Análise por difração de raios-x da interface plasma-superfície durante a nitretação a plasma

O presente trabalho apresenta o desenvolvimento de um equipamento utilizado para acompanhamento e monitoramento do processo de nitretação a plasma enquanto ele ocorre, ou seja, de forma in-situ. Os resultados obtidos com a utilização deste equipamento são demonstrados e confirmam a potencialidade da técnica na caracterização de mecanismos de nitretação a plasma. Ensaios de adaptação à técnica foram realizados, visando adquirir experiência no reconhecimento e detecção de fases formadas durante o processo e de possibilidades de caracterização proporcionadas pela técnica. Desta forma a influência de três composições gasosas na formação de camadas nitretadas em aço médio carbono AISI 1045 foi avaliada de forma in-situ por difração de raios-X e post-mortem por metalografia, GDOS e microdureza Vickers. A composição gasosa de 76% N2 – 24% H2 mostrou alto poder de nitretação, e formou camadas de compostos espessas e zonas de difusão profundas, com aumentos consideráveis de dureza. A composição gasosa de 5% N2 – 95% H2, formou camadas de compostos pequenas e zonas de difusão profundas, além de aumentos de dureza superficial. Em uma segunda avaliação, amostras de aço AISI 1045, foram nitretadas em duas composições gasosas: 5% N2 – 95% H2 e 25% N2 – 75% H2, nas temperaturas de 450ºC, 480ºC, 520ºC, 540ºC e 560ºC. Com o acompanhamento in-situ por difração de raios-X de trechos específicos de 2Θ correspondentes às linhas de difração das fases γ’ e ε, foi possível obter o tempo de incubação da fase γ’ para cada combinação composição gasosa - temperatura, que foram comparados com dados já existentes para nitretação a gás. Também foi possível o acompanhamento do crescimento, desenvolvimento e de mudanças na largura das linhas destas fases O tempo de incubação da fase γ’ permitiu a comparação entre os resultados das nitretações a plasma e os resultados previstos por um diagrama de Lehrer, e uma boa correlação entre as fases previstas pelo diagrama e as encontradas na prática foi encontrada. As amostras foram avaliadas ainda por difração de raios-X em ângulos rasantes, que permitiu a caracterização das camadas mais superficiais das amostras e, com base nestes resultados e nos resultados das análises in-situ, obteve-se um mapa prático de previsão de fases para a nitretação a plasma.

Modelação da interacção entre um plasma de arco de alta pressão e cátodos refractários

Nesta dissertação apresento um estudo detalhado de vários aspectos da interacção entre um plasma de arco de alta pressão e cátodos refractários. Um modelo da camada de plasma junto ao cátodo num plasma sujeito a uma pressão da ordem de uma ou várias atmosferas é reconsiderado com base em recentes resultados teóricos. A física da camada de plasma junto ao cátodo é analisada para valores da queda de tensão na camada de plasma junto ao cátodo até 50V, de acordo com recentes resultados experimentais que mostram que a queda de tensão na camada de plasma junto ao cátodo numa descarga de arco de alta pressão pode atingir valores tão elevados. São identificados os mecanismos que originam a não monotonia da dependência da densidade de fluxo de energia (proveniente do plasma para a superfície do cátodo) em relação à temperatura da superfície do cátodo, para um valor fixo da queda de tensão junto ao cátodo. Uma descrição fechada da interacção plasma-cátodo é obtida por meio da resolução numérica do problema não linear com condições de fronteira para a distribuição da temperatura no interior do corpo do cátodo. São apresentados resultados da modelação numérica da descarga difusa nas condições de funcionamento de uma lâmpada de descarga experimental, sendo bom o acordo entre os resultados numéricos e os dados experimentais. Manchas solitárias num cátodo plano infinito e modos difuso e mancha axialmente simétricos em cátodos finitos de descargas de arco de alta pressão são estudados num grande intervalo de corrente. São analisados aspectos gerais e apresentados resultados numéricos referentes a cátodos de tungsténio planos e de forma cilíndrica a operar num plasma de argon à pressão atmosférica para correntes de arco até 100 kA. Émostrado, em particular, que a temperatura da superfície do cátodo no interior de uma mancha solitária varia relativamente pouco, podendo ser estimada com uma precisão de cerca de 200 − 300K sem ser necesário resolver a equação da condução térmica no corpo do cátodo. O comportamento assimptótico das soluções para um cátodo finito no caso limite de altas correntes é encontrado e confirmado pelos resultados numéricos. É confirmado um padrão geral das características tensão-corrente de vários modos de transferência de corrente em cátodos finitos sugerido previamente com base numa análise de bifurcações. É estudada a transição de modos mancha num cátodo finito no limite de cátodos de grandes dimensões para o modo mancha solitária num cátodo plano infinito. É estabelecido que o modo mancha solitária representa uma forma limite do modo mancha de alta tensão num cátodo finito. É considerada a questão da distinção entre modo difuso e modo mancha num cátodo finito. É desenvolvida uma abordagem para o cálculo de pontos de bifurcação nos quais soluções mancha tridimensionais bifurcam-se a partir de soluções que descrevem o modo difuso e modos mancha axialmente simétricos. Em particular, é calculado o primeiro ponto de bifurcação posicionado na solução que descreve o modo difuso e, por conseguinte, o seu limite de estabilidade, isto é, a corrente abaixo da qual o modo difuso torna-se instável. São apresentados os resultados da modelação numérica efectuada para o caso de um cátodo de tungsténio de forma cilíndrica a operar num plasma de alta pressão. É estudado o efeito produzido no limite de estabilidade pelas variações dos parâmetros de controle (dimensões do cátodo, função de trabalho do material do cátodo, tipo e pressão do gás que produz o plasma). Foi encontrado que o comportamento do limite de estabilidade sujeito a estas variações está em conformidade com as tendências observadas experimentalmente. Foi encontrado que o limite de estabilidade é muito mais sensível às variações dos parâmetros de controle do que as características tensão-corrente do modo difuso, sendo o efeito mais forte produzido pelas variações das dimensões do cátodo e da função de trabalho do material do cátodo. Este resultado está em conformidade com o facto experimental de que a transição difuso-mancha é de difícil reprodução.

