Surface modification by metal ion implantation forming metallic nanoparticles in insulating matrix.

There is special interest in the incorporation of metallic nanoparticles in a surrounding dielectric matrix for obtaining composites with desirable characteristics such as for surface plasmon resonance, which can be used in photonics and sensing, and controlled surface electrical conductivity. We investigated nanocomposites produced through metallic ion implantation in insulating substrate, where the implanted metal self-assembles into nanoparticles. During the implantation, the excess of metal atom concentration above the solubility limit leads to nucleation and growth of metal nanoparticles, driven by the temperature and temperature gradients within the implanted sample including the beam-induced thermal characteristics. The nanoparticles nucleate near the maximum of the implantation depth profile (projected range), that can be estimated by computer simulation using the TRIDYN. This is a Monte Carlo simulation program based on the TRIM (Transport and Range of Ions in Matter) code that takes into account compositional changes in the substrate due to two factors: previously implanted dopant atoms, and sputtering of the substrate surface. Our study suggests that the nanoparticles form a bidimentional array buried few nanometers below the substrate surface. More specifically we have studied Au/PMMA (polymethylmethacrylate), Pt/PMMA, Ti/alumina and Au/alumina systems. Transmission electron microscopy of the implanted samples showed the metallic nanoparticles formed in the insulating matrix. The nanocomposites were characterized by measuring the resistivity of the composite layer as function of the dose implanted. These experimental results were compared with a model based on percolation theory, in which electron transport through the composite is explained by conduction through a random resistor network formed by the metallic nanoparticles. Excellent agreement was found between the experimental results and the predictions of the theory. It was possible to conclude, in all cases, that the conductivity process is due only to percolation (when the conducting elements are in geometric contact) and that the contribution from tunneling conduction is negligible.

Experimental analysis of fiber reinforced cementitious matrix (FRCM) confined masonry columns

The increasing use of Fiber Reinforced methods for strengthening existing brick masonry walls and columns, especially for the rehabilitation of historical buildings, has generated considerable research interest in understanding the failure mechanism in such systems. This dissertation is aimed to provide a basic understanding of the behavior of solid brick masonry walls unwrapped and wrapped with Fiber Reinforced Cementitious Matrix Composites. This is a new type of composite material, commonly known as FRCM, featuring a cementitious inorganic matrix (binder) instead of the more common epoxy one. The influence of the FRCM-reinforcement on the load-carrying capacity and strain distribution during compression test will be investigated using a full-field optical technique known as Digital Image Correlation. Compression test were carried on 6 clay bricks columns and on 7 clay brick walls in three different configuration, casted using bricks scaled respect the first one with a ratio 1:2, in order to determinate the effects of FRCM reinforcement. The goal of the experimental program is to understand how the behavior of brick masonry will be improved by the FRCM-wrapping. The results indicate that there is an arching action zone represented in the form of a parabola with a varying shape according to the used configuration. The area under the parabolas is considered as ineffectively confined. The effectively confined area is assumed to occur within the region where the arching action had been fully developed.

