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

Estudo da viabilidade técnica para obtenção de superfície duplex em aço inoxidável martensítico AISI 410 através do processo de deposição a plasma por gaiola catódica

The technique of plasma nitriding by the cathode cage mainly stands out for its ability to produce uniform layers, even on parts with complex geometries. In this study, it was investigated the efficiency of this technique for obtaining duplex surface, when used, simultaneously, to nitriding treatment and thin film deposition at temperatures below 500°C. For this, were used samples of AISI 41 0 Martensitic Stainless Steel and performed plasma treatment, combining nitriding and deposition of thin films of Ti and/or TiN in a plasma atmosphere containing N2-H2. It was used a cathodic cage of titanium pure grade II, cylindrical with 70 mm diameter and 34 mm height. Samples were treated at temperature 420ºC for 2 and 12 hours in different working pressures. Optical Microscopy (OM), Scanning Electron Microscopy (SEM) with micro-analysis by Energy Dispersive Spectroscopy (EDS), X-Ray Diffraction (XRD), Atomic Force Microscopy (AFM) and analysis of Vickers Microhardness were used to investigate coating properties such as homogeneity and surface topography, chemical composition, layer thickness, crystalline phase, roughness and surface microhardness. The results showed there is a direct proportionality between the presence of H2 in plasma atmosphere and the quantity of titanium in surface chemical composition. It was also observed that the plasma treatment at lowpressure is more effective in formation of TiN thin film

Construção de um aparato experimental para monitoramento in situ da deposição de filmes finos de titânio por magnetron sputtering

The technique of surface coating using magnetron sputtering is one of the most widely used in the surface engineering, for its versatility in obtaining different films as well as in the micro / nanometric thickness control. Among the various process parameters, those related to the active species of the plasma are of the most fundamental importance in the mechanism and kinetics of deposition. In order to identify the active species of the plasma, parameters such as gas flow, pressure and density of electric power were varied during titanium coating on glass substrate. By flowing argon gas of 10, 20, 30, 40 and 50 sccm (cubic centimeters per minute) for each gas flow a sequential scan of the electric current of 0.10, 0.20, 0.30, 0.40 , 0.50 A. The maximum value of 0.50 A was chosen based both on literature data and on limitations of the equipment. The monitoring of plasma species present during the deposition was carried out in situ by the technique of optical emission spectroscopy (OES) through the spectrometer Ocean Optics USB2000 Series. For this purpose, an apparatus was developed to adapt the OES inside the plasma reactor to stay positioned closest to the target. The radiations emitted by the species were detected by an optical fiber placed behind the glass substrate and their intensities as a function of wavelength were, displayed on a monitor screen. The acquisition time for each condition of the plain parameters was related to the minima of spectral lines intensities due to the film formed on the substrate. The intensities of different emission lines of argon and titanium were then analyzed as a function of time, to determine the active species and estimate the thickness of the deposited films. After the deposition, the coated glasses thin films were characterized by optical transmittance through an infrared laser. It was found that the thickness and deposition rate determined by in situ analysis were consistent with the results obtained by laser transmittance

Efeito Kerr magneto-óptico; Ressonância ferromagnética; Acoplamento bilinear; Acoplamento biquadrático

In this work, we investigated the magnetic properties of a monocrystalline Fe thin film and of Fe(80 Å)/Cr(t)/Fe(80 Å) tri-layers, with the nonmagnetic metallic Cr spacer layer thickness varying between 9 Å < t < 40 Å. The samples were deposited by the DC Sputtering on Magnesium Oxide (MgO) substrates, with (100) crystal orientation. For this investigation, experimental magneto-optical Kerr effect (MOKE) magnetometry and ferromagnetic resonance (FMR) techniques were employeed. In this case, these techniques allowed us to study the static and dynamical magnetization properties of our tri-layers. The experimental results were interpreted based on the phenomenological model that takes into account the relevant energy terms to the magnetic free energy to describe the system behavior. In the case of the monocrystalline Fe film, we performed an analytical discussion on the magnetization curves and developed a numerical simulation based on the Stoner-Wohlfarth model, that enables the numerical adjustment of the experimental magnetization curves and obtainment of the anisotropy field values. On the other hand, for the tri-layers, we analyzed the existence of bilinear and biquadratic couplings between the magnetizations of adjacent ferromagnetic layers from measurements of magnetization curves. With the FMR fields and line width angular dependencies, information on the anisotropy in three layers was obtained and the effects of different magnetic relaxation mechanisms were evidenced. It was also possible to observe the dependence of the epitaxy of the multilayers with growth and sputtering parameters. Additionally it was developed the technique of AC magnetic susceptibility in order to obtain further information during the investigation of magnetic thin films

