Electrochemical studies of the interface Fe/0.5 mol L(-1) H(2)SO(4) in the presence of benzotriazole and tolytriazole

The effect of benzotriazole (BTAH) and tolytriazole (TTAH) on the electrochemical behaviour of the Fe/0.5 mol L(-1) H(2)SO(4) interface at 25 degrees C was studied using cronopotentiometry, anodic and cathodic polarization curves and electrochemical impedance spectroscopy. BTAH and TTAH are inhibitors of anodic iron dissolution and the subsequent hydrogen evolution in 0.5 mol L(-1) H(2)SO(4) medium. Mass transport is an important step in the anodic process of inhibitive film formation. Electrochemical impedance spectroscopy was used to investigate the iron dissolution mechanism in the presence of the inhibitors and showed that BTAH and TTAH are adsorbed on the iron surface, thereby changing its dissolution mechanism in sulfate media. Starting from an iron dissolution model, it was possible to suggest two different mechanisms for iron dissolution in 0.5 mol L(-1) H(2)SO(4) containing BTAH or TTAH that involve a complex Fe(II)-inhibitor. (C) 2009 Elsevier B.V. All rights reserved

On the open-circuit interaction between methanol and oxidized platinum electrodes

In the present work, results of the interaction between methanol and oxidized platinum surfaces as studied via transients of open-circuit potentials are presented. The surface oxidation before the exposure to interaction with 0.5 M methanol was performed at different polarization times at 1.4 V vs reversible hydrogen electrode (RHE). In spite of the small changes in the initial oxide content, the increase of the pre-polarization time induces a considerable increase of the time needed for the oxide consumption during its interaction with methanol. The influence of the identity of the chemisorbing anion on the transients was also investigated in the following media: 0.1 M HClO4, 0.5 M H2SO4, and 0.5 M H2SO4 + 0.1 mM Cl-. It was observed that the transient time increases with the energy of anion chemisorption and, more importantly, without a change in the shape of the transient, meaning that free platinum sites are available at the topmost layer all over the transient and not only in the potential region of small oxide `coverage`. The impact of the pre-polarization time and the effect of anion chemisorption on the transients are rationalized in terms of the presence of surface and subsurface oxygen driven by place exchange.

Exploring corrosion protection of Mg via ionic liquid pretreatment

We present the development of a 10–100 nanometer thick surface film upon pure Mg on exposure to an ionic liquid (IL) based on the bis(trifluoromethanesulfonyl)amide (TFSA) anion. This film formation is the result of the oxidative reactivity of the metal in the IL, with the subsequent effect of ultimately protecting the underlying metal from corrosion in aqueous chloride containing solution. Film formation was studied in the IL using an electrochemical droplet cell. It was seen that this film is adherent and subsequently facilitates appreciable protection against corrosion as judged by subsequent electrochemical testing in the form of potentiodynamic polarization and impedance spectroscopy, along with direct observation. The physical film morphology was studied by electron microscopy and focused ion beam.

Stability of oxide films formed on mild steel in turbulent flow conditions of alkaline solutions at elevated temperatures

In the industries involving alkaline solutions in different process streams, the nature and stability of oxide films formed on the metallic surfaces determine the rates of erosion–corrosion of the equipment. In the present study the characteristics of the oxide films formed on AISI 1020 steel in a 2.75 M sodium hydroxide solution at temperatures up to 175°C, have been investigated by employing electrochemical techniques of cyclic voltammetry and chronoamperometry. The experiments were carried out in an autoclave system based upon a ‘rotating cylinder electrode’ geometry to determine the effects of turbulence on the stability of the films. The results suggest that little protection is afforded in the active region (at about −0.8 V_SHE). In the passive region at low potentials (−0.6 V to −0.4 V_SHE), it appears the films are compact and more stable, and therefore provide good protection. At higher potentials (>−0.4 V_SHE) in the passive region, the results suggest that film formation and dissolution occur simultaneously and the increase in temperature and turbulence causes a breakdown of the passive film resulting in a situation similar to nonprotective magnetite growth.

An investigation of a phosphinate-based ionic liquid for corrosion protection of magnesium alloy AZ31

This work reports a preliminary exploration of the potential of the ionic liquid trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate (P_6,6,6,14M₃PPh) for use as a conversion coating agent for corrosion protection of magnesium alloy AZ31. Results obtained for the as received IL did not indicate any measureable improvement in protection. However, when the IL was allowed to reach equilibrium/saturation with moisture from the atmosphere, treatment with this ‘wet’ solution resulted in a substantial improvement in corrosion resistance. Preliminary electrochemical, optical, and spectroscopic characterization of the film will be presented along with a possible mechanism for film formation.

