A redução de peso é uma questão tecnológica fundamental para a indústria aeroespacial, uma vez que diminui o consumo de combustível, resultando em redução de custos e contribuindo para a redução da emissão de gases de efeito estufa. Devido à relação favorável entre resistência mecânica e peso, as ligas de alumínio de elevada resistência mecânica contribuem favoravelmente para este aspecto. Entretanto, como estas ligas são dificilmente soldáveis pelos processos tradicionais envolvendo fusão, o procedimento de junção utilizado em aeronaves é a rebitagem, resultando em ganho de peso. O processo de soldagem por fricção (friction stir welding -FSW), desenvolvido no início dos anos noventa pelo The Welding Institute (TWI) do Reino Unido, se constituiu em um grande avanço para a soldagem das ligas de alumínio utilizadas na indústria aeroespacial, pois permite a produção de soldas mais confiáveis e virtualmente livres de defeitos. Entretanto, o aquecimento das peças e a deformação mecânica durante a FSW geram zonas com diferentes características microestruturais que, de acordo com a literatura, apresentam resistências à corrosão diferentes. Por oferecerem elevada resolução lateral, as técnicas eletroquímicas locais são úteis para elucidar as diferenças de reatividade local de eletrodos heterogêneos, como no caso de metais soldados. No presente trabalho técnicas eletroquímicas locais foram empregadas para caracterização da resistência à corrosão em meio contendo cloreto das diferentes zonas geradas pela soldagem de topo da liga de alumínio 2024-T3 por FSW, comparando-a com a exibida pelo metal base. O estudo foi complementado com a caracterização microestrutural destas regiões e também por ensaios macroscópicos de corrosão. Os resultados dos procedimentos de caracterização microestrutural confirmaram que a FSW provoca modificações na microestrutura das regiões afetadas pelo processo, principalmente no que concerne à distribuição das nanopartículas precipitadas durante o envelhecimento natural da liga. Por sua vez, os resultados dos ensaios macroscópicos de corrosão e eletroquímicos locais mostraram-se concordantes na determinação da região mais sensível à corrosão, que foi verificada como sendo as zonas termicamente afetada (Heat Affected Zone - HAZ) e termomecanicamente afetada (Thermomechanically Affected Zone - TMAZ) do lado do avanço da ferramenta de soldagem, mostrando também que as regiões afetadas pelo processo de soldagem apresentam resistência à corrosão inferior à do metal base. Através do uso da espectroscopia de impedância eletroquímica local (Local Electrochemical Impedance Spectroscopy - LEIS) foi evidenciado que o acoplamento galvânico entre as diferentes zonas geradas durante o processo de soldagem não desempenha um papel relevante na aceleração do processo corrosivo, o que está em desacordo com os resultados publicados em diversos estudos realizados com esta liga soldada por FSW. O trabalho apresenta ainda uma contribuição teórica original demonstrando que medidas de ângulo de contato e de espectroscopia de impedância eletroquímica em uma gota séssil podem ser usadas simultaneamente para a determinação da capacitância da dupla camada elétrica. As previsões do modelo teórico foram confirmadas tanto através de resultados obtidos com um sistema modelo como também em determinações realizadas nas diferentes regiões geradas pela soldagem por FSW da liga 2024-T3. / Weight reduction is a fundamental technological issue for the aerospace industry, as it decreases the fuel consumption, resulting in reduced both costs and greenhouse gases emission. Due to the favorable relation between strength and weight, high strength aluminum alloys favorably contribute to this aspect, but they remain difficult to weld by conventional processes involving fusion, and, therefore, the junction procedure used in aircraft is riveting, resulting in weight gain. The friction stir welding (FSW) process, developed in the early nineties by the \"The Welding Institute\" (TWI), United Kingdom, is a major breakthrough for the welding of aluminum alloys as it allows the production of more reliable and virtually defect-free welds. However, the heating of the parts and the mechanical deformation during FSW generate zones with different microstructures with different corrosion resistances. As they offer high lateral resolution, local electrochemical techniques are useful for elucidating differences in local reactivity of heterogeneous electrodes, as the case of welded metals. In the present work, local electrochemical techniques were employed to characterize the corrosion resistance in chloride environment of the different zones generated by butt welding the 2024-T3 aluminum alloy by FSW, and to compare this response with that displayed by the base metal. The study was complemented with the microstructural characterization of these regions and also by macroscopic corrosion tests. The results of the microstructural characterization confirmed that FSW causes changes in the microstructure of the regions