Alvaro Meneguzzi

Electroactive poly(aromatic amine) films for iron protection in sulfate medium

Polyaniline (PANil and poly(1,5-diaminonaphthalene) (PDAN) films can be deposited on iron from aqueous sulfuric acid. The films exhibit electroactive properties similar to those of PANi and PDAN generated on platinum. Electrosynthesis performed in the presence of both monomers leads to a composite film which presents excellent adhesion properties on iron. The composite film imparts a form of anodic protection for at least 9 days in pH 4 sulfate medium.

The effect of sanitary landfill leachate aging on the biological treatment and assessment of photoelectrooxidation as a pre-treatment process

The sanitary landfill leachate is a dark liquid, of highly variable composition, with recalcitrant features that hamper conventional biological treatment. The physical-chemical characteristics of the leachate along the landfill aging, as well as their effects on the efficiency of the conventional treatment, were evaluated at this paper. The feasibility of photoelectrooxidation process as an alternative technique for treatment of landfill leachates was also determined. Photoelectrooxidation experiments were conducted in a bench-scale reactor. Analysis of the raw leachate revealed many critical parameters demonstrating that the recalcitrance of leachate tends to increase with time, directly influencing the decline in efficiency of the conventional treatment currently employed. The effects of current density and lamp power were investigated. Using a 400 W power lamp and a current density of 31.5 mA cm(-)(2), 53% and 61% efficiency for the removal of ammoniacal nitrogen and chemical oxygen demand were respectively achieved by applying photoelectrooxidation process. With the removal of these pollutants, downstream biological treatment should be improved. These results demonstrate that photoelectrooxidation is a feasible technique for the treatment of sanitary landfill leachate, even considering this effluents high resistance to treatment.

Water absorbed by polyaniline emeraldine tends to organize, forming nanodrops

Interactions, in terms of both binding energies and microscopic organization, of water molecules absorbed by hydrophilic polyaniline emeraldine base have been investigated using quantum mechanical calculations, molecular dynamics simulation, FTIR spectroscopy, and (1)H NMR. From an enthalpic point of view, water molecules interact more favorably with imine nitrogen atoms than with amine ones, even though the latter are entropically favored with respect to the former because of their two binding sites. Quantum mechanical results show that interaction energies of water molecules reversibly absorbed but organized individually around a binding site range from 3.0 to 6.3 kcal/mol, which is in good agreement with activation energies of 3-5 kcal/mol previously determined by thermodynamic measurements. The irreversible absorption of water to produce C-OH groups in rings of diimine units has been examined considering a three steps process in which water molecules act as both acidic and nucleophilic reagent. Although calculations predict that the whole process is disfavored by 5-8 kcal/mol only, FTIR and (1)H NMR detected the existence of reversibly absorbed water but not of C-OH groups. Both the binding energies and the structural information provided by molecular dynamics simulations have been used to interpret the existence of two types of physisorbed water molecules: (i) those that interact individually with polymer chains and (ii) those immersed in nanodrops that are contained within the polymeric matrix. The binding energies calculated for these two types of water molecules are fully consistent with the thermodynamic activation energies previously reported.

Polyaniline Emeraldine Salt in the Amorphous Solid State: Polaron versus Bipolaron

The polaronic and bipolaronic forms of polyaniline emeraldine salt (PAni-ES) in the amorphous solid state have been simulated using classical molecular dynamics (MD) and hybrid quantum mechanical/molecular mechanical-molecular dynamics (QM/MM-MD) approaches. It should be remarked that the electronic state of PAni-ES has been theoretically investigated in the gas phase, solution phase, and crystalline state, but this is the first study in the amorphous solid state, which is the most typical for this conducting polymer. MD simulations were carried out using force-field parametrizations explicitly developed for polaronic and bipolaronic models. QM/MM-MD calculations were performed using a quantum mechanical zone defined by four repeat units. In addition of the structural and electronic characteristics of the two forms of PAni-ES, MD and QM/MM-MD simulations indicate that the bipolaronic is the most stable state of amorphous PAni-ES. Complementary studies have been carried out using different experimental techniques. Although the morphology and topography of doped and undoped PAni are very similar, comparison of their UV-vis spectra supports the preference toward the bipolaronic form of PAni-ES.

