A nanotecnologia é um fenômeno que se aplica a praticamente todos os setores da ciência, sendo que na área cosmética o elevado investimento neste campo tem reforçado a idéia de que produtos nanotecnológicos proporcionam vantagens reais aos consumidores. A crescente exigência do consumidor e os avanços no conhecimento sobre obtenção e estabilidade dos sistemas dispersos viabilizam o desenvolvimento de veículos diferenciados como, por exemplo, nanoemulsões, que além da inerente estabilidade, apresentam aspecto sensorial agradável, alta capacidade de espalhabilidade e hidratação, além de poderem facilitar a penetração de ativos. Existem dois métodos de obtenção de nanoemulsões: os que empregam baixa ou alta energia de emulsificação. O uso de óleos vegetais em produtos cosméticos tem sido intensamente valorizado, baseando-se no conceito de que são seguros e biocompatíveis. O óleo de maracujá é extensamente empregado em formulações cosméticas e o óleo essencial de lavanda é citado na literatura pelo efeito cicatrizante e antiinflamatório, dentre outros. Esta pesquisa teve como objetivo desenvolver nanoemulsões à base de óleo de maracujá e óleo essencial de lavanda nas concentrações de 1,0, 2,0 e 5,0%, a partir de método a frio de baixa energia de emulsificação, bem como avaliar a influência da adição de outros componentes e dos parâmetros relacionados ao método de obtenção na estabilidade e tamanho de glóbulos das nanoemulsões e posteriormente avaliar a atividade antiinflamatória tópica da emulsão contendo 5,0% do óleo essencial em camundongos sem pêlo. Os resultados demonstraram que a adição do óleo essencial de lavanda no sistema provocou redução no tamanho de glóbulos e aumento da estabilidade física e que o método de emulsificação a frio foi eficaz na formação de nanoemulsões estáveis. O valor de EHL, o par de tensoativos, a proporção entre as fases aquosa/ oleosa e tensoativa, bem como a adição de silicones e eletrólitos e a velocidade de agitação influenciam sobremaneira as características e a estabilidade das dispersões obtidas. No estudo de estabilidade acelerada, observou-se a alteração significativa dos valores de pH e condutividade elétrica, o que possivelmente é decorrente da hidrólise de compostos presentes no óleo essencial. Os valores de potencial zeta e tamanho de glóbulos não demonstraram alteração relevante em 30 dias de estabilidade acelerada. Na avaliação in vivo, a nanoemulsão adicionada de 5,0% do óleo essencial de lavanda apresentou resultados significativos quando comparado aos demais grupos, o que sugere boa perspectiva na utilização tópica do óleo essencial de lavanda, sendo este merecedor de estudos complementares para a elucidação dos mecanismos antiinflamatórios envolvidos, dos componentes fito-químicos responsáveis por esta ação e da concentração a ser utilizada. / Nanotechnology is a phenomenon that applies to mainly all sectors of science and in the cosmetics area the high investment in this field has strengthened the idea that nanotechnology products offer real advantages to consumers. The growing demand of consumers and the advances in knowledge about production and stability of dispersed systems enable the development of differentiated vehicles such as nanoemulsions, which besides the inherent stability, have pleasant sensory aspect, high spread ability and hydration power, in addition they can facilitate the penetration of actives. There are two methods of obtaining nanoemulsions: those that employ low or high energy of emulsification. The use of vegetable oils in cosmetics has been intensely valued, based on the concept that is safe and biocompatible. Passion fruit oil is widely used in cosmetic formulations and lavender essential oil is reported in the literature for healing and anti-inflammatory effects, among others. The aim of this study was to develop nanoemulsion based in passion fruit oil and lavender essential oil in the concentrations of 1.0, 2.0 and 5.0%, from low-energy method of emulsification, not employing heating, and evaluate the influence of the addition of other materials and parameters related to the production method in the system stability and droplets size of nanoemulsions and then evaluate the anti-inflammatory activity of topical nanoemulsion containing 5.0% of lavender essential oil in hairless mice. The results demonstrated that the addition of lavender essential oil in the system caused reduction in the droplets size and increasing in the physical stability and that the method of emulsification used was effective in the formation of stable nanoemulsions. The HLB value, the pair of surfactants, the ratio between aqueous/oily and surfactant phase, the addition of silicones and electrolytes and speed of agitation particularly affect the characteristics and stability of the obtained dispersions. In the accelerated stability tests, there was a significant change in the pH and electrical conductivity values, which is possibly resulting from the hydrolysis of compounds present in the essential oil. The values of zeta potential and droplets size showed no relevant change in 30 days of accelerated stability. In the in vivo evaluation, the nanoemulsion added of 5.0% of the lavender essential oil showed significant results when compared to the other groups, which suggests good perspective on topical use of this oil, which is worthy of further studies to the elucidation of the anti-inflammatory mechanisms involved, the phyto-chemical components responsible for this action and the concentration of use.

