Adaptive filters play an important role in the fields related to digital signal processing and communication, such as system identification, noise cancellation, channel equalization, and beamforming. In practical applications, the computational complexity of an adaptive filter is an important consideration. The Least Mean Square (LMS) algorithm is widely used because of its low computational complexity (O(N)) and simplicity in implementation. The least squares algorithms, such as Recursive Least Squares (RLS), Conjugate Gradient (CG), and Euclidean Direction Search (EDS), can converge faster and have lower steady-state mean square error (MSE) than LMS. However, their high computational complexity ($O(N^2)$) makes them unsuitable for many real-time applications. A well-known approach to controlling computational complexity is applying partial update (PU) method to adaptive filters. A partial update method can reduce the adaptive algorithm complexity by updating part of the weight vector instead of the entire vector or by updating part of the time. An analysis for different PU adaptive filter algorithms is necessary and meaningful. The deficient-length adaptive filter addresses a situation in system identification where the length of the estimated filter is shorter than the length of the actual unknown system. It is related to the partial update adaptive filter, but has different performance. It can be viewed as a PU adaptive filter, in that the deficient-length adaptive filter also updates part of the weight vector. However, it updates the same part of the weight vector for each iteration, while the partial update adaptive filter updates a different part of the weight vector for each iteration. In this work, basic PU methods are applied to the adaptive filter algorithms which have not been fully addressed in the literature, including CG, EDS, and Constant Modulus Algorithm (CMA) based algorithms. A new PU method, the selective-sequential method, is developed for LSCMA. Mathematical analysis is shown including convergence condition, steady-state performance, and tracking performance. Computer simulation with proper examples is also shown to further help study the performance. The performance is compared among different PU methods or among different adaptive filtering algorithms. Computational complexity is calculated for each PU method and each adaptive filter algorithm. The deficient-length RLS and EDS are also analyzed and compared to the performance of the PU adaptive filter. In this dissertation, basic partial-update methods are applied to adaptive filter algorithms including CMA1-2, NCMA, Least Squares CMA (LSCMA), EDS, and CG. A new PU method, the selective-sequential method, is developed for LSCMA. Mathematical derivation and performance analysis are provided including convergence condition, steady-state mean and mean-square performance for a time-invariant system. The steady-state mean and mean-square performance are also presented for a time-varying system. Computational complexity is calculated for each adaptive filter algorithm. Numerical examples are shown to compare the computational complexity of the PU adaptive filters with the full-update filters. Computer simulation examples, including system identification and channel equalization, are used to demonstrate the mathematical analysis and show the performance of PU adaptive filter algorithms. They also show the convergence performance of PU adaptive filters. The performance is compared between the original adaptive filter algorithms and different partial-update methods. The performance is also compared among similar PU least-squares adaptive filter algorithms, such as PU RLS, PU CG, and PU EDS. Deficient-length RLS and EDS are studied. The performance of the deficient-length filter is also compared with the partial update filter. In addition to the generic applications of system identification and channel equalization, two special applications of using partial update adaptive filters are also presented. One application is using PU adaptive filters to detect Global System for Mobile Communication (GSM) signals in a local GSM system using the Open Base Transceiver Station (OpenBTS) and Asterisk Private Branch Exchange (PBX). The other application is using PU adaptive filters to do image compression in a system combining hyperspectral image compression and classification. Overall, the PU adaptive filters can usually achieve comparable performance to the full-update filters while reducing the computational complexity significantly. The PU adaptive filters can achieve similar steady-state MSE to the full-update filters. Among different PU methods, the MMax method has a convergence rate very close to the full-update method. The sequential and stochastic methods converge slower than the MMax method. However, the MMax method does not always perform well with the LSCMA algorithm. The sequential LSCMA has the best performance among the PU LSCMA algorithms. The PU CMA may perform better than the full-update CMA in tracking a time-varying system. The MMax EDS can converge faster than the MMax RLS and CG. It can converge to the same steady-state MSE as the MMax RLS and CG, while having a lower computational complexity. The PU LMS and PU EDS can also perform a little better in a system combining hyperspectral image compression and classification. / Ph. D.

