Orientador: Fernando Alvarez / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-23T23:30:17Z (GMT). No. of bitstreams: 1 Cucatti_SilviaAzevedodosSantos_M.pdf: 4655575 bytes, checksum: a7bdbfd34373445d40dd8ae10065030e (MD5) Previous issue date: 2013 / Resumo: A presente dissertação aborda a nanoestruturação de ligas metálicas de ferro a partir de bombardeamento iônico com Xe+ e seu efeito nas propriedades físicas de superfície, microestrutura, e na difusão de nitrogênio após nitretação à plasma pulsado. O atual interesse em modificação de superfícies surge da possibilidade de obtenção de novas propriedades físicas, mecânicas e tribológicas dos materiais. Particularmente, o bombardeamento iônico com gases nobres tem se mostrado um método importante para modificar a cinética de difusão de nitrogênio e a eficiência do processo, além das propriedades finais do material devido a criação de defeitos criados pelo impacto iônico tanto na superfície como, por efeito cascada, no volume. Sendo assim, estudar as mudanças geradas por bombardeamento iônico em ligas metálicas é fundamental tanto do ponto de vista tecnológico como dos fenômenos físicos básicos para um melhor entendimento da difusão de nitrogênio. Duas ligas metálicas de ferro foram investigadas: aço AISI 316L (alta liga) e AISI 4140 (baixa liga). A investigação da topografia das amostras estudadas após o bombardeamento mostrou que este procedimento induz a formação de padrões nanométricos dependentes da orientação cristalina da superfície e aumenta a rugosidade dos materiais analisados. Estudos de presença de microstrain realizados por difração de raios-X a baixo ângulo mostram que o bombardeamento gera defeitos na superfície e em volume por efeito cascada, em profundidades com ordens de magnitude maiores que a distância de frenamento dos íons Xe+. Verificou-se que a microestrutura e a dureza de seção transversal das ligas nitretadas são modificadas por bombardeamento iônico prévio ao procedimento de nitretação. Amostras pré-bombardeadas da liga AISI 4140 possuem agulhas de até alguns ?m de composts de nitretos enquanto tais compostos em amostras não sujeitas ao prébombardeamento são pequenos, granulares e descontínuos. Para a liga AISI 316L, foi observada uma camada de compostos única e compacta para amostras pré-bombardeadas, diferentemente da camada dupla, tipicamente encontrada em amostras sem tratamento prévio. Além disso, para esta liga, um perfil de dureza maior e mais suave foi encontrado para amostras pré-bombardeadas. Relacionamos as modificações da difusão de nitrogênio por bombardeamento iônico com o aumento do sticking factor do nitrogênio devido a múltiplas colisões resultantes da nanoestruturação e presença de canais extras de difusão / Abstract: This dissertation deals with the nanostructuration by low energy ion beam Xe+ (< 1keV) bombardment on the surface properties, microstructure and nitrogen diffusion after pulsed plasma nitridation of iron alloys. The current interest in surface modification arises from the possibility of obtaining new physical, mechanical and tribological properties of materials. In particular, noble gases ion bombardment is an important method for improve nitrogen diffusion modification, since the efficiency of the nitriding process and the material final properties are influenced by defects created by the ionic impact on both surface and bulk, the later by cascade collision effects. Therefore, the understanding of the modifications generated by ionic bombardment on metallic alloys is essential for better understanding nitrogen diffusion. Two type of alloys were investigated in this study: steels AISI 316L (high alloy) and AISI 4140 (low alloy). Investigations of the topography after bombardment showed that this procedure induces the formation of nanometric patterns within crystalline grains, increasing the roughness of the analyzed materials. Studies of the microstrain created by the ion bombardment by X-ray diffraction show that the bombardment generates bulk defects at distances orders of magnitude larger than the Xe+ ion stopping distance by cascade collisions. It was found that microstructure and cross-section hardness of nitrided alloys are modified by pre- ionic bombardment. Pre-bombarded AISI 4140 samples form long and needle-shaped nitrides compounds while the ones found in standard samples are small and discontinuous. For the AISI 316L alloy, differently from the double nitride layer normally found in nitrided standard samples, the pre-bombardment treatment leads to a single thick compact case, higher hardness and a smoother hardness gradient. We can correlate the nitrogen diffusion modifications by ionic bombardment with the increasing of the surface sticking factor and the presence of extra diffusion channels, due to the increasing roughness and defects in bulk after Xe+ bombardment, respectively / Mestrado / Física / Mestra em Física

