Resumo O dimorfismo sexual de Kinosternon scorpioides foi avaliado utilizando-se duas técnicas diferentes (morfometria linear e geométrica) a partir de imagens e medições lineares da carapaça e plastrão de adultos (machos e fêmeas). A morfometria linear indicou que as médias de altura da carapaça, largura da carapaça e plastrão são estatisticamente diferentes entre os sexos, sendo as fêmeas mais largas e altas. Na avaliação da morfometria geométrica, a ANOVA demonstrou que existe variação de tamanho do plastrão, e na forma da carapaça e do plastrão, expressando uma tendência de forma para cada sexo. O dimorfismo sexual, portanto, é verificado para esta espécie, notadamente pelo plastrão. Este trabalho indica uma ferramenta adicional para o conhecimento fenotípico dos animais, contribuindo no estudo de populações ameaçadas.

Abstract The sexual dimorphism of the Kinosternon scorpioides was evaluated using two different techniques (linear and geometric morphometry) from images and linear measurements of the carapace and plastron of adults (male and female). Linear morphometry indicated that the height and width of carapace and plastron are statistically different between sexes, with females being wider and taller. In the evaluation of geometric morphometry, ANOVA demonstrated variation in the size of the plastron and the shape of the carapace and plastron, expressing a tendency in shape for each sex. Sexual dimorphism, therefore, is verified for this species, notably by the plastron. This study indicates an additional tool for the phenotypic knowledge of animals, contributing to the study of threatened populations.

Resumo Materiais cerâmicos do tipo carbeto, como carbeto de molibdênio dopado com níquel, têm promissora atividade de degradação fotocatalítica. A adição de níquel ao carbeto de molibdênio visa aumentar seu rendimento de reação e também suas características. Este trabalho teve por objetivo estudar a atividade fotocatalítica dos materiais Mo2C e Mo2C dopado com 5% e 10% de níquel para a degradação do corante têxtil Maxilon Blue GRL 300. As propriedades estruturais foram caracterizadas por difração de raios X e microscopia eletrônica de varredura. Para a determinação da energia de band gap, foi utilizada espectroscopia de refletância difusa. As amostras dos testes de fotocatálise foram analisadas por espectroscopia UV-visível. O melhor rendimento de reação foi observado para a amostra de carboneto de molibdênio dopado com 5% de níquel em testes fotocatalíticos, atingindo um rendimento em torno de 92% na concentração final da solução de corante.

Abstract Carbide-type ceramic materials such as nickel-doped molybdenum carbide have promising photocatalytic degradation activity. The addition of nickel to the molybdenum carbide aims to increase its reaction yield and also its characteristics. The objective of this paper was to study the photocatalytic activity of Mo2C and 5% and 10% nickel-doped Mo2C materials used for the degradation of the Maxilon Blue GRL 300 textile dye. The structural properties were characterized by X-ray diffraction and scanning electron microscopy. For the determination of band gap energy, diffuse reflectance spectroscopy was used. The samples of the photocatalysis tests were analyzed by UV-visible spectroscopy. The best reaction yield was observed for the 5% nickel-doped molybdenum carbide sample in photocatalytic tests, reaching a yield of around 92% in the final concentration of the dye solution.

Resumo Os óxidos de molibdênio são materiais tecnológicos muito interessantes, que apresentam diversos usos industriais. A adição de um segundo metal pode melhorar suas propriedades catalíticas, bem como alterar o comportamento eletrônico. Várias metodologias para adicionar um segundo metal podem ser encontradas na literatura, porém a comparação entre elas é dificilmente encontrada. Aqui duas rotas de processamento foram aplicadas para a síntese de óxido de molibdênio com adição de cobalto: via sólida e via úmida. Molibdato de amônio e nitrato de cobalto foram usados como materiais de partida e a adição de cobalto foi realizada antes da calcinação. Os materiais iniciais foram caracterizados por MEV, FTIR, FRX e DRX. Os produtos de calcinação foram avaliados por MEV, FRX, DRX e espectroscopia UV-vis. Produto calcinado cuja dopagem foi realizada via estado sólido apresentou menor tamanho de cristal (~25 nm), maior retenção de cobalto (desvio, δ ~10%) e band gap levemente menor em comparação com aquele dopado por via úmida (~40 nm e δ>11%).

