Hard x-ray photoelectron spectroscopy of bulk and thin films of Heusler compounds

X-ray photoemission spectroscopy (XPS) is one of the most universal and powerful tools for investigation of chemical states and electronic structures of materials. The application of hard x-rays increases the inelastic mean free path of the emitted electrons within the solid and thus makes hard x-ray photoelectron spectroscopy (HAXPES) a bulk sensitive probe for solid state research and especially a very effective nondestructive technique to study buried layers.rnThis thesis focuses on the investigation of multilayer structures, used in magnetic tunnel junctions (MTJs), by a number of techniques applying HAXPES. MTJs are the most important components of novel nanoscale devices employed in spintronics. rnThe investigation and deep understanding of the mechanisms responsible for the high performance of such devices and properties of employed magnetic materials that are, in turn, defined by their electronic structure becomes feasible applying HAXPES. Thus the process of B diffusion in CoFeB-based MTJs was investigated with respect to the annealing temperature and its influence on the changes in the electronic structure of CoFeB electrodes that clarify the behaviour and huge TMR ratio values obtained in such devices. These results are presented in chapter 6. The results of investigation of the changes in the valence states of buried off-stoichiometric Co2MnSi electrodes were investigated with respect to the Mn content α and its influence on the observed TMR ratio are described in chapter 7.rnrnMagnetoelectronic properties such as exchange splitting in ferromagnetic materials as well as the macroscopic magnetic ordering can be studied by magnetic circular dichroism in photoemission (MCDAD). It is characterized by the appearance of an asymmetry in the photoemission spectra taken either from the magnetized sample with the reversal of the photon helicity or by reversal of magnetization direction of the sample when the photon helicity direction is fixed. Though recently it has been widely applied for the characterization of surfaces using low energy photons, the bulk properties have stayed inaccessible. Therefore in this work this method was integrated to HAXPES to provide an access to exploration of magnetic phenomena in the buried layers of the complex multilayer structures. Chapter 8 contains the results of the MCDAD measurements employing hard x-rays for exploration of magnetic properties of the common CoFe-based band-ferromagnets as well as half-metallic ferromagnet Co2FeAl-based MTJs.rnrnInasmuch as the magnetoresistive characteristics in spintronic devices are fully defined by the electron spins of ferromagnetic materials their direct measurements always attracted much attention but up to date have been limited by the surface sensitivity of the developed techniques. Chapter 9 presents the results on the successfully performed spin-resolved HAXPES experiment using a spin polarimeter of the SPLEED-type on a buried Co2FeAl0.5Si0.5 magnetic layer. The measurements prove that a spin polarization of about 50 % is retained during the transmission of the photoelectrons emitted from the Fe 2p3/2 state through a 3-nm-thick oxide capping layer.rn

Rigorous results in Spin Glasses and Monomer-Dimer systems

In this work I reported recent results in the field of Statistical Mechanics of Equilibrium, and in particular in Spin Glass models and Monomer Dimer models . We start giving the mathematical background and the general formalism for Spin (Disordered) Models with some of their applications to physical and mathematical problems. Next we move on general aspects of the theory of spin glasses, in particular to the Sherrington-Kirkpatrick model which is of fundamental interest for the work. In Chapter 3, we introduce the Multi-species Sherrington-Kirkpatrick model (MSK), we prove the existence of the thermodynamical limit and the Guerra's Bound for the quenched pressure together with a detailed analysis of the annealed and the replica symmetric regime. The result is a multidimensional generalization of the Parisi's theory. Finally we brie y illustrate the strategy of the Panchenko's proof of the lower bound. In Chapter 4 we discuss the Aizenmann-Contucci and the Ghirlanda-Guerra identities for a wide class of Spin Glass models. As an example of application, we discuss the role of these identities in the proof of the lower bound. In Chapter 5 we introduce the basic mathematical formalism of Monomer Dimer models. We introduce a Gaussian representation of the partition function that will be fundamental in the rest of the work. In Chapter 6, we introduce an interacting Monomer-Dimer model. Its exact solution is derived and a detailed study of its analytical properties and related physical quantities is performed. In Chapter 7, we introduce a quenched randomness in the Monomer Dimer model and show that, under suitable conditions the pressure is a self averaging quantity. The main result is that, if we consider randomness only in the monomer activity, the model is exactly solvable.

Systematic functionalization of molecules for molecular self-assembly

This thesis describes the investigation of systematically varied organic molecules for use in molecular self-assembly processes. All experiments were performed using high-resolution non-contact atomic force microscopy under UHV conditions and at room temperature. Using this technique, three different approaches for influencing intermolecular and molecule-surface interaction on the insulating calcite(10.4) surface were investigated by imaging the structure formation at the molecular scale. I first demonstrated the functionalization of shape-persistent oligo(p-benzamide)s that was engineered by introducing different functional groups and investigating their effect on the structural formation on the sample surface. The molecular core was designed to provide significant electrostatic anchoring towards the surface, while at the same time maintaining the flexibility to fine-tune the resulting structure by adjusting the intermolecular cohesion energy. The success of this strategy is based on a clear separation of the molecule-substrate interaction from the molecule-molecule interaction. My results show that sufficient molecule-surface anchoring can be achieved without restricting the structural flexibility that is needed for the design of complex molecular systems. Three derivatives of terephthalic acid (TPA) were investigated in chapter 7. Here, the focus was on changing the adhesion to the calcite surface by introducing different anchor functionalities to the TPA backbone. For all observed molecules, the strong substrate templating effect results in molecular structures that are strictly oriented along the calcite main crystal directions. This templating is especially pronounced in the case of 2-ATPA where chain formation on the calcite surface is observed in contrast to the formation of molecular layers in the bulk. At the same time, the amino group of 2-ATPA proved an efficient anchor functionality, successfully stabilizing the molecular chains on the sample surface. These findings emphasizes, once again, the importance of balancing and fine-tuning molecule-molecule and molecule-surface interactions in order to achieve stable, yet structurally flexible molecular arrangements on the sample surface. In the last chapter, I showed how the intrinsic property of molecular chirality decisively influences the structure formation in molecular self-assembly. This effect is especially pronounced in the case of the chiral heptahelicene-2-carboxylic acid. Deposition of the enantiopure molecules results in the formation of homochiral islands on the sample surface which is in sharp contrast to the formation of uni-directional double rows upon deposition of the racemate onto the same surface. While it remained uncertain from these previous experiments whether the double rows are composed of hetero- or homochiral molecules, I could clearly answer that question here and demonstrate that the rows are of heterochiral origin. Chirality, thus, proves to be another important parameter to steer the intermolecular interaction on surfaces. Altogether, the results of this thesis demonstrate that, in order to successfully control the structure formation in molecular self-assembly, the correct combination of molecule and surface properties is crucial. This is of special importance when working on substrates that exhibit a strong influence on the structure formation, such as the calcite(10.4) surface. Through the systematic variation of functional groups several important parameters that influence the balance between molecule-surface and molecule-molecule interaction were identified here, and the results of this thesis can, thus, act as a guideline for the rational design of molecules for use in molecular self-assembly.

Morphology control in metallocene-catalyzed polyolefin synthesis

The main aim of the work presented in this dissertation was the morphology control in metallocene-catalyzed polyolefin synthesis. This was studied by selective immobilization techniques on a variety of supports such as porous polyurethane particles (Chapter 3), electrospun fibers (Chapter 4 and 5), inorganic-organic hybrid core-shell particles (Chapter 6) and hollow silica particles (Chapter 7). Another aspect of this dissertation was modulating a catalytic activity by controlling a size of boron-based cocatalysts (Chapter 8).

