Due to the increasing usage of Sn in different electronics, such as solders and in touchscreens, together with Boliden Rönnskärs increased intake of electronic waste as a secondaryraw material, a Zn-containing product called Zn-clinker has increasing amounts of Sn. TheZn-clinker is shipped to Boliden Zn-smelter in Odda, where the Zn-clinker is mixed in withcalcine (roasted concentrate) and leached in several steps. Since Zn-clinker is a product froma halogen removal in a clinker-furnace, the feed material (Mixed Oxide), for this furnace, wasalso investigated since there are plans to replace clinkering with soda-washing in the future.Most of the Sn ends up in the leaching residue which then is deposited in the mountaincaverns close by the Boliden Odda smelter. Boliden is studying the possibility to recoverPb/Ag and Sn content from the leaching residue and create a valuable by-product. Bystudying how the leaching of Sn behaves, together with a characterization of the materials, thefollowing question should be answered: “During which sulphuric acid leaching conditions, ofZn-clinker and Mixed Oxide, is the leaching of Sn minimized?” The leaching results for Zn-clinker showed that 8-10% Sn will leach out, despite changingtemperature, redox potential, time and pH. A characterization of the material with SEM-EDSand XRD-analysis was also conducted to see if Sn could be identified in any phases in thematerials. The studies provided enough evidence that Zn2SnO4 could be concluded to be themain phase in the leaching residue for Zn-clinker, a form that would not leach underconditions presented in this project. However, 8-10% of the Sn will come together with Feand when Fe leach out, so does Sn. The leaching results for Mixed Oxide pointed towards that different phases from them foundin Zn-clinker was present. Sn losses varied between 10-20% but raised to 47% whentemperature was changed to 80 °C during leaching. The SEM-EDS analysis showed that theidentified Sn-phases contained more Sn than in Zn-clinker and together with the leachingresults, a conclusion that Sn would mainly be found as SnO2 or SnO in the Mixed Oxide, butthere is still uncertainty about the distributions of these forms. Unfortunately half of the As leached out during the soda-washing for Mixed Oxide, creating aleachate with Cl, F and As that need to be taken care of. This could be challenging andpresenting a costly side-project for the route different from the Zn-clinker route used today.Another observation was that PbCO3 formed during the soda-washing, a phase that willconsume more sulphuric acid during leaching.

Este trabalho tem como objetivo a obtenção das taxas de sedimentação da plataforma continental e do talude superior, no trecho centro norte do Embaiamento São Paulo (Santos a Cabo Frio), além da verificação do uso do método 210Pb/137Cs, comparados a métodos mais tradicionais como o 14C, para a obtenção destas taxas de sedimentação. Um segundo objetivo é verificar se ocorre a transferência de metais, provenientes da área costeira contígua, para o oceano aberto. Para a realização deste trabalho, foram coletados, em diferentes projetos de pesquisa, 12 testemunhos que foram analisados em função da granulometria e dos teores de CaCO3 e metais (Pb, Cu e Zn). Estes mesmos testemunhos foram submetidos, também, a análise da espectrometria gama para obtenção dos níveis de atividade de 210Pb e 137Cs. A partir da medição destes níveis, após alguns cálculos matemáticos baseados no modelo CIC, puderam ser obtidas as taxas de sedimentação. Os resultados indicaram colunas sedimentares bastante homogêneas, predominantemente siliciclásticas. As taxas de sedimentação obtidas, na ordem de milímetros/ano, são compatíveis com os dados encontrados em outras partes do litoral brasileiro e do mundo, onde o aporte atual de sedimentos não é significativo. Com base nestes dados, pode-se afirmar que o método 210Pb/137Cs é bastante confiável para a obtenção de taxas de sedimentação e identificação dos processos sedimentares atuantes nas áreas