affected by the process, especially with regard to the distribution of the precipitated nanoparticles during the natural aging of the alloy. The results of the macroscopic corrosion and of the local electrochemical tests showed good agreement in the determination of the most sensitive regions to corrosion, which were found to be the heat affected (HAZ) and the thermomechanically affected (TMAZ) zones of the advancing side of the weld tool. They also showed that the regions affected by the welding procedure have a lower corrosion resistance than the base metal. By using Local Electrochemical Impedance Spectroscopy (LEIS), it was shown that the galvanic coupling between the different areas generated during the welding process does not need to be taken into account in the description of the corrosion process, which is at odds with the results published in several studies of this alloy welded by FSW. The work also present an original theoretical contribution, demonstrating that contact-angle measurements and electrochemical impedance spectroscopy in a sessile drop can be used simultaneously to determine the capacity of the interface. The theoretical model predictions were confirmed by the experimental results obtained both with a model system and in the different regions generated by FSW of aluminum alloy 2024-T3.

A redução de peso é uma questão tecnológica fundamental para a indústria aeroespacial, uma vez que diminui o consumo de combustível, resultando em redução de custos e contribuindo para a redução da emissão de gases de efeito estufa. Devido à relação favorável entre resistência mecânica e peso, as ligas de alumínio de elevada resistência mecânica contribuem favoravelmente para este aspecto. Entretanto, como estas ligas são dificilmente soldáveis pelos processos tradicionais envolvendo fusão, o procedimento de junção utilizado em aeronaves é a rebitagem, resultando em ganho de peso. O processo de soldagem por fricção (friction stir welding -FSW), desenvolvido no início dos anos noventa pelo The Welding Institute (TWI) do Reino Unido, se constituiu em um grande avanço para a soldagem das ligas de alumínio utilizadas na indústria aeroespacial, pois permite a produção de soldas mais confiáveis e virtualmente livres de defeitos. Entretanto, o aquecimento das peças e a deformação mecânica durante a FSW geram zonas com diferentes características microestruturais que, de acordo com a literatura, apresentam resistências à corrosão diferentes. Por oferecerem elevada resolução lateral, as técnicas eletroquímicas locais são úteis para elucidar as diferenças de reatividade local de eletrodos heterogêneos, como no caso de metais soldados. No presente trabalho técnicas eletroquímicas locais foram empregadas para caracterização da resistência à corrosão em meio contendo cloreto das diferentes zonas geradas pela soldagem de topo da liga de alumínio 2024-T3 por FSW, comparando-a com a exibida pelo metal base. O estudo foi complementado com a caracterização microestrutural destas regiões e também por ensaios macroscópicos de corrosão. Os resultados dos procedimentos de caracterização microestrutural confirmaram que a FSW provoca modificações na microestrutura das regiões afetadas pelo processo, principalmente no que concerne à distribuição das nanopartículas precipitadas durante o envelhecimento natural da liga. Por sua vez, os resultados dos ensaios macroscópicos de corrosão e eletroquímicos locais mostraram-se concordantes na determinação da região mais sensível à corrosão, que foi verificada como sendo as zonas termicamente afetada (Heat Affected Zone - HAZ) e termomecanicamente afetada (Thermomechanically Affected Zone - TMAZ) do lado do avanço da ferramenta de soldagem, mostrando também que as regiões afetadas pelo processo de soldagem apresentam resistência à corrosão inferior à do metal base. Através do uso da espectroscopia de impedância eletroquímica local (Local Electrochemical Impedance Spectroscopy - LEIS) foi evidenciado que o acoplamento galvânico entre as diferentes zonas geradas durante o processo de soldagem não desempenha um papel relevante na aceleração do processo corrosivo, o que está em desacordo com os resultados publicados em diversos estudos realizados com esta liga soldada por FSW. O trabalho apresenta ainda uma contribuição teórica original demonstrando que medidas de ângulo de contato e de espectroscopia de impedância eletroquímica em uma gota séssil podem ser usadas simultaneamente para a determinação da capacitância da dupla camada elétrica. As previsões do modelo teórico foram confirmadas tanto através de resultados obtidos com um sistema modelo como também em determinações realizadas nas diferentes regiões geradas pela soldagem por FSW da liga 2024-T3. / Weight reduction is a fundamental technological issue for the aerospace industry, as it decreases the fuel consumption, resulting in reduced both costs and greenhouse gases emission. Due to the favorable relation between strength and weight, high strength aluminum alloys favorably contribute to this