Corrosion of the component phases presents in high copper dental amalgams. Application of electrochemical impedance spectroscopy and electrochemical noise analysis

The corrosion resistance of three of the constituent phases in high copper dental amalgams has been investigated by electrochemical methods in 0.9% NaCl solution. Polarization curves show corrosion potentials most positive for gamma(1)-Ag2Hg3, followed by Ag-Cu, and gamma-Ag3Sn in agreement with the order of corrosion resistance deduced from the corrosion currents. Complex plane impedance plots at the open circuit potential showed distorted semicircles with diffusional components at low frequency for Ag-Hg and Ag-Cu, while for gamma-Ag3Sn a layer of corrosion products is formed, partially or completely covering the surface of the electrode. Impedance and noise spectra have been compared in the frequency domain, and show good agreement. (C) 2004 Elsevier Ltd. All rights reserved.

Electrochemical noise analysis of chalcopyrite carbon paste electrodes by Acidithiobacillus ferrooxidans

The electrochemical response of chalcopyrite was studied using electrochemical noise analysis (ENA). The assay was carried out under constant aeration using 30 mL in two electrochemical cells containing iron-free mineral salts solution. These cells were initially monitored for 56 hours, After 72 hours, 7.25x 10(10) cells mL(-1) of A, ferrooxidans strain LR were added in both cells and monitored until 128 h. Subsequent to this period, 0.927 mmol L-1 of silver ions and 400 mmol L-1 of chloride ions were added each one separately. Both conditions were monitored until 168 hours. According to results obtained, it was observed that Cl- ions addition induced an accelerated corrosion process. However, there is a tendency of the system to reach the stationary state due to repassivation of the electrodic surface. In the other side, the Ag+ addition contributed for the maintenance of the oxidant atmosphere, in spite of controversial effect caused by considerable variations in the R-n values, resulting in a instability in the chalcopyrite reactivity.

Electrochemical noise analysis of bioleaching of bornite (Cu5FeS4) by Acidithiobacillus ferrooxidans

Electrochemical noise (EN) is a generic term describing the phenomenon of spontaneous fluctuations of potential or current noise of electrochemical systems. Since this technique provides a non-destructive condition for investigating corrosion processes, it can be useful to study the electrochemical oxidation of mineral sulfides by microorganisms, a process known as bacterial leaching of metals. This technique was utilized to investigate the dissolution of a bornite electrode in the absence (first 79 h) and after the addition of Acidithiobacillus ferrooxidans (next 113 h) in salts mineral medium at pH 1.8, without addition of the energy source (Fe2+ ions) for this chemolithotrophic bacterium. Potential and current noise data have been determined simultaneously with two identical working bornite electrodes which were linked by a zero resistance ammeter (ZRA). The mean potential, E-coup, coupling current, I-coup, standard deviations of potential and current noise fluctuations and noise resistance, R-n, have been obtained for coupled bornite electrodes. Noise measurements were recorded twice a day in an unstirred solution at 30 degrees C. Significant changes in these parameters were observed when the A. ferrooxidans suspension was added, related with bacterial activity on reduced species present in the sulfide moisture (Fe2+, S2-). ENA was a suitable tool for monitoring the changes of the corrosion behavior of bornite due to the presence of bacterium. (C) 2006 Elsevier B.V. All rights reserved.

The effect of chloride ions and A. ferrooxidans on the oxidative dissolution of the chalcopyrite evaluated by electrochemical noise analysis (ENA)

It is believed that the dissolution of chalcopyrite (CuFeS2) in acid medium can be accelerated by the addition of Cl- ions, which modify the electrochemical reactions in the leaching system. Electrochemical noise analysis (ENA) was utilized to evaluate the effect of the Cl- ions and Acidithiobacillus ferrooxidans on the oxidative dissolution of a CPE-chalcopyrite (carbon paste electrode modified with chalcopyrite) in acid medium. The emphasis was on the analysis of the admittance plots (Ac) calculated by ENA. In general, a stable passive behavior was observed, mainly during the initial stages of CPE-chalcopyrite immersion, characterized by a low passive current and a low dispersion of the Ac plots, mainly after bacteria addition. This can be explained by the adhesion of bacterial cells on the CPE-chalcopyrite surface acting as a physical barrier. The greater dispersions in the Ac plots occurred immediately after the Cl- ions addition, in the absence of bacteria characterizing an active-state. In the presence of bacteria the addition of Clions only produced some effect after some time due to the barrier effect caused by bacteria adhesion. © (2009) Trans Tech Publications.

