O objetivo deste trabalho é avaliar o efeito autorreparador de um primer alquídico base solvente (SB) e um primer acrílico base água (WB) aditivados com nanocontainers de haloisita carregados com inibidor de corrosão dodecilamina (DDA) aplicados em aço carbono. O efeito inibidor da dodecilamina foi avaliado através de ensaios eletroquímicos de espectroscopia de impedância eletroquímica (EIS) em diferentes condições, sendo verificada que a sua eficiência aumenta em meio ácido. Com o intuito de aumentar o lúmen da haloisita, gerando mais capacidade de carregamento de inibidor, a haloisita foi tratada com ácido sulfúrico 2 mol/L por 6 h a 55 °C. A haloisita tratada foi caracterizada através de análises termogravimétricas (TGA) e microscopia eletrônica de varredura (MEV). Em seguida, a dodecilamina foi carregada em haloisita tratada, através da técnica de pulso de vácuo. A cinética de liberação do inibidor de dentro da haloisita foi estudada através da técnica de EIS, onde foi constatada que a sua atuação é dependente do pH, com maior velocidade de liberação em pH 2. Os nanocontainers foram adicionados em um primer alquídico base solvente e um primer acrílico base água para a avaliação da resistência à corrosão dos sistemas através de espectroscopia de impedância eletroquímica (EIS), técnica de varredura com eletrodo vibratório (SVET) e ensaios acelerados de corrosão em câmara de névoa salina (SSC). A aderência dos dois sistemas foi avaliada através do ensaio de aderência por tração (pull-off). Para os dois sistemas avaliados foi possível verificar o efeito autorreparador, porém ele não foi tão longo, provavelmente devido à baixa eficiência no carregamento da dodecilamina na haloisita. A análise de custo da haloisita carregada com dodecilamina mostrou a necessidade de otimização dos processos de carregamento a fim de viabilizar o projeto na indústria de tintas. / The aim of this work is to evaluate the self-healing effect of a solvent based (SB) alkyd primer and a water based (WB) acrylic primer loaded with dodecylamine (DDA) corrosion inhibitor encapsulated in halloysite nanocontainers on carbon steel. The inhibitor effect of dodecylamine was evaluated by electrochemical impedance spectroscopy (EIS) under different conditions, and it was verified that its efficiency increases in acid medium. To enlarge halloysite lumen and increase its loading capacity, halloysite was treated with 2 mol/L sulfuric acid for 6 h at 55 °C. Halloysite before and after treatment was characterized by thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). Thereafter, the dodecylamine was loaded into treated halloysite by the vacuum pulse technique. The release kinetics of the inhibitor from within halloysite nanotubes were studied through the EIS technique where it was found that the action of halloysite is pH-dependent, with a higher release kinetics at pH 2. The nanocontainers were loaded in a solvent based alkyd primer and a water based acrylic primer for the evaluation of the corrosion resistance of the systems through electrochemical impedance spectroscopy (EIS), scanning vibration electrode technique (SVET) and accelerated corrosion tests in a salt spray chamber (SSC). The adhesion of the two systems was evaluated through the pull-off adhesion test. For the two systems evaluated, it was possible to verify the self-healing effect, but this effect was not long, probably due to the low loading efficiency of dodecylamine in halloysite nanotubes. The cost analysis of halloysite loaded with dodecylamine showed that the loading process needs an optimization in order to make this project feasible in the coating industry.

Darbe tiriamas magnetroniniu plazminiu būdu suformuotų Mg-Al-Zr lydinių anodinis tirpimas, bei antikorozinės savybės. Magnetroniniu plazminiu būdu buvo suformuotos dangos su skirtingu cirkonio kiekiu (t.y. 95%, 90,4%, 76,2%, 71% ir 67%). Dangos formuojamos ant stiklo paviršiaus. Voltamperiniais ir elektrocheminio impedanso metodais ištirtas Mg-Al-Zr lydinių anodinis atsparumas ir korozinė elgsena 0.1 M (NH4)3BO3 + 0.1 M NaCl tirpale, kurio pH 8,5. MP lydinių korozinis atsparumas didėja, didinant Zr koncentraciją lydinyje. Taip pat lydiniai, kuriuose didesnė Mg koncentracija, bet mažesnė Zr aktyviai anodiškai tirpsta. Atominės jėgos mikroskopo metodu (AJM) nustatyta lydinių morfologija, dangos su didesne Zr koncentracija charakterizuojamos mažesniais kristalitų dydžiais. Aptartos MP metodo pritaikymo galimybės. / The goal of this work was to study anodic dissolution and anticorrosion properties of Mg-Al-Zr alloys formed by magnetron sputtering. Magnetron sputtering technique was applied to deposit Mg-Al-Zr alloys with different amount of Zr, on glass substrates. Anodic dissolution and anticorrosive stability of the sputtered alloys were studied by voltammetric and electrochemical impedance spectroscopy methods in 0.1 M (NH4)3BO3 + 0.1 M NaCl solution (pH 8,5). EIS and voltammetric measurements indicated a lesser anodic dissolution and a superior anticorrosive resistance in Mg-Al-Zr alloys with higher Zr concentration. Atomic force microscopy demonstrated (AFM) that by increasing amount of Zr in sputtered samples the grain size decrease.

