O processo de Biorreatores com Membranas (BRM) foi desenvolvido no final da década de 1960, consistindo em um sistema que associa o tratamento biológico de efluentes com o mecanismo de separação por membranas, e apresenta vantagens com relação ao tratamento convencional, tais como maior eficiência de tratamento e um menor espaço físico de instalação para a mesma capacidade de tratamento. O fenômeno de incrustação das membranas (em inglês, fouling) representa a principal limitação desse processo, de modo que uma das condições operacionais mais importantes na prevenção da incrustação em um sistema BRM Submerso (BRMS) é a vazão de aeração. Diante desta situação, o objetivo do trabalho consiste em avaliar os efeitos das condições hidrodinâmicas no desempenho do processo, tais como vazão de aeração, densidade de empacotamento do módulo de membranas e geometria dos aeradores. O sistema utilizado no trabalho consistiu em um BRMS automatizado, operando em pressão constante e de forma contínua, durante um período de 4 dias. Os módulos foram construídos com membranas poliméricas de microfiltração do tipo fibra oca, cujo material foi a poli(éter)-imida (PEI). Três diferentes vazões de aeração foram estudadas (2, 5 e 8 L.min-1), mostrando, a partir dos resultados, que existe uma vazão de aeração limite benéfica ao sistema e que, acima deste valor, um melhor desempenho não pode ser atingido, inclusive, podendo prejudicá-lo. Para o sistema de estudo, a vazão de 5 L.min-1 apresentou o melhor desempenho, seguido de 8 e 2 L.min-1. O estudo da densidade de empacotamento do módulo mostrou que esta é uma variável que também exerce influência no desempenho do processo de BRMS. Módulos com dois diferentes diâmetros foram testados (2,54 cm e 1,91 cm); o melhor resultado foi observado no módulo de maior diâmetro. A menor densidade de empacotamento resulta em um maior espaçamento entre as fibras, provocando uma aeração mais homogênea no interior do feixe de membranas. As duas geometrias de aeração testadas (Modo 1 e Modo 2) apresentaram resultados semelhantes de fluxo permeado, indicando que o Modo 2 de aeração não melhorou o desempenho do processo como se esperava. A maior homogeneidade de aeração no interior de feixe, a partir de aeradores construídos com as próprias fibras, não foi atingida, mostrando que um novo projeto de aeradores deve ser estudado. Em todas as condições hidrodinâmicas testadas, a eficiência do tratamento foi verificada, uma vez que a remoção de matéria orgânica para COT e DQO foi de 96% e 93%, respectivamente. Propriedades do permeado, como condutividade elétrica, pH e turbidez foram mensuradas, apresentando variações menores que as medidas do efluente, revelando a capacidade que o sistema apresenta em suportar as variações na corrente de alimentação. / The Membrane Bioreactor (MBR) process was developed in the late 1960. The system consists in a combination of biological process and membrane separation mechanism, and the advantages with respect of conventional treatment are the higher treatment efficiency and a smaller area of installation for the same treatment capacity. The main limitation of this process is the membrane fouling, in a way that air flow rate represents an important operating condition to prevent the fouling formation in Submerged Membrane Bioreactors (SMBR). In this sense, the aim of this work is to evaluate the effects of hydrodynamic conditions on process performance, such as air flow rate, packing density of the membrane module and aeration geometry. The system used consists in a pilot-scale SMBR, which operates at constant pressure and continuous mode during a period of 4 days. The modules were built with hollow fiber polymeric microfiltration membrane and the material is poly(ether)imide (PEI). For the three different air flow rates studied (2, 5 and 8 L.min-1), results showed there is a limit value for this parameter, in which above this value a better performance will not be obtained, even can be worse. The air flow rate of 5 L.min-1 presented the best performance, followed by 8 and 2 L.min-1. The module packing density study for two diameters (0.75 and 1 inch), the best result was observed in the larger diameter module, because lower packing density causes more space between fibres, increasing the aeration homogeneity inside de fibre bundle. Both aeration geometry tested showed similar permeate flows, indicating the different geometry used did not affect the performance process. The aerators constructed with the hollow fibers did not promote aeration homogeneity inside the bundle, and new aeration geometry must be projected. For all hydrodynamics conditions, the system treatment was efficient in removing organical matter, since the removal for TOC and COD was 96% and 93%, respectively. Permeate properties such as electrical conductivity, pH and turbidity measurements presented minor variations than effluent properties measurements, showing the system capacity to withstand with feed stream variations.