Tuning of magnetic exchange interactions between organic radicals through bond and space

The dissertation entitled "Tuning of magnetic exchange interactions between organic radicals through bond and space" comprises eight chapters. In the initial part of chapter 1, an overview of organic radicals and their applications were discussed and in the latter part motivation and objective of thesis was described. As the EPR spectroscopy is a necessary tool to study organic radicals, the basic principles of EPR spectroscopy were discussed in chapter 2. rnAntiferromagnetically coupled species can be considered as a source of interacting bosons. Consequently, such biradicals can serve as molecular models of a gas of magnetic excitations which can be used for quantum computing or quantum information processing. Notably, initial small triplet state population in weakly AF coupled biradicals can be switched into larger in the presence of applied magnetic field. Such biradical systems are promising molecular models for studying the phenomena of magnetic field-induced Bose-Einstein condensation in the solid state. To observe such phenomena it is very important to control the intra- as well as inter-molecular magnetic exchange interactions. Chapters 3 to 5 deals with the tuning of intra- and inter-molecular exchange interactions utilizing different approaches. Some of which include changing the length of π-spacer, introduction of functional groups, metal complex formation with diamagnetic metal ion, variation of radical moieties etc. During this study I came across two very interesting molecules 2,7-TMPNO and BPNO, which exist in semi-quinoid form and exhibits characteristic of the biradical and quinoid form simultaneously. The 2,7-TMPNO possesses the singlet-triplet energy gap of ΔEST = –1185 K. So it is nearly unrealistic to observe the magnetic field induced spin switching. So we studied the spin switching of this molecule by photo-excitation which was discussed in chapter 6. The structural similarity of BPNO with Tschitschibabin’s HC allowed us to dig the discrepancies related to ground state of Tschitschibabin’s hydrocarbon(Discussed in chapter 7). Finally, in chapter 8 the synthesis and characterization of a neutral paramagnetic HBC derivative (HBCNO) is discussed. The magneto liquid crystalline properties of HBCNO were studied by DSC and EPR spectroscopy.rn

Control over microstructure evolution and device performance in solution processable organic field-effect transistors

Die Arbeit beschäftigt sich mit der Kontrolle von Selbstorganisation und Mikrostruktur von organischen Halbleitern und deren Einsatz in OFETs. In Kapiteln 3, 4 und 5 eine neue Lösungsmittel-basierte Verabeitungsmethode, genannt als Lösungsmitteldampfdiffusion, ist konzipiert, um die Selbstorganisation von Halbleitermolekülen auf der Oberfläche zu steuern. Diese Methode als wirkungsvolles Werkzeug erlaubt eine genaue Kontrolle über die Mikrostruktur, wie in Kapitel 3 am Beispiel einer D-A Dyad bestehend aus Hexa-peri-hexabenzocoronene (HBC) als Donor und Perylene Diimide (PDI) als Akzeptor beweisen. Die Kombination aus Oberflächenmodifikation und Lösungsmitteldampf kann die Entnetzungseffekte ausgleichen, so dass die gewüschte Mikrostruktur und molekulare Organisation auf der Oberfläche erreicht werden kann. In Kapiteln 4 und 5 wurde diese Methode eingesetzt, um die Selbstorganisation von Dithieno[2, 3-d;2’, 3’-d’] benzo[1,2-b;4,5-b’]dithiophene (DTBDT) und Cyclopentadithiophene -benzothiadiazole copolymer (CDT-BTZ) Copolymer zu steuern. Die Ergebnisse könnten weitere Studien stimulieren und werfen Licht aus andere leistungsfaähige konjugierte Polymere. rnIn Kapiteln 6 und 7 Monolagen und deren anschlieβende Mikrostruktur von zwei konjugierten Polymeren, Poly (2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene) PBTTT und Poly{[N,N ′-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis (dicarboximide)-2,6-diyl]-alt-5,5′- (2,2′-bithiophene)}, P(NDI2OD-T2)) wurden auf steife Oberflächen mittels Tauchbeschichtung aufgebracht. Da sist das erste Mal, dass es gelungen ist, Polymer Monolagen aus der Lösung aufzubringen. Dieser Ansatz kann weiter auf eine breite Reihe von anderen konjugierten Polymeren ausgeweitet werden.rnIn Kapitel 8 wurden PDI-CN2 Filme erfolgreich von Monolagen zu Bi- und Tri-Schichten auf Oberflächen aufgebracht, die unterschiedliche Rauigkeiten besitzen. Für das erste Mal, wurde der Einfluss der Rauigkeit auf Lösungsmittel-verarbeitete dünne Schichten klar beschrieben.rn

Growth, modification and integration of carbon nanotubes into molecular electronics

Molecules are the smallest possible elements for electronic devices, with active elements for such devices typically a few Angstroms in footprint area. Owing to the possibility of producing ultrahigh density devices, tremendous effort has been invested in producing electronic junctions by using various types of molecules. The major issues for molecular electronics include (1) developing an effective scheme to connect molecules with the present micro- and nano-technology, (2) increasing the lifetime and stabilities of the devices, and (3) increasing their performance in comparison to the state-of-the-art devices. In this work, we attempt to use carbon nanotubes (CNTs) as the interconnecting nanoelectrodes between molecules and microelectrodes. The ultimate goal is to use two individual CNTs to sandwich molecules in a cross-bar configuration while having these CNTs connected with microelectrodes such that the junction displays the electronic character of the molecule chosen. We have successfully developed an effective scheme to connect molecules with CNTs, which is scalable to arrays of molecular electronic devices. To realize this far reaching goal, the following technical topics have been investigated. 1. Synthesis of multi-walled carbon nanotubes (MWCNTs) by thermal chemical vapor deposition (T-CVD) and plasma-enhanced chemical vapor deposition (PECVD) techniques (Chapter 3). We have evaluated the potential use of tubular and bamboo-like MWCNTs grown by T-CVD and PE-CVD in terms of their structural properties. 2. Horizontal dispersion of MWCNTs with and without surfactants, and the integration of MWCNTs to microelectrodes using deposition by dielectrophoresis (DEP) (Chapter 4). We have systematically studied the use of surfactant molecules to disperse and horizontally align MWCNTs on substrates. In addition, DEP is shown to produce impurityfree placement of MWCNTs, forming connections between microelectrodes. We demonstrate the deposition density is tunable by both AC field strength and AC field frequency. 3. Etching of MWCNTs for the impurity-free nanoelectrodes (Chapter 5). We show that the residual Ni catalyst on MWCNTs can be removed by acid etching; the tip removal and collapsing of tubes into pyramids enhances the stability of field emission from the tube arrays. The acid-etching process can be used to functionalize the MWCNTs, which was used to make our initial CNT-nanoelectrode glucose sensors. Finally, lessons learned trying to perform spectroscopic analysis of the functionalized MWCNTs were vital for designing our final devices. 4. Molecular junction design and electrochemical synthesis of biphenyl molecules on carbon microelectrodes for all-carbon molecular devices (Chapter 6). Utilizing the experience gained on the work done so far, our final device design is described. We demonstrate the capability of preparing patterned glassy carbon films to serve as the bottom electrode in the new geometry. However, the molecular switching behavior of biphenyl was not observed by scanning tunneling microscopy (STM), mercury drop or fabricated glassy carbon/biphenyl/MWCNT junctions. Either the density of these molecules is not optimum for effective integration of devices using MWCNTs as the nanoelectrodes, or an electroactive contaminant was reduced instead of the ionic biphenyl species. 5. Self-assembly of octadecanethiol (ODT) molecules on gold microelectrodes for functional molecular devices (Chapter 7). We have realized an effective scheme to produce Au/ODT/MWCNT junctions by spanning MWCNTs across ODT-functionalized microelectrodes. A percentage of the resulting junctions retain the expected character of an ODT monolayer. While the process is not yet optimized, our successful junctions show that molecular electronic devices can be fabricated using simple processes such as photolithography, self-assembled monolayers and dielectrophoresis.