Darbe tiriamos magnetroniniu plazminiu (MP) būdu suformuotų Mg – Al – Zr lydinių morfologinės, korozinės ir puslaidininkinės savybės. Magnetroninio plazminio dulkinimo metodu buvo suformuotos 5Mg-Al-95Zr, 33Mg-Al-67Zr, 29Mg-Al-71Zr, 24Mg-Al-76Zr, 8Mg-Al-90Zr dangos ant stiklo paviršiaus. Atominės jėgos mikroskopo (AJM) metodu nustatyta, kad magnetroniniu plazminiu būdu suformuotos Mg – Al – Zr lydinių dangos charakterizuojamos mažesniais kristalitų dydžiais ir tolygesne mikrostruktūra. Fotoelektrocheminiais ir elektrocheminio impedanso spektroskopijos metodais ištirta lydinių korozinė elgsena 0,1 M (NH4)3BO3 + 0,1 M NaCl ( pH = 8,5) tirpale. Mott – Shottky analizės metodu nustatytas puslaidininkinių paviršiaus sluoksnių laidumo pobūdis: 5Mg-Al-95Zr, 33Mg-Al-67Zr, 29Mg-Al-71Zr, 24Mg-Al-76Zr, 8Mg-Al-90Zr dangų atveju jis donorinis (n – tipo). Aptartos Mott – Shottky metodo taikymo magnetroninėms dangoms tirti galimybės. / The aim of present work was to study corrosion properties of magnetron sputtered Mg – Al – Zr alloys and characterise semiconductor properties of the surface layers developed during corrosion. Atomic force microscopy (AFM) demonstrated, that sputtered alloys had a smaller grain size and a smoother surface. Fotocorrosion and electrochemical behaviour of tha alloys was studied in 0,1 M (NH4)3BO3 + 0,1 M NaCl ( pH = 8,5) solution. The Mott – Schottky plots of 5Mg-Al-95Zr, 33Mg-Al-67Zr, 29Mg-Al-71Zr, 24Mg-Al-76Zr, 8Mg-Al-90Zr electrodes showed a linear relationship between modified capacitance (C-2) on applied potential. It was concluded n – type semiconductivity for the layers on 5Mg-Al-95Zr, 33Mg-Al-67Zr, 29Mg-Al-71Zr, 24Mg-Al-76Zr, 8Mg-Al-90Zr alloys.

I detta arbete har elektrokemisk impedansspektroskopi använts för att producera reproducerbara impedansdata för katodmaterialet NMC811. Data som skulle kunna användas som basen för parametrisering och konstruktionen av en fysik-baserad modell. Dessutom har effekten av laddningstillstånd, temperatur, och historian av cellen på impedansen undersökts. Baserat på resultaten av preliminära test så har experiment konstruerats i vilka katodens impedans i en NMC811//Grafit cell har undersökts vid olika temperaturer och laddningstillstånd, både efter laddning och urladdning av cellen. Reproducerbara resultat kunde erhållas och det visades hur laddningstillstånd och temperatur har en stor påverkan på impedansen. Tyvärr så kunde inget sägas om hystereseffekten på grund av dålig stabilitet i lågfrekvensområdet av impedansmätningarna. / In this work, electrochemical impedance spectroscopy has been used to try and produce reproducible impedance data for the cathode material NMC811. Data that could serve as the basis of parameter extraction for the construction of a physics-based model. Furthermore, the effect of state of charge, temperature, and history of the cell on the impedance has been analysed. Based on the results of preliminary tests, an experimental cycle was constructed in which the cathode impedance of a NMC811//Graphite cell was measured at varying temperatures and state of charge, both following charge and discharge of the cell. Reproducible results were achieved, and it was shown how the state of charge and temperature of the cell had a major effect on the measured impedance. Unfortunately, no conclusions could be made about the history effect on impedance due to poor stability in the low frequency regions of the impedance measurements.

