Effect of Ho substitution on the ionic conductivity of La2Mo1.7W0.3O9 oxygen ion conductor

Partial substitutions of Ho at the La-site of La₂Mo_1.7W_0.3O_9−δ were carried out. Compound La_2−xHo_xMo_1.7W_0.3O_9−δ (x = 0, 0.05, 0.1, 0.15, 0.2, 0.3, 0.5) has been synthesized by solid state reaction technique. The specimens were characterized by XRD, SEM, DSC for crystal structure, surface morphology, phase transition and ac impedance spectroscopy for conductivity and other electrical parameter determination. Partial substitution of Ho at the La-site of La₂Mo_1.7W_0.3O_9−δ, increases the conductivity within the substitutional range, x ≤ 0.2. The phase transition of La₂Mo₂O₉ is suppressed in doped compound and a transition from Arrhenius to VTF behavior of temperature dependence of conductivity is observed around 500 °C. The conductivity is found to be high in the intermediate temperature region and at high temperature the conductivity of La_2−xHo_xMo_1.7W_0.3O_9−δ (0.05 ≤ x ≤ 0.2) is almost similar with that of La₂Mo₂O₉. The decrease in energy barrier enhances the thermally assisted process to start at lower temperature.     

Influence of processing parameters on regeneration kinetics and morphology of porous cellulose from cellulose–NaOH–water solutions

The kinetics of cellulose regeneration in acetic acid bath from cellulose–8% NaOH–water solutions and gels is studied as a function of gelation conditions, acid concentration and bath temperature. The diffusion coefficient of NaOH from cellulose solution or gel into regenerating bath was calculated. It does not depend either on gelation mode or on acid concentration. On the contrary, cellulose regeneration from non-gelled solutions is slower than from a gel. The increase in bath temperature induces diffusion coefficient increase obeying Arrhenius law. Scanning electron microscopy images of regenerated swollen-in-water freeze-dried cellulose and of the same samples dried in supercritical CO₂ show highly porous morphology. CEMEF is a Member of the European Polysaccharide Network of Excellence (EPNOE), .     

New gelators of urea-containing triazine derivatives: effects of aggregation and optical features in different organic solvents

New gelators for urea-containing triazine derivatives were synthesised, and their gelation potential was examined using different organic solvents. These compounds were found to form the organogels with a variety of organic solvents, such as hexane and other solvents. The elongated alkyl tails of the gelators displayed an obvious decrease in the critical gelation concentrations of apolar solvents and an increase in the compatibility of gelation in polar solvents. The resulting thermo-reversible gels were characterised by using the dropping ball method and a number of other instruments. The melting temperature (Tm) of the gels in decalin and CCl₄ increased with the gelator concentrations. The intermolecular hydrogen bonding of gelation in different organic solvents was observed using an FT-IR spectrometer. Temperature-dependent UV–vis and fluorescence analysis showed that the organogels displayed diverse aggregations and various fluorescence effects in different organic solvents. Blue fluorescence and J-aggregation in decalin and the quenched effect and π–π stacking in CCl₄ were observed. Further, the morphological self-assembled feature in different organic solvents was studied with a scanning electron microscope, and the morphological features demonstrated that there were different aggregations in different solvents. In conductivity electrolyte experiments, the organogel electrolytes exhibited high conductivity (σ) compared with the corresponding tetrabutylammonium perchlorate (TBAP)/THF solution. The conductivity of the gel electrolytes increased with the concentration of the electrolyte salts and temperature. When the sol–gel temperature was achieved, a high ion conductivity was observed compared with the corresponding TBAP/THF solution. When the ratio of the added electrolyte salts exceeded 5%, gelation was inhibited. Furthermore, the effect of the electrolyte salts on the Tm of the gel was confirmed. The added electrolyte salts affected the gelation ability, but did not affect the sol–gel temperature.     

