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.

Evidence for a disaggregation of the universe.

Combining the kinematical definitions of the two dimensionless parameters, the deceleration q(x) and the Hubble t 0 H(x), we get a differential equation (where x=t/t 0 is the age of the universe relative to its present value t 0). First integration gives the function H(x). The present values of the Hubble parameter H(1) [approximately t 0 H(1)≈1], and the deceleration parameter [approximately q(1)≈−0.5], determine the function H(x). A second integration gives the cosmological scale factor a(x). Differentiation of a(x) gives the speed of expansion of the universe. The evolution of the universe that results from our approach is: an initial extremely fast exponential expansion (inflation), followed by an almost linear expansion (first decelerated, and later accelerated). For the future, at approximately t≈3t 0 there is a final exponential expansion, a second inflation that produces a disaggregation of the universe to infinity. We find the necessary and sufficient conditions for this disaggregation to occur. The precise value of the final age is given only with one parameter: the present value of the deceleration parameter [q(1)≈−0.5]. This emerging picture of the history of the universe represents an important challenge, an opportunity for the immediate research on the Universe. These conclusions have been elaborated without the use of any particular cosmological model of the universe

Shaking table tests of structures with hysteretic dampers: experimental results vs. prediction using non-linear static methods

The use of seismic hysteretic dampers for passive control is increasing exponentially in recent years for both new and existing buildings. In order to utilize hysteretic dampers within a structural system, it is of paramount importance to have simplified design procedures based upon knowledge gained from theoretical studies and validated with experimental results. Non-linear Static Procedures (NSPs) are presented as an alternative to the force-based methods more common nowadays. The application of NSPs to conventional structures has been well established; yet there is a lack of experimental information on how NSPs apply to systems with hysteretic dampers. In this research, several shaking table tests were conducted on two single bay and single story 1:2 scale structures with and without hysteretic dampers. The maximum response of the structure with dampers in terms of lateral displacement and base shear obtained from the tests was compared with the prediction provided by three well-known NSPs: (1) the improved version of the Capacity Spectrum Method (CSM) from FEMA 440; (2) the improved version of the Displacement Coefficient Method (DCM) from FEMA 440; and (3) the N2 Method implemented in Eurocode 8. In general, the improved version of the DCM and N2 methods are found to provide acceptable accuracy in prediction, but the CSM tends to underestimate the response.

Combining a Similar Coefficient Identification Algorithm with the Boundary Element Method

The boundary element method (BEM) has been applied successfully to many engineering problems during the last decades. Compared with domain type methods like the finite element method (FEM) or the finite difference method (FDM) the BEM can handle problems where the medium extends to infinity much easier than domain type methods as there is no need to develop special boundary conditions (quiet or absorbing boundaries) or infinite elements at the boundaries introduced to limit the domain studied. The determination of the dynamic stiffness of arbitrarily shaped footings is just one of these fields where the BEM has been the method of choice, especially in the 1980s. With the continuous development of computer technology and the available hardware equipment the size of the problems under study grew and, as the flop count for solving the resulting linear system of equations grows with the third power of the number of equations, there was a need for the development of iterative methods with better performance. In [1] the GMRES algorithm was presented which is now widely used for implementations of the collocation BEM. While the FEM results in sparsely populated coefficient matrices, the BEM leads, in general, to fully or densely populated ones, depending on the number of subregions, posing a serious memory problem even for todays computers. If the geometry of the problem permits the surface of the domain to be meshed with equally shaped elements a lot of the resulting coefficients will be calculated and stored repeatedly. The present paper shows how these unnecessary operations can be avoided reducing the calculation time as well as the storage requirement. To this end a similar coefficient identification algorithm (SCIA), has been developed and implemented in a program written in Fortran 90. The vertical dynamic stiffness of a single pile in layered soil has been chosen to test the performance of the implementation. The results obtained with the 3-d model may be compared with those obtained with an axisymmetric formulation which are considered to be the reference values as the mesh quality is much better. The entire 3D model comprises more than 35000 dofs being a soil region with 21168 dofs the biggest single region. Note that the memory necessary to store all coefficients of this single region is about 6.8 GB, an amount which is usually not available with personal computers. In the problem under study the interface zone between the two adjacent soil regions as well as the surface of the top layer may be meshed with equally sized elements. In this case the application of the SCIA leads to an important reduction in memory requirements. The maximum memory used during the calculation has been reduced to 1.2 GB. The application of the SCIA thus permits problems to be solved on personal computers which otherwise would require much more powerful hardware.

Transition from isentropic to isothermal expansion in laser produced plasma

The transition that the expansion flow of laser-produced plasmas experiences when one moves from long, low intensity pulses (temperature vanishing at the isentropic plasma-vacuum front,lying at finite distance) to short, intense ones (non-zero, uniform temperature at the plasma-vacuum front, lying at infinity) is studied. For plznar geometry and lqge ion number Z, the transition occurs for dq5/dt=0.14(27/8)k712Z’1zn$/m4f, 12nK,,; mi, and K are laser intensity, critical density,ion mass, and Spitzer’s heat conduction coefficient. This result remains valid for finite Zit,h ough the numerical factor in d$/dt is different. Shorter wavelength lasers and higher 4 plasmas allow faster rising pulses below transition.

Linear Sparse Differential Resultant Formulas

Let P be a system of n linear nonhomogeneous ordinary differential polynomials in a set U of n-1 differential indeterminates. Differential resultant formulas are presented to eliminate the differential indeterminates in U from P. These formulas are determinants of coefficient matrices of appropriate sets of derivatives of the differential polynomials in P, or in a linear perturbation Pe of P. In particular, the formula dfres(P) is the determinant of a matrix M(P) having no zero columns if the system P is ``super essential". As an application, if the system PP is sparse generic, such formulas can be used to compute the differential resultant dres(PP) introduced by Li, Gao and Yuan.