Le comportement mécanique de matériaux granulaires est intrinsèquement lié aux propriétés individuelles des grains constitutifs ainsi qu’à leur assemblage (texture, distribution des vides, contact entre grains…). Soumis à un chargement extérieur, cet assemblage se déforme incluant le déplacement relatif entre les particules mais également la déformation propre des grains jusqu’à leur rupture si elle se produit. Pour étudier la rupture d'une seule particule, des études expérimentales et numériques ont été réalisées. Quatre particules sphériques formées de billes d’argile expansée légère ont été testées en compression à déplacement contrôlé jusqu’à la rupture (essai brésilien). Des photos ont été prises avec une fréquence d’acquisition de 4 images par seconde pour suivre la déformation des grains durant l’essai. La structure interne d'une particule a une influence significative sur l'initiation de la fissure. Pour approfondir cet effet, une micro-tomographie par rayons X a été utilisé pour scanner une particule afin d'obtenir la structure géométrique réelle en 3D. Ensuite, un modèle numérique 3D basé sur la géométrie des particules incluant la porosité interne a été construit avec Abaqus pour les mêmes conditions de chargement. Une comparaison des résultats des tests de laboratoire et des simulations a été faite. Sur la base des résultats, l’initiation des fissures, leur localisation dans le grain et la classification des ruptures de particules ont été établies. Afin d’étudier le rôle de l’anisotropie et en particulier de la fabrique d’un matériau granulaire soumis à un chargement externe, cinq essais de compression biaxiaux ont été réalisé sur un assemblage de grains quasi-sphériques placés dans une chambre confinée. Des photos ont été prises pendant les tests et ont été enregistrées selon une fréquence définie. Un programme écrit sous Matlab a été utilisé pour traiter les photos, obtenir le champ de déplacement et analyser les résultats. Un intérêt particulier a concerné l’orientation des contacts, le tenseur de fabrique et son évolution durant le chargement. L'impact de certains facteurs clés tels que la densité de compactage, la pression de confinement, la taille des plateaux de chargement, la taille des particules et l’épaisseur des échantillons sur la déformation des échantillons ont été étudiés. Une attention particulière s’est portée sur les grains subissant une rupture. Nous avons déterminé le nombre de contact sur ces grains et les avons reproduits, dans le modèle numérique (grain 3D) soumis à un chargement diamétral, par le biais de contraintes cinématiques / The mechanical behaviour of granular materials is deeply related to both the individual particle properties and to the assembly of grains (fabric, void distribution …). Subjected to an external loading, the assembly deforms which is not only dependent on relative grain displacements but also on the grain deformation and to grain breakage when occurring. Experimental and numerical studies of single particles were performed. Four approximately spherical particles of light expanded clay were tested to investigate the breakage phenomenon under diametric displacement-controlled compression load. Photos were taken with a frame rate of 4 images per second during the testing. Since the interior of a heterogeneous particle has significant influence on the failure initiation, an X-Ray micro tomography system was used to scan particles. Moreover, the post-processing enables us to obtain the real 3D volumetric structure. Then a 3D numerical model including pore structure was built in Abaqus for the same loading conditions. A comparison of results from laboratory tests and simulations was made. Based on the results, the crack initiation process, its location and classification of particle failures were set. For purpose of understanding the anisotropy and in particular fabric of packing of granular material when disturbed under external loading, five biaxial compression tests were performed on an assembly of approximately spherical particles settled in a chamber under confining pressure. During the test, photos were taken by the camera and saved to a computer at periodic intervals. Software written with Matlab codes was used to process the photos, determine the displacement field and analyse the results. Focus on contact orientation, fabric tensor and its evolution during testing were put on. Impact of some key factors such as packing density, confining pressure, sizes of the covers, sizes of the particles and thickness of samples on the packing characteristic were analysed. In order to understand mechanical behaviour and kinematic of multiple particles under external load considering particle breakage, six biaxial compression tests were performed on an assembly of approximately spherical particles. Photos were taken to record the location of each particle during the tests. Software written with of Matlab codes was used to process the photos and trace the displacement of all particles in order to analyze kinematical behaviour of the particles. A particular attention was payed to given particles subjected grain breakage within the assembly. Their contacts and relative displacements were introduced in the numerical model of single grain breakage and conclusions were derived

O processo de Biorreatores com Membranas (BRM) foi desenvolvido no final da década de 1960, consistindo em um sistema que associa o tratamento biológico de efluentes com o mecanismo de separação por membranas, e apresenta vantagens com relação ao tratamento convencional, tais como maior eficiência de tratamento e um menor espaço físico de instalação para a mesma capacidade de tratamento. O fenômeno de incrustação das membranas (em inglês, fouling) representa a principal limitação desse processo, de modo que uma das condições operacionais mais importantes na prevenção da incrustação em um sistema BRM Submerso (BRMS) é a vazão de aeração. Diante desta situação, o objetivo do trabalho consiste em avaliar os efeitos das condições hidrodinâmicas no desempenho do processo, tais como vazão de aeração, densidade de empacotamento do módulo de membranas e geometria dos aeradores. O sistema utilizado no trabalho consistiu em um BRMS automatizado, operando em pressão constante e de forma contínua, durante um período de 4 dias. Os módulos foram construídos com membranas poliméricas de microfiltração do tipo fibra oca, cujo material foi a poli(éter)-imida (PEI). Três diferentes vazões de aeração foram estudadas (2, 5 e 8 L.min-1), mostrando, a partir dos resultados, que existe uma vazão de aeração limite benéfica ao sistema e que, acima deste valor, um melhor desempenho não pode ser atingido, inclusive, podendo prejudicá-lo. Para o sistema de estudo, a vazão de 5 L.min-1 apresentou o melhor desempenho, seguido de 8 e 2 L.min-1. O estudo da densidade de empacotamento do módulo mostrou que esta é uma variável que também exerce influência no desempenho do processo de BRMS. Módulos com dois diferentes diâmetros foram testados (2,54 cm e 1,91 cm); o melhor resultado foi observado no módulo de maior diâmetro. A menor densidade de empacotamento resulta em um maior espaçamento entre as fibras, provocando uma aeração mais homogênea no interior do feixe de membranas. As duas geometrias de aeração testadas (Modo 1 e Modo 2) apresentaram resultados semelhantes de fluxo permeado, indicando que o Modo 2 de aeração não melhorou o desempenho do processo como se esperava. A maior homogeneidade de aeração no interior de feixe, a partir de aeradores construídos com as próprias fibras, não foi atingida, mostrando que um novo projeto de aeradores deve ser estudado. Em todas as condições hidrodinâmicas testadas, a eficiência do tratamento foi verificada, uma vez que a remoção de matéria orgânica para COT e DQO foi de 96% e 93%, respectivamente. Propriedades do permeado, como condutividade elétrica, pH e turbidez foram mensuradas, apresentando variações menores que as medidas do efluente, revelando a capacidade que o sistema apresenta em suportar as variações na corrente de alimentação. / The Membrane Bioreactor (MBR) process was developed in the late 1960. The system consists in a combination of biological process and membrane separation mechanism, and the advantages with respect of conventional treatment are the higher treatment efficiency and a smaller area of installation for the same treatment capacity. The main limitation of this process is the membrane fouling, in a way that air flow rate represents an important operating condition to prevent the fouling formation in Submerged Membrane Bioreactors (SMBR). In this sense, the aim of this work is to evaluate the effects of hydrodynamic conditions on process performance, such as air flow rate, packing density of the membrane module and aeration geometry. The system used consists in a pilot-scale SMBR, which operates at constant pressure and continuous mode during a period of 4 days. The modules were built with hollow fiber polymeric microfiltration membrane and the material is poly(ether)imide (PEI). For the three different air flow rates studied (2, 5 and 8 L.min-1), results showed there is a limit value for this parameter, in which above this value a better performance will not be obtained, even can be worse. The air flow rate of 5 L.min-1 presented the best performance, followed by 8 and 2 L.min-1. The module packing density study for two diameters (0.75 and 1 inch), the best result was observed in the larger diameter module, because lower packing density causes more space between fibres, increasing the aeration homogeneity inside de fibre bundle. Both aeration geometry tested showed similar permeate flows, indicating the different geometry used did not affect the performance process. The aerators constructed with the hollow fibers did not promote aeration homogeneity inside the bundle, and new aeration geometry must be projected. For all hydrodynamics conditions, the system treatment was efficient in removing organical matter, since the removal for TOC and COD was 96% and 93%, respectively. Permeate properties such as electrical conductivity, pH and turbidity measurements presented minor variations than effluent properties measurements, showing the system capacity to withstand with feed stream variations.