costeiras e de plataforma, respeitando-se como limite a isóbata de 100 metros. Em profundidades maiores que esta, a técnica não se mostra um \"proxy\" confiável, pois os dados obtidos foram muito conflitantes, sendo mais recomendado o uso do 14C. Os metais provenientes da zona costeira, aparentemente, não estão alcançando a plataforma continental, mas em alguns pontos isolados, já se nota um aumento em especial do Pb, não atingindo entretanto, os níveis de alerta da resolução CONAMA 344/04. / The objective of the present work is the obtainment of the sedimentation rates of the continental shelf and the upper slope on the central north area from São Paulo Bight (from Santos to Cabo Frio), besides checking the use of the 210Pb/137Cs method when compared to more traditional methods like 14C for obtainment of this sedimentation rates. The second objective is the checking if there is a metal transference deriving from the adjacent coastal area to the open ocean. In this work a total of 12 cores were collected from different research projects and they were analyzed considering the granulometry and CaCO3 and metals (Pb, Cu and Zn) contents. These same samples were also analyzed through gamma spectrometry for obtainment of the activity levels of 210Pb and 137Cs. The sedimentation rates were obtained after mathematical computing based on CIC model. The results indicated rather homogeneous sedimentary columns, predominantly siliciclastics. The obtained sedimentation rates, in a millimeters/year basis, are consistent to the data found in other areas of the Brazilian Coastal and the World Coastal where the actual deposit of sediments is not significant. Based on this data it is possible to state that 210Pb/137Cs method is a really reliable method for obtainment of sedimentation rates and identification of the sedimentary processes occurring on the coastal and shelf areas, respecting 100 meters isobath as the limit. The technique is not a reliable proxy when considering deeper areas as there was much conflict on the resultant data and in this cases, the best recommendation is the use of 14C method. Apparently, the metals deriving from the coastal zone are not reaching the continental shelf, but the growth of Pb can be noticed on some isolated spots although they not reach the warning levels from CONAMA 344/04 resolution

Mercury (Hg) is a highly toxic non-essential heavy metal. Soil, water and air contamination by Hg leads to its accumulation in fish, birds and mammals, thus entering human food. Due to the hazardous effects to the ecosystem, it is necessary that contaminated soils be rehabilitated. Phytoremediation is a cheap technique that can be utilizated with this objective, however, it is necessary to be knowledgeable about plant behavior during metal exposure. Therefore, the aim of this study was to characterize biological and biochemical aspects of Hg toxicity and the role of Zn to alleviate these effects in P. glomerata plants. For both experiments, plants were grown in vitro and acclimated ex vitro, for the application of treatments. Nine days later, growth and biochemical parameters of oxidative stress were evaluated. In the first experiment, plants were exposed to four concentrations (0.0, 1.0, 25 and 50 μM Hg). In the second experiment, four treatments of Hg and Zn were added to the nutrient solution (without Zn or Hg (control); 50 μM Zn; 50 μM Hg and; 50 μM Zn + 50 μM Hg). The Hg concentration was higher in shoot than in roots only in treatments without Hg (control and 50 μM Zn). Fresh and dry weight of roots and shoot decreased and a high malondialdeide (MDA) concentration was observed at 50 μM Hg, indicating that tissue damage occurred. The antioxidant enzyme activity and non-enzymatic concentration increased with the presence of Zn+Hg. Plants exposed to Zn showed a decrease in fresh and dry weight, but there was no significant increase in MDA production. There was an interaction between Zn and Hg. The antioxidant system of P. glomerata plants was important in oxidative damage