Syntheses and structures of molybdenum and tungsten complexes capable of epoxidaton and copper coordination polymers and dendrimers

We are interested in the syntheses of new complexes and in their characterization by single crystal X-ray diffraction techniques. Once we understand the structures, studies aimed at understanding uses of these complexes in the field of catalytic epoxidation using complexes soluble in water and syntheses of thin films (not assessed) were conducted. The syntheses, characterization and catalytic properties of a series of mononuclear, dinuclear and tetranuclear molybdenum and tungsten oxo complexes are described. The syntheses and structural characterization of two copper coordination polymers with 3,5-dihydroxylbenzoate ligand, and five paddlewheel shaped copper dendrimers coordinated with Fréchet-type dendrons are also detailed. The background of this dissertation is outlined in Chapter 1. Chapter 2 describes the syntheses, and characterization of two new mononuclear molybdenum(VI) and tungsten(VI) oxo complexes, MoO2Cl2(OPPh2CH2OH)2, and WO2Cl2(OPPh2CH2OH)2, bearing hydrophilic phosphine oxide ligand. The catalytic properties of these complexes for the epoxidation of cis-cyclooctene were also studied. Two new dinuclear molybdenum(VI) and tungsten(VI) oxo complexes Mo2O4Cl2[(HOCH2)PhPOO]2, and (CH3O)2(O)W(μ-O)(μ-O2PPh2)2W(O)(CH3O)2, bearing organophosphinate ligand are described in Chapter 3 and 4. Chapter 4 and 5 describes the syntheses and characterization of tetranuclear molybdenum(V) oxo complexes bearing various organophosphinate ligands. The catalytic abilities of these complexes for the epoxidation of cis-cyclooctene in the presence of hydrogen peroxide as oxidant were explored as well. Various spectroscopic methods, such as IR, UV-vis, and NMR are used to characterize the nature of these complexes. Crystal structures of compounds MoO2Cl2(OPPh2CH2OH)2, WO2Cl2(OPPh2CH2OH)2, Mo2O4Cl2[(HOCH2)PhPOO]2, (CH3O)2(O)W(μ-O)(μ-O2PPh2)2W(O)(CH3O)2, and Mo4(µ3-O)4(µ-O2PR2)4O4 (R=Ph, Me, ClCH2, o-C6H4(CH2)2) are also presented. The syntheses, and structural characterization of three copper(II) coordination polymers bearing 3,5-dihydroxybenzoate ligand are described in Chapter 6. Two copper(II) coordination polymers, [Cu2(3,5-dhb)2(pyridine)4]n, and [Cu2(3,5-dhb)4]n were afforded based on different amount of pyridine used in the reaction. The structures of these complexes are further built into 2D or 3D networks via inter or intra hydrogen bonds. The syntheses and structural characterization of the zinc(II) monomer, Zn(3,5-dhb)2(pyridine)2 is also described in this Chapter. Chapter 7 describes the syntheses, and characterization of five dendronized dicopper complexes bearing different generations of Fréchet-type dendrons. The structures of 3,5- bis(benzoyloxl)benzoic acid, 3,5-(PhCOO)2PhCOOH (G1), Cu2(3,5-dhb)4(THF)2, Cu2(G1)4(pyridine)2, and Cu2(G1)4(CH3OH)2 were characterized unambiguously by single X-ray diffraction. In addition, all compounds were characterized by FT-IR, UV-vis spectroscopy and elemental analyses.

A new Time-Of-Flight Mass Spectrometer (TOF-MS) for noble gas analysis

Noble gas analysis in early solar system materials, which can provide valuable information about early solar system processes and timescales, are very challenging because of extremely low noble gas concentrations (ppt). We therefore developed a new compact sized (33 cm length, 7.2cm diameter, 1.3 L internal volume) Time-of-Flight (TOF) noble gas mass spectrometer for high sensitivity. We call it as Edel Gas Time-of-flight (EGT) mass spectrometer. The instrument uses electron impact ionization coupled to an ion trap, which allows us to ionize and measure all noble gas isotopes. Using a reflectron set-up improves the mass resolution. In addition, the reflectron set-up also enables some extra focusing. The detection is via MCPs and the signals are processed either via ADC or TDC systems. The objective of this work is to understand the newly developed Time-Of-Flight (TOF) mass spectrometer for noble gas analysis in presolar grains of the meteorites. Chapter 1 briefly introduces the basic idea and importance of the instrument. The physics relevant to time-of-flight mass spectrometry technique is discussed in the Chapter 2 and Chapter 3 will present the oxidation technique of nanodiamonds of the presolar grains by using copper oxide. Chapter 4 will present the details about EGT data analysis software. Chapter 5 and Chapter 6 will explain the details about EGT design and operation. Finally, the performance results will be presented and discussed in the Chapter 7, and whole work is summarized in Chapter 8 and also outlook of the future work is given.

Documentation of sediment cores during SONNE Expedition SO228 from the western tropical Pacific

The core descriptions (chapter 7) summarize the most important results of the analysis of each sediment core following procedures applied during ODP/IODP expeditions. All cores were opened, described, and color-scanned. In the core descriptions the first column displays the lithological data that are based on visual analysis of the core and are supplemented by information from binocular and smear slide analyses. The sediment classification largely follows ODP/IODP convention. Lithological names consist of a principal name based on composition, degree of lithification, and/or texture as determined from visual description and microscopic observations. In the structure column the intensity of bioturbation together with individual or special features (turbidites, volcanic ash layers, plant debris, shell fragments, etc.) is shown. The hue and chroma attributes of color were determined by comparison with the Munsell soil color charts and are given in the color column in the Munsell notation. A GretagMacbethTM Spectrolino spectrophotometer was used to measure percent reflectance values of sediment color at 36 wavelength channels over the visible light range (380-730 nm) on all of the cores. The digital reflectance data of the spectrophotometer readings were routinely obtained from the surface (measured in 1 cm steps) of the split cores (archive half). The Spectrolino is equipped with a measuring aperture with folding mechanism allowing an exact positioning on the split core and is connected to a portable computer. The data are directly displayed within the software package Excel and can be controlled simultaneously. From all the color measurements, for each core the red/blue ratio (700 nm/450 nm) and the lightness are shown together with the visual core description. The reflectance of individual wavelengths is often significantly affected by the presence of minor amounts of oxyhydroxides or sulphides. To eliminate these effects, we used the red/blue ratio and lightness.

