Luminescent nanoparticles of MgAl(2)O(4):Eu, Dy prepared by citrate sol-gel method

MgAl(2)O(4):Eu, Dy nanoparticles were prepared by citrate sol-gel method and thermally treated at 600, 700, 800 and 900 degrees C. The trivalent europium ion is partially reduced to the divalent state at 700 and 800 degrees C. Infrared spectra of the phosphors showed bands around 700 and 520 cm(-1) corresponding to the AlO(6) groups. X-ray diffraction patterns present sharp reflections of samples heated from 700 to 900 degrees C indicating the MgAl(2)O(4) spinel phase. Grain size in the range 20-30 nm were observed by measurement of transmission electron microscopy (TEM). The emission spectra of the phosphors show a broadened band at 480 nm assigned to the 4f(G)5d -> 4f(7) ((8)S(7/2)) transition of Eu(2+) ion overlapped to the (4)F(9/2) -> (6)H(15/2) transition of the Dy(3+) ion. Besides, the (4)F(9/2) -> (6)H(13/2) transition (579 nm) of Dy(3+) ion is overlapped with the (5)D(0) -> (7)F(0) (578 nm) and (5)D(0) -> (7)F(1) (595 nm) transitions from the Eu(3+) ion. Excitation spectra of the sample heated at 900 degrees C monitoring the excitation at 615 nm of (5)D(0) -> (7)F(2) transition of Eu(3+) ion exhibit a broad band assigned to the O -> Eu(3+) ligand-to-metal charge-transfer states (LMCT) around 280 nm. The samples present green persistent luminescence after exposure to UV radiation. The chromaticity coordinates were obtained from the luminescence emission spectrum. (C) 2008 Elsevier B.V. All rights reserved.

Efeitos quimicos do recuo do cromo em alguns complexos hexacoordenados no estado solido

Os efeitos químicos do recuo do 51Cr formado pela reação (n,y) foram investigados nos compostos: [Cr(NH3) 5ONO] (NO3)2, [Cr(NH3) 5NO3] (NO3)2 e [Cr(NH3)5 NCS] (NO3)2, irradiados no estado sólido. Após dissolução dos cristais, os fragmentos resultantes da irradiação foram analisados por cromatografia com resina trocadora de íons e eletroforese em papel. A distribuição inicial das espécies é discutida em termos da formação de complexos polinucleares e da não ocorrência de conversão interna em compostos de cromo (III). Os efeitos de reversão térmica indicam uma considerável influência do oxigênio atmosférico e de defeitos cristalinos no comportamento químico das espécies.

Recuperação do cromo contido nas cinzas provenientes da incineração de resíduos sólidos das indústrias coureira e calçadista visando a obtenção de cromato de sódio (VI)

O processo de transformação da pele em couro envolve uma seqüência complexa de reações químicas e processos mecânicos, no qual o curtimento representa fundamental estágio, por propiciar à pele características como qualidade, estabilidade hidrotérmica e excelentes propriedades para uso. O sulfato básico de cromo trivalente é o agente curtente predominantemente empregado no curtimento de peles em todo o mundo. É produzido a partir do cromato de sódio, industrialmente obtido do minério de cromo. Consideráveis quantidades de resíduos sólidos contendo cromo são geradas pelas indústrias coureira e calçadista. Estes resíduos tem sido motivo de preocupação constante, uma vez que são considerados perigosos devido a presença do cromo. O processo de incineração destes resíduos é uma importante alternativa a ser considerada, em decorrência de suas características de redução de massa, volume e possibilidade de aproveitamento da energia térmica dos gases de combustão. O processo de incineração dos resíduos das indústrias coureira e calçadista dá origem a cinzas contendo cerca de 40% de cromo que pode ser submetida a um processo de recuperação. Este trabalho apresenta os resultados da pesquisa sobre a utilização das cinzas, provenientes da incineração dos resíduos sólidos da indústria coureira e da indústria calçadista, para a produção de cromato de sódio(VI). No processo de planejamento e de condução dos experimentos foram utilizadas as técnicas de Planejamento Fatorial 2k, Metodologia de Superfície de Resposta e Análise de Variância na avaliação da produção de cromato de sódio(VI). Os fatores investigados foram: temperatura, taxa de aquecimento, tempo de reação, vazão de ar e quantidade de dolomita. A partir das variáveis selecionadas identificaram-se como parâmetros importantes a temperatura e a taxa de aquecimento. As superfícies de resposta tridimensionais obtidas a partir dos modelos de segunda ordem ajustados aos dados experimentais, apresentaram o comportamento do efeito conjugado dos fatores temperatura e taxa de aquecimento sobre a variável resposta grau de oxidação, desde a temperatura de inicio da reação química até a temperatura limite utilizada industrialmente. As condições de operação do processo de produção de cromato de sódio(VI) foram otimizadas. Os níveis ótimos dos fatores de controle aplicados as cinzas dos resíduos da indústria calçadista, geradas em uma planta piloto com incinerador de leito fixo, com tecnologia de gaseificação e combustão combinadas, apresentaram um grau de oxidação superior a 96% para as cinzas coletadas no ciclone e de 99,5% para as cinzas coletas no reator de gaseificação. Os resíduos sólidos, as cinzas e o produto de reação foram caracterizados por análises químicas, fluorescência de raio-X, microscopia eletrônica de varredura e difração de raio-X.

