Through the history of mankind, novel materials have played a key role in techno- logical progress. As we approach the limits of scaling it becomes difficult to squeeze out any more extensions to Moore’s law by just reducing device feature sizes. It is important to look for an alternate semiconductor to silicon in order to continue making the progress predicted by Moore’s law. Among the various semiconductor options being explored world-wide, the III-nitride semiconductor material system has certain unique characteristics that make it one of the leading contenders. We explore the III-nitride semiconductor material system for the unique advantages that it offers over the other alternatives available to us. This thesis studies the device applications of epitaxial III-nitride films and nanos- tructures grown using plasma assisted molecular beam epitaxy (PAMBE) The material characterisation of the PAMBE grown epitaxial III-nitrides was car- ried out using techniques like high resolution X-ray diffraction (HR-XRD), field emis- sion scanning electron microscopy (FESEM), room temperature photoluminescence (PL) and transmission electron microscopy (TEM). The epitaxial III-nitrides were then further processed to fabricate devices like Schottky diodes, photodetectors and surface acoustic wave (SAW) devices. The electrical charcterisation of the fabricated devices was carried out using techniques like Hall measurement, IV and CV measure- ments on a DC probe station and S-parameter measurements on a vector network analyser connected to an RF probe station. We begin our work on Schottky diodes by explaining the motivation for adding an interfacial layer in a metal-semiconductor Schottky contact and how high-k di- electrics like HfO2 have been relatively unexplored in this application. We report the work carried out on the Pt/n-GaN metal-semiconductor (MS) Schottky and the Pt/HfO2/n-GaN metal-insulator-semiconductor (MIS) Schottky diode. We report an improvement in the diode parameters like barrier height (0.52 eV to 0.63 eV), ideality factor (2.1 to 1.3) and rectification ratio (35.9 to 98.9 @2V bias) after the introduction of 5 nm of HfO2 as the interfacial layer. Temperature dependent I-V measurements were done to gain a further understanding of the interface. We observe that the barrier height and ideality factor exhibit a temperature dependence. This was attributed to inhomogeneities at the interface and by assuming a Gaussian distribution of barrier heights. UV and IR photodetectors using III-nitrides are then studied. Our work on UV photodetectors describes the growth of epitaxial GaN films. Au nanoparticles were fabricated on these films using thermal evaporation and annealing. Al nanostruc- tures were fabricated using nanosphere lithography. Plasmonic enhancement using these metallic nanostructures was explored by fabricating metal-semiconductor-metal (MSM) photodetectors. We observed plasmonic enhancement of photocurrent in both cases. To obtain greater improvement, we etched down on the GaN film using reac tive ion etching (RIE). This resulted in further increase in photocurrent along with a reduction in dark current which was attributed to creation of new trap states. IR photodetectors studied in this thesis are InN quantum dots whose density can be controlled by varying the indium flux during growth. We observe that increase in InN quantum dot density results in increase in photocurrent and decrease in dark current in the fabricated IR photodetectors. We then explore the advantages that InGaN offers as a material that supports surface acoustic waves and fabricate InGaN based surface acoustic wave devices. We describe the growth of epitaxial In0.23 Ga0.77 N films on GaN template using molecular beam epitaxy. Material characterisation was carried out using HR-XRD, FESEM, PL and TEM. The composition was determined from HR-XRD and PL measurements and both results matched each other. This was followed by the fabrication of interdigited electrodes with finger spacing of 10 µm. S-parameter results showed a transmission peak at 104 MHz with an insertion loss of 19 dB. To the best of our knowledge, this is the first demonstration of an InGaN based SAW device. In summary, this thesis demonstrates the practical advantages of epitaxially grown film and nanostructured III-nitride materials such as GaN, InN and InGaN using plasma assisted molecular beam epitaxy for Schottky diodes, UV and IR photodetec- tors and surface acoustic wave devices.