aspect, but they remain difficult to weld by conventional processes involving fusion, and, therefore, the junction procedure used in aircraft is riveting, resulting in weight gain. The friction stir welding (FSW) process, developed in the early nineties by the \"The Welding Institute\" (TWI), United Kingdom, is a major breakthrough for the welding of aluminum alloys as it allows the production of more reliable and virtually defect-free welds. However, the heating of the parts and the mechanical deformation during FSW generate zones with different microstructures with different corrosion resistances. As they offer high lateral resolution, local electrochemical techniques are useful for elucidating differences in local reactivity of heterogeneous electrodes, as the case of welded metals. In the present work, local electrochemical techniques were employed to characterize the corrosion resistance in chloride environment of the different zones generated by butt welding the 2024-T3 aluminum alloy by FSW, and to compare this response with that displayed by the base metal. The study was complemented with the microstructural characterization of these regions and also by macroscopic corrosion tests. The results of the microstructural characterization confirmed that FSW causes changes in the microstructure of the regions affected by the process, especially with regard to the distribution of the precipitated nanoparticles during the natural aging of the alloy. The results of the macroscopic corrosion and of the local electrochemical tests showed good agreement in the determination of the most sensitive regions to corrosion, which were found to be the heat affected (HAZ) and the thermomechanically affected (TMAZ) zones of the advancing side of the weld tool. They also showed that the regions affected by the welding procedure have a lower corrosion resistance than the base metal. By using Local Electrochemical Impedance Spectroscopy (LEIS), it was shown that the galvanic coupling between the different areas generated during the welding process does not need to be taken into account in the description of the corrosion process, which is at odds with the results published in several studies of this alloy welded by FSW. The work also present an original theoretical contribution, demonstrating that contact-angle measurements and electrochemical impedance spectroscopy in a sessile drop can be used simultaneously to determine the capacity of the interface. The theoretical model predictions were confirmed by the experimental results obtained both with a model system and in the different regions generated by FSW of aluminum alloy 2024-T3.

Master of Science / Department of Chemistry / Jun Li / This study is focused on exploring the mechanisms of DNA dynamics at carbon electrode surfaces under a strong electric field for the development of novel DNA hybridization sensors. Oligonucleotides with FAM6 attached at the distal end are covalently tethered on the carbon electrode surface. The fluorescence emission from the FAM6 is strongly quenched in close proximity to the electrode surface. The modulation to the fluorescence intensity is correlated with the reversible reorientation of the negatively charged DNA molecules under the electric field within the electric double layer. The orientation dynamics are apparently determined by the interplay of the electropotential, salt concentration, and stiffness of the DNA molecules. We have observed that dsDNAs switch with fast dynamics (in < 0.05 second) followed by relaxation at a slower rate (in > 0.1 second) when the electric field is altered by stepping the electropotential to a more positive or negative value. The DNA reorientation exhibits strong dependence on the PBS buffer concentration and electric double layer thickness. A preliminary calculation based on dipole-surface energy transfer theory indicates that the critical distance between FAM6 and glassy carbon surface is 10.95 nm. In connection with the fluorescence study, the effect of DNA hybridization on electrochemical impedance spectroscopy (EIS) has also been investigated by two methods in an attempt to develop a fast electronic detection method. First, EIS at high AC amplitude (141 mV rms) with DNA-modified glassy carbon electrodes before and after target DNA hybridization have shown notable change at high frequencies, likely related to the DNA reorientation processes. Second, reversible EIS detection of DNA hybridization has been demonstrated with patterned regular carbon nanofiber arrays at normal AC amplitude (10 mV rms). The combination of these two methods will be explored in future studies. The effects of the electric field on surface-tethered molecular beacons (MBs) have also been studied with fluorescence spectroscopy. An increase in fluorescence at negative bias is observed accompanying the opening of the MB stem, which leads to larger separation between fluorophore and quencher. At positive bias, the rehybridization of the MB stem leads to a decrease in fluorescence intensity.

