INTRODUÇÃO: A exposição prolongada às partículas ambientais está associada à mortalidade prematura devido às causas cárdio-respiratórias e ao câncer do pulmão. O tamanho e composição destas partículas estão relacionados à maior toxicidade, agravada pela retenção prolongada destas partículas no pulmão. Pode-se postular que partículas com diferentes composições elementares podem ter distribuição diferente ao longo da árvore traqueobrônquica. A captura por micro-dissecção a laser (CML) aparece neste cenário como uma alternativa rápida e eficaz para se obter amostras para estudo da distribuição destas partículas no pulmão. OBJETIVOS: Testar a eficácia da CML no estudo de partículas retidas no pulmão comparando com outra técnica de análise de cortes de parafina (P), já consagrada na literatura. Comparar também o perfil elementar de partículas retidas ao longo da árvore traqueobrônquica e linfonodos em duas cidades com perfis distintos de poluição, através da CML, associada à espectometria de raios-X por dispersão de energia (RX-DE) aliada à microscopia eletrônica de varredura (MEV). MÉTODOS: Vinte e quatro casos autopsiados foram obtidos em duas cidades com perfis distintos de poluição (São Paulo e São José do Rio Preto). As amostras de parênquima pulmonar obtidas do lobo médio do pulmão direito foram coletadas em três regiões: tecido peribrônquico, parênquima pulmonar periférico e linfonodos hilares. Para P, a análise foi feita em áreas visualizadas no MEV correspondentes às áreas de antracose. Estas áreas de antracose foram também micro-dissecadas, usando CML e analisadas através do RX-DE aliado ao MEV. RESULTADOS: Quando os dois métodos foram comparados, a maioria dos elementos encontrados, mostrando diferença significante, foi vista na CML, exceto pelo Ca e Mg (mais comumente encontrados em P). A análise elementar das partículas depositadas ao longo da árvore traqueobrônquica mostra dois grupos de distribuição dos elementos, com deposição predominante peribronquiolar ou com deposição predominante linfonodal. A análise elementar das áreas peribrônquicas descrimina melhor (95.8 %), o tipo de exposição à poluição, sem diferença significante para os outros locais estudados. CONCLUSÃO: Os perfis elementares das partículas retidas ao longo da árvore traqueobrônquica mostram dois grupos com padrão de distribuição distinta. A região proximal é o principal local para discriminação do tipo de exposição do indivíduo, sendo a antracose o carimbo da exposição à poluição. A CML se mostrou também uma ferramenta útil para discriminar áreas de interesse no estudo da análise elementar de partículas retidas no pulmão quando comparada com a análise nos cortes de parafina. / RATIONALE: Prolonged exposure to ambient particles is associated with premature mortality due to cardio respiratory diseases and lung cancer. Size and composition of these particles determine toxicity, aggravated by their long term retention in the lungs. In this context, it is plausible to postulate that different particles with different elemental composition must have distinct distribution patterns along the bronchial tree. Laser capture microdissection (LCM) appears as a rapid and efficient alternative for obtaining representative lung tissue for particle analysis. OBJECTIVES: To test laser capture microdissection (LCM) as a new tool for studying particle retention, comparing to a classical method using paraffin sections (PS). To compare the elemental profile of particles retained along the bronchial tree and lymph nodes in two cities with distinct pollution backgrounds by using LCM, through energy dispersive x-ray (EDX) and scanning electron microscopy (SEM). METHODS: Twenty-four right lung middle lobes from autopsied cases were obtained in two cities with different pollution backgrounds. Lung samples were collected from three distinct regions in the lungs at the time of autopsy: peribronchial tissue, peripheral parenchyma and hylar lymph nodes. For PS, analysis was performed in areas visualized in the SEM correspondent to anthracotic areas. These areas of anthracosis were also microdissected using LCM and analyzed for elemental composition through EDX allied to SEM. RESULTS: When the two methods were compared, the majority of the elements showing significant difference was predominantly found when LCM was used, except for Ca and Mg (more related to PS) Elemental analysis of particles deposited along the bronchial tree shows two groups of distribution: elements with preferable peribronchiolar or preferable lymph node deposition. Elemental profile of peribronchial areas discriminate accurately (95.8 %) the type of pollution exposure, with no statistical difference noted for the other sites. CONCLUSIONS: Elemental profiling of the particles retained along the bronchial tree shows two groups with distinct distribution patterns. The proximal bronchial tree is the main site for discrimination of pollution exposure, with an elemental finger print of anthracosis. LCM has also proven to be a useful tool in discriminating areas of interest for elemental analysis of particles retained in the lung when compared to analysis in PS.