Dans notre travail de thèse, nous nous sommes attachés à répondre à cette question : peut-t-on améliorer la résécabilité tumorale dans le métastases hépatiques et péritonéales du cancer colorectal? Pour cela nous nous sommes appuyés sur deux éléments : la fluorescence du vert d’indocyanine et sa détection par la caméra NIR. Dans un premier temps, après une mise au point en laboratoire, nous avons appliqué cette technique aux résections hépatiques. Nous avons montré que cette technique a un double intérêt : la détection des lésions tumorales et l’amélioration de la marge de résection oncologique. La question encore ouverte est le pourcentage de cellules cancéreuses ou précancéreuses présentent dans cette couronne fluorescente. Dans un deuxième temps nous avons appliqué cette technique dans la carcinose péritonéale. Il s’agit d’une première étude de faisabilité car nous n’avons retrouvé aucune publication sur ce sujet. Nous avons pu montrer des similitudes avec l’étude sur le foie. La fluorescence de l’ICG permet de détecter des tumeurs du péritoine difficilement visibles à l’œil nu grâce à l’intensité et à la qualité de la fluorescence même. Les perspectives sont centrées sur deux axes: l’agent fluorescent, le vert d’indocyanine, et les caméras NIR / In our work of PhD, we endeavored to answer this question: do we can improve tumor resectability in the liver and peritoneal metastases of colorectal cancer? For this, we relied on two elements: the fluorescence of indocyanine green and its detection by NIR camera. Initially, after formal laboratory development, we applied this technique to liver resections. We have shown that this technique has two advantages: the detection of tumor lesions and improving the margin of oncologic resection. The still open question is the percentage of cancerous or precancerous cells present in the fluorescent ring. Secondly, we applied this technique in peritoneal carcinomatosis. This is a first feasibility study because we did not find any publications on this topic. We could show similarities with the study on the liver. The fluorescence from ICG can detect tumors of the peritoneum hardly visible to the naked eye through the intensity and quality of the fluorescence. The outlook is focused on two areas: the fluorescent agent, indocyanine green, and NIR cameras

La limitation optique (LO) est un processus de protection des détecteurs optiques (yeux, caméras…) vis-à-vis des agressions laser. Le développement rapide de ces derniers aux fréquences des télécommunications a encouragé l’ingénierie moléculaire pour la LO dans cette fenêtre spectrale, en particulier à 1500 nm. Un des principaux mécanismes de la LO est l’absorption multiphotonique et plus particulièrement l’absorption à deux photons (ADP). Il s’agit d’un phénomène d’optique non-linéaire du troisième ordre au cours duquel un électron est promu de l’état fondamental vers l’état excité par absorption simultanée de deux photons. De plus, des travaux récents ont mis en évidence que le phénomène de LO peut être exalté par des processus d’absorption à l’état excité (AEE) induits par ADP. Dans ce contexte, cette thèse décrit la synthèse d’une nouvelle famille de chromophores de type aza-dipyrrométhène de bore (Aza-Bodipy), fonctionnalisés par des groupements donneur ou accepteur d’électrons. Ces molécules ont un comportement de limiteur optique sur toute la gamme spectrale voulue, avec un maximum d’efficacité vers 1300 nm. Les résultats ont été interprétés sur la base de deux phénomènes : l’ADP, suivie de l’AEE pour un procédé d’absorption globale à trois photons. Ces deux processus ont été mesurés séparément et des relations structure-activité ont été établies, afin de rationnaliser les données de LO. L’importance du transfert de charge et la superposition spectrale des deux phénomènes sont alors apparues comme les paramètres clefs à optimiser. En vue d’une application dans un dispositif optique réel, il est nécessaire que les chromophores soient incorporés dans un matériau solide, qui peut être poli et transformé. Ainsi, les composés synthétisés ont été insérés avec succès dans une matrice sol-gel. Pour la première fois, des matériaux de qualité optique ont été réalisés, possédant des propriétés de LO dans l’infra-rouge très performantes et meilleures qu’en solution. / The optical power limiting (OPL) is a protection process of detectors (eyes, cameras…) against laser aggression. The rapid development of frequency-tunable pulsed lasers up to telecommunication wavelengths led to the design of new materials for nonlinear absorption in this spectral range, in particular at 1500 nm. Mutiphotonic absorption, such as the two-photon absorption (TPA) is one of the mechanisms involved in the OPL. TPA is a third order nonlinear phenomenon that promotes a molecule to an excited state by the simultaneous absorption of two photons. Moreover, the overall OPL efficiency can be enhanced by excited state absorption (ESA). In this context, this thesis describes the synthesis of a new family of versatile near infra-red dyes, namely aza-borondipyrromethene (Aza-Bodipy) featuring several sites of functionalization by electro-donating or electro-withdrawing moieties. These molecules present the typical behavior of optical limiters at telecommunication wavelengths, with a maximal efficiency around 1300 nm. OPL curves were interpreted on the basis of two phenomena: TPA, followed by ESA for an overall 2+1 photons absorption. These two processes have been measured independently and structure-activity relationships have been established in order to rationalize OPL experiments. The charge transfer effect and the spectral overlap between TPA and ESA are therefore the key parameters. For practical use of OPL functions, it is required for the chromophores to be introduced into a solid material, which enables polishing and other post-processing. Therefore, Aza-Bodipy dyes have been successfully incorporated to a solid matrix using the sol-gel technique. For the first time, optical quality materials have been prepared featuring OPL properties in the infra-red, which are better than the ones in solution.