O processo de Biorreatores com Membranas (BRM) foi desenvolvido no final da década de 1960, consistindo em um sistema que associa o tratamento biológico de efluentes com o mecanismo de separação por membranas, e apresenta vantagens com relação ao tratamento convencional, tais como maior eficiência de tratamento e um menor espaço físico de instalação para a mesma capacidade de tratamento. O fenômeno de incrustação das membranas (em inglês, fouling) representa a principal limitação desse processo, de modo que uma das condições operacionais mais importantes na prevenção da incrustação em um sistema BRM Submerso (BRMS) é a vazão de aeração. Diante desta situação, o objetivo do trabalho consiste em avaliar os efeitos das condições hidrodinâmicas no desempenho do processo, tais como vazão de aeração, densidade de empacotamento do módulo de membranas e geometria dos aeradores. O sistema utilizado no trabalho consistiu em um BRMS automatizado, operando em pressão constante e de forma contínua, durante um período de 4 dias. Os módulos foram construídos com membranas poliméricas de microfiltração do tipo fibra oca, cujo material foi a poli(éter)-imida (PEI). Três diferentes vazões de aeração foram estudadas (2, 5 e 8 L.min-1), mostrando, a partir dos resultados, que existe uma vazão de aeração limite benéfica ao sistema e que, acima deste valor, um melhor desempenho não pode ser atingido, inclusive, podendo prejudicá-lo. Para o sistema de estudo, a vazão de 5 L.min-1 apresentou o melhor desempenho, seguido de 8 e 2 L.min-1. O estudo da densidade de empacotamento do módulo mostrou que esta é uma variável que também exerce influência no desempenho do processo de BRMS. Módulos com dois diferentes diâmetros foram testados (2,54 cm e 1,91 cm); o melhor resultado foi observado no módulo de maior diâmetro. A menor densidade de empacotamento resulta em um maior espaçamento entre as fibras, provocando uma aeração mais homogênea no interior do feixe de membranas. As duas geometrias de aeração testadas (Modo 1 e Modo 2) apresentaram resultados semelhantes de fluxo permeado, indicando que o Modo 2 de aeração não melhorou o desempenho do processo como se esperava. A maior homogeneidade de aeração no interior de feixe, a partir de aeradores construídos com as próprias fibras, não foi atingida, mostrando que um novo projeto de aeradores deve ser estudado. Em todas as condições hidrodinâmicas testadas, a eficiência do tratamento foi verificada, uma vez que a remoção de matéria orgânica para COT e DQO foi de 96% e 93%, respectivamente. Propriedades do permeado, como condutividade elétrica, pH e turbidez foram mensuradas, apresentando variações menores que as medidas do efluente, revelando a capacidade que o sistema apresenta em suportar as variações na corrente de alimentação. / The Membrane Bioreactor (MBR) process was developed in the late 1960. The system consists in a combination of biological process and membrane separation mechanism, and the advantages with respect of conventional treatment are the higher treatment efficiency and a smaller area of installation for the same treatment capacity. The main limitation of this process is the membrane fouling, in a way that air flow rate represents an important operating condition to prevent the fouling formation in Submerged Membrane Bioreactors (SMBR). In this sense, the aim of this work is to evaluate the effects of hydrodynamic conditions on process performance, such as air flow rate, packing density of the membrane module and aeration geometry. The system used consists in a pilot-scale SMBR, which operates at constant pressure and continuous mode during a period of 4 days. The modules were built with hollow fiber polymeric microfiltration membrane and the material is poly(ether)imide (PEI). For the three different air flow rates studied (2, 5 and 8 L.min-1), results showed there is a limit value for this parameter, in which above this value a better performance will not be obtained, even can be worse. The air flow rate of 5 L.min-1 presented the best performance, followed by 8 and 2 L.min-1. The module packing density study for two diameters (0.75 and 1 inch), the best result was observed in the larger diameter module, because lower packing density causes more space between fibres, increasing the aeration homogeneity inside de fibre bundle. Both aeration geometry tested showed similar permeate flows, indicating the different geometry used did not affect the performance process. The aerators constructed with the hollow fibers did not promote aeration homogeneity inside the bundle, and new aeration geometry must be projected. For all hydrodynamics conditions, the system treatment was efficient in removing organical matter, since the removal for TOC and COD was 96% and 93%, respectively. Permeate properties such as electrical conductivity, pH and turbidity measurements presented minor variations than effluent properties measurements, showing the system capacity to withstand with feed stream variations.

