SVET, SKP and EIS study of the corrosion behaviour of high strength Al and Al-Li alloys used in aircraft fabrication

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Influência da temperatura e do pH do meio sobre a resistência à corrosão das ligas Al(20204-T3), Al(7010-T7) e Al(7050-T7) utilizadas na indústria aeronáutica

Pós-graduação em Engenharia Mecânica - FEG

Estudo da corrosão em ligas de alumínio utilizadas na indústria aeronáutica

A resistência e o mecanismo de corrosão das ligas de alumínio 2024, 7010, 7050 e 7475 foram estudados em solução de NaCl. Os efeitos do tratamento térmico nas ligas, concentração de oxigênio, pH, adição de oxi-ânions e temperatura do meio constituem algumas das variáveis estudadas. Primeiramente, procedeu-se à caracterização físicoquímica dos materiais através de análise química e metalográfica, mediante microscopia eletrônica de varredura e espectroscopia de energia dispersiva. As ligas 2024, 7010, 7050 e 7475 como recebidas, recozidas e envelhecidas, revelaram a existência de partículas ternárias e quaternárias, constituídas por Al:Cu:Fe e Mg ou Zn. Também foi observado um maior número de partículas pequenas de composição variável situando-se, preferencialmente, nos contornos dos grãos. Os resultados dos ensaios de corrosão em meios aerados e desaerados indicam que o cromato é efetivo como inibidor da corrosão localizada em ambas ligas e que o molibdato somente na liga 7050. O efeito inibidor do tungstato se revela em meio desaerado e é comparativamente menor daquele observado com os outros oxi-ânions. As análises quantitativas de superfície das ligas após os ensaios de imersão indicam que ainda na presença de inibidor, se pites foram nucleados, eles crescem.

Análise de corrosão, dureza e fratura de conjuntos implantes / componentes protético de Titânio c.p., após serem submetidos a ciclos de fadiga em um meio fluoretado com diferentes PH

Atualmente o titânio é empregado como biomaterial devido à sua biocompatibilidade e resistência à corrosão. Entretanto, íons fluoretos, freqüentemente empregados em dentifrícios bucais, podem interferir no processo de corrosão. O objetivo deste estudo foi analisar a influência de um meio fluoretado com diferentes pH nas propriedades mecânicas e na resistência à corrosão dos conjuntos implantes/componentes protéticos à base de Ti c.p., a partir dos testes de fadiga, microscopia eletrônica de varredura (MEV) e dureza. Foram simulados cinco anos de uso regular de meios de higiene oral com conteúdo de 1500 ppm de NaF, com dois diferentes pH, 7,4 e 5,3, mediante imersão das amostras nesses meios durante 184 horas e também em água destilada, grupo controle. As amostras foram testadas num durômetro Micromet 2001 (500gf/30s). Os dados dos testes de dureza foram analisados pelo teste de Wilcoxon, demonstrando que as amostras sofreram influência negativa na dureza após a ação dos íons fluoreto. Entretanto, essa influência não ocorreu nos testes de fadiga realizados em uma máquina de ensaios mecânicos MTS-810, fixada a 100.000 ciclos, 15Hz e programada com força de fadiga a 150 N. Pela análise de MEV foram constatadas evidências de corrosão na superfície das amostras após ação de íons fluoretos, entretanto pelo EDS não se verificou incorporação de íons fluoretos sobre a superfície dos conjuntos. Concluiu-se que a concentração de flúor e o pH das soluções não exerceram influência nas propriedades mecânicas.

Protective film growth on tin in perchlorate and citric acid electrolytes

Voltammetry has been employed to study the influence of systematic additions of citric acid on the E-I curves of Tin in 0.5 M NaClO4, in order to verify the film growth in the presence of the organic acid and the inhibition of the pitting corrosion of the metal. The minimum concentration of the organic acid needed to change the GI curves is 10(-2) M, in the pH range 1.0-4.0. At pH 3.0 and 4.0, the scan rate dependence on current density, in the potential region of formation and reduction of the film, showed that in a first stage adsorption occurs. In a second stage, the v(1/2) dependence found can he explained by ohmic resistance control. The formation of tin/citric acid complexes, 10(-2) M, is suggested. The pitting inhibition may be due to the formation of a mixed layer of tin in citric acid concentrations higher than 10(-2) oxide and tin citrate complexes on the electrode surface. (C) 2001 Elsevier Science B.V. All rights reserved.