As características das células musculares e da junção miotendínea do músculo pterigóideo mediai de ratos adultos e com envelhecimento foram estudadas, empregando-se as técnicas de microscopia de luz e eletrônica de varredura e de transmissão. A microscopia de luz mostrou que as fibras musculares inserem-se na superfície óssea mandibular através de tecido colágeno composto por numerosos fibroblastos. Os cortes examinados sob luz polarizada revelaram a presença de fibras colágenas tipo\' e li\' nesta região. Além disso, puderam-se notar os capilares sangüíneos em grande número. Observações ao microscópio eletrônico de varredura ressaltaram as estriações presentes no músculo esquelético. O tecido conjuntivo que constitui o endomísio foi notado quando as amostras foram tratadas com solução de hidróxido de sódio e foi possível observar os diferentes diâmetros apresentados pelas fibras musculares. A microscopia eletrônica de transmissão evidenciou o alinhamento dos sarcômeros e as concentrações de mitocôndrias junto à lâmina basal na terminação da fibra muscular. O estudo da junção miotendínea dos ratos adultos e com envelhecimento identificou as fibras colágenas e os feixes de miofibrilas formando interdigitações que promovem o aumento da superfície de contato nesta região. Os aspectos observados nos músculos de ratos adultos mostraram-se bastante similares aos encontrados nos ratos com envelhecimento. / The mediai pterygoid muscle cells and myotendinous junction characteristics of adult and aging rats were studied, using light microscopy and scanning and transmission electron microscopy techniques. The Iight microscopy showed the muscle fibers inserting in the mandible surface through collagen tissue and numerous fibroblasts. The samples examined in polarized light revealed the presence of type I and 11I collagen fibers in this site. Furthermore, the numerous blood capillaries could be noticed. Observations at the scanning electron microscope evidenced strias present in the skeletal muscle. The connective tissue that constitutes the endomysium could be noticed when the samples were treated with sodium hydroxide solution and it was possible to observe the muscle fibers different diameters. The transmission electron microscopy revealed the sarcomeres alignment and the mitochondria concentration by the basal lamina in the muscle fiber termination. The adult and aging rats myotendinous junction study showed the collagen fibers and the myofibrils bundles developing finger-like processes that increases the contact areas in this site. The aspects seen in adult rats pterygoid muscles were very similar to the ones seen in the aging rats.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / Este estudo avaliou o efeito de diferentes métodos de silanização e aplicação do ácido hidrofluorídrico (HF) sobre a resistência à microtração de uma cerâmica de dissilicato de lítio a um cimento resinoso. Quarenta blocos de IPS e.max Press /Ivoclar Vivadent (5x5x6mm) foram cimentados a blocos de resina Z250/3M ESPE (5x5x6mm) usando o cimento resinoso RelyX ARC/3M ESPE de acordo com os seguintes métodos de tratamento superficial: G1: 20s de ácido fluorídrico (HF) + silano não hidrolisado Primer-Activactor/Dentsply (SNH) seco à temperatura ambiente; G2: 20s HF + silano pré-hidrolisado RelyX Ceramic-Primer/3M ESPE (SPH) seco à temperatura ambiente; G3: 10s HF + SNH seco com ar quente (50oC-2min); G4: 10sHF + SPH seco com ar quente (50oC-2min); G5: sem ácido, SNH seco com ar quente (50oC-2min); G6: sem ácido, SPH seco com ar quente (50oC-2min); G7: sem ácido, SNH seco à temperatura ambiente; G8: sem ácido, SPH seco à temperatura ambiente. Antes de cada método de silanização, os blocos cerâmicos receberam acabamento com lixas de carbeto de silício (220-600) e limpeza com ácido fosfórico 37% (1min). A cimentação foi realizada com carga vertical de 1kg por 10min. Os conjuntos de cerâmica/cimento/resina