Made available in DSpace on 2017-07-21T20:43:46Z (GMT). No. of bitstreams: 1 Jean Cleber Bertoni.pdf: 7862049 bytes, checksum: 4c77f7ebc3fc211aac8ad8a7de58ccad (MD5) Previous issue date: 2015-01-30 / There are currently extensive research on aluminum alloys, mainly due to its wide application in the automotive and aerospace industries, due to the following characteristics, among them, low density, high thermal conductivity and high corrosion resistance at room temperature. Al-Fe alloys have a high degree of microstructural change due to changes in their properties when appropriate techniques are applied. The Al-Fe alloy was studied in the composition of 1.5% Fe by weight, which was subjected to the treatment laser surface remelting in order to enhance its surface characteristics. The characterization of these alloys in order to determine the variation of the chemical composition at different depths was performed by Grazzing incidence x-ray diffraction (GIXRD). In this technique, the angle of incidence of the X-ray beam was fixed and the detector moved in 2θ, it is possible to obtain the XRD patterns at different depths by varying the angle of incidence. In this work, the characterizations the micro and nano structural sample of alloy Al-1.5wt.%Fe treated by laser surface remelting (LSR) were performed, on the treated surface, as well as the transverse section, this study was performed at treated samples surface and at the isolated weld fillet on samples, where were applied laser beam speeds of 20, 40 and 60 mm / s. In this study we used different characterization techniques, such as, optical microscopy, scanning electron microscopy, energy dispersive spectroscopy, together with atomic force microscopy, and the Vickers hardness. Also in this work the technique of GIXRD was used to obtain depth profiles of near the surface chemical composition of the alloy. The analysis was performed in the micrometer range varying the angle of incidence between 0.5° to 6° in steps of 0.5° and analysis with incident angles 3° and 6° in steps of 0.02° for each 10 sec. As a result by examining the microstructure was characterized melted zone, the heat affected zone and the substrate, a particular features were found for each velocity of the laser beam, generally the treated area showed a more homogenous microstructure consisting of grains smaller feature, with low roughness and high hardness. The heat affected zone was more notorious the morphology of grains elongated feature in the treated and untreated interface for low laser beam scanning velocities. By means of the technique of X-ray diffraction various metastable phases were found, such as aluminum oxide, nitrides, etc., with different intensities of peaks as a consequence of the variation of angle of incidence. / Atualmente há uma ampla investigação sobre ligas de alumínio, principalmente devido a sua larga aplicação na indústria automotiva e aeroespacial, devido as seguintes características, entre elas, a baixa densidade, alta condutividade térmica e elevada resistência à corrosão a temperatura ambiente. Ligas de Al-Fe possuem um alto grau de modificação microestrutural, devido a mudanças em suas propriedades quando técnicas adequadas forem aplicadas. A liga Al-Fe foi estudada na composição de 1,5% de Fe em peso, a qual foi submetida ao tratamento de refusão superficial a laser de modo a aprimorar suas características superficiais. A caracterização dessas ligas com a finalidade de determinar à variação de composição química em diferentes profundidades foi realizado mediante a difração de raios X com ângulo de incidência rasante (DRXIR). Nesta técnica, o ângulo de incidência do feixe de raios X foi fixado e o detector moveu-se em 2θ, sendo possível obter os difratogramas em diferentes profundidades com a variação do ângulo de incidência. Neste trabalho, as caracterizações a nível micro e nano estrutural das amostras da liga Al-1,5%Fe tratadas por refusão superficial a laser (RSL) foram realizadas, tanto na superfície tratada e bem como na parte transversal, este estudo foi realizado nas amostras tratadas em toda a superfície, quanto nas amostras com trilhas isoladas que foram aplicadas as velocidades de feixe laser de 20, 40 e 60 mm/s. Para isso foram utilizados diferentes técnicas de caracterização, tais como, microscópio ótico, microscópio eletrônico de varredura, espectroscopia por energia dispersiva, acompanhada da microscopia de força atômica, bem como da microdureza Vickers. Também neste trabalho a técnica de DRXIR foi utilizada para obtenção de perfis de profundidade da composição química próxima à superfície da liga. A análise foi realizada em escala micrométrica por meio da variação do ângulo de incidência entre 0,5° a 6° com passos de 0,5°, bem como as análises com ângulos incidentes de 3º e 6º com passos de 0,02º a cada 10 s. Como resultado mediante o estudo microestrutural foram caracterizados a zona fundida, a zona afetada termicamente e o substrato, sendo encontradas características particulares para cada velocidade do feixe de laser, de modo geral a zona tratada mostrou ter uma característica microestrutural mais homogênea formada por grãos menores, com baixa rugosidade e de alta dureza. A zona afetada termicamente mostrou ser mais notória a morfologia de grãos com característica alongada na interface tratada e não tratada para baixas velocidades de varredura do feixe laser. Por meio da técnica de difração de raios X diferentes fases metaestáveis foram encontradas, tais como, óxido de alumínio, nitretos, etc, com diferentes intensidades de picos como consequência da variação do ângulo de incidência.

