Polymer/inorganic nanoparticle hybrid thin films, primarily composed of functional inorganic nanoparticles, are of great interest to researchers because of their interesting electronic, photonic, and optical properties. In the past two decades, layer-by-layer (LbL) assembly has become one of the most powerful techniques to fabricate such hybrid thin films. This method offers an easy, inexpensive, versatile, and robust fabrication technique for multilayer formation, with precisely controllable nanostructure and tunable properties. In this thesis, various ways to control the structure of hybrid thin films, primarily composed of polyelectrolytes and indium tin oxide (ITO), are the main topics of study. ITO is one of the most widely used conductive transparent oxides (TCOs) for applications such as flat panel displays, photovoltaic cells, and functional windows. In this work, polyethyleneimine (PEI) was used to stabilize the ITO suspensions and improve the film buildup rate during the LbL assembly of poly(sodium 4-styrenesulfonate) (PSS) and ITO. The growth rate was doubled due to the stronger interaction forces between the PSS and PEI-modified ITO layer. The assembly of hybrid films was often initiated by a polyelectrolyte precursor layer, and the characteristics of the precursor layer were found to significantly affect the assembly of the hybrid thin films. The LbL assembly of ITO nanoparticles was realized on several substrates, including cellulose fibers, write-on transparencies, silicon wafers, quartz crystals, and glasses. By coating the cellulose fibers with ITO nanoparticles, a new type of conductive paper was manufactured. By LbL assembly of ITO on write-on transparencies, transparent conductive thin films with conductivity of 10⁻⁴ S/cm and transparency of over 80 % in the visible range were also prepared. As a result of this work on the mechanisms and applications of LbL grown films, the understanding of the LbL assembly of polyelectrolytes and inorganic nanoparticles was significantly extended. In addition to working with ITO nanoparticles, this thesis also demonstrated the ability to grow bicomponent [PEI/SiO₂]n thin films. It was further demonstrated that under the right pH conditions, these films can be grown exponentially (e-LbL), resulting in much thicker films, consisting of mostly the inorganic nanoparticles, in much fewer assembly steps than traditional linearly grown films (l-LbL). These results open the door to new research opportunities for achieving structured nanoparticle thin films, whose functionality depends primarily on the properties of the nanoparticles.

<p>The object of this work is to obtain a fundamentalunderstanding of the principal issues concerning the handlingof an aqueous WC-Co powder suspension.</p><p>The WO3 surface layer on the oxidised tungsten carbidepowder dissolves at pH>3 with the tungsten concentrationincreasing linearly with time. Adding cobalt powder to thetungsten carbide suspension resulted in a significant reductionof the dissolution rate at pH<10. Electrokinetic studiesindicated that the reduced dissolution rate may be related tothe formation of surface complexes; the experiments showed thatCo species in solution adsorb on the oxidised tungsten carbidepowder.</p><p>The surface forces of oxidised tungsten and cobalt surfaceswere investigated using the atomic force microscope (AFM)colloidal probe technique. The interactions at various ionicstrengths and pH values are well described by DLVO theory. Theadsorption of cobalt ions to tungsten oxide surfaces resultedin an additional non-DLVO force and a reduced absolute value ofthe surface potential. It was shown that the adsorption ofpoly(ethylene imine) (PEI) to the WO3 surfaces induces anelectrosteric repulsion.</p><p>The properties of spray-dried WC-Co granules were related tothe WC primary particle size, and the poly(ethylene glycol)(PEG) binder and PEI dispersant content in aqueous WC-Cosuspensions. The granule characterisation includes a new methodfor measuring the density of single granules. The increase inthe fracture strength of granules produced from suspensionsthat were stabilised with PEI was related to a more densepacking of the WC-Co particles.</p><p>The AFM was used to study the friction and adhesion ofsingle spray-dried WC-Co granules containing various amounts ofPEG binder. The adhesion and friction force between two singlegranules (intergranular friction) and between a granule and ahard metal substrate (die-wall friction) have been determinedas a function of relative humidity. The granule-wall frictionincreases with binder content and relative humidity, whereasthe granule-granule friction is essentially independent of therelative humidity and substantially lower than the granule-wallfriction at all PEG contents.</p><p><b>Key words:</b>Hard Metal, Cemented Carbide, WC-Co, TungstenCarbide, Cobalt, Oxidation, Dissolution, Surface Complexation,XPS, AFM, Colloidal Probe, Hamaker Constant, Cauchy, WO3,CoOOH, ESCA, Zeta-Potential, Surface Potential, Poly(ethyleneimine), PEI, Suspension, van der Waals, Steric, Spray-Dried,Poly(ethylene glycol), Strength, Density, Friction, Adhesion,Granule, PEG, Pressing, FFM.</p>