This study addresses the influence of elevated pressures, fuel type, fuel flow rate and co-flow air on the flame structure and flickering behaviour of laminar oscillating diffusion flames. Photomultipliers, high speed photography and schlieren, accompanied with digital image processing techniques have been used to study the flame dynamics. Furthermore, the effects of pressure on the flame geometry and two-dimensional soot temperature distribution in a laminar stable diffusion flame have been investigated, utilising narrow band photography and two-colour pyrometry technique in the near infra-red region. This study provides a broad dataset on the diffusion (sooty) flame properties under pressures from atmospheric to 16 bar for three gaseous hydrocarbon fuels (methane, ethylene and propane) in a co-flow burner facility.It has been observed that the flame properties are very sensitive to the fuel type and flow rate at elevated pressures. The cross-sectional area of the stable flame shows an average inverse dependence on pressure to the power of n, where n was found to be 0.8±0.2 for ethylene flame, 0.5±0.1 for methane flame and 0.6±0.1 for propane flame. The height of a flame increases firstly with pressure and then decreases with further increase of pressure. It is observed that the region of stable combustion was markedly reduced as pressure was increased. An ethylene flame flickers with at least three dominant modes, each with corresponding harmonics at elevated pressures. In contrast, methane flames flicker with one dominant frequency and as many as six harmonic modes at elevated pressures. The increase in fuel flow rate was observed to increase the magnitude of oscillation. The flickering frequency, however, remains almost constant at each pressure. The dominant flickering frequency of a methane diffusion flame shows a power-law dependence on chamber pressure.It has been observed that the flame dynamics and stability are also strongly affected by the co-flow air velocity. When the co-flow velocity reached a certain value, the buoyancy driven flame oscillation was completely suppressed. The schlieren imaging has revealed that the co-flow of air is able to push the initiation point of outer toroidal vortices beyond the visible flame to create a very stable flame. The oscillation frequency was observed to increase linearly with the air co-flow rate. The soot temperature results obtained by applying the two-colour method in the near infra-red region shows that in diffusion flames the overall temperatures decrease with increasing pressure. It is shown that the rate of temperature drop is greater for a pressure increase at lower pressures in comparison with higher pressures.

Une analyse du comportement thermomécanique du caoutchouc naturel est réalisée en combinant deux techniques d'imagerie quantitative. La corrélation d'images visibles sert à estimer les déformations puis l'énergie de déformation alors que des images infrarouges permettent d'estimer, via l'équation de diffusion, les quantités de chaleur mise en jeu. La construction de bilans d'énergie montre alors l'importance relative des mécanismes dissipatifs et de couplage thermomécanique. A basse fréquence pour de faibles déformations, les résultats permettent de retrouver le fameux effet d'inversion thermoélastique. A déformation plus importante, les résultats montrent une compétition sur le plan énergétique entre élasticité entropique et mécanismes de cristallisation/fusion sous contrainte. Aucun effet dissipatif significatif n'est détecté à basse comme en haute fréquence alors que dans chaque cas, sur le plan mécanique, une aire d'hystérésis caractérise la réponse cyclique du matériau. / An analysis of the thermomechanical behavior of the natural rubber is carried out by combining two quantitative imaging techniques. The digital image correlation of visible images is used to estimate the strain and then the deformation energy whereas infrared images make it possible to estimate, via the heat equation, the amounts of heat involved in the material transformation. The construction of energy balance enables us to determine the relative importance of the dissipative and thermomechanical coupling mechanisms. For low frequency and low extension ratio, the results show the famous thermoelastic inversion effect. From an energy standpoint, a competition between entropic elasticity and stress-induced crystallization/fusion mechanisms is observed for more significant extension ratios. No significant dissipative effect can be detected at low or high loading frequency whereas in each case, a stress-strain hysteresis characterizes the cyclic response of the material.

