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+

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+

Implantação iônica por imersão em plasma e deposição de filmes finos poliméricos provenientes da mistura hexametildisilazano/argônio

Thin polymeric films deposited by plasma are very atractive for many industrial and scientific applications, in areas such as electronics, mechanics, coatings, biomaterials, among others, due to its favorable properties such as good adhesion to the substrate, high crosslinking, nanomectric thickness, homogeneity, etc. In this work, thin films were deposited by plasma immersion ion implantation and deposition technique from a hexamethyldisilazane/argon mixture at different proportions. These films were subjected to several characterizations, such as, contact angle, which presented values near to 100 degrees, surface energy, with values near to 31 mJ/m2, hardness with values between 0.7 and 2.6 GPa, thickness from 100 to 200 nm, refractive index from 1.56 to 1.64, molecular structure presenting the following functional groups in the infrared spectra region: CHx from 2960 to 2900 cm-1; Si-H around 2130 cm-1; CH3 in Si-(CH3)x around 1410 cm-1; CH3 in Si-(CH3)x in 1260 cm-1; N-H around 1180 cm-1; CH2 in Si-CH2-Si bonds around 1025 cm-1; Si-O in Si-O-Si from 1020 to 1100 cm-1; Si-N in Si-H-Si bonds around 940 cm-1; CH3 in Si-(CH3)3 in 850 cm-1; Si-C bonds in Si-(CH3)2 around 800 cm-1; and Si-H in 680 cm-1 . From these characterizations, it was possible to conclude that the concentration of argon or hexamethyldisilazane in the mixture changed the resulting polymer

Produção de estrutura com gradiente de porosidade a partir da sinterização por plasma da mistura de pós Ti-Nb-Sn

Porous structures are being widely investigated for use in biomedical implants, aiming to mechanically integrate and functionally the implant inside the bone tissue. Moreover, this structure is also important for drugs that can be stored and can induce and accelerate the process of osseointegration. With the purpose to investigate this effect, Ti, Nb and Sn metal powders, were sintered by plasma using a hollow cathode discharge. Sintering was performed in argon plasma set at 4 mbar pressure and temperatures of 500 ° C, 600 ° C and 700 ° C. Samples were also sintered in the electrical resistance furnace at 1200 ° C in order to compare plasma sintering with the conventional method. It was observed that plasma samples sintered with the hollow cathode configuration showed a gradient in porosity, while the samples sintered in the resistive furnace did not. Furthermore, differences in the microstructure of the samples were found, were a surface with higher porosity and ales porous core were obtained at different temperatures. The percolation profile of distilled water and the chemical compositions of the porous layers of the plasma treated samples were the main results obtained. Based on these results, we can conclude that this structure is particularly important for application in the biomedical field such as scaffolds for drug delivery and implants

Weathering resistance of thin plasma polymer films on pre-coated steel

O trabalho apresentado teve origem no projecto de investigação “Tailored Thin Plasma Polymers Films for Surface Engineering of Coil Coated Steel”, financiado pelo Programa Europeu ECSC Steel Research. Sistemas de aço galvanizado pré-pintado em banda à base de poliéster e poliuretano foram submetidos a um processo de polimerização por plasma onde um filme fino foi depositado de modo a modificar as propriedades de superfície. Foram usados reactores de cátodo oco, microondas e rádio frequência para a deposição do polímero fino. Os sistemas preparados foram analisados de modo a verificar a influência do processo de polimerização por plasma na alteração das propriedades barreira dos sistemas pré-pintados em banda. Foi estudado o efeito dos diferentes passos do processo de polimerização por plasma, bem como o efeito de diferentes variáveis operatórias. A mistura precursora foi variada de modo a modificar as propriedades da superfície de modo a poder vir a obter maior hidrofobicidade, maior resistência a marcas digitais, bem como maior facilidade de limpeza. Os testes foram conduzidos em solução de NaCl 0,5 M. Para o trabalho foram usadas técnicas de análise da morfologia da superfície como Microscopia de Força Atómica e Microscopia Electrónica de Varrimento. As propriedades electroquímicas dos sistemas foram estudadas por Espectroscopia de Impedância Electroquímica. A estrutura dos filmes gerados no processo de polimerização por plasma foi caracterizada por Microscopia de Transmissão Electrónica. A modificação das propriedades ópticas devido ao processo de polimerização por plasma foi também obtida.