Gegenstand dieser Arbeit war das Stabilitätsverhalten von binären kolloidalen Suspensionen mit hohen Feststoffkonzentrationen (z. B. keramische Suspensionen). Dabei wurde die Stabilität mit Hilfe des Sedimentationsverhaltens bewertet und mit dem Grenzflächenzustand korreliert, der als effektives Zetapotenzial erfasst wurde. Die Untersuchungen erfolgten an drei Oxiden mit unterschiedlichen physiko-chemischen Eigenschaften, wobei die Suspensionszusammensetzung und der pH-Wert über weite Bereiche variiert wurden. Ein wesentliches Ergebnis dieser Arbeit besteht im Nachweis, dass die Löslichkeit der einzelnen partikulären Komponenten in den binären Suspensionen zu einer gegenseitigen Beeinflussung der Grenzflächeneigenschaften führt und dadurch das Stabilitätsverhalten des gesamten Systems maßgeblich bestimmt. Von Relevanz ist zudem das Mischungsverhältnis, von dem zum einen das Löse- und Adsorptionsverhalten und zum anderen die Morphologie von Heteroaggregaten abhängt und das auf diese Weise auch für das makroskopische Verhalten entscheidend ist. Die Arbeit zeigt deutlich, dass das Reich der Kolloide neben universellen Mechanismen von stoffspezifischen Phänomenen beherrscht wird. Daraus folgt, dass eine allumfassende Behandlung der Stabilität nicht möglich ist. Vielmehr kann nur an Beispielen demonstriert werden, welche Art von Phänomenen auftreten und wie sie genutzt oder vermieden werden können.

Cancer is the second leading cause of death in the United States and its onset is highly incident in the lungs, with very low long-term survival rates. Chemotherapy plays a significant role for lung cancer treatment, and pulmonary delivery may be a potential route for anticancer drug delivery to treat lung tumors. Coenzyme Q₁₀ (CoQ₁₀) is a poorly-water soluble compound that is being investigated for the treatment of carcinomas. In this work, we hypothesize that formulations of CoQ10 may be developed for pulmonary delivery with a satisfactory pharmacokinetic profile that will have the potential to improve a pharmacodynamic response when treating lung malignancies. The formulation design was to use a vibrating-mesh nebulizer to aerosolize aqueous dispersions of CoQ₁₀ stabilized by phospholipids physiologically found in the lungs. In the first study, a method was developed to measure the surface tension of liquids, a physicochemical property that has been shown to influence the aerosol output characteristics from vibrating-mesh nebulizers. Subsequently, this method was used, together with analysis of particle size distribution, zeta potential, and rheology, to further evaluate the factors influencing the capability of this nebulizer system to continuously and steadily aerosolize formulations of CoQ₁₀ prepared with high pressure homogenization. The aerosolization profile (nebulization performance and in vitro drug deposition of nebulized droplets) of formulations prepared with soybean lecithin, dimyristoylphosphatidylcholine (DMPC), dipalmitoylphosphatidylcholine (DPPC) and distearoylphosphatidylcholine (DSPC) were evaluated. The rheological behavior of these dispersions was found to be the factor that may be indicative of the aerosolization output profile. Finally, the pulmonary deposition and systemic distribution of CoQ₁₀ prepared as DMPC, DPPC, and DSPC dispersions were investigated in vivo in mice. It was found that high drug amounts were deposited and retained in the mouse lungs for at least 48 hours post nebulization. Systemic distribution was not observed and deposition in the nasal cavity occurred at a lower scale than in the lungs. This body of work provides evidence that CoQ₁₀ may be successfully formulated as dispersions to be aerosolized using vibrating-mesh nebulizers and achieve high drug deposition in the lungs during inhalation. / text