Obtenção de óxidos a base de níquel e cobalto para reação de oxidação parcial do metano

Nickel-based catalysts supported on alumina have been widely used in various reactions to obtain synthesis gas or hydrogen. Usually, higher conversion levels are obtained by these catalysts, however, the deactivation by coke formation and sintering of metal particles are still problems to be solved. Several approaches have been employed in order to minimize these problems, among which stands out in recent years the use of additives such as oxides of alkali metals and rare earths. Similarly, the use of methodologies for the synthesis faster, easier, applicable on an industrial scale and to allow control of the microstructural characteristics of these catalysts, can together provide the solution to this problem. In this work, oxides with spinel type structure AB2O4, where A represents divalent cation and B represents trivalent cations are an important class of ceramic materials investigated worldwide in different fields of applications. The nickel cobaltite (NiCo2O4) was oxides of spinel type which has attracted considerable interest due to its applicability in several areas, such as chemical sensors, flat panel displays, optical limiters, electrode materials, pigments, electrocatalysis, electronic ceramics, among others. The catalyst precursor NiCo2O4 was prepared by a new chemical synthesis route using gelatine as directing agent. The polymer resin obtained was calcined at 350°C. The samples were calcined at different temperatures (550, 750 and 950°C) and characterized by X ray diffraction, measurements of specific surface area, temperature programmed reduction and scanning electron microscopy. The materials heat treated at 550 and 750°C were tested in the partial oxidation of methane. The set of techniques revealed, for solid preparations, the presence of the phase of spinel-type structure with the NiCo2O4 NixCo1-xO solid solution. This solid solution was identified by Rietveld refinement at all temperatures of heat treatment. The catalyst precursors calcined at 550 and 750°C showed conversion levels around 25 and 75%, respectively. The reason H2/CO was around 2 to the precursor treated at 750°C, proposed reason for the reaction of partial oxidation of methane, one can conclude that this material can be shown to produce synthesis gas suitable for use in the synthesis Fischer-Tropsch process

Análise de efluente e histologia da pele, fígado e rim de Pacus (Piaractus mesopotamicus) suplementados com cromo trivalente

The objective of this work was to evaluate the skin, liver and kidney histology of young pacus supplemented in diet with trivalent chromium and to evaluate the residue of chromium in water effluent. Randomised delineation by using factorial scheme 4x2, with four levels of chromium (0, 6, 12, 18 mg/L), two stocking densities (4 and 20 kg/m(3)), and four repetitions were used. Pacus with 100 g were used, for 90 days. An increase of the number of mucus cells and club cells in the epidermis of the pacus supplemented with 18 chromium mg/kg was observed in any stocking density. The same effect was observed in the liver, and in the highest density (20 kg/m(3)) the alterations already occurred at the level of 6 mg/kg with the inclusion of chromium, initially with congestion of sinusoids and getting worse at the level of 18 mg/kg with necrosis. The kidney didn't present visible morphologic alterations when supplemented and submitted to the stocking densities. The concentration of chromium in the effluent of pacus was 3.27 mu g/L in the higher level of supplementation (18 mg/L). In conclusion the level of 18 supplement mg/kg was not shown beneficial to the growth of pacus and the stocking density, due to the possible stress, accelerated the alteration histology process of tissues.

