Electrical conductivity relaxation in PVOH-LiClO4-Al2O3

We report on electrical conductivity relaxation measurements of solid polymer electrolytes (SPE) based on poly(vinyl alcohol) (PVOH) and LiClO₄ in which nanoporous Al₂O₃ particles with average pore diameter of 58 Å were dispersed. A power law frequency dependence of the real part of the electrical conductivity is observed as a function of temperature and composition. This behaviour is typical of systems in which correlated ionic motions in the SPE bulk material are responsible for ionic conductivity. This variation is well fitted to a Jonscher expression σ′(ω) = σ₀[1 + (ω/ω₀)^p] where σ₀ is the dc conductivity, ω₀ the characteristic angular frequency relaxation and p is the fractional exponent between 0 and 1. For a prototype membrane with composition 0.9PVOH − 0.1LiClO₄ + 7 wt.%Al₂O₃, it was found that the temperature dependence of σ₀ and ω₀, may be described by the VTF relationship, ? = ?₀ exp[−B/(T − T₀)], with approximately the same constant B and reference temperature T₀, indicating that ion mobility is coupled to the motions of the polymer chains. Moreover, p decreased with increasing temperature, from 0.68 at T = 319 K, to 0.4 at T = 437 K, indicating weaker correlation effects among mobile ions when the temperature is increased.     

Microstructural studies on BaCl2 doped poly(vinyl alcohol)

We have studied the effect of BaCl₂ dopant on the optical and microstructural properties of a polymer poly(vinyl alcohol) (PVA). Pure and BaCl₂ doped PVA films were prepared using solvent casting method. These films were characterized using FTIR, UV-visible, XRD and DSC techniques. The observed peaks around 3425 cm⁻¹, at 1733 cm⁻¹ and 1640 cm⁻¹ in the FTIR spectra were assigned to O-H, CC stretching and acetyle CO group vibrations, respectively. In the doped PVA shift in these bands can be understood on the basis of intra/inter molecular hydrogen bonding with the adjacent OH group of PVA. The UV-visible spectra shows the absorption bands around 196 nm and shoulders around 208 nm with different absorption intensities for doped PVA, which are assigned to n→π* transition. This indicates the presence of unsaturated bonds mainly in the tail-head of the polymer. Optical band energy gap is estimated using UV-visible spectra and it decreases with increasing dopant concentration. The powder XRD shows an increase in crystallinity in the doped PVA, which arises due to the interaction of dopant with PVA causing a molecular rearrangement within the amorphous phase of polymer. These modifications also influence the optical property of the doped polymer. The DSC study also supports increasing crystalline thickness and degree of crystallinity due to doping.     

Generation of H2 gas from polystyrene and poly(vinyl alcohol) by milling and heating with Ni(OH)2 and Ca(OH)2

A two-step process to generate H₂ gas; first by milling polystyrene (PS) or poly(vinyl alcohol) (PVA) with Ni(OH)₂ and Ca(OH)₂, followed by heating of the milled product in the second-step was performed in this work. Polymer and hydroxide mixtures obtained after milling for 60 min and heating to 700 °C showed H₂, CH₄, H₂O, CO, and CO₂ as the main gaseous products with H₂ as the dominant gas generated between 350 and 500 °C. Analysis of the gaseous products by TG-MS and gas-chromatography, and solid products by TG-DTA and XRD shows that CO₂ gas was fixed as CaCO₃ at temperatures between 350 to 600 °C allowing generation of H₂ gas with concentrations over 95% for PS and over 98% for PVA. The results in this study show that milling of solid based hydrocarbon compounds with nickel and calcium hydroxides allows dispersion of nickel to hydrocarbon surfaces and facilitates C-C bond rupture in polymer(s) during heating at temperatures below 500 °C, at the same time calcium adsorbs CO₂. This process could be developed to treat hydrocarbon based wastes such as plastics, biomass or combinations at low temperatures avoiding syngas purification and separation steps.     

