Nitretação em plasma com gaiola catódica: investigação do mecanismo e estudo comparativo com a nitretação em plasma de tensão contínua

The ionic plasma nitriding is one of the most important plasma assisted treatment technique for surface modification, but it presents some inherent problems mainly in nitriding pieces with complex geometries. In the last four years has appeared a plasma nitriding technique, named ASPN (Active Screen Plasma Nitriding) in which the samples and the workload are surrounded by a metal screen on which the cathodic potential is applied. This new technique makes possible to obtain a perfect uniform nitrided layer apart from the shape of the samples. The present work is based on the development of a new nitriding plasma technique named CCPN (Cathodic Cage Plasma Nitriding) Patent PI 0603213-3 derived from ASPN, but utilizes the hollow cathode effect to increase the nitriding process efficiency. That technique has shown great improvement on the treatment of several types of steels under different process conditions, producing thicker and harder layers when compared with both, ASPN and ionic plasma nitriding, besides eliminating problems associated with the later technique. The best obtained results are due to the hollow cathode effect on the cage holes. Moreover, characteristic problems of ionic plasma nitriding are eliminated due to the fact that the luminescent discharge acts on the cage wall instead of on the samples surface, which remains under a floating potential. In this work the enhancement of the cathodic cage nitriding layers proprieties, under several conditions for some types of steels was investigated, besides the mechanism for nitrides deposition on glass substrate, concluding that the CCPN is both a diffusion and a deposition process at the same time

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

Graphene and Semicondutor or Metallic Nanoparticles for Energy Conversion

The purpose of the present PhD thesis is to investigate the properties of innovative nano- materials with respect to the conversion of renewable energies to electrical and chemical energy. The materials have been synthesized and characterized by means of a wide spectrum of morphological, compositional and photophysical techniques, in order to get an insight into the correlation between the properties of each material and the activity towards different energy conversion applications. Two main topics are addressed: in the first part of the thesis the light harvesting in pyrene functionalized silicon nanocrystals has been discussed, suggesting an original approach to suc- cessfully increase the absorption properties of these nanocrystals. The interaction of these nanocrystals was then studied, in order to give a deeper insight on the charge and energy extraction, preparing the way to implement SiNCs as active material in optoelectronic devices and photovoltaic cells. In addition to this, the luminescence of SiNCs has been exploited to increase the efficiency of conventional photovoltaic cells by means of two innovative architectures. Specifically, SiNCs has been used as luminescent downshifting layer in dye sensitized solar cells, and they were shown to be very promising light emitters in luminescent solar concentrators. The second part of the thesis was concerned on the production of hydrogen by platinum nanoparticles coupled to either electro-active or photo-active materials. Within this context, the electrocatalytic activity of platinum nanoparticles supported on exfoliated graphene has been studied, preparing an high-efficiency catalyst and disclosing the role of the exfoliation technique towards the catalytic activity. Furthermore, platinum nanoparticles have been synthesized within photoactive dendrimers, providing the first proof of concept of a dendrimer-based photocatalytic system for the hydrogen production where both sensitizer and catalyst are anchored to a single scaffold.

Contribuição da catodoluminescência para o entendimento da diagênese da formação Jandaíra: áreas do campo de petróleo da fazenda Belém e Lajedo do Rosário

The general objective of this study was to contribute to the understanding of the chemical evolution of fluids that percolate through carbonate rocks of the Jandaíra Formation. The oxidation and reduction conditions in which grains, source and cement were formed was investigated using the cathodoluminescence technique (CL). The study area is located in the west part of the Potiguar Basin (Fazenda Belém field) and Rosário Ledge (Felipe Guerra municipality, State of Rio Grande do Norte, Brazil). The analysis of thin sections of carbonate rocks under CL revealed that grains (allochemical or not) and diagenetic products (micritization, dolomitization, neomorphism and cementation) exhibit since absence of luminescence the various luminescence colors (yellow, orange, red, brown, and blue) in a variety of intensities. As pure calcite shows dark blue luminescence, the occurrence of different luminescence colors in calcite crystals suggest one or more punctual crystal defects such as free electron, free space and impurity. The dyeing of thin sections with alizarin and potassium ferrocyanide revealed the absence of ferrous carbonate in the different lithotypes of Jandaíra Formation. Therefore, the different colors and intensities of CL observed in these rocks are probably caused by the presence of ion activators such as Mn2+ and is not an activator/inhibitor combination. In the same way, the absence of luminescence is very probably caused by the absence of activator ions and not due to the low concentration of inhibitor ions such as Fe2+. The incorporation of Mn2+ in the different members of the Jandaíra Formation must have been controlled by the redox state of the depositional environment and diagenesis. Therefore, it is possible that the luminescent members have been formed (e.g.,ooids) or have been modified (gastropod neomorphism) under reduction conditions in the depositional environments, in subsurface during the burial, or, in the case of Rosario Ledge samples , during the post-burial return to surface conditions. As regards the sudden changes from low to moderate and to strong luminescence, these features should indicate the precipitation of a fluid with chemical fluctuations, which formed the frequent zonations in the block cement of the Rosario Ledge samples. This study suggests that the different intensities and colors of CL should be correlated with the Mn2+ and Fe2+ contents, and stable isotopes of samples to determine the salinity, temperature, pH e Eh conditions during deposition

Implications of low breakdown voltage of component subcells on external quantum efficiency measurements of multijunction solar cells

The electrical and optical coupling between subcells in a multijunction solar cell affects its external quantum efficiency (EQE) measurement. In this study, we show how a low breakdown voltage of a component subcell impacts the EQE determination of a multijunction solar cell and demands the use of a finely adjusted external voltage bias. The optimum voltage bias for the EQE measurement of a Ge subcell in two different GaInP/GaInAs/Ge triple-junction solar cells is determined both by sweeping the external voltage bias and by tracing the I–V curve under the same light bias conditions applied during the EQE measurement. It is shown that the I–V curve gives rapid and valuable information about the adequate light and voltage bias needed, and also helps to detect problems associated with non-ideal I–V curves that might affect the EQE measurement. The results also show that, if a non-optimum voltage bias is applied, a measurement artifact can result. Only when the problems associated with a non-ideal I–V curve and/or a low breakdown voltage have been discarded, the measurement artifacts, if any, can be attributed to other effects such as luminescent coupling between subcells.