Fisuración y deformaciones en tabiquerías

A diferencia de otros parámetros, el efecto de la existencia de huecos en la aparición y desarrollo de los procesos de fisuración en los paños de fábrica no ha sido considerado por las distintas normativas existentes en la actualidad. En nuestros días se emplea una variada gama de tipologías de elementos de cerramiento para realizar las particiones en las obras de edificación, cada una de ellas con características mecánicas diferentes y distinta metodología de ejecución, siendo de aplicación la misma normativa relativa al cálculo y control de las deformaciones. Tal y como expresamos en el Capitulo 1, en el que se analiza el Estado del Conocimiento, los códigos actuales determinan de forma analítica la flecha probable que se alcanza en los elementos portantes estructurales bajo diferentes condiciones de servicio. Las distintas propuestas que existen respecto para la limitación de la flecha activa, una vez realizado el cálculo de las deformaciones, bien por el método de Branson ó mediante los métodos de integración de curvaturas, no contemplan como parámetro a considerar en la limitación de la flecha activa la existencia y tipología de huecos en un paño de fábrica soportado por la estructura. Sin embargo se intuye y podríamos afirmar que una discontinuidad en cualquier elemento sometido a esfuerzos tiene influencia en el estado tensional del mismo. Si consideramos que, de forma general, los procesos de fisuración se producen al superarse la resistencia a tracción de material constitutivo de la fábrica soportada, es claro que la variación tensional inducida por la existencia de huecos ha de tener cierta influencia en la aparición y desarrollo de los procesos de fisuración en los elementos de partición o de cerramiento de las obras de edificación. En los Capítulos 2 y 3 tras justificar la necesidad de realizar una investigación encaminada a confirmar la relación entre la existencia de huecos en un paño de fábrica y el desarrollo de procesos de fisuración en el mismo, se establece este aspecto como principal Objetivo y se expone la Metodología para su análisis. Hemos definido y justificado en el Capítulo 4 el modelo de cálculo que hemos utilizado para determinar las deformaciones y los procesos de fisuración que se producen en los casos a analizar, en los que se han considerado como variables: los valores de la luz del modelo, el estado de fisuración de los elementos portantes, los efectos de la fluencia y el porcentaje de transmisión de cargas desde el forjado superior al paño de fábrica en estudio. Además se adoptan dos valores de la resistencia a tracción de las fábricas, 0.75MPa y 1.00MPa. La capacidad de representar la fisuración, así como la robustez y fiabilidad ha condicionado y justificado la selección del programa de elementos finitos que se ha utilizado para realizar los cálculos. Aprovechando la posibilidad de reproducir de forma ajustada las características introducidas para cada parámetro, hemos planteado y realizado un análisis paramétricos que considera 360 cálculos iterativos, de cuya exposición es objeto el Capítulo 5, para obtener una serie representativa de resultados sobre los que se realizará el análisis posterior. En el Capítulo 6, de análisis de los resultados, hemos estudiado los valores de deformaciones y estados de fisuración obtenidos para los casos analizados. Hemos determinado la influencia que tiene la presencia de huecos en la aparición de los procesos de fisuración y en las deformaciones que se producen en las diferentes configuraciones estructurales. Las conclusiones que hemos obtenido tras analizar los resultados, incluidas en el Capítulo 7, no dejan lugar a dudas: la presencia, la posición y la tipología de los huecos en los elementos de fábricas soportadas sobre estructuras deformables son factores determinantes respecto de la fisuración y pueden tener influencia en las deformaciones que constituyen la flecha activa del elemento, lo que obliga a plantear una serie de recomendaciones frente al proyecto y frente a la reglamentación técnica. La investigación desarrollada para esta Tesis Doctoral y la metodología aplicada para su desarrollo abre nuevas líneas de estudio, que se esbozan en el Capítulo 8, para el análisis de otros aspectos que no han sido cubiertos por esta investigación a fin de mejorar las limitaciones que deberían establecerse para los Estados Límite de Servicio de Deformaciones correspondientes a las estructuras de edificación. SUMMARY. Unlike other parameters, the effect of the existence of voids in the arising and development of cracking processes in the masonry walls has not been considered by current Codes. Nowadays, a huge variety of enclosure elements types is used to execute partitions in buildings, each one with different mechanical characteristics and different execution methodology, being applied the same rules concerning deflection calculation and control. As indicated in Chapter 1, which analyzes the State of Art, current codes analytically determine the deflection likely to be achieved in structural supporting elements under different service conditions. The different proposals that exist related to live deflection limitation, once performed deformations calculation, either by Branson´s method or considering curvatures integration methods, do not consider in deflection limitation the existence and typology of voids in a masonry wall structured supported. But is sensed and it can be affirmed that a discontinuity in any element under stress influences the stress state of it. If we consider that, in general, cracking processes occur when masonry material tensile strength is exceeded, it is clear that tension variation induced by the existence of voids must have some influence on the emergence and development of cracking processes in enclosure elements of building works. In Chapters 2 and 3, after justifying the need for an investigation to confirm the relationship between the existence of voids in a masonry wall and the development of cracking process in it, is set as the main objective and it is shown the analysis Methodology. We have defined and justified in Chapter 4 the calculation model used to determine the deformation and cracking processes that occur in the cases analyzed, in which were considered as variables: model span values, bearing elements cracking state, creep effects and load transmission percentage from the upper floor to the studied masonry wall. In addition, two masonry tensile strength values 0.75MPa and 1.00MPa have been considered. The cracking consideration ability, robustness and reliability has determined and justified the selection of the finite element program that was used for the calculations. Taking advantage of the ability of accurately consider the characteristics introduced for each parameter, we have performed a parametric analyses that considers 360 iterative calculations, whose results are included in Chapter 5, in order to obtain a representative results set that will be analyzed later. In Chapter 6, results analysis, we studied the obtained values of deformation and cracking configurations for the cases analyzed. We determined the influence of the voids presence in the occurrence of cracking processes and deformations in different structural configurations. The conclusions we have obtained after analyzing the results, included in Chapter 7, leave no doubt: the presence, position and type of holes in masonry elements supported on deformable structures are determinative of cracking and can influence deformations which are the element live deflection, making necessary to raise a number of recommendations related to project and technical regulation. The research undertaken for this Doctoral Thesis and the applied methodology for its development opens up new lines of study, outlined in Chapter 8, for the analysis of other aspects that are not covered by this research, in order to improve the limitations that should be established for Deflections Serviceability Limit States related to building structures.

Ensayos acelerados de fiabilidad de células solares de concentración

SUMMARY Concentration Photovoltaic Systems (CPV) have been proposed as an alternative to conventional systems. During the last years, there has been a boom of the CPV industry caused by the technological progress in all the elements of the system. and mainly caused by the use of multijunction solar cells based on III-V semiconductors, with efficiencies exceeding to 43%. III-V solar cells have been used with high reliability results in a great number of space missions without concentration. However, there are no previous results regarding their reliability in concentration terrestrial applications, where the working conditions are completely different. This lack of experience, together with the important industrial interest, has generated the need to evaluate the reliability of the cells. For this reason, nowadays there are several research centers around the undertaking this task. The evaluation of the reliability of this type of devices by means of accelerated tests is especially problematic when they work at medium or high concentration, because it is practically impossible to emulate real working conditions of the cell inside climatic chambers. In fact, as far as we know, the results that appear in this Thesis are the first estimating the Activation Energy of the failure mechanism involved, as well as the warranty of the III-V concentrator solar cells tested here. To evaluate the reliability of III-V very high concentrator solar cells by means of accelerated tests, a variety of activities, described in this Thesis have been carried out. The First Part of the memory presents the theoretical part of the Doctoral Thesis. After the Introduction, chapter 2 presents the state of the art in degradation and reliability of CPV systems and solar cells. Chapter 3 introduces some reliability definitions and the application of specific statistical functions to the evaluation of the reliability and parameters. From these functions, important parameters will be calculated to be used later in the experimental results of Thesis. The Second Part of the memory contains the experimental. Chapter 4 shows the types of accelerated tests and the main goals pursuit with them when carried out over CPV systems and solar cells. In order to evaluate quantitatively the reliability of the III-V concentrator solar cells used in these tests, some modifications have been introduced which discussion will be tackled here. Based on this analysis the working plan of the tests carried out in this Doctoral Thesis is presented. Chapter 5 presents a new methodology as well as the necessary instrumentation to carry out the tests described here. This new methodology takes into account the adaptation, improvement and novel techniques needed to test concentrator solar cells. The core of this memory is chapter 6, which presents the results of the characterization of the cells during the accelerated life tests and the analysis of the aforementioned results with the purpose of getting quantitative values of reliability in real working conditions. The acceleration factor of the accelerated life tests, under nominal working conditions has been calculated. Accordingly, the validity of the methodology as well as the calculations based on the reliability assessment, have also been demonstrated. Finally, quantitative values of degradation, reliability and warranty of the solar cells under field nominal working conditions have been calculated. With the development of this Doctoral Thesis the reliability of very high concentrator GaAs solar cells of small area has been evaluated. It is very interesting to generalize the procedures described up to this point to III-V multijunction solar cells of greater area. Therefore, chapter 7 develops this generalization and introduces also a useful thermal modeling by means of finite elements of the test cells’ circuits. In the last chapter, the summary of the results and the main contributions of this Thesis are outlined and future research activities are identified. RESUMEN Los Sistemas Fotovoltaicos de Concentración (SFC) han sido propuestos como una alternativa a los sistemas convencionales de generación de energía. Durante los últimos años ha habido un auge de los SFC debido a las mejoras tecnológicas en todos los elementos del sistema, y principalmente por el uso de células multiunión III-V que superan el 43% de rendimiento. Las células solares III-V han sido utilizadas con elevada fiabilidad en aplicaciones espaciales sin concentración, pero no existe experiencia de su fiabilidad en ambiente terrestre a altos niveles de concentración solar. Esta falta de experiencia junto al gran interés industrial ha generado la necesidad de evaluar la fiabilidad de las células, y actualmente hay un significativo número de centros de investigación trabajando en esta área. La evaluación de la fiabilidad de este tipo de dispositivos mediante ensayos acelerados es especialmente problemática cuando trabajan a media o alta concentración por la casi imposibilidad de emular las condiciones de trabajo reales de la célula dentro de cámaras climáticas. De hecho, que sepamos, en los resultados de esta Tesis se evalúa por primera vez la Energía de Activación del mecanismo de fallo de las células, así como la garantía en campo de las células de concentración III-V analizadas. Para evaluar la fiabilidad de células solares III-V de muy alta concentración mediante ensayos de vida acelerada se han realizado diversas actividades que han sido descritas en la memoria de la Tesis. En la Primera Parte de la memoria se presenta la parte teórica de la Tesis Doctoral. Tras la Introducción, en el capítulo 2 se muestra el estado del arte en degradación y fiabilidad de células y Sistemas Fotovoltaicos de Concentración. En el capítulo 3 se exponen de forma resumida las definiciones de fiabilidad y funciones estadísticas que se utilizan para la evaluación de la fiabilidad y sus parámetros, las cuales se emplearán posteriormente en los ensayos descritos en este Tesis. La Segunda Parte de la memoria es experimental. En el capítulo 4 se describen los tipos y objetivos de los ensayos acelerados actualmente aplicados a SFC y a las células, así como las modificaciones necesarias que permitan evaluar cuantitativamente la fiabilidad de las células solares de concentración III-V. En base a este análisis se presenta la planificación de los trabajos realizados en esta Tesis Doctoral. A partir de esta planificación y debido a la necesidad de adaptar, mejorar e innovar las técnicas de ensayos de vida acelerada para una adecuada aplicación a este tipo de dispositivos, en el capítulo 5 se muestra la metodología empleada y la instrumentación necesaria para realizar los ensayos de esta Tesis Doctoral. El núcleo de la memoria es el capítulo 6, en él se presentan los resultados de caracterización de las células durante los ensayos de vida acelerada y el análisis de dichos resultados con el objetivo de obtener valores cuantitativos de fiabilidad en condiciones reales de trabajo. Se calcula el Factor de Aceleración de los ensayos acelerados con respecto a las condiciones nominales de funcionamiento a partir de la Energía de Activación obtenida, y se demuestra la validez de la metodología y cálculos empleados, que son la base de la evaluación de la fiabilidad. Finalmente se calculan valores cuantitativos de degradación, fiabilidad y garantía de las células en condiciones nominales en campo durante toda la vida de la célula. Con el desarrollo de esta Tesis Doctoral se ha evaluado la fiabilidad de células III-V de área pequeña, pero es muy interesante generalizar los procedimientos aquí desarrollados para las células III-V comerciales de área grande. Por este motivo, en el capítulo 7 se analiza dicha generalización, incluyendo el modelado térmico mediante elementos finitos de los circuitos de ensayo de las células. En el último capítulo se realiza un resume del trabajo y las aportaciones realizadas, y se identifican las líneas de trabajo a emprender en el futuro.

