Estudo do efeito de cério como sensibilizador e ativador, em matrizes de difenilfosfinatos de lantânio, dopadas com európio e/ou térbio

This paper aims the preparation, characterization and study of luminescence, particularly as for the cerium ion action as activator or sensitizer, in diphenylphosphinate of lanthanum compounds trivalent ions cerium-, europium-, and/or terbium-doped. The following compounds were prepared and studied: i) La1-(x+y)CexEuy(DFF)3; ii) La1-(x+y)CexTby(DFF)3; iii) La1-(x+y+z)CexEuyTbz(DFF)3, with x = 10%, y = 5% e z = 5%. The diphenylphosphinate of lanthanum, Ln[(Ph2)PO2]3, are complexes obtained by the mixture of lanthanides chlorides with diphenylphosphinic acid, ethanol medium. These compounds make white powders, crystalline, insoluble in normal temperature and pressure, and are chemically and thermally stable. When doping with Ce3+, Eu3+ and/or Tb3+, the compounds present characteristic luminescence. Luminescent materials are made of a host matrix incorporated with few amounts of ions called activators, which are able to present luminescence after being excited by UV light or high energy radiation, and sensitizer ions, which have the role of absorbing excitation energy and transfer it to the activator, for it to emit luminescence radiation. The infrared vibrational spectroscopy indicates that the coordination occurs by the oxygens of phosphorile group with ΔνPO of about 40 cm-1 compared to the free ligand. The X Ray difractograms of compounds Eu- and/or Tb-doped are similar, but they present profile of diffraction different observed by Stucchi and col. In previous papers, indicated an influence of Ce in the crystalline phase formation of these matrices. In luminescence spectrums, the excitation that can be made by the levels of ligand in 273 nm, or cerium ion in area between 300 and 400 nm were observed. In the emission spectrum, with excitation in 273 nm, is possible to observe the emission of Ce3+ below 400 nm and the Eu3+ in 592, 611 and 617 nm, and the...as a sensitizer to.

Scaffold nanoestruturado utilizando-se celulose bacteriana/fosfatos de cálcio para regeneração óssea

Pós-graduação em Biotecnologia - IQ

Estudo estrutural, morfológico, elétrico e óptico de cristais de a-Ag2WO4 dopados com Mo6+ via co-precipitação assistida por PVP

Pós-graduação em Química - IQ

Caracterização de filmes de BaxSr1-xTiO3 Sintetizados pelo método hidrotermal assistido por micro-ondas e depositados por eletroforese

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Produção de biodiesel etílico utilizando óxidos mistos derivados de hidróxidos duplos lamelares como catalisadores

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Influência de elementos terras raras nas propriedades catalíticas de óxidos derivados de hidrotalcitas para produção de biodiesel etílico

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Magnetic Tuning of All-Organic Binary Alloys between Two Stable Radicals

Mixtures of 2-(4,5,6,7-tetrafluorobenzimidazol-2-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (F4BImNN) and 2-(benzi-midazol-2-yl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (BImNN.) crystallize as solid solutions (alloys) across a wide range of binary compositions. (F4BImNN)(x)(BImNN)((1-x)) with x < 0.8 gives orthorhombic unit cells, while x >= 0.9 gives monoclinic unit cells. In all crystalline samples, the dominant intermolecular packing is controlled by one-dimensional (1D) hydrogen-bonded chains that lead to quasi-1D ferromagnetic behavior. Magnetic analysis over 0.4-300 K indicates ordering with strong 1D ferromagnetic exchange along the chains (J/k = 12-22 K). Interchain exchange is estimated to be 33- to 150-fold weaker, based on antiferromagnetic ordered phase formation below Neel temperatures in the 0.4-1.2 K range for the various compositions. The ordering temperatures of the orthorhombic samples increase linearly as (1 - x) increases from 0.25 to 1.00. The variation is attributed to increased interchain distance corresponding to decreased interchain exchange, when more F4BImNN is added into the orthorhombic lattice. The monoclinic samples are not part of the same trend, due to the different interchain arrangement associated with the phase change.