Otimização do processo de recuperação do cromo de efluentes de curtumes por microemulsões no extrator Morris

The tanning industries are those which transform animal hide or skin into leather. Due to the complexity of the transformation process, greater quantities of chemicals are being used which results in the generation of effluents with residual solids. The chromium in the residual waters generated by tanning tend to be a serious problem to the environment, therefore the recovery of this metal could result in the reduction of manufacturing costs. This metal is usually found in a trivalent form which can be converted into a hexavalent compound under acidic conditions and in the presence of organic matter. The present study was carried out with the objective to recover chromium through an extraction/re-extraction process using micro emulsions. Micro emulsions are transparent and thermodynamically stable system composed of two immiscible liquids, one forming the continuous phase and the other dispersed into micro bubbles, established by an interfacial membrane formed by surface active and co-surface active molecules. The process of recovering the chromium was carried out in two stages. The first, an extraction process, where the chromium was extracted in the micro emulsion phase and the aqueous phase in excess was separated. In the second stage, a concentrated acid was added to the micro emulsion phase rich in chromium in order to obtain a Winsor II system, where the water that formed in the micro emulsion phase separates into a new micro emulsion phase with a higher concentration of chromium, due to the lowering of the hydrophiles as well as the ionisation of the system. During the experimental procedure, a study was initiated with a synthetic solution of chromium sulphate passing onto the effluent. A Morris extractor was used in the extraction process. Tests were carried out according to the plan and the results were analysed by statistical methods in order to optimise the main parameters that influence the process: the total rate of flow (Q), stirring speed (w) and solvent rate (r). The results, after optimization, demonstrated that the best percentuals in relation to the chromium extraction (99 %) were obtained in the following operational conditions: Q= 2,0 l/h, w= 425 rpm and r= 0,375. The re-extraction was carried out at room temperature (28 °C), 40 °C and 50°C using hydrochloric acid (8 and 10 M) and sulphuric acid (8 M) as re-extracting agents. The results obtained demonstrate that the process was efficient enough in relation to the chromium extraction, reaching to re-extraction percentage higher than 95 %.

Structural Characterization of Nanocrystalline Sb-Doped SnO2 Xerogels by Multiedge X-ray Absorption Spectroscopy

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Estudo do comportamento térmico e da luminescência de filmes de quitosana com os íons Eu3+ e Tb3+

Films of chitosan with trivalent lanthanides ions Eu3+ and Tb3+ were respectively prepared in the ratio of 3:1 m/m (chitosan: lanthanide) and 6:1 m/m (chitosan: lanthanide). There were no formations of films in a ratio of 1:1 m/m (chitosan: lanthanides). The films of chitosan with the Tb3+ ion have the same transparent appearance than the pure chitosan films. The film of chitosan with Eu3+ ion has a muddy appearance. These films present good resistance to tear. The appearance of the compounds prepared in ratio 1:1m/m is a white powder. The films and compounds of chitosan were characterized by Elementary Analysis (CHN), Thermal Analysis (TG/DTG) and Spectroscopy of Luminescence. The CHN analysis was made only for compounds prepared in ratio 1:1m/m, suggesting that these compounds possess the formula QUILn.6H2O, where QUI = Chitosan and Ln = Lanthanide. The results of the curves TG/DTG indicated that there are strong interactions between Eu3+ or Tb3+ and chitosan, causing a lesser lost of mass in the films. The luminescence analysis showed that the films of chitosan with the ions Eu3+ and Tb3+ present emissions in the region of the visible one, with bands of the chitosan and of the Eu3+ ion. The luminescence analysis of the compounds of chitosan with the Eu3+ and Tb3+ ions suggest that the chitosan does not transfer into energy to the ions lanthanides, however the chemical neighborhood around of the ion lanthanides breaks the selection rules and, conseqüently the 4f-4f transitions of the lanthanide ions are observed

Síntese, caracterização e estudo fotofísico de complexos de 4,4- diaminoestilbeno-2,2-dissulfonato com íons lantanídeos

