To form Cu interconnects, dual-damascene techniques like chemical mechanical planarization (CMP) and post-CMP became inevitable for removing the "overburden" Cu and for planarizing the wafer surface. During the CMP processing, Cu interconnects and barrier metal layers experience different electrochemical interactions depending on the slurry composition, pH, and ohmic contact with adjacent metal layers that would set corrosion process. Ruthenium as a replacement of existing diffusion barrier layer will require extensive investigation to eliminate or control the corrosion process during CMP and post CMP. Bimetallic corrosion process was investigated in the ammonium citrate (a complexing agent of Cu in CMP solutions) using micro test patterns and potentiodynamic measurements. The enhanced bimetallic corrosion of copper observed is due to noble behavior of the ruthenium metal. Cu formed Cu(II)-amine and Cu(II)-citrate complexes in alkaline and acidic solutions and a corrosion mechanism has been proposed. The currently used metallization process (PVD, CVD and ALD) require ultra-high vacuum and are expensive. A novel method of Si surface metallization process is discussed that can be achieved at room temperature and does not require ultra-high vacuum. Ruthenation of Si surface through strong Si-Ru covalent bond formation is demonstrated using different ruthenium carbonyl compounds. RBS analysis accounted for monolayer to sub-monolayer coverage of Si surface. Interaction of other metal carbonyl (like Fe, Re, and Rh) is also discussed. The silicon (111) surface modifications with vinyl terminated organic compounds were investigated to form self-assembled monolayers (SAMs) and there after these surfaces were further functionalized. Acrylonitrile and vinylbenzophenone were employed for these studies. Ketone group of vinylbenzophenone anchored to Si surface demonstrated reactivity with reducing and oxidizing agents.

Made available in DSpace on 2017-06-01T17:57:32Z (GMT). No. of bitstreams: 1 Ronaldo Pontes.pdf: 4668306 bytes, checksum: 48d4fe1ec07bae512f5d789ae55d9ec8 (MD5) Previous issue date: 2006-03-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Exposing concrete structures to the saline mist, they can suffer chlorides attacks and could cause reinforcement corrosion. The structures parts with faces directed to dominant winds are more susceptible, especially those with great surface in relation to the volume, such as pillars and beams. This work objective is to evaluate the level of marine aggressiveness, in marine edge of Boa Viagem quarter, Recife-PE, in function of the distance to the sea, measuring the value of chloride deposition, using the wet candle method, with the support of the environment management. The results indicate that chloride ions reach surface structure in different levels of concentration, depending on the distance from its origin, in this case, the sea. The conclusion is that chloride deposition decreases, in an exponential relation, when there is an increase of the distance to the sea, and that aggressiveness is significantly as far as 400 m from the marine edge / Diante da exposição à névoa salina, as estruturas em concreto podem sofrer ataques por cloretos, provocando corrosão das armaduras. As peças com faces voltadas aos ventos dominantes estão mais suscetíveis, especialmente aquelas que possuem grande superfície em relação ao volume, como são os casos de pilares e vigas. Este trabalho tem como objetivo avaliar os níveis de agressividade marinha, na orla marítima do Bairro de Boa Viagem, Recife-PE, em função de sua distância em relação ao mar, medindo a taxa de deposição de cloretos, pelo método da vela úmida, tendo como apoio o monitoramento do ambiente. Os resultados indicam que os íons cloreto chegam à superfície das estruturas a distintos níveis de concentração, dependendo da distância em relação à sua fonte geradora, no caso, o mar. Conclui-se que a deposição de cloretos decresce, numa relação do tipo exponencial, à medida que há um aumento do distanciamento em relação ao mar, e que a agressividade é significativa até 400 m da orla marítima