Expressão, purificação e caracterização de proteínas dos fitovírus SBMV e RSPaV

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

How do titanium and Ti6A14V corrode in fluoridated medium as found in the oral cavity? an in vitro study

The purpose of this work was to evaluate the corrosion of commercially pure (CP) titanium and Ti6Al4V in vitro at different F- concentrations regularly found in the oral cavity by using different electrochemical tests and surface analysis techniques. electrochemical impedance spectroscopy (EIS), open circuit potential (OCP) and potentio-dynamic polarization tests were associated to advanced characterization techniques such as SEM, EDS, AFM, ICP-MS and XPS. OCP tests revealed a higher reactivity of both CP titanium and Ti6Al4V at 12,300 ppm F- concentration than that recorded at 227 ppm F-. Also, a significant decrease of the corrosion resistance of both materials was noticed by EIS in fluoride solutions. Material loss caused by corrosion was noticed on titanium surfaces by SEM and AFM in the presence of high F- concentration. CP titanium degraded by pitting corrosion while Ti6Al4V suffered from general corrosion showing micro-cracks on surface. Furthermore, a high release of metallic ions from the test samples after immersion at high F concentrations was detected by ICP-MS, that can be potentially toxic to oral tissues. (C) 2014 Elsevier B.V. All rights reserved.

Electrochemical behavior and corrosion resistance of Ti-15Mo alloy in naturally-aerated solutions, containing chloride and fluoride ions

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Electrochemical studies of copper, copper-aluminium and copper-aluminium-silver alloys: Impedance results in 0.5M NaCl

The electrochemical behaviour of Cu, Cu-Al and Cu-Al-Ag alloys in aqueous solutions of NaCl (0.5 M, pH = 3.00) was studied by means of voltammetric methods and electrochemical impedance spectroscopy. The surfaces were examined by SEM and EDX analysis. Cu-Al-Ag alloy shows a potentiodynamic behaviour similar to that of the pure copper electrode while the Cu-Al alloy presents some minor differences. In the active dissolution region the electrodes suffer pitting corrosion and in the other potential regions there are the formation of a passivant film with composition depending on the potential. The impedance responses of the electrodes are discussed. An electrodissolution mechanism is proposed and the effect of the alloying elements upon the impedance response and polarisation curves is explained. The main effects are due to the production of copper and silver chlorides and aluminium oxides/ hydroxides at the corroding interface. The addition of Al or (Al + Ag) increases the corrosion resistance of pure copper. © 1995.

The role of nicotine, cotinine and caffeine on the electrochemical behavior and bacterial colonization to cp-Ti

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

Investigação de técnicas para o acompanhamento do desgaste de um par engrenado utilizando tribologia e análise da resposta dinâmica processada via função densidade probabilidade Beta

Pós-graduação em Engenharia Mecânica - FEIS

Corrosion protection of aluminium alloy by cerium conversion and conducting polymer duplex coatings

The corrosion protection of AA6063 aluminium alloy by cerium conversion, polyaniline conducting polymer and by duplex coatings has been investigated. The electrochemical behaviour was evaluated in aerated 3.5 wt.% NaCl. All coatings tested shifted the corrosion and pitting potentials to more positive values, indicating protection against corrosion. The duplex coatings are significantly more effective than each coating alone: corrosion and pitting potentials were shifted by +183 and +417 mV(SCE), respectively, by duplex coatings in relation to the untreated aluminium alloy. Optical microscopy and scanning electron microscopy are in agreement with the electrochemical results, reinforcing the superior performance of duplex coatings. (C) 2012 Elsevier Ltd. All rights reserved.

