Influence of heavy rare earth ions substitution on microstructure and magnetism of nanocrystalline magnetite

In this work we report results on the influence of heavy rare earth ions substitution on microstructure and magnetism of nanocrystalline magnetite. A series of Fe(2.85)RE(0.15)O(4) (RE = Gd, Dy, Ho, Tm and Yb) samples have been prepared by high energy ball milling. Structure/microstructure investigations of two selected samples Fe(2.85)Gd(0.15)O(4) and Fe(2.85)Tm(0.15)O(4), represent an extension of the previously published results on Fe(3)O(4)/gamma-Fe(2)O(3), Fe(2.85)Y(0.15)O(4) and Fe(2.55)In(0.45)O(4) [Z. Cvejic, S. Rakic, A. Kremenovic, B. Antic, C. Jovalekic. Ph. Colomban, Sol. State Sciences 8 (2006) 908], while magnetic characterization has been done for all the samples. Crystallite/particle size and strain determined by X-ray diffractometry and Transmission electron microscopy (TEM) confirmed the nanostructured nature of the mechanosynthesized materials. X-ray powder diffraction was used to analyze anisotropic line broadening effects through the Rietveld method. The size anisotropy was found to be small while strain anisotropy was large, indicating nonuniform distribution of deffects in the presence of Gd and Tm in the crystal structure. Superparamagnetic(SPM) behavior at room temperature was observed for all samples studied. The Y-substituted Fe(3)O(4) had the largest He and the lowest M(S). We discuss the changes in magnetic properties in relation to their magnetic anisotropy and microstructure. High field irreversibility (H>20kOe) in ZFC/FC magnetization versus temperature indicates the existence of high magnetocrystalline and/or strain induced anisotropy. (C) 2008 Elsevier B.V. All rights reserved.

Structural Characterization of Rare-Earth Doped Yttrium Aluminoborate Laser Glasses Using Solid State NMR

The structure of laser glasses in the system (B(2)O(3))(0.6){(Al(2)O(3))(0.4-x)(Y(2)O(3))(x)} (0.1 <= x <= 0.25) has been investigated by means of (11)B, (27)Al, and (89)Y solid state NMR as well as Y-3d core-level X-ray photoelectron spectroscopy, (11)B magic-angle spinning (MAS) NMR spectra reveal that the majority of the boron atoms are three-coordinated, and a slight increase of four-coordinated boron content with increasing x can be noticed. (27)Al MAS NMR spectra show that the alumina species are present in the coordination states four, five and six. All of them are in intimate contact with both the three- and the four-coordinate boron species and vice versa, as indicated by (11)B/(27)Al rotational echo double resonance (REDOR) data. These results are consistent with the formation of a homogeneous, nonsegregated glass structure. For the first time, (89)Y solid state NMR has been used to probe the local environment of Y(3+) ions in a glass-forming system. The intrinsic sensitivity problem associated with (89)Y NMR has been overcome by combining the benefits of paramagnetic doping with those of signal accumulation via Carr-Purcell spin echo trains. Both the (89)Y chemical shifts and the Y-3d core level binding energies are found to be rather sensitive to the yttrium bonding state and reveal that the bonding properties of the yttrium atoms in these glasses are similar to those found in the model compounds YBO(3) and YAl(3)(BO(3))(4), Based on charge balance considerations as well as (11)B NMR line shape analyses, the dominant borate species are concluded to be meta- and pyroborate anions.

Preparation and structural characterization of rare-earth doped lead lanthanum zirconate titanate ceramics

A new preparation route towards rare-earth (RE) doped polycrystalline lead lanthanum zirconate titanate (PLZT) ceramics (RE = Y(3+), Nd(3+), Yb(3+)), based on the use of doped lanthanum oxide or zirconia, is reported. Structural characterization by X-ray powder diffraction reveals that secondary phase formation can be substantially diminished in comparison to conventional preparation methods. The distribution of the rare-earth dopants was investigated as a function of concentration by static (207)Pb spin echo NMR spectra, using Fourier Transformation of Carr-Purcell-Meiboom-Gill spin echo trains. For the Nd- and Yb-doped materials, the interaction of the (207)Pb nuclei with the unpaired electron spin density results in significant broadening and shifting of the NMR signal, whereas these effects are absent in the diamagnetic Y(3+) doped materials. Based on different concentration dependences of the NMR lineshape parameters, we conclude that the structural role of the Nd(3+) dopants differs significantly from that of Yb(3+). While the Nd(3+) ions appear to be statistically distributed in the PLZT lattice, incorporation of Yb(3+) into PLZT appears to be limited by the appearance of doped cubic zirconia as a secondary phase. (C) 2009 Elsevier Masson SAS. All rights reserved.

