Ce travail porte sur l'étude de la gazéification de biomasse en Réacteur à Flux Entrainé (RFE), dans le contexte du développement de procédés pour la production de biocarburants de deuxième génération. L'objectif de cette thèse est de modéliser les différents phénomènes qui régissent la conversion de la biomasse dans des conditions représentatives d'un RFE. La pyrolyse et la gazéification de particules de hêtre de taille comprise entre 315 et 415 µm ont été étudiées entre 800 et 1400°C en four à chute de laboratoire. L'influence de l'ajout de H2O, de CO2 et de O2 sur les produits de gazéification a été explorée, et les essais ont été simulés à partir d'un modèle 1D. L'ajout de H2O ou de CO2 permet de diminuer les rendements en char de manière significative. En phase gaz, l'influence principale de ces deux espèces est la modification de la composition en espèces majoritaires avec la réaction de gaz à l'eau. L'ajout de O2 a pour effet d'améliorer la conversion du carbone de la biomasse en gaz, et de réduire de manière significative la production de suies et de char. Le modèle, basé sur une chimie détaillée, permet de simuler ces essais de façon très satisfaisante sur toute la gamme de variation des conditions opératoires. La pyrolyse et la gazéification de particules de hêtre tamisées entre 1,12 et 1,25 mm a été étudiée en présence de O2. À 800, 1000 et 1200°C, la conversion de ces « grosses » particules est plus faible que celles des petites particules, mais à 1400°C la taille de particule n'a pas d'influence. Enfin, une étude expérimentale a été menée dans un RFE pilote pour étudier l'influence de la quantité de O2, de la taille de particule et de la pression sur la gazéification de particules de bois. Ces essais ont été simulés de façon satisfaisante en adaptant le modèle 1D. / The present work deals with biomass gasification in Entrained Flow Reactor (EFR) in the context of the development of new Biomass-to-Liquid processes. The objective of this study is to develop a comprehensive model to better understand the phenomena controlling biomass gasification in conditions representative of an EFR. Biomass pyrolysis and gasification of beech particles sieved between 315 and 450 µm have been studied between 800 and 1400°C in a drop tube furnace. The influence of H2O, CO2 and O2 addition on gasification products has been investigated and the tests have been simulated with a 1D model. The addition of H2O or CO2 leads to a significantly lower char yield. The main influence of these two oxidants in gas phase is the modification of major species composition with water gas shift reaction. With the addition of O2, the carbon conversion into gas is improved and the char and soot yields are significantly lower. The simulations are in very good agreement with the experimental results. Biomass pyrolysis and gasification of beech particles sieved between 1.12 and 1.25 mm have been studied in presence of O2. Between 800 and 1200°C the carbon conversion into gas is lower than with the smaller particles but at 1400°C the particle size has no influence. At last, the influence of O2 addition, particle size and pressure on biomass gasification has been studied in a pilot scale EFR. These experimental results have been satisfactorily simulated by adapting the 1D model.

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%.