Estudo da nitretação a plasma aplicada em ferramentas para fresamento

Este trabalho tem como objetivo estudar a influência do tratamento superficial, através da técnica de nitretação a plasma, no processo de fresamento com fresas de aço rápido AISI M2. Foram investigados os efeitos deste tratamento superficial no processo de corte, variando-se a forma de refrigeração/lubrificação das fresas com fluído de corte convencional (emulsão) em abundância, com minimização e sem fluído (lubrificação a seco). Na nitretação, a composição da mistura de gases utilizada nos experimentos foi de 5% N2 e 95% H2 em volume, a uma pressão de tratamento de 5 mbar (3,8 Torr). A temperatura utilizada foi de 440oC, durante um tempo de tratamento de 30 minutos, resultando em uma camada nitretada com uma zona de difusão com aproximadamente 8µm de profundidade. As ferramentas empregadas no processo de fresamento foram investigadas através de medição de forças de usinagem, medições de desgaste na superfície de incidência (flanco) e na superfície de saída (face), sendo as camadas nitretadas caracterizadas por metalografia óptica e microdureza. Foi observado um desempenho superior das fresas nitretadas apenas para as condições de corte a seco.

Caracterização da resistência a corrosão de camadas obtidas por nitretação a plasma e deposição física de vapor sobre aço inoxidável AISI 316 L

A técnica de revestimento duplex combina dois processos: o tratamento de nitretação a plasma da superfície e a deposição de uma camada via PVD. O processo de nitretação a plasma sob condições controladas pode produzir a chamada “fase S” sem a presença de nitretos de cromo, o que confere ao aço tratado maior dureza e melhor resistência à corrosão. Os revestimentos de nitreto de titânio melhoram a dureza superficial do material, porém defeitos e poros podem expor o substrato ao meio. Este trabalho consiste no estudo da resistência à corrosão do aço inoxidável austenítico AISI 316L revestido com camada duplex em meio contendo cloretos. As camadas nitretadas a plasma foram obtidas pelo processo de nitretação iônica e os revestimentos Ti/TiN foram obtidos pelo processo de deposição física de vapor assistida por plasma (PAPVD). Os corpos de prova foram inicialmente avaliados por microscopia eletrônica de varredura (MEV) e a composição das fases foi identificada por difração de raios-x (DRX). A dureza foi avaliada por nanoidentação e a rugosidade superficial também foi medida. Os testes de resistência à corrosão foram feitos por voltametria cíclica (VC) e os ensaios de corrosão acelerada em câmara de névoa salina. A amostra nitretada a 400°C por 4 horas e mistura gasosa de 5%N2- 95%H2 apresentou o melhor desempenho de resistência à corrosão em meio contendo cloretos. A resistência à corrosão foi associada à estrutura obtida após o tratamento por nitretação a plasma e deposição física de vapores (PVD).

Nitretação a plasma em aço inoxidável 17-4 PH

Este trabalho tem por objetivo otimizar os parâmetros de nitretação a plasma para a formação de camadas nitretadas com propriedades tribológicas adequadas para a utilização em ponteiras de conexão utilizadas em “risers” de completação de poços de petróleo. Para atingir este objetivo, amostras de aço inoxidável endurecível por precipitação 17-4 PH foram nitretadas a plasma em um reator com mistura gasosa de 76%N2 e 24%H2 durante 4 horas. As temperaturas utilizadas no processo foram 400, 450, 480 e 550°C. As camadas nitretadas produzidas foram avaliadas quanto à morfologia, espessura, composição, dureza, resistência à corrosão e resistência ao desgaste. Os resultados demonstraram que as condições de nitretação utilizadas foram eficientes no endurecimento superficial das amostras. A utilização de temperatura elevada (550°C) não é adequada para a nitretação de aços inoxidáveis endurecíveis por precipitação 17-4 PH. A amostra nitretada a 450°C apresentou a melhor combinação de propriedades para aplicação nas ponteiras de “risers” de completação.

Nitretação a plasma em furos não passantes

Este trabalho tem por objetivo avaliar a influência dos parâmetros pressão, freqüência e fator de trabalho, bem como a interação destes fatores, na capacidade de gerar plasma estável e com propriedades nitretantes no interior de furos não passantes de pequeno diâmetro. Para atingir estes objetivos foram realizados experimentos utilizando um reator equipado com fonte de potência pulsada de 2 KW, mistura gasosa composta de 76% de Nitrogênio e 24% de Hidrogênio, amostras de aço ABNT 1045 normalizadas. As nitretações foram realizadas pelo período de uma hora a temperatura de 500 0C. Foram empregadas freqüências de 100, 1000 e 5000 Hz, fatores de trabalho de 0,5 (50%), 0,75 (75%), 1 (100%), as pressões utilizadas foram de 2, 3 e 4 Torr e furos não passantes de φ3 x 40 mm, φ4 x 60 mm, φ5 x 75 mm. Para determinar a significância de cada parâmetro e de suas interações foi utilizado o modelo estatístico Multi-Factor Anova, com projeto fatorial cruzado a 3 fatores e 3 níveis para cada fator. Com o uso do programa Statgraphics foram geradas as equações que mais se ajustaram ao modelo. Estas equações determinam a máxima profundidade de geração de plasma nitretante no interior dos furos de pequeno diâmetro para as condições de tratamento expostas acima.

