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

This diploma thesis is focused on optimization of particle size distribution using concrete additions. To design a concrete of excellent properties, it is often necessary to achieve a higher packing density of the mixture by designing a suitable particle size distribution curve. Concrete with special properties and various types of powder additions are also described.

Active pharmaceutical ingredients (APIs) are frequently delivered to the patient in the solid-state as part of an approved dosage form (tablets, capsules, etc.). Understanding and controlling the solid-state chemistry of APIs is therefore an important aspect of the drug development process. APIs can exist in a variety of distinct solid forms, including polymorphs, solvates, hydrates, co-crystals and amorphous solids. Each form displays unique physicochemical properties that can profoundly influence the bioavailability, manufacturability, stability and other performance characteristics of the drug. Most APIs are purified and isolated by crystallisation from an appropriate solvent during the final step in synthetic process. The main objective of a crystallisation process is to produce crystals with desired properties such as particle size distribution (PSD), shape and purity. All pharmaceutical dosage forms must be produced in uniform units, and good content of uniformity is only possible when the size of the active component is carefully controlled. For on-line control of crystallisations of Quetiapine Fumarate to achieve desired PSD and no changed physicochemical purity was used the Lasentec Focus Beam Reflectance Measurement (FBRM) system.

Les Hydrocarbures Aromatiques Polycycliques (HAP) sont des polluants dont la concentration est réglementée dans l’air ambiant, en raison de leurs caractères cancérigène et/ou mutagène. Ces composés, émis lors de combustions incomplètes, peuvent réagir dans l’atmosphère avec les principaux oxydants atmosphériques pour former des dérivés oxygénés (OHAP) et nitrés (NHAP), dont la toxicité est potentiellement encore plus importante. Dans ce contexte, ce travail a été réalisé par la combinaison de deux approches complémentaires : études de réactivité en atmosphère contrôlée et études de terrain, afin de mieux comprendre le devenir (formation/dégradation) de ces composés dans l’atmosphère. Ainsi, des particules naturelles, prélevées dans l’air ambiant, ont été exposées en réacteur à différents oxydants atmosphériques(O3, OH et NO2/O3). Les résultats montrent la dégradation effective des HAP et le benzo[a]pyrène, seul HAP réglementé aujourd’hui en Europe, apparait comme le composé le plus réactif. De plus, la formation significative de OHAP et NHAP a été mise en évidence, même si les quantités observées sont trop faibles pour boucler le bilan de masse, illustrant la formation de produits non détectés/détectables dans ce travail. La dégradation des HAP ayant été démontrée sur des particules naturelles, la question du lieu majoritaire de dégradation (atmosphère/support de prélèvement) a été étudiée au cours de différents échantillonnages atmosphériques, mettant en parallèle des préleveurs équipés ou non de pièges à ozone de type dénudeur. Ces études, bien que n’ayant pas permis de répondre définitivement à cette question, ont montré la formation de certains dérivés de HAP sur les supports d’échantillonnage. Suite à ces conclusions, des mesures ont été déployées sur le terrain, sur des sites de typologies différentes dans la région parisienne. Les concentrations en HAP, OHAP et NHAP mesurées se sont avérées 10 fois plus importantes sur un site trafic que sur un site périurbain. De plus, les différentes espèces mesurées sur chacun des sites ont montré que, contrairement aux HAP et OHAP, les NHAP majoritaires différaient selon la typologie du site. Ainsi, le site trafic a été identifié comme étant majoritairement influencé par des sources primaires, à l’opposé du site périurbain sur lequel les espèces secondaires étaient plus abondantes. Les études granulométriques ont montré que la distribution entaille des OHAP et NHAP particulaires était liée à leurs origines (primaire/secondaire). De plus, les OHAP et NHAP apparaissent associés à 85 % à la fraction la plus fine de l’aérosol (Dp < 2,5 µm), accentuant l’intérêt de leur étude d’un point de vue sanitaire. Enfin, la combinaison de l’étude de la distribution granulométrique de certains composés identifiés comme primaire ou secondaire, à celle des profils chimiques des NHAP ouOHAP, a permis de proposer des pistes quant à l’origine majoritaire de ces familles de composés dans l’air ambiant. / Polycyclic Aromatic Hydrocarbon (PAH) concentrations are regulated in ambient air because of theirmutagenic and carcinogenic properties. They are largely emitted by combustion processes and may react withmain atmospheric oxidants to form oxygenated (OPAH) and nitrated (NPAH) derivatives, which can be moretoxic than their parent PAHs. In this work, PAH derivatives were studied using the combination of twocomplementary approaches: laboratory reactivity experiments in controlled conditions and field studies, inorder to better understand their source and fate in the atmosphere. Reactivity study of PAHs adsorbed onnatural particles was carried out by exposing ambient particles to atmospheric oxidants (O3, OH and NO2/O3)in appropriate reactors. Large decays of PAH concentrations were observed, benzo[a]pyrene (B[a]P, which isthe only regulated PAH in Europe), appearing as the most reactive. The formation of OPAHs and NPAHs wasshowed. Nevertheless, quantities of both NPAHs and OPAHs formed were not sufficient to explain the totalamount of PAHs that react, highlighting the formation of other compounds, not detected in this work. PAHdegradation may occur in the atmosphere during the transport of air masses or directly on the filter during thesampling. The study of the major degradation processes was performed during field studies, using two highvolume samplers, one being equipped with an ozone scrubber. Even if, results were not enough to clearlyconclude about the relative importance of both degradation processes, the significant formation of some PAHderivatives on the sampling filter was observed. Then, field campaigns were led on different typologies ofsampling sites around Paris. PAH, OPAH and NPAH concentrations were about ten times higher at traffic sitethan at the suburban one. Moreover, for both OPAHs and PAHs, the major compounds were similar at bothsites, in contrary to the case of NPAHs that appeared different. The traffic site appeared strongly influenced byprimary emissions, whereas high amounts of secondary species were quantified at suburban site. Particle sizedistribution of OPAHs and NPAHs showed their strong association to the finest part of aerosols (Dp < 2.5 μm),highlighting the strong interest of this study considering sanitary impacts. Finally, the study of the particle sizedistribution of primary and/or secondary identified compounds, combined with chemical NPAH and OPAHprofiles, allowed to provide indications about the major origin of PAH derivatives in the atmosphere.

