Este trabalho consiste na caracterização química, física e termoanalítica de algumas amostras de batons e dos componentes de suas formulações. O estudo termoanalítico foi desenvolvido a partir das técnicas TG/OTG sob atmosfera dinâmica de ar ou enriquecida com O2 e por DSC sob atmosfera dinâmica de N2, com razão de aquecimento de 10°C min-1 em ambos os casos. Os testes de estabilidade com exposição das amostras a 4, 25 e 43°C e à luz solar indireta permitiram avaliar as propriedades organolépticas, físicas e térmicas. Os resultados da análise de ponto de fusão obtidos pelo método convencional foram comparados àqueles encontrados por ensaios de DSC. A estabilidade térmica foi determinada pela exposição a 43°C em estufa convencional e a partir da técnica de TG no estudo da cinética de decomposição, utilizando-se os métodos dinâmico e isotérmico. Foi realizada a predição do prazo de validade de 2,4 anos para uma amostra específica de batom foi determinada por meio do estudo cinético pelo método isotérmico, aplicando-se a equação de Arrhenius. A performance de três diferentes antioxidantes quanto à estabilidade térmica de uma amostra de batom foi avaliada, verificando-se, melhor comportamento da mistura de tocoferáis aplicada a 1%. / This work consists of the chemical, physical and thermoanalytical characterization of some samples of lipsticks and the components of their formulation. The thermoanalytical study was developed by means of TG/DTG techniques under dynamic air atmosphere or air enriched with O2 and by DSC in dynamic nitrogen atmosphere, with heating rate of 10°C min-1 in both cases. The stability tests with the submitled samples at 4, 25, 43°C and sunlight allowed to evaluate the organoleptic, physical and thermal properties. The analytical results of melting point obtained from conventional methods were compared to the ones measured by DSC. The thermal stability was determined by exposition at 43°C in a conventional stove and by TG technique in the study of decomposition\'s kinetic, using dynamic and isothermal methods. A shelf-life prediction of 2.4 years for a specific sample of Iipstick was determined by means of a kinetic study, using an isothermal method and applying Arrhenius\' equation. The performance of three different antioxidants concerning the thermal stability of a Iipstick sample was evaluated, the tocopherol mix showed the better performance when applied at 1%.

O comportamento térmico, a obtenção e caracterização de formas cristalinas do anti-histamínico loratadina foram investigado. A escolha do anti-histamínico loratadina como objeto de estudo resulta do seu interesse farmacológico. A loratadina é a Denominação Comum Internacional (DCI) dada ao etil 4-(8-cloro-5,6-dihidro-11H-benzo[5,6]cicloheptano[1,2-b]piridino-11-ilideno)-1-piperidinocarboxilato, que é um potente antialérgico e anti-histamínicos tricíclico, não-sedativo de ação prolongada. Formas cristalinas foram preparadas e estudadas com vista à identificação de formas polimórficas. Os solventes utilizados na preparação das soluções foram: álcool etílico, acetonitrila, álcool isopropílico, acetona, álcool metílico, éter isopropílico, éter metil terc-butílico, tolueno, clorofórmio. A cristalização foi realizada por evaporação do solvente em diferentes temperaturas. A calorimetria exploratória diferencial (DSC), termogravimetria e termogravimetria derivada (TG/DTG), análise térmica diferencial (DTA), difração de raios X (DRX) e a ressonância magnética nuclear (RMN) foram às técnicas utilizadas na caracterização das formas polimórficas. A maioria das amostras obtidas pelas técnicas de cristalização consistiam de misturas de formas cristalinas, contendo, por vezes, formas metaestáveis e formas amorfas. Identificaram-se duas formas cristalinas como polimorfos da loratadina, cujas curvas DSC mostrou interconversão entre ambas. / The preparation, characterization and thermal behavior of the crystalline forms of the antihistamine loratadine has been developed. The selection of loratadine as an object of study results from its pharmacological interest. Loratadine is the International Common Denomination (ICD) given to ethyl 4-(8-chloro-5,6-dihydro-11H-benzo [5,6] cyclohepta[1,2-b]pyridin-11-ylidene)-1-piperidinecarboxylate, a potent anti-allergic and anti-histamincs, tricyclic, non-sedating long acting. Crystalline forms were prepared and studied for the identification of polymorphic forms. The solvents used in preparing the solutions were: ethanol, acetonitrile, isopropyl alcohol, acetone, methyl alcohol, isopropyl ether, methyl tert-butyl ether, toluene, chloroform. The crystallization was performed by evaporating the solvent at different temperatures. The differential scanning calorimetry (DSC), thermogravimetry and derivative thermogravimetry (TG/DTG), differential thermal analysis (DTA), X-ray diffraction (XRD) and nuclear magnetic resonance (NMR) techniques were used to characterize the polymorphic forms. Most of the samples obtained by the crystallization were mixtures of crystalline forms, containing sometimes forms metastable and amorphous forms. It was identified as two crystalline polymorphic forms of loratadine, whose DSC curves demonstrated that they are interconvertable.