A técnica da Distribuição do Tamanho de Cristais - DTC (Crystal Size Distribution - CSD), que relaciona a densidade de cristais com a distribuição do tamanho, foi aplicada à população de plagioclásio de diques máficos do Enxame de Cabo Frio - Búzios (RJ). Os diques possuem larguras variáveis, de alguns centímetros a 20 metros, e orientação em torno de N45E. A textura dos diques é geralmente fina, localmente microporfirítica e intergranular no centro dos diques mais largos. Bordas resfriadas de alguns centímetros de largura são frequentes nos contatos com as rochas metamórficas encaixantes. Foram estudados dois diques na Praia das Conchas com espessura de 0,8m e 8,2m e, um outro na Praia da Lagoinha, com 2m de largura. As amostras foram coletadas junto às margens (~10 cm do contato) e no centro dos diques. O tamanho médio dos cristais de plagioclásio varia de 0,07 a 0,13 mm na borda dos diques mais finos (<= 2 m de largura) e de 0,09 a 0,20 mm na borda do dique mais largo. No centro do dique de Lagoinha e no dique largo de Praia das Conchas o tamanho de plagioclásio é da ordem de 0,19 ± 0,02 mm e 0,60 ± 0,07 mm, respectivamente. As DTCs nas bordas dos diques, independentemente de sua largura, mostraram um padrão tipicamente encurvado, e que tem sido atribuído na literatura como evidência para misturas de magmas com populações de cristais de tamanhos distintos. No entanto, no centro do dique largo (8,2m) de Praia das Conchas, a DTC é log-linear consistente com uma cristalização magmática simples. A química mineral mostrou que os cristais maiores (precoces) de plagioclásio apresentam um teor mais elevado em An (bytownita-labradorita) que os cristais menores (tardios) da matriz (labradorita-andesina). Além disso, a olivina é mais rica em Fo na borda que no centro do dique e, respectivamente, o piroxênio mais enriquecido em Ca. Esses resultados indicam que as margens resfriadas são mais máficas que o centro sugerindo uma evolução química normal com o resfriamento do magma. Portanto, as DTCs encurvadas provavelmente refletem taxas de cristalização heterogêneas possivelmente induzidas pela despressurização durante a ascensão do magma basáltico seguida de rápido resfriamento. O padrão da DTC log-linear no centro do dique de 8,2m de largura é atribuído ao maior tempo de residência do magma que favoreceria os processos de difusão química e re-equilíbrio textural. Os cálculos da taxa de resfriamento utilizando a inclinação da DTC permitiram estimar que o centro do dique largo da Praia das Conchas estaria completamente cristalizado (~ 900 °C) em torno de 73 dias. O estudo da Orientação Preferencial de Forma (OPF) de plagioclásio mostrou que a petrotrama tende a isotrópica nas margens dos diques com largura menor que 2 metros, o que poderia refletir uma rápida cristalização de plagioclásio por despressurização. Quando a trama é localmente definida, como no dique largo da Praia das Conchas, a lineação de plagioclásio é subhorizontal sugerindo que o fluxo magmático moveu-se predominantemente na lateral do dique. / The method of Crystal Size Distribution (CSD), which relates crystal density with size distribution, has been applied on the plagioclase population of the Mafic Dyke Swarm of Cabo Frio-Búzios (RJ). The dykes are NE-trending with widths from a few centimetres to 20m. The texture is generally fine grained and locally microporphyritic and intergranular at the center of the larger dykes. Chilled margins of a few centimetres in width are common at contacts with the metamorphic basement. Two dykes of 0.8m and 8.2m in width of the Conchas Beach and another of 2m in width at the Lagoinha Beach have been studied. Samples were collected at the margins (~10cm from the contact) and at the center of the dykes. The average characteristic size of the plagioclase crystals varies from 0.07 to 0.13mm at the margins of the narrow dykes (<=2m of width) and from 0.09 to 0.20mm at the margins of the large dyke. At the center of the Lagoinha and Conchas dykes the plagioclase size varies from 0.19 ±0.02mm and 0.60±0.07mm respectively. The CSDs at the dyke margins, irrespective of the dyke width, are typically concave-up, and in literature such patterns have been attributed as evidence of magma mixing with distinct crystal populations. However, at the center of the largest dyke (8.2m) of Conchas Beach, the CSD is log-linear, consistent with simple steady-state crystallization pattern. The mineral chemistry shows that the plagioclase phenocrysts have a high An content (bytownite-labradorite) than the groundmass grains (labradorite-andesine). At the margins olivine is richer in Fo than