La région Nord-Pas-de-Calais figure parmi les régions françaises les plus concernées par les dépassements de valeurs limites journalières de concentrations de PM₁₀ (50 µg m-³). Sur le littoral, le niveau de fond atmosphérique particulaire demeure parfois élevé, bien que relativement éloigné des sources principales de particules que sont le trafic routier et l'industrie. Alors que de nombreuses études ont été réalisées sur les émissions en milieu industrialo-portuaire, il ressort un manque de connaissances concernant l'impact des émissions issues du secteur maritime, qu'il s'agisse d'apports naturels (sels marins) ou anthropiques (trafic maritime). Dans ce travail, deux campagnes de mesures ont été menées : en 2013 au Cap Gris-Nez et au premier trimestre 2014, simultanément au Cap Gris-Nez et dans le port de Calais. La concentration en PM₁₀ a été suivie et la composition chimique (métaux, ions hydrosolubles, EC, OC, traceurs organiques) en a été déterminée. Sur le site du Cap Gris-Nez en 2013, l'évolution des niveaux de PM₁₀ est similaire à celle observée en région, reflétant la fluctuation du fond atmosphérique. Les espèces majoritairement sont NO₃-, OC, SO₄²-, CI-, Na⁺ et NH₄⁺ et représentent 69% de la masse de PM₁₀. La proportion de ces espèces varie selon la saison et les conditions météorologiques (température, vitesse et direction du vent). Les situations de fortes teneurs de PM₁₀ sont caractérisées par une plus grande proportion de nitrate d'ammonium. Les données recueillies sur le site de Calais ont permis de montrer que les émissions du trafic maritime ont pour effet d'augmenter le nombre de particules ultrafines dans l'atmosphère. Sous cette influence, les concentrations en NOx et SO₂ apparaissent plus élevées, ainsi que celles des espèces V, Ni et Co qui peuvent être proposées comme traceurs du trafic maritime. L'utilisation de la factorisation matricielle nous a permis d'identifier 10 sources de particules et d'en estimer les contributions. Ainsi, en moyenne en 2013 au Cap Gris-Nez, 41% des PM₁₀ sont issus des aérosols inorganiques secondaires, 37% des sels marins et 10% de la combustion de biomasse. Pour cette dernière, la contribution peut atteindre 17% en hiver. Enfin, le trafic maritime (5%) contribue davantage à la concentration de PM₁₀ que le trafic routier (2%). / The Nord-Pas-de-Calais region is one of the most concerned areas in France by exceedance of the PM₁₀ mean daily limit value (50 µg m-³). The particulate atmospheric background level can also be high on the coastal zone, despite the absence of any urban and industrial sources at its vicinity. Numerous studies have been performed regarding those sources, but there is still a lack of knowledge about the impact of emissions resulting from the marine compartment, including natural emissions (sea salts) and anthropogenic emissions (maritime traffic). Two measurement campaigns have been achieved, in 2013 at Cape Gris-Nez and in the first trimester 2014, simultaneously at Cape Gris-Nez and in the harbour of Calais. Concentrations of PM₁₀ were recorded and chemical composition was determined (metals, water soluble ions, Ec, OC, organic tracers). In 2013, the evolutions of PM₁₀ levels at Cape Gris-Nez and in the region similar, reflecting the atmospheric background fluctuation. NO₃-, OC, SO₄²-, CI-, Na⁺ and NH₄⁺ were found as the major species and correspond to 69% of PM₁₀ mass. The proportion of these species evolves depending on the season and the meteorological conditions (temperature, wind speed and direction). High PM₁₀ concentration situations are characterized by high proportion of ammonium nitrate. Data collected in Calais show that maritime traffic emissions increase the number of ultrafine particles in the atmosphere. Under this influence, NOx and SO₂ concentrations are higher, as those of V, Ni and Co, species that could be used as maritime traffic tracers. 10 sources were identified and apportioned by matrix factorization. In average, in 2013 at Cape Gris-Nez, 41% of PM₁₀ come from secondary inorganic aerosols, 37% from sea salts and 10% from biomass combustion. This last contribution can reach 17% in winter. Maritime traffic represents a higher contribution to PM₁₀ than road traffic, 5% against 2%.