Geometric and Combinatorial Aspects of NonEquilibrium Statistical Mechanics

Non-Equilibrium Statistical Mechanics is a broad subject. Grossly speaking, it deals with systems which have not yet relaxed to an equilibrium state, or else with systems which are in a steady non-equilibrium state, or with more general situations. They are characterized by external forcing and internal fluxes, resulting in a net production of entropy which quantifies dissipation and the extent by which, by the Second Law of Thermodynamics, time-reversal invariance is broken. In this thesis we discuss some of the mathematical structures involved with generic discrete-state-space non-equilibrium systems, that we depict with networks in all analogous to electrical networks. We define suitable observables and derive their linear regime relationships, we discuss a duality between external and internal observables that reverses the role of the system and of the environment, we show that network observables serve as constraints for a derivation of the minimum entropy production principle. We dwell on deep combinatorial aspects regarding linear response determinants, which are related to spanning tree polynomials in graph theory, and we give a geometrical interpretation of observables in terms of Wilson loops of a connection and gauge degrees of freedom. We specialize the formalism to continuous-time Markov chains, we give a physical interpretation for observables in terms of locally detailed balanced rates, we prove many variants of the fluctuation theorem, and show that a well-known expression for the entropy production due to Schnakenberg descends from considerations of gauge invariance, where the gauge symmetry is related to the freedom in the choice of a prior probability distribution. As an additional topic of geometrical flavor related to continuous-time Markov chains, we discuss the Fisher-Rao geometry of nonequilibrium decay modes, showing that the Fisher matrix contains information about many aspects of non-equilibrium behavior, including non-equilibrium phase transitions and superposition of modes. We establish a sort of statistical equivalence principle and discuss the behavior of the Fisher matrix under time-reversal. To conclude, we propose that geometry and combinatorics might greatly increase our understanding of nonequilibrium phenomena.

Matrix Designs and Methods for Secure and Efficient Compressed Sensing

The idea of balancing the resources spent in the acquisition and encoding of natural signals strictly to their intrinsic information content has interested nearly a decade of research under the name of compressed sensing. In this doctoral dissertation we develop some extensions and improvements upon this technique's foundations, by modifying the random sensing matrices on which the signals of interest are projected to achieve different objectives. Firstly, we propose two methods for the adaptation of sensing matrix ensembles to the second-order moments of natural signals. These techniques leverage the maximisation of different proxies for the quantity of information acquired by compressed sensing, and are efficiently applied in the encoding of electrocardiographic tracks with minimum-complexity digital hardware. Secondly, we focus on the possibility of using compressed sensing as a method to provide a partial, yet cryptanalysis-resistant form of encryption; in this context, we show how a random matrix generation strategy with a controlled amount of perturbations can be used to distinguish between multiple user classes with different quality of access to the encrypted information content. Finally, we explore the application of compressed sensing in the design of a multispectral imager, by implementing an optical scheme that entails a coded aperture array and Fabry-Pérot spectral filters. The signal recoveries obtained by processing real-world measurements show promising results, that leave room for an improvement of the sensing matrix calibration problem in the devised imager.

Weighted geometric mean of large-scale matrices: numerical analysis and algorithms

Computing the weighted geometric mean of large sparse matrices is an operation that tends to become rapidly intractable, when the size of the matrices involved grows. However, if we are not interested in the computation of the matrix function itself, but just in that of its product times a vector, the problem turns simpler and there is a chance to solve it even when the matrix mean would actually be impossible to compute. Our interest is motivated by the fact that this calculation has some practical applications, related to the preconditioning of some operators arising in domain decomposition of elliptic problems. In this thesis, we explore how such a computation can be efficiently performed. First, we exploit the properties of the weighted geometric mean and find several equivalent ways to express it through real powers of a matrix. Hence, we focus our attention on matrix powers and examine how well-known techniques can be adapted to the solution of the problem at hand. In particular, we consider two broad families of approaches for the computation of f(A) v, namely quadrature formulae and Krylov subspace methods, and generalize them to the pencil case f(A\B) v. Finally, we provide an extensive experimental evaluation of the proposed algorithms and also try to assess how convergence speed and execution time are influenced by some characteristics of the input matrices. Our results suggest that a few elements have some bearing on the performance and that, although there is no best choice in general, knowing the conditioning and the sparsity of the arguments beforehand can considerably help in choosing the best strategy to tackle the problem.