Dans le domaine aéronautique, le soudage par friction-malaxage (FSW – Friction Stir Welding) apparait comme un procédé innovant d’assemblage des fuselages, allégeant la structure avion en remplaçant la technique actuelle de rivetage. La simulation numérique est un support permettant de mieux comprendre et maîtriser ce procédé. L’alliage d’aluminium étudié dans ce projet est de type AA2024-T3 et tire principalement ses propriétés du durcissement structural. Modéliser l’évolution de la précipitation s’avère essentiel pour définir les propriétés finales de la soudure. Le modèle choisi doit prendre en considération les familles de précipités formés et les processus de germination, croissance et coalescence. Il doit être précis, robuste et rapide pour être applicable au procédé FSW. Un modèle de classe couplé à des calculs d’équilibre thermodynamiques a été choisi dans cette étude. Pour définir la cinétique de croissance d’un précipité, une cinétique de croissance initialement établie pour un alliage binaire a été étendue à un alliage multicomposé. Connaissant la distribution en taille des familles de précipités, les propriétés mécaniques sont définies selon un modèle empirique. La calibration anisotherme a été réalisée via un essai de DSC où signaux expérimentaux et simulés ont été comparés pour déterminer la teneur initiale des phases en présence et définir les paramètres matériaux de l’alliage. L’essai isotherme a établi le lien entre état de précipitation et propriétés mécaniques résultantes. Le modèle est appliqué à la simulation des évolutions microstructurales au cours d’une soudure FSW afin de prédire les propriétés finales du joint soudé. Les évolutions thermiques sont déterminées via l’utilisation d’un modèle macroscopique développé parallèlement dans une thèse, également portée par la Chaire Daher. Les données numériques obtenues sont comparées à des expériences instrumentées, montrant une bonne estimation des duretés. Les profils expérimentaux sont retrouvés, de même que les caractéristiques des différents domaines, validant l’approche et sa capacité à simuler efficacement les évolutions des processus de précipitation. / In the aeronautic industry, the friction stir welding (FSW) process is seen as an interesting option to lighten aircraft structure by replacing the standard riveting technology used to join parts. Numerical simulation is chosen to improve understanding of the different mechanisms occurring during FSW. The aluminum alloy studied is an AA2024-T3 grade. Its mechanical properties mainly derive from structural hardening mechanisms. An accurate model of precipitate evolution is essential to define hardness profile of the weld. The chosen simulation has to be robust and time-efficient in order to be suitable for the FSW process modeling. It must consider the two families of precipitates (GPB zones and S phase) and model nucleation, growth and coarsening phenomena. A PSD model is chosen and coupled with thermodynamic equilibrium calculations. To define the growth kinetics of precipitates, an exact analytical solution is extended to a multi-component alloy. Knowing the distribution of precipitates size, the mechanical properties are defined based on an empirical model. The amount and properties of phases are initialized through non-isothermal DSC calibration and comparison between experimental heat flux and simulated one. Isothermal test is selected to establish the link between precipitation state and mechanical properties. The model is applied to the simulation of microstructural evolution in FSW in order to predict the final properties of the weld. Thermal changes are determined through the use of a macroscopic model developed during a twin project within the Chair Daher. Numerical results are compared with instrumented experiments and show a good estimate of hardness. The experimental profiles are found, as well as the characteristics of the different areas. This validates the approach and its efficiency to simulate the evolution of the precipitation process.