Análisis de los factores determinantes de la repetición del proceso de compra en el comercio electrónico entre empresas y consumidores finales. Aplicación al mercado español

Las Tecnologías de la Información y la Comunicación en general e Internet en particular han supuesto una revolución en nuestra forma de comunicarnos, relacionarnos, producir, comprar y vender acortando tiempo y distancias entre proveedores y consumidores. A la paulatina penetración del ordenador, los teléfonos inteligentes y la banda ancha fija y/o móvil ha seguido un mayor uso de estas tecnologías entre ciudadanos y empresas. El comercio electrónico empresa–consumidor (B2C) alcanzó en 2010 en España un volumen de 9.114 millones de euros, con un incremento del 17,4% respecto al dato registrado en 2009. Este crecimiento se ha producido por distintos hechos: un incremento en el porcentaje de internautas hasta el 65,1% en 2010 de los cuales han adquirido productos o servicios a través de la Red un 43,1% –1,6 puntos porcentuales más respecto a 2010–. Por otra parte, el gasto medio por comprador ha ascendido a 831€ en 2010, lo que supone un incremento del 10,9% respecto al año anterior. Si segmentamos a los compradores según por su experiencia anterior de compra podemos encontrar dos categorías: el comprador novel –que adquirió por primera vez productos o servicios en 2010– y el comprador constante –aquel que había adquirido productos o servicios en 2010 y al menos una vez en años anteriores–. El 85,8% de los compradores se pueden considerar como compradores constantes: habían comprado en la Red en 2010, pero también lo habían hecho anteriormente. El comprador novel tiene un perfil sociodemográfico de persona joven de entre 15–24 años, con estudios secundarios, de clase social media y media–baja, estudiante no universitario, residente en poblaciones pequeñas y sigue utilizando fórmulas de pago como el contra–reembolso (23,9%). Su gasto medio anual ascendió en 2010 a 449€. El comprador constante, o comprador que ya había comprado en Internet anteriormente, tiene un perfil demográfico distinto: estudios superiores, clase alta, trabajador y residente en grandes ciudades, con un comportamiento maduro en la compra electrónica dada su mayor experiencia –utiliza con mayor intensidad canales exclusivos en Internet que no disponen de tienda presencial–. Su gasto medio duplica al observado en compradores noveles (con una media de 930€ anuales). Por tanto, los compradores constantes suponen una mayoría de los compradores con un gasto medio que dobla al comprador que ha adoptado el medio recientemente. Por consiguiente es de interés estudiar los factores que predicen que un internauta vuelva a adquirir un producto o servicio en la Red. La respuesta a esta pregunta no se ha revelado sencilla. En España, la mayoría de productos y servicios aún se adquieren de manera presencial, con una baja incidencia de las ventas a distancia como la teletienda, la venta por catálogo o la venta a través de Internet. Para dar respuesta a las preguntas planteadas se ha investigado desde distintos puntos de vista: se comenzará con un estudio descriptivo desde el punto de vista de la demanda que trata de caracterizar la situación del comercio electrónico B2C en España, poniendo el foco en las diferencias entre los compradores constantes y los nuevos compradores. Posteriormente, la investigación de modelos de adopción y continuidad en el uso de las tecnologías y de los factores que inciden en dicha continuidad –con especial interés en el comercio electrónico B2C–, permiten afrontar el problema desde la perspectiva de las ecuaciones estructurales pudiendo también extraer conclusiones de tipo práctico. Este trabajo sigue una estructura clásica de investigación científica: en el capítulo 1 se introduce el tema de investigación, continuando con una descripción del estado de situación del comercio electrónico B2C en España utilizando fuentes oficiales (capítulo 2). Posteriormente se desarrolla el marco teórico y el estado del arte de modelos de adopción y de utilización de las tecnologías (capítulo 3) y de los factores principales que inciden en la adopción y continuidad en el uso de las tecnologías (capítulo 4). El capítulo 5 desarrolla las hipótesis de la investigación y plantea los modelos teóricos. Las técnicas estadísticas a utilizar se describen en el capítulo 6, donde también se analizan los resultados empíricos sobre los modelos desarrollados en el capítulo 5. El capítulo 7 expone las principales conclusiones de la investigación, sus limitaciones y propone nuevas líneas de investigación. La primera parte corresponde al capítulo 1, que introduce la investigación justificándola desde un punto de vista teórico y práctico. También se realiza una breve introducción a la teoría del comportamiento del consumidor desde una perspectiva clásica. Se presentan los principales modelos de adopción y se introducen los modelos de continuidad de utilización que se estudiarán más detalladamente en el capítulo 3. En este capítulo se desarrollan los objetivos principales y los objetivos secundarios, se propone el mapa mental de la investigación y se planifican en un cronograma los principales hitos del trabajo. La segunda parte corresponde a los capítulos dos, tres y cuatro. En el capítulo 2 se describe el comercio electrónico B2C en España utilizando fuentes secundarias. Se aborda un diagnóstico del sector de comercio electrónico y su estado de madurez en España. Posteriormente, se analizan las diferencias entre los compradores constantes, principal interés de este trabajo, frente a los compradores noveles, destacando las diferencias de perfiles y usos. Para los dos segmentos se estudian aspectos como el lugar de acceso a la compra, la frecuencia de compra, los medios de pago utilizados o las actitudes hacia la compra. El capítulo 3 comienza desarrollando los principales conceptos sobre la teoría del comportamiento del consumidor, para continuar estudiando los principales modelos de adopción de tecnología existentes, analizando con especial atención su aplicación en comercio electrónico. Posteriormente se analizan los modelos de continuidad en el uso de tecnologías (Teoría de la Confirmación de Expectativas; Teoría de la Justicia), con especial atención de nuevo a su aplicación en el comercio electrónico. Una vez estudiados los principales modelos de adopción y continuidad en el uso de tecnologías, el capítulo 4 analiza los principales factores que se utilizan en los modelos: calidad, valor, factores basados en la confirmación de expectativas –satisfacción, utilidad percibida– y factores específicos en situaciones especiales –por ejemplo, tras una queja– como pueden ser la justicia, las emociones o la confianza. La tercera parte –que corresponde al capítulo 5– desarrolla el diseño de la investigación y la selección muestral de los modelos. En la primera parte del capítulo se enuncian las hipótesis –que van desde lo general a lo particular, utilizando los factores específicos analizados en el capítulo 4– para su posterior estudio y validación en el capítulo 6 utilizando las técnicas estadísticas apropiadas. A partir de las hipótesis, y de los modelos y factores estudiados en los capítulos 3 y 4, se definen y vertebran dos modelos teóricos originales que den respuesta a los retos de investigación planteados en el capítulo 1. En la segunda parte del capítulo se diseña el trabajo empírico de investigación definiendo los siguientes aspectos: alcance geográfico–temporal, tipología de la investigación, carácter y ambiente de la investigación, fuentes primarias y secundarias utilizadas, técnicas de recolección de datos, instrumentos de medida utilizados y características de la muestra utilizada. Los resultados del trabajo de investigación constituyen la cuarta parte de la investigación y se desarrollan en el capítulo 6, que comienza analizando las técnicas estadísticas basadas en Modelos de Ecuaciones Estructurales. Se plantean dos alternativas, modelos confirmatorios correspondientes a Métodos Basados en Covarianzas (MBC) y modelos predictivos. De forma razonada se eligen las técnicas predictivas dada la naturaleza exploratoria de la investigación planteada. La segunda parte del capítulo 6 desarrolla el análisis de los resultados de los modelos de medida y modelos estructurales construidos con indicadores formativos y reflectivos y definidos en el capítulo 4. Para ello se validan, sucesivamente, los modelos de medida y los modelos estructurales teniendo en cuenta los valores umbrales de los parámetros estadísticos necesarios para la validación. La quinta parte corresponde al capítulo 7, que desarrolla las conclusiones basándose en los resultados del capítulo 6, analizando los resultados desde el punto de vista de las aportaciones teóricas y prácticas, obteniendo conclusiones para la gestión de las empresas. A continuación, se describen las limitaciones de la investigación y se proponen nuevas líneas de estudio sobre distintos temas que han ido surgiendo a lo largo del trabajo. Finalmente, la bibliografía recoge todas las referencias utilizadas a lo largo de este trabajo. Palabras clave: comprador constante, modelos de continuidad de uso, continuidad en el uso de tecnologías, comercio electrónico, B2C, adopción de tecnologías, modelos de adopción tecnológica, TAM, TPB, IDT, UTAUT, ECT, intención