Solid state NMR as a new approach for the structural characterization of rare-earth doped lead lanthanum zirconate titanate laser ceramics

To facilitate the design of laser host materials with optimized emission properties, detailed structural information at the atomic level is essential, regarding the local bonding environment of the active ions (distribution over distinct lattice sites) and their extent of local clustering as well as their population distribution over separate micro- or nanophases. The present study explores the potential of solid state NMR spectroscopy to provide such understanding for rare-earth doped lead lanthanum zirconate titanate (PLZT) ceramics. As the NMR signals of the paramagnetic dopant species cannot be observed directly, two complementary approaches are utilized: (1) direct observation of diamagnetic mimics using Sc-45 NMR and (2) study of the paramagnetic interaction of the constituent host lattice nuclei with the rare-earth dopant, using Pb-207 NMR lineshape analysis. Sc-45 MAS NMR spectra of scandium-doped PLZT samples unambiguously reveal scandium to be six-coordinated, suggesting that this rare-earth ion substitutes in the B site. Static Pb-207 spin echo NMR spectra of a series of Tm-doped PLZT samples reveal a clear influence of paramagnetic rare-earth dopant concentration on the NMR lineshape. In the latter case high-fidelity spectra can be obtained by spin echo mapping under systematic incrementation of the excitation frequency, benefiting from the signal-to-noise enhancement afforded by spin echo train Fourier transforms. Consistent with XRD data, the Pb-207 NMR lineshape analysis suggests that statistical incorporation into the PLZT lattice occurs at dopant levels of up to 1 wt.% Tm3+, while at higher levels the solubility limit is reached. (C) 2008 Elsevier Masson SAS. All rights reserved.

Crystal structures and thermal behavior of alkaline earth tricyanomethanides

The alkaline earth tricyanomethanides Mg(tcm)(2) center dot 2H(2)O, Ca(tcm)(2), Sr(tcm)(2) - H2O and Ba(tcm)(2) center dot 2H(2)O were prepared from aqueous solutions of the respective chlorides and silver tricyanomethanide. Their IR spectra and thermal behavior are described. The crystal structures of Ca(tcm)(2) and Ba(tcm)(2) center dot 2H(2)O were determined by single crystal X-ray diffraction. The structure of Ca(tcm)(2) is of the type found for several transition metal tricyanomethanides [1], containing two independent interpenetrating networks. Ba(tcm)(2) center dot 2H(2)O has a unique crystal structure corresponding to a three-dimensional coordination polymer with nine fold coordinated Ba atoms connected by water molecules and tricyanomethanide anions.

The direct determination of rare earth elements in basaltic and related rocks using ICP-MS: Testing the efficiency of microwave oven sample decomposition procedures

Tests are described showing the results obtained for the determination of REE and the trace elements Rb, Y, Zr, Nb, Cs, Ba, Hf, Ta, Pb, Th and U with ICP-MS methodology for nine basaltic reference materials, and thirteen basalts and amphibolites from the mafic-ultramafic Niquelandia Complex, central Brazil. Sample decomposition for the reference materials was performed by microwave oven digestion (HF and HNO(3), 100 mg of sample), and that for the Niquelandia samples also by Parr bomb treatment (5 days at 200 degrees C, 40 mg of sample). Results for the reference materials were similar to published values, thus showing that the microwave technique can be used with confidence for basaltic rocks. No fluoride precipitates were observed in the microwave-digested solutions. Total recovery of elements, including Zr and Hf, was obtained for the Niquelandia samples, with the exception of an amphibolite. For this latter sample, the Parr method achieved a total digestion, but not so the microwave decomposition; losses, however, were observed only for Zr and Hf, indicating difficulty in dissolving Zr-bearing minerals by microwave acid attack.

