Estudo de Eletrodeposição de Ligas Cu-Sn em Meio de Citrato de Sódio

Revestimentos produzidos a partir de ligas de Cu-Sn apresentam grande interesse em função de suas propriedades, originando uma grande capacidade de aplicação industrial, especialmente em indústrias de componentes e materiais eletrônicos. Tais ligas também têm sido comercialmente utilizadas como revestimentos em metais diferentes, como o aço, para protegê-los contra a corrosão e melhorar sua aparência. Na presente dissertação, técnicas de voltametria cíclica, cronoamperometria e voltametria de varredura anódica linear foram utilizadas para o estudo dos processos de deposição de Cu e/ou Sn a partir de dois conjuntos de soluções contendo CuCl2.2H2O e SnCl2.2H2O nas razões de Cu:Sn = 1:10 e 10:1, além de Na3C6H5O7 1,00 mol/L, em pH = 6,0. As curvas de voltametria cíclica realizadas sobre o eletrodo de grafita foram utilizadas para o cálculo das constantes de equilíbrio dos complexos de ambos os metais com citrato de sódio, bem como na determinação dos potenciais catódicos aplicados nos ensaios de cronoamperometria. Após a deposição da liga nos potenciais estipulados para cada uma das duas soluções, os revestimentos de liga Cu-Sn foram ressolubilizados em solução de NaNO3 0,5 mol/L, empregando varredura anódica linear para a avaliação de suas composições químicas. Os resultados iniciais mostraram que a variação da concentração de Cu (II) e do potencial aplicado influenciaram no teor de cobre na liga. Contudo, percebeu-se que o teor de estanho não sofreu grandes variações, independente das concentrações das soluções e do potencial aplicado. Na solução com maior concentração de cobre foram alcançados teores dos metais na liga em maior proximidade com o da liga de bronze comercial. Com base nesses resultados, foram produzidos revestimentos de ligas sobre substrato de aço carbono, a partir de soluções contendo CuCl2.2H2O e SnCl2.2H2O na razão de 10:1, empregando a técnica de cronoamperometria potenciostática. Quatro diferentes valores de potencial (-0,39V, -0,67V, -1,00V, -1,20V e -1,94V vs. Ag/AgClsat.) foram aplicados, obtendo-se camadas cujas colorações variaram do rosa claro ao marrom escuro, sempre sem brilho. A eficiência de corrente catódica (Ef) decresceu conforme o potencial aplicado se tornou mais negativo. Nesta mesma direção, verificou-se um aumento do teor de estanho na liga depositada e menores tamanhos de grão. Porém, quando o potencial tornou-se mais negativo (-1,20V e -1,94V), observou-se a presença de cristalitos de diferentes tamanhos e de dendritos. Revestimentos com melhores resistências à corrosão em solução de NaCl 0,5 mol/L foram produzidos nos potenciais de -1,00V e -1,20V, cujas composições foram 99,40 % m/m Cu / 0,60 % m/m Sn e 97,70 % m/m Cu / 2,30 % m/m Sn, respectivamente. As análises por DRX permitiram verificar que estes revestimentos eram constituídos, principalmente, da fase α-CuSn

Análise tribológica na interface aço carbono SAE 1020 e poliamida 11 em sistemas de deslizamento automotivos

Sistemas deslizantes com interface formada com aços baixa liga e polímeros variados são vastamente utilizados na indústria automotiva em sistemas de transmissão de torque submetidas à carregamento axial. Geralmente esses sistemas são acoplados aos sistemas de direção e interagem quase diretamente com o usuário final do veículo. Para conhecer as condições de desgaste mais severas as quais esses sistemas são submetidos e tentar minimiza-las, foi proposta a análise tribológica, em tribômetro do tipo pino-no-disco, da interface aço SAE 1020 com poliamida 11 em água destilada, solução aquosa com 5% em massa de cloreto de sódio e solução aquosa com 184,21 g/l. de areia natural, de acordo com as normas técnicas automotivas VW PV1210:2010-02 e VW PV2982:2013-07. Os ensaios foram realizados em frequências de 3,0 Hz e 1,5 Hz com quantidade fixada em 10.000 ciclos de rotação. O potencial de corrosão em circuito aberto foi monitorado ao longo dos ensaios e a taxa de desgaste foi calculada. Foram evidenciados maiores coeficientes de atrito, maiores taxas de desgaste e maiores amplitudes de potencial de corrosão nas amostras ensaiadas em solução de areia; com valores mais brandos para as amostras ensaiadas em água destilada e valores intermediários para as amostras ensaiadas em solução de cloreto de sódio.

