Along with higher data rates and application-enriched user terminals, LTE has even higher requirements to conserve the battery power in mobile devices compared to the WCDMA terminals. In LTE, Discontinuous Reception (DRX) has been introduced as one of the key solutions to conserve battery power in mobile terminal. It is very meaningful to investigate the possible impact of DRX on power consumption and also the VoIP performance. This study evaluates several different parameter settings for DRX, and tries to find a reasonable trade-off between VoIP performance and battery life. This study report proposes DRX parameter setting to achieve maximum possible power saving with minimum VoIP degradation. Based on the assumed power saving model and simulation scenario presented in chapter 4 and chapter 5 of this report respectively, the proposed parameter settings can achieve up to ~60% of the terminal power saving. Furthermore, it is concluded that longer DRX cycles are not suitable for VoIP traffic since they introduces longer delays and degrades the VoIP performance particularly in downlink. / This study has evaluated different DRX parameter settings for VoIP traffic both in uplink and downlink and found out different gains in terms of power saving and network performance. It is shown that key parameters include On-duration Timer, Inactivity Timer and length of DRX cycle. These three parameters have major impact on both VoIP and power saving. Different combinations of these parameters show different results. DRX affects downlink and uplink in a different manner. In the downlink, a user cannot be scheduled and thus receive any DL data during the period of inactivity. Downlink assignments can only be sent when receiving UE is awake. This is one reason that length of DRX cycle and length of On-duration period is more important parameters in downlink. It is found out that increasing the length of DRX cycle, keeping relatively constant average awake time of terminal, introduces larger delays in downlink and thus degrades the performance. On the other hand, uplink is affected by DRX only when there is fragmentation. In uplink, whenever a user has available data it can a scheduling request, which is independent of DRX state and can be sent even if UE is sleeping, and thus can get UL scheduling grant. However, if the grant is fragmented, UE might not always be able to receive remaining fragments due to DRX state. That is why Inactivity Timer plays a more important role in UL. If poor radio conditions are expected, it is important to have larger Inactivity Timer period. From the power saving point of view, the length of On-duration Timer and Inactivity Timer should be chosen as smaller as possible. However, these parameters should not be reduced below a certain threshold. For example reducing On-duration Timer below 2ms shows a major degradation in VoIP performance while not showing a comparable gain in receiver power. This study has proposed a DRX parameter setting to achieve maximum power saving with minimum VoIP degradation. Based on the assumed power saving model and the simulation settings presented in chapter 4 and chapter 5 of this report respectively, the proposed DRX settings show that ~60% of total power can be saved while keeping the VoIP capacity loss <= 12%. / This thesis is about battery saving in LTE

Submitted by SEBASTIÃO CANDIDO DAS DÔRES null (sebastiao.cd@hotmail.com) on 2016-09-04T17:38:27Z No. of bitstreams: 1 Dissertacao versao final.pdf: 2282030 bytes, checksum: c50870331ee344908dee97aaabb84ab1 (MD5) / Rejected by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br), reason: Solicitamos que realize uma nova submissão seguindo as orientações abaixo: Foram realizadas duas submissões, apenas uma submissão contendo o arquivo correto deve ser feita. Corrija estas informações e realize uma nova submissão contendo o arquivo correto. Agradecemos a compreensão. on 2016-09-06T19:21:10Z (GMT) / Submitted by SEBASTIÃO CANDIDO DAS DÔRES null (sebastiao.cd@hotmail.com) on 2016-09-07T02:01:54Z No. of bitstreams: 1 Dissertacao versao final.pdf: 2282030 bytes, checksum: c50870331ee344908dee97aaabb84ab1 (MD5) / Approved for entry into archive by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br) on 2016-09-08T17:00:11Z (GMT) No. of bitstreams: 1 dores_sc_me_ilha.pdf: 2282030 bytes, checksum: c50870331ee344908dee97aaabb84ab1 (MD5) / Made available in DSpace on 2016-09-08T17:00:11Z (GMT). No. of bitstreams: 1 dores_sc_me_ilha.pdf: 2282030 bytes, checksum: c50870331ee344908dee97aaabb84ab1 (MD5) Previous issue date: 2016-07-12 / O objetivo deste trabalho foi estudar os processos de cristalização em vidro 80TeO2-20WO3 preparados em atmosfera ambiente e rica em O2. Os vidros obtidos foram pulverizados em diferentes tamanhos de partículas. Para o estudo de cristalização, medidas de análise térmica diferencial (DTA) foram realizadas em diferentes taxas de aquecimento. Dados complementares de difração de raios-X (DRX) e de espectroscopia Raman foram obtidos com amostras submetidas a diferentes tratamentos térmicos, variando-se ora a temperatura ora o tempo. Dos dados de DTA foi possível