Plastskräp har blivit ett global problem på grund av nedskräpning och otillräcklig avfallshantering. Användning av biologiskt nedbrytbart material kan underlätta problemet, även om det inte är en universallösning. Produkter gjorda av biologiskt nedbrytbart material skall ändå till avfallshantering eftersom nedbrytningen kan vara långvarig och variera mycket beroende av omgivningen. Därmed är användningen av biologiskt nedbrytbart material endast berättigat då det är svårt att samla in materialet eller avskilja det från organiskt material. Studiens mål var att undersöka biologiskt nedbrytbara material som kan användas i produkter som fungerar under många olika driftsförhållanden och inte kan återställas efter användning. I den litterära delen av denna studie definieras nedbrytning genom egenskaper och förhållanden som påverkar nedbrytningsprocessen. Nedbrytning av polyestrar och cellulosa och de standardprocessarna som används i nedbrytningsexperimenten betraktades. Standardprocesserna för nedbrytning studerades för att få en klarare inblick i den eftertraktade nedbrytningsgraden och de standardiserade förhållandena för nedbrytningen i olika miljöer. En sammanfattning av olika nedbrytningsexperiment och analysmetoder är också inkluderade för att försäkra att experimenten som utfördes är både giltiga och jämförbara med andra forskningsresultat inom fältet. I detta forskningsprojekt utfördes nedbrytningsexperiment i färskvatten- och hemkompostmiljöer. Målet med projektet var att bedöma ifall materialen kunde brytas ned i ett brett spektrum av miljöer, ifall de var mindre skadliga för naturen än konventionella material som används av dagens industri och för att uppskatta nedbrytningstakten. Nedbrytningstiden var 140 dagar och experimentet utfördes med 10 olika material: betecknade som A-J. Materialen analyserades 8 gånger under nedbrytningsperioden förutom materialen I och J som analyserades en gång efter 140 dagar. Materialen analyserades mekaniskt, strukturellt och termiskt med hjälp av dragprovning, FTIR och DSC. Provernas viktförändring bestämdes också. Nedbrytning observerades visuellt från provernas yta och genom mekaniska prover. Materialen som placerades i hemkomposten visade klara tecken på nedbrytning då färgen hade förändrats och förstärkningsfibrerna hade blivit synliga. Materialen som placerats i hemkompostmiljö visade också klara tecken på tillväxt av mikroorganismer och biomassa som uppstått på ytan av materialen. Sammanfattningsvist, visade materialen B, C och G de mest lovande resultaten med klara tecken på biologisk nedbrytning och de hade en snabbare nedbrytningstakt än de andra materialen som undersöktes. Material D visade klara tecken på biologisk nedbrytning på ytan men dess nedbrytningstakt var uppskattad att vara mycket långsammare. Därmed rekommenderas det att använda material A, B, D och G istället för konventionella icke biologiskt nedbrytbara material. Dessa material har potential att sänka den negativa inverkan och de långsiktiga riskerna av plastskräp för miljön. / Plastic debris has become a global crisis due to littering and misplaced waste management. The use of biodegradable materials can ease the problem, but it is not always the answer. Products made of biodegradable materials are still to be waste managed since biodegradation can be a long process and is highly dependent on the environment conditions. Hence, the use of biodegradable materials is justified only when retrieving the product after use is impossible or prohibitively expensive or separating it from organic matter is difficult. This study was made to investigate biodegradable materials that can be used in products that are operating in broad range of operational conditions and cannot be retrieved back after use in most cases. In the literature part of this study the biodegradation is defined along with properties and conditions that affect the biodegradation process. Biodegradation of polyesters and cellulose, and standards used in the biodegradation experiments were reviewed. Biodegradation standards were studied in order to have a clearer picture of the pursued degree of biodegradation and standardized properties in the biodegradation experiments. Review of different biodegradation tests and analysis methods are included as well to ensure that the experiments performed in this work are valid and comparable with other biodegradation studies.  In this study, the biodegradation experiment was conducted in freshwater and home compost environments. The aim was to determine if the materials were able to biodegrade in wide range of environments, to make sure they are less harmful than the conventional materials used in the industry and to estimate the rate of biodegradation. The duration of the experiments were 140 days with 10 different materials: A – J. The materials were analyzed 8 times during the aging period, except materials I and J, which were analyzed only once after 140 days. The samples were analyzed mechanically, structurally, and thermally using tensile test, FTIR and DSC measurements, respectively. Also, the samples weight changes were analyzed.  The degradation was visually observed from the surfaces of the samples and from mechanical testing in both experimental environments. Home compost environment showed clear signs of biodegradation where reinforcement fibers became visible and changed the color of some of the samples. Also, home compost samples had microorganisms growing on them, and biomass was developing around them. To conclude, material B, C and G had the most promising results with clear signs of biodegradation and had faster estimated biodegradation rate compared with the other studied materials. Material D had signs of biodegradation on the surface as well. However, the biodegradation rate was estimated to be much slower. In conclusion, it is recommended to use the studied materials A, B, D and G instead of the conventional non-biodegradable polymers. These materials have potential to lower the negative impact and long-term risks of plastic debris to the environment.