at the center, and respectively, pyroxene is richer in Ca. These results indicate that the chilled margin is more mafic than the center suggesting a normal chemical evolution in a cooling magma. Nevertheless, the concave-up CSDs probably depict heterogeneous crystallization rates possibly induced by depressurization during the ascent of the basaltic magma followed by rapid cooling. The log-linear CSD pattern at the center of the Conchas dyke (8.2m width) is attributed to a higher residence time of the magma which favors the processes of chemical diffusion and textural re-equilibration. The calculated cooling rates using the CSD slope enables us to estimate that the larger dyke of Conchas would be completely crystallized (at ~900oC) in 73 days. The study of the Shape Preferred Orientation (SPO) in plagioclase shows an isotropic petrofabric at the margins of the dykes <=2m, which could reflect a rapid crystallization of plagioclase by depressurization. When the fabric is defined, as in the larger Conchas Beach dyke, the plagioclase lineation is subhorizontal, suggesting that the magma flow was predominantly lateral to the dyke plane.

Neste trabalho estudou-se a copolimerização em emulsão de estireno e acrilato de butila em processo semicontínuo onde o produto final é um látex com alto teor de sólidos. Foi dado enfoque à distribuição de tamanhos de partículas do látex e seus efeitos no produto. Foi realizada uma série de experimentos de copolimerização em emulsão em um reator de vidro, empregando receitas com teores de sólidos de até 64% em massa. Durante os experimentos, amostras eram retiradas periodicamente do reator visando analisar o teor de polímeros (conversão dos monômeros) por gravimetria, a concentração de monômero residual por cromatografia gasosa headspace, o diâmetro médio das partículas por espectroscopia de espalhamento dinâmico de luz e a distribuição de tamanhos de partículas por microscopia eletrônica de transmissão. A viscosidade do látex final era obtida em viscosímetro Brookfield. Aplicando estratégias para renucleação de novas partículas no decorrer do processo, foram obtidos látices com distribuição bimodal de tamanhos de partículas e com viscosidades reduzidas. Aplicou-se um modelo matemático para descrever o processo, incluindo a evolução no tempo da distribuição de tamanhos de partículas, calculada a partir de equações de balanço populacional para as partículas e para os radicais dentro das partículas. Para a solução das equações empregou-se discretização por método de classes e a técnica de pivô fixo. O modelo tem apenas dois parâmetros ajustáveis, referentes às eficiências de captura de radicais por micelas e por partículas. Estes parâmetros foram ajustados para os dados experimentais de um ensaio, e usados, sem reajuste, para outros ensaios em condições diferentes. Os resultados do modelo mostraram boa adequação aos resultados experimentais. / The aim of this work was the study of the high solid contents emulsion copolymerization of styrene and butyl acrylate in semi-batch process. In this context the particle size distribution and its effects on the product viscosity was studied. Copolymerization reactions were carried out in a glass reactor, and recipes with solid contents up to 64 wt.% were used. During each run, samples are periodically taken from the reactor, and analysis are performed to measure the polymer content (monomer conversion) by gravimetry, the concentrations of the residual monomers by head-space gas chromatography, the average particle size by dynamic light scattering, and the particle size distribution by transmission electronic microscopy. The viscosity of the final emulsion is also measured using a Brookfield viscosimeter. By applying operating strategies to nucleate new particles along the process, latexes with bimodal particle size distributions and low viscosities were obtained. A mathematical model was employed for simulating the polymerization process, including the evolution of the particle size distribution along the process, calculated from population balance equations for the particles and the radicals inside the particles. The numerical solution was obtained using the discretized population balance equations by the method of classes and the fixed pivot technique. The model has only two adjustable parameters, the efficiencies for radical capture by micelles and by particles. These two parameters were fitted to the experimental data of one run and used, without further readjustment, for other runs under different conditions. The model results presented satisfactory agreement with the experimental data.