(234)U/(238)U activity ratio disequilibrium technique for studying uranium mobility in the Opalinus Clay at Mont Terri, Switzerland

Mobility of naturally occurring U-238 and U-234 radionuclides was studied in a low permeability, reducing claystone formation (Opalinus Clay) near its contact with an overlying oxidising aquifer (Dogger Limestones) at Mont Terri, Switzerland. Our data point to a limited redistribution of U in some of the studied samples. Observed centimetre-scale U mobility is explained by slow diffusive transport of U-234 in the pore waters of the Opalinus Clay driven by spatially variable in situ supply (by alpha-recoil) of U-234 from the rock matrix. Metre-scale mobility is interpreted as a result of infiltration of meteoric water into the overlying aquifer which developed gradients of U concentration across the two rock formations. This triggered a slow in-diffusion of U with (U-234/U-238) > 1 into the Opalinus Clay as attested by a clear-cut pattern of decreasing bulk rock (U-234/U-238) inwards the Opalinus Clay, away from the Dogger Limestones.

Steady-state diffusion imaging for MR in-vivo evaluation of reparative cartilage after matrix-associated autologous chondrocyte transplantation at 3 tesla--preliminary results

OBJECTIVES: To demonstrate the feasibility of time-reversed fast imaging with steady-state precession (FISP) called PSIF for diffusion-weighted imaging of cartilage and cartilage transplants in a clinical study. MATERIAL AND METHODS: In a cross-sectional study 15 patients underwent MRI using a 3D partially balanced steady-state gradient echo pulse sequence with and without diffusion weighting at two different time points after matrix-associated autologous cartilage transplantation (MACT). Mean diffusion quotients (signal intensity without diffusion-weighting divided by signal intensity with diffusion weighting) within the cartilage transplants were compared to diffusion quotients found in normal cartilage. RESULTS: The global diffusion quotient found in repair cartilage was significantly higher than diffusion values in normal cartilage (p<0.05). There was a decrease between the earlier and the later time point after surgery. CONCLUSIONS: In-vivo diffusion-weighted imaging based on the PSIF technique is possible. Our preliminary results show follow-up of cartilage transplant maturation in patients may provide additional information to morphological assessment.

Passive-Active Geometric Calibration for View-Dependent Projections onto Arbitrary Surfaces

In this paper we present a hybrid technique for correcting distortions that appear when projecting images onto geometrically complex, colored and textured surfaces. It analyzes the optical flow that results from perspective distortions during motions of the observer and tries to use this information for computing the correct image warping. If this fails due to an unreliable optical flow, an accurate -but slower and visiblestructured light projection is automatically triggered. Together with an appropriate radiometric compensation, view-dependent content can be projected onto arbitrary everyday surfaces. An implementation mainly on the GPU ensures fast frame rates.

Optimized Demineralization Technique for the Measurement of Stable Isotope Ratios of Nonexchangeable H in Soil Organic Matter

To make use of the isotope ratio of nonexchangeable hydrogen (δ2Hn (nonexchangeable)) of bulk soil organic matter (SOM), the mineral matrix (containing structural water of clay minerals) must be separated from SOM and samples need to be analyzed after H isotope equilibration. We present a novel technique for demineralization of soil samples with HF and dilute HCl and recovery of the SOM fraction solubilized in the HF demineralization solution via solid-phase extraction. Compared with existing techniques, organic C (Corg) and organic N (Norg) recovery of demineralized SOM concentrates was significantly increased (Corg recovery using existing techniques vs new demineralization method: 58% vs 78%; Norg recovery: 60% vs 78%). Chemicals used for the demineralization treatment did not affect δ2Hn values as revealed by spiking with deuterated water. The new demineralization method minimized organic matter losses and thus artificial H isotope fractionation, opening up the opportunity to use δ2Hn analyses of SOM as a new tool in paleoclimatology or geospatial forensics.