regulation, however, at 50 μM Hg these mechanisms were not able to revert the damage caused by Hg. Zinc addition parcially prevented Hg damage, observed by the significant decrease in lipid peroxidation and higher survival percentage. / O mercúrio (Hg) é um metal pesado não-essencial altamente tóxico aos organismos. A contaminação dos solos, ar e água por este metal leva a sua acumulação em peixes, aves e mamíferos e a intoxicação humana, através da alimentação. Devido aos efeitos danosos do Hg ao ecossistema, é necessário que estas áreas sejam reabilitadas. A fitorremediação é uma técnica de baixo custo que pode ser utilizada com tal objetivo. Para que a planta seja utilizada na fitorremediação, no entanto, é necessário haver conhecimento sobre o comportamento vegetal quando exposto ao contaminante. Portanto, o objetivo deste trabalho foi caracterizar aspectos fisiológicos e bioquímicos da toxidez do Hg e o papel do Zn em aliviar estes efeitos em plantas de P. glomerata. Foram realizados dois experimentos, cujas plantas foram cultivadas in vitro e aclimatizadas ex vitro, quando foram aplicados os tratamentos. Após nove dias de exposição aos tratamentos, foram avaliados parâmetros de crescimento e parâmetros bioquímicos ligados ao estresse oxidativo. No primeiro experimento, as plantas foram expostas a quatro concentrações de Hg (0,0, 1,0, 25 e 50 μM). Já no segundo experimento, o Hg e o Zn foram adicionados à solução nutritiva de modo a formar quatro tratamentos (sem Zn e Hg (controle); 50 μM Zn; 50 μM Hg; 50 μM Zn + 50 μM Hg). A concentração de Hg foi maior nas raízes do que na parte aérea das plantas expostas ao Hg e sua presença induziu o estresse oxidativo, bem como causou danos aos tecidos vegetais nas concentrações de 25 e 50 μM Hg. A concentração de Hg foi maior na parte aérea do que nas raízes apenas nos tratamentos em que o Hg não foi adicionado à solução nutritiva (controle e 50 μM Zn). A massa fresca e seca das raízes e da parte aérea diminuiu e foi observado aumento da concentração de malondialdeído (MDA) nos tecidos em relação ao controle, quando expostos a 50 μM Hg, indicando que houve dano aos tecidos. A atividade das enzimas antioxidantes e a concentração de antioxidantes não enzimáticos aumentaram com a presença de Hg e com a adição de Zn. O tratamento de Zn diminuiu a massa fresca e seca das plantas, por outro lado não houve alteração na peroxidação lipídica. Houve interação entre os elementos Zn e Hg quando fornecidos simultaneamente na solução nutritiva. O sistema antioxidante de P. glomerata foi importante na regulação do dano oxidativo. No entanto, em 50 μM Hg, estes mecanismos não foram suficientes para reverter o dano causado por este elemento. O Zn parcialmente evitou os danos causados pelo Hg, observados pela significante diminuição da peroxidação lipídica e pela maior porcentagem de sobrevivência de plantas neste tratamento.

Sem resumo / Sem abstract

Submitted by Onia Arantes Albuquerque (onia.ufg@gmail.com) on 2018-11-06T13:54:30Z No. of bitstreams: 2 Dissertação - Jhonny Willians de Oliveira Maciel - 2018.pdf: 3229754 bytes, checksum: 23b20bfd316d193ccfafa525bf314c79 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2018-11-07T09:38:43Z (GMT) No. of bitstreams: 2 Dissertação - Jhonny Willians de Oliveira Maciel - 2018.pdf: 3229754 bytes, checksum: 23b20bfd316d193ccfafa525bf314c79 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-11-07T09:38:43Z (GMT). No. of bitstreams: 2 Dissertação - Jhonny Willians de Oliveira Maciel - 2018.pdf: 3229754 bytes, checksum: 23b20bfd316d193ccfafa525bf314c79 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2018-09-28 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / New supramolecular systems based on metal complexes of formula [Fe(H2pcpa)2(H2O)2] (3), [Mn(Hpcpa)(H2O)3]n•1/2H2O (4), [Zn(Hpcpa)(H2O)3]n•1/2H2O (5) and [Cu2(Hpcpa)2(bipy)2]•5,6H2O (6) [H2pcpa- and Hpcpa2- ion derivative of EtH2pcpa (1) = N-(4-carboxyphenyl)oxamic ethyl ester] have been synthesized and describe in this work. The structure of 3 consists of discrete Fe(II) units, each metal ion is six-coordinate in a distorted octahedral environment with four oxamate-oxygens from a H2pcpa- ligand in the basal plane and two water molecules in the apical position. 