de continuidad, satisfacción, confianza percibida, justicia, emociones, confirmación de expectativas, calidad, valor, PLS. ABSTRACT Information and Communication Technologies in general, but more specifically those related to the Internet in particular, have changed the way in which we communicate, relate to one another, produce, and buy and sell products, reducing the time and shortening the distance between suppliers and consumers. The steady breakthrough of computers, Smartphones and landline and/or wireless broadband has been greatly reflected in its large scale use by both individuals and businesses. Business–to–consumer (B2C) e–commerce reached a volume of 9,114 million Euros in Spain in 2010, representing a 17.4% increase with respect to the figure in 2009. This growth is due in part to two different facts: an increase in the percentage of web users to 65.1% en 2010, 43.1% of whom have acquired products or services through the Internet– which constitutes 1.6 percentage points higher than 2010. On the other hand, the average spending by individual buyers rose to 831€ en 2010, constituting a 10.9% increase with respect to the previous year. If we select buyers according to whether or not they have previously made some type of purchase, we can divide them into two categories: the novice buyer–who first made online purchases in 2010– and the experienced buyer: who also made purchases in 2010, but had done so previously as well. The socio–demographic profile of the novice buyer is that of a young person between 15–24 years of age, with secondary studies, middle to lower–middle class, and a non–university educated student who resides in smaller towns and continues to use payment methods such as cash on delivery (23.9%). In 2010, their average purchase grew to 449€. The more experienced buyer, or someone who has previously made purchases online, has a different demographic profile: highly educated, upper class, resident and worker in larger cities, who exercises a mature behavior when making online purchases due to their experience– this type of buyer frequently uses exclusive channels on the Internet that don’t have an actual store. His or her average purchase doubles that of the novice buyer (with an average purchase of 930€ annually.) That said, the experienced buyers constitute the majority of buyers with an average purchase that doubles that of novice buyers. It is therefore of interest to study the factors that help to predict whether or not a web user will buy another product or use another service on the Internet. The answer to this question has proven not to be so simple. In Spain, the majority of goods and services are still bought in person, with a low amount of purchases being made through means such as the Home Shopping Network, through catalogues or Internet sales. To answer the questions that have been posed here, an investigation has been conducted which takes into consideration various viewpoints: it will begin with a descriptive study from the perspective of the supply and demand that characterizes the B2C e–commerce situation in Spain, focusing on the differences between experienced buyers and novice buyers. Subsequently, there will be an investigation concerning the technology acceptance and continuity of use of models as well as the factors that have an effect on their continuity of use –with a special focus on B2C electronic commerce–, which allows for a theoretic approach to the problem from the perspective of the structural equations being able to reach practical conclusions. This investigation follows the classic structure for a scientific investigation: the subject of the investigation is introduced (Chapter 1), then the state of the B2C e–commerce in Spain is described citing official sources of information (Chapter 2), the theoretical framework and state of the art of technology acceptance and continuity models are developed further (Chapter 3) and the main factors that affect their acceptance and continuity (Chapter 4). Chapter 5 explains the hypothesis behind the investigation and poses the theoretical models that will be confirmed or rejected partially or completely. In Chapter 6, the technical statistics that will be used are described briefly as well as an analysis of the empirical results of the models put forth in Chapter 5. Chapter 7 explains the main conclusions of the investigation, its limitations and proposes new projects. First part of the project, chapter 1, introduces the investigation, justifying it from a theoretical and practical point of view. It is also a brief introduction to the theory of consumer behavior from a standard perspective. Technology acceptance models are presented and then continuity and repurchase models are introduced, which are studied more in depth in Chapter 3. In this chapter, both the main and the secondary objectives are developed through a mind map and a timetable which highlights the milestones of the project. The second part of the project corresponds to Chapters Two, Three and Four. Chapter 2 describes the B2C e–commerce in Spain from the perspective of its demand, citing secondary official sources. A diagnosis concerning the e–commerce sector and the status of its maturity in Spain is taken on, as well as the barriers and alternative methods of e–commerce. Subsequently, the differences between experienced buyers, which are of particular interest to this project, and novice buyers are analyzed, highlighting the differences between their profiles and their main transactions. In order to study both groups, aspects such as the place of purchase, frequency with which online purchases are made, payment methods used and the attitudes of the purchasers concerning making online purchases are taken into consideration. Chapter 3 begins by developing the main concepts concerning consumer behavior theory in order to continue the study of the main existing acceptance models (among others, TPB, TAM, IDT, UTAUT and other models derived from them) – paying special attention to their application in e–commerce–. Subsequently, the models of technology reuse are analyzed (CDT, ECT; Theory of Justice), focusing again specifically on their application in e–commerce. Once the main technology acceptance and reuse models have been studied, Chapter 4 analyzes the main factors that are used in these models: quality, value, factors based on the contradiction of expectations/failure to meet expectations– satisfaction, perceived usefulness– and specific factors pertaining to special situations– for example, after receiving a complaint justice, emotions or confidence. The third part– which appears in Chapter 5– develops the plan for the investigation and the sample selection for the models that have been designed. In the first section of the Chapter, the hypothesis is presented– beginning with general ideas and then becoming more specific, using the detailed factors that were analyzed in Chapter 4– for its later study and validation in Chapter 6– as well as the corresponding statistical factors. Based on the hypothesis and the models and factors that were studied in Chapters 3 and 4, two original theoretical models are defined and organized in order to answer the questions posed in Chapter 1. In the second part of the Chapter, the empirical investigation is designed, defining the following aspects: geographic–temporal scope, type of investigation, nature and setting of the investigation, primary and secondary sources used, data gathering methods, instruments according to the extent of their use and characteristics of the sample used. The results of the project constitute the fourth part of the investigation and are developed in Chapter 6, which begins analyzing the statistical techniques that are based on the Models of Structural Equations. Two alternatives are put forth: confirmatory models which correspond to Methods Based on Covariance (MBC) and predictive models– Methods Based on Components–. In a well–reasoned manner, the predictive techniques are chosen given the explorative nature of the investigation. The second part of Chapter 6 explains the results of the analysis of the measurement models and structural models built by the formative and reflective indicators defined in Chapter 4. In order to do so, the measurement models and the structural models are validated one by one, while keeping in mind the threshold values of the necessary statistic parameters for their validation. The fifth part corresponds to Chapter 7 which explains the conclusions of the study, basing them on the results found in Chapter 6 and analyzing them from the perspective of the theoretical and practical contributions, and consequently obtaining conclusions for business management. The limitations of the investigation are then described and new research lines about various topics that came up during the project are proposed. Lastly, all of the references that were used during the project are listed in a final bibliography. Key Words: constant buyer, repurchase models, continuity of use of technology, e–commerce, B2C, technology acceptance, technology acceptance models, TAM, TPB, IDT, UTAUT, ECT, intention of repurchase, satisfaction, perceived trust/confidence, justice, feelings, the contradiction of expectations, quality, value, PLS.

