Lamb mode diversity imaging fornon-destructivetesting of plate-likestructures

Several Lamb wave modes can be coupled to a particular structure, depending on its geometry and transducer used to generate the guided waves. Each Lamb mode interacts in a particular form with different types of defects, like notches, delamination, surface defects, resulting in different information which can be used to improve damage detection and characterization. An image compounding technique that uses the information obtained from different propagation modes of Lamb waves for non-destructive testing of plate-like structures is proposed. A linear array consisting of 16 piezoelectric elements is attached to a 1 mm thickness aluminum plate, coupling the fundamental A0 and SO modes at the frequencies of 100 kHz and 360 kHz, respectively. For each mode two images are obtained from amplitude and phase information: one image using the Total Focusing Method (TFM) and one phase image obtained from the Sign Coherence Factor (SCF). Each TFM image is multiplied by the SCF image of the respective mode to improve contrast and reduce side and grating lobes effects. The high dispersive characteristic of the A0 mode is compensated for adequate defect detection. The information in the SCF images is used to select one of the TFM mode images, at each pixel, to obtain the compounded image. As a result, dead zone is reduced, resolution and contrast are improved, enhancing damage detection when compared to the use of only one mode. (C) 2013 Elsevier Ltd. All rights reserved. (AU)

Photocatalytic degradation of phenolic compounds with new TiO2 catalysts

[EN] New TiO2 catalysts have been synthesised by means of a sol–gel method in which aggregates have been selected before thermal treatment. Sieving and calcination temperature have been proved to be key factors in obtaining catalysts with greater photoactivity than that of Degussa P-25. These new catalysts have been characterized by means of transmission electron microscopy (TEM), BET surface area, diffuse reflectance spectroscopy (DRS), UV–vis spectroscopy, Fourier transformed infrared (FTIR) and X-ray diffraction (XRD). The different parameters studied were compared to those obtained from two commercial catalysts (Degussa P-25 and Hombikat-UV100). The photocatalytic efficiency of the new catalysts was evaluated by the degradation of various phenolic compounds using UV light (maximum around 365 nm, 9mW). The catalyst sieved and calcinated at 1023 K, ECT-1023t, showed phenol degradation rates 2.7 times higher than those of Degussa P-25. Also in the degradation of different phenolic compounds, this catalyst showed a higher activity than that of the commercial one. The high photoactivity of this new catalyst has been attributed to the different distribution of surface defects (determined from FTIR studies) and its increased capacity to yield H2O2

Polymer controlled mineralization of zinc phosphate hydrates and applications in corrosion protection, catalysis and biomedicine

