Recubrimientos autolubricantes cuasicristalinos tipo composite depositados mediante proyección térmica para aplicaciones espaciales y de alta temperatura

Los recubrimientos lubricantes sólidos son requeridos para reducir la fricción y prevenir el desgaste en componentes que operan a altas temperaturas o en vacío (vehículos espaciales, industria química, motores diésel, turbinas aeronáuticas y de generación de energía…). Los lubricantes líquidos pierden sus características cuando las condiciones de presión, temperatura o ambientales son severas (oxidación, inestabilidad térmica, volatilidad,…), por ejemplo los aceites minerales convencionales se descomponen a temperaturas próximas a 200 ºC. Por tanto, la única manera de poder conseguir una adecuada lubricación a temperaturas extremas es por medio de sólidos, que cada vez más, se aplican en forma de recubrimientos. Estos recubrimientos podrían ser empleados en componentes de vehículos espaciales reutilizables, donde se pueden alcanzar, en la reentrada en la atmósfera, temperaturas de 700 ºC (bisagras, rodamientos, articulaciones y zonas de sellado en las superficies de control, y rodamientos de las turbobombas y las cajas de engranajes). Dichos recubrimientos también deberían ser capaces de proporcionar una lubricación efectiva a bajas temperaturas para las operaciones en tierra, para las operaciones de arranque en frío, incluso en el espacio. El conjunto de requisitos que tendrían que satisfacer las capas tribológicas relacionadas con estas condiciones extremas es muy diverso, lo que hace que el concepto de capas tipo composite (aquéllas constituidas por varios componentes) sea, en principio, muy adecuado para estas aplicaciones. Recubrimientos composite proyectados térmicamente constituidos por una matriz dura y conteniendo lubricantes sólidos pueden ser una buena solución desde el punto de vista tribológico. El “Lewis Research Centre” de la NASA ha estado desarrollando recubrimientos autolubricantes tipo composite, constituidos por la combinación de materiales duros como el carburo de cromo, junto con lubricantes sólidos como plata o la eutéctica de fluoruros de calcio y bario, en una matriz de NiCr, para su uso en aplicaciones terrestres a alta temperatura. Estos recubrimientos han sido aplicados mediante proyección térmica, siendo denominados como series PS100, PS200, PS300 y PS400, reduciendo de forma significativa el coeficiente de fricción y mejorando la resistencia al desgaste en un amplio margen de temperaturas. Otra nueva familia de materiales con comportamiento tribológico prometedor son las aleaciones cuasicristalinas (QC). Presentan características muy atractivas: alta dureza, baja fricción, alto límite elástico de compresión... Son muy frágiles como materiales másicos, por lo que se intentan aplicar en forma de recubrimientos. Se pueden depositar mediante proyección térmica. Algunos de estos materiales cuasicristalinos, como AlCoFeCr, poseen coeficientes de dilatación próximos al de los materiales metálicos, alta estabilidad térmica, baja conductividad térmica y una elevada resistencia a la oxidación y a la corrosión en caliente. En esta tesis se han desarrollado recubrimientos tipo composite conteniendo cuasicristales como componente antidesgaste, NiCr como componente tenaz, y Ag y la eutéctica de BaF2-CaF2, como lubricantes sólidos. Estos recubrimientos han sido depositados con diferentes composiciones (denominadas TH100, TH103, TH200, TH400, TH600…) mediante distintos procesos de proyección térmica: plasma en aire (PS), plasma en baja presión (LPPS) y combustión a alta velocidad (HVOF). Los recubrimientos se han generado sobre el sustrato X-750, una superaleación base níquel, endurecible por precipitación, con muy buena resistencia mecánica y a la oxidación hasta temperaturas de 870 ºC y, además, es empleada en aplicaciones aeroespaciales e industriales. Los recubrimientos han sido caracterizados microestructuralmente en INTA (Instituto Nacional de Técnica Aeroespacial), mediante SEM-EDS (Scanning Electronic Microscopy-Energy Dispersive Spectroscopy) y XRD (X-Ray Diffraction), y tribológicamente mediante medidas de microdureza y ensayos en tribómetro POD (Pin On Disc) para determinar los coeficientes de fricción y de desgaste. Los recubrimientos han sido ensayados tribológicamente a alta temperatura en INTA y en vacío en AMTTARC (Aerospace and Space Materials Technology Testhouse – Austrian Research Centres), en Seibersdorf (Austria). Se ha estudiado la influencia de la carga normal aplicada, la velocidad lineal y el material del pin. De entre las diferentes series de recubrimientos cuasicristalinos tipo composite desarrolladas, dos de ellas, TH100 y TH103 han presentado una excelente calidad microestructural (baja porosidad, distribución uniforme de fases…) y se han mostrado como excelentes recubrimientos antidesgaste. Sin embargo, estas capas presentan un pobre comportamiento como autolubricantes a temperatura ambiente, aunque mejoran mucho a alta temperatura o en vacío. Los resultados del trabajo presentado en esta tesis han proporcionado nuevo conocimiento respecto al comportamiento tribológico de recubrimientos autolubricantes