The work in this thesis mainly focuses on the preparation and characterization of several phosphates and solid oxide systems with the aim of developing new proton conducting materials for intermediate temperature fuel cells (ITFCs). Soft chemical methods such as sol-gel methods and conventional solid state methods were applied for the synthesis of these materials. Aluminum phosphate obtained by a solution method is single phase and belongs to one of the Al(H₂PO₄)₃ allotropies with hexagonal symmetry. The material is stable up to 200°C and decomposes into Al(PO₃)₃ at a higher temperature. The electrical conductivity of pure Al(H₂PO₄)₃ is on the order of 10⁻⁶-10⁻⁷ S/cm, very close to the value for the known proton conductors AlH₃(PO₄)₂•3H₂O and AlH₂P₃O₁₀•2H₂O. Much higher conductivity is observed for samples containing even a trace amount of excess H₃PO₄. It is likely that the conduction path gradually changes from grain interior to the surface as the acid content increases. The conductivity of Al(H₂PO₄)₃-0.5H₃PO₄ exhibited a good stability over the measured 110 hours. Although tin pyrophosphate (SnP₂O₇) has been reported to show a significantly high conductivity (~10⁻² S/cm) at 250°C in various atmospheres, we observed large discrepancies in the electrical properties of SnP₂O₇ prepared by different methods. Using an excess amount of phosphorous in the synthetic procedure generally produces SnP₂O₇ with much higher conductivity (several orders of magnitude higher) than samples with stoichiometric Sn:P ratios in their synthetic procedure. Solid state ³¹P NMR confirmed the presence of residual phosphoric acid for samples with excess starting phosphorous. Transmission Electron Microscope (TEM) confirmed an amorphous layer covered the SnP₂O₇ granules which was probably phosphoric acid or condensed phases. Thereby, it is quite likely that the high conductivity of SnP₂O₇ results mainly from the contribution of the residual acid. The conductivity of these samples exhibited a good stability over the measured 80 hours. Based on the observations for SnP₂O₇, we developed a nano core-shell structure based on BPO₄ and P₂O₅ synthesised by solid state methods. The particle size of BPO₄ using this method varied between 10-20 nm depending on the content of P₂O₅. TEM confirmed the existence of an amorphous layer that is homogeneously distributed. The composite exhibits the highest conductivity of 8.8×10⁻² S/cm at 300°C in air for 20% extra P₂O₅ and demonstrates a good stability during the whole measured 110 hours. Polytetrafluoroethylene (PTFE) was introduced into the composites in order to increase malleability for fabrication. The conductivity and mechanical strength were optimized by adjusting the PTFE and P₂O₅ content. These organic-inorganic composites demonstrate much better stability at elevated temperature (250°C) over conventional SiC-H₃PO₄-PTFE composites which are common electrolytes for phosphoric acid fuel cells (PAFCs). Fuel cells based on BPO₄-H₃PO₄-PTFE composite as the electrolyte were investigated using pure H₂ and methanol as fuels. A maximum power density of 320 mW/cm² at a voltage of 0.31 V and a maximum current density of 1.9 A/cm² at 200°C were observed for H₂/O₂ fuel cells. A maximum power density of 40 mW/cm² and maximum current of 300 mA/cm² 275°C were observed when 3M methanol was used in the cell. Phosphoric acid was also introduced into materials with internal open structures such as phosphotungstic acid (H₃PW₁₂O₄₀) and heteropolyacid salt ((NH₄)₃PW₁₂O₄₀), for the purpose of acquiring additional connections. The hybrids obtained have a cubic symmetry with enlarged unit cell volume, probably due to the incorporation of phosphoric acid into the internal structures. Solid state ³¹P NMR performed on H₃PW₁₂O₄₀-xH₃PO₄ (x = 0-3) showed additional peaks at high acid content which could not assigned to phosphorus from the starting materials, suggesting a strong interaction between H₃PW₁₂O₄₀ and H₃PO₄. The conductivity of hybrids was improved significantly compared with samples without phosphoric acid. Fourier transform infrared spectra (FT-IR) suggest the existence of large amount of hydrogen bonds (OH••••O) that may responsible for the high conductivity. A H₂/O₂ fuel cell based on H₃PW₁₂O₄₀-H₃PO₄-PTFE exhibited a peak power density of 2.7 mW/cm² at 0.3 V in ambient temperature. Solid oxide proton conductors based on yttrium doped BaZrO₃ were investigated by introducing potassium or lanthanum at the A-sites. The materials were prepared by different methods and were obtained as a single phase with space group Pm-3m (221). The unit cell of these samples is slightly smaller than the undoped one. The upper limit of solid solution formation on the A-sites for potassium is between 5 ~ 10% as introducing more K results in the occurrence of a second phase or impurities such as YSZ (yttrium stabilized zirconium). K doped Barium zirconates showed an improved water uptake capability even with 5% K doping, whereas for La doped ones, water uptake is strongly dependent on particle size and synthetic history. The conductivity of K doped BaZrO₃ was improved by a factor of two (2×10⁻³ S/cm) at 600°C compared with undoped material. Fuel cells based on Pt/Ba₀₋₉₅K₀₋₀₅Zr₀₋₈₅Y₀₋₁₁Zn₀₋₀₄O[subscript(3-δ)]/Pt under humidified 5% H₂/air conditions gave a maximum power density 7.7 mWcm⁻² at 718°C and an interfacial resistance 4 Ωcm⁻². While for La doped samples, the conductivity was comparable with undoped ones; the benefits of introducing lanthanum at A-sites may not be so obvious as deficiency of barium is one factor that leads to the diminishing conductivity.