Estudo da adesão de pinos endodônticos modificados superficialmente por plasma de oxigênio

The work presents the effect of plasma treatment when applied in fibers or carbon/glass posts in the adhesion fiber/resin and posts/cement. This has for objective the modification of the surface of the fibers, as well as the wettability of the posts, seeking the improvement of the adhesion and of the connection fiber/resin in the processing of polymeric composites reinforced with the same ones. 120 posts (Reforpost) were used and 30 meters of fibers of carbon and of glass (Fibrex), of the company Angelus. The samples were divided in three groups of 40 specimens: GROUP I - 20 posts of glass fiber and 20 of carbon without treatment to it shapes, GROUP II -20 posts of glass fiber and 20 of carbon treated to it shapes in the surface and GROUP III - 20 posts of glass fiber and 20 of carbon make with fibers in natura after plasma treatment. The plasma treatment was accomplished with oxygen and with temperature in the camera fixed at 200°C, for one hour of exhibition. The posts and the fibers were characterized before and after the treatment. The wettability was measure by pendent drop method, and interface fiber/resin and posts/cement were observed by optical and electronic microscopy. It was observed that both wettability and texture were increased with plasma treatment

Avaliação do desempenho do aço D6 tratado termicamente e netretado em plasma com gaiola catódica visando aplicação industrial

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 300ºC 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 300ºC for heat samples. A superficial hardness of 1000HV and a 108µm thickness for the nitrided layer were found in these samples

Avaliação do desempenho do aço AISI D2 tratado termicamente e nitretado em plasma com gaiola catódica visando aplicação industrial

In the research, steel samples tool AISI D2, treated thermally, in the conditions: relief of tension, when maximum, seasoned and seasoned was treated thermally in the temperature of revenimento and revenida had been nitrited in plasma with cathodic cage, in atmosphere of 80%N2:20%H2. One used pressure of 2,5 mbar, 400 and 480°C temperatures with treatment time of 3 and 4 hours, with the objective to evaluate its performance in pipes cut tool. It was compared that the performance of the same steel when only thermally treated, both with tension relief. It was evaluated its hardness. Microstructural aspects (the layer thickness, interface, graisn size, etc) and crystalline phases on the surface. Besides, it was verified accomplishment possibility of nitriding simultaneous to annealing treatment. The tempering samples had presented hardness levels of 600 HV, while in nitrited samples these values had been 1100 HV

Desenvolvimento de um sistema de nitretação por plasma em fonte pulsada e sua influencia sobre a nitretação do titânio

The pulsed plasma nitriding is a solution currently used in the metallurgical industry to resolve problems earlier in the processing of parts by using plasma DC voltage. These problems consisted mainly of edge effect and opening arches caused due to non-uniformity of electric fields on uneven surfaces. By varying the pulse width can reduce these effects. However, variations in pulse width can drastically affect the population of the plasma species and hence the final microstructure of the nitrided layer. In literature, little is known about the effect of process parameters on the properties of the plasma species and, consequently, the surface properties. We have developed a system of nitriding with pulsed source with fixed period of 800  pulse width is variable. Examined the variation of these parameters on the properties of nitrided surface when keeping constant temperature, gas composition, flow, pressure and power. It was found that the values of width and pulse repetition time of considerable influence in the intensities of the species present in plasma. Moreover, we observed the existence of the edge effect for some values of pulse widths, as well as changes in surface roughness and hardness