Thermoresponsive conductivity of poly(N‐isopropylacrylamide)/potassium chloride gel electrolytes

A series of thermoresponsive polymer gel electrolytes (PGEs) based on poly(N‐isopropylacrylamide) in aqueous potassium chloride was synthesized by radiation‐induced polymerization and gelation using γ rays from a ⁶⁰Co source. The electric conductivity and swelling properties of the PGE were determined as a function of temperature. It was found that the electric conductivity of the PGE depended strongly on the swelling ratio; most notably, it changed drastically near the volume phase‐transition temperature of the PGE. The temperature/conductivity profile of the PGE exhibits a maximum peak at a certain temperature that is defined as the maximum conductivity temperature (T_max). The T_max of all of the PGEs prepared by low‐dose irradiation agreed with the temperature, near the end of the volume phase transition, where the PGE was completely shrunken. Consequently, the conductivity of gels should provide a good method with which the totally shrunken temperature of the thermoresponsive gels can be monitored with good temperature precision. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 134–141, 2002     

Interactions between ethyl(hydroxyethyl) cellulose and lysine-based surfactants in aqueous media

In this work, the interaction between ethyl(hydroxyethyl) cellulose (EHEC) and three dimeric lysine-based surfactants of distinct chain length (C₆, C₈ and C₁₀) have been assessed and the system was evaluated in terms of its temperature-dependent gelling capacity. The viscosity profile depends on the specific surfactant, its concentration and temperature. The observed profiles reflected polymer–polymer associations at elevated temperatures and polymer-surfactant interactions, implying the formation of micellar-type associations. The systems induce gelation at higher temperatures. Longer chain-length surfactants induce gelation at lower concentrations due to their stronger tendency to self-assemble. The thermo-responsive gels showed gel strength generally lower than 20 Pa.sⁿ and a fractal dimension of 2.3–2.4, respectively, indicating the formation of soft gels comprising a tight and homogeneous network. The weakest gel was produced in the presence of the C₆ surfactant. 2D Small-Angle Light Scattering patterns showed a pronounced effect of temperature in terms of the evolution of large hydrophobic clusters, an event precluded when high concentrations of the longer chain surfactants were used.     

Sol-Gel Transition and Equilibrium Shear Modulus of Poly(vinyl chloride) and Plasticizers

The elasticity of poly(vinyl chloride) gels with molecular weight distribution (M_w/M_n), of 2.16 have been studied in the region beyond their gel points. Dynamic storage modulus G′, and equilibrium gel shear modulus of elasticity G_e, at low frequencies (ω) have specific developments as a function of polymer concentrations c, and plasticizers. The scaling elasticity from G_e = kε^z equation holds at different PVC plasticizer gels. The scaling exponent z, and constant k. ε is defined as the relative distance, ε = (|c − c_g|)/c_g, the calculated z = 2.45 ± 0.15. Furthermore, this analysis provides constant k with certain informations about the dependency of gel elasticity on the kind of plasticizer. Near the sol-gel transition temperature T, G_e decreases rapidly with increasing temperature. The normalized moduli G_eM/cRT, of the gels at different temperature, and/or c were dependent on the relative distance from the gelation point ε, and PVC and plasticizers concentration respectively. These results suggested mesh size of gel network near the gelation point for PVC with bis(2-ethylhexyl) phthalate (DOP) or di-n-butyl sebacate (DBS) plasticizers that has been newly reported.     

Effects of the polymerization temperature on the structure,morphology and conductivity of polyaniline prepared with ammonium peroxodisulfate

Polyaniline (PANI) samples were prepared by the oxidation of aniline with ammonium peroxodisulfate in a reaction vessel placed in a bath thermostated to particular temperature, T_b, from −20 °C to 40 °C. Temperature–time profiles of reaction mixtures were monitored except for the reaction at −20 °C that proceeded in the solid state. The temperature regime was found to influence the molecular structure, morphology, crystallinity and electrical conductivity of PANI. The increase in T_b results in an increased content of meanwhile unspecified structure defects in the formed PANI chains (the presence of attached self-doping groups is improbable), decreased crystallinity, toughness and compactness of PANI microparticles and increased steepness of the temperature dependence of PANI conductivity. The PANI prepared in the solid-state polymerization at −20 °C shows, besides a rather high crystallinity, the unusually high position of the quinonoid band maximum: 643 nm, which suggests a high regularity of its chains. A correlation between the temperature dependence of PANI conductivity at low temperatures (range from 13 to 318 K) on one hand and the temperature regime of PANI preparation on the other hand, is reported for the first time. The dependences obtained only poorly meet the variable random hopping model.     