Facile synthesis of graphene oxide hybrids bridged by copper ions for increased conductivity

In this article, we report a facile method for preparing graphene oxide (GO) hybrid materials consisting of copper ions (Cu2+) complexed with GO, where Cu2+ acted as bridges connecting GO sheets. The method of film formation is based on cross-linking GO using Cu2+ followed by filtration onto nanoporous supports. This binding can be rationalized due to the chemical interaction between the functional groups on GO and the metal ion. We observed that there was a decrease in charge transfer resistance through electrochemical study. It suggests that the presence of metal ions in GO films could introduce new energy levels along the electron transport pathway and open up possible conduction channels. We also found that the hybrid graphene film assembled with Cu2+ dramatically decreases resistance through flash light reduction.

The effect of treatment temperature on corrosion resistance and hydrophilicity of an ionic liquid coating for mg-based stents

Mg alloys are attractive candidate materials for biodegradable stents. However, there are few commercially available Mg-based stents in clinical use because Mg alloys generally undergo rapid localized corrosion in the body. In this study, we report a new surface coating for Mg alloy AZ31 based on a low-toxicity ionic liquid (IL), tributyl(methyl)phosphonium diphenyl phosphate (P1,4,4,4 dpp), to control its corrosion rate. Emphasis is placed on the effect of treatment temperature. We showed that enhancing the treatment temperature provided remarkable improvements in the performances of both corrosion resistance and biocompatibility. Increasing treatment temperature resulted in a thicker (although still nanometer scale) and more homogeneous IL film on the surface. Scanning electron microscopy and optical profilometry observations showed that there were many large, deep pits formed on the surface of bare AZ31 after 2 h of immersion in simulated body fluid (SBF). The IL coating (particularly when formed at 100 °C for 1 h) significantly suppressed the formation of these pits on the surface, making corrosion occur more uniformly. The P1,4,4,4 dpp IL film formed at 100 °C was more hydrophilic than the bare AZ31 surface, which was believed to be beneficial for avoiding the deposition of the proteins and cells on the surface and therefore improving the biocompatibility of AZ31 in blood. The interaction mechanism between this IL and AZ31 was also investigated using ATR-FTIR, which showed that both anion and cation of this IL were present in the film, and there was a chemical interaction between dpp(-) anion and the surface of AZ31 during the film formation.

Estudo tribológico de biolubrificantes com adição de nanopartículas de óxidos (zinco e cobre)

Currently, vegetable oils have been studied for bio-lubricants base that fits the new environmental standards. Since, in a world full of finite natural resources, mineral oils bring consequences to the environment due to its low biodegradability and toxicity, also it is important to consider that synthetic oils have a high cost The aim of this work is to obtain a biolubricant additived with oxide nanoparticles (ZnO and CuO) for better resistance to friction and wear, which is not toxic to the environment and have better adherence under boundary lubrication. The methodology consisted in the synthesis of bio-lubricants (soybean and sunflower base) by epoxidation reaction. Then, some physical-chemical analysis in bio-lubricants are made to characterize theses lubricants, such as, density, acidity, iodine value, viscosity, viscosity index. Later, the lubricants were additive with nanoparticles. The tribological performance was evaluated by the equipment HFRR (High Frequency Reciprocating Rig) consisting of a wear test ball-plan type. The characterization of wear analysis was performed by SEM / EDS. The results show that bio-lubricants may be synthesized by reaction of epoxidation with good conversion. Tribological point of view, the epoxidized oils are more effective than lubricant additived with the oxide nanoparticles, they had lower coefficients of friction and better rate of film formation in the study. However, because they are environmentally friendly, bio-lubricants gain the relevant importance in tribological field

Material processing by plasma shock wave generated in an inverse Z-pinch plasma expander

The applicability of plasma shock wave for material processing was investigated using modified inverse Z-pinch device. Shock wave expanding speed and plasma spectral analysis were studied using an internal magnetic,probe and spatially collimated light spectroscopy. The material processing capability of the device was shown by many different surface analysis techniques such as AES, IRS, EPM and SEM. The interactions between a plasma shock wave of similar to4x10(6) cm/s speed with a Si substrate surface shows some ion implantation capability using a nitrogen plasma and thin film formation using a methane plasma.

