Ultrasound has been established as one of the most widely used imaging modalities for diagnostic purposes, due to the several advantages it provides in comparison with other techniques. Hence, ways to further improve the confidence in diagnoses provided by ultrasound are constantly being investigated. One of them is the introduction of Ultrasound Contrast Agents, which can enhance the weak echoes produced by the small vessels, improving the imaging performance. In this study, a setup was created and six ultrasound imaging techniques were implemented by using the Verasonics Research System®, in order to take advantage of the different behavior between the tissue and the Polyvinyl-Alcohol microbubbles, when exposed to ultrasound. These were: Fundamental B-mode, Ultraharmonic, PulseInversion, Subharmonic Pulse Inversion, Ultraharmonic Pulse Inversion, Combination of the Sub- and Ultraharmonic Pulse Inversion. For the assessment of the bubbles’ response, the amplitude spectra were used, which showed a limited detection around the ultraharmonic region. For the evaluation of the imaging performance of the techniques, the Contrast-to-Tissue (CTR) and Contrast-to-Noise Ratios (CNR) were calculated. The Combination of the Sub- and Ultraharmonic Pulse Inversion reported the highest imaging performance among all the techniques. A comparison with previous articles provided a similar pattern in terms of CTR. / Technology

[pt] O presente trabalho tem como foco a caracterização do concreto reforçado com fibras de álcool polivinílico (CRFPVA) com diferentes frações volumétricas para utilização como pavimento aeroportuário. Para isso foram determinados os parâmetros como resistência residual e tenacidade dos compósitos através de ensaios de flexão em três pontos definidos pela norma EN 14651 para serem aplicados no dimensionamento de lajes apoiadas em base elástica, proposto pela TR-34 e comparar estes resultados ao dimensionamento e a ensaios do pavimento de concreto de cimento Portland convencional regulamentado pela Federal Aviation Administration (FAA), através da circular AC150/5320-6F. Também foram utilizadas fibras de polipropileno, que são amplamente empregadas na construção de pisos industriais, para comparação com os CRFPVA. Os CRF apresentaram comportamento deflection softening e, acréscimo de tensões pós fissuração e tenacidade com o aumento da fração volumétrica de fibras. Ensaios de flexão cíclicos foram realizados mostrando que para carregamentos de até 70% da carga de primeira fissura, para corpos de prova não fissurados ou, 70% da carga em CMOD1 para corpos de prova pré-fissurados, combinados com 100 mil ciclos, há pouco ou nenhum dano aparente para os CRF. Finalmente, os ensaios estruturais em lajes sobre apoio elástico apresentaram com a adição de fibras, ganhos de até 2,8 vezes no valor da carga de primeira fissura comparado ao concreto convencional, além de redução das deformações e da fissuração das lajes, mostrando o CRF como uma alternativa para a aplicação em pavimentos aeroportuários. / [en] The present work focuses on the characterization of polyvinyl alcohol fiber reinforced concrete (PVA-FRC) with different volume content to be applied as airport pavement. The parameters that characterize the FRC were obtained through three point bending tests defined by EN 14651 and were applied in the slabs on ground design as proposed by TR-34. The results were compared to the design and tests of the plain Portland cement concrete pavement regulated by the Federal Aviation Administration (FAA) advisory circular AC150/5320-6F. Polypropylene fiber reinforced concrete (PP-FRC), which are widely used in industrial floor design and construction, were also tested for comparison. The FRC showed a deflection softening behavior improving the post-cracking strength and toughness values with the increase in the fiber content. Cyclic bending tests were performed with noncracked and pre-cracked specimens with 70 per cent of the first crack load and 70 per cent of the CMOD1 load respectively for 100k cycles. These tests showed little or no damage to the FRC samples compared to the monotonic bending tests. Finally, the structural scale tests on slabs on ground showed that with the fiber addition, the value of the load at first crack is improved up to 2.8 times compared to the plain concrete slab and also reduced deflection and displacement are seen, indicating that he PVAFRC, and also the PP-FRC are suitable to be used as airport pavement.