foram armazenados em água destilada (37C) por 24 horas e depois seccionados em máquina de corte Isomet 1000 a fim de obter palitos (n = 40) de 1mm2 de área da seção transversal, que foram submetidos ao teste de microtração em máquina de ensaio universal Emic (v = 0,5mm/min). O modo de fratura foi avaliado em microscópio eletrônico de varredura. A análise estatística foi realizada utilizando ANOVA / Dunnett (p-valor = 0,000). As médias MPa e desvio padrão foram: G1-21,5 (8,9) BC; G2-30,5 (7,2) A; G3-19.4 (9.1) BC; G4-24,0 (9,0) B; G5-8.1 (3.2) D; G6 -18,0 (6,2) C; G7-7.8 (2,6) D; G8-6.3 (2,5) D. Grupos 2, 3, 4 e 6 não tiveram falhas prematuras dos palitos contra os grupos 1, 5, 7 e 8, que apresentaram 2,2; 44,4; 75,6 e 33,3% de perdas prematuras, respectivamente. O teste de correlação foi realizado apresentando significância estatística, com valor de -0,736 (p-valor = 0,000), mostrando que, a medida que o percentual de perda prematura aumenta, a média da MPa diminui. Quanto ao modo de fratura, observou-se 44,97% de falhas do tipo mista, 51,70% de falhas do tipo adesiva, 3,33% de falhas do tipo coesiva do cimento. Quando é realizada a supressão do condicionamento com HF como pré-tratamento da superfície cerâmica IPS e.max Press, a aplicação de silano SPH, associada ao seu tratamento térmico, deve ser o método de silanização recomendado, embora os valores mais elevados de resistência de união tenham sido os obtidos quando utilizado o condicionamento com HF por 20s. Quando é realizada a redução do tempo de condicionamento com HF para 10s, a aplicação do silano (SPH ou SNH) deve ser sempre associada ao seu tratamento térmico. O SNH só deve ser usado se as superfícies das cerâmicas IPS e.max Press forem tratadas com HF. / This study devaluated the effect of different types of silanization and hydrofluoric acid on the microtensile bond strength of a lithium dissilicate ceramic system. Forty IPS e.max Press /Ivoclar Vivadent blocks (5x5x6mm) were cemented to Z250/3M ESPE resin blocks (5x5x6mm) using RelyX ARC/3M ESPE resin-cement according to the following silanization methods: G1: 20s hydrofluoric acid (HF) + non-hydrolyzed silane Primer-Activactor/Dentsply (NHS) dried at room temperature; G2: 20sHF + pre-hydrolyzed silane RelyX Ceramic-Primer/3M ESPE (PHS) dried at room temperature; G3: 10sHF + NHS dried with hot air (50oC-2min); G4: 10sHF + PHS + hot air; G5: NHS + hot air; G6: PHS + hot air; G7: NHS dried at room temperature; G8: PHS dried at room temperature. Before each silanization method, all ceramic blocks were abraded with SiC grit papers (220-600) and cleaned with 37% phosphoric acid (1min). The cementation was made with vertical load of 01 kg for 10 min. After cementation procedure, all ceramic/ciment/resin blocks were stored in distilled water (37oC) for 24h before being cut to obtain stick-shapped specimens (n=45) of approximately 1mm2 cross-sectional area for microtensile test (v=0.5mm/min). Statistical analysis was performed using ANOVA/Dunnett (p-value = 0,000). The mean MPa(SD) values were: G1-21.5(8.9)BC; G2-30.5(7.2)A; G3-19.4(9.1)BC; G4-24.0(9.0)B; G5-8.1(3.2)D; G6-18.0(6.2)C; G7-7.8(2.6)D; G8-6.3(2.5)D. Groups 2, 3, 4 and 6 had no sticks premature fail against groups 1, 5, 7 and 8, that had 2.2, 44.4, 75.6 and 33.3% of sticks premature fails, respectively. As the correlation coefficient was statistically significant, -0.736 (p-value = 0.000), it could be argued that as the percentage of premature loss increased the MPa mean decreases. The failure mode was 44.97% of mixed failures, 51.70% of adhesive failures, 3.33% of cohesive failures of the cement. When the pretreatment is performed without HF conditioning of the IPS e.max Press ceramic surface, then PHS with hot air application should be the silanization method recommended, although higher bond strength values were obtained when HF conditioning for 20s was used with this type of silane. When the time of HF conditioning is reduced for 10 sec, the application of silane (SPH or SNH) must be always related to its heat treatment. NHS should only be used if IPS e.max Press ceramic surfaces are treated with HF.