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.

Influência dos parâmetros de processo na deposição de nitreto de titânio por plasma em gaiola catódica

Titanium nitride films were grown on glass using the Cathodic Cage Plasma Deposition technique in order to verify the influence of process parameters in optical and structural properties of the films. The plasma atmosphere used was a mixture of Ar, N2 and H2, setting the Ar and N2 gas flows at 4 and 3 sccm, respectively and H2 gas flow varied from 0, 1 to 2 sccm. The deposition process was monitored by Optical Emission Spectroscopy (OES) to investigate the influence of the active species in plasma. It was observed that increasing the H2 gas flow into the plasma the luminescent intensities associated to the species changed. In this case, the luminescence of N2 (391,4nm) species was not proportional to the increasing of the H2 gas into the reactor. Other parameters investigated were diameter and number of holes in the cage. The analysis by Grazing Incidence X-Ray Diffraction (GIXRD) confirmed that the obtained films are composed by TiN and they may have variations in the nitrogen amount into the crystal and in the crystallite size. The optical microscopy images provided information about the homogeneity of the films. The atomic force microscopy (AFM) results revealed some microstructural characteristics and surface roughness. The thickness was measured by ellipsometry. The optical properties such as transmittance and reflectance (they were measured by spectrophotometry) are very sensitive to changes in the crystal lattice of the material, chemical composition and film thicknesses. Therefore, such properties are appropriate tools for verification of this process control. In general, films obtained at 0 sccm of H2 gas flow present a higher transmittance. It can be attributed to the smaller crystalline size due to a higher amount of nitrogen in the TiN lattice. The films obtained at 1 and 2 sccm of H2 gas flow have a golden appearance and XRD pattern showed peaks characteristics of TiN with higher intensity and smaller FWHM (Full Width at Half Maximum) parameter. It suggests that the hydrogen presence in the plasma makes the films more stoichiometric and becomes it more crystalline. It was observed that with higher number of holes in the lid of the cage, close to the region between the lid and the sample and the smaller diameter of the hole, the deposited film is thicker, which is justified by the most probability of plasma species reach effectively the sample and it promotes the growth of the film

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

Modificação superficial de filmes de poliéster usando plasma a baixa temperatura

A polyester film has a vast application field, due some properties that are inherent of this kind of material such as, good mechanical resistance, chemical resistance to acids and bases and low production cost. However, this material has some limitations as low superficial tension, flat surface, low affinity to dyers, and poor adhesion which impede the use of the same ones for some finality as good wettability. Among the existent techniques to increase the superficial tension, plasma as energy source is the more promising technique, because of their versatility and for not polluting the environment. The plasma surface polymeric modification has been used for many researchers, 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, polyester films were treated with oxygen plasma varying the treatment time from 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) varying the percentage of each gas the mixture from 0 to 100%, the treatment time remaining constant to all treatments (10 min). After plasma treatment the samples were characterized by contact angle, surface tension, Raman spectroscopy, Infrared attenuated total reflection (IR-ATR) and atomic force microscopy, with the aim to study the wettability increase of treated polyester films as its variables. In the (O2/N2) plasma treatment of polyester films can be observed an increase of superficial roughness superior to those treated by O2 plasma. By the other hand, the chemical modification through the implantation of polar groups at the surface is obtained more easily using O2 plasma treatment

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)

Caracterização de superfícies de titânio modificado por oxidação à plasma

Recent years have seen a significant growth in surface modifications in titanium implants, resulting in shorter healing times in regions with low bone density. Among the different techniques, subtraction by chemical agents to increase oxidation has been applied for surface treatment of dental implants. However, this technique is generally unable to remove undesirable oxides, formed spontaneously during machining of titanium parts, raising costs due to additional decontamination stages. In order to solve this problem, the present study used plasma as an energy source to both remove these oxides and oxidize the titanium surface. In this respect, Ti disks were treated by hollow cathode discharge, using a variable DC power supply and vacuum system. Samples were previously submitted to a cleaning process using an atmosphere of Ar, H2 and a mixture of both, for 20 and 60 min. The most efficient cleaning condition was used for oxidation in a mixture of argon (60%) and oxygen (40%) until reaching a pressure of 2.2 mbar for 60 min at 500°C. Surfaces were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), atomic force microscopy (AFM), adhesion and cell proliferation. SEM showed less cell spreading and a larger number of projections orfilopodia in the treated samples compared to the control sample. AFM revealed surface defects in the treated samples, with varied geometry between peaks and valleys. Biological assays showed no significant difference in cell adhesion between treated surfaces and the control. With respect to cell proliferation, the treated surface exhibited improved performance when compared to the control sample. We concluded that the process was efficient in removing primary oxides as well as in oxidizing titanium surfaces