Propriedades magnéticas quase-estáticas de filmes ferromagnéticos amorfos de FeCuNbSiB

Today, one of the topics that attracts interest of the scientific community is the understanding of magnetic properties of magnetic systems with reduced dimensions, in particular, ferromagnetic thin films. In this case, the comprehension and control of these properties, as well as the development of routes to obtain them, are crucial issues in many aspects of current and future technologies for storage and transmission of information in the electro-electronic industry. There are several materials that exhibit soft magnetic properties, and we highlight the amorphous alloys and that ones obtained by partial crystallization, so-called nanocrystalline materials. The production of these alloys as magnetic ribbons is very common in scientific and technological area, but there are just a few works related to the production of these alloys as thin films. In this work, we studied the quasi-static magnetic properties of ferromagnetic thin films based on FeCuNbSiB in a wide range of thicknesses, from 20 to 500 nm, produced by sputtering. In particular, after the structural characterization performed via X-ray diffraction, the magnetic properties of the sets of samples were investigated using experimental magnetization curve, obtained using a vibrating sample magnetometer, as well as through theoretical curves obtained by theoretical modeling and numerical computation. The modeling process is based on the Stoner Wohlfarth model applied to three dimensions, and adds some energy terms, using as reference experimental results of magnetization. In this case, from the comparison between theoretical and experimental results and the analysis of the constant anisotropy behavior as a function of film thickness, we aim to obtain further information on the magnetization process of the samples, to identify routes for the production of thin films and develop a theoretical to films to use it, in the future, in the obtainment of the theoretical curves of some magnetic measurements, such as magnetoimpedance and magnetoresistance

Deposição de filmes de ZrO2 modificados sobre substratos metálicos

This work makes use of the Pechini process for synthesis of the solutions and the dip-coating process for the addition of zirconium oxide films pure and doped cerium metal substrates. The metals with ceramic substrates were subjected to severe conditions of salinity. The x-ray fluorescence of the substrate showed a great diversity of chemical elements. The x-ray diffraction of the samples showed the phase of iron substrate because the thickness of nano-thin film. Tests using an LPR probe showed that the film presents with zirconia corrosion independent of film thickness. The substrates of ZrO2-doped ceria showed low chemical attack of the salt in films with less than 15 dives. The results imply that ultrathin films are shown in protecting metallic substrates

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

Estudo da viabilidade técnica para obtenção de superfície duplex em aço inoxidável martensítico AISI 410 através do processo de deposição a plasma por gaiola catódica

The technique of plasma nitriding by the cathode cage mainly stands out for its ability to produce uniform layers, even on parts with complex geometries. In this study, it was investigated the efficiency of this technique for obtaining duplex surface, when used, simultaneously, to nitriding treatment and thin film deposition at temperatures below 500°C. For this, were used samples of AISI 41 0 Martensitic Stainless Steel and performed plasma treatment, combining nitriding and deposition of thin films of Ti and/or TiN in a plasma atmosphere containing N2-H2. It was used a cathodic cage of titanium pure grade II, cylindrical with 70 mm diameter and 34 mm height. Samples were treated at temperature 420ºC for 2 and 12 hours in different working pressures. Optical Microscopy (OM), Scanning Electron Microscopy (SEM) with micro-analysis by Energy Dispersive Spectroscopy (EDS), X-Ray Diffraction (XRD), Atomic Force Microscopy (AFM) and analysis of Vickers Microhardness were used to investigate coating properties such as homogeneity and surface topography, chemical composition, layer thickness, crystalline phase, roughness and surface microhardness. The results showed there is a direct proportionality between the presence of H2 in plasma atmosphere and the quantity of titanium in surface chemical composition. It was also observed that the plasma treatment at lowpressure is more effective in formation of TiN thin film