determinar as temperaturas de transição vítrea e de cristalização, assim como observar a formação de três fases cristalinas, identificadas como -TeO2, -TeO2 e do WO3 através dos dados de DRX e de Raman. Foi possível observar uma resposta térmica diferente entre as amostras preparadas nas atmosfera ambiente e rica em O2. Os vidros preparados em atmosfera ambiente apresentam na média uma maior estabilidade térmica quando comparada com aquela dos preparados em O2. A energia de ativação associada a cada fase observada foi determinada usando o método de Kissinger e, pelos modelos JMAK e Matusita, foi possível concluir que o processo de cristalização ocorreu preferencialmente na superfície e no volume. / The purpose of this work was to investigate the crystallization processes in 80TeO2-20WO3 glass prepared in ambient and oxygen atmospheres. The obtained glasses were powdered in different grain sizes. For the crystallization study, differential thermal analysis measurements were performed at different heating rates. Additional data from X-ray diffraction and Raman spectroscopy were obtained with samples submitted to different thermal treatments, either by varying the temperature either time. From differential thermal analysis data, it was possible to determine the glass transition and crystallization temperatures, and to observe three crystallization processes, which were identified from X-ray diffraction and Raman data as belonging to the -TeO2, -TeO2, and WO3 phases. It was possible to observe a different thermal response of the samples prepared in ambient atmosphere and rich in O2. The glasses prepared in ambient atmosphere present in average a higher thermal stability when compared with those prepared in O2 atmosphere. The activation energy associated with each observed phase, was determined using the Kissinger method, and by using the JMAK and Matusita models it was concluded that the crystallization process occurred preferentially on the surface and volume.

Orientador: João Carlos Silos Moraes / Resumo: O objetivo deste trabalho foi estudar os processos de cristalização em vidro 80TeO2-20WO3 preparados em atmosfera ambiente e rica em O2. Os vidros obtidos foram pulverizados em diferentes tamanhos de partículas. Para o estudo de cristalização, medidas de análise térmica diferencial (DTA) foram realizadas em diferentes taxas de aquecimento. Dados complementares de difração de raios-X (DRX) e de espectroscopia Raman foram obtidos com amostras submetidas a diferentes tratamentos térmicos, variando-se ora a temperatura ora o tempo. Dos dados de DTA foi possível determinar as temperaturas de transição vítrea e de cristalização, assim como observar a formação de três fases cristalinas, identificadas como -TeO2, -TeO2 e do WO3 através dos dados de DRX e de Raman. Foi possível observar uma resposta térmica diferente entre as amostras preparadas nas atmosfera ambiente e rica em O2. Os vidros preparados em atmosfera ambiente apresentam na média uma maior estabilidade térmica quando comparada com aquela dos preparados em O2. A energia de ativação associada a cada fase observada foi determinada usando o método de Kissinger e, pelos modelos JMAK e Matusita, foi possível concluir que o processo de cristalização ocorreu preferencialmente na superfície e no volume. / Abstract: The purpose of this work was to investigate the crystallization processes in 80TeO2-20WO3 glass prepared in ambient and oxygen atmospheres. The obtained glasses were powdered in different grain sizes. For the crystallization study, differential thermal analysis measurements were performed at different heating rates. Additional data from X-ray diffraction and Raman spectroscopy were obtained with samples submitted to different thermal treatments, either by varying the temperature either time. From differential thermal analysis data, it was possible to determine the glass transition and crystallization temperatures, and to observe three crystallization processes, which were identified from X-ray diffraction and Raman data as belonging to the -TeO2, -TeO2, and WO3 phases. It was possible to observe a different thermal response of the samples prepared in ambient atmosphere and rich in O2. The glasses prepared in ambient atmosphere present in average a higher thermal stability when compared with those prepared in O2 atmosphere. The activation energy associated with each observed phase, was determined using the Kissinger method, and by using the JMAK and Matusita models it was concluded that the crystallization process occurred preferentially on the surface and volume. / Mestre