ZUSAMMENFASSUNG Die Tauglichkeit von Hybridmaterialien auf der Basis von Zinkphosphathydrat-Zementen zum Einsatz als korrosionshemmende anorganische Pigmente oder zur prothetischen und konservierenden Knochen- und Zahntherapie wird weltweit empirisch seit den neunziger Jahren intensiv erforscht. In der vorliegenden Arbeit wurden zuerst Referenzproben, d.h. alpha-und beta-Hopeite (Abk. a-,b-ZPT) dank eines hydrothermalen Kristallisationsverfahrens in wässerigem Milieu bei 20°C und 90°C hergestellt. Die Kristallstruktur beider Polymorphe des Zinkphosphattetrahydrats Zn3(PO4)2  4 H2O wurde komplett bestimmt. Einkristall-strukturanalyse zeigt, daß der Hauptunterschied zwischen der alpha-und beta-Form des Zinkphosphattetrahydrats in zwei verschiedenen Anordnungen der Wasserstoffbrücken liegt. Die entsprechenden drei- und zweidimensionalen Anordnungen der Wasserstoffbrücken der a-und b-ZPT induzieren jeweils unterschiedliches thermisches Verhalten beim Aufwärmen. Während die alpha-Form ihr Kristallwasser in zwei definierten Stufen verliert, erzeugt die beta-Form instabile Dehydratationsprodukt. Dieses entspricht zwei unabhängigen, aber nebeneinander ablaufenden Dehydratationsmechanismen: (i) bei niedrigen Heizraten einen zweidimensionalen Johnson-Mehl-Avrami (JMA) Mechanismus auf der (011) Ebene, der einerseits bevorzugt an Kristallkanten stattfindet und anderseits von existierenden Kristalldefekten auf Oberflächen gesteuert wird; (ii) bei hohen Heizraten einem zweidimensionalen Diffusionsmechanismus (D2), der zuerst auf der (101) Ebene und dann auf der (110) Ebene erfolgt. Durch die Betrachtung der ZPT Dehydratation als irreversibele heterogene Festkörperstufenreaktion wurde dank eines „ähnlichen Endprodukt“-Protokolls das Dehydratationsphasendiagramm aufgestellt. Es beschreibt die möglichen Zusammenhänge zwischen den verschiedenen Hydratationszuständen und weist auf die Existenz eines Übergangszustandes um 170°C (d.h. Reaktion b-ZPT  a-ZPT) hin. Daneben wurde auch ein gezieltes chemisches Ätzverfahren mit verdünnten H3PO4- und NH3 Lösungen angewendet, um die ersten Stufe des Herauslösens von Zinkphosphat genau zu untersuchen. Allerdings zeigen alpha- und beta-Hopeite charakteristische hexagonale und kubische Ätzgruben, die sich unter kristallographischer Kontrolle verbreitern. Eine zuverlässige Beschreibung der Oberfächenchemie und Topologie konnte nur durch AFM und FFM Experimente erfolgen. Gleichzeitig konnte in dieser Weise die Oberflächendefektdichte und-verteilung und die Volumenauflösungsrate von a-ZPT und b-ZPT bestimmt werden. Auf einem zweiten Weg wurde eine innovative Strategie zur Herstellung von basischen Zinkphosphatpigmenten erster und zweiter Generation (d.h. NaZnPO4  1H2O und Na2ZnPO4(OH)  2H2O) mit dem Einsatz von einerseits oberflächenmodifizierten Polystyrolatices (z.B. produziert durch ein Miniemulsionspolymerisationsverfahren) und anderseits von Dendrimeren auf der Basis von Polyamidoamid (PAMAM) beschritten. Die erhaltene Zeolithstruktur (ZPO) hat in Abhängigkeit von steigendem Natrium und Wassergehalt unterschiedliche kontrollierte Morphologie: hexagonal, würfelförmig, herzförmig, sechsarmige Sterne, lanzettenförmige Dendrite, usw. Zur quantitativen Evaluierung des Polymereinbaus in der Kristallstruktur wurden carboxylierte fluoreszenzmarkierte Latices eingesetzt. Es zeigt sich, daß Polymeradditive nicht nur das Wachstum bis zu 8 µm.min-1 reduzierten. Trotzdem scheint es auch als starker Nukleationsbeschleuniger zu wirken. Dank der Koordinationschemie (d.h. Bildung eines sechszentrigen Komplexes L-COO-Zn-PO4*H2O mit Ligandenaustausch) konnten zwei einfache Mechanismen zur Wirkung von Latexpartikeln bei der ZPO Kristallisation aufgezeigt werden: (i) ein Intrakorona- und (ii) ein Extrakorona-Keimbildungsmechanismus. Weiterhin wurde die Effizienz eines Kurzzeit- und Langzeitkorrosionschutzes durch maßgeschneiderte ZPO/ZPT Pigmente und kontrollierte Freisetzung von Phosphationen in zwei Näherungen des Auslösungsgleichgewichts abgeschätzt: (i) durch eine Auswaschungs-methode (thermodynamischer Prozess) und (ii) durch eine pH-Impulsmethode (kinetischer Prozess. Besonders deutlich wird der Ausflösungs-Fällungsmechanismus (d.h. der Metamorphismus). Die wesentliche Rolle den Natriumionen bei der Korrosionshemmung wird durch ein passendes zusammensetzungsabhängiges Auflösungsmodell (ZAAM) beschrieben, das mit dem Befund des Salzsprühteste und der Feuchtigkeitskammertests konsistent ist. Schließlich zeigt diese Arbeit das herausragende Potential funktionalisierter Latices (Polymer) bei der kontrollierten Mineralisation zur Herstellung maßgeschneiderter Zinkphosphat Materialien. Solche Hybridmaterialien werden dringend in der Entwicklung umweltfreundlicher Korrosionsschutzpigmente sowie in der Dentalmedizin benötigt.