Die vorliegende Thesis befasst sich mit der Mischungsentwicklung eines zementreduzierten Ökobetons für die Verwendung in einem ökologisch verbesserten Deckensystem. Dafür wurden mithilfe eines in Microsoft Excel aufgestellten physikalischen Analysemodells – dem Compaction-Interaction Packing Model nach FENNIS – Rezepturen entwickelt, die durch eine optimierte Packungsdichte einen geringeren Zementleimbedarf aufweisen. Dabei gelang es, Zement teilweise durch feine Kalksteinmehle zu ersetzen und eine CO2-sparende Mischung mit einem reduzierten Zementgehalt von 150 kg je Kubikmeter Beton herzustellen, welche die an sie gestellten Anforderungen erfüllt – u. a. bezogen auf Festigkeit (Festigkeitsklasse C 20/25), Verarbeitbarkeit (Konsistenzklasse C3) und Alkalität (pH-Wert > 10). Diese Eigenschaften wurden experimentell geprüft. Zwar wurden bei der auf empirischen Daten beruhenden Prognose von Festigkeit und Konsistenz im Modell nur teilweise realitätsnahe Werte ermittelt, das Modell stellte sich insgesamt jedoch als zielführendes Instrument bei der Mischungsentwicklung von Ökobetonen heraus.:1 Einleitung 2 Verringerung der Umwelteinwirkungen bei der Betonherstellung 3 Methodik der Mischungsentwicklung zementreduzierter Ökobetone 4 Packungsdichteberechnung mit dem Compaction-Interaction Packing Model nach FENNIS 5 Mischungsentwicklung eines Ökobetons im Rahmen des Forschungsvorhabens GRO-COCE 6 Herstellung der Auswahlmischungen und experimentelle Ermittlung von Betoneigenschaften 7 Eingrenzung einer Zielmischung 8 Diskussion der Ergebnisse 9 Zusammenfassung und Ausblick / The present thesis deals with the mix development of a cement-reduced eco-concrete for the use in an ecologically improved ceiling system. For this purpose, a physical analysis model built in Microsoft Excel – the Compaction-Interaction Packing Model according to FENNIS – was used to develop recipes which, due to an optimised packing density, have a low cement paste requirement. It was possible to partially replace cement with fine limestone powders and to produce a CO2-saving mixture with a reduced cement content of 150 kg per cubic metre of concrete, which meets the requirements placed on it – among other things with regard to strength (strength class C 20/25), workability (consistency class C3) and alkalinity (pH-value > 10). These properties were tested experimentally. Although only partially realistic values were determined in the model for the prediction of strength and consistency based on empirical data, the model turned out to be a suitable instrument for mix developments of eco-concretes.:1 Einleitung 2 Verringerung der Umwelteinwirkungen bei der Betonherstellung 3 Methodik der Mischungsentwicklung zementreduzierter Ökobetone 4 Packungsdichteberechnung mit dem Compaction-Interaction Packing Model nach FENNIS 5 Mischungsentwicklung eines Ökobetons im Rahmen des Forschungsvorhabens GRO-COCE 6 Herstellung der Auswahlmischungen und experimentelle Ermittlung von Betoneigenschaften 7 Eingrenzung einer Zielmischung 8 Diskussion der Ergebnisse 9 Zusammenfassung und Ausblick

Doctoral thesis „Ballistic-proof concretes“ deals with description, design and development of material based on ultra-high performance fibre reinforced cementitious composite with increased ballistic resistance i.e. increased resistance against high-strain rate dynamic loading induced by interaction of high-velocity moving objects. High mechanical properties, essential for such a material, are reached especially by maximal reduction of water-to-binder coefficient using high-range water reducing agents, high-strength aggregates and dense structure by precise selection and dosage of raw materials in the recipe. The main goal is to prepare a methodology for design of such a materials, observation of material behaviour on ballistic loading and quantitative description of material response for protective structures design. Properties of designed materials within this thesis are comparing with properties of commercially available and commonly used cementitious composites in order to create a concept for material limits in the field of ballistic protection. This concept enables to estimate ballistic protection of present or newly-designed materials and structures.

Bei der Verwendung von Hartkugelpackungen als Modelle für verschiedene Systeme in Physik, Chemie und den Ingenieurwissenschaften kommen einige Fragen auf, z.B. nach dem Zusammenhang zwischen der Packungsdichte und der Radienverteilung der Kugeln bzw. der Packungsstruktur. Der erste Teil dieser Arbeit beschäftigt sich mit dem Problem der optimalen Packungsdichte von zufällig dichten Packungen. Es wird ein Optimierungsalgorithmus vorgestellt, der aus einer vorgegebenen Klasse von Radienverteilungen diejenige bestimmt, für die die Packungsdichte maximal wird. Die Packungsstruktur kann man durch verschiedene statistische Größen charakterisieren, die im zweiten Teil dieser Arbeit beschrieben werden. Dabei wird die Abhängigkeit dieser Größen von der Packungsdichte und der Radienverteilung untersucht und gezeigt, dass in monodispersen Packungen mit zunehmender Dichte erhebliche strukturelle Veränderungen auftreten: Im Dichteintervall zwischen 0,64 und 0,66 erfolgt offenbar ein Übergang von ungeordneten zu kristallinen Packungen, bei weiterer Verdichtung entwickelt sich schließlich eine FCC-Struktur.