The number of wireless connected devices are growing exponentially and the importance of this research area is growing as well to meet the known and looming challenges and expectations. The 5:th Generation telecommunications standard is partly embodied by the Machine-to-Machine (M2M) and Internet of Things (IoT) technologies and standards to handle a big part of these devices and connections. An example within the IoT paradigm is military training systems where each system can consist of thousands of battery operated mobile devices and their shifting requirements shall be fullled in an energy-aware manner to increase battery operating times. Military training radio networks enables realistic combat training. The services and features provided in commercial telecommunications networks are desirable in these often proprietary and task specic networks, increasing capabilities and functionalities. To facilitate the current and future R&D of LTE based networks for adoption in military training networks and services this doctoral thesis intends to provide the starting ground for the energy-aware LTE based wireless communications. The thesis first presents general solutions on how to meet traffic deadlines in wireless networks for large number of nodes, and then continues with solutions for energy-aware LTE-based communications for the User Equipments (UEs). The work builds on the problem formulation how to provide energy-aware resource handling for LTE-based military training networks from where three research questions are derived. From the research questions we derive different hypotheses and then test these within the investigated area to answer the research questions. The contributions of this work are within areas of resource handling and power saving for mobile devices. In the first area an admission control using deterministic analysis is proposed fullling traffic requirements for military training mobile nodes. This admission control is enhanced for multiple-channel base stations, and evaluated using mobile nodes with different heterogeneous traffic requirements. In the second part energy-awareness is in focus for LTE/LTE-A based networks. The main power saving method for LTE/LTE-A UEs, Discontinuous Reception (DRX) mechanism, is evaluated and models for DRX in Idle and Connected state are proposed including metrics for wake-up delay and power saving. Additionally a mean queuing delay analysis is proposed for a variant of the Connected state DRX. Using these models and metrics, practical design guidelines for tuning of DRX parameters are proposed, including optimization of DRX parameters for either minimizing delay or maximizing power saving.

L’objectif de ce travail est l’étude et la modélisation d’un capteur de gaz à base d’oxyde métallique semiconducteur de type p (cas de CuO). Pour cela, des couches minces de CuO ont été élaborées dans l‘équipe microcapteurs de IM2NP à partir de deux techniques différentes : la pulvérisation cathodique réactive magnétron radio-fréquence et l’oxydation thermique des couches minces de cuivre déposées par évaporation thermique sous vide. Différentes techniques de caractérisation ont été mises en oeuvre pour évaluer les propriétés des couches minces obtenues en vue de les optimiser pour l’application capteur. La microscopie à force atomique (AFM) et la microscopie électronique à balayage (MEB) ont révélé une nanostructure homogène dont la morphologie présente la porosité désirée. Les analyses par diffraction de rayons X (DRX) ont montré que ces couches minces présentent une monophase de CuO avec une orientation préférentielle (111), les études optiques par ellipsométrie dans le domaine visible ont permis d’estimer les pourcentages de porosité dans chaque couche. Ces couches possèdent la cristallinité et la pureté requises pour l'utilisation en capteurs de gaz. Les performances de ces couches minces de CuO ont été évaluées pour la détection de l’ozone et de l’éthanol. Sur la base de ces résultats, un modèle dynamique a été développé simulant la réaction entre les espèces oxygénées ionisées adsorbées à la surface d'un semiconducteur de type p avec un gaz, qui permet d’évaluer l’influence des paramètres de fonctionnement (Température de fonctionnement, pression d’oxygène et concentration de gaz). / The objective of this work is to study and model a gas sensor based on a p-type metal oxide semiconductor (case of CuO). For this, thin layers of CuO have been developed in the microsensor team at the IM2NP laboratory from two different techniques: radio frequency reactive magnetron sputtering and thermal oxidation of thin copper films deposited by thermal evaporation under vacuum. Different characterization techniques have been implemented to evaluate the properties of the thin films obtained in order to optimize them for sensor applications. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) revealed a homogeneous nanostructured morphology which has the desired porosity. Diffraction analysis (XRD) showed that these thin films have a single phase of CuO with a preferred orientation (111). Optical studies by ellipsometry in the visible spectral region were used to estimate the percentage of porosity in each layer. These layers have the crystallinity and purity required for use in gas sensors. The performances of these thin layers of CuO were evaluated for the detection of ozone and ethanol. Based on these results, a dynamic model was developed to simulate the reaction between the ionized oxygen species adsorbed on the surface of a p-type semiconductor with a gas, which is used to evaluate the influence of operating parameters (working temperature, oxygen concentration and gas pressure).