O grande desafio da Implantodontia é alcançar resultados a longo prazo com maior preservação dos tecidos ósseos, resposta adequada dos tecidos conjuntivos e manutenção da estabilidade secundária adequada para a retenção de próteses. Estes fatores evitam a perda indesejável tanto do tratamento reabilitador quanto dos tecidos ósseos de suporte. A região extraoral apresenta menores espessuras ósseas em comparação às regiões de maxila e mandíbula, especialmente no osso temporal. Portanto, os seguintes aspectos foram investigados: (i) Análise pelo Método dos Elementos Finitos (FEA) de 16 modelos virtuais, com aplicação de forças estáticas de tensão e compressão nos pontos médios entre os implantes. Três implantes maxilofaciais extraorais foram posicionados no osso temporal, onde um deles foi posicionado sobre o processo mastóide. Este estudo foi totalmente realizado em ambiente computacional. Foram empregados dois tipos de conexões protéticas e intermediários retos de conicidades 20º e 45º, posicionados virtualmente no modelo de osso temporal, com paralelismo entre eles. Foi desenhada uma barra virtual para retenção protética do tipo barra-clipe da prótese auricular. Foram consideradas as melhores configurações aquelas apresentando distribuição uniforme e branda das tensões de von Mises sobre o tecido ósseo adjacente aos implantes. (ii) Confecção de corpos de prova com graus variáveis de pigmentação para (a) melhorar a reprodutibilidade da coloração (b) entender e reduzir o processo de descoloração para melhorar a longevidade das próteses. Um elastômero maxilofacial tipo A foi pigmentado intrinsecamente de acordo com os seis tons da Escala de Fitzpatrick. Uma técnica de pigmentação foi desenvolvida a partir dos resultados obtidos a partir de uma Escala de Fitzpatrick impressa em papel e dos pigmentos intrínsecos de cores primárias. Este dimetil-metilvinil-siloxano reforçado por platina A 223-30 (Factor II, Inc., Lakeside, AZ, USA) apresenta dureza \"Shore-A\" 30. As amostras foram expostas a fotoenvelhecimento acelerado, e sua degradação mapeada com Espectroscopia UV/Vis/NIR. Concluiu-se que: (i) Os implantes com conexão cone Morse plataforma 3.7 tem melhor comportamento biomecânico com intermediários de 45o e altura de 2mm. Sugere-se planejamento cirúrgico visando a instalação a 3 horas para o temporal esquerdo e 9 horas para o temporal direito, mais 6 horas (mastóide). Implantes com conexão cone Morse plataforma 4.0 apresentaram comportamento biomecânico desejável com intermediários de 20o e alturas de 2mm or 4mm. Para implantes com conexão cone Morse plataforma 4.0, sugere-se a instalação a 6-9-12 horas para o temporal direito, e 12-6-3 para o esquerdo, visando comportamento biomecânico adequado. Sugere-se que os implantes extraorais Brånemark hexágono externo com plataforma 4.1 regular ou expandida sejam preferencialmente empregados com intermediários de 20o. (ii) O SiO2 5% pode ser adicionado à preparação do silicone para retardar o desbotamento da prótese maxilofacial. O TiO2 traz mudanças visuais significativas e pode ser considerado como opacificador. / Major challenges in Implantology include: achieving longevity of implants, bone tissue preservation, connective tissue suitable answer and maintenance of secondary stability in order to retain prosthesis. These factors avoid the undesirable loss of both rehabilitation treatment and supporting bone tissues. The extraoral region has less bone depth compared to the maxilla and mandible regions, especially for the temporal bone. Therefore, the following aspects were investigated: (i) Finite Elements Analysis (FEA) of 16 virtual models, with static application of tension and compression forces in medium points between implants. Three extraoral maxillofacial implants were placed on the temporal bone, which one of them was placed on the mastoid process. This study was made entirely in a computational environment. Two prosthetic connection types and straight Intermediários were employed, with conicities of 20º and 45º, placed virtually on the temporal bone model, mutually parallel. A virtual bar for bar-clip prosthetic retention of auricular prosthesis was designed. The best configurations were considered to be the ones presenting uniform and mild von Mises tension distribution over the bone tissue around the implants. (ii) Generation of samples with varying degree of pigmentation to (a) improve the reproducibility of the colouration (b) understand and minimise the discolouration process to improve prosthetics longevity. A maxillofacial elastomer type A was intrinsically pigmented according to the six tones of the Fitzpatrick Scale. A pigmentation technique was developed from spectroscopy outcomes of paper printed Fitzpatrick Scale and the primary colors pigments. This platinum reinforced dimethyl methylvinyl siloxane A 223-30 (Factor II, Inc., Lakeside, AZ, USA) presents \"Shore-A\" hardness 30. The samples were exposed to accelerated photo aging, and their degradation mapped with UV/Vis/NIR Spectroscopy. The effects of exclusion of oxygen and inclusion of nanoparticle fillers during prosthetic formulation were investigated. It was concluded that: (i) Morse taper prosthetic connection 3.7 platform implants, should be employed with 45o abutments with 2mm height. The surgical planning shall be for placement 3 hours for the left temporal bone and 9 hours for the right, and in 6 hours (mastoid). Morse taper prosthetic connection 4.0 platform implants behaved biomechanically desirably with 20o abutments in 2mm or 4mm heights. For the Morse taper connection 4.0 platform implants, their placement shall be in 6-9-12 hours, for the right temporal, and 12-3-6, for the left temporal, in order to achieve proper biomechanical behaviour. The Brånemark extraoral external hexagon implant, with 4.1 platform (normal or expanded) should preferrably be used with 20o abutments. (ii) The SiO2 5% may be added to the silicone preparation in order to slow maxillofacial prosthesis colour fading. The TiO2 brings visually significant changes and may be considered as an opacifier.