Influência das espécies ativas na absorção de intersticiais durante a carbonitretação a plasma do TI

Physical-chemical properties of Ti are sensible to the presence of interstitial elements. In the case of thermochemical treatments plasma assisted, the influence of different active species is not still understood. In order to contribute for such knowledge, this work purposes a study of the role played by the active species atmosphere into the Ar N2 CH4 carbonitriding plasma. It was carried out a plasma diagnostic by OES (Optical Emission Spectroscopy) in the z Ar y N2 x CH4 plasma mixture, in which z, y and x indexes represent gas flow variable from 0 to 4 sccm (cm3/min). The diagnostic presents abrupt variations of emission intensities associated to the species in determined conditions. Therefore, they were selected in order to carry out the chemical treatment and then to investigate their influences. Commercial pure Ti disks were submitted to plasma carbonitriding process using pre-established conditions from the OES measurements while some parameters such as pressure and temperature were maintained constant. The concentration profiles of interstitial elements (C and N atoms) were determined by Resonant Nuclear Reaction Analysis (NRA) resulting in a depth profile plots. The reactions used were 15N(ρ,αγ)12C and 12C(α,α)12C. GIXRD (Grazing Incidence X-Ray Diffraction) analysis was used in order to identify the presence of phases on the surface. Micro-Raman spectroscopy was used in order to qualitatively study the carbon into the TiCxN1 structure. It has been verified which the density species effectively influences more the diffusion of particles into the Ti lattice and characteristics of the layer formed than the gas concentration. High intensity of N2 + (391,4 nm) and CH (387,1 nm) species promotes more diffusion of C and N. It was observed that Hα (656,3 nm) species acts like a catalyzer allowing a deeper diffusion of nitrogen and carbon into the titanium lattice.

Caracterização Microestrutural e Tribocorrosiva de Sistemas Metalocerâmicos Odontológicos do Tipo Ni-Cr/Porcelana E Ni-Cr/Ti/Porcelana

The partial fixed prosthodontics restoration is used to rehabilitate form and function of partial or total compromised teeth, having to remain permanently joined to remainder tooth. The most useful material on prosthodontics is the feldspar porcelain, commercialized as aluminosilicate powders. Dental porcelains are presented with limited mechanical properties to rehabilitate extensive spaces. The association with Ni-Cr metallic systems (metal-ceramic system) allows that the metallic substructure compensates the fragile porcelain nature, preserving the thermal insulation and aesthetics desirable, as well as reducing the possibility of cracking during matication efforts. Cohesive flaws by low mechanical strength connect the metallic substructure to the oral environment, characterized by a electrolytic solution (saliva), by aggressive temperature, pH cyclic changes and mechanical requests. This process results on ionic liberation that could promote allergic or inflammatory responses, and/or clinical degradation of ceramometal system. The aim of this study was to evaluate the presence of an intermediate titanium layer on the microscopic fracture behavior of porcelains on ceramometal systems. Plasma deposition of titanium films result in regular passivating oxide layers which act as barriers to protect the metallic substrate against the hazardous effects of corrosive saliva. Tribocorrosion tests were performed to simulate the oral environment and mechanical stress, making it possible the early detection of crack formation and growth on metal-ceramic systems, which estimate the adherence between the compounds of this system. Plain samples consisting of dental feldspar porcelain deposited either onto metallic substrates or titanium films were fired and characterized by scanning electron microscopy. The result showed that the titanium film improved the adherence of the system compared to conventional metal-ceramic interfaces, thus holding crack propagation

Influência das espécies do plasma de N2 + O2 nas propriedades físicoquímicas das superfícies do pet