Construção de um aparato experimental para monitoramento in situ da deposição de filmes finos de titânio por magnetron sputtering

The technique of surface coating using magnetron sputtering is one of the most widely used in the surface engineering, for its versatility in obtaining different films as well as in the micro / nanometric thickness control. Among the various process parameters, those related to the active species of the plasma are of the most fundamental importance in the mechanism and kinetics of deposition. In order to identify the active species of the plasma, parameters such as gas flow, pressure and density of electric power were varied during titanium coating on glass substrate. By flowing argon gas of 10, 20, 30, 40 and 50 sccm (cubic centimeters per minute) for each gas flow a sequential scan of the electric current of 0.10, 0.20, 0.30, 0.40 , 0.50 A. The maximum value of 0.50 A was chosen based both on literature data and on limitations of the equipment. The monitoring of plasma species present during the deposition was carried out in situ by the technique of optical emission spectroscopy (OES) through the spectrometer Ocean Optics USB2000 Series. For this purpose, an apparatus was developed to adapt the OES inside the plasma reactor to stay positioned closest to the target. The radiations emitted by the species were detected by an optical fiber placed behind the glass substrate and their intensities as a function of wavelength were, displayed on a monitor screen. The acquisition time for each condition of the plain parameters was related to the minima of spectral lines intensities due to the film formed on the substrate. The intensities of different emission lines of argon and titanium were then analyzed as a function of time, to determine the active species and estimate the thickness of the deposited films. After the deposition, the coated glasses thin films were characterized by optical transmittance through an infrared laser. It was found that the thickness and deposition rate determined by in situ analysis were consistent with the results obtained by laser transmittance

Síntese e caracterização de espinélios a base de Cu, Fe e Cr para pigmentos cerâmicos

Inorganic pigment comprises a host lattice, which is part of the chromophore component (usually a transition metal cation) and possible components modifiers, which stabilize, add or restate the properties pigments. Among the materials with spinel, ferrites, and the chromite stand out, because they have broad technological importance in the area of materials, applicability, pigments, catalytic hydrogenation, thin film, ceramic tiles, among others. The present work, pigments containing CuFe2O4, CuCr2O4,e CuFeCrO4, were synthesized by a method that makes use of gelatin as organic precursor using their application to ceramic pigments. The pigments were characterized by X-ray diffraction (XRD), Infrared spectroscopy, scanning electron microscopy (SEM) spectroscopy in the UV-visible and Colorimetry. The results confirmed the feasibility of the synthetic route used, with respect to powders synthesized, there is the formation of spinel phase from 500°C, with an increase in crystallinity and the formation of other phases. The pigments were shown to be crystalline and the desired phases were obtained. The copper chromite have hues ranging from green to black according to the calcination temperature, while the copper chromite doped with iron had brownish. The ferrites showed copper color and darker brown to black, which may indicate an interesting factor because of the importance of black pigment