4 and 5 is a neutral zigzag chain of Mn(II) and Zn(II) ions, respectively, bridged by Hpcpa2- ligands exhibiting the bidentate/monodentate coordination mode. Each metal ion is building a somewhat distorted octahedral surrounding. The distance between metals ions intrachain is 11.456 Å (4) and 11.325 Å (5). Complex 6 consists of a dimer in which the Cu(II) ions is found in a square-shaped pyramidal geometry connected by two Hpcpa2- and the 2,2'-bipyridine as a terminal ligand. / Foram obtidos novos sistemas supramoleculares baseados em compostos de coordenação com o ligante ácido N-(4-carboxifenil) oxâmico etil éster (EtH2pcpa/1) e os metais Fe(II), Mn(II), Cu(II) e Zn(II). As sínteses, caracterizações espectroscópicas e elucidação das estruturas cristalinas de quatro compostos inéditos de fórmula [Fe(H2pcpa)2(H2O)2] (3), [Mn(Hpcpa)(H2O)3]n•1/2H2O (4), [Zn(Hpcpa)(H2O)3]n•1/2H2O (5) e [Cu2(Hpcpa)2(bipy)2]•5,6H2O (6) foram descritas nesse trabalho. O complexo 3 formou monocristais de cor laranja amarronzada, cuja a estrutura consiste em um monômero de Fe(II). Cada íon de Fe(II) é hexacoordenado com esfera de coordenação composta de duas moléculas de água posicionadas em trans e quatro oxigênios-oxamato de dois ligante H2pcpa-. Os compostos 4 e 5 formaram monocristais transparentes incolores cujas estruturas cristalinas são formadas por cadeias em ziguezague neutras de íons Mn(II) e Zn(II), respectivamente. Cada íon metálico está hexacoordenado com as três moléculas de água posicionadas em Meridional, dois oxigênios-oxamato de um ligante Hpcpa2- e um oxigênio-carboxilato de um outro grupo do Hpcpa2-. A distância entre os metais intracadeia Mn...Mn no complexo 4 é de 11,456 Å e Zn...Zn no complexo 5 é de 11,325 Å. O complexo 6 formou monocristais azuis, a estrutura consiste em um dímero em que o íon de Cu(II) encontra-se penta coordenado em uma geometria piramidal de base quadrada com dois íons de Cu(II) ligados por dois ligantes Hpcpa2- e com o ligante 2,2'-bipiridina atuando como ligante terminal.

Fundação de Amparo a Pesquisa no Estado do Rio Grande do Sul / Propylene is a chemical compound with high value added, widely used in the industry and usually obtained from petroleum. However, there is the need of the development of alternative routes for the production of this compound from renewable sources. The use of acetone for the production of propylene is a good option, because this oxygenated compound can be obtained by biomass conversion. The use of a one step process also adds an advantage to the propylene production from acetone, uniting in a single reactor two consecutive reactions: acetone hydrogenation, followed by dehydration of the formed isopropanol. For this, there are necessary two catalysts with distinct properties, one containing metallic sites, for hydrogenation, and another where there are acidic sites, for dehydration. The main objective of this work is to obtain propylene from acetone in one single step, using Cu/Zn/Al mixed oxide derived from hydrotalcite-like compounds and acid form of Beta zeolite as catalysts. For that, the catalysts were obtained by the coprecipitation method at variable pH followed by calcination, for the mixed oxide, and by hydrothermal synthesis, for the zeolite. The catalysts were also characterized as their with distinct properties. The hydrogenation and dehydration reactions have been studied individually and together by varying the catalyst or mixture of catalysts employed and the composition and flow rate of the feed. First, they were evaluated the thermodynamic boundaries of the reaction systems in which was observed that the acetone hydrogenation is strongly limited by the equilibrium and which are the preferential products of each reaction. For the reaction test, it was used the factorial experimental