Nanofiber-based spectroscopy of organic molecules

This thesis reports on the experimental realization of nanofiber-based spectroscopy of organic molecules. The light guided by subwavelength diameter optical nanfibers exhibits a pronounced evanescent field surrounding the fiber which yields high excitation and emission collection efficiencies for molecules on or near the fiber surface.rnThe optical nanofibers used for the experiments presented in this thesis are realized as thernsub-wavelength diameter waist of a tapered optical fiber (TOF). The efficient transfer of thernlight from the nanofiber waist to the unprocessed part of the TOF depends critically on therngeometric shape of the TOF transitions which represent a nonuniformity of the TOF. Thisrnnonuniformity can cause losses due to coupling of the fundamental guided mode to otherrnmodes which are not guided by the taper over its whole length. In order to quantify the lossrnfrom the fundamental mode due to tapering, I have solved the coupled local mode equationsrnin the approximation of weak guidance for the three layer system consisting of fiber core andrncladding as well as the surrounding vacuum or air, assuming the taper shape of the TOFsrnused for the experiments presented in this thesis. Moreover, I have empirically studied therninfluence of the TOF geometry on its transmission spectra and, based on the results, I haverndesigned a nanofiber-waist TOF with broadband transmission for experiments with organicrnmolecules.rnAs an experimental demonstration of the high sensitivity of nanofiber-based surface spectroscopy, I have performed various absorption and fluorescence spectroscopy measurements on the model system 3,4,9,10-perylene-tetracarboxylic dianhydride (PTCDA). The measured homogeneous and inhomogeneous broadening of the spectra due to the interaction of the dielectric surface of the nanofiber with the surface-adsorbed molecules agrees well with the values theoretically expected and typical for molecules on surfaces. Furthermore, the self-absorption effects due to reasorption of the emitted fluorescence light by circumjacent surface-adsorbed molecules distributed along the fiber waist have been analyzed and quantified. With time-resolved measurements, the reorganization of PTCDA molecules to crystalline films and excimers can be observed and shown to be strongly catalyzed by the presence of water on the nanofiber surface. Moreover, the formation of charge-transfer complexes due to the interaction with localized surface defects has been studied. The collection efficiency of the molecular emission by the guided fiber mode has been determined by interlaced measurements of absorption and fluorescence spectra to be about 10% in one direction of the fiber.rnThe high emission collection efficiency makes optical nanofibers a well-suited tool for experiments with dye molecules embedded in small organic crystals. As a first experimental realization of this approach, terrylene-doped para-terphenyl crystals attached to the nanofiber-waist of a TOF have been studied at cryogenic temperatures via fluorescence and fluorescence excitation spectroscopy. The statistical fine structure of the fluorescence excitation spectrum for a specific sample has been observed and used to give an estimate of down to 9 molecules with center frequencies within one homogeneous width of the laser wavelength on average for large detunings from resonance. The homogeneous linewidth of the transition could be estimated to be about 190MHz at 4.5K.

Magnetic resonance imaging for diagnosis and assessment of cartilage defect repairs

Clinical magnetic resonance imaging (MRI) is the method of choice for the non-invasive evaluation of articular cartilage defects and the follow-up of cartilage repair procedures. The use of cartilage-sensitive sequences and a high spatial-resolution technique enables the evaluation of cartilage morphology even in the early stages of disease, as well as assessment of cartilage repair. Sequences that offer high contrast between articular cartilage and adjacent structures, such as the fat-suppressed, 3-dimensional, spoiled gradient-echo sequence and the fast spin-echo sequence, are accurate and reliable for evaluating intrachondral lesions and surface defects of articular cartilage. These sequences can also be performed together in reasonable examination times. In addition to morphology, new MRI techniques provide insight into the biochemical composition of articular cartilage and cartilage repair tissue. These techniques enable the diagnosis of early cartilage degeneration and help to monitor the effect and outcome of various surgical and non-surgical cartilage repair therapies.

Determining bridge deck deterioration through the use of 3D photogrammetry

The bridge inspection industry has yet to utilize a rapidly growing technology that shows promise to help improve the inspection process. This thesis investigates the abilities that 3D photogrammetry is capable of providing to the bridge inspector for a number of deterioration mechanisms. The technology can provide information about the surface condition of some bridge components, primarily focusing on the surface defects of a concrete bridge which include cracking, spalling and scaling. Testing was completed using a Canon EOS 7D camera which then processed photos using AgiSoft PhotoScan to align the photos and develop models. Further processing of the models was done using ArcMap in the ArcGIS 10 program to view the digital elevation models of the concrete surface. Several experiments were completed to determine the ability of the technique for the detection of the different defects. The cracks that were able to be resolved in this study were a 1/8 inch crack at a distance of two feet above the surface. 3D photogrammetry was able to be detect a depression of 1 inch wide with 3/16 inch depth which would be sufficient to measure any scaling or spalling that would be required be the inspector. The percentage scaled or spalled was also able to be calculated from the digital elevation models in ArcMap. Different camera factors including the distance from the defects, number of photos and angle, were also investigated to see how each factor affected the capabilities. 3D photogrammetry showed great promise in the detection of scaling or spalling of the concrete bridge surface.