This is a work involving fundamental studies of chemistry where the synthesis and structural characterization, as well as a possible future application of these new compounds as luminescent sensors or sunscreen agents, complexes with 4,4 diaminostilbene-2,2-disulfonic (DSD) and trivalent lanthanide ions La3+, Nd3+, Eu3+, Gd3+ and Yb3+, were synthesized in the ratio of 3 mmol: 1 mmol (DSD: lanthanides). The complexes obtained with these ions were present in powder form and were characterized by complexometric titration with EDTA CHN Elemental analysis, molecular absorption spectroscopy in the ultraviolet region, the absorption spectroscopy in the infrared, thermal analysis (TG / DTG), Nuclear Magnetic Resonance - NMR 1H and Luminescence Spectroscopy. The complexometric titration and CHN analysis, confirmed the TG / DTG which suggest that these complexes have the following general chemical formulas: [La2(C14H12S2O6N2)2(H2O)2Cl2].7H2O,[Nd2(C14H12S2O6N2)2(H2O)2Cl2].6H2O,[Eu2(C14 H12S2O6N2)2(H2O)2Cl2].7H2O,[Gd2(C14H12S2O6N2)2(H2O)2Cl2].4H2O e [Yb2(C14H12S2O6N2)2(H2O)2].6H2O. The disappearance of the bands in the infrared spectrum at 2921 cm-1 and 2623 cm-1 and the displacement of the bands in the spectra of the amine complex indicate that the lanthanide ion is coordinated to the oxygen atoms and the sulfonate groups of the nitrogens amines, suggesting the formation of the dimer. The disappearance of the signal and the displacement signal SO3H amines in the 1H NMR spectrum of this complex are also indicative coordination and dimer formation. The Thermogravimetry indicates that the DSD is thermally stable in the range of 40º to 385°C and their complexes with lanthanide ions exhibit weight loss between 4 and 5 stages. The Uv-visible spectra indicated that the DSD and complexes exhibit cis isomers. The analysis of luminescence indicates that the complexes do not exhibit emission in the region of the lanthanides but an intense emission part of the binder. This is related to the triplet states of the ligand, which are in the lowest energy state emitting lanthanide ions, and also the formation of the dimer that suppress the luminescence of ion Eu3+. The formation of dimer was also confirmed by calculating the europium complex structure using the model Hamiltonian PM6 and Sparkle

Interface Formation and Electrical Transport in SnO2:Eu3+/GaAs Heterojunction Deposited by Sol-Gel Dip-Coating and Resistive Evaporation

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Thermal decomposition of solid state compounds of lanthanide and yttrium benzoates in CO2 atmosphere

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Thermal Behaviour Studies of Solid State Lanthanide (III) and Yttrium (III) Compounds of Cinnamylidenepyruvic Acid in an Atmosphere of Air

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Revisão: efeito dos metais doadores nas propriedades elétricas e microestruturais dos varistores cerâmicos à base de SnO2

O estudo da adição de dopantes trivalentes é uma das principais pesquisas na área de varistores. Vários autores têm buscado entender os efeitos destes dopantes nas propriedades elétricas e microestruturais destas cerâmicas eletrônicas. Tanto metais de transição quanto terras raras são adicionados em cerâmicas à base de SnO2 a fim de verificar o seu comportamento. O que se tem observado é que alguns destes óxidos tais como Cr2O3 e La2O3 melhoram significativamente as propriedades elétricas dos varistores, enquanto que outros como o Bi2O3 e Er2O3, por exemplo, não produzem tal efeito. A evolução do desempenho do comportamento varistor tem sido também atribuída às espécies de oxigênio produzidas pela reação com estes dopantes. Esta revisão apresenta resultados de estudos recentes do comportamento varistor frente a adição de metais doadores.

Thermal decomposition of crystalline Ni-II-Cr-III layered double hydroxide: A structural study of the segregation process

A structural study of the thermal evolution of Ni0.69Cr0.31(OH)(2)(CO3)(0.155)(.)nH(2)O into NiO and tetragonal NiCr2O4 is reported. The characteristic structural parameters of the two coexisting crystalline phases, as well as their relative abundance, were determined by Rietveld refinement of powder x-ray diffraction (PXRD) patterns. The results of the simulations allowed us to elucidate the mechanism of the demixing process of the oxides. It is demonstrated that nucleation of a metastable nickel chromite within the common oxygen framework of the parent Cr-III-doped bunsenite is the initial step of the cationic redistribution. The role that trivalent cations play in the segregation of crystalline spinels is also discussed.

Synthesis, characterization and thermal behaviour of solid-state compounds of yttrium and lanthanide benzoates

Solid-state Ln(Bz)(3)center dot H(2)O compounds where Ln stands for trivalent yttrium or lanthanides and Bz is benzoate have been synthesized. Simultaneous thermogravimetry-differential thermal analysis (TG-DTA), X-ray powder diffractometry, infrared spectroscopy and chemical analysis were used to characterize and to study the thermal behaviour of these compounds. The results led to information about the composition, dehydration, thermal stability and thermal decomposition of the isolated compounds.