There is huge academic interest and clinical need associated with the development of biomarker immunoassays where general aims are the generation of highly specific, convenient and sensitive sensing formats. In this project, a powerful electrochemical technique, electrochemical impedance spectroscopy (EIS), is applied in the establishment of powerful biomarker detecting protocols. Firstly, ultrasensitive, label-free and reusable insulin sensors, based on an antibody-PEGylated thiol self-assembly monolayer (PEG thiol SAM) interface, were produced and characterised via Faradaic EIS, presenting a detection limit (LOD) of 1.2 pM, a linear range across four orders of magnitude, and high sensitivity in even 50 % serum. By applying similar surface chemistry, a label-free biosensor, specific for the detection of α-synuclein antibodies, was fabricated. The α-synuclein interfaces used enabled the reliable detecting of this biomarker in patient sample serum. The concentration levels in the control and a patient group were determined to be significantly different, and, significantly, this difference was consistently across two different cohorts. Strikingly, this could potentially underpin an entirely new means of early Parkinson’s disease (PD) diagnosis. Non-Faradaic EIS methods were additionally applied to label-free insulin assays at both PEG thiol SAM and zwitterionic polymer film interfaces. The latter presented not only an exceptionally non-fouling interface, but also one seemingly both highly biocompatible and facilitating enhanced receptor: target binding. Finally, impedance assays, though potent, generally, operate by sampling only one of a limited number of available experimental variables, typically, Rct for Faradaic EIS, or C or Z for non-Faradaic EIS. Work carried out herein also explores the generation and utility of a portfolio of mathematically derived immittance functions all obtained from the same raw data sets. A particular focus was the examination of whether these were capable of increasing assay sensitivity and efficiency above normal impedance treatments.

Micro- and nano-electrodes have distinct advantages over large electrodes, including their decreased iR drop and enhanced mass transport due to radial diffusion characteristics which leads to the ready establishment of a steady state (or near steady-state) signal without convection. This enhanced mass transport also leads to increased current densities and signal to noise ratios. However, there is a need for fabrication techniques which reproducibly give micro- and nano-electrodes of controlled size and shape. The optimisation of systematic arrays on the nano-scale, open up possibilities for developing highly sensitive electrode devices, for use in physical chemistry and the determination of fast electrode kinetics and rates of reaction, as well as to provide highly sensitive electroanalytical devices, able to detect very low concentrations of substrates. This thesis first presents work involving the fabrication and characterisation on silicon substrates of square platinum microelectrodes. There is already an established theory for the behaviour of microdisc electrodes however, it is easier to make microsquares reproducibly using pixellated photomasks. The voltammetric and ac impedance characteristics of these electrodes in background electrolyte and in the presence of ferri/ferrocyanide redox couple are presented and the response is theoretically analysed. A combination of computer simulation, theory and experimentation show that these electrodes have increased current densities (14% greater) compared with a microdisc of equivalent radius and an alternative theoretical expression is presented to calculate the limiting current of microsquares at all dimensions. This thesis then discusses the development and optimisation of novel nano-band cavity array electrodes (CaviArE), using standard photo-microlithographic techniques. The resulting architecture encloses a Platinum nanoband of 50 nm width within each array element that is positioned half way up the vertical edges of shallow square cavities (depressions), with a total depth of 1050 nm. The width of the square cavity and the separation of the array elements can be controlled and systematically altered, with great accuracy. The CaviArE devices are shown to give quantitative pseudo-steady-state responses characteristic of multiple nanobands, whilst passing overall currents consistent with a macroelectrode. The array has a much enhanced signal-tonoise ratio compared with an equivalent microsquare array, as it has 