cuasicristalinos tipo composite depositados por proyección térmica. Sin embargo, dichos resultados, aunque son muy prometedores, no han puesto de manifiesto el adecuado comportamiento autolubricante que se pretendía y, además, como ocurre en cualquier trabajo de investigación, durante el desarrollo del mismo siempre aparecen nuevas dudas por resolver. Se proponen nuevas líneas de trabajo futuro que complementen los resultados obtenidos y que puedan encaminar hacia la obtención de un recubrimiento que mejore su comportamiento autolubricante. ABSTRACT Solid lubricant coatings are required to reduce friction and prevent wear in components that operate at high temperatures or under vacuum (space vehicles, chemical industry, diesel engines, power generation turbines and aeronautical turbines, for instance). In these cases neither greases nor liquid lubricants can be employed and the only practicable approach to lubrication in such conditions is by means of solids. These are increasingly applied in the form of coatings which should exhibit low shear strength, whilst maintaining their chemical stability at extremes temperatures and in the space environment. In the space field, these coatings would be employed in re-usable space plane applications, such as elevon hinges, where temperatures of 700 ºC are reached during re-entry into the Earth’s atmosphere. These coatings should also be capable of providing effective lubrication at lower temperatures since “cold start” operation may be necessary, even in the space environment. The diverse and sometimes conflictive requirements in high temperature and space-related tribological coatings make the concept of composite coatings highly suitable for these applications. Thermal-sprayed composites containing solid lubricants in a hard matrix perform well tribologically. NASA‘s Lewis Research Centre had developed self-lubricating composite coatings for terrestrial use, comprising hard materials like chromium carbide as well as solid lubricant additives such as silver and BaF2-CaF2 eutectic on a Ni-Cr matrix. These coatings series, named PS100, PS200, PS300 and PS400, are applied by thermal spray and significantly reduce friction coefficients, improving wear resistance over a wide temperature range. Quasicrystalline alloys (QC) constitute a new family of materials with promising tribological behaviour. Some QC materials exhibit a combination of adequate antifriction properties: low friction coefficient, high hardness and high yield strength under compression, and can be easily produced as coatings on top of metallic and non-metallic materials. Among these QC alloys, AlCoFeCr has high hardness (700 HV0.1), a thermal expansion coefficient close to that of metals, high thermal stability, low thermal conductivity and good oxidation and hot corrosion resistance. However most QC materials have the disadvantage of being very brittle. In order to take advantage of the excellent tribological properties of QCs, thick composite lubricant coatings were prepared containing them as the hard phase for wear resistance, Ag and BaF2-CaF2 eutectic as lubricating materials and NiCr as the tough component. These coatings were deposited in different composition mixtures (named TH100, TH103, TH200, TH400, TH600…) by different thermal spray processes: air plasma spray (PS), low pressure plasma spray (LPPS) and high velocity oxy-fuel (HVOF), on X-750 substrates. X-750 is an age-hardenable nickel-base superalloy with very good strength and a good resistance to oxidising combustion gas environments at temperatures up to about 870 ºC and it is widely used in aerospace and industrial applications. Coatings have been characterized microstructurally, at INTA (National Institute for Aerospace Technology), by means of SEM-EDS (Scanning Electronic Microscopy- Energy Dispersive Spectroscopy) and XRD (X-Ray Diffraction), and tribologically by microhardness measurements and pin-on-disc testing to determine friction coefficients as well as wear resistance. The coatings were tested tribologically at high temperature at INTA and under vacuum at AMTT-ARC (Aerospace and Space Materials Technology Testhouse – Austrian Research Centres), in Seibersdorf (Austria). Different loads, linear speeds and pin materials were studied. TH100 and TH103 QC alloy matrix composite coatings were deposited by HVOF with excellent microstructural quality (low porosity, uniform phase distribution) and showed to be excellent wear resistant coatings. However these QC alloy matrix composite coatings are poor as a self-lubricant at room temperature but much better at high temperature or in vacuum. The results from the work performed within the scope of this thesis have provided new knowledge concerning the tribological behavior of self-lubricating quasicrystalline composite coatings deposited by thermal spraying. Although these results are very promising, they have not shown an adequate self-lubricating behavior as was intended, and also, as in any research, the results have in addition raised new questions. Future work is suggested to complement the results of this thesis in order to improve the selflubricating behaviour of the coatings.