Le travail présenté dans ce mémoire de thèse porte sur la préparation de nouveaux nanocomposites polystyrène-argile en utilisant des argiles modifiées par divers tensioactifs cationiques polymérisables fluorés. Des systèmes de référence ont aussi été envisagés en utilisant des tensioactifs classiques de structure proche de celles des surfmers (surfmers et tensioactifs hydrocarbonés) et ce, afin de mettre en évidence le rôle joué par le groupement polymérisable et l’atome de fluor sur la structure et les propriétés des nanocomposites obtenus. Les propriétés de surface des tensioactifs ont été étudiées en termes de CMC, tensions de surface et enthalpies de micellisation de Gibbs afin d’évaluer le comportement en solution de ces tensioactifs. Ces tensioactifs ont été par la suite utilisés pour modifier une montmorillonite sodée via un processus d’échange cationique. Les organoargiles ainsi obtenues ont été caractérisées par IR, ATG et DRX. Les données DRX obtenues sont en faveur d’un alignement de la majorité des surfmers fluorés en bicouche La préparation des nanocomposites polystyrène-argile contenant diverses quantités d’organoargiles variant de 1 à 15% en utilisant la technique de polymérisation radicalaire en masse ou en solution, a montré l’effet positif de l’introduction d’une chaîne fluorée et d’une fonction polymérisable sur la stabilité thermique des nanocomposites. Des morphologies exfoliées ont été obtenues pour la majorité des nanocomposites fluorés préparés. Une relation structure-propriétés de surface et propriétés thermique a été établie sur la base des analyses ATG, DRX et TEM/MEB. / The work presented in this thesis focuses on the preparation of new polystyrene-clay nanocomposites using fluorinated polymerizable cationic surfactants as modifiers. Reference systems have also been proposed using conventional surfactants of similar structure than surfmers. The main objective is to highlight the role of the polymerizable group and the fluorine atoms on the structure and the properties of the obtained nanocomposites. The surface properties of surfactants were studied in terms of CMC, surface tensions and Gibbs enthalpies of micellization to evaluate the solution behavior of these surfactants. These surfactants were subsequently used to modify a sodium montmorillonite via cation exchange process. The resultant organoclays were characterized by IR, TGA and XRD analysis. XRD data are in favor of an alignment of the majority of fluorinated surfmers to form a bilayer structure while conventional surfactants tend to form a pseudotrimolecular layer. Determination of surfmer reactivity ratios by NMR was used to predict the behavior of these derivatives in radical copolymerization with styrene. Preparation of polystyrene-clay nanocomposite containing various amounts of organoclays from 1 to 15 wt% by radical polymerization process in bulk or solution, showed the positive effect of the introduction of fluorinated chain and polymerizable functional group on thermal stability of nanocomposites. Exfoliated morphologies were obtained for the majority of the fluorinated nanocomposite. A structure-surface and thermal properties relationship was established on the basis of TGA, XRD and TEM / SEM analysis.

