Estudo e desenvolvimento de um capacitor eletrolítico de nióbio

It seeks to find an alternative to the current tantalum electrolytic capacitors in the market due to its high cost. Niobium is a potential substitute, since both belong to the same group of the periodic table and because of this have many similar physical and chemical properties. Niobium has several technologically important applications, and Brazil has the largest reserves, around 96%. There are including niobium in reserves of tantalite and columbite in Rio Grande do Norte. These electrolytic capacitors have high capacitance specifies, ie they can store high energy in small volumes compared to other types of capacitors. This is the main attraction of this type of capacitor because is growing demand in the production of capacitors with capacitance specifies increasingly high, this because of the miniaturization of various devices such as GPS devices, televisions, computers, phones and many others. The production route of the capacitor was made by powder metallurgy. The initial niobium powder supplied by EEL-USP was first characterized by XRD, SEM, XRF and laser particle size, to then be sieved into three particle size, 200, 400 e 635mesh. The powders were then compacted and sintered at 1350, 1450 and 1550°C using two sintering time 30 and 60min. Sintering is one of the most important parts of the process as it affects properties as porosity and surface cleaning of the samples, which greatly affected the quality of the capacitor. The sintered samples then underwent a process of anodic oxidation, which created a thin film of niobium pentóxido over the whole porous surface of the sample, this film is the dielectric capacitor. The oxidation process variables influence the performance of the film and therefore the capacitor. The samples were characterized by electrical measurements of capacitance, loss factor, ESR, relative density, porosity and surface area. After the characterizations was made an annealing in air ate 260ºC for 60min. After this treatment were made again the electrical measurements. The particle size of powders and sintering affected the porosity and in turn the specific area of the samples. The larger de area of the capacitor, greater is the capacitance. The powder showed the highest capacitance was with the smallest particle size. Higher temperatures and times of sintering caused samples with smaller surface area, but on the other hand the cleaning surface impurities was higher for this cases. So a balance must be made between the gain that is achieved with the cleaning of impurities and the loss with the decreased in specific area. The best results were obtained for the temperature of 1450ºC/60min. The influence of annealing on the loss factor and ESR did not follow a well-defined pattern, because their values increased in some cases and decreased in others. The most interesting results due to heat treatment were with respect to capacitance, which showed an increase for all samples after treatment

Obtenção de pós de tântalo metálico a partir da redução aluminotérmica com ignição a plasma

Metallic tantalum has a high commercial value due to intrinsic properties like excellent ductility, corrosion resistance, high melt and boiling points and good electrical and thermal conductivities. Nowadays, it is mostly used in the manufacture of capacitors, due to excellent dielectric properties of its oxides. In the nature, tantalum occurs in the form of oxide and it is extracted mainly from tantalite-columbite ores. The tantalum is usually produced by the reduction of its oxide, using reductants like carbon, silicon, calcium, magnesium and aluminum. Among these techniques, the aluminothermic reduction has been used as the industrial method to produce niobium, tantalum and their alloys, due to the easy removal of the Al and Al2O3 of the system, easing further refining. In conventional aluminothermic reduction an electrical resistance is used to trigger the reaction. This reaction self-propagates for all the volume of material. In this work, we have developed a novel technique of aluminothermic reduction that uses the hydrogen plasma to trigger the reaction. The results obtained by XRD, SEM and EDS show that is possible to obtain a compound rich in tantalum through this technique of aluminothermic reduction in the plasma reactor

Preparation of pyrochlore-free PMN by an alternative chemical method

This work reports the synthesis of the MgNb(2)O(6) and the ferroelectric lead magnesium niobate Pb(Mg(1/3)Nb(2/3))O(3) (PMN) using fine precursor powders obtained from a chemical Oxide Precursor Method (OPM). To obtain pyrochlore-free PMN ceramics, the synthesis of the precursor MgNb(2)O(6) powders was studied for 2-25 mol% excess of MgO and 10 mol% excess of PbO. Structural and microstructural properties of the sintered ceramics obtained by the cited method and by the classical columbite method were studied and compared. Results lead to good quality, pyrochlore-free PMN ceramic prepared by OPM, presenting greater grain size if compared with ceramic prepared by columbite method.