0.167% of the area and is therefore markedly less affected by non-Faradaic currents, while it passes comparable Faradaic currents. At high sweep rates the response is also virtually unaffected by solution stirring. The impedammetric characteristics presented show different diffusional regimes at high, medium and low frequencies, associated with diffusion within individual square cavities, outside of the cavity and finally across the whole array as the diffusional fields of the neighbouring array elements overlap. Justification and fitting of equivalent circuits to these frequency regions provide details about the charge transfer, capacitance and diffusional processes occurring. The results show that these systems are highly sensitive to surface transfer effects and a rate constant for ferricyanide of 1.99 cm s-1 was observed, suggesting fast kinetic processes can be detected. Together, these characteristics make nanoband electrode arrays, with this architecture, of real interest for sensitive electroanalytical applications, and development of devices for industrial application is currently being undertaken.

<p>In polymer electrolyte fuel cells (PEFC) chemical energy, in for example hydrogen, is converted by an electrochemical process into electrical energy. The PEFC has a working temperature generally below 100 °C. Under these conditions water management and transport of oxygen to the cathode are the parameters limiting the performance of the PEFC.</p><p>The purpose of this thesis was to better understand the complex processes in different parts of the PEFC. The rate-limiting processes in the cathode were studied using pure oxygen while varying oxygen pressure and humidity. Mass-transport limitations in the gas diffusion layer using oxygen diluted in nitrogen or helium was also studied. A large capacitive loop was seen at 1-10 Hz with 5-20 % oxygen. When nitrogen was changed to helium, which has a higher binary diffusion coefficient, the loop decreased and shifted to a higher frequency.</p><p>Steady-state and electrochemical impedance spectroscopy (EIS) models have been developed that accounts for water transport in the membrane and the influence of water on the anode. Due to water drag, the membrane resistance changes with current density. This gives rise to a low frequency loop in the complex plane plot. The loop appeared at a frequency of around 0.1 Hz and varied with <em>D</em>/<em>L_m</em>², where <em>D</em> is the water diffusion coefficient and <em>L_m</em> is the membrane thickness. The EIS model for the hydrogen electrode gave three to four semicircles in the complex plane plot when taking the influence of water concentration on the anode conductivity and kinetics into account. The high-frequency semicircle is attributed to the Volmer reaction, the medium-frequency semicircle to the pseudocapacitance resulting from the adsorbed hydrogen, and the low-frequency semicircles to variations in electrode performance with water concentration. These low-frequency semicircles appear in a frequency range overlapping with the low-frequency semicircles from the water transport in the membrane. The effects of current density and membrane thickness were studied experimentally. An expected shift in frequency, when varying the membrane thickness was seen. This shift confirms the theory that the low-frequency loop is connected to the water transport in the membrane.</p>

Electrochemical Impedance Spectroscopy (EIS) was used to develop a novel methodology for studying ionic interaction with lipids arranged in a lipid cubic phase (LCP). Studying different types of ions, both cations and anions, validated the method. A free-standing LCP membrane was formed between two cell compartments and impedance experiments were carried out in a 2-electrode setup to estimate dielectric properties of the membrane, exposed to the following electrolyte solutions at different concentrations: KCl, CsBr, CaCl2, MgCl2, CsCl, NaCl, NaOAc and NaTryptophan. Two different LCP were used in this setup, i.e: Monoloein/water and the ternary system of monoolein/dioleoylphosphatidylcholine/water (MO/DOPC/H2O). SAXRD measurements were performed to determine the space group of the cubic phase and confirm the stability of the LCP during measurements. Membrane resistances and capacitances were found from equivalent circuit fitting to the impedance data. The membrane resistance was shown to be related to ionic interaction with the lipid head group in the water channels of the LCP. Membrane capacitance were correlating to condensing and swelling effect of LCP due to the exposure of ions. The results correlated well with the SAXRD results and earlier published data. The results also indicate that these membranes become less permeable to ions as they increase in size as well as in charge or polarity.  