Today, ethanol, as well as other biofuels, has been increasingly gaining popularity as a major alternative liquid fuel to replace conventional gasoline for road transportation. One of the key challenges for the future use of bioethanol is to increase its availability in the market via an efficient and economic way. However, one major concern in using the existing gas-pipelines to transport fuel-grade ethanol or blended fuel is the potential corrosion and stress corrosion cracking (SCC) susceptibility of carbon steel pipelines in these environments. Both phenomenological and mechanistic investigations have been carried out in order to address the possible degradation phenomena of X-65 pipeline carbon steel in simulated fuel-grade ethanol (SFGE). Firstly, the susceptibilities of stress corrosion cracking of this steel in SFGE were studied. Ethanol chemistry of SFGE was shown to have great impact on the stress corrosion crack initiation/propagation and the corrosion mode transition. Inclusions in the steel can increase local plastic strain and act as crack initiation sites. Secondly, the anodic behavior of carbon steel electrode was investigated in detail under different ethanol chemistry conditions. General corrosion and pitting susceptibility under unstressed condition were found to be sensitive to the ethanol chemistry. Low tendency to passivate and the sensitivity to ethanol chemistry are the major reasons which drive corrosion process in this system. Oxygen plays a critical role in controlling the passivity of carbon steel in ethanol. Thirdly, the detailed study was carried out to understand the SCC mechanism of carbon steel in SFGE. A film related anodic dissolution process was identified to be a major driving force during the crack propagation. Fourthly, more detailed electrochemical impedance spectroscopy (EIS) studies using phase angle analysis and transmission line simulation reveal a clearer physical picture of the stress corrosion cracking process in this environment. Fifthly, the cathodic reactions of carbon steel in SFGE were also investigated to understand the oxygen and hydrogen reactions. Hydrogen uptake into the pipeline steel and the conditions of the fractures related to hydrogen embrittlement were identified and studied.

This work presents a fracture mechanics analysis of the cathodic delamination problem for the polyurethane/titanium and polyurea/steel interfaces. The nonlinear behavior of both polymers was investigated. The recent Marlow model was used to define the strain energy function of the polymers. Viscoelastic effects of the polyurea were also studied. The Marlow model was associated with a nine-term Prony series. This model was seen to represent experimental data relatively well for a wide range of strain rates both in tension and compression. The driving force for delamination, the strain energy release rate G, is presented for both interfaces. Cathodic delamination data for several temperatures are presented as crack growth rate as a function of crack driving force. The approach recognizes that both temperature and stress can be used as accelerated life testing parameters. / text

Galvanic anode technology has in recent years come to the fore as a cost-effective method of successfully mitigating the corrosion of reinforcing steel in concrete structures. Developments in the field of cathodic protection have included the introduction of a novel Hybrid anode system, which uses the same sacrificial anode to pass a short-term impressed current before being connected to the steel directly to provide a long-term galvanic current. Galvanic and hybrid technologies are often seen as less powerful solutions in the treatment of reinforcement corrosion, and the test methodologies which determine the efficacy of cathodic protection systems favour impressed current technologies. The work completed has investigated the application of traditional and novel corrosion assessment techniques to laboratory samples to assess the protection offered by the hybrid treatment methodology in both treatment phases. In addition, the response of both galvanic and hybrid anodes to environmental conditions has been recorded and assessed before being discussed in the context of steel protection criteria. Finally, an investigation is presented into the on-site deterioration of commercially pure titanium feeder wire installed as part of the hybrid anode system and potential solutions to the problem have been documented. The research undertaken found that the hybrid anode system is capable of protecting steel in challenging, aggressive environments. This was confirmed by steel corrosion rate and indicative steel potential measurements. The responsive behaviour investigation showed that the current output of galvanic and hybrid anodes responds rapidly to changes in the corrosion risk posed to the steel and that this has a direct effect on anode system lifetimes. An assessment of the polarisation-based protection criteria applied to steel in concrete has found that the standard inhibits the use of responsive behaviour, and that revisions which consider the present risk of steel corrosion by considering the corrosion current resulting from the relative aggressivity of the concrete environment would be more valid in their application. A cathodic protection system based on the concepts of pit re-alkalisation and pH maintenance can fully utilise galvanic anode responsive behaviour. It was discovered that the deterioration of commercially pure titanium feeder wire seen on site installations was due to anodising in the presence of chloride media which had the potential to lead to pitting corrosion. The pitting risk varied depending on the duration of the treatment and proximity to the installed anode. An anodically grown oxide delayed the onset of corrosion in aqueous KBr solution, but did not significantly increase the pitting potential.