NANOSCALE ELECTROCHEMISTRY BY IN-SITU TRANSMISSION ELECTRON MICROSCOPY

Nanoscale research in energy storage has recently focused on investigating the properties of nanostructures in order to increase energy density, power rate, and capacity. To better understand the intrinsic properties of nanomaterials, a new and advanced in situ system was designed that allows atomic scale observation of materials under external fields. A special holder equipped with a scanning tunneling microscopy (STM) probe inside a transmission electron microscopy (TEM) system was used to perform the in situ studies on mechanical, electrical, and electrochemical properties of nanomaterials. The nanostructures of titanium dioxide (TiO2) nanotubes are characterized by electron imaging, diffraction, and chemical analysis techniques inside TEM. TiO2 nanotube is one of the candidates as anode materials for lithium ion batteries. It is necessary to study their morphological, mechanical, electrical, and electrochemical properties at atomic level. The synthesis of TiO2 nanotubes showed that the aspect ratio of TiO2 could be controlled by processing parameters, such as anodization time and voltage. Ammonium hydroxide (NH4OH) treated TiO2 nanotubes showed unexpected instability. Observation revealed the nanotubes were disintegrated into nanoparticles and the tubular morphology was vanished after annealing. The nitrogen compounds incorporated in surface defects weaken the nanotube and result in the collapse of nanotube into nanoparticles during phase transformation. Next, the electrical and mechanical properties of TiO2 nanotubes were studied by in situ TEM system. Phase transformation of anatase TiO2 nanotubes into rutile nanoparticles was studied by in situ Joule heating. The results showed that single anatase TiO2 nanotubes broke into ultrafine small anatase nanoparticles. On further increasing the bias, the nanoclusters of anatase particles became prone to a solid state reaction and were grown into stable large rutile nanoparticles. The relationship between mechanical and electrical properties of TiO2 nanotubes was also investigated. Initially, both anatase and amorphous TiO2 nanotubes were characterized by using I-V test to demonstrate the semiconductor properties. The observation of mechanical bending on TiO2 nanotubes revealed that the conductivity would increase when bending deformation happened. The defects on the nanotubes created by deformation helped electron transportation to increase the conductivity. Lastly, the electrochemical properties of amorphous TiO2 nanotubes were characterized by in situ TEM system. The direct chemical and imaging evidence of lithium-induced atomic ordering in amorphous TiO2 nanotubes was studied. The results indicated that the lithiation started with the valance reduction of Ti4+ to Ti3+ leading to a LixTiO2 intercalation compound. The continued intercalation of Li ions in TiO2 nanotubes triggered an amorphous to crystalline phase transformation. The crystals were formed as nano islands and identified to be Li2Ti2O4 with cubic structure (a = 8.375 Å). This phase transformation is associated with local inhomogeneities in Li distribution. Based on these observations, a new reaction mechanism is proposed to explain the first cycle lithiation behavior in amorphous TiO2 nanotubes.

Electro-oxidation of Au(1 1 1) in contact with aqueous electrolytes: New insight from in situ vibration spectroscopy

We carried out a comprehensive study of Au(1 1 1) oxidation–reduction in the presence of (hydrogen-) sulfate ions on ideally smooth and stepped Au(S)[n(1 1 1)-(1 1 1)] single crystal electrodes using cyclic voltammetry, in situ scanning tunneling microscopy (STM) and vibration spectroscopy, such as surface-enhanced infrared absorption spectroscopy (SEIRAS) and shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). Surface structure changes and the role of surface defects in the potential regions of double layer charging and gold oxidation/reduction are discussed based on cyclic voltammetry and in situ STM data. SEIRAS and SHINERS provide complementary information on the chemical nature of adsorbates. In particular, the potential-dependent formation and stability ranges of adsorbed sulfate, hydroxide-species and of gold surface oxide could be resolved in detail. Based on our experimental observations, we proposed new and extended mechanisms of gold surface oxidation and reduction in 1.0 M H2SO4 and 1.0 M Na2SO4.