Ultrasound directed self-assembly (DSA) utilizes the acoustic radiation force associated with a standing ultrasound wave field to organize particles dispersed in a fluid medium into specific patterns. The ability to tailor the organization and packing density of spherical particles using ultrasound DSA in a viscous fluid medium is crucial in the context of (additive) manufacturing of engineered materials with tailored properties. However, the fundamental physics of the ultrasound DSA process in a viscous fluid medium, and the relationship between the ultrasound DSA process parameters and the specific patterns of particles that result from it, are not well-understood. Researchers have theoretically described the acoustic radiation force and the acoustic interaction force that act on spherical particles in a standing ultrasound wave field in both inviscid and viscous media. In addition, they have solved the forward and inverse ultrasound DSA problem in an inviscid medium, in which they relate the patterns of particles and the ultrasound DSA operating parameters. However, no theoretical model exists that allows simulating the steady-state and transient local particle packing density in a viscous medium during ultrasound DSA. Thus, in this dissertation, we (i) theoretically derive and experimentally validate a model to determine the steady-state locations where spherical particles assemble during ultrasound DSA as a function of medium viscosity and particle volume fraction. (ii) We also theoretically derive and experimentally validate a model to quantify the steady-state and transient local packing density of spherical particles within the pattern features that result from ultrasound DSA. Using these models, we quantify and predict the locations where spherical particles assemble during ultrasound DSA in a viscous medium, considering the effects of medium viscosity and particle volume fraction. We demonstrate that the deviation between locations where particles assemble in viscous and inviscid media first increases and then decreases with increasing particle volume fraction and medium viscosity, which we explain by means of the sound propagation velocity of the mixture. In addition, we quantify and predict the steady-state and transient local packing density of spherical particles within the pattern features, using ultrasound DSA in combination with vat photopolymerization (VP). We show that the steady-state local particle packing density increases with increasing particle volume fraction and increases with decreasing particle size. We also show that the transient local particle packing density increases with increasing particle volume fraction, decreasing particle size, and decreasing fluid medium viscosity. Increasing particle size and decreasing fluid medium viscosity decreases the time to reach steady-state. Finally, we implement single and multiple scattering in the calculation of the acoustic radiation force for spherical particles in a viscous medium and quantify their relative contributions to the calculation of the acoustic radiation force as a function of ultrasound DSA operating parameters and material properties. We demonstrate that the deviation between considering single and multiple scattering may reach up to 100%, depending on the ultrasound DSA process parameters and material properties. Also, increasing the particle volume fraction increases the need to account for multiple scattering. Quantifying and predicting the local packing density of spherical particles during ultrasound DSA in a viscous medium, as a function of ultrasound DSA process parameters is crucial towards using ultrasound DSA in engineering applications, in particular (additive) manufacturing of engineered polymer matrix composite materials with tailored properties whose properties depend on the spatial organization and packing density of particles in the matrix material. / Doctor of Philosophy / Ultrasound directed self-assembly (DSA) is a technique that uses ultrasound waves to arrange small particles submerged in a fluid into specific patterns. When combined with other manufacturing techniques, ultrasound DSA can be used to fabricate composite materials that derive their properties from the spatial organization of particles in a matrix material. However, ultrasound DSA in viscous fluids is not well-understood. Researchers have studied the forces associated with ultrasound waves that move small spherical particles in an inviscid fluid medium (fluids that experience little to no internal resistance to flow), and they have demonstrated intricate control of the patterns of particles that form using ultrasound DSA. However, that knowledge is not currently available for ultrasound DSA in viscous media. In this dissertation, we develop and evaluate theoretical models to understand ultrasound DSA of small spherical particles in a viscous fluid medium. We simulate where particles organize and how densely they pack together. We also determine the difference of the time-dependent motion of particles in a viscous fluid compared to that in an inviscid fluid medium and relate the difference to the number of particles submerged in the fluid and the viscosity of the fluid. Additionally, we examine the effect of particle size and fluid viscosity on the speed by which the particles reach their final location. We also study how ultrasound waves interact with multiple small particles in a viscous fluid, focusing on the forces that move these particles. We explore two models that account for single and multiple ultrasound wave scattering. Scattering is the process by which ultrasound waves deflect in different directions when they encounter a particle. The results show that the difference between single and multiple scattering models can be significant, depending on the ultrasound DSA process parameters and the properties of the fluid and particles. In general, the importance of accounting for multiple scattering increases with the number of particles submerged in the fluid. Understanding particle packing density when using ultrasound DSA in a viscous fluid is essential in many engineering applications, in particular manufacturing of composite materials that derive their properties from the spatial arrangement of particles in a matrix material.