M.Tech. (Department of Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology / Corrosion responses of some carbon steels, stainless steel and copper alloys in the presence of a culture of bacteria (referred to as SRB-Sulphate-reducing bacteria) found in industrial heat exchangers, was studied to recommend best alloys under this service condition, with techno-economic consideration. Water from cooling towers in three plants in a petrochemical processing complex were analysed for SRB presence. Two of the water samples showed positive indication of SRB presence. The mixed cultures obtained from plant one were grown in prepared media and incubated at 35 °C for 18 days. Potentiodynamic polarisation studies in anaerobic conditions were done on the selected alloys in aqueous media with and without the grown SRB. Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) were then used to study the corrosion morphology and corrosion products formation. The voltamograms show higher icorr for alloys under the SRB compared to the control media, indicating the SRB indeed increased the corrosion rates. The surface analysis showed pitting on steel alloy ASTM A106-B. Localised attack to the grain boundaries on a selective area, was seen on ASTM A516-70 dislodging the grains, and intergranular corrosion was seen throughout the exposed area of ASTM A179. Copper alloys showed pitting on ASTM B111 grade C71500 (70-30), and denickelification on ASTM B111 grade C70600 (90-10), and is a good alternative material for use apart from carbon steel alloys, recording a low corrosion rate of 0.05 mm/year. The EDS analysis supported the findings showing higher weight percent of iron and sulphur on surface of the alloys after exposure to the SRB media. This implies that the presence of the sulphur ion indeed increased the corrosion rate. ASTM A516-70 carbon steel was chosen as a suitable alternative material to the stainless steel in this environment. The Tafel plot recorded a corrosion rate of 1.08 mm/year for ASTM A516-70 when exposed to SRB media.

Corrosion represents the single most frequent cause for product replacement or loss of product functionality with a 5% coat to the industrial revenue generation of any country in this dissertation the efficacy of using filled coatings as a protection coating are investigated. Fillers disrupt the polymer-substrate coating interfacial area and lead to poor adhesion. Conflicting benefits of increasing surface hardness and corrosion with long term durability through loss of adhesion to the substrate are investigated. The effects of filler type, filler concentration and exposure to harsh environments such as supercritical carbon dioxide on salt water corrosion are systematically investigated. The constants maintained in the design of experiments were the substrate, AISI-SAE 1018 steel substrate, and the corrosive fluid synthetic sea salt solution (4.2 wt%) and the polymer, Bismaleimide (BMI). Adhesion strength through pull-off, lap shear and shear peel tests were determined. Corrosion using Tafel plots and electrochemical impedance spectroscopy was conducted. Vickers hardness was used to determine mechanical strength of the coatings. SEM and optical microscopy were used to examine dispersion and coating integrity. A comparison of fillers such as alumina, silica, hexagonal boron nitride, and organophilic montmorillonite clay (OMMT) at different concentrations revealed OMMT to be most effective with the least decrease in adhesion from filler-substrate contact. Subsequently examining filler concentration, a 3 wt% OMMT was found to be most effective. A comparison of unmodified and modified BMI with 3 wt% OMMT exposed and not exposed to supercritical carbon dioxide showed that the BMI provided better corrosion protection; however, OMMT provided better wear, shear, and hardness performance.

There is a consistent need in many industries, especially oil and gas, to develop coatings which have higher corrosion resistance and better hardness to extend the lifetime of equipment when it is exposed to hostile environments. Electrodeposition has been a favorable method in the synthesis of metal coatings because of its low cost, convenience, ability to work at low temperatures, and ability to control surface morphology and structure. The inclusion of ceramic nanoparticles in metal matrix composites has previously been investigated as a technique to not only increase the corrosion resistance of the native metal but also to improve the hardness and mechanical properties. Cerium oxide nanoparticles were modified through the grafting of organic groups with increasing hydrophobicity for use in nickel coatings on stainless steel to further improve the corrosion properties while maintaining the hardness of the nanocomposite coatings. The process of modifying the cerium oxide nanoparticles involved the use of aryl diazonium salts and resulted in multilayers forming on the surface of the nanoparticles. Praseodymium oxide nanoparticles were also investigated as additives to nickel coatings, since praseodymium oxide has not yet been studied as a possible corrosion protection enhancement in coatings. These coatings were evaluated for composition and corrosion using many different types of instrumental and electrochemical techniques. With the addition of both the modified cerium oxide nanoparticles and the praseodymium oxide nanoparticles into nickel coatings, an increase in coating hardness and corrosion resistance was observed over pure nickel, resulting in an improvement of the lifetime of these coatings.

