Characterization of the columbite precursor and (1-x)PMN-xPT powders prepared by Ti-modified columbite route

This study proposes to synthesize (1-x)PMN-xPT powders, where 0.10 < x < 0.45, using the T-modified columbite route. This methodology consists in the preparation of the MNT columbite precursor via the polymeric precursor method, followed by the solid state reaction with PbO to get the PMN-PT powders. It was verified that from 15 mol% of Ti, the MNT presents the coexistence of two main phases with different crystal symmetry: Rutile and Columbite. However, the synthesis of (1-x)PMN-xPT powders is not affected by this event. A detailed study of structural effects in MNT and PMN-PT powders as function of Ti content was made using the Rietveld method. It was also demonstrated that powders possess high chemical and microstructural homogeneity.

Study of Ti-modified columbite route and the effect of lithium doping in 0.9PMN-0.1PT ceramics

The influence of lithium on the structural characteristics of PMN-PT ceramic was studied. The synthesis of PMN-PT powders using this precursor leads to the formation of high amount of perovskite phase. The insertion of Li(+) ions in B-site affects the microstructure because the rise in mass transport changes the mechanical characteristics of sintered ceramic. Higher values of K(m) and T(m) were gotten when lithium is inserted into perovskite phase. Secondary phase was found when lithium content increase beyond 1 mol%, besides the occurrence of transgranular fractures in sintered ceramic. Also, the additive acts increasing the relaxor behavior.

(1-x)PMN-xPT ceramics prepared by conventional and modified columbite route: Effect on electrical properties

This study aims to demonstrate how the chemical homogeneity of B cations affects the microstructure and electrical responses of (1-x) PMN-xPT ceramics. Two methodologies were employed to synthesize three different compositions, with x assuming the values 0.10, 0.28, and 0.35. If compared to conventional method, the Ti-modified columbite route, which is characterized by higher B cation homogeneity, leads to PMN-PT powders and ceramics with lower content of PNT pyrochlore phase and, for 0.65PMN-0.35PT composition, minor amount of tetragonal phase is found. Conclusively, PMN-PT ceramics obtained by modified route favors B cations homogeneity, enhancing the dielectric, ferroelectric and piezoelectric properties.

Synthesis and characterization of 0.9PMN-0.1PT powders by the use of a modified columbite precursor

The complex perovskite compound 0.9PbMg 1/3Nb 2/3O 3-0.1PbTiO 3 is one of the most promising relaxor ceramic because the addition of lead titanate increases T m, by about 5°C/mol% from intrinsic T m value for pure PMN (near -7 to -15°C). A Ti-modified columbite precursor was used to prepare PMN-PT powders containing single perovskite phase. This variation on columbite route includes Ti insertion in MgNb 2O 6 orthorhombic structure so that individual PT synthesis becomes unnecessary. Furthermore, effects of Li additive on columbite and PMN-PT structures were studied by XRD to verify the phase formation at each processing step. XRD data were also used for the structural refinement by Rietveld method. The additive acts increasing columbite powders crystallinity, and the amount of perovskite phase was insignificantly decreased by lithium addition. By SEM micrographs it was observed that Li presence in PMN-PT powders leads to the formation of rounded primary particles and for lmol% of additive, the grain size is not changed, different from when this concentration is enhanced to 2mol%.

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.

Structural effects of Li and K additives on the columbite precursor and 0.9PMN-0.1PT powders

Single-phase perovskite 0.9Pb(Mg1/3Nb2/3)O-3-0.1PbTiO(3) (PMN-PT) powders were prepared by using a Ti-modified columbite precursor (MNT) obtained by the polymeric precursor method. The innovation consists in the preparation of Ti-modified columbite in order to react directly with a stoichiometric amount of PbO to obtain pyrochlore-free PMN-PT powders. It has been shown that titanium oxide forms a solid solution with columbite (MN) and does not affect the obtaining of a single-phase columbite precursor. Thus, a high amount of perovskite phase can be obtained by reaction with PbO at 800 degreesC for 2 h. Effects of K and Li additives on the structure of MNT and PMN-PT were studied. X-ray diffraction studies were carried out to verify the phase formation at each processing step and these data were used for structural refinement by the Rietveld method. Both K and Li additives increase the crystallinity of MNT powders, being this effect more intense for the Li-doped samples. For PMN-PT samples the additives cause an insignificant decrease in the amount of perovskite phase. The morphology of the PMN-PT powder depends on the type of the additive. (C) 2003 Elsevier B.V All rights reserved.