Skanskas bergtäkt, Vikan kross, i Göteborg producerar ett ersättningsmaterial till naturgruset i form av helkrossad betongballast. Utvinningen av naturgrus ska fasas ut eftersom det utvinns från grusåsar vilket är negativt för naturen då grusåsarna renar vatten och fungerar som naturliga vattenreservoarer. Historiskt sett har naturgruset använts till betongtillverkning under en väldigt lång tid och år 2013 investerade Vikan kross i en anläggning för att kunna producera helkrossad betongballast och på så vis fasa ut naturgruset från deras betongtillverkning. År 2014 stod anläggningen klar för att börja tillverka helkrossad betongballast. En lång uppstartsperiod där många tester utfördes för att få den helkrossade betongballasten att efterlikna naturgruset i form och egenskaper. I dagsläget producerar Vikan kross en bra ersättningsprodukt till naturgruset men produktionsledning har kommit underfund med att fuktkvoten på det ingående materialet till vindsikten har en stor påverkan på slutprodukten. Skanska gav mig i uppdrag att undersöka hur vindsiktens inställningar bör justeras beroende på vilken fuktkvot det ingående materialet har för att kunna bibehålla en acceptabel kornstorleksfördelning. Skanska har även önskemål att mängden filler (ballastkorn mindre än 63 μm) i slutprodukten skall öka från den mängd som finns i slutprodukten i dagsläget. En provtagningsplan baserad på tidigare tester och erfarenheter upprättades för att på så vis kunna följa vägen fram till ett bra resultat. Metoden som använts är provtagning av det ingående materialet samt det utgående materialet från vindsikten. Materialen har analyserats med hjälp av siktanalyser där kornstorleksfördelning har tagits fram. Vindsiktens inställningar har sedan varierats och ytterligare provtagning samt analyser har genomförts. När vindsikten ansågs producera helkrossad betongballast med så bra kornstorleksfördelning som möjligt bevattnades det ingående materialet till vindsikten. Vatten tillfördes för att höja fuktkvoten och på så vis förstå hur vindsiktens inställningar bör justeras för att behålla kornstorleksfördelningen inom de gränsvärden som finns. Resultatet visar att om det ingående materialet till vindsikten har en avvikande fuktkvot (&gt; 1 vikt-%) är det möjligt att erhålla en kornstorleksfördelning som efterliknar den kornstorleksfördelning som erhålls när materialet har en normal fuktkvot (&lt; 1 vikt-%). Mängden filler har inte ökat i slutprodukten eftersom att den ingående mängden filler till vindsikten redan är så låg att den inte går att justera med hjälp av enbart vindsikten. Orsaken till att mängden filler är lägre än vad som tidigare observerats kopplas till bergets geologi. Det berg som krossats under testperioden var väldigt hårt och där med produceras en mindre mängd filler. För en ökad mängd filler i slutprodukten krävs en förändring i krossprocessen före vindsikten. / Skanska Asfalt och Betong AB is the owner of the quarry Vikan kross in Gothenburg. They produce manufactured sand as a replacement product for the natural sand that is used in todays fin aggregates for concrete production. The Swedish government is limiting the extraction of natural sand because of environmental reasons. In 2013 Vikan kross invested in a plant to produce manufactured sand thus phasing out the natural sand from their concrete production. In 2014 the plant was ready to start producing manufactured sand. Through a long start-up period, many tests were done to get the manufactured sand to mimic the natural sand as much as possible. Today Vikan kross is producing a good replacement product for the natural sand, but the production team has come to the conclusion that the moisture content in the input material to the air classifier has a major impact on the final product. Skanska assigned me to investigate how the air classifiers settings should be adjusted depending on the moister content of the input material in order to maintain an acceptable particle size distribution. Skanska also wished that the amount of fines (particles smaller than 63 μm) in the manufactured sand should increase from the amount present today. A plan based on previous tests and experiences was set up in order to reach a good result. The method used was to take tests of the input materials as well as the output materials from the air classifier. The materials have been analyzed by using sieving methods to determinate the particle size distribution. The settings of the air classifier were then adjusted and further tests and analysis was done. When the air classifier was producing manufactured