Phasengleichgewichte, Kristallstrukturen und elektrische Eigenschaften der Verbindungen in ternären Systemen M-M’-{Sn, Sb, Bi}

In dieser Arbeit wurden isotherme Schnitte der ternären Systeme Ti-Fe-Sb, Zr-Fe-Sb und Nb-Fe-Sb bei 800 bzw. 600 °C untersucht. Die Bildung von vier von den Binärbereichen getrennten ternären Verbindungen im System Ti-Fe-Sb, drei im System Zr-Fe-Sb und einer Verbindung im System Nb-Fe-Sb wurde festgestellt bzw. bestätigt. In den ersten zwei Systemen ist die Bildung von festen Lösungen auf der Basis von binären sowie ternären Phasen stark ausgeprägt. Es wurde die Abhängigkeit des Strukturtyps der Laves-Phasen M(Fe???Sb?)??? (M = Ti, Zr, Nb) von der Elektronenkonzentration und den Atomradien der Komponenten gezeigt. 18 isotype Verbindungen M?Me’???X??? (M = Zr, Hf; M’ = Fe, Co, Ni; X = Sn, Sb, Bi) des geordneten Fe?P-Strukturtyps wurden synthetisiert. Die Untersuchungen der Transporteigenschaften dieser Verbindungen belegen deren metallischen Charakter. Es wurde die Bildung der neuen equiatomen Verbindungen in den Systemen Zr-Cu-Sn und Hf-Cu-Sn der Strukturtypen TiNiSi bzw. LiGaGe und der Verbindung HfFe???Sb des TiNiSi-Strukturtyps festgestellt. Die Transporteigenschaften der Reihe von festen Lösungen V???Ti?FeSb wurden untersucht. Es wurde gezeigt, dass die größte Erhöhung des Seebeck-Koeffizienten bei der kleinen Konzentration der vierten Komponente erreicht wird. Der höchste Wert des Seebeck-Koeffizienten (370 ?V/K bei 380 K) wurde für die Zusammensetzung V????Ti????FeSb festgestellt. Die Serie der quaternären Phasen Sc???Nb???NiSn, ZrNiIn???Sb???, HfNiIn???Sb???, ZrCo???Cu???Sn und HfCo???Cu???Sn. zeigt die Möglichkeit der Phasenbildung der Strukturtypen AlLiSi, LiGaGe bzw. TiNiSi auch im Fall der Abwesenheit einer oder beider ternärer Randverbindungen. Für die Verbindung Sc???Nb???NiSn wurden Halbleitereigenschaften festgestellt. Insgesamt wurde die Kristallstruktur der 25 neuen, zum ersten Mal synthetisierten ternären und quaternären Verbindungen bestimmt. Schlüsselwörter: Phasendiagramm, Phasengleichgewicht, Kristallstruktur, intermetallische Verbindungen, Halb-Heusler-Verbindungen, thermoelektrische Materialien, elektrischer Widerstand, Seebeck-Koeffizient.

In Situ SHINERS at Electrochemical Single-Crystal Electrode/Electrolyte Interfaces: Tuning Preparation Strategies and Selected Applications

We have studied Au(55 nm)@SiO2 nanoparticles (NPs) on two low-index phases of gold and platinum single crystal electrodes in ClO4– and SO42– ion-containing electrolytes by both electrochemical methods and in-situ shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS). We showed the blocking of the electrode with surfactants originating from the synthesis of as-prepared SHINERS NPs. We introduce an efficient procedure to overcome this problem, which provides a fundamental platform for the application of SHINERS in surface electrochemistry and beyond. Our method is based on a hydrogen evolution treatment of the SHINERS-NP-modified single-crystal surfaces. The reliability of our preparation strategy is demonstrated in electrochemical SHINERS experiments on the potential-controlled adsorption and phase formation of pyridine on Au(hkl) and Pt(hkl). We obtained high-quality Raman spectra on these well-defined and structurally carefully characterized single-crystal surfaces. The analysis of the characteristic A1 vibrational modes revealed perfect agreement with the interpretation of single-crystal voltammetric and chronoamperometric experiments. Our study demonstrates that the SHINERS protocol developed in this work qualifies this Raman method as a pioneering approach with unique opportunities for in situ structure and reactivity studies at well-defined electrochemical solid/liquid interfaces.