Lors du traitement de nitruration, la diffusion de l'azote dans les aciers entraîne la transformation des carbures de revenu en nitrures. Durant cette transformation, du carbone est relâché dans la matrice ferritique. L'étude expérimentale a mis en avant que cette décarburation est observable quel que soit le type de nitruration et pouvait aller jusqu'à 20 % dans le cas où la couche nitrurée ne comportait pas de couche de combinaison. Cette décarburation est induite par la réaction du carbone relâché au cours de la transformation de la cémentite avec l'hydrogène issu de la décomposition de l'ammoniac pour former une espèce carbonée, cette réaction a lieu tant qu'aucune couche de combinaison n'est présente à la surface. Cette redistribution du carbone influe sur la microstructure et les profils de contraintes résiduelles des couches nitrurées. Grâce aux résultats expérimentaux, ce phénomène a été implémenté dans le modèle de simulation de la nitruration développé au laboratoire. Cette implémentation porte essentiellement sur les conditions initiales et aux limites qui ont été obtenues en complétant les résultats expérimentaux par une simulation thermodynamique permettant de simuler des profils d'azote et de carbone proches de ceux obtenus expérimentalement. Le modèle permet également de calculer la variation de volume accompagnant la précipitation et ainsi de calculer les champs des contraintes résiduelles générées à la température de nitruration et leurs modifications lors du refroidissement. Le caractère polyphasé du matériau est pris en compte, la simulation permettant de connaître les contraintes résiduelles dans la ferrite, les précipités et les contraintes résiduelles macroscopiques grâce à un modèle micromécanique de transition d'échelles de type auto-cohérent. Cette approche multiphysique est applicable à l'ensemble des aciers au carbone allié (Cr, Mo, V). Ce modèle a été plus particulièrement appliqué à la nuance industrielle 33CrMoV12-9. L'ensemble de cette étude a permis de comprendre l'influence du carbone sur les propriétés mécaniques des couches nitrurées et de mettre au point un cycle industriel de nitruration en se basant sur les résultats expérimentaux et la simulation. / During the nitriding treatment, the diffusion of nitrogen in the steels causes the transformation of initial carbides into nitrides. During this transformation, carbon is released into the ferritic matrix. The experimental study has highlighted that the decarburization of the nitride layer occurs regardless of the type of nitriding and could reach 20% when the nitriding surface is not composed of compound layer This decarburization is induced by the reaction of the carbon released during the transformation of the cementite, with the hydrogen produced by the decomposition of ammonia to give a carburized species ?, this reaction occurs as long as any compound layer exists at the surface of the sample. This carbon redistribution has an influence on the microstructure and the residual stresses of the nitride layers. Based on experimental results, this phenomenon has been implemented in the nitriding simulation model developed in the laboratory. This implementation focuses on initial and boundary conditions obtained by complementing the experimental results with a thermodynamic simulation, to simulate nitrogen and carbon profiles close to those obtained experimentally. The model also calculates the volume change due to ? the precipitation and calculates the fields of residual stresses generated at the nitriding temperature and their evolution during cooling.. The multiphase character of the material is taken into account; the simulation allowing knowing the residual stresses in the ferrite, the precipitates and macroscopic residual stresses through a micromechanical model of scale transition like self-consistent. This multiphysics approach is applicable to all alloy carbon steels (Cr, Mo, V). This model has specifically been applied to industrial grade 33CrMoV12-9. The entire study allows understanding the influence of carbon on the mechanical properties of nitrided layers and the development of an industrial nitriding cycle based on experimental results and simulation