A transmissão de dados e informação na fibra óptica vem aumentando nos últimos anos. O interesse para avaliar melhor a confiabilidade mecânica tomou-se uma necessidade, depois que uma fibra, de um cabo instalado, estava se partindo com muita facilidade. O foco principal deste trabalho foi voltado para estabelecer metodologias para avaliar o estado de degradação dos polímeros usados. Através destas técnicas, buscou-se encontrar parâmetros (E\', E\", tan &#948, Tg, etc.) que pudessem indicar o estado de degradação dos revestimentos. Diferentes técnicas foram empregadas para avaliar o revestimento das fibras tais como: calorimetria exploratória diferencial (DSC), diferencial fotocalorimetria (DPC), análise térmica dinâmico mecânico (DMTA) e espectroscopia na região do infravermelho (FIIR). A partir da técnica desenvolvida, DMTA, esta pode ser empregada para avaliar a confiabilidade mecânica de várias fibras comercias. As técnicas DMTA e FIIR mostraram ser muito promissoras, pois consegue-se, através delas, obter muitos dados a respeito das características dos polímeros. / The datas and information transmission in the optical fiber have been increasing in the last years. The interest to evaluate the mechanical reliability became necessary, after that a optical fiber, from a cable installed, was cracking very easily. The principal aim of this work was establishing methodologies to evaluate the polymer degradation state. Through of this techniques we search to find out parameters (E\', E\", tan &#948, Tg. etc) that could denote the degradation state of the coatings. Different techniques were utilized to evaluate the coating of the optical fibers such as: differential scanning calorimeter (DSC), differential photocalorimeter (DPC), dynamic mechanic thermal analyzer (DMTA) and infrared spectroscopy (FIIR). From the method development (DMTA), it was possible to evaluate the mechanical realiability of many commercial fibers. DMTA and FTIR techniques shown to be very promising to obtain very dates to respect of polymer characteristics.

Peatlands are considered to be valuable ecosystems on the Planet and play an important role in many processes globally likewise and in the landscape. They are important for maintaining a global biodiversity, play an important role in landscape hydrology and can be a source of drinking water. They can help minimize floods and contribute to climate change mitigation. The peat bogs are one of the largest terrestrial carbon reservoirs. They have been storing carbon for centuries. Many of peat functions are affected due to human activities. It can result into release of greenhouse gases into atmosphere and the excretion of organic carbon into watercourses. The subject of the thesis is understanding of the mechanisms of water binding in peat and exploring possible dependencies within the depth profile of the peatlands using thermal analytical methods, more preciously using thermogravimetry (TG) and differential scanning calorimetry (DSC). The stability of water molecule bridge (WaMB) was investigated. It was found out that the minimum temperature required for WaMB abatement decrease and the whole structure becomes less stable with increasing peat layer depth. Water release processes were evaluated with the meaning of the TGA measurements. A decreasing trend in the degradation of thermolabile substances and an increasing trend in thermostable substances within the peat profile were observed.

Sedan människor började använda energetiska material har risken för oönskade explosioner alltid varit ett problem. Många produktionsanläggningar och förråd har förstörts på grund av oönskad antändning energetiska material. Idag är nitrocellulosa en komponent i de flesta kanonkrut. En negativ egenskap hos nitrocellulosa är att den bryts ner över tid och eftersom det är en naturprodukt så kommer det alltid att finnas en viss skillnad mellan olika batcher. Genom att ersätta nitrocellulosa med en produkt som inte bryts ner men som fortfarande ger liknande övriga egenskaper kan kanonkrutssäkerheten öka. Termoelaster undersöktes då de är smältbara och tåliga. Smältpunkt och glastransitionstemperaturen bestämdes med differentiell svepkalorimetri, viskositeten mättes vid flera temperaturer med en reometer och mekaniska egenskaper utvärderades i en dragprovningsmaskin. De två mest lovande polymererna blandades sedan med hexamin som är ett inert material för att simulera ett kompositkrut. Agglomerering av hexamin undveks genom tillsats av små mängder pyrogen kiseldioxid. Fyllnadsgraden i systemet nådde 70 viktprocent hexamin i en polymer. Kompositmaterialen dragprovades och resultaten jämfördes med motsvarande data för två nitrocellulosabaserat krut. Kompositmaterialen hade lägre brottgräns än det ena nitrocellulosabaserade krutet men högre brottgräns än det andra nitrocellulosabaserade krutet. Kompositmaterialen hade högre E-modul än det nitrocellulosabaserade krutet men lägre brottöjning. Resultaten är lovande och visar att termoelasterna har stor potential att användas i kompositkrut. Med fortsatt undersökning och optimering av kompositmaterialen kan ett säkrare alternativ till nitrocellulosa skapas.