Ion Beam irradiation of copper nitride: electronic vs elastic-collision mechanism

Copper nitride is a metastable material which results very attractive because of their potential to be used in functional device. Cu3 N easily decomposes into Cu and N2 by annealing [1] or irradiation (electron, ions, laser) [2, 3]. Previous studies carried out in N-rich Cu3 N films irradiated with Cu at 42MeV evidence a very efficient sputtering of N whose yield (5×10 3 atom/ion), for a film with a thickness of just 100 nm, suggest that the origin of the sputtering has an electronic nature. This N depletion was observed to be responsible for new phase formation ( Cu2 O) and pure Cu [4]

Investigação da estabilidade de fases da zircônia-escândia

Nesse trabalho foi proposto investigar a estabilidade de fases do sistema zircônia-escândia (ScSZ) por meio do estudo termodinâmico de nanopartículas, na faixa de 0 a 20% em mol de Sc2O3, e a partir da introdução de um segundo aditivo (Dy2O3 e Nb2O5) ao ZrO2 contendo 10% em mol de Sc2O3 (10ScSZ). A estabilidade de fases do ScSZ foi avaliada com base em dados termodinâmicos determinados pelas técnicas de microcalorimetria de adsorção de água e calorimetria de dissolução à alta temperatura. As soluções sólidas foram sintetizadas pelo método de coprecipitação de hidróxidos. Dados termodinâmicos foram determinados para as formas polimórficas encontradas (monoclínica, tetragonal, cúbica, romboédrica β e γ) por difração de raios X no ScSZ. Esse trabalho resultou no diagrama de fases em nanoescala de tamanho de partícula-composição. Os efeitos produzidos pela introdução de aditivos na matriz de 10ScSZ foram investigados visando obter a possível estabilização da estrutura cúbica (c) e a supressão da transformação de fase c-β, característica do sistema binário. As composições foram sintetizadas por coprecipitação de hidróxidos e por reações em estado sólido para fins comparativos. Os materiais foram sinterizados convencionalmente e por sinterização assistida por campo elétrico. A estabilização completa da fase cúbica ocorreu a partir de teores molares de 1% de Dy2O3 e 0,5% de Nb2O5. O menor teor de Nb2O5 necessário para a estabilização da fase foi atribuído à provável formação da fase líquida durante a sinterização e ao menor tamanho do íon Nb5+. Os resultados de difratometria de raios X em alta temperatura e análise térmica mostraram que houve supressão da transição c-β. As amostras contendo 0,5% mol de Nb2O5 apresentaram valores de condutividade iônica similares aos do 10ScSZ sem aditivos em uma ampla faixa de temperatura com elevada estabilidade em um período de 170 h a 600 °C.

Mechanical alloying of MoSi2 with ternary alloying elements. Part 2 - computer simulation

A computer model of the mechanical alloying process has been developed to simulate phase formation during the mechanical alloying of Mo and Si elemental powders with a ternary addition of Al, Mg, Ti or Zr. Using the Arhennius equation, the model balances the formation rates of the competing reactions that are observed during milling. These reactions include the formation of tetragonal C11(b) MOSi2 (t-MoSi2) by combustion, the formation of the hexagonal C40 MoSi2 polymorph (h-MoSi2), the transformation of the tetragonal to the hexagonal form, and the recovery of t-MoSi2 from h-MoSi2 and deformed t-MoSi2. The addition of the ternary additions changes the free energy of formation of the associated MoSi2 alloys, i.e. Mo(Si, Al)(2), Mo(Mg, Al)(2), (Mo, Ti)Si-2 (Mo, Zr)Si-2 and (Mo, Fe)Si-2, respectively. Variation of the energy of formation alone is sufficient for the simulation to accurately model the observed phase formation. (C) 2003 Elsevier B.V. All rights reserved.