Estudio de la tolerancia al daño de los materiales y sistemas de pretensado

La mayoría de las estructuras de hormigón pretensadas construidas en los últimos 50 años han demostrado una excelente durabilidad cuando su construcción se realiza atendiendo las recomendaciones de un buen diseño así como una buena ejecución y puesta en obra de la estructura. Este hecho se debe en gran parte al temor que despierta el fenómeno de la corrosión bajo tensión típico de las armaduras de acero de alta resistencia. Menos atención se ha prestado a la susceptibilidad a la corrosión bajo tensión de los anclajes de postensado, posiblemente debido a que se han reportado pocos casos de fallos catastróficos. El concepto de Tolerancia al Daño y la Mecánica de la Fractura en estructuras de Ingeniería Civil ha empezado a incorporarse recientemente en algunas normas de diseño y cálculo de estructuras metálicas, sin embargo, aún está lejos de ser asimilado y empleado habitualmente por los ingenieros en sus cálculos cuando la ocasión lo requiere. Este desconocimiento de los aspectos relacionados con la Tolerancia al Daño genera importantes gastos de mantenimiento y reparación. En este trabajo se ha estudiado la aplicabilidad de los conceptos de la Mecánica de la Fractura a los componentes de los sistemas de postensado empleados en ingeniería civil, empleándolo para analizar la susceptibilidad de las armaduras activas frente a la corrosión bajo tensiones y a la pérdida de capacidad portante de las cabezas de anclajes de postensado debido a la presencia de defectos. Con este objeto se han combinado tanto técnicas experimentales como numéricas. Los defectos superficiales en los alambres de pretensado no se presentan de manera aislada si no que existe una cierta continuidad en la dirección axial así como un elevado número de defectos. Por este motivo se ha optado por un enfoque estadístico, que es más apropiado que el determinístico. El empleo de modelos estadísticos basados en la teoría de valores extremos ha permitido caracterizar el estado superficial en alambres de 5,2 mm de diámetro. Por otro lado la susceptibilidad del alambre frente a la corrosión bajo tensión ha sido evaluada mediante la realización de una campaña de ensayos de acuerdo con la actual normativa que ha permitido caracterizar estadísticamente su comportamiento. A la vista de los resultados ha sido posible evaluar como los parámetros que definen el estado superficial del alambre pueden determinar la durabilidad de la armadura atendiendo a su resistencia frente a la corrosión bajo tensión, evaluada mediante los ensayos que especifica la normativa. En el caso de las cabezas de anclaje de tendones de pretensado, los defectos se presentan de manera aislada y tienen su origen en marcas, arañazos o picaduras de corrosión que pueden producirse durante el proceso de fabricación, transporte, manipulación o puesta en obra. Dada la naturaleza de los defectos, el enfoque determinístico es más apropiado que el estadístico. La evaluación de la importancia de un defecto en un elemento estructural requiere la estimación de la solicitación local que genera el defecto, que permite conocer si el defecto es crítico o si puede llegar a serlo, si es que progresa con el tiempo (por fatiga, corrosión, una combinación de ambas, etc.). En este trabajo los defectos han sido idealizados como grietas, de manera que el análisis quedara del lado de la seguridad. La evaluación de la solicitación local del defecto ha sido calculada mediante el empleo de modelos de elementos finitos de la cabeza de anclaje que simulan las condiciones de trabajo reales de la cabeza de anclaje durante su vida útil. A partir de estos modelos numéricos se ha analizado la influencia en la carga de rotura del anclaje de diversos factores como la geometría del anclaje, las condiciones del apoyo, el material del anclaje, el tamaño del defecto su forma y su posición. Los resultados del análisis numérico han sido contrastados satisfactoriamente mediante la realización de una campaña experimental de modelos a escala de cabezas de anclaje de Polimetil-metacrilato en los que artificialmente se han introducido defectos de diversos tamaños y en distintas posiciones. ABSTRACT Most of the prestressed concrete structures built in the last 50 years have demonstrated an excellent durability when they are constructed in accordance with the rules of good design, detailing and execution. This is particularly true with respect to the feared stress corrosion cracking, which is typical of high strength prestressing steel wires. Less attention, however, has been paid to the stress corrosion cracking susceptibility of anchorages for steel tendons for prestressing concrete, probably due to the low number of reported failure cases. Damage tolerance and fracture mechanics concepts in civil engineering structures have recently started to be incorporated in some design and calculation rules for metallic structures, however it is still far from being assimilated and used by civil engineers in their calculations on a regular basis. This limited knowledge of the damage tolerance basis could lead to significant repair and maintenance costs. This work deals with the applicability of fracture mechanics and damage tolerance concepts to the components of prestressed systems, which are used in civil engineering. Such concepts have been applied to assess the susceptibility of the prestressing steel wires to stress corrosion cracking and the reduction of load bearing capability of anchorage devices due to the presence of defects. For this purpose a combination of experimental work and numerical techniques have been performed. Surface defects in prestressing steel wires are not shown alone, though a certain degree of continuity in the axial direction exist. A significant number of such defects is also observed. Hence a statistical approach was used, which is assumed to be more appropriate than the deterministic approach. The use of statistical methods based in extreme value theories has allowed the characterising of the surface condition of 5.2 mm-diameter wires. On the other hand the stress corrosion cracking susceptibility of the wire has been assessed by means of an experimental testing program in line with the current regulations, which has allowed statistical characterisasion of their performances against stress corrosion cracking. In the light of the test results, it has been possible to evaluate how the surface condition parameters could determine the durability of the active metal armour regarding to its resistance against stress corrosion cracking assessed by means of the current testing regulations. In the case of anchorage devices for steel tendons for prestressing concrete, the damage is presented as point defects originating from dents, scratches or corrosion pits that could be produced during the manufacturing proccess, transport, handling, assembly or use. Due to the nature of these defects, in this case the deterministic approach is more appropriate than the statistical approach. The assessment of the relevancy of defect in a structural component requires the computation of the stress intensity factors, which in turn allow the evaluation of whether the size defect is critical or could become critical with the progress of time (due to fatigue, corrosion or a combination of both effects). In this work the damage is idealised as tiny cracks, a conservative hypothesis. The stress intensity factors have been calculated by means of finite element models of the anchorage representing the real working conditions during its service life. These numeric models were used to assess the impact of some factors on the rupture load of the anchorage, such the anchorage geometry, material, support conditions, defect size, shape and its location. The results from the numerical analysis have been succesfully correlated against the results of the experimental testing program of scaled models of the anchorages in poly-methil methacrylate in which artificial damage in several sizes and locations were introduced.