Effects of SDS on the sol–gel transition of konjac glucomannan in SDS aqueous solutions

The interaction between konjac glucomannan (KGM) and an anionic surfactant, sodium dodecyl sulfate (SDS) is studied by rheological, circular dichroism (CD), conductivity, electron spin resonance (ESR), and FT-IR measurements. Since KGM is a neutral polysaccharide and has no significant hydrophobic side groups, the critical micelle concentration value of SDS is not influenced with the addition of KGM, and no marked binding occurs between them. SDS makes no conformational changes of KGM with or without heat treatment. The weak alkaline character of SDS induces the deacetylation of KGM chains and makes it form gels with heat treatment. At the same pH value, the gelation time needed for KGM by using SDS as the coagulant is shorter than that by using Na₂CO₃. The addition of SDS promotes the gelation process of KGM, indicating that although the interaction is weak, SDS micelles seem to play an important role in the gelation of KGM.     

Electrical Properties Investigation in PA12/PANI Composites

Summary: Volume conducting PA-12 based composites powders were chemically prepared by in situ polymerization and aniline doping at room temperature. These kinds of polyamide / PANI composites were investigated regarding their electrical properties. Their ac and dc electrical properties measured in the frequency range of 10⁻²–10⁷ Hz are reported and the frequency dependence of electrical conductivity was investigated as a function of PANI concentration leading to the determination of the conductivity. The experimental conductivity was found to increase continuously with PANI content and explained by percolation theory with a relatively low percolation threshold of about 0.4 wt.%. The dielectric behavior of various PANI polymer composites has been characterized by the critical frequency ω_c (denoting the crossover from the dc plateau of the conductivity to its frequency dependent ac behaviour). Modelling the conductivity behavior versus volume fraction using Slupkowski approach has revealed that the considered parameters are not sufficient to describe the electrical conductivity behavior.     

Mixing behaviour of a conjugated molecular wire candidate and an insulating fatty acid within Langmuir–Blodgett films

The conductivity, weight loss and A.C. impedance studies were carried out to establish the influence the presence of neutral copolymer (Vinyl pyrrodlidone/Vinyl acetate copolymer) with anionic surfactant (Disodium laurethsulfosuccinate) in cyclohexane propionic acid (CHPA) on the corrosion behaviour of carbon steel. The protection efficiency (P%) of AS in the absence and presence of polymer increases with increase in AS concentration until it reaches a maximum constant value near the CMC of AS and decreases with increase in solution temperature. The protective efficiency of AS can be enhanced and its critical micelle concentration shifts to low value by adding of 0.05 g/l of polymer. The critical micelle concentration of AS in the absence and presence of polymer increases with increase in temperature. The calculated thermodynamic parameters of micellization (ΔG_mic), (ΔH_mic) and (ΔS_mic) in the presence of neutral copolymer molecules with AS show that these processes are spontaneous and exothermic in nature and indicate the association between AS and neutral copolymer molecules.     

Self-Foaming Metal-Organic Gels Based on Phytic Acid and Their Mechanical,Moldable, and Load-Bearing Properties.

A catalogue of metal-organic gels are synthesized from phytic acid (PA) and a diversity of metal ions (Fe³⁺, Cr³⁺, Al³⁺, Ce³⁺, Y³⁺, Co²⁺, Ni²⁺, Mn²⁺, Cu²⁺, Zn²⁺, Mg²⁺) upon heating at 80 °C. PA−M gels have various morphologies, including irregular granular (PA−Fe, PA−Al, PA−Ce, PA−Cr, PA−Ni, PA−Co), spongy (PA−Y), and hollow tremella-like (PA−Cu) morphologies. Interestingly for PA−Fe-1 : 4 (PA:Fe³⁺=1 : 4) a large amount of gas is generated during the gelation process leading to a self-foaming gel. The PA−Fe-1 : 4 self-foaming gel shows reversible gel-sol phase transition. The gel is unusually weakened and transformed into a sol at room temperature, and the sol is reversed to gelation when heated again at 80 °C. PA−Fe-1 : 4 gel also shows shapeable and load-bearing properties, and it can bear up to 200 times of its weight, depending on the gas amount fixed in the foam gel and the aging time. This work provides a catalogue of self-foaming supramolecular gels with tunable properties based on naturally abundant resources.     