Aplicação de sabões de ácidos graxos epoxidados como inibidores de corrosão em oleoduto

Corrosion usually occurs in pipelines, so that it is necessary to develop new surface treatments to control it. Surfactants have played an outstanding role in this field due to its capacity of adsorbing on metal surfaces, resulting in interfaces with structures that protect the metal at low surfactant concentrations. The appearance of new surfactants is a contribution to the area, as they increase the possibility of corrosion control at specific conditions that a particular oil field presents. The aim of this work is to synthesize the surfactants sodium 12 hydroxyocadecenoate (SAR), sodium 9,10-epoxy-12 hydroxyocadecanoate (SEAR), and sodium 9,10:12,13-diepoxy-octadecanoate (SEAL) and apply them as corrosion inhibitors, studying their action in environments with different salinities and at different temperatures. The conditions used in this work were chosen in order to reproduce oil field reality. The study of the micellization of these surfactants in the liquid-gas interface was carried out using surface tensiometry. It was observed that cmc increased as salt concentration was increased, and temperature and pH were decreased, while cmc decreased with the addition of two epoxy groups in the molecule. Using the values of cmc and the Gibbs equation, the values of Gibbs free energy of adsorption, area per adsorbed molecule, and surface excess were calculated. The surface excess increases as salt concentration and temperature decreases, increasing as pH is increased. The area per adsorbed molecule and the free energy of adsorption decrease with salt concentration, temperature, and pH increase. SAXS results showed that the addition of epoxy group in surfactant structure results in a decrease in the repulsion between the micelles, favoring the formation of more oblong micellar structures, ensuring a better efficiency of metal coverage. The increase in salt and surfactant concentrations provides an increase in micellar diameter. It was shown that the increase in temperature does not influence micellar structure, indicating thermal stability that is advantageous for use as corrosion inhibitor. The results of inhibition efficiency for the surfactants SEAR and SEAL were considered the best ones. Above cmc, adsorption occurred by the migration of micelles from the bulk of the solution to the metal surface, while at concentrations below cmc film formation must be due to the adsorption of semi-micellar and monomeric structures, certainly due to the presence of the epoxy group, which allows side interactions of the molecule with the metal surface. The metal resistance to corrosion presented values of 90% of efficiency. The application of Langmuir and Frumkin isotherms showed that the later gives a better description of adsorption because the model takes into account side interactions from the adsorbing molecules. Wettability results showed that micelle formation on the solid surface occurs at concentrations in the magnitude of 10-3 M, which isthe value found in the cmc study. This value also justifies the maximum efficiencies obtained for the measurements of corrosion resistance at this concentration. The values of contact angle as a function of time suggest that adsorption increases with time, due to the formation of micellar structures on metal surface

Caracterização e estudo da corrosão do amálgama dentário Dispersalloy por meio das técnicas de polarização potenciodinâmica e espectroscopia de impedância

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Synthesis, characterization and electropolymerization of a new polypyrrole iron(II) Schiff-base complex

This work presents the synthesis of the complex [Fe(L)(2)](PF6)(2) (.) H2O (L = 2,6-bis[1-(3-pyrrol-1-yl-propylimino)ethyl]pyridine (Fig. 1) and its characterization through elemental and thermal analysis, X-ray diffraction and UV-Vis, IR and H-1 NMR spectra. The use of this compound in the preparation of modified electrodes is also described. The best electrochemical parameters to achieve optimum film formation have been established and the effects of both the upper-limit of the applied scanning potential (E-aul) and the number of scans on the efficiency of film formation have been investigated. Film surface morphology has been characterized by atomic force microscopy. (C) 2004 Elsevier Ltd. All rights reserved.

Temporal evolution of sulfated zirconia sol-gel during dip coating: Analysis of mass drainage with time-varying refractive index

The formation of sulfated zirconia films from a sol-gel derived aqueous suspension is subjected to double-optical monitoring during batch dip coating. Interpretation of interferometric patterns, previously obscured by a variable refractive index, is now made possible by addition of its direct measurement by a polarimetric technique in real time. Significant sensitivity of the resulting physical thickness and refractive index curves (uncertainties of ±7 nm and ±0.005, respectively) to temporal film evolution is shown under different withdrawal speeds. As a first contribution to quantitative understanding of temporal film formation with varying nanostructure during dip coating, detailed analysis is directed to the stage of the process dominated by mass drainage, whose simple modeling with temporal t-1/2 dependence is verified experimentally. © 2006 Elsevier B.V. All rights reserved.

Produção de etanol a 40-42ºC em uma co-cultura de Saccharomyces cerevisiae e Issatchenkia orientalis

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Construção de filmes ultra finos de Bismarck Brown R por eletropolimerização e sua aplicação

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)