In this study, the surface degradation behavior was studied for typical examples from bulk metallic glasses (BMGs), metallic glass composites (MGCs) and high entropy alloys (HEAs) alloy systems that are of scientific and commercial interest. The corrosion and wear behavior of two Zr-based bulk metallic glasses, Zr41.2Cu12.5Ni10Ti13.8Be22.5 and Zr57Cu15.4Ni12.6Al10Nb5, were evaluated in as-cast and thermally relaxed states. Significant improvement in corrosion rate, wear behavior, and friction coefficient was seen for both the alloys after thermal relaxation. Fully amorphous structure was retained with thermal relaxation below the glass transition temperature. This improvement in surface properties was explained by annihilation of free volume, the atomic scale defects in amorphous metals resulting from kinetic freezing. Recently developed MGCs, with in situ crystalline ductile phase, demonstrate a combination of mechanical properties and fracture behavior unseen in known structural metals. The composites showed higher wear rates but lower coefficient of friction compared to monolithic amorphous glasses. No tribolayer formation was seen for the composites in sharp contrast to that of the monolithic metallic glasses. Corrosion was evaluated by open circuit potential (OCP) analysis and potentiodynamic polarization. Site-specific corrosion behavior was studied by scanning vibration electrode technique (SVET) to identify formation of galvanic couples. Scanning kelvin probe microscope was used to map elecropositivity difference between the phases and linked to wear/corrosion behavior. Phases with higher elecropositivity were more susceptible to surface degradation. Wear and corrosion synergy in marine environment was evaluated for two high entropy alloys (HEAs), CoCrFeMnNi and Al0.1CoCrFeNi. Between the two alloys, Al0.1CoCrFeNi showed better wear resistance compared to CoCrFeMnNi in dry and marine conditions due to quicker passivation, a higher magnitude of polarization resistance and significantly larger pitting resistance.

A polianilina é dos polímeros condutores mais estudados e com diversas aplicações, dentre elas o uso no recobrimento de aços para proteção à corrosão. Este trabalho objetivou encontrar as condições de eletrossíntese de polianilinas em meio aquoso neutro e a avaliação de proteção à corrosão, tendo como substrato o aço inox 304. As polianilinas eletrossintetizadas foram uma forma pura (PAni) e outra modificada com a adição de melamina (PAni/MM). Dentre as justificativas deste trabalho está a necessidade de aprofundar os escassos estudos em eletrossínteses em meio aquoso neutro. Neste trabalho, são apresentados as condições de eletrossíntese das polianilinas, a caracterização preliminar das polianilinas por UV-visível, FTIR e MEV, ensaios de polarização potenciodinâmica e impedância eletroquímica do aço inox 304 sem e com filmes das polianilinas para avaliar a resistência à corrosão em meio aquoso de NaCl 0,5 mol/L. O trabalho mostrou que a eletrossíntese das polianilinas em meio aquoso neutro é viável. Além disso, foi verificada a seguinte ordem do potencial de corrosão, do menor para o maior: aço inox 304 puro, aço inox 304 com PAni e aço inox 304 com PAni/MM. / Polyaniline is one of the most studied conducting polymers and with various applications, including use on steels for corrosion protection. This work aimed to find the conditions for electrosynthesis of polyanilines in neutral aqueous media and to evaluated the corrosion protection of 304 stainless steel. The electrosynthesizeds polyanilines were one pure form (PAni) and one with the addition of melamine (PAni/MM). One of the justifications of this work is the need to deepen the scarce studies in electrosynthesis in neutral aqueous media. In this work, we will see the conditions for electrosynthesis of polyanilines, the UV-visible, FTIR and SEM polyanilines preliminary characterization, the potentiodynamic polarization experiments and impedance spectroscopy of 304 stainless steel without and with films from polyanilines for evaluate the corrosion resistance in NaCl 0,5 mol/L aqueous media. This work showed that electrosynthesis of polyanilines is feasible in neutral aqueous media. In addition, it was verified the following order of corrosion potencial, from lowest to highest: pure 304 stainless steel, 304 stainless steel with PAni and 304 stainless with PAni/MM.