Cardiovascular diseases are the leading causes of death worldwide and improved diagnostic methods are needed for early intervention and to select the most suitable treatment for patients. Currently, carotid artery plaque vulnerability is typically determined by visually assessing ultrasound B-mode images, which is influenced by user-subjectivity. Since plaque vulnerability is correlated to the mechanical properties of the plaque, quantitative techniques are needed to estimate plaque stiffness as a surrogate for plaque vulnerability, which would reduce subjectivity during plaque assessment. The work in this thesis focused on three noninvasive ultrasound-based techniques to quantitatively assess plaque vulnerability and measure arterial stiffness. In Study I, a speckle tracking algorithm was validated in vitro to assess strain in common carotid artery (CCA) phantom plaques and thereafter applied in vivo to carotid atherosclerotic plaques where the strain results were compared to visual assessments by experienced physicians. In Study II, hard and soft CCA phantom plaques were characterized with shear wave elastography (SWE) by using phase and group velocity analysis while being hydrostatically pressurized followed by validating the results with mechanical tensile testing. In Study III, feasibility of assessing the stiffness of simulated plaques and the arterial wall with SWE was demonstrated in an ex vivo setup in small porcine aortas used as a human CCA model. In Study IV, SWE and pulse wave imaging (PWI) were compared when characterizing homogeneous CCA soft phantom plaques. The techniques developed in this thesis have demonstrated potential to characterize carotid artery plaques. The results show that the techniques have the ability to noninvasively evaluate the mechanical properties of carotid artery plaques, provide additional data when visually assessing B-mode images, and potentially provide improved diagnoses for patients suffering from cerebrovascular diseases. / <p>Doctoral thesis in medical technology and medical sciences</p><p>QC 20160921</p>

Este trabalho trata do estudo da introdução de fibras poliméricas como agente porogênico na manufatura de membranas cerâmicas de alta resistência mecânica. Membranas cerâmicas são utilizadas para a separação de substâncias onde a estabilidade química e a resistência à alta temperatura são requeridas; na engenharia mecânica é também aplicada como mancais aerostáticos. A escolha do processo de manufatura destas membranas e o projeto da porosidade da estrutura cerâmica é de grande importância. Quando se utiliza da adição de elementos porogênicos, que são substâncias que se decompõem durante a queima deixando poros (abertos e fechados), altera não somente a porosidade como também a seletividade e permeabilidade da membrana, bem como diminui suas propriedades mecânicas. Este trabalho objetiva membranas com poros micrométricos e submicrométricos para aplicações em microfiltração ou em mancais aerostáticos, porém que tenham a maximização da sua resistência mecânica. Para isso foi idealizada a obtenção de membranas permeáveis com a menor porosidade possível. Então, propôs-se a adição de fibras poliméricas (fibras de polipropileno, fibras de carbono e fibras de álcool polivinílico) como agentes porogênicos em uma massa cerâmica de alumina que após granulada foi prensada na forma de pastilhas e sinterizadas. As membranas foram caracterizadas por ensaios de permeabilidade ao ar, resistência mecânica por flexão a 3 pontos, volume de poros pelo Princípio de Arquimedes e morfologicamente por MEV. A caracterização morfológica das membranas e os resultados de porosidade indicaram que a percolação foi melhorada pela adição de fibras em relação a trabalhos equivalentes que se utilizaram de particulados. As melhores condições de permeação, integridade da matriz e resistência mecânica foram encontradas para as membranas com 1 vol. % de fibras de álcool polivinílico, seguida das membranas com 2 vol. % de fibras de carbono. Com base nos resultados obtidos, foi comprovado que a morfologia alongada das fibras aumenta a probabilidade de contato entre os poros, pois com apenas 2 vol. % de fibras de PVAl, obteve-se uma porosidade total de 33,3%, porosidade aparente de 17,4% e permeabilidade específica de 6,32x10-12 m², apresentando resistência à flexão de 134,3 MPa, valor este o dobro de quando utilizado 50 vol. % de sacarose como agente precursor com equivalente permeabilidade. As propriedades físicas do agente porogênico como: expansão térmica, dimensões, relação comprimento versus diâmetro afetam enormemente a porosidade, percolação dos poros e integridade da matriz. / This work deals with the study of the introduction of polymeric fibers as porogenic agent in the manufacture of ceramic membranes with high mechanical strength. Ceramic membranes are used for separation of substances where chemical stability and high temperature resistance are required, in mechanical engineering is also applied as an aerostatic bearings. The choice of these membranes manufacturing process and design the