Role of adsorbed iodine into poly(vinyl alcohol) films drawn in KI/I2 solution

We have investigated the microstructure of the poly(vinyl alcohol) (PVA) films using small- and wide-angle X-ray scattering (SAXS and WAXS, respectively) techniques. The samples were uniaxially drawn in water or KI/I₂ aqueous solution and then dried in an air-oven at 333 K for 1 h prior to SAXS and WAXS measurements. It was found that for the films drawn in KI/I₂ solution PVA chains in the microfibrillar structure are more extended upon the film drawing compared to the case of the films drawn in pure water, which is resulted from the correlation function analysis on the SAXS data. Adsorbed iodines into the film were anticipated to act as junction points between the microfibrils via the formation of the PVA-iodine complexes.     

Synthesis of hyperbranched polymers via a facile self-condensing vinyl polymerization system - Glycidyl methacrylate/Cp2TiCl2/Zn

A facile self-condensing vinyl polymerization (SCVP) system, the combination of glycidyl methacrylate, Cp₂TiCl₂ and Zn, has been firstly used to prepare novel hyperbranched polymers, consisting of vinyl polymers as the backbone, and cyclic ester polymers (poly(?-caprolactone) or poly(l-lactide)) as the side chains. The polymerizations are initiated by the epoxide radical ring-opening catalyzed by Cp₂Ti(III)Cl which is generated in situ via the reaction of Cp₂TiCl₂ with Zn. The key to success is that the polymerizations can proceed concurrently via two dissimilar chemistries possessing the opposite active initiating species, including ring-opening polymerization (ROP) and controlled/living radical polymerization (CRP). We have demonstrated that this facile one-step polymerization technique can be applied successfully to prepare highly branched polymers with a multiplicity of end reactive functionalities including Ti alkoxide, hydroxyl and vinyl functional groups.     

Influence of metal coordination on conductivity behavior in poly(butadiene-acrylonitrile)-CoCl2 system

The metal complex formation and the electrical properties of amorphous solid polymer electrolytes, based on poly(butadiene-acrylonitrile) copolymer (PBAN) and CoCl₂, have been studied over the homogeneity region of the system limited by the CoCl₂ concentration of 1.89 mol kg⁻¹. It has been found that ionic conductivity is carried out by the unipolar anion transfer at lower CoCl₂ concentrations (up to 0.10 mol kg⁻¹). As the CoCl₂ concentration increases, electronic conductivity appears in addition to ionic conductivity, and the former becomes dominant, starting from 0.38 mol kg⁻¹. It has been shown that the nature of charge carriers is determined by the composition of metal complexes formed by CoCl₂ and the macromolecular solvent PBAN. At lower concentrations, the [Co₂L₂Cl₄]⁰ dimers are the predominant species (L being macromolecule side groups CN), and their dissociation is followed by the formation of mobile Cl⁻ anions and immobile binuclear [Co₂Cl₃]⁺ complexes. As CoCl₂ concentration increases, polynuclear [Co_nL₂Cl_2n]⁰ (n > 2) complexes appear (L being CN and CC groups of PBAN). Specific features of chemical bonds in π-complexes of transition metals result in the appearance of electronic charge carriers. The abrupt increase in conductivity observed at the highest CoCl₂ concentration is connected with the formation of a percolation network of polynuclear [Co_nL₂Cl_2n]⁰ complexes.     

Aligned three-dimensional microstructures of conducting polymer composites

The composites of polypyrrole (PPy) and poly(vinyl alcohol) (PVA) with aligned 3-dimensional (3D) microstructures have been fabricated via vapor deposition polymerization (VDP) of pyrrole onto the microstructured composites of PVA and FeCl₃ (PVA-FeCl₃) formed by directional freezing. In these composites, the microstructures of PVA act as the frameworks and the conducting polymer components provide the materials with conductive function. The composites are foam-like with low weight density. However, they have good mechanical properties, and can be easily mechanically processed into various desired shapes. The apparent conductivity of the composite containing 20 wt% PPy was measured to be approximately 0.1 S cm⁻¹. The ammonia gas sensor based on this 3D composite exhibited high sensitivity. The strategy developed here can be extended to fabricate the 3D microstructured conductive composites by using other conducting polymers or water-soluble polymers.     