Abstract Molybdenum oxides are very interesting technologic materials, which present several industrial uses. The addition of a second metal may enhance its catalytic properties as well as change electronic behavior. Several methodologies for adding a second metal can be found in the literature, however, the comparison between them is hardly ever found. Here two processing routes were tested for the synthesis of molybdenum oxide with cobalt addition: solid-state and wet routes. Ammonium molybdate and cobalt nitrate were used as starting materials and cobalt addition was carried out before calcination. Starting materials were characterized by SEM, FTIR, XRF, and XRD. Calcination products were evaluated by SEM, XRF, XRD and UV-vis spectroscopy. Calcined products whose doping was performed via solid-state presented smaller crystal size (~25 nm), larger cobalt retention (deviation, δ ~10%) and slightly smaller band gap in comparison to those doped via the wet route (~40 nm and δ>11%).

Resumo Carbetos de metais de transição vêm sendo aplicados com sucesso em substituição aos catalisadores convencionais principalmente devido às suas propriedades físico-químicas. A estrutura da superfície, composição química, interação metal-suporte e condições de processamento são essenciais na aplicação dos carbetos para esse fim. O presente estudo teve como objetivo sintetizar, em leito fixo, a partir de reação gás-sólido, carbeto de molibdênio puro, bimetálico (Mo-Ni) e suportado em carvão ativado obtido através da pirólise do lodo de esgoto, e compará-los visando aplicação em reações catalíticas. O carvão foi submetido a um processo de ativação química utilizando KOH e tratamento térmico. Os materiais foram caracterizados através das análises de TG, DRX, FRX, MEV, área superficial e volume de poros através do método BET e análise granulométrica. As isotermas de adsorção e dessorção foram também obtidas para os diferentes materiais. Os resultados mostraram que a metodologia utilizada para síntese dos materiais foi satisfatória, principalmente tendo em vista o aumento significativo da área superficial dos materiais, de 13 para 141 m2/g, quando o carvão foi tratado com KOH bem como quando o mesmo foi adicionado ao carbeto (de 45 para 73 m2/g), o qual pode justificar uma aplicação catalítica.

Abstract Transition metal carbides have been successfully used as substitute materials for conventional noble metal catalyst in several important industrial reactions due to their interesting physicochemical properties. Surface structure, chemical composition and metal-support interactions, as well as processing conditions, are of utmost importance in the use of such materials in catalysis. The present study aimed to synthesize and evaluate pure molybdenum carbide with and without support, and bimetallic Mo-Ni carbide over a carbon active support derived from sewage sludge pyrolysis. The support was chemically (KOH) and physically (thermal treatment) activated before use. TG/DTG, XRD, XRF, SEM, BET and particle size evaluation were performed, together with adsorption/desorption isotherms. Results indicated that the applied synthesis method was adequate for the obtainment of pure materials. The increase in surface area of the support was significant, from 13 to 141 m².g-1 after the thermal and chemical treatment; also, supporting Mo2C over carbon provided an increase from 45 to 73 m².g-1 in surface area, which indicated its potential as a catalytic material as well as the effectiveness of the applied methodology.

Abstract Due to ever more severe environmental regulations regarding SOx, NOx and other pollutants' emissions, there has been an interest in developing new and improved catalysts for hydroprocessing reactions. Mo2C has been reported to display good selectivity and activity for those reactions, especially for HDS. Addition of another metal to the carbide structure may improve catalytic properties. Mo2C with low cobalt addition (2.5 and 5%) was obtained via gas-solid reaction in a fixed bed reactor with CH4 (5%)/H2 atmosphere. XRD and TG/DTA analysis of the precursors were carried out in order to understand its mass loss profile, doping metal presence and phase distributions. CoMoO4 as well as MoO3 were identified after calcining doped precursors at 600 °C/180min. SEM, XRD, XRF, TOC, BET and laser granulometric analysis of the reaction products were also performed. Compositions verified by XRF and theoretical values were compatible. At 700 °C both carbide (Mo2C) and oxide (MoO2) phases are present, as identified in XRD analysis and observed by SEM. At 750 °C only single phase Mo2C was verified by XRD, indicating Co dispersion on the carbide matrix. Morphology at this temperature is compatible with pure Mo2C, though XRF indicates Co presence on the material.

Resumo A perovskita de cerato de bário foi sintetizada com base no método de complexação combinando EDTA-citrato e suas propriedades catalíticas testadas na reação de oxidação do monóxido de carbono em um reator de leito fixo variando a vazão de alimentação (50 e 100 mL.min-1) e a temperatura (100 a 550 °C). A fase cristalina de interesse foi obtida com tamanho de cristalito de 133 nm, junto com uma pequena quantidade de BaCO3 (3%). Quando sintetizado pelo método de complexação combinando EDTA-citrato, o cerato de bário apresenta um formato esférico irregular com aglomerados de diferentes tamanhos e com a presença de poros de diferentes tamanhos distribuídos aleatoriamente, sendo sua área superficial específica igual a 2,61 m2.g-1. Na vazão de 50 mL.min-1 ocorreu maior conversão quando comparado com a de 100 mL.min-1, sendo mais evidente entre 300 e 400 °C. Além disso, na vazão de 50 mL.min-1 ocorreu conversão total de CO em CO2 a 400 °C, enquanto que em 100 mL.min-1 a conversão foi de aproximadamente 60%. Com o uso da perovskita como catalisador o processo de oxidação é completo a 400 °C, enquanto que na reação sem catalisador a conversão completa é alcançada somente a 550 °C. Apesar da sua pequena área superficial, o BaCeO3 é altamente reativo na oxidação do monóxido de carbono.