La micro-algue verte Chlamydomonas reinhardtii est considérée comme un modèle dans l’étude du stress métallique chez les organismes photosynthétiques. Les mécanismes de tolérance au stress induit par le cadmium ne sont pas encore clairement établis. Afin de déterminer ces mécanismes, la localisation subcellulaire et la spéciation chimique in situ du cadmium ont été déterminées chez trois souches de C. reinhardtii exposées au cadmium en condition mixotrophe (CO2 + Acétate) : (i) une souche de type sauvage (wt), (ii) la souche cell-wall less (cw15) qui est déficiente en paroi cellulaire, (iii) la souche pcs1 qui surexprime la phytochélatine synthase (PCS), enzyme ordinairement cytosolique, directement dans son chloroplaste. Pour ce faire, la toxicité du cadmium a été déterminée en mesurant la croissance ainsi que la teneur en chlorophylle et en amidon des micro-algues. Puis, la localisation du cadmium au niveau subcellulaire a été réalisée par trois techniques complémentaires (fractionnement subcellulaire, µXRF, TEM/X-EDS). La spéciation chimique in situ du cadmium a été effectuée par µXAS et XAS. Enfin, l’imagerie élémentaire et isotopique par nanoSIMS a permis de compléter les distributions élémentaires dans la cellule et de déterminer l’impact du cadmium sur les mécanismes d’assimilation du carbone. (i) Les résultats de ce travail montrent que la souche wt est la plus sensible au cadmium des trois avec une diminution de la croissance et de la teneur en chlorophylle. Lorsqu’elle ne présente pas ces signes de toxicité, le cadmium est séquestré dans l’ensemble de la cellule par des ligands thiolés et de façon mineure par les granules de polyphosphates. Suite à l’exposition à de fortes concentrations en cadmium, le cadmium intracellulaire est lié majoritairement à des ligands carboxylés probablement induits par le stress oxydatif. De plus, la présence du cadmium dans le pyrénoïde bloque l’assimilation du carbone inorganique (CO2), au profit de l’assimilation du carbone organique (acétate), qui est stocké sous forme d’amidon. (ii) La surexpression de la PCS de la souche pcs1 provoque une production d’amidon importante autour du pyrénoïde et protège la chlorophylle du stress lié au cadmium. Bien que la synthèse de phytochélatines soit potentiellement élevée, la moitié du cadmium intracellulaire est séquestrée par les granules de polyphosphates et l’amidon. (iii) La souche cw15 est la plus tolérante des trois souches et n’accumule pas la totalité du cadmium disponible, contrairement aux cellules possédant une paroi cellulaire. Similairement au wt, le cadmium intracellulaire est séquestré majoritairement par des ligands thiolés et de façon mineure par les granules de polyphosphates. L’observation de granules de polyphosphates excrétées par les micro-algues permet l’hypothèse de l’excrétion du cadmium vacuolaire induisant un flux constant de cadmium à travers la cellule. En conclusion, la séquestration du cadmium via des ligands soufre, potentiellement par des polypeptides thiolés, est le mécanisme de tolérance majoritaire mis en place par C. reinhardtii. Néanmoins, la séquestration du cadmium par les granules de polyphosphates semble apporter une plus grande tolérance vis-à-vis du stress lié au cadmium. / The green micro-alga Chlamydomonas reinhardtii is commonly used as a model for the study of the metallic stress in photosynthetic organisms. Tolerance mechanisms against stress induced by cadmium are not well understood. In order to determine these mechanisms, subcellular location and in situ speciation have been determined in three C. reinhardtii strains exposed to cadmium in mixotrophic conditions (CO2 + Acetate) : (i) a wild type strain (wt), (ii) a cell-wall less strain (cw15) which is deficient in cell-wall, (iii) the pcs1 strain which overexpresses the cytosolic enzyme phytochetlatin synthase (PCS) directly in the chloroplast. Cadmium toxicity has been determined by the monitoring of growth and chlorophyll, starch content in micro-algae. Then, cadmium location at subcellular level has been performed using three complementary techniques (subcellular fractionation, µXRF and TEM/X-EDS). In situ cadmium speciation has been studied by µXAS and XAS. Finally, elemental and isotopic imaging by nanoSIMS has allowed to complete elemental distribution in the cells and to determine the impact of cadmium on the assimilation of carbon. (i) The results of this work show that the wt strain is the most sensitive strain to cadmium stress among the three studied strains with a growth and chlorophyll content decrease. When wt cells do not show signs of toxicity, cadmium is mainly sequestered in the whole cell by thiolated ligands and in polyphosphate granules. After an exposure to high concentration of cadmium, intracellular cadmium is mainly bound to carboxylated ligands, probably induced by oxidative stress. Moreover, cadmium located in the pyrenoid blocks inorganic carbon (CO2) assimilation and increases organic carbon (acetate) assimilation which is stored as starch. (ii) The overexpresssion of PCS in the pcs1 strain induces a strong production of starch around the pyrenoid and proctects the chlorophyll against cadmium stress. Although the synthesis of phytocheltins was potentially strong, half of the intracellular cadmium is sequestered in polyphosphate granules and in starch. (iii) Unlike cell-walled cells, the cw15 strain is the most tolerant strain and does not accumulate the totality of available cadmium. Similarly to wt strain, intracellular cadmium is mainly sequestered by thiolated ligands and in polyphosphate granules. The observation of polyphosphate granules excreted by the micro-algae allows the hypothesis of the excretion of vacuolar cadmium, inducing a constant flux of cadmium through the cells. In conclusion, cadmium sequestration by sulfur ligands, potentially by thiolated polypeptides, is the main tolerance mechanism implemented by C. renhardtii. However, cadmium sequestration in polyphosphate granules seems to allow a better tolerance against cadmium stress.