Effect of modified montmorillonites on the ionic conductivity of (PEO)16LiClO4 electrolytes

Three kinds of modified montmorillonites were prepared by ion exchange method, and added into (PEO)₁₆LiClO₄ matrix to study the effect on the ionic conductivity of (PEO)₁₆LiClO₄ electrolytes. The structure of the modified montmorillonites and polymer composites were characterized by wide-angle X-ray diffraction. HP 4192A was used to measure the ionic conductivity of the polymer electrolytes. The results show that the addition of optimum content of 250-Li-mont enhances the ionic conductivity of the PEO based electrolyte by nearly 30 times more than the plain system and that is much higher than the other two modified montmorillonites. The difference of enhancement in conductivity caused by adding these three montmorillonites can be attributed to the difference in structure of the samples as characterized by wide-angle X-ray diffraction.     

Synthesis and characterization of diethanolamine-impregnated cross-linked polyvinylalcohol/glutaraldehyde membranes for CO2/CH4 separation

In this research, the cross-linking of diethanolamine (DEA) impregnated poly(vinyl alcohol) (PVA) on polytetrafluoroethylene (PTFE) by glutaraldehyde (GA) with different blend compositions (GA/PVA: 0.5, 1, 3, 5, 7 ratio%) was performed in the absence of an acid catalyst and organic solvents in order to avoid any interference in CO₂ facilitation reaction with DEA. The fabricated membranes were characterized by differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) and scanning electron microscopy (SEM). Furthermore, the effects of cross-linking agent content, feed pressure and composition as well as stability on CO₂/CH₄ transport properties were investigated in both pure and mixed gas experiments. The cross-linked membranes showed reasonable CO₂/CH₄ permselectivities in comparison with uncross-linked membranes. The best-yield CO₂-selective membranes (DEA-PVA/GA(1 wt%)/PTFE) represented the best CO₂/CH₄ selectivity of 91.13 and 665 for pure and mixed gas experiments, respectively.     

Crystallinity, morphology, mechanical properties and conductivity study of in situ formed PVdF/LiClO4/TiO2 nanocomposite polymer electrolytes

Nanocomposite polymer electrolytes composed of poly(vinylidene fluoride) (PVdF), lithium perchlorate (LiClO₄) and TiO₂ nanoparticles were prepared by a solution-cast method. The nanosized ceramic filler, TiO₂, was synthesized in situ by a sol-gel process. Differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) analysis revealed that the crystalline phase and crystallinity were slightly decreased with the addition of TiO₂ to the PVdF/LiClO₄ system. Scanning electron microscopy (SEM) micrographs showed that the PVdF/LiClO₄/TiO₂ solid polymer electrolyte (SPE) membranes had a porous structure to a certain extent, and that the pore size decreased with increasing TiO₂ content. The overfull nanoparticles tended to aggregate on the surface and inside the pores at TiO₂ content above 15 wt.% so that the porosity decreased. Regarding mechanical properties, the strength of the PVdF/LiClO₄/TiO₂ electrolytes decreased after the uptake of EC/PC solution. In contrast to the conductive behavior of wet PVdF/LiClO₄/TiO₂ membranes relative to the uptake of EC/PC solution, the conductive mechanism of the solid membranes, after the lithium ion of LiClO₄ had already been installed in the PVdF solid polymer network, was mainly influenced by the TiO₂ nanoparticles. At a TiO₂ content of 10 wt.%, the solid and wet PVdF/LiClO₄/TiO₂ systems had the maximum conductivity values of 7.1 × 10⁻⁴ and 1.8 × 10⁻³ S/cm, respectively.     

Studies on proton conductivity of polyimide/H3PO4/imidazole blends

A new anhydrous proton conducting material based on polyimide(PI)/H₃PO₄/imidazole(Imi) Blends was prepared. FTIR spectrum shows the existence of hydrogen bonds between protonated and unprotonated imidazole units. The addition of phosphoric acid can accelerate the degradation process of PIs, while the addition of imidazole in PI/H₃PO₄ blends can improve their chemical oxidation stability enormously. The proton conductivity of PI/H₃PO₄ blends increases significantly with increasing content of imidazole. Proton conductivity of PI/xH₃PO₄/yImi membranes increases with increasing temperature and content of phosphoric acid. The experimental results show that it is possible to significantly improve the operating temperature of PEM fuel cell system by replacing water with imidazole as proton solvent in the polymer membrane. Hydrogen bond seems to play an important role in the proton conductivity of this system. The decrease of proton conductivity of imidazolium phosphate shows in some degree that the interaction between imidazole and phosphoric acid is not the main reason for the conductivity increment of imidazole doped PI/H₃PO₄ system.     