Tungsten oxide nanowires and polyaniline hybrid film-based electrochromic device with multicolor display and enhanced capacitance

Electrochromic devices (ECDs) have exhibited promising applications in the fields of energy-saving intelligent buildings and next-generation displays because of their simple structure, low power consumption, and multicolor displays. W₁₈O₄₉/polyaniline (PANI) hybrid films are prepared and assembled to ECDs. Compared with pure PANI and W₁₈O₄₉ films, the hybrid film exhibits superior electrochemical and electrochromic performance, including high optical modulation (70.2%), large areal capacity (79.6 mF/cm²), and good capacitance retention. The excellent electrochemical and electrochromic performance is ascribed to the formation of the donor (PANI)-acceptor (W₁₈O₄₉) pair, the porous structure in the nanowires, and the large surface area, which enhance electron delocalization of the W₁₈O₄₉/PANI, improve the ion diffusion rate, and increase the charge storage sites. Furthermore, benefitting from the outstanding optical, electrical, and multifunctional properties, the W₁₈O₄₉/PANI hybrid film-based ECD platform is expected to play an important role in electrochromism and energy storage.     

A new way to prepare tin oxide precursor polymeric gels

Transparent tin oxide gels are elaborated in the isopropoxide/toluene/isopropanol system. The gelation occurs at room temperature without any acid or base additions. The formation of the SnO₂ precursor gels polymeric network is evidenced by Fourier transform infrared spectroscopy. The gelation time is studied as a function of the complexing ratio R = [acac]/[Sn(OR)₄], the hydrolysis ratio W = [H₂O]/[Sn(OR)₄], the concentration of tin oxide precursor C = [Sn(OR)₄], and the volume fraction of toluene P = (toluene volume) / (total solvent volume).     

Preparation of Mesoporous Titania by Templating with Polymer and Surfactant and its Characterization

Mesoporous titania was obtained by gelation from Ti-alkoxide in alcoholic solutions with addition of polymer and/or surfactant. The structure and surface morphology of the gels were characterized by N₂-adsorption measurements, scanning electron microscopy and X-ray diffraction. The specific surface area and pore volume of the gels can be increased with addition of hydrophilic polymer such as polyethyleneglycol. Surfactants like cetyltrimetylammoniumchloride are effective to control the pore size and to increase the pore volume and surface area. The surface morphology of the gels can be modified by the mixing method with polymer and/or surfactant. The effects of the templating on pore size distribution, pore shape, surface area and crystallization behaviors have been discussed.     

Proton-Reservoir Hydrogel Electrolyte for Long-Term Cycling Zn/PANI Batteries in Wide Temperature Range

Advanced aqueous batteries are promising for next generation flexible devices owing to the high safety, yet still requiring better cycling stability and high capacities in wide temperature range. Herein, a polymeric acid hydrogel electrolyte (PAGE) with 3 M Zn(ClO₄)₂ was fabricated for high performance Zn/polyaniline (PANI) batteries. With PAGE, even at −35 °C the Zn/Zn symmetrical battery can keep stable for more than 1 500 h under 2 mA cm⁻², and the Zn/PANI battery can provide ultra-high stable specific capacity of 79.6 mAh g⁻¹ for more than 70 000 cycles at 15 A g⁻¹. This can be mainly ascribed to the −SO₃⁻H⁺ function group in PAGE. It can generate constant protons and guide the (002) plane formation to accelerate the PANI redox reaction kinetics, increase the specific capacity, and suppress the side reaction and dendrites. This proton-supplying strategy by polymeric acid hydrogel may further propel the development of high performance aqueous batteries.     

Conductive composite of polyaniline and tungsten carbide

Conductive polyaniline/tungsten carbide (PANI/TC) composite was synthesized via polymerization of the aniline monomer by (NH₄)₂S₂O₈/H₂SO₄ oxidant system in the presence of an aqueous suspension of TC. The structure, thermal stability and conductivity of PANI/TC composite were studied and the results were also compared with the pure PANI. The results showed that there was a strong interaction between the TC particles and PANI molecular chains. The crystalline structure of TC remained undisturbed upon with interaction with PANI chains. The thermal stability of PANI/TC composite was better than that of pure PANI. The direct current conductivity values of PANI/TC composite decreased slowly as the temperature increased from 25 to 165°C and PANI/TC composite exhibited significantly higher conductivity than the pure PANI.     