Une micro-structuration de surface peut améliorer les propriétés en frottement d’un contact lubrifié grâce à la génération de pression hydrodynamique. Ce travail s’inscrit dans le cadre du projet ANR MicroGaMe, dont l’objectif était de structurer la surface d’une garniture mécanique en acier inoxydable austénitique. Nous avons développé un procédé basé sur l’utilisation des traitements thermochimiques à basse température (nitruration et carburation) assisté par plasmas froids. L’étude des couches obtenues après traitements a permis d’améliorer la compréhension de leur nature et de leur formation et de mettre en évidence la présence de précipités nanométriques. Lors des traitements, une déformation dans la direction perpendiculaire à la surface (appelée « gonflement »), et qui est la conséquence de fortes contraintes internes, peut être utilisée de façon originale comme moteur de structuration. Afin d’obtenir un motif « positif », nous avons traité les échantillons à travers des plaques d’acier percées par laser. La réalisation d’un motif « négatif » (cavité) nécessitant l’utilisation d’un masque discontinu, nous avons testé plusieurs voies de dépôts. La forme et les dimensions spécifiques à la garniture mécanique ne pouvant être obtenu par cette approche, nous avons également développé un procédé de gravure ionique, qui a pu être appliqué avec succès aux pièces à taille réelle / Surface patterning can improve friction properties of a lubricated contact by the generation of hydrodynamic pressure. The objective of the ANR project MicroGaMe was to pattern the surface of a mechanical seal in austenitic stainless steel. We developed a process based on the use of low-temperature plasma-assisted thermochemical treatments (nitriding and carburizing). The study of the treated layers leads to a better understanding of its nature and of the formation mechanisms and also reveals the presence of nanoprecipitates. During the treatments, a deformation occurs in a direction perpendicular to the surface (called “swelling”) as a consequence of high internal stresses, which can be used as an original patterning driving force. To obtain a “positive” pattern, we treated samples through laser-cut steel plates. A “negative” motif (cavitie) requires the use of a discontinuous mask so we tested different deposition techniques. As the specific shape and dimensions needed for the application to a mechanical seal cannot be obtained with this approach, we also develop an ion etching process, which has been successfully applied to real size piece

Os aços inoxidáveis austeníticos são materiais atrativos para serem utilizados em vários setores industriais que operam sob meios corrosivos, como por exemplo: indústria química, alcooleira, petroquímica, de papel e celulose, na prospecção de petróleo e nas indústrias têxtil e farmacêutica. Contudo, apresentam propriedades tribológicas pobres. No sentido de melhorar essas propriedades, como aumentar a dureza superficial, a resistência ao desgaste e a resistência à fadiga, vários métodos de tratamentos superficiais vêm sendo utilizados. Dentre eles, o mais eficiente é a nitretação por plasma. Este processo é realizado em uma câmara de vácuo sob uma mistura gasosa de hidrogênio e nitrogênio. É aplicada uma diferença de potencial entre o cátodo (porta amostras) e o ânodo (paredes da câmara), acelerando os íons contra a superfície da peça, aquecendo-a e arrancando elétrons de sua superfície. Os íons reagem com espécies da superfície do plasma formando compostos instáveis do tipo FeN que se recombinam para formarem nitretos estáveis. O sucesso deste tratamento se deve à baixa temperatura de operação, ao menor tempo efetivo de tratamento e ao controle da uniformidade da espessura da camada. A camada de nitretos formada durante o tratamento possui uma influência positiva na vida em fadiga de um componente, graças a dois motivos principais. O primeiro é o atraso na nucleação da trinca devido ao aumento da resistência mecânica superficial. O segundo motivo está relacionado com a introdução de tensões residuais compressivas durante o processo de endurecimento da superfície, que retarda a iniciação da trinca e diminui o fator de intensidade de tensão. Os corpos de prova foram nitretados a 400ºC durante 6 horas, com uma pressão de 4,5 mbar e utilizando uma mistura gasosa de 80% vol.H2 e 20%vol.N2. Ocorreu um aumento da resistência mecânica próxima á superfície, devido à camada de nitretos, o que ficou evidente com o sensível aumento no valor do limite de fadiga do material nitretado em