Orientador: Maria Luiza Cotrim Sartor de Oliveira / Banca: Carlos Márcio Nóbrega de Jesus / Banca: Heidge Fukumasu / Não disponível / Abstract: Diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] is a herbicide that in a previous longterm study with Wistar rats fed at 2,500 ppm concentration showed high incidence of urothelial tumors in both genders. Accordingly, USEPA categorized Diuron as a "known/likely" human carcinogen. The accepted non-genotoxic mode of action (MOA) of Diuron encompasses urothelial necrosis induced by direct cytotoxicity, followed by regenerative cell proliferation and sustained urothelial hyperplasia that may favor neoplasia development. Scanning electron microscopy (SEM), light microscopy and labeling index are essentials tools for identification and classification of cytotoxic and proliferative changes in the bladder. The present study evaluated the dose-response of Diuron regarding urothelial lesions. Sixty male Wistar rats were fed Diuron for 20 weeks mixed in the diet at 0, 60, 125, 500, 1,250, or 2,500 ppm. Simple hyperplasia was significantly increased in the Diuron 1,250 and 2,500 ppm groups, and the cell proliferation at 2,500 ppm group. By SEM, the incidences and severity of lesions were significantly greater in the 500 and 1,250 ppm. Although numerically increased, the incidence of lesions in the 2,500 ppm group did not differ significantly from the control. The present study documented a doseresponse influence of Diuron on the rat urothelium, with a no observed effect level (NOEL) of 125 ppm. / Mestre

As alterações morfológicas do envelhecimento normal do disco intervertebral confundem-se com as patológicas. O objetivo deste estudo foi elaborar um perfil destas alterações. Discos intervertebrais cervicais e lombares foram coletados de 30 indivíduos assintomáticos: 15 jovens e 15 idosos. A morfologia foi analisada por macroscopia, ressonância magnética, histologia, microscopia eletrônica de varredura (MEV) e imuno-histoquímica para os colágenos de tipo I, II, III, IV, V, VI, IX e X. Alterações degenerativas foram mais acentuadas nos discos de idosos. O anel fibroso possui lamelas oblíquas que se adensam com o envelhecimento. A análise histológica não revela um núcleo distinto em nível cervical, porém a MEV o demonstra. As fibras colágenas sofreram intenso remodelamento e formam um padrão único para cada segmento. Alterações em nível cervical são semelhantes às lombares com algumas peculiaridades: substituição cartilagínea é comum. Muitas das técnicas rotineiras de avaliação não conseguem detectar as alterações discais ultraestruturais únicas de cada segmento. / The morphological alterations of normal aging in the intervertebral disc are frequently mistaken for those considered to be pathologic. Our aim is to elaborate a morphological profile of these alterations. Human cervical and lumbar intervertebral discs were harvested from 15 young (<35 years old) and 15 elderly (>65 years old) asymptomatic individuals. Their morphology was studied utilizing macroscopic technique, magnetic resonance, histology, scanning electron microscopy (SEM) and immunohistochemistry against types I, II, III, IV, V, Vi, IX and X collagens. Degenerative changes were more evident in discs of elderly individuals but even young discs displayed significant degeneration. The annulus is composed of oblique lamellae that get denser as they age. Histology frequently did not reveal a distinct nucleus in the cervical segment but SEM did. Collagen fibers form a pattern unique to each segment. Alterations in cervical discs are similar to those in lumbar specimens but include peculiarities. Several alterations could not be detected by MR or normal histology.

