Electrochemical investigations of micro-droplets formed on metals during the deliquescence of salt particles in atmosphere

CORROSION; WATER; SPECTROSCOPY; CHLORIDE; ZINC; NUCLEATION; INTERFACE; ELECTRODE; SURFACES; GROWTH

Electrochemical impedance spectroscopy characterization of passive film formed on implant Ti-6Al-7Nb alloy in Hank's solution

The influence of potential on electrochemical behavior of Ti-6Al-7Nb alloy under simulate physiological conditions was investigated by electrochemical impedance spectroscopy (EIS). The experimental results were compared with those obtained by potentiodynamic polarization curves. All measurements were carried out in Hank's aerated solution at 25degreesC, at pH 7.8 and at different potentials (corrosion potential, 0 mV(SCE), 1000 mV(SCE), and 2000 mV(SCE)). The EIS spectra exhibited a two-step or a two-time constant system, suggesting the formation of a two-layer oxide film on the metal surface. The high corrosion resistance, displayed by this alloy in electrochemical polarization tests, is due to the dense inner layer, while its osseointegration ability can be ascribed to the presence of the outer porous layer. (C) 2004 Kluwer Academic Publishers.

Corrosion studies on the plasma-sprayed nanostructured titanium dioxide coating

Purpose: The purpose of this paper is to report the resistance of plasma-sprayed titanium dioxide (TiO2) nanostructured coatings in a corrosive environment.----- Design/methodology/approach: Weight loss studies are performed according to ASTM G31 specifications in 3.5?wt% NaCl. Electrochemical polarization resistance measurements are made according to ASTM G59-91 specifications. Corrosion resistance in a humid and corrosive environment is determined by exposing the samples in a salt spray chamber for 100?h. Microstructural studies are carried out using an atomic force microscope and scanning electron microscope.----- Findings: The nanostructured TiO2 coatings offer good resistance to corrosion, as shown by the results of immersion, electrochemical and salt spray studies. The corrosion resistance of the coating is dictated primarily by the geometry of splat lamellae, density of unmelted nanoparticles, magnitude of porosity and surface homogeneity.----- Practical implications: The TiO2 nanostructured coatings show promising potential for use as abrasion, wear-resistant and thermal barrier coatings for service in harsh environments.----- Originality/value: The paper relates the corrosion resistance of nanostructured TiO2 coatings to their structure and surface morphology.

Adhesion,Presence and Antifouling of Deinococcus geothermalis in Paper Machine Environment