relação ao não nitretado. O limite de fadiga do aço AISI 316 não tratado foi de 400MPa e do nitretado foi de 510MPa, enquanto que, para o aço AISI 304, o limite de fadiga do material não tratado foi de 380MPa e o limite para material submetido ao tratamento de nitretação foi de 560MPa. / The austenitic stainless steels are attractive materials to many industrial sectors which work on corrosive environments, as chemical industry alcohol, petrochemical, cellulose industries, in the petroleum prospection and pharmaceutical and textiles industries. However, they present poor tribological properties. In order to improve these properties, like increasing superficial hardness, wear and fatigue resistance superficial heat treatment methods have being used. The most efficient is the plasma nitriding process which occurs in a vacuum container under hydrogen and nitrogen gas mixture. A potential difference is applied between the cathode (samples receptor) and the anode (container walls), accelerating the ions against the piece, heating it and removing electron from the surface of material. These atoms react with the surface plasma species, producing unstable compounds like FeN, which recombine producing stable nitrides. The success of this treatment is due to the low temperature operation, the short effective time of treatment and to the uniformity control of the layer’s thickness. The nitrides layer produced during the treatment have a positive influence in the fatigue life of a component, thanks to two main reasons. The first is the retardation in crack nucleation due to increasing of superficial mechanical strength. The second reason is due to introduction of compressive residual stress during the surface hardening process, which retards de crack initiation process. The specimens were nitriding at 400°C during 6 hours, at a 4,5mbar pressure and using a gas mixture of 80% vol. H2 and 20% vol. N2. The surface mechanical strength increased, due to the nitrides layer, which was evident with the sensitive increase in the fatigue limit of the nitriding specimens, comparing to the untreated ones. The fatigue limit of the AlSl 316 steel in untreated condition was 400 MPa and in nitriding condition was 510 MPa, whereas AlSl 304 steel, the fatigue limit of the untreated condition was 480 MPa and the fatigue limit for the nitrided condition was 560 MPa.

Visando-se a avaliação do desempenho de um sistema de nitretação por plasma que se construiu bem como a determinação da influência das variáveis do processo sobre o desempenho das camadas nitretadas ionicamente, foram nitretadas amostras do aço \"maraging\" com a seguinte composição: Fe - 18Ni - 4.2Mo - 12.3Co - 1.7Ti - 0.15Al - 0.03C. Foram variadas as seguintes condições de processo: tempo, temperatura, freqüência do pulso e condição de tratamento térmico prévio. Foram realizadas análises metalográficas, difração de raios-X, microdureza e ensaios de abrasão do tipo \"pino-sobre-disco\" para caracterização das camadas obtidas. O equipamento de nitretação apresentou excelente desempenho no tratamento das amostras utilizadas e o aço \"maraging\", excelente resposta ao tratamento de nitretação. O tempo de tratamento de 3 horas produziu as camadas mais resistentes à abrasão. Os tratamentos com corrente contínua produziram resistências à abrasão superiores às obtidas com corrente pulsada. As amostras nitretadas após o envelhecimento apresentaram resistências superiores às envelhecidas simultaneamente com a nitretação. / Pursuing the evaluation and performance of a nitration system via plasma for us constructed, as well as the determination of the influence of variables of the process on the performance of ionically nitrated layers, it was nitrated maraging steel samples with the next compositions: Fe -18Ni - 4,2Mo - 12,3Co - 1,7Ti - 0,15AI- 0,03C. The following processing conditions were modified: time, temperature, pulse frequency end previous thermal treatment condition. Metallografic analyses, X-ray diffraction, microhardness and pin-on-dick type abrasion test were practised on samples for characterization of their layers. The nitration equipment had excellent performance in the treatment of samples used while the \"maraging\" steel showed excellent answer to the nitration treatment. A treatment time of three hours produced the more resistant layers to abrasion. The treatments with continuous current produced abrasion resistance higher than in treatment with pulsed current post-aged nitrated samples showed higher resistances than those aged during the nitration.