Um esquema de Fourier local para análise tempo-frequência de sinais não-estacionários aplicado a ruído eletroquímico

Sinais diversos estão presentes em nosso cotidiano, assim como nas medidas realizadas nas atividades de ciência e tecnologia. Dentre estes sinais, tem grande importância tecnológica aqueles associados à corrosão de estruturas metálicas. Assim, esta tese propõe o estudo de um esquema local de transformada de Fourier janelada, com a janela variando em função da curtose, aplicada a sinais de ruído eletroquímico. A curtose foi avaliada nos domínios do tempo e da frequência e processada pelo programa desenvolvido para esse fim. O esquema foi aplicado a sinais de ruído eletroquímico dos aços UNS S31600, UNS G10200 e UNS S32750 imersos em três soluções: FeCl3 0,1 mol=L (cloreto férrico), H2SO4 5%(ácido sulfúrico) e NaOH 0,1%(hidróxido de sódio). Para os aços inoxidáveis, estas soluções promovem corrosão localizada, uniforme e passivação, respectivamente. Visando testar o desempenho do esquema de Fourier desenvolvido, testes foram realizados utilizando-se inicialmente sinais sintéticos e em seguida sinais de ruído eletroquímico. Notou-se que os sinais têm características de não-estacionaridade e a maior parte da energia está presente em baixa frequência. Os intervalos de tempo e de frequência onde se concentra a maior parte da energia do sinal foram correlacionados. Para os picos máximos dos sinais de potencial e corrente obtidos de amperimetria de resistência nula, a correlação entre eles foi baixa, independente da forma de corrosão presente. Conclui-se que o método se adaptou bastante bem às características locais do sinal eletroquímico permitindo o monitoramento dos espectros tempo-frequência. O fato de ser sensível às características locais do sinal permite analisar aspectos dos sinais que do modo clássico não podem ser diretamente processados. O método da transformada de Fourier janelada variável (Variable Short-Time Fourier Transform - VSTFT) adaptou-se muito bem no monitoramento dos sinais originados de potencial de circuito aberto e amperimetria de resistência nula.

Análise de componentes principais aplicada a ruído eletroquímico

Neste trabalho foi utilizado um método matemático para classificar registros de potencial e corrente de ensaios de corrosão na técnica de amperimetria de resistência nula (ZRA). Foi aplicado o método estatístico de múltiplas variáveis simples chamado Análise dos Componentes Principais (PCA), cujo objetivo principal foi identificar padrões nestes dados de ruído eletroquímico. Foram testados o aço carbono UNS G10200, os aços inoxidáveis austenítico UNS S31600 e o superduplex UNS S32750 em meios de ácido sulfúrico (5% H2SO4), cloreto férrico (0,1 mol/L FeCl3) e hidróxido de sódio (0,1% NaOH). Os ensaios foram replicados com oito repetições para se ter reprodutibilidade e conhecimento dos aspectos estatísticos envolvidos. Os resultados mostraram que a análise de componentes principais pode ser utilizada como uma ferramenta para analisar sinais de ruído eletroquímico, identificando os clusters dos comportamentos potencial-tempo, corrente-tempo e acessoriamente identificar os outliersdos registros temporais.

Effective discrimination of acoustic emission source signals for structural health monitoring

Acoustic emission (AE) is the phenomenon where stress waves are generated due to rapid release of energy within a material caused by sources such as crack initiation or growth. AE technique involves recording the stress waves by means of sensors and subsequent analysis of the recorded signals to gather information about the nature of the source. Though AE technique is one of the popular non destructive evaluation (NDE) techniques for structural health monitoring of mechanical, aerospace and civil structures; several challenges still exist in successful application of this technique. Presence of spurious noise signals can mask genuine damage‐related AE signals; hence a major challenge identified is finding ways to discriminate signals from different sources. Analysis of parameters of recorded AE signals, comparison of amplitudes of AE wave modes and investigation of uniqueness of recorded AE signals have been mentioned as possible criteria for source differentiation. This paper reviews common approaches currently in use for source discrimination, particularly focusing on structural health monitoring of civil engineering structural components such as beams; and further investigates the applications of some of these methods by analyzing AE data from laboratory tests.

Monitoring pitting-crevice corrosion using the WBE-noise signatures method

An electrochemically integrated multi-electrode array namely the wire beam electrode (WBE) and noise signatures analysis have been applied in novel combinations to study crevice corrosion behaviour in the presence of pits. Characteristic electrochemical noise signatures were found to correlate with characteristic changes in WBE current distribution maps, which indicate corrosion rates distributions, corrosion patterns and the degree of pitting and crevice corrosion. Specifically, two characteristic noise patterns were observed: (i) the characteristic noise pattern of quick potential changes towards more negative direction with no recovery (termed noise signature I) was found to correspond with the initiation and stabilization of the anode inside crevice; and (ii) the characteristic noise pattern of the cyclic potential oscillation at a constant frequency (termed noise signature II) was found to correspond with the stable anodic dissolution in the occluded cavity site in WBE current distribution maps. A new parameter namely the localization parameter (LP) has been proposed to describe the degree of localization. The LP for crevice corrosion was found to be low compared to that for pitting corrosion.