Análisis y clasificación de maderas mediante técnicas no invasivas de baja energía

El estudio de materiales, especialmente biológicos, por medios no destructivos está adquiriendo una importancia creciente tanto en las aplicaciones científicas como industriales. Las ventajas económicas de los métodos no destructivos son múltiples. Existen numerosos procedimientos físicos capaces de extraer información detallada de las superficie de la madera con escaso o nulo tratamiento previo y mínima intrusión en el material. Entre los diversos métodos destacan las técnicas ópticas y las acústicas por su gran versatilidad, relativa sencillez y bajo coste. Esta tesis pretende establecer desde la aplicación de principios simples de física, de medición directa y superficial, a través del desarrollo de los algoritmos de decisión mas adecuados basados en la estadística, unas soluciones tecnológicas simples y en esencia, de coste mínimo, para su posible aplicación en la determinación de la especie y los defectos superficiales de la madera de cada muestra tratando, en la medida de lo posible, no alterar su geometría de trabajo. Los análisis desarrollados han sido los tres siguientes: El primer método óptico utiliza las propiedades de la luz dispersada por la superficie de la madera cuando es iluminada por un laser difuso. Esta dispersión produce un moteado luminoso (speckle) cuyas propiedades estadísticas permiten extraer propiedades muy precisas de la estructura tanto microscópica como macroscópica de la madera. El análisis de las propiedades espectrales de la luz laser dispersada genera ciertos patrones mas o menos regulares relacionados con la estructura anatómica, composición, procesado y textura superficial de la madera bajo estudio que ponen de manifiesto características del material o de la calidad de los procesos a los que ha sido sometido. El uso de este tipo de láseres implica también la posibilidad de realizar monitorizaciones de procesos industriales en tiempo real y a distancia sin interferir con otros sensores. La segunda técnica óptica que emplearemos hace uso del estudio estadístico y matemático de las propiedades de las imágenes digitales obtenidas de la superficie de la madera a través de un sistema de scanner de alta resolución. Después de aislar los detalles mas relevantes de las imágenes, diversos algoritmos de clasificacion automatica se encargan de generar bases de datos con las diversas especies de maderas a las que pertenecían las imágenes, junto con los márgenes de error de tales clasificaciones. Una parte fundamental de las herramientas de clasificacion se basa en el estudio preciso de las bandas de color de las diversas maderas. Finalmente, numerosas técnicas acústicas, tales como el análisis de pulsos por impacto acústico, permiten complementar y afinar los resultados obtenidos con los métodos ópticos descritos, identificando estructuras superficiales y profundas en la madera así como patologías o deformaciones, aspectos de especial utilidad en usos de la madera en estructuras. La utilidad de estas técnicas esta mas que demostrada en el campo industrial aun cuando su aplicación carece de la suficiente expansión debido a sus altos costes y falta de normalización de los procesos, lo cual hace que cada análisis no sea comparable con su teórico equivalente de mercado. En la actualidad gran parte de los esfuerzos de investigación tienden a dar por supuesto que la diferenciación entre especies es un mecanismo de reconocimiento propio del ser humano y concentran las tecnologías en la definición de parámetros físicos (módulos de elasticidad, conductividad eléctrica o acústica, etc.), utilizando aparatos muy costosos y en muchos casos complejos en su aplicación de campo. Abstract The study of materials, especially the biological ones, by non-destructive techniques is becoming increasingly important in both scientific and industrial applications. The economic advantages of non-destructive methods are multiple and clear due to the related costs and resources necessaries. There are many physical processes capable of extracting detailed information on the wood surface with little or no previous treatment and minimal intrusion into the material. Among the various methods stand out acoustic and optical techniques for their great versatility, relative simplicity and low cost. This thesis aims to establish from the application of simple principles of physics, surface direct measurement and through the development of the more appropriate decision algorithms based on statistics, a simple technological solutions with the minimum cost for possible application in determining the species and the wood surface defects of each sample. Looking for a reasonable accuracy without altering their work-location or properties is the main objetive. There are three different work lines: Empirical characterization of wood surfaces by means of iterative autocorrelation of laser speckle patterns: A simple and inexpensive method for the qualitative characterization of wood surfaces is presented. it is based on the iterative autocorrelation of laser speckle patterns produced by diffuse laser illumination of the wood surfaces. The method exploits the high spatial frequency content of speckle images. A similar approach with raw conventional photographs taken with ordinary light would be very difficult. A few iterations of the algorithm are necessary, typically three or four, in order to visualize the most important periodic features of the surface. The processed patterns help in the study of surface parameters, to design new scattering models and to classify the wood species. Fractal-based image enhancement techniques inspired by differential interference contrast microscopy: Differential interference contrast microscopy is a very powerful optical technique for microscopic imaging. Inspired by the physics of this type of microscope, we have developed a series of image processing algorithms aimed at the magnification, noise reduction, contrast enhancement and tissue analysis of biological samples. These algorithms use fractal convolution schemes which provide fast and accurate results with a performance comparable to the best present image enhancement algorithms. These techniques can be used as post processing tools for advanced microscopy or as a means to improve the performance of less expensive visualization instruments. Several examples of the use of these algorithms to visualize microscopic images of raw pine wood samples with a simple desktop scanner are provided. Wood species identification using stress-wave analysis in the audible range: Stress-wave analysis is a powerful and flexible technique to study mechanical properties of many materials. We present a simple technique to obtain information about the species of wood samples using stress-wave sounds in the audible range generated by collision with a small pendulum. Stress-wave analysis has been used for flaw detection and quality control for decades, but its use for material identification and classification is less cited in the literature. Accurate wood species identification is a time consuming task for highly trained human experts. For this reason, the development of cost effective techniques for automatic wood classification is a desirable goal. Our proposed approach is fully non-invasive and non-destructive, reducing significantly the cost and complexity of the identification and classification process.