Made available in DSpace on 2016-04-28T20:16:31Z (GMT). No. of bitstreams: 1 2006-Denise Ribeiro de Melo.pdf: 1195079 bytes, checksum: 56cd5f0ff98087ea5e33db0b49c330f4 (MD5) Previous issue date: 2006-08-23 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Fleas are ectoparasites commonly found in dogs and cats and the species Ctenocephalides felis (Bouch?, 1835) are the most found in these animals. Ctenocephalides felis felis life cycle is influenced by temperature and humidity. This haematophagous insect feeds for approximately 30 days; its bite can cause allergic dermatitis and also can transmit several etiologic agents to domestic animals and humans. The objectives of the work were verifying the in vitro pathogenicity of the fungi Metarhizium anisopliae and Beauveria bassiana on eggs and adults of C. felis felis and investigated by scanning electron microscopy the development of entomopathogenic fungi on flea cuticle. Fleas were exposed to conidia (108 ml 1) of Metarhizium anisopliae (isolate 959) or Beauveria bassiana (isolate 986). The eggs and the adults used in the experiments were obtained from the colony, and were aspirated for the tubes (10 each). In the tests of effectiveness, the bioassays were constituted of two groups control and four groups treated with the suspensions in the concentrations 105, 106, 107 and 108 conidia.mL-1, and for each treatment they were made ten repetitions. Each group received a milliliter of the suspension to be tested, staying immersed by three minutes. The observations were done on each 12 hours and during the experimental phase the tubes were conditioned in acclimatized chamber in 25 1 C e = 75 % of relative humidity. The results demonstrated that the concentration 108 conidia.mL-1 of the two species inhibited the larval eclosion and caused the mortality of adults. Following standard protocols for electron microscopy, the specimens were prepared 2, 15, 26 and 96 h after infection. Glutaraldehyde 2.5% was used as a fixative. The electromicrography revealed that 2 h after fungus exposure, conidia attachments encompassed the entire flea cuticle, especially on abdominal intersegmental membranes. The emergence of germ tubes and appressoria formation occurred at 15 h, thickening and branching of hyphae on the flea cuticle was noted at 26 h. Therefore, both of these fungal isolates were able to develop on cuticular surfaces of Ctenocephalides felis felis. / As pulgas s?o ectoparasitas comumente encontrados em c?es e gatos, sendo a esp?cie Ctenocephalides felis (Bouch?, 1835), a mais encontrada nestes animais. O ciclo de Ctenocephalides felis felis ? influenciado pela temperatura, umidade e a alimenta??o se completa em aproximadamente 30 dias. A sua picada pode acarretar manifesta??o de dermatites al?rgicas, como tamb?m transmitir diversos agentes etiol?gicos aos animais dom?sticos e aos homens. O objetivo do trabalho foi de verificar a patogenicidade in vitro dos fungos Metarhizium anisopliae e Beauveria bassiana sobre ovos e adultos de C. felis felis e o desenvolvimento do fungo sobre a cut?cula da pulga, atrav?s da microscopia eletr?nica de varredura. Os isolados testados foram o M. anisopliae 959 e B. bassiana 986 na concentra??o 108 con?dios/mL. Os ovos e os adultos utilizados nos experimentos foram obtidos a partir da col?nia de onde foram aspirados em n?mero de dez para os tubos de ensaios. Nos testes de efic?cia, os bioensaios foram constitu?dos de dois grupos controle e quatro grupos tratados com as suspens?es nas concentra??es 105, 106, 107 e 108 con?dios.mL-1, e para cada tratamento foram feitas dez repeti??es. Cada grupo recebeu, um mililitro da suspens?o a ser testada, permanecendo imersos por tr?s minutos. A leitura foi realizada a cada 12h e durante todo a fase experimental os tubos ficaram acondicionados em c?mara climatizada a 25 ? 