Elektrokemisk korrosionsanalys av legeringar är en essentiell del av den större materialanalysen som måste utföras när en legerings lämplighet för en viss applikation evalueras. Nickelbaserade legeringar är kända för sin utmärkta korrosionsresistans, och de Ni-Cr-Mo-baserade legeringarna 59, 625, och 718 är också så kallade superlegeringar. Superlegeringar karaktäriseras med att legeringarna behåller sina mekaniska, termiska, och korrosion egenskaper även vid temperaturer nära smältpunkten. Den elektrokemiska korrosionsanalysen av legeringarna 59, 625, och 718 utfördes med OCP, cyklisk polarisation, samt EIS. Experimenten utfördes i en tre-elektrod elektrokemisk cell med en Ag/AgCl referenselektrod och en platina motelektrod, så väl som en Gamry Reference 600+ potentiostat. Detta arbete framhäver vikten att utföra cyklisk polarisation i korrosionsanalysen eftersom metod kan upptäcka viktiga skillnader mellan till synes liknande legeringar, vilket kunde ses vid jämförelsen av legering 718 med 625 och 59. EIS visas också vara en kraftfull analytisk verktyg genom sin förmåga att approximera verkliga elektrokemiska system genom att använda elektriska kretsar, så väl som EIS:s förmåga att användas som ett komplementärt analytiskt verktyg för att assistera i interpretationen av cyklisk polarisationsdata. / Electrochemical corrosion analysis of alloys forms an essential part of the larger material analysis procedure that needs to be performed when evaluating the feasibility of an alloy for a certain application. Nickel-based alloys are known for having excellent corrosion resistance, and the Ni-Cr-Mo-based alloys 59, 625, and 718 are also known as superalloys. Superalloys are characterized by the alloy maintaining its mechanical, thermal, and corrosion properties even at temperatures close to the melting point. The electrochemical corrosion analysis of alloys 59, 625, and 718 was performed with OCP, cyclic polarization, and EIS. The experiments made use of a three-electrode electrochemical cell with an Ag/AgCl reference electrode and a platinum counter electrode, as well as a Gamry Reference 600+ potentiostat. This work highlights the importance of performing cyclic polarization in the corrosion analysis since the method can reveal important differences in seemingly similar alloys, which was seen when comparing alloy 718 with 625 and 59. EIS is also shown to be a powerful analytical tool through the method's ability to approximate real electrochemical systems using electrical circuits, as well as the ability of EIS to be used as a complementary analytical tool to assist in interpreting cyclic polarization data.

Metallic additives, also known as anticorrosive pigments, can provide sacrificial cathodic protection and complement the barrier protection afforded by heterogeneous organic coatings to metallic substrates. The unique systematic study of the corrosion resistance of an epoxy coating reinforced with different sizes (80nm, 500nm, 10um) and continuous multiple pigment volume concentration (0, 2%, 10%, 20%, 45%) below global critical pigment volume concentration of zinc particles were studied. The thesis is developing the fundamental understanding to optimize corrosion protection and predicting the protection with time. The properties of these cathodic coatings were investigated by a single-frequency electrochemical impedance spectroscopy (EIS) and open circuit potential (OCP) measurements that can be used as to understand cathodic protective state. Finite Element Analysis (FEA) has been applied here for modeling and simulating part of actual experiments. This thesis will help understanding the sensitivity and efficiency to various size and loading of metallic additives for corrosion protection.

