Enhanced luminescence from transparent Ni2+-doped MgO-Al2O3-SiO2 glass ceramics by Ga2O3 addition

Transparent Ni2+-doped MgO-Al2O3-SiO2 glass ceramics without and with Ga2O3 were synthetized. The precipitation of spinel nanocrystals, which was identified as solid solutions in the glass ceramics, could be favored by Ga2O3 addition and their sizes were about 7.6 nm in diameter. The luminescent intensity of the Ni2+-doped glass ceramics was largely enhanced by Ga2O3 addition which could mainly be caused by increasing of Ni2+ in the octahedral sites and the reduction of the mean frequency of phonon density of states in the spinel nanocrystals of solid solutions. The full width at half maximum (FWHM) of emissions for the glass ceramics with different Ga2O3 content was all more than 200 nm. The emission lifetime increased with the Ga2O3 content and the longest lifetime is about 250 mu s. The Ni2+-doped transparent glass ceramics with Ga2O3 addition have potential application as broadband optical amplifier and laser materials. (C) 2007 Elsevier Ltd. All rights reserved.

Cr4+在八面体格位中的光谱特性研究

Cr-doped and Mg, Cr-codoped Al2O3 crystals were grown by Czochralski method. The latter has a broad absorption peak in 900-1600nm region. We investigated the change of the absorption band with annealing under different atmospheres or temperatures. Through establishing a structure defect model, we successfully interpreted all the experiment results and confirmed that the extremely broad infrared absorption band belonged to Cr4+, which should occupy the octahedral sites in Al2O3.

Studies of magnetic interactions in Mn-doped β-Ga2O3 from first-principles calculations

The magnetic behavior of Mn-doped beta-Ga2O3 is Studied from first-principles calculations within the generalized gradient approximation method. Calculations show that ferromagnetic ordering is always favorable for configurations in which two Mn ions substitute either tetrahedral or octahedral sites, and the ferromagnetic ground state is also sometimes favorable for configurations where one Mn ion substitutes a tetrahedral site and another Mn ion substitutes an octahedral site. However, the configurations of the latter case are less stable than those of the former. (c) 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Propriedades luminescentes do SrGa2O4 dopado com íons de Ni2+

O objetivo deste trabalho é a síntese e investigação estrutural e óptica de amostras SrGa2O4 dopados com 1% de íons Ni2+. Estas amostras foram sintetizados por reação do estado sólido convencional, utilizando como materiais de partida de alta pureza Ga2O3, SrCO3 e NiO em quantidades estequiométricas. As amostras foram caracterizadas estruturalmente pelo método de difração de raios - X( XRD ) e as medições de difração mostraram que as amostras têm uma única fase monoclínica. Os padrões de XRD também foram refinados pelo método de Rietveld, que permitiu a determinação dos parâmetros de célula unitária. A Caracterização óptica das amostras puras e dopadas SrGa2O4 foram realizadas as medições a partir de fotoluminescência, de excitação e de absorção fotoacústica, à temperatura ambiente. Os espectros de emissão mostraram três bandas de emissão localizadas em 557 nm, 661 nm e 844 nm e foram identificadas essas bandas, respectivamente, com as seguintes transições eletrônicas :1T2 (1D) → 3A2 (3F), 3T1 (3F)→ 3A2 (3F) e 1T2 (1D) → 3T2 (3F). Os espectros de excitação mostraram seis bandas de absorção associadas às transições electrônicas do nível 3A2 (3F) para o 3T1 (3P) , T1 (3P), 1A1 (1G), 1T2 (1D), 3T1 (3F), 1E (1D) e 1T2, 1E (1G). Medidas de absorção fotoacústica também foram realizados com o fim de verificar as transições ópticas observadas nos espectros de excitação e de identificar novas bandas de absorção óptica. Os resultados demonstraram que os íons de Ni2+ ocupam dois locais octaédricos diferentes na amostra SrGa2O4 dopado. A partir das transições ópticas observadas nos espectros de excitação e fotoacústica, determinou-se o parâmetro de cristal de campo, dq, e parâmetros Racah, B e C. A proporção Dq / B ≈ 1.2 para ambos os locais são típicos para Ni2+ íons inseridos em redes de óxido e em coordenação octaédrica.