Synthesis of hydrazine by the fixation process

A critical review of the literature concerning organic derivatives of hydrazine, the ammonia-chlorine reaction and the electrolytic formation of hydrazine has been carried out. Apparatus was constructed to study the electrolysis of liquid ammonia, the formation of chloramine and the fixation of chloramine with a ketone to form an isohydrazone. In the latter case the reaction was carried out in a 3" diameter stirred tank and also in a 1" diameter, 2' high column reactor where the liquid phase was continuously recirculated. Two methods of analysis of azines and isohydrazones in a ketone solution have been developed. One is a colorimetric technique using p-dimethylaminobenzaldehyde and the other involves the hydrolysis of the organic derivative to hydrazine sulphate. Hydrazine was detected in low concentration in some of the electrolytic experiments carried out but it was concluded that this method did not show sufficient promise to warrant further investigation. The gas phase formation of chloramine and acetone isohydrazone has also been studied but in this system difficulties were encountered with the chlorine jet blocking with ammonium chloride. The formation of isohydrazones in a stirred tank reactor has been investigated in some detail and the effect of several parameters was determined. The yield was found to be extremely sensitive to chlorine concentration and in order to obtain yields of more than 90 per cent, the molar concentration of chlorine in the gas phase had to be of the order of 5 per cent. An optimum temperature in the region of 0°C was also detected. These results disagree with those quoted in previous studies but extensive experimental work has confirmed the information presented in this thesis. It has also been shown that at high yields the chloramine formation reaction took place in the gas phase.

Functional alkali tantalate 2D structures for microelectronics and related applications