Influence of normal and radial contributions of local current density on local electrochemical impedance spectroscopy

A new tri-electrode probe is presented and applied to local electrochemical impedance spectroscopy (LEIS) measurements. As opposed to two-probe systems, the three-probe one allows measurement not only of normal, but also of radial contributions of local current densities to the local impedance values. The results concerning the cases of the blocking electrode and the electrode with faradaic reaction are discussed from the theoretical point of view for a disk electrode. Numerical simulations and experimental results are compared for the case of the ferri/ferrocyanide electrode reaction at the Pt working electrode disk. At the centre of the disk, the impedance taking into account both normal and radial contributions was in good agreement with the local impedance measured in terms of only the normal contribution. At the periphery of the electrode, the impedance taking into account both normal and radial contributions differed significantly from the local impedance measured in terms of only the normal contribution. The radial impedance results at the periphery of the electrode are in good agreement with the usual explanation that the associated larger current density is attributed to the geometry of the electrode, which exhibits a greater accessibility at the electrode edge. (C) 2011 Elsevier Ltd. All rights reserved.

Local electrochemical investigation of copper patina

The patination of copper is known for its complexity and heterogeneous formation. For a deeper investigation, a locally resolved surface analysis was considered. An exact determination of the accessed area and a potentiostatic control in a three-electrode configuration was reached with the use of the electrochemical microcell technique, which enables local electrochemical measurement such as local electrochemical impedance spectroscopy and cyclic voltammetry. Such a technique provides a unique way for performing the investigation of heterogeneities on electrode surfaces. The local electrochemical measurements on the artificially patinated surface have allowed distinguishing areas of different reactivity even when the analysis of the surface revealed a homogenous chemical composition of patina. Local measurements with the electrochemical microcell showed the presence of small defects on the patina layer that can be modelled by considering a hemispherical diffusion process at small active areas surrounded by larger less reactive domains.

On the degradation mechanisms under the influence of pedological factors through the study of archeological bronze patina

This experimental thesis concerns the study of the long-term behaviour of ancient bronzes recently excavated from burial conditions. The scientific interest is to clarify the effect of soil parameters on the degradation mechanisms of ancient bronze alloy. The work took into consideration bronzes recovered from the archaeological sites in the region of Dobrudja, Romania. The first part of research work was dedicated to the characterization of bronze artefacts using non destructive (micro-FTIR, reflectance mode) and micro-destructive (based on sampling and analysis of a stratigraphical section by OM and SEM-EDX) methods. Burial soils were geologically classified and analyzed by chemical methods (pH, conductivity, anions content). Most of objects analyzed showed a coarse and inhomogeneous corroded structure, often made up of several corrosion layers. This has been explained by the silt nature of soils, which contain low amount of clay and are, therefore, quite accessible to water and air. The main cause of a high dissolution rate of bronze alloys is the alternate water saturation and instauration of the soil, for example on a seasonal scale. Moreover, due to the vicinity of the Black Sea, the detrimental effect of chlorine has been evidenced for few objects, which were affected by the bronze disease. A general classification of corrosion layers was achieved by comparing values of the ratio Cu/Sn in the alloy and in the patina. Decuprification is a general trend, and enrichment of copper within the corrosion layers, due to the formation of thick layers of cuprite (Cu2O), is pointed out as well. Uncommon corrosion products and degradation patterns were presented as well, and they are probably due to peculiar local conditions taking place during the burial time, such as anaerobic conditions or fluctuating environmental conditions. In order to acquire a better insight into the corrosion mechanisms, the second part of the thesis has regarded simulation experiments, which were conducted on commercial Cu-Sn alloys, whose composition resembles those of ancient artefacts one. Electrochemical measurements were conducted in natural electrolytes, such as solutions extracted from natural soil (sampled at the archaeological sites) and seawater. Cyclic potentiodynamic experiments allowed appreciating the mechanism of corrosion in both cases. Soil extract’s electrolyte has been evaluated being a non aggressive medium, while artificial solution prepared by increasing the concentration of anions caused the pitting corrosion of the alloy, which is demonstrated by optical observations. In particular, electrochemical impedance spectroscopy allows assessing qualitatively the nature of corroded structures formed in soil and seawater. A double-structured layer is proposed, which differ, in the two cases, for the nature of the internal passive layer, which result defectiveness and porous in case of seawater.