Synthesis and NMR studies of the polymer membranes based on poly(4-vinylbenzylboronic acid) and phosphoric acid

Proton conduction in novel anhydrous membranes based on host polymer, poly(4-vinylbenzylboronic acid), (P4VBBA) and phosphoric acid, (H₃PO₄) as proton solvent was studied. The materials were prepared by the insertion of the proton solvent into P4VBBA at different stoichiometric ratios to get P4VBBA·xH₃PO₄ composite electrolytes. Homopolymer and the composite materials were characterized by FT-IR, ¹¹B MAS NMR and ³¹P MAS NMR. ¹¹B MAS NMR results suggested that acid doping favors or leads to a four-coordinated boron arrangement. ³¹P MAS NMR results illustrated the immobilization of phosphoric acid to the polymer through condensation with boron functional groups (B-O-P and/or B-O-P-O-B). Thermogravimetric analysis (TGA) showed that the condensation of composite materials starts approximately at 140 °C. An exponential weight loss above this temperature was attributed to intermolecular condensation of acidic units forming cross-linked polymer. The insertion of phosphoric acid into the matrix softened the materials shifting T_g to lower temperatures. The temperature dependence of the proton conductivity was modeled with Arrhenius relation. P4VBBA·2H₃PO₄ has a maximum proton conductivity of 0.0013 S/cm at RT and 0.005 S/cm at 80 °C.     

腰果酚/聚乙烯醇改性酚醛树脂的制备

以腰果酚、聚乙烯醇作为苯酚与甲醛缩聚的改性剂,研究了腰果酚和聚乙烯醇的用量,催化剂类型和用量等对其性能的影响。结果表明:改性酚醛树脂的最佳条件为:苯酚、腰果酚、聚乙烯醇、甲醛的最佳摩尔比为0.85:0.32:0.02:1,最佳的催化剂为苯磺酸,用量为4.5%。     

腰果酚/聚乙烯醇改性酚醛树脂的制备

以腰果酚、聚乙烯醇作为苯酚与甲醛缩聚的改性剂,研究了腰果酚和聚乙烯醇的用量,催化剂类型和用量等对其性能的影响。结果表明:改性酚醛树脂的最佳条件为:苯酚、腰果酚、聚乙烯醇、甲醛的最佳摩尔比为0.85:0.32:0.02:1,最佳的催化剂为苯磺酸,用量为4.5%。     

Morphology-rheology relationship in hyaluronate/poly(vinyl alcohol)/borax polymer blends

In this work, we have prepared bioartificial polymer blends using hyaluronate (HA) as a biological component and poly(vinyl alcohol)-borax association (PVAs) as a synthetic component, and investigated the rheological properties as well as morphology of the blends. When plotted against the blend composition, the rheological properties showed both positive and negative deviation from the linear additive mixing rule depending on thermal history. The blend showed enhanced viscosity at the composition of 20 wt% of HA and 80 wt% of PVAs, when PVA was dissolved at high temperature. The viscosity enhancement was caused by the network formation of HA aggregates in the micrometer scale. In addition, the network structure of HA aggregates was found to be fractal with the fractal dimension of 1.7. As PVA system also forms a network structure in the nanometer scale between hydroxyl groups of PVA and borate anions, the blend system is unique in that it has network structures in both micrometer and nanometer scales in one material. On the contrary, HA formed aggregates but not any network structure in the blend of the same composition but of the negative deviation. In conclusion, we showed that HA/PVAs blend system may have diverse morphology as well as very broad spectrum of rheological properties, and could suggest that the rheology and morphology of HA/PVAs blends can be designed not only by controlling composition but also by controlling thermal and deformation history of the components.     