Protein quaternary structure determination using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and chemical crosslinking

A means of analyzing protein quaternary structure using matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI MS) and chemical crosslinking was evaluated. Proteins of known oligomeric structure, as well as monomeric proteins, were analyzed to evaluate the method. The quaternary structure of proteins of unknown or uncertain structure was investigated using this technique. The stoichiometry of recombinant E. coli carbamoyl phosphate synthetase and recombinant human farnesyl protein transferase were determined to be heterodimers using glutaraldehyde crosslinking, agreeing with the stoichiometry found for the wild type proteins. The stoichiometry of the gamma subunit of E. coli DNA polymerase III holoenzyme was determined in solution without the presence of other subunits to be a homotetramer using glutaraldehyde crosslinking and MALDI MS analysis. Chi and psi subunits of E. coli DNA polymerase III subunits appeared to form a heterodimer when crosslinked with heterobifunctional photoreactive crosslinkers.^ Comparison of relative % peak areas obtained from MALDI MS analysis of crosslinked proteins and densitometric scanning of silver stained sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) gels showed excellent qualitative agreement for the two techniques, but the quantitative analyses differed, sometimes significantly. This difference in quantitation could be due to SDS-PAGE conditions (differential staining, loss of sample) or to MALDI MS conditions (differences in ionization and/or detection). Investigation of pre-purified crosslinked monomers and dimers recombined in a specific ratio revealed the presence of mass discrimination in the MALDI MS process. The calculation of mass discrimination for two different MALDI time-of-flight instruments showed the loss of a factor of approximately 2.6 in relative peak area as the m/z value doubles over the m/z range from 30,000 to 145,000 daltons.^ Indirect symmetry was determined for tetramers using glutaraldehyde crosslinking with MALDI MS analysis. Mathematical modelling and simple graphing allowed the determination of the symmetry for several tetramers known to possess isologous D2 symmetry. These methods also distinguished tetramers that did not fit D2 symmetry such as apo-avidin. The gamma tetramer of E. coli DNA polymerase III appears to have isologous D2 symmetry. ^

Two distinct filopodia populations at the growth cone allow to sense nanotopographical extracellular matrix cues to guide neurite outgrowth

BACKGROUND The process of neurite outgrowth is the initial step in producing the neuronal processes that wire the brain. Current models about neurite outgrowth have been derived from classic two-dimensional (2D) cell culture systems, which do not recapitulate the topographical cues that are present in the extracellular matrix (ECM) in vivo. Here, we explore how ECM nanotopography influences neurite outgrowth. METHODOLOGY/PRINCIPAL FINDINGS We show that, when the ECM protein laminin is presented on a line pattern with nanometric size features, it leads to orientation of neurite outgrowth along the line pattern. This is also coupled with a robust increase in neurite length. The sensing mechanism that allows neurite orientation occurs through a highly stereotypical growth cone behavior involving two filopodia populations. Non-aligned filopodia on the distal part of the growth cone scan the pattern in a lateral back and forth motion and are highly unstable. Filopodia at the growth cone tip align with the line substrate, are stabilized by an F-actin rich cytoskeleton and enable steady neurite extension. This stabilization event most likely occurs by integration of signals emanating from non-aligned and aligned filopodia which sense different extent of adhesion surface on the line pattern. In contrast, on the 2D substrate only unstable filopodia are observed at the growth cone, leading to frequent neurite collapse events and less efficient outgrowth. CONCLUSIONS/SIGNIFICANCE We propose that a constant crosstalk between both filopodia populations allows stochastic sensing of nanotopographical ECM cues, leading to oriented and steady neurite outgrowth. Our work provides insight in how neuronal growth cones can sense geometric ECM cues. This has not been accessible previously using routine 2D culture systems.

Atmospheric, oceanic and hydrological polar motion excitation mechanisms based on a combination of geometric and gravimetric space observations