Title: Formation and transformation of atmospheric aerosol in boundary layer Author: Mgr. Adéla Holubová Šmejkalová Institute: Institute for Environmental Studies Supervisor: Ing. Vladimír Ždímal, Dr., Institute of Chemical Process Fundamen- tals of the CAS Training workplace: Institute of Chemical Process Fundamentals of the CAS Abstract: The experimental measurement of aerosol clusters from 1.17 nm in size was carried out from August 2016 till December 2018 at the National Atmospheric Observatory Košetice. Atmospheric conditions leading to aerosol clusters stabili- zation, fresh particles formation and particle growth were analyzed. Data of days with no new particle formation confrmed the connection between mixing layer height development and decrease of total aerosol number concentration together with lower gaseous pollutant concentrations. On the contrary, new particle for- mation process overcomes dilution of the atmosphere by increasing the number of freshly nucleated particles. Only decreasing gaseous pollutant concentrations were observed during these events. The atmospheric boundary layer was high du- ring new particle formation events that can mean enrichment of the atmosphere by other components transported by long-range transport or some transfer from the free troposphere. The measurement in...

Return liquor from thermal hydrolysis process (THP) can significantly add to the nitrogen load of a wastewater treatment plant (WWTP) and introduce UV quenching substances to the wastewater stream when recycled. While there are mature technologies in place to handle the inorganic nitrogen produced due to the thermal pretreatment, organic nitrogen remains a parameter of concern for utilities employing THP pretreatment. The impact of operating conditions of the THP on dissolved organic nitrogen (DON) and UV absorbance in return liquor was investigated. Operating conditions studied were (1) operating temperature (2) solids retention time (SRT) in the anaerobic digester (3) THP flash pressure (4) the effect of co-digestion of sewage sludge with food waste and, (5) polymer conditioning. Operating temperature and polymer dose had the most significant impact on DON and UV quenching. It was found that an increase in operating temperature resulted in an increase in DON, which was primarily contributed by the hydrophilic fraction. An increase in temperature also resulted in increased UV254 absorbance. However, this trend was not linear and the increase was more pronounced when the temperature was increased from 150 C to 170 C. Increasing flash pressure from 25 psi to 45 psi did not have a significant impact on the return liquor. However, increasing the flash pressure to 75 psi increased the DON and UV254 absorbing compounds. Co-digesting the sludge with food waste resulted in a slight increase in DON and a decrease in dissolved organic carbon (DOC) and UV quenching compounds. Increasing the SRT from 10 days to 15 days resulted in a slight decrease in DON but did not have any impact on UV254 absorbance. Overall, it can be concluded that optimizing operating conditions of thermal hydrolysis process can result in decreased DON and UV quenching compounds in the recycle stream. / Master of Science