Advances in the Simultaneous Multiple Surface optical design method for imaging and non-imaging applications

Classical imaging optics has been developed over centuries in many areas, such as its paraxial imaging theory and practical design methods like multi-parametric optimization techniques. Although these imaging optical design methods can provide elegant solutions to many traditional optical problems, there are more and more new design problems, like solar concentrator, illumination system, ultra-compact camera, etc., that require maximum energy transfer efficiency, or ultra-compact optical structure. These problems do not have simple solutions from classical imaging design methods, because not only paraxial rays, but also non-paraxial rays should be well considered in the design process. Non-imaging optics is a newly developed optical discipline, which does not aim to form images, but to maximize energy transfer efficiency. One important concept developed from non-imaging optics is the “edge-ray principle”, which states that the energy flow contained in a bundle of rays will be transferred to the target, if all its edge rays are transferred to the target. Based on that concept, many CPC solar concentrators have been developed with efficiency close to the thermodynamic limit. When more than one bundle of edge-rays needs to be considered in the design, one way to obtain solutions is to use SMS method. SMS stands for Simultaneous Multiple Surface, which means several optical surfaces are constructed simultaneously. The SMS method was developed as a design method in Non-imaging optics during the 90s. The method can be considered as an extension to the Cartesian Oval calculation. In the traditional Cartesian Oval calculation, one optical surface is built to transform an input wave-front to an out-put wave-front. The SMS method however, is dedicated to solve more than 1 wave-fronts transformation problem. In the beginning, only 2 input wave-fronts and 2 output wave-fronts transformation problem was considered in the SMS design process for rotational optical systems or free-form optical systems. Usually “SMS 2D” method stands for the SMS procedure developed for rotational optical system, and “SMS 3D” method for the procedure for free-form optical system. Although the SMS method was originally employed in non-imaging optical system designs, it has been found during this thesis that with the improved capability to design more surfaces and control more input and output wave-fronts, the SMS method can also be applied to imaging system designs and possesses great advantage over traditional design methods. In this thesis, one of the main goals to achieve is to further develop the existing SMS-2D method to design with more surfaces and improve the stability of the SMS-2D and SMS-3D algorithms, so that further optimization process can be combined with SMS algorithms. The benefits of SMS plus optimization strategy over traditional optimization strategy will be explained in details for both rotational and free-form imaging optical system designs. Another main goal is to develop novel design concepts and methods suitable for challenging non-imaging applications, e.g. solar concentrator and solar tracker. This thesis comprises 9 chapters and can be grouped into two parts: the first part (chapter 2-5) contains research works in the imaging field, and the second part (chapter 6-8) contains works in the non-imaging field. In the first chapter, an introduction to basic imaging and non-imaging design concepts and theories is given. Chapter 2 presents a basic SMS-2D imaging design procedure using meridian rays. In this chapter, we will set the imaging design problem from the SMS point of view, and try to solve the problem numerically. The stability of this SMS-2D design procedure will also be discussed. The design concepts and procedures developed in this chapter lay the path for further improvement. Chapter 3 presents two improved SMS 3 surfaces’ design procedures using meridian rays (SMS-3M) and skew rays (SMS-1M2S) respectively. The major improvement has been made to the central segments selections, so that the whole SMS procedures become more stable compared to procedures described in Chapter 2. Since these two algorithms represent two types of phase space sampling, their image forming capabilities are compared in a simple objective design. Chapter 4 deals with an ultra-compact SWIR camera design with the SMS-3M method. The difficulties in this wide band camera design is how to maintain high image quality meanwhile reduce the overall system length. This interesting camera design provides a playground for the classical design method and SMS design methods. We will show designs and optical performance from both classical design method and the SMS design method. Tolerance study is also given as the end of the chapter. Chapter 5 develops a two-stage SMS-3D based optimization strategy for a 2 freeform mirrors imaging system. In the first optimization phase, the SMS-3D method is integrated into the optimization process to construct the two mirrors in an accurate way, drastically reducing the unknown parameters to only few system configuration parameters. In the second optimization phase, previous optimized mirrors are parameterized into Qbfs type polynomials and set up in code V. Code V optimization results demonstrates the effectiveness of this design strategy in this 2-mirror system design. Chapter 6 shows an etendue-squeezing condenser optics, which were prepared for the 2010 IODC illumination contest. This interesting design employs many non-imaging techniques such as the SMS method, etendue-squeezing tessellation, and groove surface design. This device has theoretical efficiency limit as high as 91.9%. Chapter 7 presents a freeform mirror-type solar concentrator with uniform irradiance on the solar cell. Traditional parabolic mirror concentrator has many drawbacks like hot-pot irradiance on the center of the cell, insufficient use of active cell area due to its rotational irradiance pattern and small acceptance angle. In order to conquer these limitations, a novel irradiance homogenization concept is developed, which lead to a free-form mirror design. Simulation results show that the free-form mirror reflector has rectangular irradiance pattern, uniform irradiance distribution and large acceptance angle, which confirm the viability of the design concept. Chapter 8 presents a novel beam-steering array optics design strategy. The goal of the design is to track large angle parallel rays by only moving optical arrays laterally, and convert it to small angle parallel output rays. The design concept is developed as an extended SMS method. Potential applications of this beam-steering device are: skylights to provide steerable natural illumination, building integrated CPV systems, and steerable LED illumination. Conclusion and future lines of work are given in Chapter 9. Resumen La óptica de formación de imagen clásica se ha ido desarrollando durante siglos, dando lugar tanto a la teoría de óptica paraxial y los métodos de diseño prácticos como a técnicas de optimización multiparamétricas. Aunque estos métodos de diseño óptico para formación de imagen puede aportar soluciones elegantes a muchos problemas convencionales, siguen apareciendo nuevos problemas de diseño óptico, concentradores solares, sistemas de iluminación, cámaras ultracompactas, etc. que requieren máxima transferencia de energía o dimensiones ultracompactas. Este tipo de problemas no se pueden resolver fácilmente con métodos clásicos de diseño porque durante el proceso de diseño no solamente se deben considerar los rayos paraxiales sino también los rayos no paraxiales. La óptica anidólica o no formadora de imagen es una disciplina que ha evolucionado en gran medida recientemente. Su objetivo no es formar imagen, es maximazar la eficiencia de transferencia de energía. Un concepto importante de la óptica anidólica son los “rayos marginales”, que se pueden utilizar para el diseño de sistemas ya que si todos los rayos marginales llegan a nuestra área del receptor, todos los rayos interiores también llegarán al receptor. Haciendo uso de este principio, se han diseñado muchos concentradores solares que funcionan cerca del límite teórico que marca la termodinámica. Cuando consideramos más de un haz de rayos marginales en nuestro diseño, una posible solución es usar el método SMS (Simultaneous Multiple Surface), el cuál diseña simultáneamente varias superficies ópticas. El SMS nació como un método de diseño para óptica anidólica durante los años 90. El método puede ser considerado como una extensión del cálculo del óvalo cartesiano. En el método del óvalo cartesiano convencional, se calcula una superficie para transformar un frente de onda entrante a otro frente de onda saliente. El método SMS permite transformar varios frentes de onda de entrada en frentes de onda de salida. Inicialmente, sólo era posible transformar dos frentes de onda con dos superficies con simetría de rotación y sin simetría de rotación, pero esta limitación ha sido superada recientemente. Nos referimos a “SMS 2D” como el método orientado a construir superficies con simetría de rotación y llamamos “SMS 3D” al método para construir superficies sin simetría de rotación o free-form. Aunque el método originalmente fue aplicado en el diseño de sistemas anidólicos, se ha observado que gracias a su capacidad para diseñar más superficies y controlar más frentes de onda de entrada y de salida, el SMS también es posible aplicarlo a sistemas de formación de imagen proporcionando una gran ventaja sobre los métodos de diseño tradicionales. Uno de los principales objetivos de la presente tesis es extender el método SMS-2D para permitir el diseño de sistemas con mayor número de superficies y mejorar la estabilidad de los algoritmos del SMS-2D y SMS-3D, haciendo posible combinar la optimización con los algoritmos. Los beneficios de combinar SMS y optimización comparado con el proceso de optimización tradicional se explican en detalle para sistemas con simetría de rotación y sin simetría de rotación. Otro objetivo importante de la tesis es el desarrollo de nuevos conceptos de diseño y nuevos métodos en el área de la concentración solar fotovoltaica. La tesis está estructurada en 9 capítulos que están agrupados en dos partes: la primera de ellas (capítulos 2-5) se centra en la óptica formadora de imagen mientras que en la segunda parte (capítulos 6-8) se presenta el trabajo del área de la óptica anidólica. El primer capítulo consta de una breve introducción de los conceptos básicos de la óptica anidólica y la óptica en formación de imagen. El capítulo 2 describe un proceso de diseño SMS-2D sencillo basado en los rayos meridianos. En este capítulo se presenta el problema de diseñar un sistema formador de imagen desde el punto de vista del SMS y se intenta obtener una solución de manera numérica. La estabilidad de este proceso se analiza con detalle. Los conceptos de diseño y los algoritmos desarrollados en este capítulo sientan la base sobre la cual se realizarán mejoras. El capítulo 3 presenta dos procedimientos para el diseño de un sistema con 3 superficies SMS, el primero basado en rayos meridianos (SMS-3M) y el segundo basado en rayos oblicuos (SMS-1M2S). La mejora más destacable recae en la selección de los segmentos centrales, que hacen más estable todo el proceso de diseño comparado con el presentado en el capítulo 2. Estos dos algoritmos representan dos tipos de muestreo del espacio de fases, su capacidad para formar imagen se compara diseñando un objetivo simple con cada uno de ellos. En el capítulo 4 se presenta un diseño ultra-compacto de una cámara SWIR diseñada usando el método SMS-3M. La dificultad del diseño de esta cámara de espectro ancho radica en mantener una alta calidad de imagen y al mismo tiempo reducir drásticamente sus dimensiones. Esta cámara es muy interesante para comparar el método de diseño clásico y el método de SMS. En este capítulo se presentan ambos diseños y se analizan sus características ópticas. En el capítulo 5 se describe la estrategia de optimización basada en el método SMS-3D. El método SMS-3D calcula las superficies ópticas de manera precisa, dejando sólo unos pocos parámetros libres para decidir la configuración del sistema. Modificando el valor de estos parámetros se genera cada vez mediante SMS-3D un sistema completo diferente. La optimización se lleva a cabo variando los mencionados parámetros y analizando el sistema generado. Los resultados muestran que esta estrategia de diseño es muy eficaz y eficiente para un sistema formado por dos espejos. En el capítulo 6 se describe un sistema de compresión de la Etendue, que fue presentado en el concurso de iluminación del IODC en 2010. Este interesante diseño hace uso de técnicas propias de la óptica anidólica, como el método SMS, el teselado de las lentes y el diseño mediante grooves. Este dispositivo tiene un límite teórica en la eficiencia del 91.9%. El capítulo 7 presenta un concentrador solar basado en un espejo free-form con irradiancia uniforme sobre la célula. Los concentradores parabólicos tienen numerosas desventajas como los puntos calientes en la zona central de la célula, uso no eficiente del área de la célula al ser ésta cuadrada y además tienen ángulos de aceptancia de reducido. Para poder superar estas limitaciones se propone un novedoso concepto de homogeneización de la irrandancia que se materializa en un diseño con espejo free-form. El análisis mediante simulación demuestra que la irradiancia es homogénea en una región rectangular y con mayor ángulo de aceptancia, lo que confirma la viabilidad del concepto de diseño. En el capítulo 8 se presenta un novedoso concepto para el diseño de sistemas afocales dinámicos. El objetivo del diseño es realizar un sistema cuyo haz de rayos de entrada pueda llegar con ángulos entre ±45º mientras que el haz de rayos a la salida sea siempre perpendicular al sistema, variando únicamente la posición de los elementos ópticos lateralmente. Las aplicaciones potenciales de este dispositivo son varias: tragaluces que proporcionan iluminación natural, sistemas de concentración fotovoltaica integrados en los edificios o iluminación direccionable con LEDs. Finalmente, el último capítulo contiene las conclusiones y las líneas de investigación futura.