Les coulis d'hydrates de gaz sont une alternative intéressante en tant que fluides frigoporteurs utilisables dans les boucles de réfrigération secondaire. La génération du coulis par injection directe d'un gaz comme le CO2 au sein d'un fluide refroidi permet de surmonter les problèmes techniques liés aux méthodes de génération mécaniques. L'objectif de la thèse est d'étudier l'effet d'additifs sur l'amélioration des conditions d'écoulement du coulis ainsi que sur les modifications de leurs conditions de formation. Dans ce travail de thèse nous nous sommes donc attachés à caractériser l'effet de l'addition d'un promoteur d'hydrates, le tetrahydrofurane (THF) sur les conditions de formation de l'hydrate mixte THF+CO2 dans les systèmes eau-CO2-THF. La calorimétrie différentielle programmée, DSC, sous pression contrôlée de gaz a été employée comme technique expérimentale .Les résultats obtenus (conditions de température de formation, enthalpie et capacité calorifique de dissociation pour diverses pressions de CO2 et concentrations de THF) ont été comparés avec les prédictions d'un modèle thermodynamique combinant l'expression de van der Waals et Platteeuw et l'équation d'état RKS associée à la loi de mélange MHV2 et au modèle UNIFAC. Une autre partie de la thèse a été consacrée à l'étude des conditions de formation et d'écoulement d'un coulis d'hydrates à base de CO2 en présence d'additifs. Pour cela, un dispositif expérimental capable de mesurer le débit et les pertes de charges a été employé. Après une étude phénoménologique des conditions de formation et d'écoulement des coulis, une sélection d'additifs permettant d'améliorer ces conditions a été réalisée. Une caractérisation rhéologique du coulis en présence de l'additif le plus performant complète ce travail.

PVDF, Poly(vinylidene fluoride), is a polymer that has been studied for over four decades due to its good electromechanical properties, stability, and durability in various environments. Currently, PVDF is the only commercially available piezoelectric polymer. PVDF is a polymorph, which indicates the presence of several crystalline phases such as α, β, γ, and δ-phase. Oriented β-phase PVDF exhibits ferroelectric properties and displays the largest piezoelectricity amongst the four phases, which makes it the most desirable phase. Preparing oriented β-phase PVDF is a multi-step process, which is cost intensive, due to the time, labor and energy utilized. The main goal of this work is to prepare oriented β-phase PVDF using the electrospraying technique in a one step process. During the electrospraying process a polymer jet is ejected. This jet disintegrates into droplets due to overwhelming surface tension, resulting in a sprayed coating on the collector substrate. Because of the combination of jet ejection and the high voltage applied between the needle tip and the substrate, the droplets can be stretched and the polymer chains can be oriented. Both the stretching and the high electric field are required for the transformation of α-phase to the oriented β-phase. This study proposes that by using the electrospraying technique it is possible to transform the α-phase to the β-phase in a one step process starting from solution. This research focuses on the processing and characterization of electrosprayed PVDF as well as electrosprayed PVDF/carbon nanotubes (PVDF/CNT) nanocomposites. The specific tasks are to determine the changes to the PVDF phases due to the electrospraying technique, and to determine the changes in the PVDF morphology due to the addition of carbon nanotubes to the polymer matrix.PVDF with two different molecular weights were electrosprayed using different solvents and parameters. Initial observations after electrospraying were that, high boiling point solvents resulted in the spraying of the solution and forming films, whereas a low boiling point volatile solvent such as acetone resulted in the spinning of the solution thus forming non-woven fiber mats. The thermal and electrical properties of the electrosprayed PVDF and PVDF/CNT composites are measured using several characterization techniques, including Modulated Differential Scanning Calorimetry (MDSC), Dielectric spectroscopy, Thermally Stimulated Current (TSC), Fourier Transform Infrared Spectroscopy (FT-IR), and X-Ray Diffraction (XRD). MDSC results show that electrosprayed PVDF has a lower melting point temperature than that of PVDF commercially available pellets. In addition, electrosprayed