Une technologie prometteuse pour répondre à la demande croissante en énergie renouvelable est la gazéification de biomasse lignocellulosique pour la production de biocarburants de deuxième génération. Ce procédé nécessite une alimentation en biomasse sous forme de poudre. Les problèmes de convoyage et de manipulation liés à la faible coulabilité de la biomasse broyée sont un verrou pour l’industrialisation des procédés BtL. La torréfaction comme procédé de prétraitement, en plus d'augmenter densité énergétique de la biomasse, peut influencer également les propriétés des particules obtenues après broyage, et en conséquence, l’écoulement des poudres. L'évaluation de l'écoulement des poudres de biomasse sous différentes conditions de consolidation est essentielle pour concevoir des technologies de manipulation et de convoyage efficaces.L'objectif de ce travail est d'évaluer l'effet des conditions de torréfaction et de broyage sur l’écoulement de poudres de biomasse. Une première partie consiste en une étude expérimentale dans laquelle la coulabilité d'échantillons torréfiés sous différentes intensités a été évaluée à l'aide d'un appareil de cisaillement annulaire. La coulabilité est corrélée à l'intensité de la torréfaction (mesurée par la perte de masse globale) pour deux essences différentes. La forme des particules semble être le paramètre qui influence de manière prédominante la coulabilité des poudres à l'état consolidé. La caractérisation de la coulabilité à l’état non consolidée a été effectuée à l'aide d'un tambour rotatif par l’analyse des avalanches des poudres. Des corrélations entre les caractéristiques des particules et la coulabilité sont ainsi établies. La modélisation de l'écoulement de la biomasse à l'aide de la Méthode des Éléments Discrets (DEM) constitue une deuxième partie de cette recherche. La taille submillimétrique des particules de biomasse, ainsi que leur faible densité, leur forme allongée et leur comportement cohésif sont des défis pour l’implémentation d’un modèle de réaliste d’écoulement particulaire en DEM. Un modèle DEM des particules de biomasse est mis en œuvre à l'aide d'une représentation simplifiée (assemblement de sphères) à gros grains de la forme des particules, ainsi que d'un modèle de force cohésif. Une procédure systématique de calibration des paramètres DEM permet d'obtenir un ensemble de paramètres ajustés. L'évolution expérimentale des contraintes de cisaillement d’une poudre dans un état consolidé peut alors être reproduite de façon réaliste. De même, le comportement d’avalanche des poudres dans un tambour tournant est également bien reproduit par les simulations, de façon qualitative et quantitative. Ces résultats mettent en évidence le potentiel des simulations DEM pour étudier l'effet des caractéristiques des particules, qui sont influencées par la torréfaction et les conditions de broyage, sur le comportement d'écoulement de la biomasse en poudre. / Gasification of lignocellulosic biomass for production of second-generation biofuels is a promising technology to meet renewable energy needs. However, feeding and handling problems related to the poor flowability of milled biomass considerably hinder the industrial implementation of Biomass-to-Liquid processes. Torrefaction as pretreatment step, in addition to improving energy density of biomass, also affects the properties of the milled particles (namely size and shape) that significantly influence flow behavior. The evaluation of biomass flow characteristics under different flow conditions is essential to design efficient and trouble-free handling solutions.The aim of this work is to assess the effect of the torrefaction and grinding conditions on the biomass flow behavior. A first part consists of an experimental study in which the flow properties of samples torrefied under different intensities were obtained using a ring shear tester. Flowability is correlated to the intensity of torrefaction, as measured by the global mass loss, for two different wood species. Particle shape seems to be the predominant parameter influencing flowability of powders in a consolidated state. Characterization of non-consolidated flowability through avalanching analysis using an in-house rotating drum was also conducted. Correlations between particle characteristics and flow behavior are thus established.The modelling of biomass flow using the Discrete Element Method (DEM) constitutes a second major part of this research. Challenging aspects of biomass particle modeling are their submillimetric size, low density, elongated shape and cohesive behavior. A material DEM model is implemented using a simplified (multisphere) upscaled representation of particle shape, along with a cohesive contact model. A systematic calibration procedure results in an optimal set of DEM parameters. The experimental shear stress evolution and yield locus can then be realistically reproduced. The avalanching behavior of the powders is also well captured by simulations, both qualitatively and quantitatively. These results highlight the potential of DEM simulations to investigate the effect of particle characteristics, which are driven by torrefaction and grinding conditions, on the flow behavior of powdered biomass.