Effect of lithium additive on the microstructure and electrical responses of 0.9PMN-0.1PT ceramics

Structural effects of lithium additive on 0.9PMN-0.1PT powders prepared by Ti-modified columbite route were studied. The substitution of Li+ ions for Mg2+ ions in the B-site sub-lattice of 0.9PMN-0.1PT perovskite structure was explained in terms of lead and oxygen vacancies generation originated as consequence of the ionic compensation of negatively charged Li'(Mg) sites. The rise in mass transport as consequence of the increasing of Pb2+ and O2- vacancies produces more agglomerated particles during the powder synthesis and changes the mechanical characteristics between grain and grain boundary of sintered ceramic. The relation between K-m and T-m values, the difference between ionic radii of B cation and the molar volume were used to explain the changes in the relaxor behavior and diffusiveness of phase transition as function of lithium doping, which are corroborated by the results obtained through the ferroelectric characterization.

Efeito da adição de dopantes durante a síntese do precursor columbita para a preparação da cerâmica ferroelétrica relaxora PMN

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

Influência do oxalato de amônio na formação do precursor columbita obtido pelo método Pechini

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

Study of potassium additive on the phase formation and ferroelectric properties of 0.9PMN-0.1PT ceramics

A recent and innovative method to include Ti into the columbite precursor has permitted to synthesize 0.9PMN-0.1PT powders with high homogeneity. The present work describes this methodology, named modified columbite method, showing that the reaction between MN(T)and PbO at 800 degrees C for 2 h results in perovskite single-phase. The crystal structure alterations in the columbite and perovskite phases obtained by this methodology and the effects of potassium doping were investigated by the Rietveld method. Changes in the powder morphology, density and weight loss during the sintering process were also studied. Conclusively, potassium does not affect significantly the perovskite amount, but reduces the particle and grain sizes. This dopant also changes the relaxor behavior of 0.9PMN-0.1 PT ceramic, reducing the dielectric loss and enhancing the diffuseness of the phase transition. (C) 2005 Published by Elsevier Ltd and Techna Gronp S.r.l.

Wet-chemical synthesis of magnesium niobate nanoparticles powders

Nanosized and highly reactive magnesium mobate (MgNb2O6) powders were successfully synthesized by a new wet-chemical method by means of the dissolution of Nb2O5 center dot 5H(2)O and in a solution of oxalic acid followed by the addition of stoichiometric amounts of magnesium carbonate. The Nb-Mg-oxalic acid solution was evaporated resulting in a dry and amorphous powder that was calcined in the temperature range from 200 to 900 degrees C for 2 h. The crystallization process from the amorphous state to the crystalline MgNb2O6 was followed by thermal analysis. The calcined powders characterized by FT-Raman spectroscopy, X-ray diffraction (XRD) and their morphology examined by high resolution scanning electron microscopy (HR-SEM). Pure MgNb2O6, free from the second phases and obtained at 800 degrees C was confirmed by a combined analysis using XRD and FT-Raman. The average diameter of the particles was calculated from the HR-SEM image as 70 urn approximately. This technique allows a better mixing of the constituent elements and thus a better reactivity of the mixture to obtain pre-reaction products with high purity at lower temperatures and reducing cost. It can offer a great advantage in the PMN-PT formation with respect to the solid-state synthesis. (c) 2006 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Influence of the LiNbO3 and KNbO3 seeds on the sintering and electrical properties of PMN ceramic

The effect of LiNbO3 and KNbO3 seeds on the microstructure and dielectric characteristics of PMN ceramic prepared by columbite route have been investigated with the addition of 0, 1, and 2-wt% of seeds. X-ray diffraction, Scanning Electron Microscopy and an impedance analyzer were used to characterize the influence of seeds on physical characteristics and dielectric properties of PMN. LiNbO3 -seeded PMN samples present a significant increase in the amount of perovskite phase. The addition of LiNbO3 seeds in sintered PMN ceramics at 1100degreesC during 4 h causes a decrease in the porosity and the amount of pyrochlore phase. Weight losses during sintering of PMN ceramics are suppressed more significantly for LiNbO3 -seeded PMN. T-m of PMN ceramics changes with seeds concentration. KNbO3 seeds displace T-m to lower temperature whereas LiNbO3 causes its elevation. Dielectric constants of approximately 13,000 at 1 kHz was measured at -5degreesC in PMN ceramics with 1-wt% of LiNbO3 seeds.