Propriedades fotoluminescentes e higroscopia do composto SrAl2O4 dopado com íons de Ni2+

Amostras foram preparadas pelo método de difusão a partir dos reagentes químicos SrCO3, Al2O3 e NiO em proporções estequiométricas. Medidas por difração de raios X mostraram que as amostras possuem uma única fase: SrAl2O4. Neste trabalho apresentamos imagens de microscopia eletrônica de varredura das amostras SrAl2O4 dopadas com 0,1%, 0,5%, 1,0%, 2,0%, 5,0% e 10,0% de íons de Ni2+, medidas de fotoluminescência, excitação da fotoluminescência da amostra SrAl2O4 dopada com 1,0% de íons de Ni2+, medidas de absorção fotoacústica das amostras SrAl2O4 dopadas com 1,0%, 2,0%, 5,0% e 10,0% de íons de Ni2+. Estas medidas foram realizadas a temperatura ambiente para investigar as transições eletrônicas dos íons divalente de níquel que entraram substitucionalmente nos sítios de Sr2+ da rede do SrAl2O4. Os resultados ópticos mostram a existência de três centros emissores de Ni2+. De acordo com a literatura, a estrutura do SrAl2O4 é composta de dois sítios octaédrico distintos de íons de Sr2+, o Sr12+ e o Sr22+, cujas distâncias médias Sr1 O e Sr2 O são, respectivamente, 2,800 Ǻ e 2,744 Ǻ. Visto que os íons de Ni2+ tendem a substituir os íons de Sr2+, devido ao fato de possuírem a mesma valência, é necessário considerar que uma parte dos íons de Ni2+ ocuparam os sítios dos íons de Al3+ na rede do SrAl2O4 para justificar a existência de um terceiro centro emissor de Ni2+ nesse composto. Uma novo sítio octaédrico para os íons de Ni2+ foi estimado a partir do valor da aresta do sítio tetraédrico ocupado pelos íons de Al3+ na rede do SrAl2O4 (considerando o raio iônico do Ni2+ como aproximadamente 40% maior do que o raio iônico do Al3+). As transições eletrônicas presentes nos espectros de excitação e absorção fotoacústica permitiram determinar os parâmetros de campo cristalino (Dq) e Racah (B e C) para os três sítios diferentes ocupados pelos íons de Ni2+ no SrAl2O4. Neste caso, os resultados mostraram que o sítio II dos íons de Ni2+ é associado à posição do Sr1 e possuem um parâmetro Dq menor e que o parâmetro Dq associado aos íons de Ni2+ que substituíram os íons de Sr no sitio I, o qual, por sua vez é associado à posição do Sr2. E, por fim, o sítio III que possui o menor parâmetro de campo cristalino Dq, portanto a maior distância íon ligante, é identificado como aquele relacionado ao rearranjo octaédrico local das antigas posições de Al3+. O caráter higroscópico do SrAl2O4:Ni2+ é observado a partir dos espectros de absorção fotoacústica e os modos de vibração de estiramento das ligações Ni OH e O H são identificadas nos espectros.

Magnetic properties of ZnO-doped cobalt ferrite

The cobalt ferrites with chemical composition Co1+xZnxFe2-2xO4 (r=0.0, 0.1, 0.2, 0.4) were obtained with conventional solid reaction. The ZnO-doped samples have lower lattice constant than CoFe2O4 by adjusting Co ions to the octahedral sites. The results show that doping ZnO could extremely improve the magnetic properties. In comparison with pure CoFe2O4, the little ZnO-doped sample has higher permeability and much lower coercivity at the condition of a little decrease of magnetization saturation. Sample with x=0.1 shows evident magnetostrictive effect at the magnetic field of 30-60 mT while pure cobalt ferrite sample does not, though the saturation magnetostriction decreases. These indicate that ZnO-doping improves the magnetostrictive sensitivity of the cobalt ferrites and have potential applications in magnetoelectric devices and magnetic detector.

Magnetic properties of tin-doped magnetite nanoparticles

Structural and magnetic characteristics of Fe3-xSnxO4 (x < 0.3) nanoparticles synthesized using the precipitation exchange method have been investigated by X-ray diffraction, transmission electron microscope, Mossbauer spectra, X-ray photoelectron spectroscopy and magnetization measurement. The mean particle dimension decreases from 8 to 6 nm, the lattice parameters enlarge, the saturation magnetization decreases, as well as the magnetization and the coercive field increase, with increasing tin-content. The paramagnetic property of the specimens indicates that the replacement of Fe3+ by Sn4+ on the octahedral sites of Fe3O4 causes a progressive lowering of the Curie temperature and the Curie temperatures of the materials are all lower than that of crystallite tin-doped magnetite. This striking debasing is due to the lessening of the grain size. This is the smallest size reported thus far for paramagnetic tin-doped magnetite particles. (c) 2006 Elsevier B.V. All rights reserved.