porosity of the ceramic structure is of great importance. When using addition of porogenic components, which are substances that decompose during the burning leaving pores (open and closed), not only alters the porosity and also the permeability and the selectivity of the membrane, as well as decreases their mechanical properties. This work aims membranes with micrometric pores and submicrometrics for microfiltration applications or aerostatic bearings, however they having the maximization their mechanic strength. To this was designed to obtain porous membranes with the lowest porosity possible. Then proposed the addition of polymeric fibers (polypropylene fiber, carbon fiber and polyvinyl alcohol fiber) as porogenic agents on a ceramic alumina mass that was granular and pressed the form of discs and sintered. The membranes were characterized by testing the air permeability, mechanical strength by three points flexural, pore volume by Archimedes principle and morphologically by SEM. Morphological characterization of membrane and the results of porosity indicated that the percolation has been improved by adding fibers in relation to the corresponding work where particulates were used. The best conditions of permeation, matrix integrity and mechanical strength were found for the membranes with 2 vol. % of polyvinyl alcohol fibers and membranes with 2 vol. % carbon fibers. Based on these results, it was proven that the elongated morphology of the fibers increases the probability of contact between the pores, because with only 2 vol. % of PVAl fibers, we obtained a total porosity of 33.3%, apparent porosity of 17.4% and the specific permeability of 6.32x10-12 m², flexural strength of 134.3 MPa, this value is twice than when it is used 50 vol. % sucrose as a precursor agent with equivalent permeability. The physical properties of porogenic agent such as thermal expansion, dimensions and relation length versus diameter affect greatly the porosity, pore percolation and integrity of the matrix.

Les nouvelles technologies sont de plus en plus demandeuses de sources de forte densité d’énergie respectueuses de l’environnement. Les accumulateurs lithium-ion semblent être la meilleure solution pour les applications mobiles et pour le domaine de l’automobile. Afin de répondre aux besoins en énergie de plus en plus importants, de nouveaux matériaux d’électrode négative sont nécessaires pour remplacer le carbone qui a désormais atteint son stade de maturité. En particulier, les composites silicium/carbone (Si/C) semblent être prometteurs pour augmenter la densité d’énergie des accumulateurs mais présentent de faibles rétentions de capacité au cours du cyclage. L’amélioration de la cyclabilité des composites Si/C fait l’objet de ce travail de thèse. La synthèse des composites par atomisation avec de l’alcool polyvinylique comme précurseur carboné suivie d’une pyrolyse est présentée. Les performances électrochimiques des matériaux résultants sont comparées à celles obtenues par d’autres composites, élaborés par lyophilisation et par broyage. Les propriétés intrinsèques des composites ont été modifiées par deux voies différentes afin d’améliorer leur cyclabilité. Dans un premiers temps, les effets de la réticulation de l’alcool polyvinylique ont été étudiés, puis ceux liés à l’ajout d’un catalyseur favorisant la graphitisation du carbone. La cyclabilité des composites Si/C peut également être améliorée en modifiant la nature du liant utilisé lors de la préparation des électrodes. L’intérêt bénéfique de l’emploi de l’acide polyacrylique en remplacement du fluorure de polyvinylidène couramment utilisé dans des électrodes à base de composites Si/C est démontré. / New technologies require more and more environment friendly sources of high energy density. Lithium-ion batteries seem to be the best solution for mobile and automotive applications. In order to meet the future energy requirements, new negative electrode materials are needed to replace carbon which has now reached a mature stage. Especially, silicon/carbon composites (Si/C) appear to be promising candidates to increase the energy density of batteries, but they still present poor capacity retention upon cycling. The improvement of Si/C composites cyclability is the subject of this thesis. The synthesis of Si/C composites by spray drying with polyvinyl alcohol as carbon precursor, followed by pyrolysis, is presented. The electrochemical performances are compared with those obtained for other composites, prepared by freeze drying and ball-milling. The intrinsic properties of the composites were modified in two different ways to improve their cyclability. First, we studied the effects of polyvinyl alcohol crosslinking, and then those related to the graphitization of carbon contained in these composites. The cyclability of Si/C composites can also be improved by changing the nature of the binder used during the electrodes preparation. The beneficial interest of using polyacrylic acid in replacement of polyvinylidene fluoride binder commonly used in Si/C based electrodes is shown.

