7 resultados para REACTIVE NITROGEN-OXIDES

em Universidade do Minho


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Dissertação de mestrado em Engenharia Mecânica

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The ternary aluminium oxynitride (AlNxOy) system offers the possibility to obtain a wide range of properties by tailoring the ratio between pure Al, AlNx and AlOy and therefore opening a significant number of possible applications. In this work the thermal behaviour of AlNxOy thin films was analysed by modulated infrared radiometry (MIRR), taking as reference the binary AlOy and AlNx systems. MIRR is a non-contact and non-destructive thermal wave measurement technique based on the excitation, propagation and detection of temperature oscillations of very small amplitudes. The intended change of the partial pressure of the reactive gas (N2 and/or O2) influenced the target condition and hence the deposition characteristics which, altogether, affected the composition and microstructure of the films. Based on the MIRR measurements and their qualitative and quantitative interpretation, some correlations between the thermal transport properties of the films and their chemical/physical properties have been found. Furthermore, the potential of such technique applied in this oxynitride system, which present a wide range of different physical responses, is also discussed. The experimental results obtained are consistent with those reported in previous works and show a high potential to fulfil the demands needed for the possible applications of the systems studied. They are clearly indicative of an adequate thermal response if this particular thin film system is aimed to be applied in small sensor devices or in electrodes for biosignal acquisition, such as those for electroencephalography or electromyography as it is the case of the main research area that is being developed in the group.

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Polycrystalline AlN coatings deposited on Ti-electrodes films were sputtered by using nitrogen both as reactive gas and sputtering gas, in order to obtain high purity coatings with appropriate properties to be further integrated into wear resistance coatings as a piezoelectric monitoring wear sensor. The chemical composition, the structure and the morphology of the films were investigated by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and atomic force microscopy techniques. These measurements show the formation of highly (101), (102) and (103) oriented AlN films with good piezoelectric and mechanical properties suitable for applications in electronic devices. Through the use of lower nitrogen flow a densification of the AlN coating occurs in the microstructure, with an improvement of the crystallinity along with the increase of the hardness. Thermal stability of aluminum nitride coatings at high temperature was also examined. It was found an improvement of the piezoelectric properties of the highly (10x) oriented AlN films which became c-axis (002) oriented after annealing. The mechanical behavior after heat treatment shows an important enhancement of the surface hardness and Young’s modulus, which decrease rapidly with the increase of the indentation depth until approach constant values close to the substrate properties after annealing. Thus, thermal annealing energy promotes not only the rearrangement of Al–N network, but also the occurrence of a nitriding process of unsaturated Al atoms which cause a surface hardening of the film.

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tThis work is devoted to the investigation of zirconium oxynitride (ZrOxNy) films with varied opticalresponses prompted by the variations in their compositional and structural properties. The films wereprepared by dc reactive magnetron sputtering of Zr, using Ar and a reactive gas mixture of N2+ O2(17:3).The colour of the films changed from metallic-like, very bright yellow-pale and golden yellow, for low gasflows to red-brownish for intermediate gas flows. Associated to this colour change there was a significantdecrease of brightness. With further increase of the reactive gas flow, the colour of the samples changedfrom red-brownish to dark blue or even to interference colourations. The variations in composition dis-closed the existence of four different zones, which were found to be closely related with the variationsin the crystalline structure. XRD analysis revealed the change from a B1 NaCl face-centred cubic zirco-nium nitride-type phase for films prepared with low reactive gas flows, towards a poorly crystallizedover-stoichiometric nitride phase, which may be similar to that of Zr3N4with some probable oxygeninclusions within nitrogen positions, for films prepared with intermediate reactive gas flows. For highreactive gas flows, the films developed an oxynitride-type phase, similar to that of -Zr2ON2with someoxygen atoms occupying some of the nitrogen positions, evolving to a ZrO2monoclinic type structurewithin the zone where films were prepared with relatively high reactive gas flows. The analysis carriedout by reflected electron energy loss spectroscopy (REELS) revealed a continuous depopulation of thed-band and an opening of an energy gap between the valence band (2p) and the Fermi level close to 5 eV.The ZrN-based coatings (zone I and II) presented intrinsic colourations, with a decrease in brightness anda colour change from bright yellow to golden yellow, red brownish and dark blue. Associated to thesechanges, there was also a shift of the reflectivity minimum to lower energies, with the increase of thenon-metallic content. The samples lying in the two last zones (zone III, oxynitride and zone IV, oxide films)revealed a typical semi-transparent-optical behaviour showing interference-like colourations only dueto the complete depopulation of the d band at the Fermi level. The samples lying in these zones presentedalso an increase of the optical bandgap from 2 to 3.6 eV.

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Dissertação de mestrado integrado em Engenharia de Materiais

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PhD in Sciences Specialty in Physics

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