Magnetic properties of ZnO-doped cobalt ferrite

The cobalt ferrites with chemical composition Co1+xZnxFe2-2xO4 (r=0.0, 0.1, 0.2, 0.4) were obtained with conventional solid reaction. The ZnO-doped samples have lower lattice constant than CoFe2O4 by adjusting Co ions to the octahedral sites. The results show that doping ZnO could extremely improve the magnetic properties. In comparison with pure CoFe2O4, the little ZnO-doped sample has higher permeability and much lower coercivity at the condition of a little decrease of magnetization saturation. Sample with x=0.1 shows evident magnetostrictive effect at the magnetic field of 30-60 mT while pure cobalt ferrite sample does not, though the saturation magnetostriction decreases. These indicate that ZnO-doping improves the magnetostrictive sensitivity of the cobalt ferrites and have potential applications in magnetoelectric devices and magnetic detector.

Studies of methane reforming with carbon dioxide on hexaaluminates

In this paper, a series of Sr1-xLaxNiAl11O19 catalysts were synthesized and their chemical and physical properties were investigated by XRD, UV-DRS, H-2-O-2 titration, TPR and Py-IR techniques. The experimental results show that the Sr1-xLaxNiAl11O19 catalysts have a magnetoplumbite structure and Ni ion is shared between tetrahedral and octahedral sites of the spinel blocks, and the amount of nickel ions in the tetrahedral environment increases with the increase of x value in Sr1-xLaxNiAl11O19. The TPR study revealed that the reducibility of the series of the catalysts depends strongly on the substitution value x, that is, a low temperature peak appears for samples without substitution, in case of samples with x = 1 high temperature peak appears, and for samples with 0sites and amount of the carbon deposition on the catalyst surface. So it is evident that carbon deposition in carbon dioxide reforming of methane can be suppressed by decreasing the acidity of the complex oxides catalysts.

On the magnetic properties of ultra-Þne zinc ferrites

Zinc ferrite belongs to the class of normal spinels where it is assumed to have a cation distribution of Zn2`(Fe3`)2(O2~)4, and it is purported to be showing zero net magnetisation. However, there have been recent reports suggesting that zinc ferrite exhibits anomaly in its magnetisation. Zinc ferrite samples have been prepared by two di¤erent routes and have been analysed using low energy ion scattering, Mo¬ ssbauer spectroscopy and magnetic measurements. The results indicate that zinc occupies octahedral sites, contrary to the earlier belief that zinc occupies only the tetrahedral sites in a normal spinel. The amount of zinc on the B site increases with decrease in particle size. The LEIS results together with the Mo¬ ssbauer results and the magnetic measurements lead to the conclusion that zinc occupies the B site and the magnetisation exhibited by ultraÞne particles of zinc is due to short range ordering

Preferential exposure of certain crystallographic planes on the surface of spinel ferrites: a study by LEIS on polycrystalline spinel ferrite surfaces

Spinel ferrites are commercially important because of their excellent magnetic and catalytic properties. The study by Low Energy Ion Scattering (LEIS) can reveal atomic scale information on the surface. The surface of selected spinel ferrites was investigated by LEIS. It has been found that it is the octahedral sites which are preferentially exposed on the surface of the spinel ferrites. So the probable planes which are exposed on spinel ferrite surfaces are D(110) or B(111). This prediction using LEIS gives scope for tailor-making compounds with catalytically active ions on the surface for various catalytic reactions.

Ternary erbium chromium sulfides : structural relationships and magnetic properties

Single crystals of four erbium-chromium sulfides have been grown by chemical vapor transport using iodine as the transporting agent. Single-crystal X-ray diffraction reveals that in Er(3)CrS(6) octahedral sites are occupied exclusively by Cr(3+) cations, leading to one-dimensional CrS(4)(5-) chains of edge-sharing octahedra, while in Er(2)CrS(4), Er(3+), and Cr(2+) cations occupy the available octahedral sites in an ordered manner. By contrast, in Er(6)Cr(2)S(11) and Er(4)CrS(7), Er(3+) and Cr(2+) ions are disordered over the octahedral sites. In Er(2)CrS(4), Er(6)Cr(2)S(11), and Er(4)CrS(7), the network of octahedra generates an anionic framework constructed from M(2)S(5) slabs of varying thickness, linked by one-dimensional octahedral chains. This suggests that these three phases belong to a series in which the anionic framework may be described by the general formula [M(2n+1)S(4n+3)](x-), with charge balancing provided by Er(3+) cations located in sites of high-coordination number within one-dimensional channels defined by the framework. Er(4)CrS(7), Er(6)Cr(2)S(11), and Er(2)CrS(4) may thus be considered as the n = 1, 2, and infinity members of this series. While Er(4)CrS(7) is paramagnetic, successive magnetic transitions associated with ordering of the chromium and erbium sub-lattices are observed on cooling Er(3)CrS(6) (T(C)(Cr) = 30 K; T(C)(Er) = 11 K) and Er(2)CrS(4) (T(N)(Cr) = 42 K, T(N)(Er) = 10 K) whereas Er(6)Cr(2)S(11) exhibits ordering of the chromium sub-lattice only (T(N) = 11.4 K).