Este trabalho trata do estudo da introdução de fibras poliméricas como agente porogênico na manufatura de membranas cerâmicas de alta resistência mecânica. Membranas cerâmicas são utilizadas para a separação de substâncias onde a estabilidade química e a resistência à alta temperatura são requeridas; na engenharia mecânica é também aplicada como mancais aerostáticos. A escolha do processo de manufatura destas membranas e o projeto da porosidade da estrutura cerâmica é de grande importância. Quando se utiliza da adição de elementos porogênicos, que são substâncias que se decompõem durante a queima deixando poros (abertos e fechados), altera não somente a porosidade como também a seletividade e permeabilidade da membrana, bem como diminui suas propriedades mecânicas. Este trabalho objetiva membranas com poros micrométricos e submicrométricos para aplicações em microfiltração ou em mancais aerostáticos, porém que tenham a maximização da sua resistência mecânica. Para isso foi idealizada a obtenção de membranas permeáveis com a menor porosidade possível. Então, propôs-se a adição de fibras poliméricas (fibras de polipropileno, fibras de carbono e fibras de álcool polivinílico) como agentes porogênicos em uma massa cerâmica de alumina que após granulada foi prensada na forma de pastilhas e sinterizadas. As membranas foram caracterizadas por ensaios de permeabilidade ao ar, resistência mecânica por flexão a 3 pontos, volume de poros pelo Princípio de Arquimedes e morfologicamente por MEV. A caracterização morfológica das membranas e os resultados de porosidade indicaram que a percolação foi melhorada pela adição de fibras em relação a trabalhos equivalentes que se utilizaram de particulados. As melhores condições de permeação, integridade da matriz e resistência mecânica foram encontradas para as membranas com 1 vol. % de fibras de álcool polivinílico, seguida das membranas com 2 vol. % de fibras de carbono. Com base nos resultados obtidos, foi comprovado que a morfologia alongada das fibras aumenta a probabilidade de contato entre os poros, pois com apenas 2 vol. % de fibras de PVAl, obteve-se uma porosidade total de 33,3%, porosidade aparente de 17,4% e permeabilidade específica de 6,32x10-12 m², apresentando resistência à flexão de 134,3 MPa, valor este o dobro de quando utilizado 50 vol. % de sacarose como agente precursor com equivalente permeabilidade. As propriedades físicas do agente porogênico como: expansão térmica, dimensões, relação comprimento versus diâmetro afetam enormemente a porosidade, percolação dos poros e integridade da matriz. / This work deals with the study of the introduction of polymeric fibers as porogenic agent in the manufacture of ceramic membranes with high mechanical strength. Ceramic membranes are used for separation of substances where chemical stability and high temperature resistance are required, in mechanical engineering is also applied as an aerostatic bearings. The choice of these membranes manufacturing process and design the porosity of the ceramic structure is of great importance. When using addition of porogenic components, which are substances that decompose during the burning leaving pores (open and closed), not only alters the porosity and also the permeability and the selectivity of the membrane, as well as decreases their mechanical properties. This work aims membranes with micrometric pores and submicrometrics for microfiltration applications or aerostatic bearings, however they having the maximization their mechanic strength. To this was designed to obtain porous membranes with the lowest porosity possible. Then proposed the addition of polymeric fibers (polypropylene fiber, carbon fiber and polyvinyl alcohol fiber) as porogenic agents on a ceramic alumina mass that was granular and pressed the form of discs and sintered. The membranes were characterized by testing the air permeability, mechanical strength by three points flexural, pore volume by Archimedes principle and morphologically by SEM. Morphological characterization of membrane and the results of porosity indicated that the percolation has been improved by adding fibers in relation to the corresponding work where particulates were used. The best conditions of permeation, matrix integrity and mechanical strength were found for the membranes with 2 vol. % of polyvinyl alcohol fibers and membranes with 2 vol. % carbon fibers. Based on these results, it was proven that the elongated morphology of the fibers increases the probability of contact between the pores, because with only 2 vol. % of PVAl fibers, we obtained a total porosity of 33.3%, apparent porosity of 17.4% and the specific permeability of 6.32x10-12 m², flexural strength of 134.3 MPa, this value is twice than when it is used 50 vol. % sucrose as a precursor agent with equivalent permeability. The physical properties of porogenic agent such as thermal expansion, dimensions and relation length versus diameter affect greatly the porosity, pore percolation and integrity of the matrix.