The goal of our study is to determine accurate time series of geophysical Earth rotation excitations to learn more about global dynamic processes in the Earth system. For this purpose, we developed an adjustment model which allows to combine precise observations from space geodetic observation systems, such as Satellite Laser Ranging (SLR), Global Navigation Satellite Systems (GNSS), Very Long Baseline Interferometry (VLBI), Doppler Orbit determination and Radiopositioning Integrated on Satellite (DORIS), satellite altimetry and satellite gravimetry in order to separate geophysical excitation mechanisms of Earth rotation. Three polar motion time series are applied to derive the polar motion excitation functions (integral effect). Furthermore we use five time variable gravity field solutions from Gravity Recovery and Climate Experiment (GRACE) to determine not only the integral mass effect but also the oceanic and hydrological mass effects by applying suitable filter techniques and a land-ocean mask. For comparison the integral mass effect is also derived from degree 2 potential coefficients that are estimated from SLR observations. The oceanic mass effect is also determined from sea level anomalies observed by satellite altimetry by reducing the steric sea level anomalies derived from temperature and salinity fields of the oceans. Due to the combination of all geodetic estimated excitations the weaknesses of the individual processing strategies can be reduced and the technique-specific strengths can be accounted for. The formal errors of the adjusted geodetic solutions are smaller than the RMS differences of the geophysical model solutions. The improved excitation time series can be used to improve the geophysical modeling.

A matrix pencil approach to the existence of compactly supported reconstruction functions in average sampling

The aim of this work is to solve a question raised for average sampling in shift-invariant spaces by using the well-known matrix pencil theory. In many common situations in sampling theory, the available data are samples of some convolution operator acting on the function itself: this leads to the problem of average sampling, also known as generalized sampling. In this paper we deal with the existence of a sampling formula involving these samples and having reconstruction functions with compact support. Thus, low computational complexity is involved and truncation errors are avoided. In practice, it is accomplished by means of a FIR filter bank. An answer is given in the light of the generalized sampling theory by using the oversampling technique: more samples than strictly necessary are used. The original problem reduces to finding a polynomial left inverse of a polynomial matrix intimately related to the sampling problem which, for a suitable choice of the sampling period, becomes a matrix pencil. This matrix pencil approach allows us to obtain a practical method for computing the compactly supported reconstruction functions for the important case where the oversampling rate is minimum. Moreover, the optimality of the obtained solution is established.

Homogeneous links and the Seifert matrix

Homogeneous links were introduced by Peter Cromwell, who pr oved that the projection surface of these links, that given by the Seifert al- gorithm, has minimal genus. Here we provide a different proof , with a geometric rather than combinatorial flavor. To do this, we fir st show a direct relation between the Seifert matrix and the decompo sition into blocks of the Seifert graph. Precisely, we prove that the Sei fert matrix can be arranged in a block triangular form, with small boxes in th e diagonal corresponding to the blocks of the Seifert graph. Then we pro ve that the boxes in the diagonal has non-zero determinant, by looking a t an explicit matrix of degrees given by the planar structure of the Seifer t graph. The paper contains also a complete classification of the homogen eous knots of genus one.

Inestabilidad de pórticos planos metálicos de edificación con inclusión de la flexibilidad de las uniones y elementos no prismáticos : un enfoque para la optimización

