH₄SCN, KSCN, NH₄NO₃, LiNO₃, NH₄ClO₄, NH₄Br in formamide at 25° has been measured in the concentration range going from ≈ 0.5 m up to the saturated solution. By the least-square method the coefficients of the straight lines relating density and concentration have been calculated. It follows that the apparent molar volumes of salts (amv in the investigated concentration range result independent of the concentration, and close to the molar volume of the pure salt. Calculated by the V° (the partial molar volume at infinite dilution) values of the tetraalkylammonium salts and following a Robinson and Stokes suggestion, ionic partial molar volumes (pmv) at infinite dilution agree for both methods. The ionic pmv at infinite dilution follow the Hepler's equation, the A and B coefficients for alkali metal cations and halide anions being independent of the sign of the ionic charge. The value of the A term has been found close to the intrinsic ionic volume plus the volume of the void space which is generated around an ion in a “random close packing distribution”.The low values of the coefficient B, which takes into account the electrostriction of the solvent, has been explained in terms of solvent structure energetically equivalent to the structure of the solution and with the small compressibility of this solvent.     

Automated Low-Pressure Carbonate Eluent Ion Chromatography System with Postsuppressor Carbon Dioxide Removal for the Analysis of Atmospheric Gases and Particles

We present a low-pressure, automated, semi-continuous Gas-Particle Ion Chromatograph to measure soluble ionogenic gases and soluble ionic constituents of PM_2.5. The system utilizes a short separation column, an isocratic carbonate eluent and post suppressor CO₂ removal. Measured constituents include ammonium, nitrate, and sulfate in the particle fraction, and nitric acid, sulfur dioxide, and ammonia among soluble gases. Two independent sampling channels are used. In one channel, a wet denuder collects soluble gases. In the second channel, following removal of large particles by a cyclone and soluble gases by a wet denuder, a hydrophobic filter-based particle collector collects and extracts the soluble components of PM_2.5. The aqueous particle extract is aspirated by a peristaltic pump onto serial cation and anion preconcentrator columns. Gas samples are similarly loaded onto another set of serial cation and anion preconcentrator columns. The cation preconcentrator is eluted with NaOH and the evolved NH₃ is passed across a membrane device whence it diffuses substantially into a deionized water receptor stream; the conductivity of the latter provides a measure of NH₃ (NH₄ ⁺). The anion preconcentrator column(s) are subjected to automated periodic analysis by ion chromatography. This system provides data every 30 min for both particles (NO₃ ^?, SO₄ ^{2 ?} and NH₄ ⁺) and gases (HNO₃, SO₂ and NH₃). Gas and particle extract samples are each collected for 15 min. The analyses of the gas and particle samples are staggered 15 min apart. The limit of detection (S/N = 3) for NO₃ ^?, SO₄ ^2? and NH₄ ⁺ are 2.6, 5.3, and 2.1 ng/m³, respectively.     

Solvent Extraction of Au(III) by the Chloride Salt of the Amine Alamine 304 and Its Application to a Solid Supported Liquid Membrane System

Abstract

The extraction of Au(III) by the chloride salt of the amine Alamine 304 (R₃NH⁺Cl^?) in xylene from hydrochloric acid solutions has been investigated. The analysis of metal distribution data by numerical calculations suggested the formation of the species R₃NH⁺AuCl₄ ^? in the organic phase with formation constant log K _ext = 5.44. The results obtained on Au(III) distribution have been implemented in a solid‐supported liquid membrane system, where in NaSCN solutions were found to be the most effective to strip the metal from the organic solution. Influence of membrane composition, metal concentration on gold transport, and the selectivity of the system have also been studied.     

SELECTIVE AND QUANTITATIVE PARTITIONING OF PERTECHNETATE IN POLYETHYLENE-GLYCOL BASED AQUEOUS BIPHASIC SYSTEMS

ABSTRACT

The partitioning behavior of technetium has been investigated in polyethylene glycol (PEG)-based aqueous biphasic systems using K₃P0₄, K₂C0₃, Na₃(citrate), (NH₄) ₃(citrate), (NH₄) ₂S0₄, and NaOH as biphase-forming salts, and PEGs with average molecular weights of 1500, 2000, 3400, and 6000. Pertechnetate quantitatively partitions to the PEG-rich phase in these systems. The distribution ratios increase with increasing salt or PEG concentration used to form the aqueous biphasic systems, consistent with the increasing phase incompatibility. At a given concentration of salt and PEG, D_Tc values in the various systems increase in the order NaOH < (NH₄) ₂S0₄ < (NH₄)3(citrate) < K₂C0₃ < K₃P0₄ and PEG-1500 < PEG-2000 < PEG-3400 < PEG-6000. The distribution ratios are lower at very high or very low pH values than they are in the 3-9 pH range. Matrix ions may also influence the D_Tcvalues by affecting the aqueous biphasic system composition. Technetium can be stripped from the loaded PEG-rich phase by contact with a clean salt solution containing SnCl₂, which reduces TcO₄ to an oxy-chloro cationic species that partitions to the salt-rich phase.