Fuktbevarare är de produkter som oftast skrivs och rekommenderas av dermatologer, och den vanligaste typen av fuktgivare är lotioner och krämer. Dessa produkter är emulsioner, vilka ofta innehåller medicinsk vit olja (MWO) på grund av deras skyddande egenskaper samt enastående hudkompabilitet. Traditionellt så har de MWO som används varit parafinska. Då naftenoljor ofta har visat sig ha bättre emulsions stabilitet, har detta examensarbete ämnat attjämföra emulsions stabiliteten för Nynas ABs nya MWO, N-MWO, med en parafinsk motsvarighet, P-MWO. Jämförelsen av de två oljorna genomfördes genom att variera följande faktorer: olje- och emulgator typ, koncentration av emulgator samt både med och utan parfym. De två emulgator system som användes bestod av Promulgen D (en kommersiell produkt från Lubrizol) samt kombinationen av Tween 80 och Span 20. Bättre emulsionsstabilitet och mindre droppstorlek och fördelning utficks då högre koncentration Promulgen D användes. En högre koncentration av Tween 80 och Span 20 gav dock inte samma gynnsamma effekt. Resultaten från samtliga tester påvisade att emulsions stabiliteten inte påverkades utav parfym. Det som istället gav störst påverkan var typ av emulgator. De prover som innehöll P-MWO samt Tween 80 och Span 20 fasseparerade. Detta berodde dock troligen mer på att P-MWO inte var kompatibel med dessa emulgatorer eftersom oljetypen inte påverkade emulsionsstabiliteten när Promulgen D användes som emulgator. / Moisturizers are the most prescribed products in dermatology, and the most common type of moisturizer delivery systems are lotions and creams. These are emulsions and often contain medical white oil (MWO) due to their protective properties and excellent skin compatibility. The MWO used in cosmetics have traditionally been paraffinic. However, as naphthenic oils often have been proven to create better emulsion stability, this thesis aimed to compare Nynas AB's new MWO, N-MWO, with a paraffinic oil, P-MWO, with similar properties regarding their emulsion stability. The two oils were compared by analyzing their emulsion stability using a rheometer and a Mastersizer 3000 while varying the following factors: type of oil, type of emulsifier, emulsifier concentration, and with and without perfume. The two emulsifying systems used were the commercial product Promulgen D from Lubrizol and the combination of Tween 80 and Span 20. Better emulsion stability and smaller droplet size distribution were obtained when a higher content of Promulgen D was added. However, a higher concentration of Tween 80 and Span 20 did not have the same favorable effect. The results showed that the addition of perfume had no effect, while the type of emulsifier influenced the emulsion stability the most. The samples made from Supela 240 and Tween 80 and Span 20 phase separated. This was more likely due to P-MWOs incompatibility with these emulsifiers as oil type did not influence the emulsion stability when Promulgen D was used as an emulsifier.

Twin screw wet granulation has been proved as a feasible alternative for traditional batch granulation process due to its continuous processing feature; considered as a significant processing method especially in the pharmaceutical industry. This thesis will explore the processibility of twin screw wet granulation with various formulations. The first section of the thesis focused on examining the processibility of wet granulation in a twin screw while using various grades of hydroxypropyl methylcellulose (HPMC) as an extended-release excipient. The method to find the processibility was by modifying the liquid-to-solid ratio for each formulation. The process window was defined by examining the amount of granules that fall in a pre-determined acceptable size range. This part focused on three substitution types of HPMC (Type 2910, Type 2208, and Type 2906) that varied in molecular weights. It was found that only Type 2910 HPMC showed a shift in the process window (also known as granulation range) in relation to the molecular weight of the formulations. A higher demand for binder liquid was found for higher molecular weight Type 2910 HPMC in order to form granules with acceptable sizes. The second part of this thesis was focused on understanding the process variables that might influence the processibility of the HPMC formulations. This part examined the impact of feed rate on the granulation range of Type 2910 HPMC specifically was examined. Multiple feed rates were tested, and it was found that the granulation range for lower molecular weight Type 2910 HPMC was easier to shrink when higher feed rates were applied. A transition in the granule formation method from liquid-bridging to compaction with respect to the feed rate was found for low molecular weight HPMC, whereas the high molecular weight HPMC always formed granules through compaction at all feed rates due to strong water retainability. / Thesis / Master of Applied Science (MASc)