Les challenges posés par les missions d’exploration du système solaire sont très différents de ceux de la Station Spatiale Internationale, puisque les distances sont beaucoup plus importantes, limitant la possibilité de ravitaillements réguliers. Les systèmes support-vie basés sur des plantes supérieures et des micro-organismes, comme le projet de l’Agence Spatiale Européenne (ESA) MELiSSA (Micro Ecological Life Support System Alternative) permettront aux équipages d’être autonomes en termes de production de nourriture, revitalisation de l’air et de recyclage d’eau, tout en fermant les cycles de l’eau, de l’oxygène, de l’azote et du carbone, pendant les missions longue durée, et deviendront donc essentiels.La croissance et le développement des plantes et autres organismes biologiques sont fortement influencés par les conditions environnementales (par exemple la gravité, la pression, la température, l’humidité relative, les pressions partielles en O2 et CO2). Pour prédire la croissance des plantes dans ces conditions non-standard, il est crucial de développer des modèles de croissance mécanistiques, permettant une étude multi-échelle des différents phénomènes, ainsi que d’acquérir une compréhension approfondie de tous les processus impliqués dans le développement des plantes en environnement de gravité réduite et d’identifier les lacunes de connaissance.En particulier, les échanges gazeux à la surface de la feuille sont altérés en gravité réduite, ce qui pourrait diminuer la croissance des plantes dans l’espace. Ainsi, nous avons étudié les relations complexes entre convection forcée, niveau de gravité et production de biomasse et avons trouvé que l’inclusion de la gravité comme paramètre dans les modèles d’échanges gazeux des plantes nécessite une description précise des transferts de matière et d’énergie dans la couche limite. Nous avons ajouté un bilan d’énergie au bilan de masse du modèle de croissance de plante déjà existant et cela a ajouté des variations temporelles sur la température de surface des feuilles.Cette variable peut être mesurée à l’aide de caméras infra-rouges et nous avons réalisé une expérience en vol parabolique et cela nous a permis de valider des modèles de transferts gazeux locaux en 0g et 2g, sans ventilation.Enfin, le transport de sève, la croissance racinaire et la sénescence des feuilles doivent être étudiés en conditions de gravité réduite. Cela permettrait de lier notre modèle d’échanges gazeux à la morphologie des plantes et aux allocations de ressources dans une plante et ainsi arriver à un modèle mécanistique complet de la croissance des plantes en environnement de gravité réduite. / Challenges triggered by human space exploration of the solar system are different from those of the International Space Station because distances and time frames are of a different scale, preventing frequent resupplies. Bioregenerative life-support systems based on higher plants and microorganisms, such as the ESA Micro-Ecological Life Support System Alternative (MELiSSA) project will enable crews to be autonomous in food production, air revitalization, and water recycling, while closing cycles for water, oxygen, nitrogen, and carbon, during long-duration missions and will thus become necessary.The growth and development of higher plants and other biological organisms are strongly influenced by environmental conditions (e.g. gravity, pressure, temperature, relative humidity, partial pressure of O2 or CO2). To predict plant growth in these non-standard conditions, it is crucial to develop mechanistic models of plant growth, enabling multi-scale study of different phenomena, as well as gaining thorough understanding on all processes involved in plant development in low gravity environment and identifying knowledge gaps.Especially gas exchanges at the leaf surface are altered in reduced gravity, which could reduce plant growth in space. Thus, we studied the intricate relationships between forced convection, gravity levels and biomass production and found that the inclusion of gravity as a parameter in plant gas exchanges models requires accurate mass and heat transfer descriptions in the boundary layer. We introduced an energy coupling to the already existing mass balance model of plant growth and this introduced time-dependent variations of the leaf surface temperature.This variable can be measured using infra-red cameras and we implemented a parabolic flight experiment, which enabled us to validate local gas transfer models in 0g and 2g without ventilation.Finally, sap transport needs to be studied in reduced gravity environments, along with root absorption and leaf senescence. This would enable to link our gas exchanges model to plant morphology and resources allocations, and achieve a complete mechanistic model of plant growth in low gravity environments.