Criterios de calidad del servicio prestado en el ámbito de la línea de atraque de las terminales portuarias de contenedores

Esta Tesis Doctoral evalúa empíricamente la calidad del servicio en la línea de atraque de las terminales portuarias de contenedores. La metodología propuesta utiliza indicadores de calidad y se basa en el concepto de la segmentación de servicio. Para ello se desarrolla la teoría del Control Estadístico de Procesos (CEP) y se utilizan los gráficos de control para clasificar el servicio en las terminales de contenedores. El propósito de la Tesis es proporcionar una metodología basada en el Control Estadístico de Procesos (CEP) para evaluar la calidad del servicio y detectar las escalas de un servicio regular de línea que se encuentran fuera de control. Por tanto, la metodología se puede utilizar para detectar eventos que son indicativos de cambio real del proceso en la línea de atraque. Esta detección puede ser compleja pues las características de los procesos en terminales de contenedores son variables. La metodología proporciona mediante los gráficos de control criterios estadísticamente objetivos de cambio. Cuando el cambio es detectado y considerado bueno sus causas deben ser identificadas y posiblemente convertirse en la nueva forma de trabajar, cuando el cambio es negativo, entonces sus causas deberían ser identificadas y eliminadas. La Tesis Doctoral está organizado de la siguiente manera: La primera parte es la introducción, e incluye los capítulos 1 al 4, la segunda parte presenta el Estado del Arte (capítulo 5) y algunos de los estudios que han inspirado esta investigación, la tercera parte se centra en la metodología utilizada (capítulo 6) y su aplicación sobre un caso de estudio (capítulo 7). Finalmente, en la cuarta parte se presentan las conclusiones y se proponen algunas de las nuevas líneas de investigación que quedan abiertas (capítulo 8). This Thesis empirically evaluates the quality of service in the berthing face of container terminals. The methodology proposed is focused on quality of service indicators and is based on the concept of service segmentation. The Statistical Process Control (SPC) theory and the control charts are used to classify container terminal service. The aim of this Thesis is to provide a methodology based on Statistical Process Control that can evaluate the quality of service and also can detect scales of shipping liner service that are out of control. Therefore, the methodology can be used to detect events that are indicative of real change in the berthing process of container vessels. The methodology proposed allows simple detection of events that are indicative of actual process change in container terminals. This detection is complex because the characteristics of the processes are variable in the container terminals; the control chart provides statistically objective criteria of change. When change is detected and considered good its cause should be identified and possibly become the new way of working, where the change is bad then its cause should be identified and eliminated. This Thesis is organized as follows: The first part is the introduction (includes Chapters 1 to 4), the second part presents the State of the Art (Chapter 5) and some of the studies that have inspired this research. The third part focuses on the methodology used (Chapter 6) and its application to a case study (Chapter 7). Finally, Part 4 presents the conclusions and suggests future research (Chapter 8).