O uso do hidrogênio produzido pela água como vetor energético pode ser uma das soluções encontradas para evitar emissões de poluentes por ser uma energia limpa e renovável. Produzir o hidrogênio por intermédio de uma célula eletrolítica a membrana trocadora de prótons (PEMEC) é uma alternativa vantajosa, pois a forma sólida da membrana garante uma densidade de corrente elétrica maior comparada à eletrólise alcalina convencional, além de outras vantagens, como por exemplo, a relativa facilidade para manutenção. Os estudos presentes neste trabalho partiram da configuração de uma célula a combustível a membrana trocadora de prótons (PEMFC), entretanto, os dois tipos de células necessitam de materiais e catalisadores diferentes. Testes revelaram que placas bipolares de grafite da PEMEC não podem ser usadas, tampouco as de grafite cobertas com níquel devido à forte corrosão ocorrida na região anódica. A eletrólise por uma PEMEC é possível, no entanto, a escolha de materiais para a região anódica define a confiabilidade do método. Os aços inoxidáveis da série 3XX apresentaram os melhores resultados com níveis comerciais de produção de 75 a 85 mL.cm-2.min-1 de H2 em temperatura ambiente, com potencial de -1,9 V. Fizeram-se experimentos em PEMEC de aço AISI 310 que mostraram bom desempenho, mas ocorrendo corrosões e inviabilizando a continuidade do processo após 6h de operação. Análise por espectroscopia de impedância eletroquímica (EIE) na PEMEC desse aço foi feita para se estudar o aumento resistivo dos componentes da célula ao longo de uma sequência de eventos em um processo corrosivo do ânodo. / The use of hydrogen produced by water as energy vector can be one of the solutions to prevent emissions of pollutants because it is a clean and renewable energy. To produce hydrogen through a proton exchange membrane electrolytic cell (PEMEC) is an advantageous alternative, because the membrane as a solid structure ensures a higher electrical current density compared to conventional alkaline electrolysis, among other advantages, such as a relative ease of maintenance. The studies in this work started from the configuration of a proton exchange membrane fuel cell (PEMFC), however, both cell types require different materials and catalysts. Tests revealed that graphite bipolar plates cannot be used in PEMEC, either nickel coated graphite due to heavy corrosion in the anodic region. Electrolysis by a PEMEC is possible, however, the choice of materials for the anode region defines the reliability of the method. The 3XX series stainless steel showed the best results with commercial production levels from 75 to 85 mL.cm-2.min-1 H2 at room temperature, with a potential of -1.9 V. Experiments were made in PEMEC steel AISI 310 which showed good performance to produce H2, but as the corrosion occurred, the process become inadequate after 6 hours of operation. Analysis by electrochemical impedance spectroscopy (EIS) in this PEMEC with bipolar steel plates was made to study the increase of the cell components resistances along a sequence of events in a process of anode corrosion.