Made available in DSpace on 2014-12-17T14:06:48Z (GMT). No. of bitstreams: 1 JulioCPB.pdf: 2433728 bytes, checksum: 9509a2a35ebc0e4009df0a9bced418db (MD5) Previous issue date: 2007-11-14 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Plasma process like ionic nitriding and cathodic cage plasma nitriding are utilized in order to become hard surface of steels. The ionic nitriding is already accepted in the industry while cathodic cage plasma nitriding process is in industrial implementation stage. Those process depend of plasma parameters like electronic and ionic temperature (Te, Ti), species density (ne, ni) and of distribution function of these species. In the present work, the plasma used to those two processes has been observed through Optical Emission Spectroscopy OES technique in order to identify presents species in the treatment ambient and relatively quantify them. So plasma of typical mixtures like N2 H2 has been monitored through in order to study evolution of those species during the process. Moreover, it has been realized a systematic study about leaks, also thought OES, that accomplish the evolution of contaminant species arising because there is flux of atmosphere to inside nitriding chamber and in what conditions the species are sufficiently reduced. Finally, to describe the physic mechanism that acts on both coating techniques ionic nitriding and cathodic cage plasma nitriding / Processos a plasma como nitreta??o i?nica e nitrteta??o por gaiola cat?dica s?o utilizados para endurecimento de superf?cies de a?os. A nitreta??o i?nica sendo j? consolidada em aplica??es industriais enquanto que o processo por gaiola cat?dica ainda se encontra em est?gio de pesquisa. Esses processos dependem dos par?metros de plasma como temperatura eletr?nica e de ?ons (Te, Ti), densidade de esp?cies (ne, ni,) e da fun??o de distribui??o das mesmas. No presente trabalho, o plasma utilizado para esses dois processos foi diagnosticado utilizando a t?cnica de Espectroscopia de Emiss?o ?ptica EEO para identificar as esp?cies presentes no ambiente de tratamento e quantifica-las relativamente. Assim, plasma de mistura gasosa t?pica como N2 H2 foi monitorado, com o intuito de estudar a evolu??o dessas esp?cies durante o processo. Al?m disso, foi realizado um estudo sistem?tico, tamb?m atrav?s de EEO, que acompanha a evolu??o das esp?cies contaminantes surgidas em vazamentos de modo a buscar condi??es onde as mesmas s?o suficientemente reduzidas. Finalmente busca-se, atrav?s do diagn?stico de plasma por EEO, descrever o mecanismo f?sico de atua??o das duas t?cnicas de tratamento: nitreta??o i?nica e gaiola cat?dica

Made available in DSpace on 2014-12-17T14:06:50Z (GMT). No. of bitstreams: 1 MariaLMM.pdf: 1059040 bytes, checksum: e385dd512eb484e085eb027acc2a89fe (MD5) Previous issue date: 2008-08-22 / In this research there was an evaluation of the best conditions of nitriding in plasma within a cathodic cage at an atmosphere of 80% N2-20%H2 in samples of tool manganese steel AISI D6, cold working, treated thermally in the following conditions: tension relief, treated thermally to temperature of maximum heat, temperate heat and temperate and temperate heat. A pressure of 2.5mbar and temperatures of 400 and 300?C com treatment time of two and three hours were used to evaluate its performance as cutting tool (punch) of bicycle backs. Hardness, micro-structural aspects (layer thickness, interface, grain size etc), and crystal phases on the surface were appraised. When treated to tension relief, thermally treated to maximum heat temperature, temperature and temperate heat, the samples presented hardness levels of 243HV, 231HV, 832HV, and 653HV, respectively. The best nitrification conditions were: four hours and 300?C for heat samples. A superficial hardness of 1000HV and a 108?m thickness for the nitrided layer were found in these samples / Neste trabalho, foi realizada a avalia??o das melhores condi??es de nitreta??o em plasma com gaiola cat?dica, em atmosfera de 80%N2 - 20%H2 em amostras de a?o ferramenta para trabalho a frio AISI D6, tratado termicamente nas condi??es: al?vio de tens?o, tratado termicamente na temperatura de revenimento m?ximo, temperada e temperada e revenida. Usou-se press?o de 2,5 mbar, temperaturas de 400 e 300?C com tempo de tratamento de 3 e 4 horas, visando avaliar o seu desempenho em ferramenta de corte (pun??o) de rabeiras de bicicletas. Estimou-se a dureza, aspectos microestruturais (espessura da camada, interface, tamanho de gr?o, etc.) e fases cristalinas presentes na superf?cie. As amostras apresentaram n?veis de durezas 243HV, 231HV, 832HV e 653HV para as amostras com al?vio de tens?o, tratada termicamente na temperatura de revenimento m?ximo, temperada e temperada e revenida, respectivamente. As melhores condi??es de nitreta??o foram 4 horas a 300?C para as amostras temperadas e revenidas. As mesmas apresentaram uma dureza superficial em torno de 1000HV e 100?m de espessura para a camada nitretada