Cyclic voltammetry was used to study the applications of a LCP for modification of the bioanode in a biofuel cell. The monoolein cubic phase was used to host Glucose oxidase (GOx) and a freely diffusing ferrocene carboxylate was used as mediator. The supported cubic phase had an intrinsic resistance in the same order of magnitude as the freestanding MO-LCP membrane as measured with EIS. / Elektrokemisk impedans spektroskopi har använts för att utveckla en ny metod för att studera joners växelverkan med lipider som bildat en kubisk fas. Olika typer av joner, både positiva och negativa, användes för att validera metoden. Ett fristående membran uppbyggt av en kubisk fas separerade två avdelningar i en elektrokemisk cell. Cellen fylldes med elektrolyt-lösningar och impedansmätningar kunde utföras mellan två platina elektroder placerade i vardera avdelning. Membranet exponerades för följande elektrolytlösningar av olika koncentration: KCl, CsBr, CaCl2, MgCl2, CsCl, NaCl, NaOAc and NaTryptofan. Två olika kubiska faser användes i denna uppställning, dvs: Monoloein/vatten och det ternära systemet monoolein/dioleoylfosfatidylkolin/vatten(MO/DOPC/H2O). Med hjälp av SAXRD kunde den kubiska fasens kristallstruktur bestämmas och dess stabilitet under mätningarna bekräftas. De dielektriska egenskaperna hos membranet bestämdes genom att anpassa impedansspektrat till en ekvivalent krets bestående av resistanser, kapacitanser och konstant-faselement. Membranresistansen visade sig vara relaterad till jonernas växelverkan med lipidhuvudgruppen i vattenkanalerna i kubiska fasen. Ju starkare växelverkan desto högre var resistansen. Membrankapacitansen kunde korreleras med kondenserande och uppsvällande effekter på kubiska fasen förorsakade av exponeringen till joner. Resultaten bekräftades av SAXRD mätningar och även tidigare publicerade data. Resultaten indikerar också tydligt att permeabiliteten hos membranet minskar med ökad jonstorlek, jonladdningoch polaritet hos jonen. Cyklisk voltammetri användes för att studera en tillämpning av kubiska fasen i en tänkt applikation som bioanod i en biobränslecell. Elektroden modifierades med en kubisk fas innehållande GOx och tillsammans med en fritt diffunderande ferrocen karboxylat som mediator, där oxidation av glukos studeras. Det visade sig att den kubiska fasen hade en resistans av samma storleksordning som det fristående membranet uppmätt med impedansspektroskopi.

An impedance bioanalyzer system comprising an in-vitro biotransducer, instrumentation and control software for the measurement of urea, potentially in blood dialysate, has been developed. The biotransducer comprises of a microlithographically fabricated interdigitated microsensor electrode (IME) onto which was cast a biorecognition layer conferred with the specificity of the enzyme urease. Urease hydrolysis of urea produces NH4+, HC03- and OH- ions that decrease the device's impedance. The temporal rate of change (kinetic) and the extent of change (equilibrium) of ion concentration were measured as the sensor's response. Five formats: [i) unPEGylated urease-containing poly(hydroxyethylmethacrylate) [p(HEMA)] hydrogel, ii) PEGylated urease-containing p(HEMA) hydrogel, iii) via glutaraldehyde crosslinking in the presence of albumin, iv) the direct covalent immobilization of urease to the IME, and v) solution borne urease]. Michaelis-Menten parameters KM, ZMAX and kcat revealed the following rank: PEGylated urease-Gel >> Free Urease > unPEGylated urease-Gel = BSA in Glutaraldehyde > covalently immobilized urease. The unPEGylated-urease sensor provided a higher enzyrne- substrate binding rate and catalysis rate than PEGylated and thus provided a faster impedimetric response to various molar concentrations of urea. Long-term stability (one month) of the PEGylated-urease hydrogel was favorable. A dedicated three-element array impedimetric instrument, the 3EIC BioAnalyzer was designed and produced. A pair of demodulating logarithmic amplifiers (AD8302) was used to calculate the change in phase and amplitude corresponding to the impedimetric response to a 4.0 kHz, 50 mVPP sine wave from a function generator (MAX038). A graphic user interface (GUI), programmed in LabVIEW 7.0 established instrument control, data acquisition via a USB-48A-30A16 μDAQ and graphical data presentation of temporal impedimetric responses.