1?C e = 75 % UR. Os resultados demonstraram que a concentra??o 108 con?dios.ml-1 das duas esp?cies avaliadas se destacou das demais devido ao efeito delet?rio observado sobre larvas e adultos. Para a observa??o do desenvolvimento do fungo, as pulgas foram processadas em diferentes per?odos ap?s a infec??o, estipulados em 2, 15, 26 e 96 horas. O fixador utilizado foi o glutaralde?do 2,5 % e o material foi processado, segundo protocolo rotineiro para a microscopia eletr?nica de varredura. Com a obten??o das eletromicrografias, pode-se observar que com 2 horas os con?dios estavam aderidos por toda a cut?cula, situando-se preferencialmente nas membranas intersegmentais do abdome. Com 15 horas observouse a forma??o do tubo de germina??o e a cabe?a do apress?rio. Ap?s 26 horas foi poss?vel observar as ramifica??es e o engrossamento das hifas sobre a cut?cula das pulgas, indicando que os fungos testados foram capazes de se desenvolver sobre a cut?cula das mesmas.

The vectorial nature (polarization) of light plays a significant role in light-matter interaction that leads to a variety of optical devices. The polarization property of light has been exploited in imaging, metrology, data storage, optical communication and also extended to biological studies. Most of the past studies fully explored and dealt with the conventional polarization state of light that has spatially symmetric electrical field geometry such as linear and circular polarization. Recently, researchers have been attracted to light whose electric field vector varies in space, the so-called optical vector vortex beam (VVB). Such light is expected to further enhance and improve the efficiency of optical systems. For instance, a radially polarized light under focusing condition is capable of a tighter focus more than the general optical beams with a uniform polarization structure, which improves the resolution of the imaging system [1]. Interaction of ultrafast laser pulses with matter leads to numerous applications in material processing and biology for imaging and generation of microfluidic systems. A femtosecond pulse, with very high intensities of (10^{12} - 10^{13} W/cm^2), has the potential to trigger a phenomenon of optical breakdown at the surface and therefore induce permanent material modification. With such high intensities and taking into account the fact that most materials possess large bandgap, the interaction is completely nonlinear in nature, and the target material can be modified locally upon the surface and even further in bulk. The phenomenon of optical breakdown can be further investigated by studying the nonlinear absorption. Properties like very short pulse duration and the high irradiance of ultrashort laser pulse lead to more precise results during the laser ablation process over the long pulsed laser. The duration of femtosecond laser pulse provides a high resolution for material processing because of the significant low heat-affected zone (HAZ) beyond the desired interaction spot generated upon irradiating the material. Under certain condition, the interaction of intense ultrashort light pulses with the material gives rise to the generation of periodic surface structures with a sub-micron periodicity, i.e., much smaller than the laser wavelength. The self-oriented periodic surface structures generated by irradiating the material with multiple femtosecond laser pulses results in improving the functionality of the material's surface such as controlling wettability, improving thin film adhesion, and minimizing friction losses in automobile engines, consequently, influences positively on many implementations. In this work, we introduced a new method to study complex polarization states of light by imprinting them on a solid surface in the form of periodic nano-structures. Micro/Nanostructuring of diamond by ultrafast pulses is of extreme importance because of its potential applications in photonics and other related fields. We investigated periodic surface structures usually known as laser-induced periodic surface structures (LIPSS) formed by Gaussian beam as well as with structured light carrying orbital angular momentum (OAM), generated by a birefringent optical device called a q-plate (QP). We generated conventional nano-structures on diamond surface using linearly and circularly polarized Gaussian lights at different number of pulses and variable pulse