sand with a particle size distribution as good as possible, the input material was watered. Water was added to raise the moisture content to understand how the settings of the air classifier should be adjusted to maintain a particle size distribution within the limit values. The result shows that if the input material to the air classifier has a deviating moisture content (&gt; 1 wt-%) it is possible to obtain a particle size distribution that mimics the particle size distribution obtained when the material has a normal moisture content (&lt;1 wt-%). The amount of fines has not increased in the manufactured sand because the amount of fines in the input material is already so low that it can’t be adjusted by only changing the settings of the air classifier. The reason for the amount of fines being lower than previously observed is linked to the geology of the material. The material that had been crushed during this test period was very hard and thus produced a small amount of fines. For an increased amount of fines in the manufactured sand, a change is necessary in the process prior to the air classifier.

Les modèles d'érosion et de transport couramment utilisés sont construits à partir de données empiriques obtenues avec des sédiments de granulométries quasi uniformes. Or, il y a beaucoup de situations pour lesquelles la granulométrie des sédiments n’est pas uniforme. Les expériences réalisées en laboratoire et dans les rivières montrent que l’érosion et le transport des sédiments dépendent de la dispersion du diamètre des grains. Cette observation est à l’origine de cette thèse qui a pour objectif l’étude de l’influence de la distribution du diamètre des grains sur le transport de sédiments. Cette influence est envisagée à partir du développement d’un modèle numérique. La prédiction de l’érosion et du transport de sédiments tient de la résolution de deux problèmes : le premier est lié à l’écoulement au dessus du lit, le second à la mise en mouvement du sédiment. Le modèle développé détermine explicitement le mouvement des grains dans le lit de sédiments lorsque sa face supérieure est soumise à un écoulement. Pour cela, il mobilise la Méthode des Eléments Discrets (DEM), développée par Cundall et Strack (1979). Afin de reproduire l’effet de la topographie du lit sur le champ de vitesse du fluide, le modèle DEM est couplé avec le modèle d’écoulement FLOWSTAR. Le modèle FLOWSTAR est proposé par Carruthers et al. (2004) pour déterminer l’écoulement moyen dans une couche limite turbulente atmosphérique au-dessus des collines de faible pente. Le modèle numérique développé est appliqué à différents types d’arrangements de grains. Il permet d’estimer l’évolution du débit de sédiments au cours du temps pour différentes vitesses de frottement. Les seuils d’érosion des lits et l’évolution des débits de sédiments en fonction de la vitesse de frottement sont conformes à l’expérience. L’utilisation de l’approche DEM permet par ailleurs de connaître le comportement des grains dans et à la surface du lit au cours du temps (profil vertical de la vitesse des grains à l’intérieur de l’arrangement par exemple) / The models for the erosion and transport of sediments that are currently used rely on empirical data obtained from experiments with sediments having a uniform or unimodal distribution. But there are many practical situations for which the size distribution is significantly different from this assumed distribution, and laboratory and field experiments have shown that the erosion threshold and the transport rate depend on the size distribution and the range of particle sizes. The aim of this study is therefore to investigate and explain the influence of size distribution on erosion and transport rates, using a numerical model that has been developed specifically to study this problem. The sediment bed is assumed to consist of individual, non-cohesive, spherical particles, and the physical interactions between the particles are modelled explicitly, using the Discrete Element Method developed by Cundall and Strack (1979). The flow above the bed is computed using the FLOWSTAR model (Carruthers et al 2000) which was originally developed to compute the flow in the atmospheric boundary layer above arbitrary topography. These two models are coupled, and the resulting numerical code has been used to investigate the temporal evolution of erosion and transport rates agree well with experimental measurements, and the DEM provides additional information concerning the temporal evolution of the particle size distribution within the bed.