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Cancer is the second leading cause of death in the United States and its onset is highly incident in the lungs, with very low long-term survival rates. Chemotherapy plays a significant role for lung cancer treatment, and pulmonary delivery may be a potential route for anticancer drug delivery to treat lung tumors. Coenzyme Q₁₀ (CoQ₁₀) is a poorly-water soluble compound that is being investigated for the treatment of carcinomas. In this work, we hypothesize that formulations of CoQ10 may be developed for pulmonary delivery with a satisfactory pharmacokinetic profile that will have the potential to improve a pharmacodynamic response when treating lung malignancies. The formulation design was to use a vibrating-mesh nebulizer to aerosolize aqueous dispersions of CoQ₁₀ stabilized by phospholipids physiologically found in the lungs. In the first study, a method was developed to measure the surface tension of liquids, a physicochemical property that has been shown to influence the aerosol output characteristics from vibrating-mesh nebulizers. Subsequently, this method was used, together with analysis of particle size distribution, zeta potential, and rheology, to further evaluate the factors influencing the capability of this nebulizer system to continuously and steadily aerosolize formulations of CoQ₁₀ prepared with high pressure homogenization. The aerosolization profile (nebulization performance and in vitro drug deposition of nebulized droplets) of formulations prepared with soybean lecithin, dimyristoylphosphatidylcholine (DMPC), dipalmitoylphosphatidylcholine (DPPC) and distearoylphosphatidylcholine (DSPC) were evaluated. The rheological behavior of these dispersions was found to be the factor that may be indicative of the aerosolization output profile. Finally, the pulmonary deposition and systemic distribution of CoQ₁₀ prepared as DMPC, DPPC, and DSPC dispersions were investigated in vivo in mice. It was found that high drug amounts were deposited and retained in the mouse lungs for at least 48 hours post nebulization. Systemic distribution was not observed and deposition in the nasal cavity occurred at a lower scale than in the lungs. This body of work provides evidence that CoQ₁₀ may be successfully formulated as dispersions to be aerosolized using vibrating-mesh nebulizers and achieve high drug deposition in the lungs during inhalation.

Attractive particle interactions which lead to the hetero-aggregation or 'sliming' of silicate clay gangue and valuable sulphide mineral particles are encountered in a number of hydrometallurgical and flotation processes. Sliming leads to poor recovery of the valuable minerals and high recovery of the clay gangue minerals in flotation concentrates. In the present work, the hetero-aggregation mechanism of hydrophilic mica clay mineral sericite (or muscovite) and hydrophobic chalcocite was investigated by probing the particle interactions and the prevailing interfacial chemistry under dispersion conditions where the individual chalcocite and sericite particles displayed negative zeta potentials. The mitigation/suppression of the hetero-aggregation was examined via the prudent control of dispersion conditions and pulp chemistry (i.e., pH modification and solution speciation control) and the use of two, anionic, polymeric dispersants with different molecular weight and functionality (carboxylate-substituted polyacrylamide, Cyquest 3223 and sulphonate-substituted polymaleic acid, P80 co-polymers) as dispersants. The adsorption behaviour of both polymers onto both minerals under industrially relevant suspension conditions have been quantified in terms of the polymer adsorption density and the adsorbed layer characteristics. These interfacial layer properties which impact on the mineral particles' zeta potentials and interactions, and also underpin the dispersion efficacy of polymers were characterized, using interfacial and solution analytical methods and TM-AFM imaging analysis.