O grande desafio da Implantodontia é alcançar resultados a longo prazo com maior preservação dos tecidos ósseos, resposta adequada dos tecidos conjuntivos e manutenção da estabilidade secundária adequada para a retenção de próteses. Estes fatores evitam a perda indesejável tanto do tratamento reabilitador quanto dos tecidos ósseos de suporte. A região extraoral apresenta menores espessuras ósseas em comparação às regiões de maxila e mandíbula, especialmente no osso temporal. Portanto, os seguintes aspectos foram investigados: (i) Análise pelo Método dos Elementos Finitos (FEA) de 16 modelos virtuais, com aplicação de forças estáticas de tensão e compressão nos pontos médios entre os implantes. Três implantes maxilofaciais extraorais foram posicionados no osso temporal, onde um deles foi posicionado sobre o processo mastóide. Este estudo foi totalmente realizado em ambiente computacional. Foram empregados dois tipos de conexões protéticas e intermediários retos de conicidades 20º e 45º, posicionados virtualmente no modelo de osso temporal, com paralelismo entre eles. Foi desenhada uma barra virtual para retenção protética do tipo barra-clipe da prótese auricular. Foram consideradas as melhores configurações aquelas apresentando distribuição uniforme e branda das tensões de von Mises sobre o tecido ósseo adjacente aos implantes. (ii) Confecção de corpos de prova com graus variáveis de pigmentação para (a) melhorar a reprodutibilidade da coloração (b) entender e reduzir o processo de descoloração para melhorar a longevidade das próteses. Um elastômero maxilofacial tipo A foi pigmentado intrinsecamente de acordo com os seis tons da Escala de Fitzpatrick. Uma técnica de pigmentação foi desenvolvida a partir dos resultados obtidos a partir de uma Escala de Fitzpatrick impressa em papel e dos pigmentos intrínsecos de cores primárias. Este dimetil-metilvinil-siloxano reforçado por platina A 223-30 (Factor II, Inc., Lakeside, AZ, USA) apresenta dureza \"Shore-A\" 30. As amostras foram expostas a fotoenvelhecimento acelerado, e sua degradação mapeada com Espectroscopia UV/Vis/NIR. Concluiu-se que: (i) Os implantes com conexão cone Morse plataforma 3.7 tem melhor comportamento biomecânico com intermediários de 45o e altura de 2mm. Sugere-se planejamento cirúrgico visando a instalação a 3 horas para o temporal esquerdo e 9 horas para o temporal direito, mais 6 horas (mastóide). Implantes com conexão cone Morse plataforma 4.0 apresentaram comportamento biomecânico desejável com intermediários de 20o e alturas de 2mm or 4mm. Para implantes com conexão cone Morse plataforma 4.0, sugere-se a instalação a 6-9-12 horas para o temporal direito, e 12-6-3 para o esquerdo, visando comportamento biomecânico adequado. Sugere-se que os implantes extraorais Brånemark hexágono externo com plataforma 4.1 regular ou expandida sejam preferencialmente empregados com intermediários de 20o. (ii) O SiO2 5% pode ser adicionado à preparação do silicone para retardar o desbotamento da prótese maxilofacial. O TiO2 traz mudanças visuais significativas e pode ser considerado como opacificador. / Major challenges in Implantology include: achieving longevity of implants, bone tissue preservation, connective tissue suitable answer and maintenance of secondary stability in order to retain prosthesis. These factors avoid the undesirable loss of both rehabilitation treatment and supporting bone tissues. The extraoral region has less bone depth compared to the maxilla and mandible regions, especially for the temporal bone. Therefore, the following aspects were investigated: (i) Finite Elements Analysis (FEA) of 16 virtual models, with static application of tension and compression forces in medium points between implants. Three extraoral maxillofacial implants were placed on the temporal bone, which one of them was placed on the mastoid process. This study was made entirely in a computational environment. Two prosthetic connection types and straight Intermediários were employed, with conicities of 20º and 45º, placed virtually on the temporal bone model, mutually parallel. A virtual bar for bar-clip prosthetic retention of auricular prosthesis was designed. The best configurations were considered to be the ones presenting uniform and mild von Mises tension distribution over the bone tissue around the implants. (ii) Generation of samples with varying degree of pigmentation to (a) improve the reproducibility of the colouration (b) understand and minimise the discolouration process to improve prosthetics longevity. A maxillofacial elastomer type A was intrinsically pigmented according to the six tones of the Fitzpatrick Scale. A pigmentation technique was developed from spectroscopy outcomes of paper printed Fitzpatrick Scale and the primary colors pigments. This platinum reinforced dimethyl methylvinyl siloxane A 223-30 (Factor II, Inc., Lakeside, AZ, USA) presents \"Shore-A\" hardness 30. The samples were exposed to accelerated photo aging, and their degradation mapped with UV/Vis/NIR Spectroscopy. The effects of exclusion of oxygen and inclusion of nanoparticle fillers during prosthetic formulation were investigated. It was concluded that: (i) Morse taper prosthetic connection 3.7 platform implants, should be employed with 45o abutments with 2mm height. The surgical planning shall be for placement 3 hours for the left temporal bone and 9 hours for the right, and in 6 hours (mastoid). Morse taper prosthetic connection 4.0 platform implants behaved biomechanically desirably with 20o abutments in 2mm or 4mm heights. For the Morse taper connection 4.0 platform implants, their placement shall be in 6-9-12 hours, for the right temporal, and 12-3-6, for the left temporal, in order to achieve proper biomechanical behaviour. The Brånemark extraoral external hexagon implant, with 4.1 platform (normal or expanded) should preferrably be used with 20o abutments. (ii) The SiO2 5% may be added to the silicone preparation in order to slow maxillofacial prosthesis colour fading. The TiO2 brings visually significant changes and may be considered as an opacifier.