Open-atmosphere structural depth profiling of multilayer samples of photovoltaic interest using laser-induced plasma spectrometry

The present work aims to assess Laser-Induced Plasma Spectrometry (LIPS) as a tool for the characterization of photovoltaic materials. Despite being a well-established technique with applications to many scientific and industrial fields, so far LIPS is little known to the photovoltaic scientific community. The technique allows the rapid characterization of layered samples without sample preparation, in open atmosphere and in real time. In this paper, we assess LIPS ability for the determination of elements that are difficult to analyze by other broadly used techniques, or for producing analytical information from very low-concentration elements. The results of the LIPS characterization of two different samples are presented: 1) a 90 nm, Al-doped ZnO layer deposited on a Si substrate by RF sputtering and 2) a Te-doped GaInP layer grown on GaAs by Metalorganic Vapor Phase Epitaxy. For both cases, the depth profile of the constituent and dopant elements is reported along with details of the experimental setup and the optimization of key parameters. It is remarkable that the longest time of analysis was ∼10 s, what, in conjunction with the other characteristics mentioned, makes of LIPS an appealing technique for rapid screening or quality control whether at the lab or at the production line.

E-beam propagation and interaction with atmosphere

This study purports to investigate whether a conductive tether left uninsulated and electrically floating in LEO could serve as an effective e-beam source to produce artificial auroras. An electrically floating tether comes out biased highly negative over most of its length. Ambient ions impacting it with KeV energies liberate secondary electrons, which are locally accelerated through the 2D tether voltage-bias, race down magnetic lines, and result in peak auroral emissions at about 120-160 km altitude. Since no current flows at either tether end, a bare-tether e-beam is fully free of spacecraft charging problems. Beam propagation and beam-atmosphere interactions need be modelled in a simple but quantitative way so as to allow a satisfactory discussion of observational options and their feasibility. The evolution in the energy spectrum of secondary electrons, their pitch distribution, and beam broadening due to collisions with neutrals, which would result in a broader but weaker tether footprint in the E-layer, need be modelled. Relations between particle/energy flux values, and ionization and accompanying emission rates, are considered.

Floating bare tether as upper atmosphere probe

Use of a conductive bare tape electrically floating in low Earth orbit as an effective electron beam source to produce artificial auroral effects, free of problems that mard tandard beams, is considered. Ambient ions impacting the tape with keV energies over most of its length liberate secondary electrons that race down the magnetic field, excite neutrals in the E layer, and result in auroral emissions. The tether would operate with both a power supply and a plasma contactor off at nighttime; power and contactor would be on at daytime for reboost. Tomographic analysis of auroral emissions from the footprint of the beam, as observed from the spacecraft, can provide density profiles of dominant neutral species in the E layer. A characteristic tether system, at altitude 300 km and moderate orbital inclination, would involve an aluminum tape with a length of 20 km, a width of 15 mm, and a thickness of 0.2 mm for a full-system mass around 1200 kg, with two thirds going into the power subsystem.

Mechanical Characterization of Tungsten-Titanium-Lanthana alloy: Influence of Temperature and Atmosphere

The target is to evaluate the mechanical behavior of Ti and La2O3 dispersed W alloy, processed by HIP and compare it with a reference pure-W. Tests were performed in both oxidant (air) and inert (vacuum) atmosphere in a temperature range from -196 to 1200 °C.

Influence of Temperature and Atmosphere in Tungsten-Titanium-Lanthana Alloys

The most promising materials to be used as Plasma Facing Components(PFC),in the International Thermonuclear Experimental Reactor (ITER), are tungsten alloys. However these materials have to withstand extreme operating conditions such as those that will be used inside the reactor.