Estudo e desenvolvimento de um capacitor eletrolítico de nióbio

It seeks to find an alternative to the current tantalum electrolytic capacitors in the market due to its high cost. Niobium is a potential substitute, since both belong to the same group of the periodic table and because of this have many similar physical and chemical properties. Niobium has several technologically important applications, and Brazil has the largest reserves, around 96%. There are including niobium in reserves of tantalite and columbite in Rio Grande do Norte. These electrolytic capacitors have high capacitance specifies, ie they can store high energy in small volumes compared to other types of capacitors. This is the main attraction of this type of capacitor because is growing demand in the production of capacitors with capacitance specifies increasingly high, this because of the miniaturization of various devices such as GPS devices, televisions, computers, phones and many others. The production route of the capacitor was made by powder metallurgy. The initial niobium powder supplied by EEL-USP was first characterized by XRD, SEM, XRF and laser particle size, to then be sieved into three particle size, 200, 400 e 635mesh. The powders were then compacted and sintered at 1350, 1450 and 1550°C using two sintering time 30 and 60min. Sintering is one of the most important parts of the process as it affects properties as porosity and surface cleaning of the samples, which greatly affected the quality of the capacitor. The sintered samples then underwent a process of anodic oxidation, which created a thin film of niobium pentóxido over the whole porous surface of the sample, this film is the dielectric capacitor. The oxidation process variables influence the performance of the film and therefore the capacitor. The samples were characterized by electrical measurements of capacitance, loss factor, ESR, relative density, porosity and surface area. After the characterizations was made an annealing in air ate 260ºC for 60min. After this treatment were made again the electrical measurements. The particle size of powders and sintering affected the porosity and in turn the specific area of the samples. The larger de area of the capacitor, greater is the capacitance. The powder showed the highest capacitance was with the smallest particle size. Higher temperatures and times of sintering caused samples with smaller surface area, but on the other hand the cleaning surface impurities was higher for this cases. So a balance must be made between the gain that is achieved with the cleaning of impurities and the loss with the decreased in specific area. The best results were obtained for the temperature of 1450ºC/60min. The influence of annealing on the loss factor and ESR did not follow a well-defined pattern, because their values increased in some cases and decreased in others. The most interesting results due to heat treatment were with respect to capacitance, which showed an increase for all samples after treatment

Estudo numérico de escoamento turbulento em padrão anular gás-líquido em dutos verticais

Multiphase flows in ducts can adopt several morphologies depending on the mass fluxes and the fluids properties. Annular flow is one of the most frequently encountered flow patterns in industrial applications. For gas liquid systems, it consists of a liquid film flowing adjacent to the wall and a gas core flowing in the center of the duct. This work presents a numerical study of this flow pattern in gas liquid systems in vertical ducts. For this, a solution algorithm was developed and implemented in FORTRAN 90 to numerically solve the governing transport equations. The mass and momentum conservation equations are solved simultaneously from the wall to the center of the duct, using the Finite Volumes Technique. Momentum conservation in the gas liquid interface is enforced using an equivalent effective viscosity, which also allows for the solution of both velocity fields in a single system of equations. In this way, the velocity distributions across the gas core and the liquid film are obtained iteratively, together with the global pressure gradient and the liquid film thickness. Convergence criteria are based upon satisfaction of mass balance within the liquid film and the gas core. For system closure, two different approaches are presented for the calculation of the radial turbulent viscosity distribution within the liquid film and the gas core. The first one combines a k- Ɛ one-equation model and a low Reynolds k-Ɛ model. The second one uses a low Reynolds k- Ɛ model to compute the eddy viscosity profile from the center of the duct right to the wall. Appropriate interfacial values for k e Ɛ are proposed, based on concepts and ideas previously used, with success, in stratified gas liquid flow. The proposed approaches are compared with an algebraic model found in the literature, specifically devised for annular gas liquid flow, using available experimental results. This also serves as a validation of the solution algorithm

Modelagem numérica de escoamento em padrão anular com transferência de calor e massa