CNPq, CAPES, FINEP / Devido à alta resistência a corrosão, os aços inoxidáveis possuem uma larga aplicabilidade em diversos setores industriais, seja indústria química, petroquímica ou alimentícia. Buscando atender solicitações ainda mais severas, métodos que melhorem a relação resistência à corrosão e propriedades mecânicas destes aços tem sido objeto de estudo de diversos pesquisadores. Com o objetivo de aumentar a resistência mecânica, dureza superficial e resistência à corrosão dos aços inoxidáveis propôs-se a introdução de nitrogênio em solução sólida pelo processo de SHTPN (Solution Heat Treatment after Plasma Nitriding), em desenvolvimento no GrMaTS/UTFPR. O nitrogênio apresenta algumas vantagens como a redução da tendência à precipitação, e a estabilização da camada passiva. Além disso, o nitrogênio reage na área anódica, o que neutraliza o efeito da acidez melhorando assim a resistência a corrosão. Neste trabalho avaliou-se a resistência à corrosão do aço inoxidável ferrítico AISI 409, após a obtenção de uma camada martensítica enriquecida com nitrogênio em solução solida por meio do processo SHTPN. Em seguida foram avaliados os efeitos da temperatura de revenimento (200, 400 e 600 °C) e da temperatura de austenitização (950 e 1050 °C) na microestrutura, dureza e resistência à corrosão da camada martensítica obtida. A resistência à corrosão foi avaliada pela técnica de polarização cíclica em solução de NaCl 0,5 mol/L e os perfis de dureza obtidos por medição de dureza Vickers com carga de 0,05 Kgf (0,49 N). A microestrutura foi avaliada por Microscopia Óptica, Eletrônica de Varredura e por Difração de Raios-X. Os resultados indicam que o tratamento de SHTPN promoveu a formação de uma camada martensítica de nitrogênio, com consequente acréscimo de dureza de 160 HV para 580 HV. O tratamento têmpera após SHTPN não afetou significativamente a dureza do aço, contudo, refinou e melhorou a distribuição da martensita de nitrogênio. Os resultados de corrosão para as condições tratadas e revenidas a 200 °C indicam resistência à corrosão superior ou equivalente à da ferrita do material não tratado (AISI 409). Já as amostras revenidas nas temperaturas de 400 e 600 °C apresentaram um decréscimo na resistência à corrosão, bem como foi observada uma diminuição da dureza da amostra revenida a 600 °C. / Due to high corrosion resistance, stainless steels have a wide applicability in many industrial sectors, such as, chemical, petrochemical and food industries. With the demand for corrosion resistance materials becoming more stringent, methods that improve the relation corrosion resistance and mechanical properties of these steels has been studied by many researchers. In order to increase the mechanical strength, surface hardness and corrosion resistance of stainless steels we proposed the introduction of nitrogen in solid solution by the process of SHTPN (Solution Heat Treatment after Plasma Nitriding), under development in GrMaTS/UTFPR . Nitrogen in solid solution has some advantages over materials that have only carbon in the structure such lower tendency for precipitation and stabilization of the passive layer. In addition, the nitrogen reacts in the anodic area, which neutralizes the effect in the acidity thus improving the corrosion resistance. This research evaluate the corrosion resistance of ferritic stainless steel AISI 409, after obtaining a martensitic layer enriched with nitrogen, in solid solution, by SHTPN process. Effects of tempering temperature (200, 400 and 600 °C) and austenitization temperature (950 to 1050 °C) in the microstructure, hardness and corrosion resistance of martensitic layer obtained. Corrosion resistance was evaluated by cyclic polarization technique, with a NaCl solution 0.5 mol/L, and hardness profiles obtained by measuring the Vickers hardness with a load of 0.05 kgf (0.49 N). Samples microstructure was investigated by optical microscopy, scanning electron microscopy and X- ray diffraction. Results indicate that the treatment of SHTPN promoted the formation of a martensitic nitrogen layer, with consequent increase of hardness of 160 HV to 580 HV on sample surface. Tempering treatments, realized after SHTPN did not significantly affect the hardness of steel, however, has refined and improved the distribution of nitrogen martensite. Corrosion results of sample treated and annealed at 200 °C indicate higher or equal resistance to that of the untreated ferrite materials (AISI 409) corrosion. Samples that were annealed at temperatures of 400 and 600 °C showed a decrease in the corrosion resistance as well as a decrease in hardness was observed in the sample tempered at 600 °C.