Hardfacing using supersonic laser depostion of stellite-6

The capability of manufacturing coatings is of central importance in engineering design. Many components require nowadays the application of additional layers, to enhance mechanical properties and protect against hostile environments. Supersonic Laser Deposition (SLD) is a novel coating method, based upon Cold Spray (CS) principles. In this technique the deposition velocities can be significantly lower than those required for effective bonding in CS applications. The addition of laser heat energy permits a change in the thermodynamic experience of impacting particles, thereby offering a greater opportunity for metallurgical bonding at lower velocities compared to the CS process technology. The work reported in this paper demonstrates the ability of the SLD process to deliver hard facing materials to engineering surfaces. Stellite-6 has been deposited on low carbon steel tubes over a range of process parameters, determining the appropriate target power and traverse speeds for coating deposition. Coating properties and parameters were examined to determine the main properties, micro-structure and processing cost. Their morphology was studied through optical microscopy, SEM and X-Ray Diffraction. The results have shown that SLD is capable of depositing Stellite-6, with enhanced properties compared to laser clad counterparts.

Numerical study of the shielding properties of macroscopic hybrid ferromagnetic/superconductor hollow cylinders

We study the magnetic shielding properties of hybrid ferromagnetic/ superconductor (F/S) structures consisting of two coaxial cylinders, with one of each material. We use an axisymmetric finite-element model in which the electrical properties of the superconducting tube are modeled by a nonlinear E-J power law with a magnetic-field-dependent critical current density whereas the magnetic properties of the ferromagnetic material take saturation into account. We study and compare the penetration of a uniform axial magnetic field in two cases: 1) a ferromagnetic tube placed inside a larger superconducting tube (Ferro-In configuration) and 2) a ferromagnetic tube placed outside the superconducting one (Ferro-Out configuration). In both cases, we assess how the ferromagnetic tube improves the shielding properties of the sole superconducting tube. The influence of the geometrical parameters of the ferromagnetic tube is also studied: It is shown that, upon an optimal choice of the geometrical parameters, the range of magnetic fields that are efficiently shielded by the high-temperature superconductor tube alone can be increased by a factor of up to 7 (2) in a Ferro-Out (Ferro-In) configuration. The optimal configuration uses a 1020 carbon steel with a thickness of 2 mm and a height that is half that of the superconducting cylinder (80 mm). © 2009 IEEE.

A mathematical model of crevice and pitting corrosion—I. The physical model

A predictive and self-consistent mathematical model incorporating the electrochemical, chemical and ionic migration processes characterizing the propagation stage of crevice and pitting corrosion in metals is described. The model predicts the steady-state solution chemistry and electrode kinetics (and hence metal penetration rates) within an active corrosion cavity as a function of the many parameters on which these depend, such as external electrode potential and crevice dimensions. The crevice is modelled as a parallel-sided slot filled with a dilute sodium chloride solution. The cavity propagation rates are found to be faster in the case of a crevice with passive walls than one with active walls. The distribution of current over the internal surface of a crevice with corroding walls can be assessed using this model, giving an indication of the future shape of the cavity. The model is extended to include a solid hydroxide precipitation reaction and considers the effect of consequent changes in the chemical and physical environment within the crevice on the predicted corrosion rates. In this paper, the model is applied to crevice and pitting corrosion in carbon steel.

Electrochemical Sensing and Biosensing Platform Based on Chemically Reduced Graphene Oxide

In this paper, the characterization and application of a chemically reduced graphene oxide modified glassy carbon (CR-GO/GC) electrode, a novel electrode system, for the preparation of electrochemical sensing and biosensing platform are proposed. Different kinds of important inorganic and organic electroactive compounds (i.e., probe molecule (potassium ferricyanide), free bases of DNA (guanine (G), adenine (A), thymine (T), and cytosine (C)), oxidase/dehydrogenase-related molecules (hydrogen peroxide (H2O2/beta-nicotinamide adenine dinucleotide (NADH)), neurotransmitters (dopamine (DA)), and other biological molecules (ascorbic acid (AA), uric acid (UA), and acetaminophen (APAP)) were employed to study their electrochemical responses at the CR-GO/GC electrode, which shows more favorable electron transfer kinetics than graphite modified glassy carbon (graphite/GC) and glassy carbon (GC) electrodes.