O objetivo deste trabalho foi caracterizar por meio de técnicas eletroquímicas e físicoquímicas o comportamento das camadas de silano aplicadas diretamente sobre as chapas de aço-carbono ABNT 1008 pela técnica de imersão, como uma proteção contra a corrosão. O estudo compreendeu a avaliação do comportamento das monocamadas de BTSE [Bis-1,2-(trietoxisilil)etano], VS (Viniltrietoxisilano) e BTSPA [Bis-(y-trimetoxisililpropil)amina], variando as condições de cura (tempo e temperatura) e também da dupla camada de silano. A dupla camada consistiu na combinação de BTSE como primeira camada e uma segunda camada de VS ou BTSPA. A espectroscopia de impedância eletroquímica (EIS) em solução de NaCl 0,1 M possibilitou detectarem a resistência à corrosão das camadas de silano, revelando que a sua eficiência aumenta com o aumento da temperatura e do tempo de cura e também que uma dupla camada apresenta um efeito protetor mais eficiente que o das monocamadas. Assim, a dupla camada de BTSE + BTSPA forneceu o melhor resultado, comprovando que confere melhor proteção ao aço-carbono. Com a medida ângulo de contato foi possível caracterizar a hidrofobicidade da superfície metálica revestida com o filme de silano, constatando-se que as camadas de BTSE, VS e BTSPA, e as duplas camadas curadas em altas temperaturas são mais hidrofóbicas que o aço-carbono. As curvas de polarização confirmaram os resultados obtidos por EIS, mostrando que a densidade de corrente de corrosão (icorr) diminui com o tempo e a temperatura de cura. A espectroscopia no infravermelho (IR) permitiu acompanhar a extensão da reação de polimerização dos silanos. A microscopia eletrônica de varredura (SEM) e as análises por espectroscopia de energia dispersiva de Raios-X (EDX) evidenciaram o efeito da cura na morfologia e topografia da superfície. Logo, conclui-se que os filmes à base de silanos como pré-tratamentos de aço são eficientes contra a corrosão. / The aim of this work is to characterize by means of electrochemical and physicochemical techniques the behavior of the silane layers applied directly on steel plates as a protection against corrosion. The silane film was obtained by the dip coat technique. This study present the evaluation of the behavior of monolayers of BTSE [Bis-1,2- (triethoxysilyl)ethane, BTSPA [Bis-(y-trimethoxysilylpropyl)amino] and VS (Vinyltriethoxysilane), varying the curing conditions (time and temperature) and also with a double silane layer, consisting of a combination of BTSE as first layer and a VS or BTSPA second layer. The electrochemical impedance spectroscopy (EIS) in a NaCl 0.1 M solution allowed the corrosion resistance assessment of the silane layers, showing that their protection efficiency increase for higher curing temperatures and curing times. Double layers were always more protective than monolayers. The contact angle measurements allowed to characterize the hydrophobicity of the metallic surface coated with the silane film, showing that the layers of BTSE, VS and BTSPA cured at higher temperatures are more hydrophobic and, therefore, more protective. The polarization curves confirmed the results obtained by EIS, showing that the corrosion current densities (icorr) decreased when the curing time and temperature were increased. The infrared spectroscopy (IR) showed the extension of the polymerization reaction of the silane layers. The SEM images and the EDX analyses evidenced the effect of the cure on the morphology and topography of the surface. Thus, the results lead to conclude that silane based films are good alternatives as pre-treatments for steel against corrosion.