Physical characterization of K-doped 0.9PMN-0.1PT synthesized by an association of the columbite route and the polymeric precursor method

The solid solution 0.9PbMg 1/3Nb 2/3O 3-0.1PbTiO 3 is one of the most widely investigated relaxor ceramic, because of its high dielectric constant and low sintering temperatures. PMN-PT powders containing single perovskite phase were prepared by using a Timodified columbite precursor obtained by the polymeric precursor method. Such precursor reacts directly with stoichiometric amount of PbO to obtain pyrochlore-free PMN-PT powders. The structural effects of K additive included in the columbite precursor and 0.9PMN-0.1PT powders were also studied. The phase formation at each processing step was verified by XRD analysis, being these results used for the structural refinement by the Rietveld method. It was verified the addition of K in the columbite precursor promotes a slight increasing in the powder crystallinity. There was not a decrease in the amount of perovskite phase PMN-PT for 1mol% of K, and the particle and grain size were reduced, making this additive a powerful tool for grain size control.

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.

Thermal properties of MOSi2 with minor aluminum substitutions

Mo(Si1-xAlx)(2) compositions (x = 0-0.1) have been prepared by a modified SHS route under uniaxial hydrostatic pressure. Oxidation studies carried out by thermal analysis and sheet resistivity indicate an improvement in the low temperature (700-900 K) oxidation resistance with increasing aluminum addition. Dilatometric results show a decrease in the a value up to x = 0.05 substitution. With the aluminum substitution, both thermal expansion coefficient and thermal conductivity show decrease in their values except in the biphasic region. The x = 0.05 composition containing both C11(b) and C40 phases is a promising material for high temperature thermal barrier coating as it shows higher oxidation resistance and a similar K/alpha value as compared to pure MoSi, (c) 2006 Elsevier Ltd. All rights reserved.

Novel microporous silicates and mesoporous MCM materials derivatised with inorganic and organometallic complexes

Os materiais microporosos e mesoporosos são potenciais catalisadores heterogéneos. Os zeólitos e outros materiais microporosos do tipo zeolítico tradicionais, têm átomos tetracoordenados no esqueleto. Nos últimos anos, um vasto número de titanossilicatos contendo Ti(IV) hexacoordenado e Si(IV) tetracoordenado, com estruturas tridimensionais, têm sido alvo de grande interesse. Um dos objectivos desta tese foi preparar silicatos microporosos, contendo átomos metálicos com número de coordenação superior a quatro, e possuindo quer novas estruturas quer propriedades físicas e químicas interessantes. Neste contexto, foi preparado um novo ítriossilicato de sódio, AV-1, análogo do raro mineral montregianite, Na4K2Y2Si16O38·10H2O. Este material é o primeiro sólido microporoso que contem quantidades estequiométricas de sódio (e ítrio) no esqueleto. Foi, também, sintetizado um silicato de cério, AV-5, análogo estrutural do mineral montregianite com potencial aplicação em optoelectrónica. Nesta tese é, ainda, descrita a síntese e caracterização estrutural de um silicato de cálcio hidratado, AV-2, análogo do raro mineral rhodesite (K2Ca4Na2Si16O38.12H2O). Na continuação do trabalho desenvolvido em Aveiro na síntese de novos titanossilicatos surgiu o interesse de preparar novos zirconossilicatos microporosos por síntese hidrotérmica. Foram preparados dois novos materiais análogos dos minerais petarasite Na5Zr2Si3O18(Cl,OH)·2H2O (AV-3) e kostylevite, K2Si3O9·H2O (AV-8). Foram, também, obtidos análogos sintéticos dos minerais parakeldyshite e wadeite, por calcinação a alta temperatura de AV-3 e de umbite sintética. A heterogeneização de complexos organometálicos na superfície de materiais mesoporosos do tipo M41S permite associar a grande actividade catalítica e a presença de sítios activos localizados típicos dos complexos organometálicos, com a robustez e fácil separação, características dos materiais mesoporosos siliciosos. Nesta dissertação relata-se a derivatização dos materiais MCM-41 e MCM-48 através da reacção de [SiMe2{(h5-C5H4)2}]Fe e [SiMe2{(h5-C5H4)2}]TiCl2 com os grupos silanol das superfícies mesoporosas. Os materiais MCMs derivatizados com ansa-titanoceno foram testados na epoxidação de cicloocteno a 323 K na presença de hidrogenoperóxido de t-butilo. Estudou-se a heterogeneização dos sais de complexos com ligação metal-metal [Mo2(MeCN)10][BF4]4, [Mo2(m-O2CMe)2(MeCN)6][BF4]2 e [Mo2(m- O2CMe)2(dppa)2(MeCN)2][BF4]2 via imobilização nos canais do MCM-41. A imobilização dos catalisadores homogéneos na superfície do MCM-41 envolve a saída dos ligandos nitrilo lábeis, preferencialmente em posição axial, através da reacção com os grupos Si-OH da sílica. Verificou-se que a ligação Mo-Mo se mantém intacta nos produtos finais. É provável que estes materiais sejam eficientes catalisadores heterogéneos em reacções de polimerização. As técnicas de caracterização utilizadas nesta tese foram a difracção de raios-X de pós, a microscopia electrónica de varrimento, a espectroscopia de ressonância magnética nuclear do estado sólido (núcleos 13C, 23Na e 29Si), as espectroscopias de Raman e infravermelho com transformadas de Fourier, as análises termogravimétricas e as análises de adsorção de água e azoto.