Submitted by Eliseu Antonio Cavalini null (cavaliniea1356@ig.com.br) on 2017-01-08T01:45:41Z No. of bitstreams: 1 Tese Dout V Final.pdf: 2360887 bytes, checksum: 17f60dc9305936e9dd9ea3744d049148 (MD5) / Approved for entry into archive by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br) on 2017-01-11T13:28:41Z (GMT) No. of bitstreams: 1 cavalini_ea_dr_guara.pdf: 2360887 bytes, checksum: 17f60dc9305936e9dd9ea3744d049148 (MD5) / Made available in DSpace on 2017-01-11T13:28:41Z (GMT). No. of bitstreams: 1 cavalini_ea_dr_guara.pdf: 2360887 bytes, checksum: 17f60dc9305936e9dd9ea3744d049148 (MD5) Previous issue date: 2016-12-09 / Plasmas de gases e / ou vapores orgânicos produzem filmes finos ou pós apresentando características poliméricas, especialmente quando os plasmas são derivados de monômeros das famílias dos hidrocarbonetos alcoóis, siloxanos, silazanos, e outro. Neste trabalho, os filmes finos foram obtidos a partir da mistura de ácido cítrico-etilenoglicol-metal complexador depositado a plasma, com 13,56 MHz de radiofrequência na potência de 10 a 50 W e pressão fixada a 10 Pa. Os resultados da análise de espectroscopia de infravermelho FTIR mostrou que os grupos vibracionais dos filmes estavam preservados, mas com modificações em suas estruturas moleculares. Foram observados nos resultados obtidos por espectroscopia fotoelétrica de raios-X modificações na composição química da ligação oxigênio-carbono e oxigênio-hidrogênio com variação da potência de 10 a 50 W. A taxa de deposição dos filmes finos diminuiu de 0,10 a 0,08 nm/minuto com o aumento da potência de 10 a 50 W. As propriedades óticas das amostras como o índice de refração, coeficiente de absorção, gap ótico foram investigados por espectroscopia UV- visível. Destas análises foram possíveis obter valores n de 1,54 a 1,50 e energia do gap entre 4,75 e 4,85 eV. A técnica de ângulos de contato e foi utilizada para investigar a molhabilidade das amostras, que apresentaram caráter hidrofílico em todas as condições de deposição dos filmes. A técnica de EDS foi usada para investigar as composições químicas das amostras. Além disso, os filmes obtidos apresentaram valores de condutividade elétrica superior a 10-8 (Ωcm)-1 e constantes dielétricas entre 2,4 e 2,7. / Plasmas from gases and / or organic vapors produce thin films or powders presenting polymeric characteristics, especially when the plasmas are derived from monomers of the families of hydrocarbons, alcohols, siloxanes, silazanes, and others. In this work, thin films were obtained by citric acid / ethylene glycol / complex metal deposited by 13.56 MHz RF plasma at 10 and 50 W fixed pressure 10 Pa. FTIR spectroscopy showed that the main vibrational groups of the films were preserved, but with modifications in their molecular structures. It was observed by X –ray photoelectron spectroscopy chemical composition modifications in oxygen – carbon and oxygen – hydrogen bond while the deposition power changed from 10 to 50 W. The deposition rate of the samples decreased from 0.10 to 0.08 nm / minute while the RF power increases from 10 to 50 W. The samples optical properties as refractive index n, absorption coefficient, optical gap Eg were investigated by UV – Visible spectroscopy. From these analysis were possible to obtain values of n from 1.54 to 1.50 and Eg between 4.75 and 4.85 eV. Contact angle and surface energy measurements were used to investigate the wettability of composite Polymer films, for all depositions conditions the films presented hydrophilic character. EDS was used investigate components of the samples. Moreover, the film showed electrical conductivity values greater than 10-8(Ωcm)-1 and dielectric constant between 2.2 and 2.7.