Castor oil and commercial thermoplastic polyurethane membranes modified with polyaniline: a comparative study

The study of conducting polymeric membranes is decisive in some areas, as in fuel cells and electrodialysis. This work aims the study of membranes using conventional and conductive polymers blends. Two types of polyurethane were used as conventional polymers, commercial thermoplastic polyurethane and polyurethane synthesized from castor oil and 4-4-dicyclohexylmethane isocyanate. Two kinds of conducting polymers were used, polyaniline doped with organic acid and a self doped polyaniline. The polymers and the membranes were characterized by electrical conductivity, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA) and scanning electron microscopy (SEM). The synthesis of the membranes produced was proper, featuring a complete reaction, analyzed by FTIR. The membranes also showed good mechanical properties and thermal stability (≈ 220 °C). Among the membranes studied, the polyaniline doped with p-toluenesulphonic acid obtained higher thermal and viscoelastic properties. Thus they can be used in separation techniques using membranes.

Naphthalene Containing Poly(urethane-urea) for Volatile Memory Device Applications

Current of voltage controlled electrical switching in organic molecules and polymers is attracting attention due to its potential in organic electronic memory applications. The switching phenomenon under consideration in this article is characterized as a sudden transition from a low to a high conductivity condition at a threshold voltage. For the observed volatile switching phenomenom, the lower conductivity condition is restored as soon as the applied voltage becomes smaller than a holding voltage. This switching phenomenom presents the basic requirements for application in volatile memory devices. In this Communication we report on volatile electrical switching observed in a polyurethane derivative copolymerized with diaminonaphthalene.

Integration of membrane bioreactor and advanced oxidation processes for water recovery in leather industry

AbstractNowadays, the conventional tannery wastewater treatment is not established in order to obtain water in such a quality that it could be reused in the same process. This study was then carried out in order to study an integrated wastewater treatment system, membrane bioreactor–photoelectrooxidation (MBR–PEO), for the final polishing of tannery wastewater. MBR is responsible for the remaining biochemical oxygen demand removal, while the refractory matter, quantified as chemical oxygen demand, is removed by PEO. This treatment configuration has provided two wastewater streams with quality standards for reuse as process water. The wastewater treated by the MBR could be reused in beamhouse operations, while the wastewater treated by the integrated MBR–PEO processes could be recycled for the tanyard and re-tanning steps due to its appreciable quality.

Filme autosuportado de polianilina desdopada para aplicações anticorrosivas

The intrinsically conductive polymers (PCI), such as polyaniline (PAni), have been studied as an alternative in the development of protective films of oxidizable metals against corrosion. Given the difficulty of mixing and dissolving PAni for the production of films, here we investigated the possibility of obtaining a mixture of PAni films in the oxidized, undoped state, referred to as emeraldine base, with the non-doping plasticizer 4-chloro-3-methylphenol (CMF) and a convenient solvent. Films produced in this way were characterized by FTIR and Raman spectroscopy, TGA and cyclic voltammetry. The characterization showed films thermally stable up to 200 oC with evidence of interaction between PAni and CMF, with PAni remaining in the oxidized state in the film produced, which a necessary condition for application as anodic protection in anticorrosion films.

Estudo da obtenção através de síntese eletroquímica de poliaminonaftalenos e poliaminoantracenos

The polyaromatics are a group of polymers composed by polyaminonaphthalenes, polyaminoanthracenes and polynaphthoquinones that have aromatic systems with two or three rings. In this work, films of polyaminoanthracene (PAA) and 1,5 polydiaminonaphthalene (PDAN-1,5) have been electropolymerized on Pt electrodes in a single compartment cell with three electrodes. Fourier transform infra-red (FTIR) and Raman spectroscopies have been used to confirm that the PAA structure is similar to that of polyaniline (PAni). Electrochemical studies have shown that the PAA and the PDAN-1,5 present only one redox pair. However, the PAA did not show a good electrochemical stability, in contrast to PDAN-1,5. The micrographs showed homogeneous and compact films, with globular structure and for both polymers, although PAA showed cracks produced during drying with cold air flow.

Degradation of cyanotoxins (microcystin) in drinking water using photoelectrooxidation

The discharge of sewage and industrial effluents containing high concentrations of pollutants in water bodies increases eutrophication. Cyanobacteria, some of the organisms whose growth is promoted by high nutrient concentrations, are resistant and produce several types of toxins, known as cyanotoxins, highly harmful to human beings. Current water treatment systems for the public water supply are not efficient in degradation of toxins. Advanced oxidation processes (AOP) have been tested for the removal of cyanotoxins, and the results have been positive. This study examines the application of photoelectrooxidation in the degradation of cyanotoxins (microcystins). The performance of the oxidative processes involved was evaluated separately: Photocatalysis, Electrolysis and Photoelectrooxidation. Results showed that the electrical current and UV radiation were directly associated with toxin degradation. The PEO system is efficient in removing cyanotoxins, and the reduction rate reached 99%. The final concentration of toxin was less than 1 µg/L of microcystin in the treated solution.