Made available in DSpace on 2014-12-17T14:07:08Z (GMT). No. of bitstreams: 1 RomuloRG.pdf: 2022744 bytes, checksum: b56ca8e09a24314d1127c49f3cf2e053 (MD5) Previous issue date: 2006-03-14 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The ionic nitriding process presents some limitations related with the control of the thickness of the layer and its uniformity. Those limitations that happen during the process, are produced due to edge effects, damage caused by arcing arc and hollow cathode, mainly in pieces with complex geometry and under pressures in excess of 1 mbar. A new technique, denominated ASPN (active screen shapes nitriding) it has been used as alternative, for offering many advantages with respect to dc plasma conventional. The developed system presents a configuration in that the samples treated are surrounded by a large metal screen at high voltage cathodic potencials, (varying between 0 and 1200V) and currents up to 1 A. The sample is placed in floting potential or polarized at relatively lower bias voltages by an auxiliary source. As the plasma is not formed directly in the sample surface but in the metal screen, the mentioned effects are eliminated. This mechanism allows investigate ion of the transfer of nitrogen to the substrate. Optical and electronic microscopy are used to exam morphology and structure at the layer. X-ray difration for phase identification and microhardness to evaluate the efficiency of this process with respect to dc conventional nitriding / O processo de nitreta??o i?nica apresenta uma s?rie de limita??es relacionadas com o controle da espessura da camada e de sua uniformidade. Essas limita??es s?o produzidas devido a efeitos de bordas e de c?todo oco que ocorrem durante o processo, principalmente em pe?as com geometria complexa e em press?es do processo superiores a 2 mbar. Assim uma nova t?cnica, denominada ASPN (Active screen plasma nitriding) est? sendo usada como alternativa, por oferecer muitas vantagens em rela??o ao plasma dc convencional. O sistema desenvolvido apresenta uma configura??o em que as amostras a serem tratadas permanecem envolvidas por uma tela que atua como c?todo com tens?o dc variando entre 0 e 1200V e correntes de at? 1 A. A amostra pode permanecer em potencial flutuante ou ser polarizada por uma fonte auxiliar. Como o plasma n?o ? formado diretamente na superf?cie das amostras e sim na tela, os efeitos citados s?o eliminados. Este mecanismo permite investigar a transfer?ncia de nitrog?nio para o substrato por microscopia ?ptica e microscopia eletr?nica de varredura para exames da morfologia e da estrutura, difra??o de raios-X para identifica??o de fases e os ensaios de microdureza permitem avaliar a efici?ncia deste processo em rela??o ? nitreta??o dc convencional