Phenomenon of industrial grounds placed near residential areas can be frequently detected in European cities, which may cause decrease of air quality in these areas. The aim of this diploma thesis is to determine level of concentration and size distribution of aerosol in the planetary boundary layer above the residential area and industrial complex of Škoda auto a.s. in Mladá Boleslav city by using remotely controlled airship. Thereby, the thesis extends terrestrial experiment realized in February and March 2013 which revealed no significant impact of industry and traffic on air quality. Size distribution and concentration of aerosol particles in range from 11.5nm to 10µm with integration time one second or one minute (depending on measure mode - SINGLE or SCAN) was measured by two aerosol spectrometers placed in dirigible gondola during 13 flights on February 11, 2015. SINGLE mode lead the airship in one stable flight level during one flight above residential area and industrial complex of Škoda auto a.s. Whereas SCAN mode changed flight level every two minutes during the flight of airship above sports fields in residential zone only. Exhausts of car painting halls and place of automobile loading were identified as the sources of nanoparticles, PM1 a PM2.5 and coarse aerosol in the industrial area...

Doctor of Philosophy / Department of Biological & Agricultural Engineering / Ronaldo G. Maghirang / Nanostructured particles possess unique chemical and physical properties, making them excellent candidates for air purification, smoke clearing, and obscuration. This research was conducted to investigate the aerodynamic, charging, and infrared (IR) extinction properties of nanostructured particles. Specific objectives were to: (1) measure the size distribution and concentration of aerosolized nanostructured particles; (2) evaluate their IR extinction properties; (3) determine their relative chargeability; and (4) numerically model their transport in enclosed rooms. The size distribution and concentration of two nanostructured particles (NanoActive® MgO and MgO plus) were measured in an enclosed room. The particles differed in size distribution and concentration; for example, the geometric mean diameters of NanoActive® MgO and MgO plus were 3.12 and 11.1 [Mu]m, respectively. The potential of nanostructured particles as IR obscurants was determined and compared with other particles. Four groups of particles were considered: nanostructured particles (NanoActive® MgO plus, MgO, TiO[subscript2]); nanorods (MgO, TiO[subscript2]); conventional particles (NaHCO[subscript3] and ISO fine test dust); and common obscurants (brass, graphite, carbon black). The extinction coefficients of the nanostructured particles were generally significantly smaller than those of the other particles. Graphite flakes had the greatest mass extinction coefficient (3.22 m[superscript2]/g), followed by carbon black (1.72 m[superscript2]/g), and brass flakes (1.57 m[superscript2]/g). Brass flakes had the greatest volume extinction coefficient (1.64 m[superscript2]/cc), followed by NaHCO[subscript3] (0.93 m[superscript2]/cc), and ISO fine test dust (0.91 m[superscript2]/cc). The relative chargeability of nanostructured particles was also investigated. Selected particles were passed through a Teflon tribocharger and their net charge-to-mass ratios were measured. Tribocharging was able to charge the particles; however, the resulting charge was generally small. NanoActive® TiO[subscript2] gained the highest net charge-to-mass ratio (1.21 mC/kg) followed by NanoActive® MgO (0.81 mC/kg) and ISO fine test dust (0.66 mC/kg). The transport of NanoActive® MgO plus and hollow glass spheres in an enclosed room was simulated by implementing the discrete phase model of FLUENT. In terms of mass concentrations, there was reasonable agreement between predicted and measured values for hollow glass spheres but not for NanoActive® MgO plus. In terms of number concentration, there was large discrepancy between predicted and measured values for both particles.