This thesis has two items: biofouling and antifouling in paper industry. Biofouling means unwanted microbial accumulation on surfaces causing e.g. disturbances in industrial processes, contamination of medical devices or of water distribution networks. Antifouling focuses on preventing accumulation of the biofilms in undesired places. Deinococcus geothermalis is a pink-pigmented, thermophilic bacterium, and extremely resistant towards radiation, UV-light and desiccation and known as a biofouler of paper machines forming firm and biocide resistant biofilms on the stainless steel surfaces. The compact structure of biofilm microcolonies of D. geothermalis E50051 and the adhesion into abiotic surfaces were investigated by confocal laser scanning microscope combined with carbohydrate specific fluorescently labelled lectins. The extracellular polymeric substance in D. geothermalis microcolonies was found to be a composite of at least five different glycoconjugates contributing to adhesion, functioning as structural elements, putative storages for water, gliding motility and likely also to protection. The adhesion threads that D. geothermalis seems to use to adhere on an abiotic surface and to anchor itself to the neighbouring cells were shown to be protein. Four protein components of type IV pilin were identified. In addition, the lectin staining showed that the adhesion threads were covered with galactose containing glycoconjugates. The threads were not exposed on planktic cells indicating their primary role in adhesion and in biofilm formation. I investigated by quantitative real-time PCR the presence of D. geothermalis in biofilms, deposits, process waters and paper end products from 24 paper and board mills. The primers designed for doing this were targeted to the 16S rRNA gene of D. geothermalis. We found D. geothermalis DNA from 9 machines, in total 16 samples of the 120 mill samples searched for. The total bacterial content varied in those samples between 107 to 3 ×1010 16S rRNA gene copies g-1. The proportion of D. geothermalis in those same samples was minor, 0.03 1.3 % of the total bacterial content. Nevertheless D. geothermalis may endanger paper quality as its DNA was shown in an end product. As an antifouling method towards biofilms we studied the electrochemical polarization. Two novel instruments were designed for this work. The double biofilm analyzer was designed for search for a polarization program that would eradicate D. geothermalis biofilm or from stainless steel under conditions simulating paper mill environment. The Radbox instrument was designed to study the generation of reactive oxygen species during the polarization that was effective in antifouling of D. geothermalis. We found that cathodic character and a pulsed mode of polarization were required to achieve detaching D. geothermalis biofilm from stainless steel. We also found that the efficiency of polarization was good on submerged, and poor on splash area biofilms. By adding oxidative biocides, bromochloro-5,5-dimethylhydantoin, 2,2-dibromo-2-cyanodiacetamide or peracetic acid gave additive value with polarization, being active on splash area biofilms. We showed that the cathodically weighted pulsed polarization that was active in removing D. geothermalis was also effective in generation of reactive oxygen species. It is possible that the antifouling effect relied on the generation of ROS on the polarized steel surfaces. Antifouling method successful towards D. geothermalis that is a tenacious biofouler and possesses a high tolerance to oxidative stressors could be functional also towards other biofoulers and applicable in wet industrial processes elsewhere.

Desenvolvimento de revestimentos de óxidos mistos nanoestruturados de TiO2/Al2O3 em substratos metálicos de aço AISI 1020 e estudo das propriedades anticorrosivas

Sóis liofilizados precursores de Al2O3/TiO2, foram preparados via tecnologia sol-gel, com diferentes porcentagens de óxido de titânio (5%, 10%, 15% e 20%, em massa). Os sóis liofilizados foram caracterizados por meio de diversas análises, com o intuito de obter informações sobre o comportamento térmico, fases presentes, tamanho de partícula, composição e uniformidade das amostras. Os resultados obtidos indicam que os sóis apresentam as fases boemita e anatase, com partículas de tamanho nanométrico, tem composições muito similares quando analisadas em pontos distintos, átomos bem dispersos e distribuídos. Após esta etapa, amostras de aço AISI 1020 foram recobertas com estes sóis através do método dip-coating, o comportamento corrosivo foi estudado por meio de ensaios eletroquímicos e a morfologia das camadas, analisadas por meio de microscopias. Observou-se que as camadas eram uniformes e recobriam por completo toda a superfície das amostras, os ensaios de polarização indicaram melhorias no potencial eletroquímico para amostras recobertas, em comparação com amostras de aço sem recobrimento. O monitoramento de circuito aberto apresentou bons ajustes, indicando bom comportamento da camada. Notou-se pelas microscopias a presença de pontos de corrosão em algumas amostras antes dos ensaios, suspeitando-se que os resultados obtidos teriam sido melhores, caso houvesse um maior controle do processo de recobrimento.

Effect of yttrium-rich misch metal on the microstructures, mechanical properties and corrosion behavior of die cast AZ91 alloy

Die cast AZ91-xYmm (x = 0-0.8 wt.%) magnesium alloys with excellent tensile properties and corrosion resistance behavior were successfully prepared by a simple addition of yttrium-rich misch metal (Ymm) to AZ91. Influences of Ymm on the microstructure, mechanical properties and corrosion behavior of AZ91 were investigated. The results showed that addition of Ymm to die cast AZ91 alloy could re. ne the microstructure including primary alpha-Mg and eutectic beta-Mg17Al12. When the content of Ymm reached 0.8 wt.% a small quantity of Al2Y phase would form. The tensile properties were improved greatly with addition of Ymm to AZ91. The creep rate of the AZ91-Ymm alloys, tested at 150 degrees C/50MPa, was one order of magnitude lower than that of AZ91. When addition of Ymm was more than 0.3 wt.%, the salt-spray corrosion resistance of AZ91-Ymm alloys could be 30-40 times of that of AZ91. The improvement of corrosion resistance with addition of Ymm was confirmed by the results of electrochemical polarization experiments. Mechanism of the improvement of mechanical properties and corrosion behavior caused by Ymm was also discussed.

