In situ UV-vis and EXAFS studies of ZnO quantum-sized nanocrystals and Zn-HDS formations from sol-gel route

We have pointed Out that. zinc-based particles obtained from zinc acetate sol-gel route is a mixture of quantum-sized ZnO nanoparticles, zinc acetate, and zinc hydroxide double salt (Zn-HDS). Aiming the knowledge of the mechanisms involved in the formation of ZnO and Zn-HDS phases, the thermohydrolysis of ethanolic zinc acetate solutions induced by lithium hydroxide ([LiOH]/[Zn2+] = 0.1) or water ([H2O]/[Zn2+] = 0.05) addition was investigated at different isothermal temperatures (40, 50, 60 and 70 degrees C) by in situ measurements of turbidity, UV-vis absorption spectra and extended X-ray absorption fine structures (EXAFS). Only the growth of ZnO nanoparticles was observed in sol prepared with LiOH, while a two-step process was observed in that prepared with water addition, leading the fast growth of Zn-HDS and the formation of ZnO nanoparticles at advanced stage. A mechanism of dissolution/reprecipitation governed by the water/ethanol proportion is proposed to account for relative amount of ZnO. (c) 2007 Elsevier Ltd. All rights reserved.

Selection and shell relationship in Isocheles-sawayai forest and Saint-laurent, 1967 (crustacea, anomura, diogenidae)

A populational sample of Isocheles sawayai Forest & Saint Laurent, 1967 was analysed in order to detect the validity of the shell aperture size as a parameter in the gastropod shell selection. The gastropods genus occupied by this hermit crab were: Thais, Buccinanops, Olivancillaria, Polinices and Cymatium. The power function (y = a.x(b)) was the best equation to represent biologically the regression analyses carried out among the measured parameters.

Upconversion luminescence in transparent glass ceramics containing beta-PbF2 nanocrystals doped with erbium

Frequency upconversion luminescence in erbium-doped PbGeO3-PbF2-CdF2-based transparent glass ceramics (TGC) under 980 nm infrared excitation is investigated. Upconversion emission signals around 410, 525, 550, 660, and 850 nm were generated and identified as due to the H-2(9/2) H-2(11/2), S-4(3/2), and F-4(9/2) transitions to the I-4(15/2) ground-state, and S-4(3/2)-I-4(13/2), respectively. The erbium ions excited-state emitting levels were populated via a combination of stepwise ground-state absorption (GSA), excited-state absorption (ESA), and cross-relaxation processes. The results also disclosed that both blue (410 nm) and red (660 nm) upconversion emission signals in the transparent glass ceramic sample presented twice as much intensity as compared to its vitreous counterpart. (C) 2003 Elsevier B.V. All rights reserved.

Role of the oriented attachment mechanism in the phase transformation of oxide nanocrystals

Bottom-up methods to obtain nanocrystals usually result in metastable phases, even in processes carried out at room temperature or under soft annealing conditions. However, stable phases, often associated with anisotropic shapes, are obtained in only a few special cases. In this paper we report on the synthesis of two well-studied oxides-titanium and zirconium oxide-in the nanometric range, by a novel route based on the decomposition of peroxide complexes of the two metals under hydrothermal soft conditions, obtaining metastable and stable phases in both cases through transformation. High-resolution transmission electron microscopy analysis reveals the existence of typical defects relating to growth by the oriented attachment mechanism in the stable crystals. The results suggest that the mechanism is associated to the phase transformation of these structures.

Self-assembled FePt nanocrystals with large coercivity: Reduction of the fcc-to-L1(0) ordering temperature

Herein we report the synthesis and properties of Fe55Pt45 nanoparticles, both monodisperse and self-assembled into hexagonal close-packed and cubic arrays of 4.0 +/- 0.2 nm size in an L1(0) structure, obtained by a modified polyol process. The new synthetic route improved the control over the particle composition, thereby reducing the temperature required to convert from face-centered cubic (fcc) to face-centered tetragonal (fct) phase by some 30-50 degrees C without additives. Annealing at 550 degrees C for 30 min converts the self-assembled nanoparticles into ferromagnetic nanocrystals with large coercivity, H-C = 11.1 kOe. Reducing the fcc-to-fct (L1(0)) ordering temperature avoided particle coalescence and decreased the loss in particle positional order without compromising the magnetic properties, as is generally observed when additives are used.