The impact of charge transfer and structural disorder on the thermoelectric properties of cobalt intercalated TiS2

A family of phases, CoxTiS2 (0 ≤ x ≤ 0.75) has been prepared and characterised by powder X-ray and neutron diffraction, electrical and thermal transport property measurements, thermal analysis and SQUID magnetometry. With increasing cobalt content, the structure evolves from a disordered arrangement of cobalt ions in octahedral sites located in the van der Waals’ gap (x ≤ 0.2), through three different ordered vacancy phases, to a second disordered phase at x ≥ 0.67. Powder neutron diffraction reveals that both octahedral and tetrahedral inter-layer sites are occupied in Co0.67TiS2. Charge transfer from the cobalt guest to the TiS2 host affords a systematic tuning of the electrical and thermal transport properties. At low levels of cobalt intercalation (x < 0.1), the charge transfer increases the electrical conductivity sufficiently to offset the concomitant reduction in |S|. This, together with a reduction in the overall thermal conductivity leads to thermoelectric figures of merit that are 25 % higher than that of TiS2, ZT reaching 0.30 at 573 K for CoxTiS2 with 0.04 ≤ x ≤ 0.08. Whilst the electrical conductivity is further increased at higher cobalt contents, the reduction in |S| is more marked due to the higher charge carrier concentration. Furthermore both the charge carrier and lattice contributions to the thermal conductivity are increased in the electrically conductive ordered-vacancy phases, with the result that the thermoelectric performance is significantly degraded. These results illustrate the competition between the effects of charge transfer from guest to host and the disorder generated when cobalt cations are incorporated in the inter-layer space.

Formation of beta-nickel hydroxide plate-like structures under mild conditions and their optical properties

Nanostructural beta-nickel hydroxide (beta-Ni(OH)(2)) plates were prepared using the microwave hydrothermal (MH) method at a low temperature and short reaction times. An ammonia solution was employed as the coordinating agent, which reacts with [Ni(H(2)O)(6)](2+) to control the growth of beta-Ni(OH)(2) nuclei. A trigonal beta-Ni(OH)(2) single phase was observed by X-ray diffraction (XRD) analyses, and the crystal cell was constructed with structural parameters and atomic coordinates obtained from Rietveld refinement. Field emission scanning electron microscopy (FE-SEM) images revealed that the samples consisted of hexagonal-shaped nanoplates with a different particle size distribution. Broad absorption bands assigned as transitions of Ni(2+) in oxygen octahedral sites were revealed by UV-vis spectra. Photoluminescence (PL) properties observed with a maximum peak centered in the blue-green region were attributed to different defects, which were produced during the nucleation process. We present a growth process scheme of the beta-Ni(OH)(2) nanoplates. (C) 2011 Elsevier Inc. All rights reserved.

Magnetic resonance study of a vanadium pentoxide gel

In this work we report results from continuous-wave (CW) and pulsed electron paramagnetic resonance (EPR) and proton nuclear magnetic resonance (NMR) studies of the vanadium pentoxide xerogel V2O5:nH(2)O (n approximate to 1.6). The low temperature CW-EPR spectrum shows hyperfine structure due to coupling of unpaired V4+ electron with the vanadium nucleus. The analysis of the spin Hamiltonian parameters suggests that the V4+ ions are located in tetragonally distorted octahedral sites. The transition temperature from the rigid-lattice low-temperature regime to the high temperature liquid-like regime was determined from the analysis of the temperature dependence of the hyperfine splitting and the V4+ motional correlation time. The Electron Spin Echo Envelope Modulation (ESEEM) data shows the signals resulting from the interaction of H-1 nuclei with V4+ ions. The modulation effect was observed only for field values in the center of the EPR absorption spectrum corresponding to the single crystals orientated perpendicular to the magnetic field direction. At least three protons are identified in the xerogel by our magnetic resonance experiments: (I) the OH groups in the equatorial plane, (ii) the bound water molecules in the axial V=O bond and (iii) the free mobile water molecules between the oxide layers. Proton NMR lineshapes and spin-lattice relaxation times were measured in the temperature range between 150 K and 323 K. Our analysis indicates that only a fraction of the xerogel protons contribute to the measured conductivity.