L’objectif du présent projet est de développer une méthodologie pour la modélisation fondamentale de procédés de polymérisation en émulsion sans tensioactif stabilisés par des particules inorganiques, dénommées "polymérisation en émulsion Pickering". La modélisation des systèmes de polymérisation en émulsion nécessite la modélisation de la distribution de taille des particules (PSD), qui est une propriété importante d'utilisation finale du latex. Cette PSD comprend des sous-modèles dédiés à la nucléation des particules, le transfert de masse entre les différentes phases (monomère, radicaux, stabilisant) et la coagulation des particules. Ces modèles devraient de préférence être validés expérimentalement de manière individuelle. La première partie principale du travail est consacrée à l'étude expérimentale. Cette partie peut être divisée en trois parties. La première partie décrit l'adsorption de particules inorganiques sur le polymère sans réaction. Une adsorption multicouche a été observée et l’isotherme B.E.T. a été capable de décrire cette adsorption. L'adsorption se révèle être plus importante pour une force ionique plus élevée. La dynamique d'adsorption semple être rapide et par conséquent le partage peut être considéré à l'équilibre pendant la polymérisation. La deuxième partie concerne l'étude de différents paramètres de réaction sur le nombre de particules et la vitesse de réaction dans des polymérisations ab initio. L'effet du mélange, de la concentration initiale des monomères et de la concentration de l'initiateur a été étudié. L'optimisation de ces conditions a été utile pour la partie de modélisation. La dernière partie décrit les différences entre plusieurs Laponite® à travers la polymérisation en émulsion ab initio du styrène.La deuxième partie principale du manuscrit a porté sur la modélisation de la polymérisation en émulsion Pickering. Le modèle de bilan de population et le nombre moyen de radicaux par particule ont été calculés en fonction de l'effet des particules organiques. La croissance des particules de polymère a été optimisée en ajustant les modèles d'entrée et de désorption des radicaux décrits dans la littérature aux données expérimentales. Aucune modification n'a été nécessaire, ce qui nous a permis de conclure que l'argile n'avait aucune influence sur l'échange radical. Cependant, la stabilisation joue un rôle important dans la production de particules de polymère. Le modèle de nucléation coagulante a été capable de décrire le taux de nucléation et de prédire le nombre total de particules / The aim of the present project is to develop a methodology for fundamental modeling of surfactant-free emulsion polymerization processes stabilized by inorganic particles, referred to as “Pickering emulsion polymerization”. Modeling emulsion polymerization systems requires modeling the particle size distribution (PSD), which is an important end-use property of the latex. This PSD includes submodels dedicated to particle nucleation, mass transfer between the different phases (monomer, radicals, stabilizer), and particle coagulation. These models should preferably be individually identified and validated experimentally. The first main part of the work is dedicated to the experimental study. This part can be divided in three parts. The first part describes the adsorption of inorganic particles on polymer without reaction. Multilayer adsorption was observed and B.E.T. isotherm was able to describe this adsorption. The adsorption was found to be enhanced at higher ionic strength. The adsorption dynamics were found fast and therefore clay partitioning can be considered at equilibrium during polymerization. The second part concerned the investigation of different reaction parameters on the particles number and reaction rate in ab initio polymerizations. The effect of mixing, initial monomer concentration and initiator concentration were considered. Optimization of these conditions was useful for the modeling part. The last part described the differences between several LaponiteR_ grades through the ab initio emulsion polymerization of styrene. The second main part of the manuscript focused on the modeling of the Pickering emulsion polymerization. The population balance model and average number of radicals balance were adapted regarding the effect of inxi organic particles. The growth of the polymer particles was optimized by fitting the models of radicals’ entry and desorption described available in literature to the experimental data. No modification was needed, which allowed us to conclude that the clay had no influence on radical exchange. However, LaponiteR_ stabilization played an important role in polymer particles production. Coagulative nucleation model was able to describe the nucleation rate and predict the total number of particles

Black carbon (BC) is a complex mixture of polycondensed aromatic compounds produced by the incomplete combustion of biomass during events such as wildfires and the burning of fossil fuels. Black carbon was initially considered to be a refractory form of organic matter. However, recent studies have shown that BC can be quite mobile and reactive in the terrestrial environment. Black carbon can be translocated from soils and sediments in the form of dissolved BC (DBC). A global correlation between DBC and bulk dissolved organic carbon (DOC) has been established for fluvial systems where DBC comprises approximately 10% of the total DOC pool, which suggests that DBC may be a significant contributor to the global carbon cycle. The primary objective of this thesis was to further characterize DBC and elucidate some of the specific physical and chemical processes that promote its transfer to the aqueous phase and drive the DBC-DOC relationship. The molecular composition and qualitative distribution of DBC was assessed using Fourier transform ion cyclotron resonance mass spectrometry. Black carbon in both dissolved and particulate (PBC) phases was quantified by the benzenepolycarboxylic acid method. Dissolved BC was found to contain considerable amounts of nitrogen and the export of this dissolved black nitrogen was linked to watershed land use in global rivers. The riverine flux of PBC, a previously unstudied BC removal mechanism, was significantly increased by local wildfire activity. However in-stream DBC did not appear to be affected by short-term fire events. Once translocated to surface waters, DBC is susceptible to photodegradative processes. Dissolved BC in high molecular weight DOC fractions was more photoreactive than DBC associated with lower molecular weight fractions. In the coming decades, wildfire frequency is expected to increase with climate change and natural lands will continue to be altered for anthropogenic use. These processes have already been shown to significantly impact the composition of DOC and associated DBC exported to inland waters. The quality of DBC influences its stability in soil and resistance to degradation. Therefore, it is essential that we aim to fully understand DBC dynamics in natural systems in order to assess its contribution to global carbon cycling.