As superligas a base de níquel apresentam limitações para uso em temperaturas acima de 600 °C. Por este motivo, os revestimentos protetivos podem ser usados como barreiras para evitar a propagação de nucleação e fissuras. O presente trabalho tem por objetivo avaliar as propriedades mecânicas em altas temperaturas de amostras nitretadas por plasma da superliga INCONEL 625 foram realizados ensaios de tração e fluência em amostras com e sem tratamento. Nos ensaios de tração, nas temperaturas de 200 a 700 °C, o material apresentou uma oscilação nos valores de tensão a partir do início da deformação plástica. Este comportamento da curva tensão-deformação serrilhada pode estar associado com a difusão de um soluto intersticial ou pela difusão de átomos substitucionais ou pelo envelhecimento da deformação dinâmica (DSA). Em 600 °C, o aumento da taxa de deformação promoveu um aumento da amplitude e da frequência de oscilação da tensão. Sob níveis de tensões intermediários ou elevados o mecanismo de fluência dominante da liga Inconel 625 foi por escorregamento de discordâncias mostrando-se semelhante ao de muitos metais puros e ligas de soluções sólidas. / Nickel-based superalloys have limitations for use at temperatures above 600 °C. For this reason, protective coatings can be used as barriers to avoid both nucleation and crack propagation. Thus, to evaluate the mechanical properties at high temperatures of plasma nitrided samples of the INCONEL 625 superalloy, tensile and creep tests were performed on samples with and without treatment. In the tensile tests at temperatures of 200 to 700 °C the material showed an oscillation in the tension values from the beginning of the plastic deformation. This behavior of the serrated strain-strain curve may be associated with the diffusion of an interstitial solute or by the diffusion of substitutional atoms or by dynamic strain aging effect. At 600 °C, the increase in strain rate promoted an increase of the amplitude and oscillation frequency of the stress. Under levels of intermediate of elevated stresses, the dominant creep mechanism of the Inconel 625 alloy was like that of many pure metals and alloys of solid solutions which is by slippage of dislocations.

Nitrogen-doped carbon materials have garnered much interest due to their electrocatalytic activity towards important reactions such as the reduction of hydrogen peroxide. N-doped carbon materials are typically prepared and deposited on solid conductive supports, which can sometimes involve time-consuming, complex, and/or costly procedures. Here, nitrogen-doped screen-printed carbon electrodes (N-SPCEs) were fabricated directly from a lab-formulated ink composed of graphite that was modified with surface nitrogen groups by a simple soft nitriding technique. N-SPCEs prepared from inexpensive starting materials (graphite powder and urea) demonstrated good electrocatalytic activity towards hydrogen peroxide reduction. Amperometric detection of H2O2 using N-SPCEs with an applied potential of −0.4 V (vs. Ag/AgCl) exhibited good reproducibility and stability as well as a reasonable limit of detection (2.5 µM) and wide linear range (0.020 to 5.3 mM).

Studies of single, isolated nanoparticles provide better understanding of the structure-function relationship of nanoparticles since they avoid complications like interparticle distance and nanoparticle loading that are typically associated with collections of nanoparticles distributed on electrode supports. However, interpretation of results obtained from single nanoparticle immobilization studies can be difficult to interpret since the underlying nanoelectrode platform can contribute to the measured current, or the immobilization technique can adversely affect electron transfer. Here, we immobilized ligand-free gold nanoparticles on relatively electrocatalytically inert nitrogen-doped carbon ultramicroelectrodes that were prepared via a soft nitriding method. Sizes of the particles were estimated by a recently reported electrochemical method and were found to vary linearly with deposition time. The particles also exhibited electrocatalytic activity toward methanol oxidation. This immobilization strategy shows promise and may be translated to smaller nanoelectrodes in order to study electrocatalytic properties of single nanoparticles.

<p>Pages that are darker in colour were scanned one at a time to produce a high quality image.</p> / <p>Following a review of the gas nitriding process, of the Fe-N system and of the formation of the compound layer, this study investigates the interaction between the diffusing nitrogen and the material to be nitrided.</p> <p>The formation of the compound layer and diffusion case is discussed for pure iron. AISI 1070 low alloy steel is investigated using different microstructures and the resulting effect on the nitrided microstructure is presented. The interaction of a nitride forming element is studied with a Fe/Fe-5Cr diffusion couple specimen. The strengthening mechanisms resulting from the nitriding process for all these materials are discussed using standard models from the literature. The scale of the precipitates produced in pure iron as well as in the 1070 steel pearlitic and spheroidized microstructure is found to provide marginal hardening. The interaction between N and carbides obtained during the nitriding of the 1070 martensitic microstructure gives rise to a significant hardness increase up to 130HV. The most significant hardening effect (up to 900HV) is obtained with the formation of a high density of fine CrN precipitates in the Fe-Cr specimens.</p> / Master of Applied Science (MASc)