PVDF/CNT nanocomposites show a linear increase in the percentage of crystallinity with the increase of CNT concentration in the composite. Dielectric spectroscopy results indicate that by increasing the CNT concentration in the composite, the dielectric constant and the polymer conductivity increase.From the four characterizing techniques used, two of them, FT-IR and XRD, show that it is possible to transform α-phase to β-phase PVDF in a one-step process using electrospraying. The other two techniques, TSC and dielectric spectroscopy, show α-phase for the electrosprayed samples without CNT, and some β-phase formation with samples electrosprayed with CNT. These last two techniques; TSC and dielectric spectroscopy have results that differ from the FT-IR and XRD techniques. This contradiction may be a result of the small amounts of β-phase in the sample, which cannot be detected using these techniques. Another reason may be due to the difference in the probing levels between these techniques. XRD and FT-IR probe at the molecular level, whereas TSC and dielectric probe at a much larger scale, which may make it hard to detect small amounts of β-phase.

L’objectif de cette thèse est de formuler un adjuvant phytosanitaire qui permet d’optimiser les propriétés rhéologiques d’une préparation phytosanitaire (bouillie) afin de limiter la formation de gouttes susceptibles à la dérive lors de la pulvérisation, et d’améliorer le contact des gouttes avec le végétal traite. Les propriétés rhéologiques peuvent être optimisées par la présence de polysaccharides judicieusement sélectionnés. Comme la dissolution des polysaccharides représente une difficulté car ils forment des grumeaux, le passage par une émulsion permettant de les piéger dans la phase dispersée est nécessaire. La formulation est donc une émulsion de type eau-dans-huile (E/H) dont la phase dispersée est une solution concentrée de polysaccharide. La solution de polysaccharide est destinée par la suite a être relarguée lors de la préparation phytosanitaire dans un tank de pulvérisation. La formulation doit posséder une stabilité dans le temps répondant aux réglementations en vigueur pour les formulations phytosanitaires liquides. De ce fait, lastabilité de l’émulsion a été optimisée en utilisant la composition adéquate (phase continue, phase dispersée, tensioactif) et un procédé de fabrication optimise utilisant un système rotor-stator et un homogénéisateur à haute pression. Les formulations établies ont été caractérisées par des techniques permettant d’apprécier la taille moyenne et la distributionde la taille des gouttes dispersées telles que la granulométrie par diffraction laser et la calorimétrie a balayage différentielle (DSC). La température de cristallisation des gouttelettes mesurée lors de l’analyse DSC est corrélée à leur taille. La stabilité dans le temps a été évaluée en réalisant des tests de vieillissement naturel et des tests de vieillissement accéléré. Le relargage de polysaccharide a ensuite été étudiée afin de pouvoir être réalisé dans les conditions de préparation d’une bouillie au champ. Le relargage est réalisé par une déstabilisation préalable de la formulation à l’aide d’un tensioactif desémulsionnant. Le relargage est évalué par l’évolution de la conductivité électrique de la bouillie car les polysaccharides relargués s’ionisent en milieu aqueux. L’étude de la pulvérisation a par la suite été réalisée en utilisant un pilote reproduisant une rampe de pulvérisation agricole. La pulvérisation a été optimisée en faisant varier les propriétés physicochimiques de la préparation à pulvériser (tension de surface et rhéologie) et les paramètres de la pulvérisation (pression, buse de pulvérisation). La formulation de l’adjuvant retenue est une émulsion contenant 50 % (v/v) de solution de carboxymethylcellulose a 3 % (m/m), dispersée dans une phase huileuse constituée d’ester méthylique de colza avec 10 % (m/m) de polyricinoleate de polyglycérol. Le relargage est réalisé à l’aide d’un tensioactif éthoxylé, sélectionné parmi sept tensioactifs commerciaux. L’étude rhéologique de la formulation à pulveriser montre des propriétés qui permettent delimiter la formation des gouttes de petits diamètres, confirme par les essais de pulvérisation réalisés sur le pilote. / The objective of this thesis is to develop the formulation of a phytosanitary adjuvant to optimize the rheological properties of a preparation devoted to plant protection, in order to reduce the formation