Face à la finitude des ressources de la terre et de sa capacité d’absorption de la pollution, le développement d’écobétons pour un futur industrialisé durable représente un défi majeur de la science du béton moderne. En raison de sa nature hétérogène complexe, les propriétés macroscopiques du béton dépendent fortement des constituants de sa microstructure (ex. silicates de calcium hydratés [C–S–H], Portlandite, inclusions anhydres, porosité, agrégats, etc.). De plus, la nécessité d’une exploitation rapide et optimale des matériaux cimentaires émergents dans les applications industrielles demande de nos jours une meilleure compréhension de leurs particularités chimico-mécaniques à l’échelle micrométrique. Cette thèse vise à développer une méthode de pointe de couplage de la nanoindentation et de la spectroscopie quantitative aux rayons X à dispersion d'énergie (NI-QEDS), puis à fournir une caractérisation chimico-mécanique originale des phases microstructurales présentes dans les matrices réelles de ciments mélangés. La combinaison d’analyses NI-QEDS statistiques et déterministes a ainsi permis d’élargir la compréhension des systèmes avec ciment Portland et ajouts cimentaires (ACs) conventionnels ou alternatifs. Plus spécifiquement, l’étude des C–(A)–S–H (C–S–H incluant l’aluminium ou non) dans différents systèmes à base de ciments mélangés a montré des compositions différentes pour cet hydrate (variations dans les taux de Ca, Si, Al, S et Mg), mais ses propriétés mécaniques n’ont pas été significativement affectées par l’incorporation des ACs dans des dosages typiques. Les résultats présentés ont aussi démontré le rôle important des autres phases imbriquées dans la matrice de C–(A)–S–H, soit les inclusions anhydres dures (ex. le clinker et les ACs) et les autres hydrates tels que la Portlandite et les hydrates riches en aluminium (ex. les carboaluminates) avec des propriétés mécaniques plus élevées que celles des C–(A)–S–H. La thèse est basée sur cinq articles couvrant : (1) une analyse NI-EDS de systèmes incorporant des volumes élevés de pouzzolanes naturelles; (2) le développement de la méthode NI-QEDS; des analyses statistiques NI-QEDS (3) de systèmes avec cendres volantes et laitier, et (4) d’un système combinant ciment, calcaire et argile calcinée; et (5) une exploration déterministe NI-QEDS de systèmes conventionnels et alternatifs incorporant la poudre de verre, le métakaolin, le laitier ou la cendre volante. Finalement, en plus d’avancer les derniers modèles et méthodes micromécaniques, l’outil développé a fourni une perception chimico-mécanique originale des phases microstructurales et de leur arrangement. Le dévoilement de la signature chimico-mécanique de ces pâtes de ciments mélangés particulièrement complexes offre un savoir unique pour l’ingénierie des bétons de demain. / Abstract : Facing the limitedness of the earth’s resources and pollution absorption capacity, the development of eco-concrete for a sustainable industrialized future is one of the major challenges of modern concrete science. Due to its complex heterogeneous nature, the macro-scale properties of concrete strongly depend on the microstructure constituents (e.g., calcium-silicate-hydrates [C–S–H], Portlandite, anhydrous inclusions, porosity, aggregates, etc.). Moreover, the need for rapid and optimal exploitation of emerging binding materials in industrial applications urges today a better understanding of their chemo-mechanical features at the micrometer scale. This thesis aims at developing a state-of-the-art method coupling NanoIndentation and Quantitative Energy-Dispersive Spectroscopy (NI-QEDS), and providing an original chemo-mechanical characterization of the microstructure phases in highly heterogeneous matrices of real blended-cement pastes. The combination of statistical and deterministic NI-QEDS analysis approaches opened new research horizons in the understanding of Portland-cement systems incorporating conventional and alternative supplementary cementitious materials (SCMs). More specifically, the investigations of C–(A)–S–H (C–S–H including aluminum or not) in different blended-cement systems showed variable compositions for this hydrate (i.e., Ca, Si, Al, S and Mg contents), but the mechanical properties were not significantly affected by the incorporation of SCMs in typical dosages. The presented results also showed the important role of the other phases embedded in the C–(A)–S–H matrix, i.e., hard anhydrous inclusions (e.g., clinker and SCMs) and other hydrates such as Portlandite and Al-rich hydrates (e.g., carboaluminates) with mechanical properties higher than those of the C–(A)–S–H. The thesis is based on five articles focusing on: (1) the NI-EDS investigation of high-volume natural pozzolan systems; (2) the development of the NI-QEDS method; the statistical NI-QEDS analyses of (3) fly ash and slag blended-cement systems and of (4) a limestone-calcined-clay system; and (5) the deterministic NI-QEDS exploration of alternative and conventional systems incorporating glass powder, metakaolin, slag or fly ash. Finally, the developed tool not only advanced the latest micromechanical methods and models, but also provided original chemo-mechanical insights on the microstructure phases and their arrangement. Unveiling the chemo-mechanical signature of these highly-complex blended cement pastes further provided unique knowledge for engineering concretes for tomorrow.