Alkali tantalates and niobates, including K(Ta / Nb)O3, Li(Ta / Nb)O3 and Na(Ta / Nb)O3, are a very promising ferroic family of lead-free compounds with perovskite-like structures. Their versatile properties make them potentially interesting for current and future application in microelectronics, photocatalysis, energy and biomedics. Among them potassium tantalate, KTaO3 (KTO), has been raising interest as an alternative for the well-known strontium titanate, SrTiO3 (STO). KTO is a perovskite oxide with a quantum paraelectric behaviour when electrically stimulated and a highly polarizable lattice, giving opportunity to tailor its properties via external or internal stimuli. However problems related with the fabrication of either bulk or 2D nanostructures makes KTO not yet a viable alternative to STO. Within this context and to contribute scientifically to the leverage tantalate based compounds applications, the main goals of this thesis are: i) to produce and characterise thin films of alkali tantalates by chemical solution deposition on rigid Si based substrates, at reduced temperatures to be compatible with Si technology, ii) to fulfil scientific knowledge gaps in these relevant functional materials related to their energetics and ii) to exploit alternative applications for alkali tantalates, as photocatalysis. In what concerns the synthesis attention was given to the understanding of the phase formation in potassium tantalate synthesized via distinct routes, to control the crystallization of desired perovskite structure and to avoid low temperature pyrochlore or K-deficient phases. The phase formation process in alkali tantalates is far from being deeply analysed, as in the case of Pb-containing perovskites, therefore the work was initially focused on the process-phase relationship to identify the driving forces responsible to regulate the synthesis. Comparison of phase formation paths in conventional solid-state reaction and sol-gel method was conducted. The structural analyses revealed that intermediate pyrochlore K2Ta2O6 structure is not formed at any stage of the reaction using conventional solid-state reaction. On the other hand in the solution based processes, as alkoxide-based route, the crystallization of the perovskite occurs through the intermediate pyrochlore phase; at low temperatures pyrochlore is dominant and it is transformed to perovskite at >800 °C. The kinetic analysis carried out by using Johnson-MehlAvrami-Kolmogorow model and quantitative X-ray diffraction (XRD) demonstrated that in sol-gel derived powders the crystallization occurs in two stages: i) at early stage of the reaction dominated by primary nucleation, the mechanism is phase-boundary controlled, and ii) at the second stage the low value of Avrami exponent, n ~ 0.3, does not follow any reported category, thus not permitting an easy identification of the mechanism. Then, in collaboration with Prof. Alexandra Navrotsky group from the University of California at Davis (USA), thermodynamic studies were conducted, using high temperature oxide melt solution calorimetry. The enthalpies of formation of three structures: pyrochlore, perovskite and tetragonal tungsten bronze K6Ta10.8O30 (TTB) were calculated. The enthalpies of formation from corresponding oxides, ∆Hfox, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -203.63 ± 2.84 kJ/mol, - 358.02 ± 3.74 kJ/mol, and -1252.34 ± 10.10 kJ/mol, respectively, whereas from elements, ∆Hfel, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -1408.96 ± 3.73 kJ/mol, -2790.82 ± 6.06 kJ/mol, and -13393.04 ± 31.15 kJ/mol, respectively. The possible decomposition reactions of K-deficient KTa2.2O6 pyrochlore to KTaO3 perovskite and Ta2O5 (reaction 1) or to TTB K6Ta10.8O30 and Ta2O5 (reaction 2) were proposed, and the enthalpies were calculated to be 308.79 ± 4.41 kJ/mol and 895.79 ± 8.64 kJ/mol for reaction 1 and reaction 2, respectively. The reactions are strongly endothermic, indicating that these decompositions are energetically unfavourable, since it is unlikely that any entropy term could override such a large positive enthalpy. The energetic studies prove that pyrochlore is energetically more stable phase than perovskite at low temperature. Thus, the local order of the amorphous precipitates drives the crystallization into the most favourable structure that is the pyrochlore one with similar local organization; the distance between nearest neighbours in the amorphous or short-range ordered phase is very close to that in pyrochlore. Taking into account the stoichiometric deviation in KTO system, the selection of the most appropriate fabrication / deposition technique in thin films technology is a key issue, especially concerning complex ferroelectric oxides. Chemical solution deposition has been widely reported as a processing method to growth KTO thin films, but classical alkoxide route allows to crystallize perovskite phase at temperatures >800 °C, while the temperature endurance of platinized Si wafers is ~700 °C. Therefore, alternative diol-based routes, with distinct potassium carboxylate precursors, was developed aiming to stabilize the precursor solution, to avoid using toxic solvents and to decrease the crystallization temperature of the perovskite phase. Studies on powders revealed that in the case of KTOac (solution based on potassium acetate), a mixture of perovskite and pyrochlore phases is detected at temperature as low as 450 °C, and gradual transformation into monophasic perovskite structure occurs as temperature increases up to 750 °C, however the desired monophasic KTaO3 perovskite phase is not achieved. In the case of KTOacac (solution with potassium acetylacetonate), a broad peak is detected at temperatures <650 °C, characteristic of amorphous structures, while at higher temperatures diffraction lines from pyrochlore and perovskite phases are visible and a monophasic perovskite KTaO3 is formed at >700 °C. Infrared analysis indicated that the differences are due to a strong deformation of the carbonate-based structures upon heating. A series of thin films of alkali tantalates were spin-coated onto Si-based substrates using diol-based routes. Interestingly, monophasic perovskite KTaO3 films deposited using KTOacac solution were obtained at temperature as low as 650 °C; films were annealed in rapid thermal furnace in oxygen atmosphere for 5 min with heating rate 30 °C/sec. Other compositions of the tantalum based system as LiTaO3 (LTO) and NaTaO3 (NTO), were successfully derived as well, onto Si substrates at 650 °C as well. The ferroelectric character of LTO at room temperature was proved. Some of dielectric properties of KTO could not be measured in parallel capacitor configuration due to either substrate-film or filmelectrode interfaces. Thus, further studies have to be conducted to overcome this issue. Application-oriented studies have also been conducted; two case studies: i) photocatalytic activity of alkali tantalates and niobates for decomposition of pollutant, and ii) bioactivity of alkali tantalate ferroelectric films as functional coatings for bone regeneration. Much attention has been recently paid to develop new type of photocatalytic materials, and tantalum and niobium oxide based compositions have demonstrated to be active photocatalysts for water splitting due to high potential of the conduction bands. Thus, various powders of alkali tantalates and niobates families were tested as catalysts for methylene blue degradation. Results showed promising activities for some of the tested compounds, and KNbO3 is the most active among them, reaching over 50 % degradation of the dye after 7 h under UVA exposure. However further modifications of powders can improve the performance. In the context of bone regeneration, it is important to have platforms that with appropriate stimuli can support the attachment and direct the growth, proliferation and differentiation of the cells. In lieu of this here we exploited an alternative strategy for bone implants or repairs, based on charged mediating signals for bone regeneration. This strategy includes coating metallic 316L-type stainless steel (316L-SST) substrates with charged, functionalized via electrical charging or UV-light irradiation, ferroelectric LiTaO3 layers. It was demonstrated that the formation of surface calcium phosphates and protein adsorption is considerably enhanced for 316L-SST functionalized ferroelectric coatings. Our approach can be viewed as a set of guidelines for the development of platforms electrically functionalized that can stimulate tissue regeneration promoting direct integration of the implant in the host tissue by bone ingrowth and, hence contributing ultimately to reduce implant failure.