Duas das principais formas de degradação de materiais metálicos estão relacionadas a danos mecânicos e eletroquímicos, devidos ao atrito, e à corrosão, respectivamente. Especialmente em materiais passivos, como os aços inoxidáveis, observa-se uma sinergia entre esses mecanismos de dano. Nesta dissertação foram realizados ensaios de tribocorrosão do aço superduplex UNS S32750 em solução aquosa de 3,5% em massa de NaCl. Para realizar estes ensaios foi necessário, inicialmente, instrumentar e adaptar um tribômetro do tipo pino-no-disco construído no Instituto Politécnico da UERJ. Para identificar os parâmetros de tribocorrosão mais relevantes para este sistema, foi elaborado um planejamento fatorial 23 e, a partir destes resultados, outros ensaios mais específicos foram elaborados. Técnicas eletroquímicas in situ de espectroscopia de impedância eletroquímica, polarização potenciodinâmica e amperometria de resistência nula foram usadas em amostras submetidas à solicitação tribológica. Os resultados mostraram que a carga aplicada no atrito é o fator de maior influência nas variáveis eletroquímicas medidas. Foi verificado que há efetivamente uma correlação entre os aspectos mecânicos e eletroquímicos com base no coeficiente de atrito e nos resultados dos ensaios eletroquímicos, principalmente nos obtidos de varredura potenciodinâmica e amperometria de resistência nula. Os dados eletroquímicos para a carga aplicada mostra claramente dois grupos com diferentes comportamentos, abaixo e acima da carga aplicada de 7 N. / Two of the main forms of degradation of metallic materials are related to mechanical and electrochemical damages due to friction and corrosion processes respectively. Especially in passive materials, such as stainless steels, there is a synergy between these mechanisms of damage. In this dissertation, we carried out tribocorrosion tests of superduplex steel UNS S32750 in 3.5 wt% NaCl aqueous solution. Initially, to perform these tests was necessary to instrumentate and adapt a pin-on-disk tribometer, wich had built at the Instituto Politécnico of UERJ. In order to identify most relevant tribocorrosion parameters of this system, was designed a 23 factorial design and, from these results, other more specific tests were developed. In situ electrochemical techniques of electrochemical impedance spectroscopy, potentiodynamic polarization and zero resistance amperometry were used on samples under tribological solicitation. The results showed that the applied load is the most influent factor on electrochemical measurements. It was found a close correlation between the electrochemical and mechanical aspects, based on the analysis of friction coefficient and the results of electrochemical tests, mainly those obtained from potentiodynamic sweeping and zero resistance amperometry. The electrochemical data for mechanical loads clearly shows two groups of different behaviors, below and beyond the applied charge of 7 N.