Neste trabalho foi investigado o efeito de vários tratamentos para modificação da superfície na resistência à corrosão do alumínio AA1050 com o objetivo de identificar um potencial substituto ao tratamento de cromatização. Os tratamentos adotados consistiram inicialmente de polimento da superfície até acabamento 1 m, seguido por uma etapa comercial. Este tratamento foi utilizado como preparação preliminar da superfície, anterior aos demais tratamentos testados. Amostras com o tratamento preliminar foram submetidas a diferentes tratamentos de modificação da superfície, especificamente, imersão em solução com moléculas auto-organizáveis (SAM) à base de difosfonato, imersão em água fervente para acelerar o crescimento de óxido-hidróxido de alumínio; uma combinação destes dois últimos tratamentos e cromatização em solução à base de cromo hexavalente. O comportamento de corrosão do alumínio AA1050 submetido aos diferentes tipos de tratamentos foi investigado por ensaios eletroquímicos como: medidas de potencial a circuito aberto em função do tempo de imersão, espectroscopia de impedância eletroquímica e ensaios de polarização potenciodinâmica. Utilizou-se solução de 0,5 M de Na2SO4 como meio corrosivo, tamponada a pH = 4,0. Microscopia eletrônica de varredura e análises semi-quantitativas de espectroscopia de energia dispersiva também foram utilizadas como medidas complementares nessa investigação. Observou-se que o tratamento com moléculas auto-organizáveis não se mostrou eficiente para proteção à corrosão para longos períodos de tempo em comparação aos demais tratamentos. A proteção fornecida pelos tratamentos, SAM e em solução a base de cromo hexavalente foi inferior à esperada. A etapa de boemitização ou crescimento acelerado de óxido-hidróxido de alumínio em água fervente se mostrou uma etapa essencial para aumento do desempenho frente à corrosão do alumínio AA1050. Os resultados obtidos para amostras submetidas ao tratamento de aceleração do crescimento de óxi-hidróxido seguido por imersão em solução com moléculas auto-organizáveis proporcionou uma melhora significativa na resistência à corrosão da superfície comparada aos demais tratamentos. / The aim of this work is to investigate the effect of various treatments for surface modification on the corrosion resistance of the aluminum AA1050. All the samples were firstly exposed to a preliminary surface treatment that consisted of surface polishing, up to a finishing of 1 m, succeeded by degreasing in two alkaline solutions and finally deoxidizing in an acid solution. This treatment was used as a preliminary surface preparation and adopted as a reference for comparison with the others. After this treatment, samples were exposed to various treatments for surface modification, specifically, immersion for 3 hours in a solution with self assembling molecules based on diphosphonates (SAM), immersion in boiling water for 20 minutes to promote bohemite growth (bohemitization); a combination of these two last treatments (bohemitization+SAM) and passivation in an hexavalent chromium solution. The objective was to investigate the potential of the tested treatments to replace the ones based on hexavalent chromium that generates toxic residues. The corrosion behavior of AA1050 aluminum samples with the various surface treatments was investigated by electrochemical methods such as: open circuit potential measurements, electrochemical impedance spectroscopy and potentiodynamic polarization curves. The electrolyte used was a 0.5 mol L-1 Na2SO4 solution, buffered to pH = 4.0. Surface characterization techniques, such as scanning electron microscopy and energy dispersive spectroscopy were also used in this investigation. The results showed that the treatment with self assembling molecules was not effective to protect the AA1050 aluminum for long periods of exposure to the electrolyte comparatively to the other surface treatments tested. The effect of SAM treatment or passivation with hexavalent chromium solution on the AA1050 aluminum corrosion resistance was unexpected. The bohemitization treatment that consisted of favoring oxide-hydroxide growth by immersion in boiling water increased the corrosion resistance of the AA1050 aluminum, but the highest corrosion resistance was associated to the treatment that combined bohemitization with SAM treatment.

Water diffusion is widely believed to be a driving factor in the breakdown of corrosion protection by polymer coatings. However, in the epoxy-phenolic system examined, water absorption into more cured, electrically resistive coatings is shown to increase, contradicting the common perception that hydrophobic coatings yield improvements in corrosion protection. Water uptake into epoxy-phenolic coatings was estimated as a function of time using the dielectric and resistive properties of the coating measured using electrochemical impedance spectroscopy (EIS). Bulk water uptake through the coating surface and the localised nature of corrosive failure was then confirmed using localised electrochemical impedance (LEIS). This technique also allowed comparison of resistance for coatings with different curing degrees. The greater degree of water absorption into highly cured coatings was attributed to diffusion into the polymer free volume, which increases with prolonged crosslinking. Evidence for this mechanism was found in the decreasing density of epoxy-phenolic coatings as a function of cure time. The effect of coating volume was therefore evaluated with respect to the dry coating dielectric properties. Cathodic delamination of the epoxy-phenolic coatings was achieved on tinplated steel substrates, whereas this was not possible from tin-free steel (ECCS). The electrochemical behaviour of these two substrates was examined under the same NaCl concentration, their surfaces were analysed by XPS prior to immersion, and XRD after potentiostatic polarisations. The electrochemical behaviour of the bare substrates was found to be unchanged by heating to the coating cure temperature (within the accuracy of polarisation tests carried out). Nonetheless, the delamination rate of epoxy-phenolic coatings deposited on them was dependent on the coating crosslinking (cure time). The reason coating adhesion selectively failed on tinplate substrates is believed to be the lower concentration of hydroxides on its relatively flat surface, allowing less bonding to take place at the interface with the coating. The impact of the substrate on coating resistivity was further investigated by volume resistivity measurements in the presence and absence of a metallic substrate. The resistivity of free standing films was tested in permeation cells, and showed a direct correlation between the polymer resistivity and the resistivity of the solution in which it was immersed. In comparison, attached films remained highly resistive at all examined concentrations. To conclude, the results presented here demonstrate that water uptake is not as critical to the breakdown in the protection offered by epoxy-phenolics as bonding at the metal-polymer interface. These results suggest that the complex interaction between these two dissimilar materials determines the overall coating electrochemical behaviour.

Thesis (Th. M.)--Talbot School of Theology, Biola University, 1988. / Includes bibliographical references (leaves 85-88).