Synthesis and electrochemical applications of gold nanoparticles

This review covers recent advances in synthesis and electrochemical applications of gold nanoparticles (AuNPs). Described approaches include the synthesis of AuNPs via designing and choosing new protecting ligands; and applications in electrochemistry of AuNPs including AuNPs-based bioelectrochemical sensors, such as direct electrochemistry of redox-proteins, genosensors and immunosensors, and AuNPs as enhancing platform for electrocatalysis and electrochemical sensors.

A biofuel cell with enhanced power output by grape juice

Glucose oxidase and laccase immobilized at multiwalled carbon nanotubes-ionic liquid gel modified electrodes are used as the catalysts of anode and cathode of biofuel cells (BFCs), respectively. The BFC based on glucose and air is proposed. When ferrocene monocarboxylic acid is adopted as the mediator of anode, the power output of the BFC is ca. 4.1 mu W (power density ca. 10.0 mu W cm(-2)), which is higher than the value of 2.7 mu W (power density ca. 6.6 mu W cm(-2)) by taking ferrocene dicarboxylic acid as the mediator. This implies that the mediator with formal potential closing to that of the enzyme does improve the power output. Furthermore, the power output of the BFC is greatly improved by taking grape juice as the fuel of anode rather than glucose. This system also indicates that grape juice as a fuel of the BFC not only is feasible and can also enhances the power output of the BFCs. Besides, it greatly lowers the cost and simplifies the preparation procedure of the BFCs, making the BFC towards "green" bioenergy.

Organically modified sol-gel/chitosan composite based glucose biosensor

A new type of organically modified sol-gel/chitosan composite material was developed and used for the construction of glucose biosensor. This material provided good biocompatibility and the stabilizing microenvironment around the enzyme. Ferrocene was immobilized on the surface of glassy carbon electrode as a mediator. The characteristics of the biosensor were studied by cyclic voltammetry and chronoamperometry. The effects of enzyme-loading, buffer pH, applied potential and several interferences on the response of the enzyme electrode were investigated. The simple and low-cost glucose biosensor exhibited high sensitivity and good stability.

Liposome-mediated conformation transition of DNA detected by molecular probe: methyl green

Recent studies have focused on the structural features of DNA-lipid assemblies. In this paper, we take methyl green (MG) as a probe molecule to detect the conformational change of DNA molecule induced by dimethyldioctadecylammonium bromide (DDAB) liposomes before the condensation process of DNA begins. DDAB-induced DNA topology changes were investigated by cyclic voltammetry (CV), circular dichroism (CD) and UV-VIS spectrometry. We find that upon binding to DNA, positively charged liposomes induce a conformational transition of DNA molecules from the native B-form to the C motif. Conformational transition in DNA results in the binding modes of MG to DNA, changing and being isolated from DNA to the solution. More stable complexes are formed between DNA and DDAB. That is also proved by the melting study of DNA.

Preparation of highly dispersed gold microparticles and their electrocatalytic activity for the oxidation of formaldehyde

The electrochemical preparation of highly dispersed Au microparticles on the surfaces of glassy carbon (GC) electrodes and their electrocatalytic activities for the oxidation of formaldehyde were studied. It was found that the reduction of Au3+ to Au is controlled by diffusion and the formation mechanism of Au microparticles on the GC surfaces corresponds to an instantaneous nucleation and diffusion-controlled three dimensional growth process. The particle size is about 80-90 nm in diameter after the electrochemical ageing treatment. These highly dispersed Au microparticles have high surface areas and exhibit better electrocatalytic activity than that of bulk-form Au toward the electrochemical oxidation of formaldehyde in alkaline media.

Microstructure and wear properties of laser clad Fe based amorphous composite coatings

A FeNiSiBV amorphous composite coating was developed by laser cladding of metallic powders on AISI 1020 low carbon steel substrate. The coatings were studied using X-ray diffraction, transmission electron microscopy and scanning electron microscopy. The coating reveals different microstructures along the depth of the coating. The transition zone exhibits good metallurgical bonding between the substrate and the coating. The layer consists of amorphous phase in majority and nanocrystalline phase/crystalline phase in minority. Accompanied with the nanocrystalline phase, the amorphous phase is concentrated in the middle of the coating. The crystalline phase in the coating is identified as Fe2B. A gradient distribution of the microhardness ranges from 1208 HV0.2 to 891 HV0.2 in the coating along the depth. The coating shows higher microhardness and better wear property than the substrate.