Abstract The barium cerate perovskite was synthesized using a methodology based on the EDTA-citrate complexing method and its catalytic properties were tested in fixed-bed reactor at different stream feeding gas flow rates (50 and 100 mL.min-1) and temperatures (100 to 550 °C). The intended crystalline phase was obtained with crystallite size of 133 nm, together with a small amount of unwanted BaCO3 phase (3%). When synthesized by the EDTA-citrate complexing method, the barium cerate presents an irregular spherical shape with clusters of different sizes, and the presence of pores of different size distributed randomly; its specific surface area was 2.61 m2.g-1. At flow rate of 50 mL.min-1, higher conversion then at 100 mL.min-1 was observed, becoming more apparent between 300 and 400 °C. Moreover, at 50 mL.min-1 flow rate total conversion of CO to CO2 occurred at 400 °C, while the conversion was close to 60% at 100 mL.min-1. Using the perovskite as catalyst the oxidation process is completed at 400 °C, while in reaction without catalyst the complete conversion is achieved only at 550 °C. Therefore, the BaCeO3 had strong activity in carbon monoxide oxidation, although its specific area was small.

Cerato de bário (BaCeO3) tem estrutura perovskita do tipo ABO3, na qual A e B são cátions metálicos. Estes materiais, dopados ou não, têm sido estudados por apresentarem características que os tornam promissores na aplicação em células a combustível de óxido sólido e permeação de hidrogênio e oxigênio. Porém, como os materiais cerâmicos de condutividade mista têm sido produzidos por métodos distintos de síntese, algumas condições influenciam diretamente as propriedades finais, sendo uma das mais importantes a dopagem do sítio B, que pode ter influência direta no tamanho de cristalito. Este trabalho teve como objetivo a substituição parcial do cério por 80% de praseodímio a partir do método de complexação, combinando EDTA-citrato, a fim de verificar a influência do pH da solução de síntese na obtenção da fase, nas propriedades cristalográficas e morfológicas. Foi verificado que o material apresenta estrutura cristalina ortorrômbica, com grupo espacial Pmcn e a fase foi obtida, independentemente da alteração no valor do pH da solução. Quanto ao tamanho de cristalito, com pH de síntese ajustado para 5, foi obtido maior valor, 352,7 nm, apesar de todos terem tido aumento em relação à amostra com pH corrigido para 11. Esse aumento se deu, provavelmente, pelo tempo insuficiente no qual a amostra foi submetida à ação da temperatura de síntese até a formação do gel final, ocasionando uma menor desagregação dos aglomerados formados na reação de complexação, resultado concordante com as análises de microscopia eletrônica de varredura.

Barium cerate (BaCeO3) is a type ABO3 perovskite, with A and B metal cations. Such materials, single or doped, have been studied as promising for the application in solid oxide fuel cell, and hydrogen and oxygen permeation; however, as these materials have been produced by different synthesis methods, some conditions directly influence the final properties, with a major doping site B, which may have direct influence on the crystallite size and, consequently, in the ionic and electronic conduction. This work aimed at the partial substitution of cerium for 80% praseodymium by the EDTA-citrate complexing method to verify the influence of the pH of the synthesis solution on obtaining the phase, the crystallographic and morphological properties. It was found that the material has orthorhombic crystal structure with space group Pmcn and the phase was obtained irrespective of change of the pH of the synthesis, indicating possibly that the metal cations in the perovskite were able to deprotonate the EDTA increasing the stability of the complexes formed. With the synthesis pH adjusted to 5 the crystallite size reached the highest value, 352.7 nm. This increase was probably due to insufficient time in which the sample was subjected to the action of synthesis temperature until the formation of the final gel, resulting in reduced breakdown of agglomerates formed in the complexation reaction , which can be seen in the results of scanning electron microscopy.

The thermal decomposition in argon of the monohydrated ammonium tris(oxalate)niobate, (NH4)3NbO(C2O4)3.H 2O, has been studied by TG/DTG, DTA, DSC, IR absorption and XRD. The material decomposes stepwise by the release of CO, CO2, NH3 and water. The atomic structure of the complex initially becomes amorphous and then crystallizes twice in the form of orthorhombic and monoclinic niobium pentoxide.