L'objectif de ce travail est d'améliorer l'activation de catalyseurs d'hydrotraitement CoMo/Al2O3 régénérés par l'emploi d'un nouvel additif organique, l'acide maléïque. En effet, le procédé de régénération permet la réutilisation d'un catalyseur d'hydrotraitement ayant subi une désactivation en éliminant les impuretés carbonées et en redispersant la phase active à la surface du catalyseur. Ce procédé ne permet cependant pas de retrouver l'activité initiale d'un catalyseur neuf. L'emploi d'additif organique lors de la préparation de catalyseurs régénérés permet alors d'améliorer l'activité catalytique. Au cours de ce travail, l'influence de l'acide maléïque a été étudiée à chaque étape du processus d'activation d'un catalyseur d'hydrotraitement régénéré. A l'état oxyde, l'acide maléïque n'influence pas la formation d'aluminate de cobalt tandis que cet additif consomme la phase CoMoO4 néfaste à l'activité finale dès maturation à 30°C. Cette consommation de la phase CoMoO4 s'accompagne de la formation de maléate de cobalt. Des études complémentaires menées par extraction des espèces oxydes suite à l'interaction du catalyseur régénéré avec l'acide maléïque en solution aqueuse montrent également une redispersion du molybdène sous forme d'un sel d'Anderson, AlMo6. Cette redispersion permet de sulfurer rapidement le molybdène dès 150°C tandis que le cobalt tend à se sulfurer progressivement avant décomposition du maléate. La décomposition complète du maléate de cobalt à 350°C permet alors de libérer le cobalt afin que celui-ci interagisse efficacement avec le sulfure de molybdène déjà formé conduisant à une proportion élevée en phase promue / The objective of this study is to improve the activation of regenerated CoMo/Al2O3 hydrotreating catalysts through the use of a novel organic additive, maleic acid. The regeneration process allows to re-use hydrotreating catalysts that have been deactivated leading to the removal of carbon impurities and to the redispersion of the active at the catalyst surface. However, using this process, the regenerated catalyst cannot recover completely the activity of a fresh catalyst. The use of organic additives during the preparation of regenerated catalysts can improve the final catalytic activity. In this work, the influence of maleic acid has been studied at each step of the activation procedure of a regenerated hydrotreating catalyst. At the oxide state, maleic acid does not influence the formation of cobalt aluminate while after maturation at 30°C, this additive can consume the CoMoO4 phase known to be detrimental to the activity. This disappearance of the CoMoO4 phase is accompanied by the formation of cobalt maleate. Complementary studies based on the extraction of oxide species through the interaction of the regenerated catalyst with maleic acid in aqueous solution also evidence the redispersion of molybdenum as AlMo6 Anderson salt species. This redispersion allows to rapidly sulphide molybdenum as soon as 150°C while cobalt is progressively sulphided before the maleate decomposition. The complete decomposition of cobalt maleate at 350°C makes cobalt available to interact efficiently with the already formed molybdenum sulphide leading to a high proportion of promoted phase

El cobre es uno de los mejores materiales para la conducción eléctrica y térmica. Lamentablemente, su mala resistencia al creep no permite su aplicación cuando se requiere óptimas propiedades mecánicas a altas temperaturas, tales como electrodos de soldadura por contacto. Una de las maneras de mejorar el comportamiento del cobre ante el creep es mediante la adición de dispersoides cerámicos nanométricos. El presente trabajo se encuentra en el marco del proyecto FONDECYT N° 1070294, el cual pretende estudiar el efecto del creep en aleaciones base cobre, endurecidas por dispersión. En este estudio se ha planteado, como objetivo general, la caracterización de la micro y nano estructura de aleaciones mecánicas de CuAl, Cu-V y Cu-Ti. Esta caracterización radica principalmente en el análisis de la evolución del tamaño de cristalita de las aleaciones, mediante técnicas de análisis de difracción de rayos X (DRX); en la determinación de la presencia de partículas de precipitado y en el estudio de las transformaciones de fases ocurridas durante el calentamiento de las aleaciones, a través de calorimetría diferencial de barrido (DSC) y DRX. Con el fin de estudiar la evolución de las aleaciones durante el proceso de fabricación y durante el periodo de servicio, el análisis de DSC y DRX es realizado antes de la molienda mecánica, luego de 30 horas de molienda y luego de la extrusión en caliente de los polvos aleados (esto último en la aleación de Cu-V). Luego de los análisis se evidencia que: • Todas las aleaciones estudiadas presentan tamaños de grano nanométrico (≤50 [nm]). • Las aleaciones de CuV y CuTi presentan textura a 10 y 20 horas de molienda. Tras 30 horas de molienda la textura disminuye drásticamente. No se detecta textura en la aleación de CuAl. • No se logra determinar una zona de recristalización a temperaturas menores de 1100[K].