Le béton conventionnel (BC) a de nombreux problèmes tels que la corrosion de l’acier d'armature et les faibles résistances des constructions en béton. Par conséquent, la plupart des structures fabriquées avec du BC exigent une maintenance fréquent. Le béton fibré à ultra-hautes performances (BFUP) peut être conçu pour éliminer certaines des faiblesses caractéristiques du BC. Le BFUP est défini à travers le monde comme un béton ayant des propriétés mécaniques, de ductilité et de durabilité supérieures. Le BFUP classique comprend entre 800 kg/m³ et 1000 kg/m³ de ciment, de 25 à 35% massique (%m) de fumée de silice (FS), de 0 à 40%m de poudre de quartz (PQ) et 110-140%m de sable de quartz (SQ) (les pourcentages massiques sont basés sur la masse totale en ciment des mélanges). Le BFUP contient des fibres d'acier pour améliorer sa ductilité et sa résistance aux efforts de traction. Les quantités importantes de ciment utilisées pour produire un BFUP affectent non seulement les coûts de production et la consommation de ressources naturelles comme le calcaire, l'argile, le charbon et l'énergie électrique, mais affectent également négativement les dommages sur l'environnement en raison de la production substantielle de gaz à effet de serre dont le gas carbonique (CO[indice inférieur 2]). Par ailleurs, la distribution granulométrique du ciment présente des vides microscopiques qui peuvent être remplis avec des matières plus fines telles que la FS. Par contre, une grande quantité de FS est nécessaire pour combler ces vides uniquement avec de la FS (25 à 30%m du ciment) ce qui engendre des coûts élevés puisqu’il s’agit d’une ressource limitée. Aussi, la FS diminue de manière significative l’ouvrabilité des BFUP en raison de sa surface spécifique Blaine élevée. L’utilisation du PQ et du SQ est également coûteuse et consomme des ressources naturelles importantes. D’ailleurs, les PQ et SQ sont considérés comme des obstacles pour l’utilisation des BFUP à grande échelle dans le marché du béton, car ils ne parviennent pas à satisfaire les exigences environnementales. D’ailleurs, un rapport d'Environnement Canada stipule que le quartz provoque des dommages environnementaux immédiats et à long terme en raison de son effet biologique. Le BFUP est généralement vendu sur le marché comme un produit préemballé, ce qui limite les modifications de conception par l'utilisateur. Il est normalement transporté sur de longues distances, contrairement aux composantes des BC. Ceci contribue également à la génération de gaz à effet de serre et conduit à un coût plus élevé du produit final. Par conséquent, il existe le besoin de développer d’autres matériaux disponibles localement ayant des fonctions similaires pour remplacer partiellement ou totalement la fumée de silice, le sable de quartz ou la poudre de quartz, et donc de réduire la teneur en ciment dans BFUP, tout en ayant des propriétés comparables ou meilleures. De grandes quantités de déchets verre ne peuvent pas être recyclées en raison de leur fragilité, de leur couleur, ou des coûts élevés de recyclage. La plupart des déchets de verre vont dans les sites d'enfouissement, ce qui est indésirable puisqu’il s’agit d’un matériau non biodégradable et donc moins respectueux de l'environnement. Au cours des dernières années, des études ont été réalisées afin d’utiliser des déchets de verre comme ajout cimentaire alternatif (ACA) ou comme granulats ultrafins dans le béton, en fonction de la distribution granulométrique et de la composition chimique de ceux-ci. Cette thèse présente un nouveau type de béton écologique à base de déchets de verre à ultra-hautes performances (BEVUP) développé à l'Université de Sherbrooke. Les bétons ont été conçus à l’aide de déchets verre de particules de tailles variées et de l’optimisation granulaire de la des matrices granulaires et cimentaires. Les BEVUP peuvent être conçus avec une quantité réduite de ciment (400 à 800 kg/m³), de FS (50 à 220 kg/m³), de PQ (0 à 400 kg/m³), et de SQ (0-1200 kg/m³), tout en intégrant divers produits de déchets de verre: du sable de verre (SV) (0-1200 kg/m³) ayant un diamètre moyen (d[indice inférieur 50]) de 275 µm, une grande quantité de poudre de verre (PV) (200-700 kg/m³) ayant un d50 de 11 µm, une teneur modérée de poudre de verre fine (PVF) (50-200 kg/m³) avec d[indice inférieur] 50 de 3,8 µm. Le BEVUP contient également des fibres d'acier (pour augmenter la résistance à la traction et améliorer la ductilité), du superplastifiants (10-60 kg/m³) ainsi qu’un rapport eau-liant (E/L) aussi bas que celui de BFUP. Le remplacement du ciment et des particules de FS avec des particules de verre non-absorbantes et lisse améliore la rhéologie des BEVUP. De plus, l’utilisation de la PVF en remplacement de la FS réduit la surface spécifique totale nette d’un mélange de FS et de PVF. Puisque la surface spécifique nette des particules diminue, la quantité d’eau nécessaire pour lubrifier les surfaces des particules est moindre, ce qui permet d’obtenir un affaissement supérieur pour un même E/L. Aussi, l'utilisation de déchets de verre dans le béton abaisse la chaleur cumulative d'hydratation, ce qui contribue à minimiser le retrait de fissuration potentiel. En fonction de la composition des BEVUP et de la température de cure, ce type de béton peut atteindre des résistances à la compression allant de 130 à 230 MPa, des résistances à la flexion supérieures à 20 MPa, des résistances à la traction supérieure à 10 MPa et un module d'élasticité supérieur à 40 GPa. Les performances mécaniques de BEVUP sont améliorées grâce à la réactivité du verre amorphe, à l'optimisation granulométrique et la densification des mélanges. Les produits de déchets de verre dans les BEVUP ont un comportement pouzzolanique et réagissent avec la portlandite générée par l'hydratation du ciment. Cependant, ceci n’est pas le cas avec le sable de quartz ni la poudre de quartz dans le BFUP classique, qui réagissent à la température élevée de 400 °C. L'addition des déchets de verre améliore la densification de l'interface entre les particules. Les particules de déchets de verre ont une grande rigidité, ce qui augmente le module d'élasticité du béton. Le BEVUP a également une très bonne durabilité. Sa porosité capillaire est très faible, et le matériau est extrêmement résistant à la pénétration d’ions chlorure (≈ 8 coulombs). Sa résistance à l'abrasion (indice de pertes volumiques) est inférieure à 1,3. Le BEVUP ne subit pratiquement aucune détérioration aux cycles de gel-dégel, même après 1000 cycles. Après une évaluation des BEVUP en laboratoire, une mise à l'échelle a été réalisée avec un malaxeur de béton industriel et une validation en chantier avec de la construction de deux passerelles. Les propriétés mécaniques supérieures des BEVUP a permis de concevoir les passerelles avec des sections réduites d’environ de 60% par rapport aux sections faites de BC. Le BEVUP offre plusieurs avantages économiques et environnementaux. Il réduit le coût de production et l’empreinte carbone des structures construites de béton fibré à ultra-hautes performances (BFUP) classique, en utilisant des matériaux disponibles localement. Il réduit les émissions de CO[indice inférieur 2] associées à la production de clinkers de ciment (50% de remplacement du ciment) et utilise efficacement les ressources naturelles. De plus, la production de BEVUP permet de réduire les quantités de déchets de verre stockés ou mis en décharge qui causent