Dans le contexte énergétique actuel, la conception de panneaux photovoltaïques efficaces représente une des solutions pour pallier à la pénurie prochaine des énergies fossiles. Cependant, les phénomènes de dégradation de l’encapsulant, un des matériaux passifs du panneau, sont une des origines de la baisse de rendement des modules. L’objectif de ce travail de thèse a été de concevoir, caractériser et évaluer les différentes propriétés de nouveaux encapsulants hybrides organique-inorganique contenant des ressources renouvelables. Ainsi, trois matériaux ont été élaborés à partir d’alcool polyvinylique (PVA), de résines terpéniques et de charges minérales (silice ou argile (Bentonite)). Un premier matériau comprenant PVA, résine et silicates, dans lequel composantes organique et inorganique sont liées par des liaisons covalentes fortes (hybride de classe II), a conduit à des stabilités thermiques et photochimiques, et des propriétés optiques et barrières à la vapeur d’eau et à l’oxygène, similaires à celles des encapsulants actuels.L’introduction de nanoparticules de silice dans un mélange PVA/résine via des liaisons faibles a ensuite fourni un matériau hybride de classe I aux propriétés barrières à la vapeur d’eau satisfaisantes mais avec des transparences optiques insuffisantes pour une utilisation comme encapsulant, du fait de l’agrégation des nanoparticules. Enfin, malgré une transparence optique devant être encore optimisée, un matériau hybride de classe I constitué de PVA, de résine et de Bentonite a conduit à de bonnes propriétés thermiques, photochimiques, barrières à la vapeur d’eau et surtout d’excellentes propriétés barrières à l’oxygène, ce qui ouvre de nouvelles perspectives (emballage alimentaire…). / In the current energetic context, the design of efficient solar photovoltaic panels represents one of the solutions to overcome the coming fossil fuels shortage. However, degradation phenomena of the encapsulant, one of the passive materials of the panel, have been evidenced as one of the reasons of the performance decrease. The aim of this PhD research work was to design, characterize and assess the different properties of more environment-friendly new hybrid organic-inorganic encapsulants. In this way, three materials have been developed using polyvinyl alcohol (PVA), terpenic resins and mineral fillers (silica or clay(Bentonite)). A first material including PVA, resin and silicates, in which both organic and inorganic networksare linked through strong covalent bonds (class II hybrid material), led to thermal and photochemical stabilities, and water vapor and oxygen barriers properties similar to those of commercial encapsulants.Dispersion of silica nanoparticles into PVA/terpenic resin mixture through weak bond then provided a class Ihybrid material showing rather good water vapor barrier properties but optical transmittance too low to beused as an encapsulant, due to the aggregation of the nanoparticles. Finally, despite an optical transparency that should be optimized, a class I hybrid material made of PVA, resin and Bentonite showed promisingbehavior with good thermal, photochemical and water barrier properties and remarkable oxygen barrier properties, which opens up new prospects in the field of food packaging.

Im Rahmen des Transferprojektes T01 „Textilbeschichtung mit hochviskosen Massen“ des Sonderforschungsbereiches 532 (SFB 532) wird die Realisierung und Bewertung eines integrierten Beschichtungskonzeptes zur nachhaltigen Verbesserung der Tragfähigkeit von textilbewehrten Betonbauteilen an der RWTH Aachen University untersucht. Dazu wird eine neue Auftragstechnik für hochviskose Beschichtungsmassen entwickelt, die eine vollständige Penetration von Multifilamentgarnen mit großen Garntitern und einer hohen Anzahl an Filamenten in textilen Gelegen erzielt. Des Weiteren werden aktive Beschichtungsmassen auf der Basis von Polyvinylalkohol-Zement-Compositen, die eine homogene Anbindung aller Einzelfilamente an die Zementmatrix ermöglichen, erforscht.