Made available in DSpace on 2014-12-17T14:57:58Z (GMT). No. of bitstreams: 1 KarilanyDC_TESE.pdf: 5082673 bytes, checksum: 4427463c2d2c4ca61196bdca31ba604e (MD5) Previous issue date: 2014-06-10 / In recent years there has been a significant growth in technologies that modify implant surfaces, reducing healing time and allowing their successful use in areas with low bone density. One of the most widely used techniques is plasma nitration, applied with excellent results in titanium and its alloys, with greater frequency in the manufacture of hip, ankle and shoulder implants. However, its use in dental implants is very limited due to high process temperatures (between 700 C o and 800 C o ), resulting in distortions in these geometrically complex and highly precise components. The aim of the present study is to assess osseointegration and mechanical strength of grade II nitrided titanium samples, through configuration of hollow cathode discharge. Moreover, new formulations are proposed to determine the optimum structural topology of the dental implant under study, in order to perfect its shape, make it efficient, competitive and with high definition. In the nitriding process, the samples were treated at a temperature of 450 C o and pressure of 150 Pa , during 1 hour of treatment. This condition was selected because it obtains the best wettability results in previous studies, where different pressure, temperature and time conditions were systematized. The samples were characterized by X-ray diffraction, scanning electron microscope, roughness, microhardness and wettability. Biomechanical fatigue tests were then conducted. Finally, a formulation using the three dimensional structural topology optimization method was proposed, in conjunction with an hadaptive refinement process. The results showed that plasma nitriding, using the hollow cathode discharge technique, caused changes in the surface texture of test specimens, increases surface roughness, wettability and microhardness when compared to the untreated sample. In the biomechanical fatigue test, the treated implant showed no flaws, after five million cycles, at a maximum fatigue load of 84.46 N. The results of the topological optimization process showed well-defined optimized layouts of the dental implant, with a clear distribution of material and a defined edge / Nos ?ltimos anos tem-se observado um grande crescimento em tecnologias para modifica??o de superf?cies de implantes que reduzam o tempo de espera da cicatriza??o, assim como possibilite seu uso com sucesso em ?reas de baixa densidade ?ssea. Dentre as diferentes t?cnicas, a nitreta??o por plasma desponta como forte candidata, uma vez que a mesma j? est? sendo empregada com excelentes resultados no tit?nio e suas ligas, aplicados com maior frequ?ncia na confec??o de implantes de quadril, ombro e tornozelo. Entretanto, seu uso em implantes dent?rios ? bastante limitado devido ?s altas temperaturas do processo (entre 700 C o e 800 C o ) resultando em distor??es nessas pe?as que possuem geometria complexa e alto grau de precis?o. O objetivo deste trabalho ? avaliar a osseointegra??o e resist?ncia mec?nica de amostras de tit?nio grau II nitretadas, atrav?s da configura??o de descarga em c?todo oco. Al?m disto, propor formula??es para determina??o da topologia ?tima estrutural do implante dent?rio em estudo, com o intuito de aperfei?oar sua forma, que seja eficiente, competitiva e com alta defini??o. No processo de nitreta??o, as amostras foram tratadas em temperatura a de 450 oC e press?o de 150 Pa , durante 1 hora de tratamento. Esta condi??o foi escolhida por apresentar os melhores resultados de molhabilidade em trabalhos anteriores, onde sistematizou-se diferentes condi??es de press?o, temperatura e tempo. As amostras tratadas foram caracterizadas por Difra??o de Raios-X, Microscopia Eletr?nica de Varredura, Rugosidade, Microdureza e Molhabilidade. Posteriormente, foram realizados ensaios biomec?nicos de fadiga. Finalizando com uma proposta de formula??o atrav?s do m?todo de otimiza??o topol?gica tridimensional, combinado a um processo de refino h-adaptativo. Os resultados mostraram que a nitreta??o a plasma, utilizando a t?cnica de descarga em c?todo oco, produziu mudan?as na textura superficial dos corpos de prova, aumento da rugosidade superficial, da molhabilidade e da microdureza quando comparado a amostra sem tratamento. No ensaio biomec?nico de fadiga, o implante tratado n?o apresentou sinal de falha, ap?s cinco milh?es de ciclos, a uma carga m?xima de fadiga de 84, 46 N . Os resultados do processo de otimiza??o topol?gica apresentaram leiautes otimizados bem definidos do implante dent?rio, com uma n?tida distribui??o de material e defini??o do contorno.