THE USE OF CHEMICALLY MODIFIED ELECTRODES FOR LIQUID-CHROMATOGRAPHY AND FLOW-INJECTION ANALYSIS

The use of chemically modified electrodes (CMEs) for liquid chromatography and flow-injection analysis is reviewed. Electrochemical detection with CMEs based on electrocatalysis, permselectivity, ion flow in redox films, and ion transfer across the water-solidified nitrobenzene interface is discussed in terms of improving the stability, selectivity, and scope of electrochemical detectors, and the detection of electroinactive substances. More than 90 references are included.

铜管不锈钢管腐蚀性能及铁牺牲阳极保护研究

铜管一直是电厂凝汽器的主要应用管材，但由于其抗冲刷和抵御污染物腐蚀的能力差，特别不耐氨蚀，美国和欧洲大量使用不锈钢管替代铜管作为冷凝管，然而不锈钢管在我国的运用仅处于初步阶段。 常使用锌、铝阳极对铜管进行牺牲阳极保护，然而存在着电位差过大、阳极溶解过快的问题。铁基牺牲阳极与铜电位差适当、来源广泛、价格便宜，在一些工程上有所应用，但是目前针对铁基牺牲阳极的理论研究报道很少。 本文选用紫铜管、304不锈钢管作为实验用管材，首先运用实验室全浸实验、极化曲线和电化学阻抗研究了二者在海水和淡水中的腐蚀性能以及CO2、溶解氧对其腐蚀的影响。结果表明：CO2会加速二者的腐蚀，溶解氧却对它们的腐蚀影响不同，促进铜管的腐蚀却抑制不锈钢管的腐蚀；随浸泡时间的延长，紫铜管由于表面产物膜的生成耐蚀性提高，304不锈钢管的耐蚀性却降低；淡水中，304不锈钢管和紫铜管都具有很好的耐蚀性能。随后，运用失重法和极化曲线对比研究了紫铜管、304不锈钢管的氨蚀性能，运用SEM分析和电化学阻抗研究了紫铜在不同浓度氨溶液中的腐蚀机理。发现，304不锈钢管的耐氨蚀能力远远好于铜管；溶解氧是影响氨蚀的关键因素，其对二者氨蚀的影响也不同；紫铜管在低氨浓度和高氨浓度溶液中腐蚀机理和产物不同，低氨浓度时形成保护性的产物膜（CuO 和Cu(OH)2），高氨浓度时由活化溶解控制，生成可溶的[Cu (NH3)4]2+。 选用工业纯铁、35钢为牺牲阳极材料。恒电流实验结果表明它们具有良好的牺牲阳极性能；通过极化曲线和自腐蚀电位测试分析，认为将二者用于铜管牺牲阳极保护是可行的；实验室阴极保护效果测试表明，工业纯铁和35钢对紫铜管具有良好的保护效果，保护度达90%以上。

Estudo do biomaterial Ti-6Al-4V empregando-se técnicas eletroquímicas e XPS

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

Construção de uma célula-autoclave para medidas eletroquímicas a altas temperaturas

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

Desenvolvimento de uma nova liga quaternária Ti25Ta25Nb3Sn para aplicações odontológicas

Pós-graduação em Engenharia Mecânica - FEG

Polarization Characteristics of Porous Electrode Systems with Adsorbed Intermediates Participating in the Electrode Reaction