L’estimation quantitative des précipitations à l’échelle locale est une nécessité sociétale, à cause de l’augmentation des dégâts provoqués par des inondations exacerbées par l’urbanisation croissante. Or, des estimations locales sont particulièrement difficiles à réaliser à cause de la forte variabilité des précipitations. De plus, ce genre d’estimation est sollicité par de petits organismes tels qu’une commune, pour lesquels il n’est pas envisageable d’utiliser des instruments à la pointe de la recherche technologique à cause de leur coût prohibitif. Ainsi, il est nécessaire de développer des méthodes d’estimation quantitative des précipitations applicables à un dispositif expérimental de prix abordable. Dans ce but, un dispositif expérimental innovant est utilisé dans cette thèse. Il est constitué d’instruments de mesure directe, au sol, tels que des pluviomètres et des disdromètres, et d’un prototype de radar à balayage horizontal basé sur un radar nautique commercial, associé à un MRR (Micro Rain Radar) à visée verticale qui fournissent une estimation en altitude de la pluie, respectivement sur une surface donnée et le long d’un profil vertical. Le radar à balayage horizontal est un radar en bande X, c’est-à-dire qu’il fonctionne à une longueur d’onde lui procurant une très haute résolution radiale, mais qui est très atténuée par les précipitations. Le MRR permet d’obtenir une description précise de la microphysique des précipitations et sert de relais entre les mesures au sol et les mesures en altitude du radar en bande X. Ces deux radars étant novateurs, une grande partie de cette thèse consiste à valider leurs mesures : étalonnage, filtrage d’échos aberrants, correction de l’atténuation, etc. Une fois les mesures rendues exploitables, cette thèse se focalise sur l’étude de la variabilité des précipitations afin de proposer et développer différentes méthodes de classification, selon leur type ou leur variations locales, et de vérifier leur potentiel pour l’amélioration de l’estimation des précipitations. Les résultats montrent que cet objectif ne peut être atteint que si la qualité des mesures des radars est encore améliorée : moins d’échos parasites pour le radar en bande X et prise en compte du vent vertical pour le MRR. / Due to the increase of damage associated with floods enhanced by expanding urbanisation, the quantitative estimation of precipitation on a local scale is a societal need. However, such estimations are difficult because of the high variability of precipitation. Moreover, these estimations are requested by small organisations such as local authorities which cannot afford top level research instruments. Hence, new methods of estimation applicable to a cheap experimental set are needed. Toward this goal, an innovative experimental set is used in this work. It consists of ground instruments such as raingauges and disdrometers, and two radars, a prototype of a scanning radar based on a modified marine radar and a vertically pointing MRR (Micro Rain Radar), which give estimation of rain aloft, over an area and along a profile, respectively. The scanning radar works at X-band, meaning that it uses a longwave very attenuated by precipitation, but which provides a high range resolution. The MRR yields a detailed description of microphysics of precipitation and fills the gap between ground measurements and X-band radar measurements aloft. As both these radars are innovative, a large part of this PhD thesis was spent on the measurements validation : radar calibration, abnormal echoes filtering, attenuation consideration, etc. Using these corrected measurements, this PhD focus then on the study of the variability of precipitation, and aims to propose and develop several classification methods based on precipitation type or local variability, and to check their potential for the improvement of precipitation estimation. Results show that this goal can be reached only if the radar measurements quality is further improved : less interference echoes for the X-band radar, and consideration of vertical wind for the MRR.