of droplets that may drift during spraying, and improve the contact of the droplets with the treated plant. Rheological properties can be optimized by the presence of wisely selected polysaccharides. As the dissolution of the polysaccharide is a problem because they form lumps, passing through the emulsion form to trap them in the dispersed phase is necessary. The formulation is a water-in-oil type emulsion (W/O), the dispersed phase is a concentrated solution of polysaccharide. The polysaccharide solution is devoted to be released during the preparation of the phytosanitary bulk in a spray tank. The formulation should have stability over time complying with the regulations for phytosanitary liquid formulations. Therefore, the stability of the emulsion was optimized using the appropriate composition (continuous phase, dispersed phase, surfactant) and an optimized manufacturing process using a rotorstatorsystem and a high pressure homogenizer. The formulations were characterized using techniques which allow assessing the average size and size distribution of the dispersed droplets such as laser light diffraction granulometry and differential scanning calorimetry (DSC). The crystallization temperature of the droplets measured during the DSC analysis is correlated to their size. The stability over time was assessed using natural ageing and accelerated ageing tests. The release of polysaccharide was then studied in order to be performed under the conditions of preparing of phytosanitary bulk by a farmer. The release is achieved by a prior destabilization of the formulation using a demulsifier surfactant. The release is evaluated by the evolution of the electrical conductivity of the bulk, as thepolysaccharides entrapped form ionized molecules in aqueous media. The study of the spray has subsequently been carried out using a pilot reproducing an agricultural spray boom. Spraying was optimized by varying the physicochemical properties of the bulk preparation (surface tension and rheology) and spraying parameters (pressure, spray nozzle).The retained adjuvant formulation is an emulsion containing 50 % (v/v) of solution of 3 % (w/w) of carboxymethylcellulose, dispersed in an oil phase consisting of rapeseed methyl ester with 10 % (w/w) of polyglycerol polyricinoleate. The release is achieved with an ethoxylated surfactant, selected among seven commercial surfactants. The rheological study of the spray formulation exhibits properties which limit the formation of drops of small diameter, confirmed by the tests performed on the spray pilot.

Total joint arthroplasty surgeries are known to have a high success rate but the longevity of the implants still acts as a limiting factor. Ultrahigh molecular weight polyethylene is the material of choice for the implant bearing surfaces due to its excellent clinical and tribological performance. A common problem associated with the polymer is however the loosening of the implant from its surrounding bone tissue. This phenomenon is caused by a biological reaction to released wear particles. Reducing the release of wear particles will increase the lifespan of implants and can be accomplished by increasing the wear resistance of the material. Crosslinking of the polymer by means of gamma irradiation is a well known approach to achieve an increased wear resistance but eventually leads to oxidation of the polymer. The addition of vitamin E as antioxidant is known to reduce this without significant loss of mechanical properties. A second approach is based on adding reinforcements to the polymer in order to enhance its tribological performance. This work focuses on the thermal and mechanical characterisation of newly developed UHMWPE nano-composites with a focus on the addition of vitamin E and crosslinking by gamma irradiation. Based on previously published results indicating an increased fracture toughness for different composites, Nanodiamonds, multiwalled carbon nanotubes and graphene oxide nanoparticles were dispersed throughout the matrix and consolidated. The thermal characterisation was performed using differential scanning calorimetry, making it possible to identify the different thermal transitions and degree of crystallinity of the polymer. The fracture toughness, an important property in wear due to fatigue, was furthermore characterised by performing three point bending experiments.Finally, by means of a multiaxial pin-on-plate set-up the wear resistance of the materials was analysed.