Annular flow is the prevailing pattern in transport and energy conversion systems and therefore, one of the most important patterns in multiphase flow in ducts. The correct prediction of the pressure gradient and heat transfer coefficient is essential for optimizing the system s capacity. The objective of this work is to develop and implement a numerical algorithm capable of predicting hydrodynamic and thermal characteristics for upflow, vertical, annular flow. The numerical algorithm is then complemented with the physical modeling of phenomena that occurs in this flow pattern. These are, turbulence, entrainment and deposition and phase change. For the development of the numerical model, axial diffusion of heat and momentum is neglected. In this way the time-averaged equations are solved in their parabolic form obtaining the velocity and temperature profiles for each axial step at a time, together with the global parameters, namely, pressure gradient, mean film thickness and heat transfer coefficient, as well as their variation in the axial direction. The model is validated for the following conditions: fully-developed laminar flow with no entrainment; fully developed laminar flow with heat transfer, fully-developed turbulent flow with entrained drops, developing turbulent annular flow with entrained drops, and turbulent flow with heat transfer and phase change

Diagnóstico de plasma de cátodo oco: análise da ação de plasma de argônio e Ar-H2 para a deposição de filmes finos de titânio em pós-descarga

Plasma DC hollow cathode has been used for film deposition by sputtering with release of neutral atoms from the cathode. The DC Plasma Ar-H2 hollow cathode currently used in the industry has proven to be effective in cleaning surfaces and thin film deposition when compared to argon plasma. When we wish to avoid the effects of ion bombardment on the substrate discharge, it uses the post-discharge region. Were generated by discharge plasma of argon and hydrogen hollow cathode deposition of thin films of titanium on glass substrate. The optical emission spectroscopy was used for the post-discharge diagnosis. The films formed were analyzed by mechanical profilometry technique. It was observed that in the spectrum of the excitation lines of argon occurred species. There are variations in the rate of deposition of titanium on the glass substrate for different process parameters such as deposition time, distance and discharge working gases. It was noted an increase in intensity of the lines of argon compared with the lines of titanium. Deposition with argon and hydrogen in glass sample observed a higher rate deposition of titanium as more closer the sample was in the discharge

Viabilidade técnica de uma rota não convencional para a produção de leite de cabra em pó em cooperativas do Rio Grande do Norte

Nowadays, Brazil has both the greatest goat herd and the greatest goat milk production of South America. The state of Rio Grande do Norte, located in northeast of Brazil, has an average year production of three thousand cubic meters of goat milk in natura. Part of this milk production is homemade and it comes from small farms, which unite in rural cooperatives created to encourage the production and implementation of industrial processes for preservation and processing of milk. Results presented by literature and obtained from preliminary essays in this thesis show that non conventional dryer of spouted bed with inert particles is able to produce powder milk from in natura milk (cattle or goat), with the same quality of spray dryer, however, operating at low cost. The method of drying in spouted bed consists of injecting milk emulsion on the bed of inert particles gushed by hot air. This emulsion covers the particles with a thin film, which dries and is reduced to powder during the circulation of inerts inside the bed. The powder is dragged by exhaustion air and separated in the cyclone. The friction among particles resulted from the particles circulation, encourages high taxes of shear in the thin film of emulsion, breaking the cohesive forces and making this process possible. Studying the drying process and the powder goat milk production in one unit of spouted bed with inert particles, seeing the development of a low cost technological route for powder milk production is the aim of this thesis. The powder milk produced by this route must attend the local demand of food industries which need an intermediate product to be used as a food ingredient (ice-cream, milk candy). In order to reach this aim, this thesis approaches the aspects related to physical, thermodynamics and physic-chemicals characteristics of goat milk, whose complete data are still inexistent in the literature. The properties of materials are of great importance to the project of any process which involves the operations of transportation of movement, heat and mass quantity, such as the dryers which operate in fluid dynamically active regime, like the spouted bed. It was obtained new data related to the goat milk properties in function of concentration of solids and temperature. It is also important to mention the study developed about the kinetic of solids retention in the bed of inert particles during the drying of goat milk. It was found more adequate processes conditions to the proposed technological route to be implemented in small and micro-industries, with simplifications in the system of milk injection as well as in the form of operation of the dryer. Important data were obtained for a posterior stage of this research which involves the v modeling, simulation, control and optimization of the process. The results obtained in this thesis, in relation to process performance as well as to the quality of produced powder milk validate the proposal of using the spouted bed dryer in the production of powder goat milk