des problèmes environnementaux et pourrait permettre de sauver des millions de dollars qui pourraient être dépensés dans le traitement de ces déchets. Enfin, il offre une solution alternative aux entreprises de construction dans la production de BFUP à moindre coût. / Abstract : Conventional concrete (CC) may cause numerous problems on concrete structures such as corrosion of steel reinforcement and weaknesses of concrete construction. As a result, most of structures made with CC require maintenance. Ultra-high-performance concrete (UHPC) can be designed to eliminate some of the characteristic weaknesses of CC. UHPC is defined worldwide as concrete with superior mechanical, ductility, and durability properties. Conventional UHPC includes between 800 and 1000 kg/m³ of cement particles, 25–35%wt of silica fume (SF), 0–40 wt% of quartz powder (QP), and 110–140 wt% quartz sand (QS) (the percentages are based on the total cement content of the mix by weight). UHPC contains steel fibers to improve its ductility and tension capacity. The huge amount of cement used to produce UHPC not only affects production costs and consumes natural resources, limestone, clay, coal, and electric power, but it also negatively impacts the environment through carbon dioxide (CO[subscript 2]) emissions, which can contribute to the greenhouse effect. Additionally, the particle-size distribution (PSD) of cement exhibits a gap at the micro scale that needs to be filled with more finer materials such as SF. Filling this gap solely with SF requires a high amount of SF (25% to 30% by cement weight) which is a limited resource and involves high cost. This significantly also decreases UHPC workability due to high Blaine surface area of SF. QS and QP use is also costly and consumes natural resources. As such, they are considered as impedances for wide use of UHPC in the concrete market and fail to satisfy sustainability requirements. Furthermore, based on an Environment Canada report, quartz causes immediate and long-term environmental harm because its biological effect makes it an environmental hazard. Furthermore, UHPC is generally sold on the market as a prepackaged product, which limits any design changes by the user. Moreover, it is normally transported over long distances, unlike CC components. This increases to the greenhouse-gas effect and leads to higher cost of the final product. Therefore, there is a vital need for other locally available materials with similar functions to partially or fully replace silica fume, quartz sand, or quartz powder, and thereby reduce the cement content in UHPC, while having comparable or better properties. In some countries, and Canada in particular, large quantities of glass cannot be recycled because of the high breaking potential, color mixing, or high recycling costs. Most waste glass goes into landfill sites, which is undesirable since it is not biodegradable and less environmentally friendly. In recent years, attempts have been made to use waste glass as an alternative supplementary cementitious material (ASCM) or ultra-fine aggregate in concrete, depending on its chemical composition and particle-size distribution (PSD). This thesis is based on a new type of ecological ultra-high-performance glass concrete (UHPGC) developed at the Université de Sherbrooke. The concrete’s design involved using waste glass of varying particle-size distributions obtained from cullets and optimizing the packing density of the entire material matrix. UHPGC can be designed with a reduced amount of cement (400–800 kg/m³), silica fume (SF) (50–220 kg/m³), quartz powder (QP) (0–400 kg/m³), and quartz sand (QS) (0–1200 kg/m³), while incorporating various waste-glass products: glass sand (GS) (0–1200 kg/m³) with an average mean diameter (d[subscript 50]) of 275 μm, a high amount of glass powder (GP) (200–700 kg/m³) with average diameter (d[subscript 50]) of 11 μm, a moderate content of fine glass powder (FGP) (50–200 kg/m³) with d[subscript 50] of 3.8 μm. UHPGC also contains steel fibers (to increase tensile strength and improve ductility) and superplasticizer (10–60 kg/m³) as well as having a water-to-binder ratio (w/b) as low as that of UHPC. Replacing cement and silica-fume particles with non-absorptive and smooth glass particles improves UHPGC rheology. Furthermore, using FGP as a SF replacement reduces the net total surface area of a SF and FGP blend. This decreases the net particle surface area, it reduces the water needed to lubricate particle surfaces and increases the slump flow at the same w/b. Moreover, the use of waste glass material in concrete leads to lower cumulative heat of hydration, which helps minimize potential shrinkage cracking. Depending on UHPGC composition and curing temperature, this type of concrete yields compressive strength ranging from 130 up to 230 MPa, flexural strength above 20 MPa, tensile strength above 10 MPa, and elastic modulus above 40 GPa. The mechanical performance of UHPGC is enhanced by the reactivity of the amorphous waste glass and optimization of the packing density. The waste-glass products in UHPGC have pozzolanic behavior and react with the portlandite generated by cement hydration. This, however, is not the case with quartz sand and quartz powder in conventional UHPC, which react at high temperature of 400 °C. The waste-glass addition enhances clogging of the interface between particles. Waste-glass particles have high rigidity, which increases the concrete’s elastic modulus. UHPGC also has extremely good durability. Its capillary porosity is very low, and the material is extremely resistant to chloride-ion permeability (≈ 8 coulombs). Its abrasion resistance (volume loss index) is less than 1.3. UHPGC experiences virtually no freeze–thaw deterioration, even after 1000 freeze–thaw cycles. After laboratory assessment, the developed concrete was scaled up with a pilot plane and field validation with the construction of two footbridges as a case study. The higher mechanical properties allowed for the footbridges to be designed with about sections reduced by 60% compared to normal concrete. UHPGC offers several economic and environmental advantages. It reduces the production cost of ultra-high-performance concrete (UHPC) by using locally available materials and delivers a smaller carbon footprint than conventional UHPC structures. It reduces the CO[subscript 2] emissions associated with the production of cement clinkers (50% replacement of cement) and efficiently uses natural resources. In addition, high amounts of waste glass cause environmental problems if stockpiled or sent to landfills. Moreover, the use of waste glass in UHPGC could save millions of dollars that would otherwise be spent for treatment and placing waste glass in landfills. Lastly, it provides an alternative solution to the construction companies in producing UHPC at lower cost.