This work seeks to fabricate, optimize, and characterize nanofibers of cactus Opuntia ficus-indica mucilage and Poly (vinyl alcohol) (PVA) by electrospinning. Mucilage is a neutral mixture of sugars produced by cactus and PVA is a non-toxic, water-soluble, synthetic polymer, which is widely used as a co-spinning agent for polymers. Mucilage was extracted from the cactus pad and prepared for electrospinning by mixing with acetic acid. Two types of PVA were used differentiating in high and low molecular weights. Concentrations of PVA were varied to find an adequate threshold for fiber formation. Changing the ratio of PVA to cactus mucilage produced fibers of different diameter and quality. The optimizations of the parameters used in the electrospinning setup were also a factor in creating quality fibers without deformity. An acceptable PVA to mucilage ratio mixture was reached for the use of the electrospinning process and consistent nanofibers were accomplished with the use of both the low and high molecular weight PVA. The fibers were observed using a Scanning Electron Microscope, Atomic Force Microscopy, and Differential Scanning Calorimetry. In this project we were able to obtain nanofiber meshes made with environmentally friendly materials with fiber diameters raging from 50nm to 7um sized. The produced nanofibers were made in the hope that it can be utilized in the future as an inexpensive, biocompatible, and biodegradable water filtration system.

Dans ce travail, nous nous sommes intéressés au développement d’un nouveau biocapteur enzymatique ultrasensible pour la détection conductimétrique d’une mycotoxine, l’ochratoxine A (OTA). Une peptidase, la thermolysine (TLN), a été choisie comme élément de reconnaissance. Le biocapteur proposé est basé sur l’immobilisation de la TLN dans une matrice d’alcool polyvinylique (PVA)/polyéthylènimine (PEI) contenant des nanoparticules d’or et réticulée à la surface de microélectrodes interdigitées à l’aide de vapeurs de glutaraldéhyde. Dans les conditions optimales (35 min de réticulation, mesure à pH 7 et 25°C), la réponse du biocapteur est linéaire jusqu’à 60 nM et la limite de détection est de 1 nM. Cette valeur est 700 fois plus basse que celle obtenue en utilisant une méthode d’immobilisation basée sur la co-réticulation de la TLN en présence d’albumine de sérum bovin (BSA). La matrice PVA/PEI crée un environnement aqueux favorable à l’enzyme. Par ailleurs, les interactions entre les groupements amines protonés du PEI et les charges négatives des nanoparticules citratées et de la TLN améliore leur dispersion dans la matrice et favorise la stabilisation de l’enzyme et son accessibilité au substrat (OTA). Le biocapteur conductimétrique développé est très reproductible et stable pendant 30 jours lorsqu’il est stocké à 4°C dans du tampon phosphate 20 mM pH7 entre 2 mesures. Le biocapteur a ensuite été évalué sur des échantillons d’huile d’olive commerciale dopée. Aucun prétraitement de l’échantillon n’a été nécessaire et des taux de recouvrement proches de 100% ont été obtenus, démontrant l’absence d’effet de matrice / A new ultrasensitive enzymatic biosensor for the direct conductometric detection of ochratoxin A (OTA) has been developed in this work. Thermolysin (TLN), a peptidase, was chosen as recognition element. The proposed biosensor is based on TLN immobilization into a polyvinyl alcohol (PVA)/polyethylenimine (PEI) matrix containing gold nanoparticles (AuNPs) and cross-linked at the surface of gold interdigitated microelectrodes using glutaraldehyde vapor. Under optimal conditions (35 min cross-linking time, working pH of 7 and temperature of 25◦C), the biosensor response was linear up to 60 nM OTA and the limit of detection was 1 nM. This value was 700 times lower than the detection limit obtained using the more classical method based on enzyme cross-linking in the presence of bovine serum albumin (BSA). PVA/PEI hydrogel creates a very favorable aqueous environment for the enzyme. In addition, interactions between protonated amino groups of PEI and negative charges of both citrated AuNPs and thermolysin improve their dispersion in the polymer blend, favoring enzyme stabilization and accessibility to the substrate (OTA). The developed OTA biosensor was very reproducible and stable over a 30 days period when stored at 4◦C in 20 mM phosphate buffer between two measurements. The method was further evaluated using commercial doped olive oil samples. No pretreatment of the sample was needed for testing and no matrix effect was observed. Recovery values were close to 100%, demonstrating the suitability of the proposed method for OTA screening in olive oil