En esta tesis se aborda el problema de la modelización, análisis y optimización de pórticos metálicos planos de edificación frente a los estados límites último y de servicio. El objetivo general es presentar una técnica secuencial ordenada de optimización discreta para obtener el coste mínimo de pórticos metálicos planos de edificación, teniendo en cuenta las especificaciones del EC-3, incorporando las uniones semirrígidas y elementos no prismáticos en el proceso de diseño. Asimismo se persigue valorar su grado de influencia sobre el diseño final. El horizonte es extraer conclusiones prácticas que puedan ser de utilidad y aplicación simple para el proyecto de estructuras metálicas. La cantidad de publicaciones técnicas y científicas sobre la respuesta estructural de entramados metálicos es inmensa; por ello se ha hecho un esfuerzo intenso en recopilar el estado actual del conocimiento, sobre las líneas y necesidades actuales de investigación. Se ha recabado información sobre los métodos modernos de cálculo y diseño, sobre los factores que influyen sobre la respuesta estructural, sobre técnicas de modelización y de optimización, al amparo de las indicaciones que algunas normativas actuales ofrecen sobre el tema. En esta tesis se ha desarrollado un procedimiento de modelización apoyado en el método de los elementos finitos implementado en el entorno MatLab; se han incluido aspectos claves tales como el comportamiento de segundo orden, la comprobación ante inestabilidad y la búsqueda del óptimo del coste de la estructura frente a estados límites, teniendo en cuenta las especificaciones del EC-3. También se ha modelizado la flexibilidad de las uniones y se ha analizado su influencia en la respuesta de la estructura y en el peso y coste final de la misma. Se han ejecutado algunos ejemplos de aplicación y se ha contrastado la validez del modelo con resultados de algunas estructuras ya analizadas en referencias técnicas conocidas. Se han extraído conclusiones sobre el proceso de modelización y de análisis, sobre la repercusión de la flexibilidad de las uniones en la respuesta de la estructura. El propósito es extraer conclusiones útiles para la etapa de proyecto. Una de las principales aportaciones del trabajo en su enfoque de optimización es la incorporación de una formulación de elementos no prismáticos con uniones semirrígidas en sus extremos. Se ha deducido una matriz de rigidez elástica para dichos elementos. Se ha comprobado su validez para abordar el análisis no lineal; para ello se han comparado los resultados con otros obtenidos tras aplicar otra matriz deducida analíticamente existente en la literatura y también mediante el software comercial SAP2000. Otra de las aportaciones de esta tesis es el desarrollo de un método de optimización del coste de pórticos metálicos planos de edificación en el que se tienen en cuenta aspectos tales como las imperfecciones, la posibilidad de incorporar elementos no prismáticos y la caracterización de las uniones semirrígidas, valorando la influencia de su flexibilidad sobre la respuesta de la estructura. Así, se han realizado estudios paramétricos para valorar la sensibilidad y estabilidad de las soluciones obtenidas, así como rangos de validez de las conclusiones obtenidas. This thesis deals with the problems of modelling, analysis and optimization of plane steel frames with regard to ultimate and serviceability limit states. The objective of this work is to present an organized sequential technique of discrete optimization for achieving the minimum cost of plane steel frames, taking into consideration the EC-3 specifications as well as including effects of the semi-rigid joints and non-prismatic elements in the design process. Likewise, an estimate of their influence on the final design is an aim of this work. The final objective is to draw practical conclusions which can be handful and easily applicable for a steel-structure project. An enormous amount of technical and scientific publications regarding steel frames is currently available, thus making the achievement of a comprehensive and updated knowledge a considerably hard task. In this work, a large variety of information has been gathered and classified, especially that related to current research lines and needs. Thus, the literature collected encompasses references related to state-of-the-art design methods, factors influencing the structural response, modelling and optimization techniques, as well as calculation and updated guidelines of some steel Design Codes about the subject. In this work a modelling procedure based on the finite element implemented within the MatLab programming environment has been performed. Several keys aspects have been included, such as second order behaviour, the safety assessment against structural instability and the search for an optimal cost considering the limit states according to EC-3 specifications. The flexibility of joints has been taken into account in the procedure hereby presented; its effects on the structural response, on the optimum weight and on the final cost have also been analysed. In order to confirm the validity and adequacy of this procedure, some application examples have been carried out. The results obtained were compared with those available from other authors. Several conclusions about the procedure that comprises modelling, analysis and design stages, as well as the effect of the flexibility of connections on the structural response have been drawn. The purpose is to point out some guidelines for the early stages of a project. One of the contributions of this thesis is an attempt for optimizing plane steel frames in which both non-prismatic beam-column-type elements and semi-rigid connections have been considered. Thus, an elastic stiffness matrix has been derived. Its validity has been tested through comparing its accuracy with other analytically-obtained matrices available in the literature, and with results obtained by the commercial software SAP2000. Another achievement of this work is the development of a method for cost optimization of plane steel building frames in which some relevant aspects have been taken in consideration. These encompass geometric imperfections, non-prismatic beam elements and the numerical characterization of semi-rigid connections, evaluating the effect of its flexibility on the structural response. Hence, some parametric analyses have been performed in order to assess the sensitivity, the stability of the outcomes and their range of applicability as well.