Das grundlegende Verständnis von Selbstorganisationsprozessen auf molekularem Niveau ist von entscheidender Bedeutung für den Fortschritt der Nanotechnologie. In diesem Zusammenhang werden hier Untersuchungen derartiger Prozesse an der Grenzfläche zwischen einer flüssigen Phase (z.B. einer Lösung) und einer kristallinen Festkörperoberfläche durchgeführt. Die Konzentration der Lösung und die Polarität des Lösungsmittels sind von entscheidender Bedeutung für die Kontrolle der durch Selbstorganisation gebildeten Strukturen von Molekülen an den flüssig-fest Grenzflächen zu einem Graphitsubstrat (HOPG). Im Mittelpunkt der vorliegenden Arbeit stehen die Einflüsse dieser beiden Parameter auf die Anordnung der Moleküle. Zunächst wird die Polarität der Lösungsmittel diskutiert. Lösungsmittel mit verschiedenen Polaritäten wie Phenyloctan (unpolar), Fettsäuren (moderat polar) und Fettalkohole (stark polar) wurden verwendet um Trimesinsäure (TMA) zu lösen. TMA bildet keine geordnete Struktur aus wenn es aus Phenyloctan (PO) abgeschieden wird. Ein poröses Muster ("Chicken-wire"-Struktur) entsteht aus der Lösung von TMA in Octansäure, wohingegen aus der Lösung von TMA in Undecanol ein Linienmuster durch Koadsorption von TMA und Undecanol Molekülen gebildet wird. Als nächstes werden die Auswirkungen der Ultraschallbehandlung der Lösungen zur Kontrolle der Konzentration der Lösung und die daraus resultierende unterschiedliche molekulare Packungsdichte und Strukturen beschrieben. Eine selbstassemblierte Struktur aus Zick-Zack-Dimerketten wird bei der TMA-PO Lösung nur beobachtet, wenn die Lösung für 5 Stunden Ultraschall ausgesetzt wurde. Die hoher Packungsdichte in Form der "Flower"-Struktur wird für Lösungen von TMA in Octansäure gefunden, nachdem diese für lange Zeit mit Ultraschall behandelt wurden. Ein weiterer Aspekt der vorliegenden Arbeit ist die entdeckte Veresterungsreaktion an der TMA-undecanol/HOPG Grenzfläche. 1-undecyl Monoester von TMA wurde überraschender Weise an dieser Grenzfläche gefunden, nachdem die TMA-Undecanol Lösungen, für lange Zeit Ultraschall ausgesetzt wurden. Diese Monoestermoleküle bilden sich an der flüssig-fest Grenzfläche allein auf Grund der erhöhten Konzentration von TMA (ohne jegliche externe Katalysatoren). Der physikalische Hintergrund der Prozesse des Lösens und der Ultraschallbehandlung sind der Gegenstand weiterer Untersuchungen. Selbstassemblierte Abscheidung tritt auch bei Verwendung nur der reinen Lösungsmittel (Octansäure beziehungsweise Undecanol) auf, was zu verschiedenen Mustern führt, welche ebenfalls durch Ultraschallbehandlung kontrolliert eingestellt werden können.:LIST OF ABBREVIATIONS 6 CHAPTER I: INTRODUCTION 7 CHAPTER II: BASIC PRINCIPLES 10 II.1. Principles of scanning tunneling microscopy (STM) 10 II.2. Scanning tunneling microscopy at the liquid-solid interface (LSI) 15 II.3.The interactions between solvent and solute molecules in the solution 18 II.4. The interactions between molecules and the substrate 21 II.5. Solvent effects on self-assembly at the liquid-solid interface 23 II.5.1. Solvent co-adsorption effect 23 II.5.2. Solvent influences polymorphism 24 II.5.3. The influence of solvent functionality on self-assembled structures 25 II.6. Ultrasonic influences on concentration of solution 25 CHAPTER III: EXPERIMENTAL SECTION 28 III.1. Solute: Trimesic acid (TMA) (C6H3(COOH)3) 28 III.2. Solvents 28 III.2.1. Strong non-polar solvent: phenyloctane (octylbenzene) (C14H22) 29 III.2.2. Medium polar solvents: alkanoic acids (CnH2n+1COOH, n = 6, 7, 8) 29 III.2.3. Strong polar solvents: alkanoic alcohols (CnH2n+1OH, n = 10, 11) 30 III.3. Preparation of solutions 32 III.4. Substrates 33 III.5. Tip preparation 34 CHAPTER IV: SELF-ASSEMBLY OF TRIMESIC ACID (TMA) CONTROLLED BY SOLVENT POLARITY AND CONCENTRATION OF SOLUTION 36 IV.1. Trimesic acid (TMA) dissolved in a strong non-polar phenyloctane (PO) solvent 36 Results and discussion 37 Summary 46 IV.2. TMA dissolved in medium polar solvents, alkanoic acids 47 IV.2.1. TMA in octanoic acid at different sonication time 49 IV.2.2. TMA in heptanoic and nonanoic acids at different sonication time 56 Summary 57 IV.3. TMA dissolved in strong polar alkanoic alcohol solvents 58 IV.3.1. Linear pattern (LP) from non-sonicated solutions of TMA - undecanol 59 IV.3.2. High density linear pattern from 2 hours sonicated solutions of TMA - undecanol 61 IV.3.3. LP and ester formations from solutions of TMA in undecanol sonicated over extended time (4, 6, and 8 hours) 63 IV.3.4. Monoester at HOPG substrate-undecanol interface 65 IV.3.5. Linear pattern (LP) and ester formation from TMA-decanol solution 72 Summary 73 CHAPTER V: SELF-ASSEMBLY OF SOLVENT MOLECULES INFLUENCED BY SONICATION TIME 75 V.1. Self-assembly of octanoic acid on HOPG controlled by sonication time 75 V.1.1. Self-assembly of octanoic acid from 0-2 hours sonicated liquid on HOPG 76 V.1.2. Patterns deposited from 3 to 10 hours sonicated octanoic acid liquids 78 V.2. Self-assembly of undecanol on HOPG controlled by sonication time 79 V.2.1. Undecanol on HOPG at 0- 2 hours sonication 80 V.2.2. Undecanol on HOPG from 4- 6 hours sonicated liquids 82 CHAPTER VI: SUMMARY AND OUTLOOK 85 APPENDIX 89 REFERENCES 93 ERKLÄRUNG 108 CURRICULUM VITAE 109 ACKNOWLEDGEMENT 110