Made available in DSpace on 2014-08-20T14:30:09Z (GMT). No. of bitstreams: 1 Dissertacao_aline_oliveira_ogliari.pdf: 2899521 bytes, checksum: 3a5e7870376f999dd52a171e479c76e9 (MD5) Previous issue date: 2012-12-10 / The aim of this study was to develop a simplified method for bonding to yttriastabilized zirconia ceramic. The method was based on deposition of a reactive silica layer on the ceramic surface followed by heat treatment. The study comprised six steps: (i) preparation of solutions using four concentrations of tetraethyl orthosilicate (TEOS) and zirconium tert-butoxide (ZTB) diluted in hexane; (ii) cutting and polishing of the zirconia substrate; (iii) organic silica-based treatment before (infiltration, INF) or after (coating, COA) zirconia sintering; (iv) analysis by scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS); (v) G-Raman confocal spectroscopy analysis; (vi) shear bond strength to zirconia tested after 24-h and failure analysis. An untreated (control) and a commercial reference (Rocatec Plus, 3M ESPE) groups were tested. Quantitative data were analyzed using ANOVA and Tukey s post hoc test (P < 0.05). SEM micrographs showed that zirconia surface was covered by silica nanoparticle clusters. EDS and G-Raman analyses confirmed composition of this layer. The bond strength results showed that most groups that received coating (COA) and infiltration (INF) presented higher bonding potential than the untreated (control) group. Almost all experimental groups were similar to commercial reference. Mixed failures were predominant. In conclusion, the present study introduces a novel, simple, and cost-effective method to provide adhesion to yttria-stabilized zirconia ceramic. Both the method of silica deposition (if before or after zirconia sintering) and concentration of organic silica precursors have a significant impact on the adhesion of methacrylates to the treated zirconia / O objetivo deste estudo foi desenvolver um método simplificado para obtenção de adesão a uma cerâmica de zircônia estabilizada por ítria. O método foi baseado na deposição de uma camada reativa de sílica na superfície cerâmica seguida por tratamento térmico. O estudo compreendeu seis etapas: (i) preparo de 4 soluções contendo tetraetilortosilicato (TEOS) e tert-butóxido de zircônio (ZTB) diluídos em hexano; (ii) corte e polimento do substrato de zircônia; (iii) tratamento com os precursores orgânicos antes (infiltração, INF) ou depois (cobertura, COA) da sinterização da zircônia; (iv) análise por microscopia eletrônica de varredura e espectroscopia de energia dispersiva (MEV-EDS); (v) análise por espectroscopia confocal G-Raman; (vi) avaliação de resistência de união ao cisalhamento 24h após preparo e análise de falha. Grupos sem tratamento (controle) e uma referência comercial (Rocatec Plus, 3M ESPE) foram testados. Dados quantitativos foram analisados usando ANOVA e teste post hoc de Tukey (P < 0,05). Os resultados de MEV mostraram que a superfície da zircônia foi coberta por aglomerados de nanopartículas de sílica, sendo esta composição confirmada por EDS e análise de G-Raman. Os resultados do teste mecânico mostraram que a maioria dos grupos que receberam cobertura (COA) e infiltração (INF) apresentaram maior resistência de união que o grupo sem tratamento (controle). A maioria dos grupos experimentais foram similares à referência comercial. Falhas do tipo mistas foram predominantes. Em conclusão, o presente estudo introduz um método novo, simples e de baixo custo para promover adesão a cerâmicas de zircônia estabilizada por ítria. Tanto o método de deposição de sílica (se antes ou após sinterização da zircônia) e a concentração de precursores orgânicos de sílica têm impacto significativo na adesão de metacrilatos à cerâmica tratada

De två kemiskt nära besläktade metallerna niob (Nb) och tantal (Ta) räknas av Europakommissionen som kritiska råmaterial. Detta på grund av en kraftigt ökad efterfrågan och en geografiskt koncentrerad global produktion av dem. Det här arbetet utgör en del av ett större projekt som bedrivs av EuroGeoSurveys (EGS); GeoERA FRAME, som har till syfte att kartlägga förekomsten av kritiska råmaterial inom EU. Två granitpegmatitiska prov från Kolsva fältspatgruva har undersökts med avseende på deras kemi och mineralogi; dels sådana som tentativt identifierats som kolumbitmineral och dels sådana som innehåller ett samarskitliknande mineral. I arbetet har tre huvudsakliga analysmetoder använts: 1) optisk mikroskopi, 2) svepelektronmikroskopi (SEM) med energidispersiv mikrokemisk analys (EDS), samt 3) pulverröntgendiffraktionsanalys (XRD). De kemiska analyserna som genomfördes på ”kolumbit-proven” visade att de bestod av kolumbit-(Fe), med generell formel AB2O6 och med en järndominans i A-katjonposition och niobdominans i B-katjonposition. Analyserna visad även på förekomst av mineral tillhörande pyroklorsupergruppen. De samarskitartade mineralen uppvisade en partiell likhet med samarskitgruppmineral (generell formel ABO4), men med hög grad av metamiktisering, dåliga stökiometrier, låga REE-halter, samt med varierande järn- och kalciumdominans i tentativ A-katjonposition och niobdominans i B-katjonpositionen. Även aluminiumsilikater, mineral från spinellgruppen samt hematit påvisades. Uppsprickning av de metamikta och spröda samarskitartade mineralen har möjliggjort en fluidmedierad omvandling, vilket bl.a. lett till bildning av sekundär radiogen blyglans. Resultaten av undersökningarna bekräftar att Kolsvapegmatiten representerar ett lokalt niob-tantalmineraliserat system. / The two chemically related metals niobium (Nb) and tantalum (Ta) are classified by the European Commission as critical raw materials. This is due to a highly increased demand and a limited global supply situation for these metals. This work is a part of a larger project run by EuroGeoSurveys (EGS); the GeoERA FRAME, which aims to map the distribution of critical raw materials in the EU. Two granitic pegmatite samples from the Kolsva feldspar mine were studied with regards to their chemistry and mineralogy. They had been tentatively identified as consisting of a columbite mineral and a samarskite-like mineral, respectively. In the project, three main analytical methods have been used: 1) optical microscopy, 2) scanning electron microscopy (SEM) with energy-dispersive spectroscopy (EDS), and 3) powder X-ray diffraction analysis (XRD). The analyses performed on the “columbite samples” indicated that most of them were columbite-(Fe), general formula AB2O6, with an iron dominance in the A-cation position and niobium dominance in the B-cation position. The analyses also indicated the presence of minerals belonging to the pyrochlore supergroup. The analyses of the samarskite-like minerals yielded results showing a partial resemblance to the samarskite group minerals (general formula ABO4), but with a high degree of metamictisation, poor stoichiometries, low to very low REE contents, variable iron and calcium-dominance in a tentative A-cation position and niobium-dominance in the B-cation position. Aluminium silicates, minerals from the spinel group and hematite were also observed in this assemblage. Fracturing of the brittle, metamict samarskite-like minerals have enabled a fluid-mediated alteration, which a.o. led to the formation of secondary radiogenic galena. The study confirms that the Kolsva pegmatite represents a locally Nb-Ta mineralised system.