Oxidation of Ethanol and Its Derivatives on Well Defined Pt Single Crystal Electrodes Vicinal to Pt(111): A Comparative Study

The oxidation of ethanol (EtOH) at Pt(111) electrodes is dominated by the 4e path leading to acetic acid. The inclusion of surface defects such as those present on stepped surfaces leads to an increase of the reactivity towards the most desirable 12e path leading to CO2 as final product. This path is also favored when the methyl group is more oxidized, as in the case of ethylene glycol (EG) that spontaneously decomposes to CO on Pt(111) electrodes, thus showing a more effective breaking of the C-C bond. Some trends in reactivity can be envisaged when other derivative molecules are compared at well-ordered electrodes. This strategy was used in the past, but the improvement in the electrode pretreatment and the overall information available on the subject suggest that relevant information is still missing.

Formability of high strength aluminium sheet

An initial review of the subject emphasises the need for improved fuel efficiency in vehicles and the possible role of aluminium in reducing weight. The problems of formability generally in manufacture and of aluminium in particular are discussed in the light of published data. A range of thirteen commercially available sheet aluminium alloys have been compared with respect to mechanical properties as these affect forming processes and behaviour in service. Four alloys were selected for detailed comparison. The formability and strength of these were investigated in terms of underlying mechanisms of deformation as well as the microstructural characteristics of the alloys including texture, particle dispersion, grain size and composition. In overall terms, good combinations of strength and ductility are achievable with alloys of the 2xxx and 6xxx series. Some specific alloys are notably better than others. The strength of formed components is affected by paint baking in the final stages of manufacture. Generally, alloys of the 6xxx family are strengthened while 2xxx and 5xxx become weaker. Some anomalous behaviour exists, however. Work hardening of these alloys appears to show rather abrupt decreases over certain strain ranges which is probably responsible for the relatively low strains at which both diffuse and local necking occur. Using data obtained from extended range tensile tests, the strain distribution in more complex shapes can be successfully modelled using finite element methods.Sheet failure during forming occurs by abrupt shear fracture in many instances. This condition is favoured by states of biaxial tension, surface defects in the form of fine scratches and certain types of crystallographic texture. The measured limit strains of the materials can be understood on the basis of attainment of a critical shear stress for fracture.