Estudo termo-mecânico de interconector metálico recoberto com filme de La0,8Ca0,2CrO3 e de interconector cerâmico de La0,8Sr0,2Cr0,92Co0,08O3 para PaCOS

Doped lanthanum chromite ( LaCrO3 ) has been the most common material used as interconnect in solid oxide fuel cells for high temperature ( SOFC-HT ) that enabling the stack of SOFCs. The reduction of the operating temperature, to around 800 º C, of solid oxide fuel cells enabled the use of metallic interconnects as an alternative to ceramic LaCrO3, From the practical point of view, to be a strong candidate for interconnect the material must have good physical and mechanical properties such as resistance to oxidizing and reducing environments, easy manufacture and appropriate thermo-mechanical properties. Thus, a study on the physic-mechanical interconnects La0,8Sr0,2Cr0,92Co0,08O3 ceramics for SOFC -AT obtained by the method of combustion , as well as thermo-mechanical properties of metallic interconnects (AISI 444) covered with La0,8Ca0,2CrO3 by deposition technique by spray-pyrolysis fuel cells for intermediate temperature (IT-SOFCs). The La0,8Sr0,2Cr0,92Co0,08O3 was characterized by X -ray diffraction(XRD) , density and porosity , Vickers hardness (HV) , the flexural strength at room temperature and 900 °C and scanning electron microscopy (SEM). The X -ray diffraction confirmed the phase formation and LaCrO3 and CoCr2O4, in order 6 GPa hardness and mechanical strength at room temperature was 62 MPa ceramic Interconnector. The coated metal interconnects La0,8Ca0,2CrO3 passed the identification by XRD after deposition of the film after the oxidation test. The oxidative behavior showed increased resistance to oxidation of the metal substrate covered by La0,8Ca0,2CrO3 In flexural strength of the coated metal substrate, it was noticed only in the increased room temperature. The a SEM analysis proved the formation of Cr2O3 and (Cr,Mn)3O4 layers on metal substrate and confirmed the stability of the ceramic La0,8 Ca0,2CrO3 film after oxidative test