CNPq, CAPES, FINEP / Devido à alta resistência a corrosão, os aços inoxidáveis possuem uma larga aplicabilidade em diversos setores industriais, seja indústria química, petroquímica ou alimentícia. Buscando atender solicitações ainda mais severas, métodos que melhorem a relação resistência à corrosão e propriedades mecânicas destes aços tem sido objeto de estudo de diversos pesquisadores. Com o objetivo de aumentar a resistência mecânica, dureza superficial e resistência à corrosão dos aços inoxidáveis propôs-se a introdução de nitrogênio em solução sólida pelo processo de SHTPN (Solution Heat Treatment after Plasma Nitriding), em desenvolvimento no GrMaTS/UTFPR. O nitrogênio apresenta algumas vantagens como a redução da tendência à precipitação, e a estabilização da camada passiva. Além disso, o nitrogênio reage na área anódica, o que neutraliza o efeito da acidez melhorando assim a resistência a corrosão. Neste trabalho avaliou-se a resistência à corrosão do aço inoxidável ferrítico AISI 409, após a obtenção de uma camada martensítica enriquecida com nitrogênio em solução solida por meio do processo SHTPN. Em seguida foram avaliados os efeitos da temperatura de revenimento (200, 400 e 600 °C) e da temperatura de austenitização (950 e 1050 °C) na microestrutura, dureza e resistência à corrosão da camada martensítica obtida. A resistência à corrosão foi avaliada pela técnica de polarização cíclica em solução de NaCl 0,5 mol/L e os perfis de dureza obtidos por medição de dureza Vickers com carga de 0,05 Kgf (0,49 N). A microestrutura foi avaliada por Microscopia Óptica, Eletrônica de Varredura e por Difração de Raios-X. Os resultados indicam que o tratamento de SHTPN promoveu a formação de uma camada martensítica de nitrogênio, com consequente acréscimo de dureza de 160 HV para 580 HV. O tratamento têmpera após SHTPN não afetou significativamente a dureza do aço, contudo, refinou e melhorou a distribuição da martensita de nitrogênio. Os resultados de corrosão para as condições tratadas e revenidas a 200 °C indicam resistência à corrosão superior ou equivalente à da ferrita do material não tratado (AISI 409). Já as amostras revenidas nas temperaturas de 400 e 600 °C apresentaram um decréscimo na resistência à corrosão, bem como foi observada uma diminuição da dureza da amostra revenida a 600 °C. / Due to high corrosion resistance, stainless steels have a wide applicability in many industrial sectors, such as, chemical, petrochemical and food industries. With the demand for corrosion resistance materials becoming more stringent, methods that improve the relation corrosion resistance and mechanical properties of these steels has been studied by many researchers. In order to increase the mechanical strength, surface hardness and corrosion resistance of stainless steels we proposed the introduction of nitrogen in solid solution by the process of SHTPN (Solution Heat Treatment after Plasma Nitriding), under development in GrMaTS/UTFPR . Nitrogen in solid solution has some advantages over materials that have only carbon in the structure such lower tendency for precipitation and stabilization of the passive layer. In addition, the nitrogen reacts in the anodic area, which neutralizes the effect in the acidity thus improving the corrosion resistance. This research evaluate the corrosion resistance of ferritic stainless steel AISI 409, after obtaining a martensitic layer enriched with nitrogen, in solid solution, by SHTPN process. Effects of tempering temperature (200, 400 and 600 °C) and austenitization temperature (950 to 1050 °C) in the microstructure, hardness and corrosion resistance of martensitic layer obtained. Corrosion resistance was evaluated by cyclic polarization technique, with a NaCl solution 0.5 mol/L, and hardness profiles obtained by measuring the Vickers hardness with a load of 0.05 kgf (0.49 N). Samples microstructure was investigated by optical microscopy, scanning electron microscopy and X- ray diffraction. Results indicate that the treatment of SHTPN promoted the formation of a martensitic nitrogen layer, with consequent increase of hardness of 160 HV to 580 HV on sample surface. Tempering treatments, realized after SHTPN did not significantly affect the hardness of steel, however, has refined and improved the distribution of nitrogen martensite. Corrosion results of sample treated and annealed at 200 °C indicate higher or equal resistance to that of the untreated ferrite materials (AISI 409) corrosion. Samples that were annealed at temperatures of 400 and 600 °C showed a decrease in the corrosion resistance as well as a decrease in hardness was observed in the sample tempered at 600 °C.