Sn-polymetallic greisen-type deposits associated with late-stage rapakivi granites, Brazil: fluid inclusion and stable isotope characteristics

Tin-polymetallic greisen-type deposits in the Itu Rapakivi Province and Rondonia Tin Province, Brazil are associated with late-stage rapakivi fluorine-rich peraluminous alkali-feldspar granites. These granites contain topaz and/or muscovite or zinnwaldite and have geochemical characteristics comparable to the low-P sub-type topaz-bearing granites. Stockworks and veins are common in Oriente Novo (Rondonia Tin Province) and Correas (Itu Rapakivi Province) deposits, but in the Santa Barbara deposit (Rondonia Tin Province) a preserved cupola with associated bed-like greisen is predominant. The contrasting mineralization styles reflect different depths of formation, spatial relationship to tin granites, and different wall rock/fluid proportions. The deposits contain a similar rare-metal suite that includes Sri (+/-W, +/-Ta, +/-Nb), and base-metal suite (Zn-Cu-Pb) is present only in Correas deposit. The early fluid inclusions of the Correas and Oriente Novo deposits are (1) low to moderate-salinity (0-19 wt.% NaCl eq.) CO2-bearing aqueous fluids homogenizing at 245-450 degreesC, and (2) aqueous solutions with low CO2, low to moderate salinity (0-14 wt.% NaCl eq.), which homogenize between 100 and 340 T. In the Santa Barbara deposit, the early inclusions are represented by (1) low-salinity (5-12 wt.% NaCl eq.) aqueous fluids with variable CO2 contents, homogenizing at 340 to 390 T, and (2) low-salinity (0-3 wt.% NaCl eq.) aqueous fluid inclusions, which homogenize at 320380 degreesC. Cassiterite, wolframite, columbite-tantalite, scheelite, and sulfide assemblages accompany these fluids. The late fluid in the Oriente Novo and Correas deposit was a low-salinity (0-6 wt.% NaCl eq.) CO2-free aqueous solution, which homogenizes at (100-260 degreesC) and characterizes the sulfide fluorite-sericite association in the Correas deposit. The late fluid in the Santa Barbara deposit has lower salinity (0-3 wt.% NaCl eq.) and characterizes the late-barren-quartz, muscovite and kaolinite veins. Oxygen isotope thermometry coupled with fluid inclusion data suggest hydrothermal activity at 240-450 degreesC, and 1,0-2.6 kbar fluid pressure at Correas and Oriente Novo. The hydrogen isotope composition of breccia-greisen, stockwork, and vein fluids (delta(18)O quartz from 9.9parts per thousand to 10.9parts per thousand, deltaDH(2)O from 4.13parts per thousand to 6.95parts per thousand) is consistent with a fluid that was in equilibrium with granite at temperatures from 450 to 240 degreesC. In the Santa Barbara deposit, the inferred temperatures for quartz-pods and bed-like greisens are much higher (570 and 500 degreesC, respectively), and that for the cassiterite-quartz-veins is 415 degreesC. The oxygen and hydrogen isotope composition of greisen and quartz-pods fluids (delta(18)O(qtz-H2O)=5.5-6.1parts per thousand) indicate that the fluid equilibrated with the albite granite, consistent with a magmatic origin. The values for mica (delta(18)O(mica-H2O)=33-9.8parts per thousand) suggest mixing with meteoric water. Late muscovite veins (delta(18)O(qtz-H2O)=-6.4parts per thousand) and late quartz (delta(18)O(mica-H2O)=-3.8parts per thousand) indicate involvement of a meteoric fluid. Overall, the stable isotope and fluid inclusion data imply three fluid types: (1) an early orthomagmatic fluid, which equilibrated with granite; (2) a mixed orthomagmatic-meteoric fluid; and (3) a late hydrothermal meteoric fluid. The first two were responsible for cassiterite, wolframite, and minor coluChange in the redox conditions related to mixing-of magmatic and meteoric fluids favored important sulfide mineralization in the Correas deposit. (C) 2004 Elsevier B.V. All rights reserved.