Thermal stability study of conductive polyaniline/polyimide blend films on their conductivity and ESR measurement

Conductivity stability at thermal environment of conductive polyaniline‐complexes/polyimide (PANI‐complexes/PI) blends, which were doped by camphorsulfonic acid (CSA) and dodecylbenzenesulfonic acid (DBSA), respectively, were investigated by conductivity measurements, electron spin resonance (ESR) spectra, differential and scanning thermometer (DSC). In the conversion process of PANI/Polyamic acid (PAA) to PANI/PI, the blend endeavored some kinds of alteration such as decomplexation of moisture and solvent, dissociation of dopant, crosslinking of PANI chain, and the imidization of PAA chain. PANI‐DBSA/PI showed higher thermal stability of conductivity than PANI‐CSA/PI, and both samples showed nearly linear decay of conductivity with increasing temperature showing greatly enhancement of conductivity stability. When they were exposed at near or over glass transition temperature, the conductivity decay became faster. The conductivity stability at base environment was also higher for PANI‐DBSA/PI due to difficulty in accessing of hydroxyl ion to PANI, which were resulted from dopant. DBSA‐doped blends showed increased polaron mobility and concentration at relatively high temperature, which led to extremely higher conductivity and its stability at high temperature. Copyright © 2002 John Wiley & Sons, Ltd.     

Microscopic Imaging of Chiral Amino Acids in Agar Gel through Circularly Polarized Luminescence of EuIII Complex

We recently found that [Eu(pda)₂]^? (pda: 1,10‐phenanthroline‐2,9‐dicarboxylic acid), which has an achiral structure in crystals, exhibits circularly polarized luminescence (CPL) in aqueous solutions containing chiral amino acids such as arginine and histidine. CPL measurements were performed for agar gel, which includes an aqueous solution of [Eu(pda)₂]^? and chiral arginine or histidine. The spectral shape, concentration, and pH dependences on CPL intensity in the agar gels were very close to those in aqueous solutions, indicating that the CPL of the Eu^III complex in the agar gels was induced by mechanism similar to that in aqueous solutions. We performed spatially resolved CPL measurements using a laboratory‐built microscopic CPL spectroscopic system for agar‐gel samples, where d ‐ and l ‐ amino acids were separately dispersed. We successfully recorded CPL imaging maps showing spatial dispersions of d ‐ and l ‐amino acid in the agar gels.     

Effect of solvent on the gelation properties of a metallo-organic polymer of [Fe(II) (4-octadecyl-1,2,4-triazole)3(ClO4)2]n

In this contribution we report on the preparation of thermally responsive supramolecular gels obtained through self-assembling of metallo-organic polymers of lipophilic Fe(II) complexes of 1,2,4-triazole functionalized with octadecyl chains ([Fe(II) (4-octadecyl-1,2,4-triazole)₃(ClO₄)₂]_n) in three organic solvents: toluene, cis-decalin and trans-decalin. A gel phase is formed in these solvents by cooling the homogeneous complex solutions below a well-defined temperature, the so-called gelation threshold. These gels are reversible as they form homogeneous solutions upon heating above the melting temperature. The systems have been characterized for their thermal and viscoelastic properties through differential scanning calorimetry and rheological experiments, respectively. The effect of the solvent type and concentration on the gelation behaviour of the metallo-organic polymer has been analysed. The results obtained point to structural differences and different gelation mechanisms for the gels prepared in different solvents and they also suggest the possibility to control the spin-crossover transition temperature associated to the sol-gel transition.     

Solvation of sulphonic acid groups in Nafion® membranes from accurate conductivity measurements

The wide degree of scatter of experimental data shows unambiguously that Nafion^®117 conductivity is very sensitive to climatic conditions, temperature and relative humidity. In order to allow equilibrium with the surrounding atmosphere to be reached rapidly, a conductivity cell, adapted to a small size membrane samples, has been designed. Conductivity measurements have been carried out by electrochemical impedance spectroscopy (EIS) between 10 °C and 95 °C in a broad domain of relative humidity, i.e., 10–98%. The measurement set up provides reproducible data with a total uncertainty of 30% in a large range of conductivity values. These accurate data enable a power relationship to be proposed at constant temperature between conductivity and relative humidity. This suggests that the solvation process of a sulphonic acid group involves four water molecules. Based on the assumption that a proton mobility depends weakly on temperature, a solvation enthalpy of a sulphonic acid group by water of −135 kJ mol⁻¹ is deduced from conductivity variations with the temperature.