Otimização de parâmetros mecânicos e microestruturais dos moldes em areia de sílica ligados quimicamente pelo processo de cura a frio em fundição de aço

Surface defects on steel parts borne costs of smelting industries due to the need of rework. Sand molds are frequently used in foundry industries and largely responsible for providing surface defects. This study aims to optimize the levels of the molding process variables to minimize the occurrence of surface defects in steel castings in silica sand molds chemically linked by cold cure process. The methodology used the experimental design with split plot, being considered in the study the resin percentage factors in the mold formulation, addition of iron oxide, type of paint, the paint application method, amount of ink layers, use of hot air along the lines and waiting time of the mold before casting. They were analyzed as response variables erosion defects, sand inclusion, penetration, porosity and surface finish. Tensile strength tests were performed to evaluate the influence of factors on mechanical parameters and the microstructural parameters were carried out the analysis of X-ray diffraction, scanning electron microscopy (SEM) and thermal analysis (TG / DSC / dilatometry). The results elucidate that for the faulty erosion, the only significant factor with a 95% confidence level was the type of ink and the ink alumina-based superior results obtained. For the sand inclusion of defect, there were three significant factors, with best results obtained with alumina-based paint and spray applied using hot air in the mold before casting the metal. For the defect penetration, there were four significant factors, the best results being achieved with 0.8% of resin and addition of iron oxide in the molding formulation, the paint being applied by brush and standby time of 24 hours before leak. For the defect porosity with a 95% confidence level, no significant factors. For the defect surface finish, the best results were achieved with the 0.8% formulation of the resin in the mold and application of the paint brush. To obtain the levels of the factors that optimize all defects simultaneously, we performed a weighted average of the results of each type of fault, concluding that the best levels of the factors were: 0.8% resin and addition of iron oxide in the formulation of the template, application of two coats of paint applied with a brush or spray, using hot air in the mold before casting and 24 hours of waiting ready the mold before casting. These levels of the optimized factors were used in an experiment to confirm that ratified the results, helping to reduce rework and consequently reducing costs of cast steel parts.

Macro-geographical differences influenced by family-based expression on cultured pearl grade, shape and colour in the black-lip "pearl oyster" Pinctada margaritifera: a preliminary bi-local case study in French Polynesia

In French Polynesia, the aquaculture of P. margaritifera is carried out in numerous grow-out sites, located over three archipelagos (Gambier, Society and Tuamotu). To evaluate the impact of macro-geographical effects of these growing sites on pearl quality traits, five hatcheries produced families were used as homogeneous donor oysters in an experimental graft. The molluscs were then reared in two commercial locations: Tahaa island (Society) and Rangiroa atoll (Tuamotu). At harvest, eight pearl quality traits were recorded and compared: surface defects, lustre, grade, circles, shape categories, darkness level, body and secondary colour and visual colour categories. Overall inter-site comparison revealed that: 1) all traits were affected by grow-out location except for lustre and round shape, and 2) a higher mean rate of valuable pearls was produced in Rangiroa. Indeed, for pearl grade, Rangiroa showed twice as many A-B and less reject samples than Tahaa. This was related to the number of surface defects (grade component): in Rangiroa, twice as many pearls had no defects and less pearls had up to 10 defects. Concerning pearl shape, more circled and baroque pearls were found in Tahaa (+10%). For colour variation, 10% more pearls have an attractive green overtone in Rangiroa than in Tahaa, where more grey bodycolor were harvested. Lustre does not seem to be affected by these two culture site (except at a family scale). This is the first time P. margaritifera donor family have been shown to vary in the quality of pearls they produce depending on their grow-out location.

Age-dependence of cultured pearl grade and colour in the black-lipped pearl oyster Pinctada margaritifera

Pinctada margaritifera is an economically important marine bivalve species for cultured pearl production in French Polynesian aquaculture. In order to evaluate the influence of donor oyster age on pearl quality traits, experiments were conducted over 6 years using both grafts and surgreffe operations. At harvest, 6 pearl quality traits were recorded and compared: surface defects, luster, grade, darkness level, and visual color. Analyzing the quality traits of pearls harvested in the initial graft process and those of pearls obtained from surgreffe experiments allowed a comparison of the influence of pearl sac cells originating from the initial mantle graft, which aged together with their recipient oysters. The results demonstrated a significant decrease between these successive grafts in luster, grade (A-B-C,) darkness level, and green color – traits that are of major importance in the pearl market. The duplicated graft experiment allowed the comparison of donor oyster families at 2 and 5 years old, where a mantle graft was inserted into recipient oysters aged 2.5 years old. The results showed the same tendencies to a lesser extent, with 1) an improved pearl grade, predominantly through a most important rate of 0 surface defect category, and 2) a green / grey ratio in favor of the younger donor. A comparison between the graft-surgreffe and the duplicated graft experiments also highlighted: 1) the indirect role played by the younger recipient oysters, which must be optimized for optimal pearl quality realization, and 2) the complex interplay between donor and recipient oysters.