energies. In addition, imprinting the complex polarization state of different orders of optical vector vortex beams on a solid surface was fulfilled in the form of periodic structures oriented parallel to the local electric field of optical light. We also produced a variety of unconventional surface structures by superimposing a Gaussian beam with a vector vortex beam or by superposition of different order vector vortex beams. This thesis is divided into five chapters, giving a brief description about laser-matter interaction, underlying the unique characterization of femtosecond laser over the longer pulse laser and mechanisms of material ablation under the irradiation of fs laser pulse. This chapter also presents some earlier studies reported in formation of (LIPSS) fabricated on diamond with Gaussian. The second chapter explains the properties of twisted light possessing orbital angular momentum in its wavefront, a few techniques used for OAM generation including a full explanation of the q-plate from the fabrication to the function of the q-plate, and the tool utilized to represent the polarization state of light (SoP), a Poincar'e sphere. Finally, the experimental details and results are discussed in the third and fourth chapters, respectively, following with a conclusion chapter that briefly summarizes the thesis and some potential application of our findings.

La Microscopie Electronique à Balayage Environnementale permet l'observation de liquides dans certaines conditions de pression et température. En travaillant en transmission, i.e. en mode STEM (Scanning Transmission Electron Microscopy), des nano-objets présents au sein du liquide peuvent même être analysés (mode « Wet-STEM»). Dans les solutions concentrées, l'arrangement du soluté peut changer être un paramètre microstructural important, qu’il est alors nécessaire de caractériser. Dans ce contexte, le but de ce travail est de développer la tomographie électronique sur des suspensions liquides en utilisant le mode STEM en ESEM, de manière à obtenir la structure 3D de nano-objets dispersés dans un liquide. Dans une première partie, le contraste entre des nanoparticules et le film d’eau est étudié en combinant des images expérimentales Wet-STEM (en 2D) et des simulations Monte Carlo. Deux types de nano-matériaux sont choisis : des nanoparticules d’or sphériques, de diamètre environ 40 nm, dispersées dans l’eau, ainsi qu’une suspension aqueuse de latex SBA-PMMA, contenant 3% de PMMA utilisé comme tensioactif stérique. La comparaison entre les résultats simulés et expérimentaux permet d’estimer comment le contraste entre l’eau et les nanomatériaux est affecté par l’épaisseur du film d’eau. Dans une deuxième partie, des expériences de tomographie sont réalisées à sec sur des films de polyuréthane contenant des nanotubes de carbone multiparois greffés ou non, en utilisant une platine développée précédemment au laboratoire. Le volume a pu être reconstruit correctement. Cependant, en effectuant une acquisition 3D sur des suspensions de latex SBA-PMMA, le contrôle de la température de l’échantillon s’est révélé insuffisant. Nous proposons une amélioration à la fois de la platine et des conditions d’observations permettant de mieux contrôler l’évaporation et la condensation de l’eau sur des échantillons liquides. La troisième partie est dévolue à une analyse approfondie d’une suspension de latex SBA-PMMA, de différentes concentrations (d’un état dilué à très concentré), les acquisitions étant effectuées avec les conditions optimisées. L’arrangement des particules de latex est comparé à des modèles issus de la littérature, et avec des résultats expérimentaux obtenus par cryo-SEM sur suspensions congelées. Nous présentons ensuite une étude du même latex en présence de tensioactif. La couche de tensioactif peut être mise en évidence dans les volumes reconstruits et segmentés. En conclusion, nous résumons les potentialités de la tomographie wet-STEM pour la caractérisation de nanomatériaux solides et liquides. Des perspectives sont proposées pour continuer dans l’exploration de ces potentialités et des limites de la