Seeding of PMN powders made by the Pechini method

The partial oxalate method, with the columbite route, associated with the Pechini method, was used to obtain a very fine ceramic powder at low temperature. Using this route it was possible to obtain a very reactive powder and to synthesize a lead magnesium niobate (PMN) powder with up to 100% of perovskite phase at a lower temperatures than the PbO melting point. The influence of the BaTiO3 and PbTiO3 seeds in the phase formation, along with time and temperature during the PMN calcination, was also investigated. The amount of 2% of BaTiO3 seeds promoted PMN powder formation with 100% of perovskite phase and a very narrow particle size distribution. (C) 2001 Elsevier B.V. Ltd and Techna S.r.l. All rights reserved.

Estudio de PMN cerámico dopado con KNbO3 y LiNbO 3 sintetizado por Pechini

PMN belongs to a special class of materials named relaxor ferroelectrics. It has high volumetric efficiency due to its high dielectric constant, which makes it in a perfect material for application in multilayer capacitors. When prepared the columbite route its preparation has many advantages. In this work, the preparations of columbite and PMN were done by Pechini and Partial Oxalate methods, respectively. The effects of the KNbO3 and LiNbO3 dopants added in various concentrations. The idea is founded on the correlations that they have with BaTiO3 y PbTiO3, respectively. The whole process was supervised by TG/DTA, XRD, SEM and determination of the specific surface area of the powders. LiNbO3 carries out the pre-sinterization of the particles, observed by a reduction in the surface area. There are not particle grow, but occur its lengthening. However, for KNbO3 these particle growth, but the agglomerates are softer. The effect produced by the doping during the synthesis of the PMN powder is different from the one produced in the columbite precursor. Pure precursor shows an average particle size of 0,2μm, but the addition of 5,0mol% of dopants carries out the formation of agglomerates close to 4μm. LiNbO 3 addition carries out spherical particles and pre-sinterization, while KNbO3 addition does not change the particles shape.

Estudio de la adición de K+ y LiNbO3 en las propiedades finales del relaxor PMN procesado por mezcla de polvos

PMN ceramic relaxor has been investigated by several researchers and many aspects of this material, like powder morphology, phase decomposition, weight loss during sintering process, densification, between others, still are investigated. PMN powder preparation has been shown more efficient when synthesized by columbite route, however lead addition stage for the PMN powder synthesis remains problematical. Therefore, this work proposes a new association of methodologies, using columbite route and the hydroxide precipitation method. Through use of the powder mixture technique, which permitted to obtain good green and sintered densities, was possible to observe K+ y Li + dopants reduce weight loss in sintering process and change significantly the dielectric properties. Addition of LiNbO3 seeds in conformation stage, which react in a distinct way as a function of the particle size, promotes the formation of differenced grains in the ceramic bulk. Consequently, very different dielectrics properties from conventional PMN ceramic were obtained.

Influência dos dopantes potássio e lítio na cerâmica relaxora niobato de chumbo e magnésio (PMN)

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

Estanho na Amazônia: o apogeu e o caso da produção

No Brasil, na Região Amazônica, o minério de estanho (cassiterita) é obtido por dragagem em depósitos aluvionares, extração de minério primário e lavra de pequeno porte. O concentrado de estanho obtido (Sn02, contendo 60% de estanho), sendo transformado, via redução, nos fornos elétricos, transformando-o em lingotes de estanho. O metal é primeiramente usado para a produção de folhas de flandres – chapas de aço recobertas com estanho e utilizadas para fabricação de latas para alimentos, bebidas e produtos químicos, bem como na produção de soldas e outras ligas para a indústria em geral (particularmente em segmentos elétricos e eletrônicos). A mina mais importante é a de Pitinga (pureza de 55,3%), localizada a 300 km ao norte de Manaus (AM) e proprietária da Paranapenema. Pitinga dispõe de reservas provadas de columbita-tantalita, criolita e zirconita, contendo terras raras e itrium, cuja viabilidade econômica ainda está sendo estudada. Há inda veios mineralizados no estado de Rondônia, incluindo a mina de Bom Futuro (pureza de 58%), no município de Ariquemes, onde operam os mineradores de pequeno porte. O Brasil é o quinto maior produtor do metal, após Indonésia, China e Peru.