La valorisation des minéraux calciques est un problème mondial. La flottation est une technique utilisée pour séparer ces minéraux puisqu’elle joue sur leurs propriétés superficielles. Cependant, c’est un défi scientifique important puisque les propriétés de surface des minéraux calciques sont très proches. Les difficultés de séparation de ces derniers sont donc dues, aux similitudes entre leurs propriétés chimiques de surface, mais aussi leurs propriétés électrocinétiques et leur stabilité en milieu aqueux. L’application des résultats de recherche fondamentale porte sur les minéraux purs dont 4 calcites et une apatite d’origines différentes. L’objectif principal est d’étudier les propriétés et les paramètres impliqués dans les mécanismes de séparation des minéraux calciques tels que l’importance de la solubilité, la spéciation de surface du minéral, la charge globale de la surface du minéral et la densité d’adsorption des tensio-actifs. Les propriétés électrocinétique permettent de déterminer le type de collecteur à employer pour faire flotter sélectivement les minéraux et pour choisir le pH optimal de séparation. Deux collecteurs, l’oléate et le linoléate de sodium (structure de la chaîne hydrocarbonée différente) ont été utilisés pour étudier la flottation des minéraux calciques. Une étude des mélanges de ces deux collecteurs avec différents ratios molaires a montré un contraste de séparation à pH 5 avec le ratio molaire 2 :1 à pH 5 et le ratio 1 :1 à pH 9. De plus, Les effets synergiques entre collecteur ionique (oléate ou linoléate de sodium) et non-ionique (PX type alcool) en présence ou non des déprimants tels que l’amidon et le silicate de sodium ont été étudiés pour améliorer la la sélectivité de la séparation calcite apatite. Les isothermes d’adsorption de l’oléate et du linoléate de sodium, en présence ou non d’un collecteur non-ionique, obtenus par la méthode de Gregory mettent en évidence leurs co-adsorption sur la surface de la calcite et de l’apatite. Ceci a aussi été confirmé par les déplacements des bandes de vibration symétriques et asymétriques des groupements CH2-CH3 sur les spectres infrarouges en réflexion diffuse. L’adsorption du linoléate de sodium sur la calcite orange présente différentes régions, ce qui peut être expliqué par une adsorption en multicouche résultant de la condensation bidimensionnelle du collecteur sur une surface hétérogène. Cependant, l’adsorption de l’oléate de sodium sur l’échantillon de calcite avec les impuretés de Mg est linéaire. L’apatite de Madagascar et la calcite optique présentent une saturation des sites d’adsorption à partir d’une concentration 3.10-5 M en oléate de sodium (CMC) / Valorization of calcium minerals is a global problem. Flotation is a technique used for the separation of these minerals since it plays on their surface properties. However, this is an important scientific challenge because the surface properties of calcium minerals are very similar. The difficulties of separation of these minerals are then due to the similarities between their chemical surface properties, but also their electrokinetic and their stability in aqueous solutions. The application of the basic research results will focus on 4 calcites and one apatite of different origins. The main objective is to study the properties and parameters involved in the separation mechanisms of calcium minerals such as the importance of the solubility, the surface speciation of the mineral, the overall loading of the mineral surface and the density of adsorption of surfactants. The electrokinetic properties therefore make it possible to determine the type of collector to be used to selectively float the minerals and to choose the optimum separation pH. Two collectors, sodium oleate and linoleate (different semi-developed formula), were used to study the flotation of calcium minerals. The mixture of these two collectors with different molar ratios was also studied showing a separation contrast at pH 5 with the molar ratio 2: 1 and the ratio 1: 1 at pH 9. In addition, the synergistic effects between ionic collector (oleate or sodium linoleate) and non-ionic (PX alcohol type) in the presence or absence of depressants such as starch and sodium silicate have been studied to improve recovery and selectivity. The adsorption isotherms of sodium oleate and linoleate, in the presence or absence of a non-ionic collector, obtained by the Gregory method demonstrate their co-adsorption on the surface of calcite and apatite. This was also confirmed by the displacements of the symmetric and antisymmetric vibration bands of the CH2-CH3 groups on the infrared spectra in diffuse reflectance. The adsorption of sodium linoleate on one of the calcite minerals (calcite orange) shows different regions which can be explained by multi-layer adsorption resulting from the two-dimensional condensation of the collector on a heterogeneous surface. However, the adsorption of sodium oleate on calcite orange is linear. The apatite from Madagascar and calcite optical have a saturation of the adsorption sites from a concentration of 3.10-5 M in sodium oleate (CMC)

This work focuses on the possibility of using recycled glass in the manufacture of blended portland cements. It examines the possibilities to improve pozzolanic properties of recycled glass with new milling processes, the formation of agglomerates material during the course of grinding and their subsequent effect on the hydration process of binders. It is also the optimization of the grinding process with respect to the wear of grinding bodies, grinding energy consumption and maximize the performance of the mill.

Protein (mis)folding into highly ordered, fibrillar structures, amyloid fibrils, is a hallmark of several, mainly neurodegenerative, disorders. The mechanism of this supra-molecular self-assembly reaction, as well as its relationship to protein folding are not well understood. In particular, the molecular origin of the metastability of the soluble state of proteins with respect to the aggregated states has not been clearly established. In this dissertation, it is demonstrated, that highly accurate kinetic experiments, using a novel biosensing method, can yield fundamental insight into the dynamics of proteins in the region of the free energy landscape corresponding to protein aggregation. First, a section on Method development describes the extension and elaboration of the previously established kinetic assay relying on quartz crystal microbalance measurements for the study of amyloid fibril elongation (Chapter 3). This methodology is then applied in order to study in great detail the origin of the various contributions to the free energy barriers separating the soluble state of a protein from its aggregated state. In particular, the relative importance of residual structure, hydrophobicity (Chapter 4) and electrostatic interactions (Chapter 5) for the total free energy of activation are discussed. In the last part of this thesis (Chapter 6), it is demonstrated that this biosensing method can also be used to study the binding of small molecules to amyloid fibrils, a very useful feature in the framework of the quest for potential inhibitors of amyloid formation. In addition, it is shown that Thioflavin T, to-date the most frequently employed fluorescent label molecule for bulk solution kinetic studies, can in the presence of potential amyloid inhibitor candidates be highly unreliable as a means to quantify the effect of the inhibitor on amyloid formation kinetics. In summary, the work in this thesis contributes to both the fundamental and the applied aspects of the field of protein aggregation.