Electrochemical investigations on the effect of dispersoid in PVA based solid polymer electrolytes

Various compositions of TiO₂ dispersed PVA‐PMMA‐LiBF₄‐EC based electrolytes were prepared using solution casting technique. The prepared electrolytes were characterized using AC impedance, XRD, SEM, FTIR, etc. The ionic conductivity value is increased with the increase in filler content (up to 8 wt %) and then decreased with the increase in filler content. The results are described using Vogel–Tamman–Fulcher theory. The thermal and transport properties of the electrolyte exhibiting maximum conductivity have also been studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3950–3956, 2007     

Synthesis of boronate-containing copolymers of N,N-dimethylacrylamide, their interaction with poly(vinyl alcohol) and rheological behaviour of the gels

Cross-linking of polyvinylalcohol (PVA) by boronate-containing copolymer of N,N-dimethylacrylamide (DMAA, 1) was studied and compared to cross-linking of PVA by borate buffers in weakly alkaline solutions. The copolymer of M_w=19,000 g mol⁻¹ containing 9 mol% N-acryloyl-m-aminophenylboronic acid (NAAPBA, 2) was prepared by free radical polymerization of the monomers, exhibiting copolymerization constants r₁=0.84 and r₂=2.2. Due to multipoint interaction of the copolymer with PVA via monodiols, the intermolecular cross-linking required for seven-fold and 10-fold lower boron concentrations as compared to borate buffers of pH 8.6 and 7.5, respectively. In rheological measurements, PVA-copolymer gels exhibited storage moduli (G′_max) comparable to those of PVA-borate gels prepared at 7.5-fold higher boron concentration and the same pH 8.6, what testified to the similar concentration of cross-links in the gels. Therefore, DMAA-NAAPBA copolymer is a more effective cross-linker of PVA than borate. The PVA-copolymer gel exhibited much higher relaxation time (97 s) compared to PVA-borate gels (≤20 s) indicating a longer lifetime of junction zones. The ‘shape stability’ of the gel is suggested to originate in the structure of junctions, containing several boronate-diol complexes, between the macromolecules of PVA and the copolymer.     

Characterization of poly(vinylidenefluoride-co-hexafluoropropylene)-based polymer electrolyte filled with TiO2 nanoparticles

Nanoscale TiO₂ particle filled poly(vinylidenefluoride-co-hexafluoropropylene) film is characterized by investigating some properties such as surface morphology, thermal and crystalline properties, swelling behavior after absorbing electrolyte solution, chemical and electrochemical stabilities, ionic conductivity, and compatibility with lithium electrode. Decent self-supporting polymer electrolyte film can be obtained at the range of <50 wt% TiO₂. Different optimal TiO₂ contents showing maximum liquid uptake may exist by adopting other electrolyte solution. Room temperature ionic conductivity of the polymer electrolyte placed surely on the region of >10⁻³ S/cm, and thus the film is very applicable to rechargeable lithium batteries. An emphasis is also be paid on that much lower interfacial resistance between the polymer electrolyte and lithium metal electrode can be obtained by the solid-solvent role of nanoscale TiO₂ filler.     

Mechanochemical synthesis of kaolin-KH2PO4 and kaolin-NH4H2PO4 complexes for application as slow release fertilizer

A milling process to reduce kaolin to amorphous phase in the presence of KH₂PO₄ or NH₄H₂PO₄ and allow mechanochemical (MC) reaction for incorporation of KH₂PO₄ and NH₄H₂PO₄ into the kaolin structure was investigated in this work. Mixtures of kaolin and KH₂PO₄ and NH₄H₂PO₄ in separate systems were prepared by milling in a planetary ball mill. Tests with kaolin contents ranging from 25 to 75 wt.% and mill rotational speeds from 200 to 700 rpm were performed to evaluate incorporation of KH₂PO₄ and NH₄H₂PO₄ and release of K⁺, NH₄⁺ and PO₄³⁻ ions into solution. Analyses by XRD, DTA and ion chromatography indicated that the MC process was successfully applied to incorporate both KH₂PO₄ and NH₄H₂PO₄ into the amorphous kaolin structure. Release of K⁺ and PO₄³⁻ ions from the system (kaolin-KH₂PO₄) when dispersed in water for 24 h reached only up to 10%. Under similar conditions for the system (kaolin-NH₄H₂PO₄), release of NH₄⁺ and PO₄³⁻ ions reached between 25 and 40%. These results indicated that the MC process can be developed to allow amorphous kaolin to act as a carrier of K⁺, NH₄⁺ and PO₄³⁻ nutrients to be released slowly for use as fertilizer.