design, where the feeding conditions and reaction temperature were varied, and as response variables it was obtained the composition of the organic fraction at the reactor outlet. In the hydrogenation reaction, only isopropanol was obtained and the acetone conversion was close to that of equilibrium. In the dehydration reaction of isopropanol, propylene was preferably formed, with only small concentrations of diisopropyl ether at low temperatures, being obtained complete alcohol conversion in some experimental conditions. The complete process of acetone conversion into propylene was carried out at eleven distinct experimental conditions and the olefin fraction was up to 65 % of the organic fraction. It was possible the parameters estimation of simplified kinetic models, considering the Langmuir-Hinshelwood hypothesis, appropriate to the prediction of the molar fractions of the compounds in the organic fraction for both individual as simultaneous reactions. The kinetic models were used to the analysis of the effect of process variables on the reaction products in the three reaction systems considered. / O propeno é um composto químico de alto valor agregado, largamente empregado na indústria e obtido, geralmente, a partir do petróleo. Entretanto, há a necessidade do desenvolvimento de rotas alternativas para a produção deste composto a partir de fontes renováveis. A utilização de acetona para a produção de propeno é uma boa opção, pois este composto oxigenado pode ser obtido através de conversão da biomassa. A utilização de processo em uma única etapa acrescenta, ainda, mais uma vantagem à produção de propeno a partir de acetona, unindo em um único reator duas reações consecutivas: hidrogenação de acetona, seguida da desidratação do isopropanol formado. Para tanto, são necessários dois catalisadores com propriedades distintas, um deles contendo sítios metálicos, para a hidrogenação, e outro onde haja sítios ácidos, para a desidratação. O objetivo principal deste trabalho é a obtenção de propeno a partir de acetona em uma única etapa, utilizando óxido misto de Cu/Zn/Al derivado de material do tipo hidrotalcita e forma ácida da zeólita Beta como catalisadores. Para isso, os catalisadores foram obtidos pelo método de coprecipitação a pH variável seguido de calcinação, para o óxido misto, e pela síntese hidrotérmica, para a zeólita. Os catalisadores foram, ainda, caracterizados quanto às suas propriedades físicoquímicas. As reações de hidrogenação e desidratação foram estudadas individualmente e em conjunto variando-se o catalisador ou mistura de catalisadores empregados e a composição e vazão da alimentação. Primeiramente, foram avaliados os limites termodinâmicos dos sistemas reacionais, em que se observou que a hidrogenação de acetona é fortemente limitada pelo equilíbrio e quais são os produtos preferenciais de cada reação. Para os testes reacionais foi utilizado planejamento de experimentos fatorial, onde as condições de alimentação e temperatura de reação foram variadas, e como variáveis resposta obteve-se a composição da fração orgânica na saída do reator. Na reação de hidrogenação, apenas isopropanol foi obtido e a conversão de acetona foi próxima daquela de equilíbrio. Na reação de desidratação de isopropanol, o propeno foi formado preferencialmente, com apenas pequenas concentrações de éter di-isopropílico a baixas temperaturas, sendo obtidas conversões completas do álcool em algumas condições experimentais. O processo completo de conversão de acetona em propeno foi realizado em onze condições experimentais distintas e a fração de olefina foi de até 65 % da fração orgânica. Foi possível a estimação dos parâmetros de modelos cinéticos simplificados, considerando as hipóteses de Langmuir-Hinshelwood, adequados à predição das frações molares dos compostos na fração orgânica tanto para as reações individuais como simultâneas. Os modelos cinéticos foram utilizados para a análise do efeito das variáveis de processo sobre os produtos de reação nos três sistemas reacionais considerados.