Na presente tese foi investigado o desempenho de camadas de organo-silanos sobre chapas de aço-carbono, similares às utilizadas na fabricação de veículos da indústria automobilística. As técnicas utilizadas neste estudo compreenderam a Espectroscopia de Impedância Eletroquímica (EIE) e a Resistência de Polarização Linear, por meio das quais foram determinadas respectivamente, as propriedades resistivas dos filmes e a redução das velocidades de corrosão do substrato. O estudo compreendeu a avaliação de diversos organo-silanos funcionais e não-funcionais, submetidos a diferentes condições experimentais. Os ensaios preliminares tiveram por finalidade selecionar aqueles com melhor desempenho como sistemas de proteção em monocamadas. A partir desta seleção e,, informações da literatura, novos ensaios foram conduzidos por meio de um Projeto Fatorial de Experimentos, combinando os silanos funcionais com melhor desempenho com outro silano não-funcional, designado como 1,2-bis(trietoxilsilil)etano (BTSE). Esta combinação teve por finalidade produzir camadas duplas de silanos para proteger o aço-carbono. As variáveis independentes estudadas foram a combinação entre as camadas de BTSE e do silano funcional, além das condições de hidrólise, temperatura e tempo de cura destes filmes. As variáveis dependentes ou resposta utilizadas foram: a impedância real a 0,03 Hz, obtida no ensaio de EIE, e a densidade de corrente de corrosão, originada das medidas de Resistência de Polarização Linear. Dentre as várias alternativas testadas, os melhores resultados foram apresentados pela combinação de camadas de BTSE com bis-(g-trimetoxisililpropil)amina (BTSPA) e BTSE com VS (viniltrietoxisilano) onde a primeira combinação determinou uma redução da ordem de 95% na velocidade de corrosão em relação a uma chapa sem tratamento e uma perda de espessura da ordem de 70% menor que um corpo-deprova revestido apenas com uma camada convencional de fosfatização. O BTSPA já na seleção inicial havia demonstrado excelentes resultados de proteção apenas como película monocamada, tendo seu desempenho melhorado consideravelmente em conjunto como o BTSE. Na segunda combinação, a velocidade de corrosão foi 90% menor do que num corpo-de-prova desprotegido e até 40% menor do que num corpo-de-prova revestido com uma camada de fosfato. / The aim of this thesis was the investigation performance of organo-silane layers on mild steel, similar to that used in car bodies in automotive assembly plants. The electrochemical impedance spectroscopy (EIS) and the polarization resistance (Rp) were used as tools to evaluate the resistive layers properties and the substrate corrosion rate, respectively. Several non-functional and functional silanes were evaluated under different experimental conditions. Preliminary testing was conducted in order to select the silane with best performance as monolayer protection. Based on this preliminary performance results and supplementary information from papers, new tests were conducted using a design of experiments (DOE), combining the best functional monolayers silanes with the non-functional silane 1,2- bis(triethoxylsilyl)ethane (BTSE). This combination had the intention to produce double-layers silane films to protect the mild steel. The independent variables tested in DOE were: combination between the BTSE and the functional silane layers, hydrolysis parameters, temperature and the time film curing. The real impedance values at 0,03 Hz, obtained in the EIE tests, and the polarization resistance were taken as response (dependent) variables to evaluate the design. Among the different alternatives, the best results were presented by combining the BTSE layer with the BTSPA (bis-(g trimetoxysilylpropyl)amine layer and BTSE layer with VS (vinyl triethoxy silane) layer. The first silanes combination had shown a 95% decrease in corrosion rate when compared to a non-treated sheet and a thickness loss 70% lower than on a specimen coated with ordinary phosphate layer. Already in the initial selection the BTSPA did show excellent protection results just as monolayer film, and its performance increased significantly when applied together with BTSE. The second silanes combination, had presented a 90% decrease in corrosion rate when compared to a non-treated sheet and a thickness loss 40% lower than a specimen coated with ordinary phosphate layer.