This work reports the influence of the poly (ethylene terephthalate) textile and films surface modification by plasmas of O2 and mixtures (N2 + O2), on their physical and chemical properties. The plasma surface polymeric modification has been used for many researchs, because it does not affect the environment with toxic agents, the alterations remains only at nanometric layers and this technique shows expressive results. Then, due to its good acceptance, the treatment was carried out in a vacuum chamber. Some parameters remained constant during all treatment, such as: Voltage 470 V; Pressure 1,250 Mbar; Current: 0, 10 A and gas flow: 10 cm3/min, using oxygen plasma alternating the treatment time 10 to 60 min with an increase of 10 min to each subsequent treatment. Also, the samples were treated with a gas mixture (nitrogen + oxygen) which was varied only the gas composition from 0 to 100% leaving the treatment time remaining constant to all treatment (10 min). The plasma treatment was characterized in-situ with Optics Emission Spectroscopy (OES), and the samples was characterized by contact angle, surface tension, Through Capillary tests, Raman spectroscopy, Infrared attenuated total reflection (IR-ATR) and atomic force microscopy, scanning electronic Microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS). The results showed that oxygen treated fabrics presented high wettability, due to the hydrophilic groups incorporation onto the surface formed through spputering of carbon atoms. For the nitrogen atmosphere, there is the a film deposition of amine groups. Treatment with small oxygen concentration in the mixture with nitrogen has a higher spputered species of the samples

Diagnóstico das espécies ativas do plasma usado em tratamentos termoquímicos do titânio

Plasma diagnostics by Optical Emission Spectroscopy were performed for electrical discharge in three gas mixture respecting the combinations z N2 y Ar x H2, z N2 y Ar x O2 e z N2 y Ar x CH4, in which the indexes z and y systematically vary from 1 to 4 and x varies from 0 to 4, every one has dimension SCCM, resulting in 80 combinations. From the all obtained spectrums, the species CH (387,1 nm), N2+ (391,4 nm), Hβ (486,1 nm), Hα (656,3 nm), Ar (750,4 nm), O (777,4 nm) e O (842,6 nm) were analyzed because of their abundance and importance on the kinetic of reaction from the plasma to surface, besides their high dependences on the gases flows. Particularly interesting z, y and x combinations were chosen in order to study the influence of active species on the surface modification during the thermochemical treatment. From the mixtures N2 Ar O2 e N2 Ar CH4 were chosen three peculiar proportions which presented luminous intensity profile with unexpected maximum or minimum values, denominated as plasma anomaly. Those plasma concentrations were utilized as atmosphere of titanium treatment maintaining constant the control parameters pressure and temperature. It has been verified a relation among luminous intensity associated to N2+ and roughness, nanohardness and O atoms diffusion into the crystalline lattice of treated titanium and it has been seen which those properties becomes more intense precisely in the higher points found in the optical profile associated to the N2+ specie. Those parameters were verified for the mixture which involved O2 gas. For the mixture which involves CH4 gas, the relation was determinate by roughness, number of nitrogen and carbon atoms diffused into the titanium structure which presented direct proportionality with the luminous intensity referent to the N2+ and CH. It has been yet studied the formation of TiCN phases on the surface which presented to be essentially directly proportional to the increasing of the CH specie and inversely proportional to the increasing of the specie N2+

Estudo da molhabilidade de tecidos 100% poliéster tratados em plasma N2/O2 em função do seu envelhecimento natural

This work reports the influence of the poly (ethylene terephthalate) textile surface modification by plasmas of O2 and mixtures (N2 + O2), on their physical and chemical properties. The treatment was carried out in a vacuum chamber. Some parameters remained constant during all treatment, such as: Voltage 470 V; Pressure 1,250 Mbar; Current: 0, 10 A and gas flow: 10 cm3/min. Other parameters, such as working gas composition and treatment time, were modified as the following: to the O2 plasma modified samples only the treatment time was changed (10, 20, 30, 40, 50 and 60 minutes). To the plasma with O2 and N2 only the chemical concentrations were changed. Through Capillary tests (vertical) an increase in textile wettability was observed as well as its influence on aging time and its consequence on wettability. The surface functional groups created after plasma treatments were investigated using X-ray Photoelectron Spectroscopy (XPS). The surface topography was examined by scanning electron microscope (SEM)

Determinação do perfil térmico em amostras de aço AISI M35 imersas em plasma

The heat transfer between plasma and a solid occurs mostly due the radiation and the collision of the particles on the material surface, heating the material from the surface to the bulk. The thermal gradient inside the sample depends of the rate of particles collisions and thermal conductivity of the solid. In order to study that effect, samples of AISI M35 steel, with 9,5 mm X 3,0 mm (diameter X thickness) were quenched in resistive furnace and tempereds in plasma using the plane configuration and hollow cathode, working with pressures of 4 and 10 mbar respectively. Analyzing the samples microstructure and measuring the hardness along the transversal profile, it was possible to associate the tempered temperature evaluating indirectly the thermal profile. This relation was obtained by microstructural analyzes and through the hardness curve x tempered sample temperature in resistive furnace, using temperatures of 500, 550, 600, 650 and 700°C. The microstructural characterization of the samples was obtained by the scanning electron microscopy, optic microscopy and X-ray diffraction. It was verified that all samples treated in plasma presented a superficial layer, denominated affected shelling zone, wich was not present in the samples treated in resistive furnace. Moreover, the samples that presented larger thermal gradient were treated in hollow cathode with pressure of 4 mbar