Optical properties of red, green and blue emitting rare earth benzenetricarboxylate compounds

Red, blue and green emitting rare earth compounds (RE(3+) = Eu(3+), Gd(3+) and Tb(3+)) containing the benzenetricarboxylate ligands (BTC) [hemimellitic (EMA), trimellitic (TLA) and trimesic (TMA)] were synthesized and characterized by elemental analysis, complexometric titration, X-ray diffraction patterns, thermogravimetric analysis and infrared spectroscopy. The complexes presented the following formula: [RE(EMA)(H(2)O)(2)], [RE(TLA)(H(2)O)(4)] and [RE(TMA)(H(2)O)(G)], except for Tb-TMA compound, which was obtained only as anhydrous. Phosphorescence data of Gd(3+)-(BTC) complexes showed that the triplet states (T) of the BTC(3-) anions have energy higher than the main emitting states of the Eu(3+) ((5)D(0)) and Tb(3+) ((5)D(4)), indicating that BTC ligands can act as intramolecular energy donors for these metal ions. The high values of experimental intensity parameters (Omega(2)) of Eu(3+)-(BTC) complexes indicate that the europium ion is in a highly polarizable chemical environment. Based on the luminescence spectra, the energy transfer from the T state of BTC ligands to the excited (5)D(0) and (5)D(4) levels of the Eu(3+) and Tb(3+) ions is discussed. The emission quantum efficiencies (eta) of the (5)D(0) emitting level of the Eu(3+) ion have been also determined. In the case of the Tb(3+) ion, the photoluminescence data show the high emission intensity of the characteristic transitions (5)D(4) -> (7)F(J) (J=0-6), indicating that the BTC ligands are good sensitizers. The RE(3+)-(BTC) complexes act as efficient light conversion molecular devices (LCMDs) and can be used as tricolor luminescent materials. (C) 2009 Elsevier B.V. All rights reserved.

Electroluminescent devices based on rare-earth tetrakis beta-diketonate complexes

In this paper the synthesis, photo luminescence and electroluminescence investigation of the novel tetrakis beta-diketonate of rare-earth complexes such as M[Eu(dbM)(4)] and M[Tb(acac)(4)] with a variety of cationic ligands, M=Li(+), Na(+) and K(+) have been investigated. The emission spectra of the Eu(3+) and Tb(3+) complexes displayed characteristic narrow bands arising from intraconfigurational transitions of trivalent rare-earth ions and exhibited red color emission for the Eu(3+) ion ((5)D(0) -> F(J), J=0-6) and green for the Tb(3+) ion ((5)D(4) -> (7)F(J), J = 6-0). The lack of the broaden emission bands arising from the ligands suggests the efficient intramolecular energy transfer from the dbm and acac ligands to Eu(3+) and Tb(3+) ions, respectively. In accordance to the expected, the values of PL quantum efficiency (eta) of the emitting (5)D(0) state of the tetrakis(beta-diketonate) complexes of Eu(3+) were higher compared with those tris-complexes. Therefore, organic electroluminescent (EL) devices were fabricated with the structure as follows: indium tin oxide (ITO)/hole transport layer (HTL) NPB or MTCD/emitter layer M[RE(beta-diketonate)(4)] complexes)/Aluminum (Al). All the films were deposited by thermal evaporation carried out in a high vacuum environment system. The OLED light emission was independent of driving voltage, indicating that the combination of charge carriers generates excitons within the M[RE(beta-diketonate)(4)] layers, and the energy is efficiently transferred to RE(3+) ion. As a best result, a pure red and green electroluminescent emission was observed from the Eu(3+) and Tb(3+) devices, confirmed by (X,Y) color coordinates. (C) 2008 Elsevier B.V. All rights reserved.

Equal Couples in Equal Houses : Cultural perspectives on Swedish solar and bio-pellet heating design

Knowing how to design a heating system that will work mechanically is quite different from knowling how to design a system that users perceive as responsive to their domestic practices and values. In this chapter, social anthropologist Henning argues that the challenge for designers involved in the development or marketing of green buildings with heating systems that are based on renewable sources of energy is to see things from the perspective of those who are supposed to live in these buildings. The chapter focuses on three culture-specific aspects of Swedish households and single-family houses: perceptions of house and home, of private and public space, and of male and female space. Through these three angles, some clues are given as to how design, performance and location of solar and bio-pellet heating systems could be made to resonate with predominant experiences, habits and ways of thinking among both men and women.