Floating Bare Tether as Upper Atmosphere Probe

Use of a (bare) conductive tape electrically floating in LEO as an effective e-beam source that produces artificial auroras, and is free of problems that have marred standard beams, is considered. Ambient ions impacting the tape with KeV energies over most of its length liberate secondary electrons, which race down the magnetic field and excite neutrals in the E-layer, resulting in auroral emissions. The tether would operate at night-time with both a power supply and a plasma contactor off; power and contactor would be on at daytime for reboost. The optimal tape thickness yielding a minimum mass for an autonomous system is determined; the alternative use of an electric thruster for day reboost, depending on mission duration, is discussed. Measurements of emission brightness from the spacecraft could allow determination of the (neutral) density vertical profile in the critical E-layer; the flux and energy in the beam, varying along the tether, allow imaging line-of-sight integrated emissions that mix effects with altitude-dependent neutral density and lead to a brightness peak in the beam footprint at the E-layer. Difficulties in tomographic inversion, to determine the density profile, result from beam broadening, due to elastic collisions, which flattens the peak, and to the highly nonlinear functional dependency of line-of-sight brightness. Some dynamical issues are discussed.

Sistemas multiespectrales e hiperespectrales para la observación del territorio : análisis y aplicación a la prospección de hidrocarburos.

La observación de la Tierra es una herramienta de gran utilidad en la actualidad para el estudio de los fenómenos que se dan en la misma. La observación se puede realizar a distintas escalas y por distintos métodos dependiendo del propósito. El actual Trabajo Final de Grado persigue exponer la observación del territorio mediante técnicas de Teledetección, o Detección Remota, y su aplicación en la exploración de hidrocarburos. Desde la Segunda Guerra Mundial el capturar imágenes aéreas de regiones de la Tierra estaba restringido a usos cartográficos en el sentido estricto. Desde aquellos tiempos, hasta ahora, ha acontecido una serie de avances científicos que permiten deducir características intrínsecas de la Tierra mediante mecanismos complejos que no apreciamos a simple vista, pero que, están configurados mediante determinados parámetros geométricos y electrónicos, que permiten generar series temporales de fenómenos físicos que se dan en la Tierra. Hoy en día se puede afirmar que el aprovechamiento del espectro electromagnético está en un punto máximo. Se ha pasado del análisis de la región del espectro visible al análisis del espectro en su totalidad. Esto supone el desarrollo de nuevos algoritmos, técnicas y procesos para extraer la mayor cantidad de información acerca de la interacción de la materia con la radiación electromagnética. La información que generan los sistemas de captura va a servir para la aplicación directa e indirecta de métodos de prospección de hidrocarburos. Las técnicas utilizadas en detección por sensores remotos, aplicadas en campañas geofísicas, son utilizadas para minimizar costes y maximizar resultados en investigaciones de campo. La predicción de anomalías en la zona de estudio depende del analista, quien diseña, calcula y evalúa las variaciones de la energía electromagnética reflejada o emitida por la superficie terrestre. Para dicha predicción se revisarán distintos programas espaciales, se evaluará la bondad de registro y diferenciación espectral mediante el uso de distintas clasificaciones (supervisadas y no supervisadas). Por su influencia directa sobre las observaciones realizadas, se realiza un estudio de la corrección atmosférica; se programan distintos modelos de corrección atmosférica para imágenes multiespectrales y se evalúan los métodos de corrección atmosférica en datos hiperespectrales. Se obtendrá temperatura de la zona de interés utilizando los sensores TM-4, ASTER y OLI, así como un Modelo Digital del Terreno generado por el par estereoscópico capturado por el sensor ASTER. Una vez aplicados estos procedimientos se aplicarán los métodos directos e indirectos, para la localización de zonas probablemente afectadas por la influencia de hidrocarburos y localización directa de hidrocarburos mediante teledetección hiperespectral. Para el método indirecto se utilizan imágenes capturadas por los sensores ETM+ y ASTER. Para el método directo se usan las imágenes capturadas por el sensor Hyperion. ABSTRACT The observation of the Earth is a wonderful tool for studying the different kind of phenomena that occur on its surface. The observation could be done by different scales and by different techniques depending on the information of interest. This Graduate Thesis is intended to expose the territory observation by remote sensing acquiring data systems and the analysis that can be developed to get information of interest. Since Second World War taking aerials photographs of scene was restricted only to a cartographic sense. From these days to nowadays, it have been developed many scientific advances that make capable the interpretation of the surface behavior trough complex systems that are configure by specific geometric and electronic parameters that make possible acquiring time series of the phenomena that manifest on the earth’s surface. Today it is possible to affirm that the exploitation of the electromagnetic spectrum is on a maxim value. In the past, analysis of the electromagnetic spectrum was carry in a narrow part of it, today it is possible to study entire. This implicates the development of new algorithms, process and techniques for the extraction of information about the interaction of matter with electromagnetic radiation. The information that has been acquired by remote sensing sensors is going to be a helpful tool for the exploration of hydrocarbon through direct and vicarious methods. The techniques applied in remote sensing, especially in geophysical campaigns, are employed to minimize costs and maximize results of ground-based geologic investigations. Forecasting of anomalies in the region of interest depends directly on the expertise data analyst who designs, computes and evaluates variations in the electromagnetic energy reflected or emanated from the earth’s surface. For an optimal prediction a review of the capture system take place; assess of the goodness in data acquisition and spectral separability, is carried out by mean of supervised and unsupervised classifications. Due to the direct influence of the atmosphere in the register data, a study of the minimization of its influence has been done; a script has been programed for the atmospheric correction in multispectral data; also, a review of hyperspectral atmospheric correction is conducted. Temperature of the region of interest is computed using the images captured by TM-4, ASTER and OLI, in addition to a Digital Terrain Model generated by a pair of stereo images taken by ASTER sensor. Once these procedures have finished, direct and vicarious methods are applied in order to find altered zones influenced by hydrocarbons, as well as pinpoint directly hydrocarbon presence by mean of hyperspectral remote sensing. For this purpose ETM+ and ASTER sensors are used to apply the vicarious method and Hyperion images are used to apply the direct method.