Cette thèse porte sur la croissance de films minces d’oxydes de zinc/fer (ZnxFe1-xO1+δ par ablation laser pulsée (PLD) et sur la possibilité de contrôler leurs propriétés structurales et physico-chimiques en variant les conditions d’élaboration : pression d’oxygène et température de croissance, proportions respectives de zinc/fer. Pour de fortes valeurs de x (x > 65%), les films sont monophasés de structure wurtzite type ZnO (films Fe:ZnO), avec une transparence optique dans la gamme UV-visible de 80% mais sans propriété ferromagnétique ; en fonction de leur teneur en fer (1-x), ils évoluent de très bons conducteurs électriques à quasi-isolants. Pour de faibles valeurs de x (x < 15%), les films sont également monophasés de structure spinelle type Fe3O4 (films Zn:Fe3O4). Ils présentent de très bonnes propriétés ferromagnétiques dès la température ambiante ainsi qu’une bonne conductivité électrique, les effets de localisation des porteurs de charge se manifestant en dessous de la température de Verwey. Le nombre de parois d’antiphase peut être diminué par une croissance en deux étapes, comme l’atteste les mesures de magnétorésistance. Aux taux intermédiaires de zinc (15% < x < 65%), les films sont nano-composites. Dans le cas d’une coexistence des phases Fe:ZnO et Zn:Fe3O4, la bonne conductivité de Zn:Fe3O4 jointe à la multiplicité des variantes épitaxiales et donc des interfaces fournit un matériau adapté à la thermoélectricité. Dans le cas d’une coexistence de la phase ferrromagnétique Zn:Fe3O4 avec la phase Zn:FeO antiferromagnétique de type sel gemme, un fort couplage d’échange ainsi qu’une anisotropie magnétique perpendiculaire élevée sont mis en évidence. / This thesis deals with the growth of thin films of zinc/iron oxides (ZnxFe1-xO1+δ) by pulsed laser deposition (PLD) and the possibility of controlling their structural and physicochemical properties by varying the elaboration conditions: oxygen pressure and growth temperature, respective proportions of zinc/iron. For high values of x (x> 65%), the films are single-phase with a ZnO-type wurtzite structure (Fe:ZnO films), with 80% optical transparency in the UV-visible range but without ferromagnetic properties; depending on their iron (1-x) content, they evolve from very good electrical conductors to near-insulators. For small values of x (x <15%), the films are also single-phase with a Fe3O4-type spinel structure (Zn:Fe3O4 films). They exhibit very good ferromagnetic properties at ambient temperature as well as good electrical conductivity, the localization effects of charge carriers occurring below the Verwey temperature. The number of antiphase walls can be decreased by a two-step growth, as evidenced by magnetoresistance measurements. At intermediate zinc rates (15% <x <65%), the films are nano-composites. In the case of a coexistence of the Fe:ZnO and Zn:Fe3O4 phases, the good conductivity of Zn:Fe3O4 combined with the multiplicity of epitaxial variants and thus of the interfaces provides a material suitable for thermoelectricity. In the case of a coexistence of the ferrromagnetic Zn:Fe3O4 phase with the Zn:FeO antiferromagnetic rocksalt phase, strong exchange coupling as well as high perpendicular magnetic anisotropy are demonstrated.

No description available.

This thesis deals with the establishment of zinc ions at the positive electrode of nickel-zinc batteries. The aim of the study was to measure the impedance characteristics of the positive electrode in various states of charge and observing the effect of ZnO on the changes of impedance spectra. The theoretical part is focused on nickel hydroxide as a construction material for positive electrode and its behavior during cycling in the electrolyte. The experimental part describes in detail the manufacture of the electrode system and the preparation of electrolytes with different degrees of saturation with zinc oxide. The cells were cycled and measured using impedance spectroscopy. The measured impedance curves were simulated with equivalent circuits for a better understanding of the ongoing processes.

On‐chip micro‐supercapacitors (MSCs), as promising power candidates for microdevices, typically exhibit high power density, large charge/discharge rates, and long cycling lifetimes. However, as for most reported MSCs, the unsatisfactory areal energy density (<10 µWh cm−2) still hinders their practical applications. Herein, a new‐type Zn‐ion hybrid MSC with ultrahigh areal energy density and long‐term durability is demonstrated. Benefiting from fast ion adsorption/desorption on the capacitor‐type activated‐carbon cathode and reversible Zn stripping/plating on the battery‐type electrodeposited Zn‐nanosheet anode, the fabricated Zn‐ion hybrid MSCs exhibit remarkable areal capacitance of 1297 mF cm−2 at 0.16 mA cm−2 (259.4 F g−1 at a current density of 0.05 A g−1), landmark areal energy density (115.4 µWh cm−2 at 0.16 mW cm−2), and a superb cycling stability without noticeable decay after 10 000 cycles. This work will inspire the fabrication and development of new high‐performance microenergy devices based on novel device design.