Redução aluminotérmica do óxido de tântalo usando uma tocha de plasma como ignitor

In this work was used a plasma torch of non transferred arc with argon as work gas, using a power supply with maximum DC current of 250 A and voltage of 30 V to activate the plasma and keep it switched on. The flame temperature was characterized by optical emission spectroscopy, through Boltzmann-plot-method. The torch has been used like igniter in the aluminothermic reduction of the mixture tantalum oxide and aluminum, seeking to obtain metallic tantalum. In heating of the reagents only one particle will be considered to study interactions between plasma-particle, seeking to determinate its fusion and residence time. The early powders were characterized by laser granulometry, scanning electron microscopy (SEM) and X-ray diffraction analysis. The final product of this reaction was characterized by SEM and X-ray diffraction. Crystallite size was calculated by the Scherrer equation and microdeformation was determined using Willamsom-Hall graph. With Rietveld method was possible to quantify the percentile in weight of the products obtained in the aluminothermic reaction. Semi-quantitative chemical analysis (EDS) confirmed the presence of metallic tantalum and Al2O3 as products of the reduction. As was waited the particle size of the metallic tantalum produced, presents values in nanometric scale due the short cooling time of those particles during the process

Pastas compósitas cimento/sílica/polímero para cimentação de poços de baixa profundidade sujeitas à injeção de vapor

The production of heavy oil fields, typical in the Northeastern region, is commonly stimulated by steam injection. High bottom hole temperatures are responsible not only for the development of deleterious stresses of the cement sheath but also for cement strength retrogression. To overcome this unfavorable scenario, polymeric admixtures can be added to cement slurries to improve its fracture energy and silica flour to prevent strength retrogression. Therefore, the objective of the present study was to investigate the effect of the addition of different concentrations of polyurethane (5-25%) to cement slurries containing 40% BWOC silica flour. The resulting slurries were characterized using standard API (American Petroleum Institute) laboratory tests. In addition to them, the mechanical properties of the slurries, including elastic modulus and microhardness were also evaluated. The results revealed that density, free water and stability of the composite cement/silica/polyurethane slurries were within acceptable limits. The rheological behavior of the slurries, including plastic viscosity, yield strength and gel strength increased with the addition of 10% BWOC polyurethane. The presence of polyurethane reduced the fluid loss of the slurries as well as their elastic modulus. Composite slurries also depicted longer setting times due to the presence of the polymer. As expected, both the mechanical strength and microhardness of the slurries decreased with the addition of polyurethane. However, at high bottom hole temperatures, the strength of the slurries containing silica and polyurethane was far superior than that of plain cement slurries. In summary, the use of polyurethane combined with silica is an interesting solution to better adequate the mechanical behavior of cement slurries to heavy oil fields subjected to steam injection

Efeito antibacteriano de tecidos têxteis revestidos por prata através da técnica de deposição por plasma

In this study, it has been investigated the influence of silver film deposition onto 100% polyester woven and non-woven, on the survival of Escherichia coli and Staphylococcus aureus in contact with these surfaces. The treatment was performedin a chamber containing the working gas at low pressure (~ 10-2 mbar). Some process parameters such as as voltage: 470 V; pressure: 10-2 mbar; current : 0.40 A and gas flow: 6 and 10 cm3/min were kept constant. For the treatments with purêargon plasma using a flow of 6 and 10 cm3/min, different treatment times were evaluated, such as, 10 , 20, 30, 40, 50 and 60 minutes. Contact angle (sessile drop), measurements were used to determine the surface tension of the treated fabrics and its influence on the bacteria grow as weel as the possibilities of a biofilm formation. The formation of a silver film, as well as the amount of this element was verified byEDX technique. The topography was observed through scanning electron microscopy (SEM) to determine the size of silver grains formed on the surfaces of the fabric and assess homogeneity of treatment. The X-ray diffraction (XRD) was used to analyze the structure of silver film deposition. The woven fabric treatments enabled the formation of silver particulate films with particle size larger than the non-woven fabrics. With respect to bacterial growth, all fabrics were shown to be bactericidal for Staphylococcus aureus (S. aureus), while for the Escherichia coli (E. coli), the best results were found for the non-woven fabric (TNT) treated with a flow of 10 cm3/min to both bacteria