Abstract Mineralogical-mineral chemical characterisation of Nb-Ta-bearingassemblages from the Stripåsen granitic pegmatite, NorbergJens Henriksson The occurrence of Nb-Ta-bearing minerals has earlier been briefly documented inthe Stripåsen granitic pegmatite, Norberg, central Bergslagen. This report describesthe background, preparation and basic characterisation of sampled Nb-Ta-bearingmineral assemblages from this pegmatite. These comprise (Y,REE,U,Th)-(Nb,Ta,Ti)-oxides of mainly a tantalum-dominated A 2-m B 2 X 6-w Y 1-n -type, belonging to the pyrochloresupergroup. The major primary mineral is suggested to have been afluorcalciomicrolite, ideally (Ca,Na,☐) 2 Ta 2 O 6 F. In association with abundant fractureformation related to metamictisation of the microlite minerals, they are interpreted tohave been variably altered by late-stage fluids. Thus, the system has beenextensively modified after the primary crystallisation of the pegmatite melt. Besidesthese (Y,REE,U,Th)-(Nb,Ta,Ti)-oxides, monazite-(Ce) ((Ce, LREE)PO 4 ), nativebismuth (Bi) and presumably radiogenic galena (PbS) were identified. The sampleshave mainly been studied by means of scanning-electron-microscopy with energydispersive spectroscopy (SEM-EDS), utilising reflected polarised light microscopy asa complementary tool. The study was done within the framework of the EU-supported FRAME-project which is focused on a selection of metals and minerals,among others niobium (Nb) and tantalum (Ta). / Sammanfattning Mineralogisk-mineralkemisk karakterisering av Nb-Ta-förande associationerfrån Stripåsenpegmatiten, NorbergJens Henriksson Förekomsten av Nb-Ta-förande mineral har tidigare dokumenteras iStripåsenpegmatiten, Norberg, centrala Bergslagen. Här redogörs för bakgrund,provförberedelse och grundläggande karakterisering av provtagna Nb-Ta-förandemineralassociationer från denna pegmatit. Proven som undersökts innehåller(Y,REE,U,Th)-(Nb,Ta,Ti)-oxider av främst tantaldominerad A 2-m B 2 X 6-w Y 1-n -typtillhörande pyroklorsupergruppen. Den huvudsakliga primära fasen tolkas ha varit enfluorkalciomikrolit, idealiskt (Ca,Na,☐) 2 Ta 2 O 6 F. I anslutning till rikligt förekommandesprickor som är relaterade till omfattande metamiktisering har mikroliternaomvandlats i varierande grad av sena fluider. Systemet har alltså förändrats kraftigtefter den primära kristallisationen av pegmatitsmältan. Förutom (Y,REE,U,Th)-(Nb,Ta,Ti)-oxider identifierades monazit-(Ce) ((Ce,LREE)PO 4 ), gedigen vismut (Bi)och vad som sannolikt är radiogen blyglans (PbS). Provmaterialet har huvudsakligenundersökts med genom svepelektronmikroskopi med energidispersiv spektroskopi(SEM-EDS), varvid malmmikroskopi har använts som ett kompletterande verktyg.Studien gjordes inom ramverket för det EU-stödda FRAME-projektet som blandannat fokuserar på förekomster av de kritiska och konfliktrelaterade metallerna niob(Nb) och tantal (Ta).