technique. / ESEM (Environmental Scanning Electron Microscopy) allows the observation of liquids under specific conditions of pressure and temperature. When working in the transmission mode, i.e. in STEM (Scanning Transmission Electron Microscopy), nano-objects can even be analyzed inside the liquid (“wet-STEM” mode). Moreover, in situ evaporation of water can be performed to study the materials evolution from the wet to the dry state. This work aims at developing electron tomography on liquid suspensions using STEM-in-ESEM, to obtain the 3D structure of nano-objects dispersed in a liquid. In a first part, Monte Carlo simulations and 2D wet-STEM experimental images are combined to study the contrast. Two kinds of liquid nano-materials are chosen as the sample: spherical gold particles (diameter around 40 nm) in suspension in water; latex SBA-PMMA suspension, a copolymer derived from styrene and metacrylic acid esters in aqueous solution, 3% PMMA shell included as steric surfactant. The comparison between simulated and experimental results helps to determine how water can affect the contrast of hydrated nano-materials. Tomography experiments are then performed on dry PU-carbon nanotubes nanocomposites using a previously developed home-made tomography device, and the volume is well reconstructed. When performing tomography on latex suspension, limitations are found on the temperature control of samples. We propose an optimization of the device with new observations conditions to better control water evaporation and condensation of liquid samples. Afterwards, a full 3D analysis on SBA-PMMA latex from dilute suspension to very concentrated one is performed, and a further study is presented in presence of a surfactant. The encouraging reconstruction results are used to model the particles arrangement. This shows the potentialities of wet-STEM tomography for the characterization of both solid and liquid nano-materials.

No description available.

This study explores the possibility of prediction and modification of some of the physicochemical properties of non-metallic inclusions by considering top slag-steel-ladle equilibria in an ASEA-SKF ladle furnace. To test the reliability of an available computational thermodynamic computer program, the first sub project was done. It was concluded that LiMeS, an interface for Thermo-Calc, is a useful tool for slag-steel equilibrium calculations. The second sub project was set out to find some model/s that could calculate the most accurate oxygen activity of molten steel compared to the measured one. This study concluded that both Wagner’s and Turkdogan's equations are useful. It was further seen that increasing the Al contents in the molten steel, increasing the CaO/Al2O3 ratio in the top slag, and reducing the temperature, resulted in reduction of the oxygen activity of the molten steel. In the third sub project a comparison was made between measured CaO and Al2O3 (normalised to CaO-Al2O3) in top slag, calcium aluminate inclusions, and the results of theoretical calculations. The average contents of CaO and Al2O3 in all inclusions were close to the composition of the phase Ca12Al14O33 and the contents of CaO and Al2O3 in the slags were close to the composition of the phase Ca3Al2O6 in the binary phase diagram of CaO-Al2O3. The forth sub project set out to study the effect of vacuum degassing time on non-metallic inclusions. It was concluded that during the vacuum degassing process the share of calcium aluminates compared to spinels, Ca content of the oxides, and the average equivalent circle diameters of the oxides were increasing, and oxides tended to form spherical shapes. Finally, based on the preceding four sub projects, the fifth sub project aimed to optimize the steel treatment in an ASEA-SKF ladle furnace. The final results showed that by adding 200 kg fluorite to the top slag of 1200 kg, it was possible to achieve a sulphur content of less than 10 ppm in the steel and a sulphur ratio between slag and steel of 1570, and at the same time reduce the oxygen activity of the molten steel and the degassing time. / <p>QC 20120917</p>