Koldioxidutsläpp (CO2) från energiproduktionsindustrin och transportsektorn globalt påverkar miljön negativt. Länder har enats om att minska utsläppen för att nå målet om en genomsnittlig temperaturökning på 1,5 °C till 2030. Trots detta förväntas de globala utsläppen av CO2 från fossila bränslen och industriella processer vara cirka 40 Gton per år fram till 2100. För att dra nytta av CO2-utsläppen och skapa värdefulla produkter med negativa utsläpp är mineralkarbonatisering en önskvärd process. Denna process innebär att CO2 och mineraler löses upp i en alkalisk lösning och bildar stabila produkter. Faktorer som partikelstorlek hos mineralerna och CO2-lösningshastigheten påverkar mineralkarbonatiseringens hastighet. Experiment utfördes med en batchreaktor från Paebbl AB och en matematisk modell utvecklades i Matlab. Resultaten jämfördes för olika partikelstorlekar i tre motståndsfall. Större partikelstorlek hos olivin visade sig öka tiden för total konvertering, oavsett motståndstyp. De modellerade motstånden beskrev inte tillräckligt processen och indikerade att alla tre motstånd har en samtidig och enhetlig effekt på olivinmineralisering, utöver eventuella begränsningar som föroreningar och biprodukter. Mineraliseringsexperiment med 20 μm partiklar under en timme gav 34,4% omvandling, medan 10 μm partiklar under två timmar gav 46,7% omvandling. En inledande undersökning av massöverföringsbegränsningar visade att CO2-lösningshastigheten inte är den begränsande faktorn, utan lägre omrörningshastigheter och beteendet hos (CO2 + olivin)-systemet behöver ytterligare studeras. Framtida forskning bör fokusera på att lösa dessa begränsningar. / Carbon dioxide (CO2) emissions from the energy production industry and the transportation sector globally negatively affect the environment. A prominent example is the interconnection of carbon with the greenhouse effect. Countries have agreed to mitigate their emissions and try to fulfill the target of 1.5 oC average temperature increase by 2030, but in order to do so the global emissions of CO2 from fossil fuels and industrial processes will still lead up to the astonishing amount of 40 Gtons of CO2 each year until 2100.  It is apparent that processes that try to take advantage of the emitted CO2 creating valuable products with negative emissions are highly desired. One of these is mineral carbonation, where CO2 and minerals dissolve in an alkaline solution and form stable products. Many factors affect the rate at which mineral carbonation happens. The effect of the particle size of the mineral in the process will be investigated, along the CO2 dissolution rate through the overall gas-liquid mass transfer coefficient (kLa), in order to get a better understanding of the process. Experiments were conducted with a batch reactor provided by Paebbl AB and a mathematical model was developed in Matlab. The experimental and numerical results, in regards to the particle size, were then compared for the cases of three resistances. This model can be developed further for use in a continuous mineralization process. The results revealed that increasing the particle size of olivine leads to a significant increase in the time required for total conversion, irrespective of the resistance type. The modelled resistances were found to inadequately describe the process, suggesting a simultaneous and uniform effect of all three resistances on olivine mineralization, in addition to the effect of other possible limitations such as impurities and by-products. Mineralization experiments with 20μm particles and a duration of 1 hour led to 34.4% conversion, whereas experiments with 10μm particles and a duration of 2 hours resulted in 46.7% conversion. Finally, the initial investigation of the mass transfer limitations in a system of CO2 and water led to an average kLa coefficient of 191 h-1, suggesting that the CO2 dissolution rate is not the limiting factor. However, the impact of lower stirring rates remains unexplored due to the absence of appropriate instrumentation and the behaviour of the (CO2 + olivine) system should also be studied. Future research should aim to address these limitations.

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...