Made available in DSpace on 2014-12-17T14:07:19Z (GMT). No. of bitstreams: 1 KleberJBR.pdf: 2080899 bytes, checksum: a6de36601fae047815a4f83a4734f672 (MD5) Previous issue date: 2007-03-22 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Nowadays, in the plastic industry are used mills that accomplish the recycling of residues generated in the production of its components. These mills contain cut sheets that suffer accelerated wear, once they are submitted constantly to the tribologic efforts, decreasing its useful life. To reduce this problem, it s used noble steels or takes place superficial treatments. The ionic nitriding process presents some limitations related to the uniformity of the layer in pieces with complex geometry, committing its application in pieces as knives, head offices, engagements, etc. However, the new technique of nitriding in cathodic cage eliminates some problems, as the restrictions rings, inherent to the conventional ionic nitriding. In present work, was studied the use viabilization of steels less noble, as SAE 1020, SAE 4320 and SAE 4340, nitreded by two different techniques, to substitute the AISI 01 steels, usually used in the cut knifes fabrication, seeking to reduce the costs and at the sane time to increase the useful life of these knifes. The steel most viable was the SAE 4340, nitrided in cathodic cage, because it presented uniformity in thickness and in the hardness of the layer, besides of increased 58% in the average its useful life / Atualmente, na ind?stria de pl?sticos s?o utilizados moinhos que realizam a reciclagem dos res?duos gerados na produ??o de seus componentes. Esses moinhos cont?m l?minas de corte que sofrem desgaste acelerado, uma vez que s?o constantemente submetidas a esfor?os tribol?gicos, diminuindo sua vida ?til. Para amenizar este problema, s?o utilizados a?os nobres ou realizam-se tratamentos superficiais nos a?os convencionais. O processo de nitreta??o i?nica apresenta uma s?rie de limita??es relacionadas com a uniformidade da camada em pe?as de geometria complexa, comprometendo sua aplica??o em pe?as como facas, matrizes, engrenagens, etc. Uma nova t?cnica de nitreta??o a plasma, denominada nitreta??o i?nica em gaiola cat?dica elimina alguns problemas, como os an?is de restri??es, inerentes a nitreta??o i?nica convencional. No presente trabalho foi estudado a viabiliza??o do uso de a?os menos nobres como SAE 1020, SAE 4320 e SAE 4340, nitretados por ambas t?cnicas de nitreta??o, em substitui??o aos a?os AISI 01, normalmente usados na fabrica??o de facas de corte, com o objetivo de reduzir os custos e ao mesmo tempo proporcionar o aumento da vida ?til dessas facas de corte. O a?o que apresentou os melhores resultados foi o SAE 4340 nitretado em gaiola cat?dica, pois apresentou uniformidade na espessura e na dureza da camada nitretada, promovendo um aumento m?dio de 58% de sua vida ?til

Commercial alkaline accumulators with positive electrode based on nickel hydroxide generally comprise beta modification of the active material at present due to its excellent stabilization of performance during electrochemical cycling. This dissertation refers to a research work accomplished by author, which has been aimed to utilization of alpha nickel hydroxide in alkaline batteries including exploration of possibilities to attain its stability in strong alkali medium of the electrolyte. I have focused my effort to elucidate reasons for its transformation tendency and to find way of their suppression.