Decisions with Impact on Energy Reduction Opportunities : Swedish manufacturers and buyers of new single-family houses

This article discusses some of the complexities of human decision-making. It aims, in particular, at relating the nature of decision-making to the illusory dichotomies of change and stability, individual actions and cultural sharing. Serving as an illustration to the discussion of the article is ongoing fieldwork in contexts of buying, selling and constructing pre-fabricated detached houses in the central Sweden, and the very specific question of how decisions to install one kind of heating-system rather than another come about. A common reductionism is to narrow down the understanding of decisions about heating systems and energy consumption to conscious choices made by individual householders. I have asked myself whether, on the contrary, anyone actually makes such decisions at all. Perhaps some of these decisions are merely outcomes of interaction between different individuals with their respective responsibilities and focuses of interest.

The Application Of Renewable Energy For Prefab Houses In Germany

Within the framework of the REBUS project the German building industry has been investigated regarding their energy concepts. The intention was to evaluatethe establishment of renewable energy sources on the German market for new built houses and prefab houses in particular. For this purpose the products of 85manufacturers of prefab houses have been analyzed. Of special interest was the applicationof heating and hot water systems driven by solar energy and biomass. The results show that both techniques are well accepted and established. Almost 90% of themanufacturers offer solar systems on request and almost 70% heating systems based on Pellets. 24% offered solar and 7% as standard options in their range. From theachieved figures the potential of the Swedish market can be worked out. Strategies to introduce renewable energy to a greater extent to Swedish house manufacturers and builders might also be found.

Combined solar and pellet heating systems for single-family houses : How to achieve decreased electricity usage, increased system efficiency and increased solar gains

In Sweden, there are about 0.5 million single-family houses that are heated by electricity alone, and rising electricity costs force the conversion to other heating sources such as heat pumps and wood pellet heating systems. Pellet heating systems for single-family houses are currently a strongly growing market. Future lack of wood fuels is possible even in Sweden, and combining wood pellet heating with solar heating will help to save the bio-fuel resources. The objectives of this thesis are to investigate how the electrically heated single-family houses can be converted to pellet and solar heating systems, and how the annual efficiency and solar gains can be increased in such systems. The possible reduction of CO-emissions by combining pellet heating with solar heating has also been investigated. Systems with pellet stoves (both with and without a water jacket), pellet boilers and solar heating have been simulated. Different system concepts have been compared in order to investigate the most promising solutions. Modifications in system design and control strategies have been carried out in order to increase the system efficiency and the solar gains. Possibilities for increasing the solar gains have been limited to investigation of DHW-units for hot water production and the use of hot water for heating of dishwashers and washing machines via a heat exchanger instead of electricity (heat-fed appliances). Computer models of pellet stoves, boilers, DHW-units and heat-fed appliances have been developed and the parameters for the models have been identified from measurements on real components. The conformity between the models and the measurements has been checked. The systems with wood pellet stoves have been simulated in three different multi-zone buildings, simulated in detail with heat distribution through door openings between the zones. For the other simulations, either a single-zone house model or a load file has been used. Simulations were carried out for Stockholm, Sweden, but for the simulations with heat-fed machines also for Miami, USA. The foremost result of this thesis is the increased understanding of the dynamic operation of combined pellet and solar heating systems for single-family houses. The results show that electricity savings and annual system efficiency is strongly affected by the system design and the control strategy. Large reductions in pellet consumption are possible by combining pellet boilers with solar heating (a reduction larger than the solar gains if the system is properly designed). In addition, large reductions in carbon monoxide emissions are possible. To achieve these reductions it is required that the hot water production and the connection of the radiator circuit is moved to a well insulated, solar heated buffer store so that the boiler can be turned off during the periods when the solar collectors cover the heating demand. The amount of electricity replaced using systems with pellet stoves is very dependant on the house plan, the system design, if internal doors are open or closed and the comfort requirements. Proper system design and control strategies are crucial to obtain high electricity savings and high comfort with pellet stove systems. The investigated technologies for increasing the solar gains (DHW-units and heat-fed appliances) significantly increase the solar gains, but for the heat-fed appliances the market introduction is difficult due to the limited financial savings and the need for a new heat distribution system. The applications closest to market introduction could be for communal laundries and for use in sunny climates where the dominating part of the heat can be covered by solar heating. The DHW-unit is economical but competes with the internal finned-tube heat exchanger which is the totally dominating technology for hot water preparation in solar combisystems for single-family houses.