The topic of osmund iron is of great interest in both historical and metallurgical perspective. Between the 14th and the 17th century osmund iron was exported extensively from Sweden but it has been difficult to characterize and confirm what exactly osmund iron is. Further research should be conducted to improve the understanding of this kind of iron.   This work is primarily focused on medieval osmund iron. It is trying to determine what can be stated about their production methods and how to identify osmund pieces. A literature review was performed, to present an overview of iron production methods in medieval Europe. A metallurgical analysis was conducted on a number of osmund samples from the polish shipwreck ‘Miedsiowiec’, W5., together with samples from bar irons and iron billets from the same ship. Analysis was performed using LOM and SEM with EDS, analysing the crystallographic structure of the samples, and performing slag analysis using EDS to establish statistical trends. One of the aims was to evaluate a previously suggested hypothesis, namely that osmunds were shipped to Danzig from Stockholm, and then refined into iron bars and billets.  The studied iron bars and billets were purely ferritic with some slag inclusions. By looking at the shape of the slag inclusions, it can be stated that the bars and billets were forged differently from the osmund pieces. The osmunds were found to be made by indirect reduction as seen by the prevalence of cementite. It could not be confirmed if the bars and billets were forged by osmunds.  The osmunds showed different trace element compositions, than the iron bars and billets. The microstructure of all the osmunds varies greatly, which was to be expected. The osmunds had a higher carbon content and fewer slag inclusions. The hypothesis that osmunds were refined into iron bars and billets is not supported by the findings of this study. / Osmundjärn är av stort arkeometallurgiskt intresse, som en svensk exportvara som exporterades mellan 1300- och 1600-talet. Det är dock svårt att definitivt avgöra vad osmundjärn är för något. Det krävs därför ytterligare analyser och studier inom detta område för att förbättra vår förståelse av osmundjärn.   Denna studie behandlar upphittade medeltida osmundjärn och stångjärn i syfte att avgöra hur dessa har tillverkats. En litteraturstudie genomfördes som omfattande medeltida järntillverkningsprocesser, den existerande forskningen om osmundjärn samt relevanta forskningsmetoder. Järnproverna som erhölls kommer från den polska skeppsvraket ’Miedsiowiec’, W5. Mikrostrukturen av proverna analyserades med ljusmikroskop och en SEM-EDS analys utfördes. En föregående publicering om osmundar har föreslagit att osmundar exporterades från Stockholm till Gdansk, där de välldes och bearbetades till stångjärn. Osmundarna och stångjärnen som erhölls undersöktes också för att korrektheten i denna hypotes. Stångjärnens mikrostrukturer var ferritiska med ett flertal inneslutningar. Två av de så kallade iron billets hade anisotropiskt formad slagg, jämfört med de så kallade iron bars som hade isotropiskt format slagg. Det bedömdes att osmundarna var tillverkade i en masugn, på grund av perliten som hittades i mikrostrukturen i samtliga osmundar. Mikrostrukturen i alla osmundar varierade dock kraftigt, som väntat. Osmundarna hade också högre kolhalt, och färre slaggpartiklar. Hypotesen om att osmundar bearbetades till stångjärn stöds därför inte av resultaten som hittats i denna studie.

Pour assurer l'entretien des voies navigables, les sédiments de canaux sont régulièrement curés et généralement mis en dépôt. Cette pratique peut s'avérer dangereuse pour l'environnement lorsque ces sédiments sont contaminés. Le but de ce travail était d'identifier la spéciation du zinc dans un sédiment pollué et dans le sol sous-jacent après dépôt. Le transfert du zinc du sédiment vers le sol au cours du temps a été suivi par analyse des eaux, du sédiment et du sol. Les formes chimiques du zinc dans les phases solides ont été déterminées en combinant des techniques de micro-analyse (MEB-EDS, u-PIXE, u-RBS, u-SXRF) et la spectroscopie EXAFS, après fractionnement physique et chimique des échantillons. Les spectres EXAFS ont été exploités par analyse en composantes principales. Les principaux résultats de ce travail sont les suivants: * Dans le sédiment initial, le zinc est majoritairement présent sous forme de sphalérite (ZnS) et associé aux oxyhydroxydes de fer mal cristallisés. Trois espèces minoritaires, la willémite (Zn2SiO4), la zincite (ZnO) et un phyllosilicate zincifère ont été également identifiées. La présence de willémite, de zincite, et d'au moins une partie de la sphalérite, est attribuée aux activités anthropiques de grillage du minerai de zinc. La fixation d'une partie du zinc par les oxyhydroxydes de fer et les phyllosilicates résulte de l'altération des minéraux primaires. * L'oxydation des sulfures est le processus majeur contribuant à la mise en solution du zinc au cours du temps. La réduction des oxyhydroxydes de fer survenant lors des périodes d'hydromorphie concourt, dans une moindre mesure, à la mise en solution du zinc associé. * Au cours du temps, la proportion de ZnS diminue dans le sédiment au profit des formes secondaires. Un enrichissement en zinc a été mesuré après 16 mois de dépôt dans les premiers centimètres du sol sous-jacent. La majorité du zinc est alors sous forme de ZnS du fait d'une importante migration particulaire per descensum. Une autre partie du métal présent dans le sol est associée aux phyllosilicates et oxyhydroxydes de fer. Les conditions physico-chimiques du milieu (pH, Eh, concentrations en zinc, silice et fer dissous) sont favorables à la précipitation du zinc et de la silice libre sous forme de phyllosilicate zincifère, et à celle du fer dissous sous forme d'oxyhydroxydes de fer amorphes susceptibles de fixer le zinc. * Les bilans géochimiques montrent que la quantité de zinc exportée en solution, pendant la période de suivi du dépôt (16 mois), est faible en regard du stock contenu dans le sédiment, mais que cette quantité augmente de façon significative au cours du temps. Cependant, la majorité du zinc exporté en solution est vraisemblablement refixée par les phases d'altération. * Les phases d'altération comme les oxyhydroxydes de fer et les phyllosilicates pourraient être exploitées à des fins de rémédiation.