Este trabalho tem por objetivo avaliar os efeitos do hidrogênio em três diferentes tipos de aços de alta resistência mecânica. São descritos os fenômenos de introdução, difusão e aprisionamento de hidrogênio (H) dentro dos metais, em conjunto com os diferentes tipos de danos provocados devido à presença do hidrogênio. Os materiais de estudo são aços da família Advanced High Strength Steels (AHSS): aços Dual Phase (DP 1000 e DP 1200) e aço Martensítico (M 190). A introdução de hidrogênio nos materiais foi realizada através de carregamento catódico, o qual é representativo para as condições industriais a que se destinam. De modo a avaliar a influência do H nas propriedades mecânicas dos aços, os seguintes ensaios foram propostos: ensaio de carregamento com H, para determinar o conteúdo total de H (saturação) e conteúdo de H difusível (suscetibilidade a fragilização); ensaio de tração ao ar, para determinar a tensão no final da região elástica e resistência à tração na região do entalhe e ensaio de tração com carga constante em ambiente hidrogenado, para avaliar os efeitos provocados pela presença do H e determinar o patamar abaixo do qual o H não apresenta efeito crítico sobre o material. Os efeitos provocados pela aplicação de diferentes densidades de correntes (0,2 – 1,0 mA/cm²) foram avaliados nos ensaios de quantificação de H difusível. Conforme os resultados obtidos todos os aços apresentaram perdas na resistência mecânica à tração quando em ambiente hidrogenado, ou seja, sofreram fragilização por H. Os aços DP 1200 e M 190 (de microestrutura predominantemente martensítica) foram fortemente afetados, conforme evidenciado pela notável queda nos valores de tensão necessários para provocar a falha. Por outro lado, o aço DP 1000, de menor resistência mecânica, demonstrou menor suscetibilidade à fragilização, o que é atribuído a menor permeabilidade do H na microestrutura austenítica. / This work aims to evaluate the effects of hydrogen in three high- strength steel grades. The phenomena of hydrogen (H) entry, transport and trapping inside the metals, together with the different types of damages due to the presence of hydrogen are presented. The study materials are a range of AHSS steel grades: Dual Phase Steel (DP 1000 and DP 1200) and Martensitic Steel (M 190). The hydrogen entry was performed by cathodic charging, which is suitable for industrial applications. In order to evaluate the influence of H on the steel mechanical properties, the following tests were done: H charging, to measure total H content (saturation point) and diffusible H content (embrittlement susceptibility); uniaxial tensile test of uncharged samples to determine notched tensile strength values and the strength levels at the end of elastic region and constant load tensile testing carried out in hydrogen environment, to determine the threshold values where hydrogen has an effect on the material. DP 1200 and M 190 were strongly affected by H pre-charging, as shown by the significant drop in stress required to break them. On the other hand, DP 1000 showed a lower embrittlement susceptibility, which is attributed to its lower mechanical strength. The current densities effects (0.2 up to 1.0 mA/cm²) were evaluated during H charging to measure diffusible H content. All steels showed a drop in the tensile strength i.e. experienced hydrogen embrittlement. Steels with higher tensile strength, as DP 1200 and M 190, showed a much bigger drop that is related to the favorable characteristics of martensitic microstructure regarding to the hydrogen permeability and diffusivity.

Made available in DSpace on 2014-12-17T15:15:04Z (GMT). No. of bitstreams: 1 AnaKGA_DISSERT.pdf: 1807771 bytes, checksum: 5500fb357c9de3200037867308a2a9b6 (MD5) Previous issue date: 2014-07-25 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Iron nitrite films, with hundred of nanometers thick, were deposited using the Cathodic cage plasma nitriding method, with a N2/H2 plasma, over a common glass substract. The structure, surface morphology and magnetic properties were investigated using X-ray diffractometry (XRD), atomic force microscopy (AFM) and vibrating sample magnetometer (VSM). XRD shows the formation of γ FeN phase and a combination of ζFe2N + ɛFe3N phases. The film s saturation magnetization and coercivity depends on morphology, composition, grain size and treatment temperature. Temperature raising from 250 ?C to 350 ?C were followed by an increase in saturation magnetization and film s surface coercivity on the parallel direction in relative proportion. This fact can be attributed to the grain sizes and to the different phases formed, since iron rich fases, like the ɛFe3N phase, emerges more frequently on more elevated treatment s temperature. Using this new and reasonably low cost method, it was possible to deposit films with both good adhesion and good magnetic properties, with wide application in magnetic devices / Filmes de nitreto de ferro, com centenas de nanometros de espessura foram depositados pelo m?todo de deposi??o/nitreta??o por Gaiola Cat?dica utilizando um plasma de N2/H2 sobre um substrato de vidro comum. A estrutura, morfologia da superf?cie e propriedades magn?ticas foram investigadas com o uso de Difratometria de Raio-X (DRX), Microscopia de For?a At?mica (MFA) e Magnet?metro de Amostra Vibrante (MAV). A DRX exibe a forma??o da fase γ FeN e mistura de fases ζFe2N + ɛFe3N. A magnetiza??o de satura??o e coercividade dos filmes de nitreto de ferro dependem da morfologia, composi??o, tamanho de gr?o e temperatura de tratamento. Com o aumento da temperatura de 250 para 350 ?C, a magnetiza??o de satura??o e a coercividade na dire??o paralela ? superf?cie dos filmes tamb?m aumentam em propor??o relativa. Isto pode ser atribu?do aos tamanhos de gr?os e ?s diferentes fases formadas, j? que fases ricas em ferro como ɛFe3N surgem com frequ?ncia maior em temperaturas de tratamento mais elevadas. Neste estudo foi poss?vel a deposi??o de filmes de boa ades?o e boas propriedades magn?ticas com grande aplica??o em dispositivos magn?ticos por um m?todo novo e de baixo custo