Este estudo procurou avaliar as mudanças físicas e/ou químicas que ocorrem na hidroxiapatita (HAP) sintética e na presente no esmalte dental sob ação de aquecimento térmico em forno ou irradiação com o laser de Er,Cr:YSGG (2,79 m). Busca-se obter variações em sua estrutura a fim de torná-los mais resistentes à desmineralização, visando e prevenir a formação da cárie dental. A HAP sintética foi produzida pela reação das soluções de Ca(NO3) e (NH4)2HPO4 com controle de temperatura e pH. O esmalte foi coletado do dentes bovinos e triturados. As amostras em pó de HAP sintética e esmalte foram submetidas a aquecimento térmico em forno nas temperaturas de 200 °C, 400 °C, 600 °C, 800 °C e 1000 °C. Foram feitas irradiações laser com 5,79 J/cm2, 7,65 J/cm2, 10,55 e 13,84 J/cm2 para a HAP sintética e de 7,53 J/cm2, 10,95 J/cm2 e 13,74 J/cm2 para o esmalte. As amostras foram avaliadas por difração de raios-X(DRX) para análise das fases cristalográficas presentes e análise pelo método de Rietveld para comprovação destas fases cristalográficas e determinação de respectivas proporções no material. Foram obtidos também as variações de parâmetros de rede da cela unitária (eixo-a, eixo-c e volume), tamanho dos cristalitos e taxas de ocupações dos sítios dos átomos de Ca e P de ambos os materiais. As amostras foram ainda analisadas por espectroscopia de absorção no infravermelho por transformada de Fourier (FTIR), que mostrou as variações composicionais ocasionadas pelos tratamentos calculando-se as áreas das bandas referentes aos radicais carbonato, fosfato, água adsorvida e hidroxila. A termografia no infravermelho foi usada para medir a temperatura superficial gerada pelo feixe do laser nas amostras sólidas de esmalte. Com relação às fases cristalográficas presentes só foram encontradas além da fase majoritária de hidroxiapatita, as fases de fosfato de octacálcio (OCP) nas amostra de HAP sintética e tricálcio 9 fosfato da fase b (b -TCP) no esmalte aquecido a 800 °C. Apresentaram-se mudanças nos parâmetros de rede da cela unitária da HAP sintética e do esmalte, com diminuição do eixo-a, volume e tamanho dos cristalitos até as temperaturas entre 400 °C e 600 °C e também nas amostras irradiadas a laser. Acima da temperatura de 600 °C há o aumento destes parâmetros de rede. A relação Ca/P em todas as amostras sofreram diminuições, sendo que na amostra de esmalte irradiada a 7,53 J/cm2 apresentou Ca/P igual a 1,6817 e a irradiada a 13,74 J/cm2 apresentou Ca/P igual a 1,6831. A espectroscopia mostrou que os efeitos tanto do aquecimento como da irradiação laser podem ser observados principalmente nas bandas de carbonato, água adsorvida e hidroxila e que as mudanças da rede cristalográfica podem ser correlacionadas com substituições de carbonato em sítios de hidroxilas e fosfatos. Ambos os tratamentos causam também diminuição da concentração de carbonatos, sendo que este efeito ocorreu com maior intensidade nas irradiações a laser e houve ainda diminuição na quantidades de água adsorvida e hidroxilas. Todas estas alterações modificam as propriedades do material, como sua solubilidade e consequentemente influenciam na resistência à desmineralização de interesse para processos como prevenção da cárie dental e erosão dental. / The study evaluate the physical changes and/or chemical that occurs in synthetic hydroxyapatite (HAP) and in enamel under action of thermal heating in oven or laser irradiation of Er,Cr:YSGG that may cause changes in its structure to make them more resistant to demineralization aiming the formation of dental caries. The synthetic HAP was produced by reaction of solutions of Ca(NO3) and (NH4)2HPO4 with controlled temperature and pH. The enamel powder was collected from the bovine teeth. Samples of powder enamel and synthetic HAP were subjected to thermal heating in oven at temperatures of 200 °C, 400 °C, 600 °C, 800 °C and 1000 °C. For the laser irradiation of materials, were made with 5,79 J/cm2 of irradiation, 7,65 J/cm2, 10,55 J/cm2 and 13,84 J/cm2 for synthetic HAP and 7,53 J/cm2, 10,95 J/cm2, and 13,74 J/cm2 for the enamel. The samples were evaluated by X-ray diffraction (XRD) for analysis of crystallographic phases and analysis by the Rietveld method, to determine their respective proportions in the material, as well as results of changes of the lattice unit cell parameters (axisa, axis-c and volume), crystallites sizes and the occupation rate of sites of Ca and P atoms. The samples were analyzed by Fourier transform infrared spectroscopy (FTIR), which should compositional changes