Mechanical characterisation of tungsten-1wt.% yttrium oxide as a function of temperature and atmosphere

This study evaluates the mechanical behaviour of an Y2O3-dispersed tungsten (W) alloy and compares it to a pure W reference material. Both materials were processed via mechanical alloying (MA) and subsequent hot isostatic pressing (HIP). We performed non-standard three-point bending (TPB) tests in both an oxidising atmosphere and vacuum across a temperature range from 77 K, obtained via immersion in liquid nitrogen, to 1473 K to determine the mechanical strength, yield strength and fracture toughness. This research aims to evaluate how the mechanical behaviour of the alloy is affected by oxides formed within the material at high temperatures, primarily from 873 K, when the materials undergo a massive thermal degradation. The results indicate that the alloy is brittle to a high temperature (1473 K) under both atmospheres and that the mechanical properties degrade significantly above 873 K. We also used Vickers microhardness tests and the dynamic modulus by impulse excitation technique (IET) to determine the elastic modulus at room temperature. Moreover, we performed nanoindentation tests to determine the effect of size on the hardness and elastic modulus; however, no significant differences were found. Additionally, we calculated the relative density of the samples to assess the porosity of the alloy. Finally, we analysed the microstructure and fracture surfaces of the tested materials via field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). In this way, the relationship between the macroscopic mechanical properties and micromechanisms of failure could be determined based on the temperature and oxides formed

Influencia de la atmósfera de sinterización en las propiedades mecánicas de los aceros P/M AISI 430.LInfluence of sintering atmosphere on the mechanical properties of steel P/M AISI 430L

Se ha estudiado el acero inoxidable pulvimetalúrgico AISI 430L, comparando la sinterización en dos atmósferas diferentes; en vacío, y en una atmósfera que contiene nitrógeno. Se ha desarrollado un tratamiento térmico con objeto de incrementar las propiedades mecánicas, mediante la modificación microestructural de los nitruros complejos de hierro y cromo precipitados durante la etapa de sinterización. Se han evaluado las propiedades físicas y a la vez se ha realizado un análisis microestructural con el fin de relacionar la microestructura con el incremento en las propiedades mecánicas. Influence of sintering atmosphere on the mechanical properties of steel P / M AISI 430L. It has studied the stainless steel powder metallurgy AISI 430L. It has compared the sintering in two different atmospheres; in vacuum, and in an atmosphere containing nitrogen. It has developed a heat treatment with the aim of improving the mechanical properties. This has been done through microstructural modification of complex nitrides of iron and chromium precipitates during the phase of sintering. Physical properties have been evaluated and are been performing a microstructural analysis for microstructure related to the increase in mechanical properties.