Current-potential relationships are derived for porous electrode systems following a homogeneous model and whenadsorbed intermediates participate in the electrode reaction. Limiting Tafel slopes were deduced and compared with thecorresponding behavior on planar electrode systems. The theoretical results showed doubling of Tafel slopes when theslow-step is a charge-transfer reaction and a nonlogarithmic current-voltage behavior when the slow-step is a chemical reaction.Comparison of the experimental results with theory for the case of oxygen reduction on carbon surfaces in alkalinemedia indicates that a slow chemical reaction following the initial charge-transfer reaction to be the likely rate-controllingstep. Theoretical relationships are utilized to determine the exchange current density and the surface coverage by the adsorbedintermediates during the course of oxygen reduction from alkaline solutions on "carbon." Tafel slope measurementson planar and porous electrodes for the same reaction are suggested as one of the diagnostic criteria for elucidatingthe mechanistic pathways of electrochemical reactions.

Electrochemical aspects of leaching of ocean nodules in the presence and absence of microorganisms

instead of using chemical-reducing agents to facilitate the reduction and dissolution of manganese and iron oxide in the ocean nodule, electrochemical reduction based on two approaches, namely, cathodic polarization and galvanic interaction, can also be considered as attractive alternatives. Galvanic leaching of ocean nodules in the presence of pyrite and pyrolusite for complete recovery of Cu, Ni and Co has been discussed. The key for successful and efficient dissolution of copper, nickel and cobalt from ocean nodules depends on prior reduction of the manganese and ferric oxides with which the above valuable nonferrous metals are interlocked. Polarization studies using a slurry electrode system indicated that maximum dissolution of iron and manganese due to electrochemical reduction occurred at negative DC potentials of -600 mV (SCE) and -1400 mV (SCE). The present work is also relevant to galvanic bioleaching of ocean nodules using autotrophic microorganisms, such as Thiobacillus ferrooxidans and T thiooxidans, which resulted in significant dissolution of copper, nickel and cobalt at the expense of microbiologically generated acids. Various electrochemical and biochemical mechanisms are outlined and the electroleaching and galvanic processes so developed are shown to yield almost complete dissolution of all metal values. (C) 2002 Elsevier Science B.V. All rights reserved.

Electrochemical processing of ocean manganese nodules with microbial enhancement to recover valuable metals

In this paper, electroleaching and electrobioleaching of ocean manganese nodules are discussed along with the role of galvanic interactions in bioleaching. Polarization studies using a manganese nodule slurry electrode system indicated that the maximum dissolution of iron and manganese due to electrochemical reduction occurred at negative DC potentials of -600 and -1,400 mV(SCE). Electroleaching and electrobioleaching of ocean manganese nodules in the presence of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans at the above negative applied DC potentials resulted insignificant dissolution of copper, nickel and cobalt in 1 M H2SO4 and in sulfuric acid solution at pH 0.5 and 2.0. Mechanisms involved in electrobioleaching of ocean manganese nodules are discussed. Galvanic leaching of ocean manganese nodules in the presence of externally added pyrite and pyrolusite for enhancement of dissolution was also studied. Various electrochemical and biochemical parameters were optimized, and the electroleaching and galvanic processes thus developed are shown to yield almost complete dissolution of all metal values. This electrobioleaching process developed in the laboratory may be cost effective, energy efficient and environmentally friendly.

Electrochemical oxidation of boron containing compounds on titanium carbide and its implications to direct fuel cells

Electrochemical oxidation of sodium borohydride (NaBH(4)) and ammonia borane (NH(3)BH(3)) (AB) have been studied on titanium carbide electrode. The oxidation is followed by using cyclic voltammetry, chronoamperometry and polarization measurements. A fuel cell with TiC as anode and 40 wt% Pt/C as cathode is constructed and the polarization behaviour is studied with NaBH(4) as anodic fuel and hydrogen peroxide as catholyte. A maximum power density of 65 mW cm(-2) at a load current density of 83 mA cm(-2) is obtained at 343 K in the case of borhydride-based fuel cell and a value of 85 mW cm(-2) at 105 mA cm(-2) is obtained in the case of AB-based fuel cell at 353 K. (C) 2011 Elsevier Ltd. All rights reserved.