Addition of nano particles to cooling fluids has shown marked improvement in the heat transfer capabilities. Nanofluids, liquids that contain dispersed nanoparticles, are an emerging class of fluids that have great potential in many applications. There is a need to understand the fundamental behavior of nano dispersed particles with respect to their agglomeration characteristics and how it relates to the heat transfer capability. Such an understanding is important for the development and commercialization of nanofluids. In this work, the stability of nano particles was studied by measuring the zeta potential of colloidal particles, particle concentration and size. Two different sizes of silica nano particles, 10 nm and 20 nm are used in this investigation at 0.2 vol. % and 0.5 vol. % concentrations. The measurements were made in deionized (DI) water, buffer solutions at various pH, DI water plus HCl acid solution (acidic pH) and DI water plus NaOH solution (basic pH). The stability or instability of silica dispersions in these solutions was related to the zeta potential of colloidal particles and confirmed by particle sizing measurements and independently by TEM observations. Low zeta potentials resulted in agglomeration as expected and the measured particle size was greater. The heat transfer characteristics of stable or unstable silica dispersions using the above solutions were experimentally determined by measuring heat flux as a function of temperature differential between a nichrome wire and the surrounding fluid. These experiments allowed the determination of the critical heat flux (CHF), which was then related to the dispersion characteristics of the nanosilica in various fluids described above. The thickness of the diffuse layer on nano particles was computed and experimentally confirmed in selected conditions for which there was no agglomeration. As the thickness of the diffuse layer decreased due to the increase in salt content or the ionic content, the electrostatic force of repulsion cease to exist and Van der Waal's force of agglomeration prevailed causing the particles to agglomerate affecting the CHF. The 10nm size silica particle dispersions showed better heat transfer characteristics compared to 20nm dispersion. It was also observed that at low zeta potential values, where agglomeration prevailed in the dispersion, the silica nano particles had a tendency to deposit on the nickel chromium wire used in CHF experiments. The thickness of the deposition was measured and the results show that with a very high deposition, CHF is enhanced due to the porosity on the wire. The 10nm size silica particles show higher CHF compared to 20nm silica particles. In addition, for both 10nm and 20nm silica particles, 0.5 vol. % concentration yielded higher heat transfer compared to 0.2 vol. % concentration. It is believed that although CHF is significantly increased with nano silica containing fluids compared to pure fluids, formation of particle clusters in unstable slurries will lead to detrimental long time performance, compared to that with stable silica dispersions.

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

The process of milling drugs to obtain samples with a desirable particle size range has been widely used in the pharmaceutical industry, especially for the production of drugs for inhalation. However by subjecting materials to milling techniques surfaces may become thermodynamically activated which may in turn lead to formation of amorphous material. Polymorphic conversions have also been noted after milling of certain materials. Salt and cocrystal formation is a good way of enhancing the properties of an API but little or no work has been published which investigates the stability of these entities when subjected to milling. Different milling techniques (ball and jet) and temperatures (ambient and cryogenic) were used to investigate the milling behaviour of polymorphs, salts and cocrystals. All materials were analysed by XRPD and DSC to investigate any physical changes, i.e. changes in melting point and by inverse gas chromatography (IGC) to investigate whether any changes in the surface energetics occurred as a result of milling. Another aim of this thesis was to see if it was possible to predict the milling behaviour of polymorphs by calculating the attachment energies of the different crystal facets using Materials Studio 4.0. These results were compared to the IGC data to see if the predicted surface changes had occurred. The data collected in this study showed that different milling techniques can have a different effect on the same material. For example ball milling at ambient temperature and jet micronisation of the SFZ tosylate salt caused a notable increase in the melting point of the material whereas ball milling at cryogenic temperatures did not cause this to happen. The IGC data collected for this form also showed a contrast between cryomilling and the other two techniques. The study also showed that the formation of salts and cocrystals does not necessarily offer any increased stability in terms of physical properties or surface energetics. Changes in melting point were observed for the SFZ tosylate salt and the IMC:Benzamide cocrystal. Changes in the specific surface energies were also observed indicating that the nature of the surfaces was also changing. The materials which appeared to be affected the least were the two stable polymorphs, gamma IMC and SFZ III. The computational approach used has many limitations. The software does not allow for conversion to the amorphous form or polymorphic conversions. Such conversions were seen to occur, particularly for the metastable polymorphs used, meaning that this computational approach may only be suitable for stable polymorphs.

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.