A rotating cylinder reactor was designed for the synthesis of niobium carbide powders at 1173 K. Niobium carbide, NbC, was prepared by carbothermal reduction starting from commercial niobium pentoxide powders. The reactor was heated using a custom-made, two-part, hinged, electric furnace with programmable temperature control. The design and operational details of the reactor are presented. The longitudinal temperature gradient inside the reactor was determined. Total reaction time was monitored by a gas chromatograph equipped with an FID detector for determination of methane concentrations. The results show that time of reaction depended on rotation speed. NbC was also prepared in a static-bed alumina reactor using the same conditions as in the previous case. The niobium carbide powders were characterized by X-ray diffraction and compared with commercially available products. Morphological, particle size distribution and surface area analyses were obtained using SEM, LDPS and BET, respectively. Therefore, the present study offers a significant technological contribution to the synthesis of NbC powders in a rotating cylinder reactor.

In this work we have synthesized an organometallic oxalic precursor from tantalum oxide. This oxide was solubilized by heating with potassium hydrogen sulfate. In order to precipitate Ta2O5.nH2O, the fused mass obtained was dissolved in a sulfuric acid solution and neutralized with ammonia. The hydrated tantalum oxide precipitated was dissolved in an equimolar solution of oxalic acid/ammonium oxalate. The synthesis and the characterization of the tantalum oxalic precursor are described. Pyrolysis of the complex in a mixture of hydrogen and methane at atmospheric pressure was studied. The gas-solid reaction made it possible to obtain tantalum carbide, TaC, in the powder form at 1000oC. The natural sintering of TaC powder in an inert atmosphere at 1400°C during 10 hours, under inert atmosphere made it possible to densify the carbide to 96% of the theoretical value.

Foi isolada uma cepa de Schistosoma mansoni proveniente de dois pacientes tratados com hycanthone, por duas vezes, na dose de 2,5mg/kg, i.m., em janeiro e em abril de 1970, e com niridazole (25mg/kg dia x 5 oral), em abril de 1971. O número de ovos por grama de fezes nestes pacientes antes do tratamento era de 2675 e 1025, respectivamente e, após o terceiro tratamento, em torno de 100 ovos/g. Miracídios obtidos das fezes destes pacientes, infectaram caramujos (Biomphalaria glabrata), que passaram a eliminar cercárias (cepa WW). Estas foram utilizadas para infecção experimental de camundongos albinos. Os animais infectados foram tratados com esquemas múltiplos de hycanthone, niridazole e oxamniquine. Estudos comparativos das cepas WW e LE (esta última mantida rotineiramente em nossos laboratórios) mostraram diferenças acentuadas quando à sensibilidade aos esquistossomicidas usados. De fato, com hycanthone, na dose de 80mg/kg, i.m. houve 100% de alteração do oograma nos camundongos infectados com a cepa L.E. e de 0,0% nos infectados com a cepa WW. Com a oxamniquine e niridazole as diferenças foram menores, mas, ainda assim, suficientes para indicar maior resistência da cepa WW a estes esquistossomicidas. Esta é a primeira vez na literatura, que se demonstra resistência em cepas de S. mansoni provenientes de pacientes tratados.

There has been isolated a Schistosoma mansoni strain from two patients submitted to two courses of treatment with hycanthone (2,5mg/kg, i.m.), in January and April, 1970, and to one course with niridazole (25mg/kg/day x 5, per os), in April, 1971. Before treatment, the number of eggs in the faeces of those patients was, per gram, 2,675 and 1,025, respectively; after completion of treatment, such number had come down to around 100 eggs/gram. Miracidia hatched from the patients faeces could infect Biomphalaria glabrata snails, which elimmated cercariae (WW strain) that were used for experimental infection of albino mice. The infected animais were, afterwards, treated with hycanthone, niridazole and oxamniquine under various schedules. Comparative studies of WW and LE strains (the latter being routinely kept in our laboratories) revealed marked differences in their sensitivity to the schistosomicides employed. Actually, after treatment with hycanthone, at the dosage of 80 mg/kg, i.m., a 100% oogram changes were observed in the intestinal wall of mice inoculated with LE strain, whereas no alterations could be detected in the mice infected with WW strain. As regards oxamniquine and niridazole the changes were smaller although still quite sufficient to indicate greater resistance of WW strain to these schistosomicides. It is worth while remembering that, in the pertaining literature, it is the first time that resistance in S. mansoni strains from treated patients has been demonstrated.