due to treatment related to carbonate, phosphate, adsorbed water and hydroxyl radicals content. The infrared was used to measure the surface temperature generated by the laser beam in the solid samples of enamel. Besides the major hydroxyapatite crystallographic phases, there was formations of octacalcium phosphate (OCP) and phase of tricalcium phosphate (-TCP ) in enamel heated at 800 °C. There was reduction of the axis-a, volume and size of crystallites to the temperatures between 400 °C and 600 °C and also on laser irradiated samples. Above the temperature of 600 °C it is observed the effect in the lattice parameters. The Ca/P relation in all the samples decreased. The enamel samples irradiated by 7,53 J/cm2 showed Ca/P equal to 1,6817 and by 13,74 J/cm2 Ca/P was 1,6831. Spectroscopy results showed that both the heating and laser irradiation cause changes primarily in the bands of carbonate, water adsorbed and hydroxyl and the crystallographic changes of the lattice may be correlated with changes in carbonate in the sites of hydroxyl and phosphates. The effects of heating in oven and laser irradiation causes reduction of carbonate content, and this effect was more evident in laser irradiated samples, there was also decreases in water and adsorbed hydroxyl contents. All these changes alter the properties of the material, as its solubility and therefore affect the demineralization process and can be useful for caries prevention as well as dental erosion prevention.

Ce travail de thèse porte sur l’effet de la fluoration sur la réactivité du dioxyde de titane. Dans ce travail, trois familles de TiO2, dont l’anatase pure, le rutile pure et le TiO2 de la phase mixte anatase/rutile ont été fluorées par la méthode dite du choc thermique à différentes températures, de 400 – 950°C. Les influences de la fluoration sur les propriétés et la composition élémentaire de leur surface ont été étudiées par spectroscopie photoélectronique à rayonnements X (XPS). L’évolution de la structure cristalline, la morphologie et les propriétés optiques de ces catalyseurs en fonction de la fluoration a été également étudiée en détail par diffraction des rayons X, nanosonde Auger et spectroscopie de réflectance diffuse UV - Visible. Leur activité photocatalytique a été évaluée par la dégradation du bleu de méthylène en solution. Jusqu’à 500°C, la fluoration est uniquement surfacique et ne modifie ni la structure ni la morphologie des particules TiO2. Cependant la fluoration augmente la teneur en groupement OH de surface, ce qui contribue à l’augmentation de l’activité photocatalytique. Par contre, au-delà de 500°C, la méthode de fluoration forme une phase parasite anisotrope, K2Ti6O13 qui réduit les performances photocatalytiques. La réactivité de surface des catalyseurs fluorés a été également évaluée par l’adsorption de sondes gazeuses acide SO2 et basique NH3, couplée à l’analyse XPS. Les résultats montrent que tous les catalyseurs possèdent des surfaces amphotères dont l’acidité et la basicité sont significativement influencées par la fluoration. / The thesis aimed to investigate the influences of fluorination on the reactivity of titanium dioxide. In this work, three crystallographic families of TiO2: pure anatase, pure rutile and TiO2 P25 (mixed phase anatase/rutile), were fluorinated by thermal shock method at different temperatures, from 400 to 950°C. The influence of fluorination on the properties and elementary composition of their surface was studied by X ray photoelectron spectroscopy (XPS). The evolution of crystal structure, morphology and optic properties of these catalysts versus the fluorination was also studied in detail by X ray diffraction, Auger nanoprobe and diffuse reflectance UV – Visible spectroscopy. Their photocatalytic activity was evaluated by the degradation of methylene blue in solution. According to the results, the fluorination below 600°C only occurs on the surface and does not modify the structure and the particle size of TiO2. However, the fluorination enhances the surface hydroxyl groups, which are assigned to the improvement of photocatalytic activity. For the fluorination over 600°C, the parasite anisotropic K2Ti6O13 phase is formed, resulting in the reduction of photocatalytic performances.The surface reactivity of our catalysts was also evaluated by the adsorption of probe molecules acid SO2 and basic NH3, coupled with XPS analysis. The results show that the surface of all catalysts is amphoteric with the acidity and basicity significantly affected by fluorination.