Preparação de óxidos mistos de níquel e zinco nanoparticulados a partir de combustíveis alternativos

The field of "Materials Chemistry" has been developing in recent years and there has been a great increase of interest in the synthesis and chemical and physical properties of new inorganic solids. New routes of synthesis and synthesis modified has been developed with the aim not only to optimize the processes in laboratory scale, but also on an industrial scale, and make them acceptable by current environmental legislation. The phenomenology of current solid state chemistry properties coupled with the high temperature superconductivity, ferromagnetism, porosity molecular and colors are evidence affected by the synthesis method, which in turn can influence the technological application of these materials. From this understanding, mixed oxides of nickel and zinc nanoparticulate were synthesized by microwave-assisted combustion route using three specific types of organic fuels employing the weight ratios 1:1/2 and 1:1 of cation metallic/fuel, in order to investigate the influence of such proportions to obtain the solids. The new fuels were chosen to replace, for example, urea or glycine that are the fuels most commonly preferred in this kind of synthesis. The powders without heat treatment were studied by Thermogravimetric analysis (TGA), X-Ray Diffraction (XRD) and then calcined at 900°C. After heat treatment, the samples were characterized by analysis of X Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). The modified synthesis route porposed was effective for obtaining powders. Both the alternative fuels chosen as the different weight ratios employed, influenced in the morphology and obtaining oxides

Temperature dependence and magnetocrystalline anisotropy studies of self-assembled L1(0)-Fe55Pt45 ferromagnetic nanocrystals

Temperature dependence and uniaxial magnetocrystalline anisotropy properties of the chemically synthesized 4 nm L1(0)-Fe55Pt45 nanoparticle assembly by a modified polyol route are reported. As-prepared nanoparticles are superparamagnetic presenting fcc structure, and annealing at 550 degrees C converts the assembly into ferromagnetic nanocrystals with large coercivity (H-C>1 T) in an L1(0) phase. Magnetic measurements showed an increasing in the ferromagnetically ordered fraction of the nanoparticles with the annealing temperature increases, and the remanence ratio, S=M-R/M-S congruent to 0.76, suggests an (111) textured film. A monotonic increase of the blocking temperature T-B, the uniaxial magnetocrystalline anisotropy constant K-U, and the coercivity H-C with increasing annealing temperature was observed. Magnetic parameters indicate an enhancement in the magnetic properties due to the improved Fe55Pt45 phase stabilizing, and the room-temperature stability parameter of 67, which indicates that the magnetization should be stable for more than ten years, makes this material suitable for ultrahigh-density magnetic recording application.(c) 2007 American Institute of Physics.

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)

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.

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.