Effect of Process Conditions on Microstructure and Corrosion Resistance of Cold-Sprayed Ti Coatings

Ti and Ti alloys can be applied to steels as a protective coating in view of its excellent resistance to corrosive environment. Cold spraying, as a new coating technique, has potential advantages in fabrication of Ti coating in comparison with conventional thermal spraying techniques. In this study, Ti coatings were prepared on carbon steel substrates by cold spraying via controlling the process conditions. The microstructure of coatings was observed by SEM. The porosity of coatings was estimated by image analysis and the bond strength was tested for comparison of the process conditions. Potentiodynamic polarization and open-circuit potential (OCP) measurements were performed to understand the corrosion behavior of the coatings. The SEM examination shows that the coatings become more compact with the increases of pressure and temperature of driving gas. The potentiodynamic polarization curves indicate that the coating which has lower porosity has lower corrosion current. The polarization and OCP measurement reveal that cold-sprayed Ti coating can provide favorable protection to carbon steel substrate. The polishing treatment of coating surface polishes the rough outer layer including the small pores as well as decreases the actual surface area of the coating, leading to the considerable improvement of corrosion resistance.

Capillary electrophoresis with boron doped diamond electrode for amperometric detection of low molecular weight biological substrate

The research work in this thesis included the sensitive and selective separation of biological substance by capillary electrophoresis with a boron doped diamond electrode for amperometric detection. Chapter 1 introduced the capillary electrophoresis and electrochemical detection. It included the different modes of capillary electrophoresis, polyelectrolyte multilayers coating for open tubular capillary electrochromatography, different modes of electrochemical detection and carbon based electrodes. Chapter 2 showed the synthesized and electropolymerized N-acetyltyramine with a negatively charged sulfobutylether-β-cyclodextrin on a boron doped diamond (BDD) electrode followed by the electropolymerzation of pyrrole to form a stable and permselective film for selective dopamine detection. For comparison, a glassy carbon (GC) electrode with a combined electropolymerized permselective film of polytyramine and polypyrrole-1-propionic acid was used for selective detection of dopamine. The detection limit of dopamine was improved from 100 nM at a GC electrode to 5 nM at a BDD electrode. Chapter 3 showed field-amplified sample stacking using a fused silica capillary coated with gold nanoparticles embedded in poly(diallyldimethylammonium) chloride, which has been investigated for the electrophoretic separation of indoxyl sulphate, homovanillic acid and vanillylmandelic acid. The detection limit of the three analytes obtained by using a boron doped diamond electrode was around 75 nM, which was significantly below their normal physiological levels in biological fluids. This combined separation and detection scheme was applied to the direct analysis of these analytes and other interfereing chemicals including uric and ascorbic acids in urine samples without off-line sample treatment or preconcentration. Chapter 4 showed the selective detection of Pseudomonas Quinolone Signal, PQS for quorum sensing from its precursor HHQ, using a simply boron doped diamond electrode. Furthermore, by combining poly(diallyldimethylammonium) chloride modified fused silica capillary with a BDD electrode for amperometric detection, PQS was separated from HHQ and other analogues. The detection limit of PQS was as low as 65 nM. Different P. aeruginosa mutant strains were studied. Chapter 5 showed the separation of aminothiols by layer-by-layer coating of silica capillary with a boron doped diamond electrode. The capillary was layer-by-layer coated with the polycation poly(diallyldimethylammonium) chloride and negatively charged silica nanoparticles. All the aminothiols was separated and detected using a BDD electrode in an acidic electrolyte. It was a novel scheme for the separation and detection of glutathione reduced and oxidized forms, which is important for estimated overstressed level in the human system.

Voltammetric studies of gold, protons, and [HCl2](-) in ionic liquids

The comparative study of the voltammetry of H[NTf2], HCl and H[AuCl4] in [C(4)mim][NTf2] has provided an insight into the influence of protons on the reduction of [AuCl4](-) at Au, Pt or glassy carbon (GC) electrodes, and has allowed the identification of an unprecedented proton-induced electroless deposition of Au on relatively inert GC surfaces. For the first time, clear evidence of the quantitative formation of [HCl2](-) has been obtained in HCl/[C(4)mim][NTf2] mixtures, and the electrochemical behavior of these mixtures analyzed. In particular, a significant shift of the dissociation equilibrium toward the formation of chloride and the solvated proton (H-IL(+)), following electrochemical reduction of H-IL(+) has been observed in the time-scale of the experiments.