Anisotropic growth of oxide nanocrystals: Insights into the rutile TiO2 phase

In this work, we report the synthesis of titanium oxide nanocrystals, especially the rutile TiO2 phase with nanorod morphology, by a method based on peroxotitanium complex decomposition. The results indicate that the anisotropic morphology reported for rutile TiO2 nanocrystals is related to the oriented attachment process. Despite the predominance of rutile nanocrystals at longer treatment times, the nanocrystals were obtained also in the anatase type, according to the degradation time adopted. XANES results evidenced the absence of structural correlation between the peroxytitanium complex and phase evolution, and the coexistence of the two phases strongly suggests a correlation of the oriented attachment mechanism and the rutile phase stabilization.

Quantitative estimates of time-averaging in terebratulid brachiopod shell accumulations from a modern tropical shelf

Quantitative estimates of time-averaging in marine shell accumulations available to date are limited primarily to aragonitic mollusk shells. We assessed time-averaging in Holocene assemblages of calcitic brachiopod shells by direct dating of individual specimens of the terebratulid brachiopod Bouchardia rosea. The data were collected from exceptional (brachiopod-rich) shell assemblages, occurring surficially on a tropical mixed carbonate-siliciclastic shelf (the Southeast Brazilian Bight, SW Atlantic), a setting that provides a good climatic and environmental analog for many Paleozoic brachiopod shell beds of North America and Europe. A total of 82 individual brachiopod shells, collected from four shallow (5-25 m) nearshore (<2.5 km from the shore) localities, were dated by using amino acid racemization (D-alloisoleucine/L-isoleucine value) calibrated with five AMS-radiocarbon dates (r(2) = 0.933). This is the first study to demonstrate that amino acid racemization methods can provide accurate and precise ages for individual shells of calcitic brachiopods.The dated shells vary in age from modern to 3000 years, with a standard deviation of 690 years. The age distribution is strongly right-skewed: the young shells dominate the dated specimens and older shells are increasingly less common. However, the four localities display significant differences in the range of time-averaging and the form of the age distribution. The dated shells vary notably in the quality of preservation, but there is no significant correlation between taphonomic condition and age, either for individual shells or at assemblage level.These results demonstrate that fossil brachiopods may show considerable time-averaging, but the scale and nature of that mixing may vary greatly among sites. Moreover, taphonomic condition is not a reliable indicator of pre-burial history of individual brachiopod shells or the scale of temporal mixing within the entire assemblage. The results obtained for brachiopods are strikingly similar to results previously documented for mollusks and suggest that differences in mineralogy and shell microstructure are unlikely to be the primary factors controlling the nature and scale of time-averaging. Environmental factors and local fluctuations in populations of shell-producing organisms are more likely to be the principal determinants of time-averaging in marine benthic shelly assemblages. The long-term survival of brachiopod shells is incongruent with the rapid shell destruction observed in taphonomic experiments. The results support the taphonomic model that shells remain protected below (but perhaps near) the surface through their early taphonomic history. They may be brought back up to the surface intermittently by bioturbation and physical reworking, but only for short periods of time. This model explains the striking similarities in time-averaging among different types of organisms and the lack of correlation between time-since-death and shell taphonomy.

Photoluminescence in quantum-confined SnO2 nanocrystals: Evidence of free exciton decay

Nanocrystalline SnO2 quantum dots were synthesized at room temperature by hydrolysis reaction of SnCl2. The addition of tetrabutyl ammonium hydroxide and the use of hydrothermal treatment enabled one to obtain tin dioxide colloidal suspensions with mean particle radii ranging from 1.5 to 4.3 nm. The photoluminescent properties of the suspensions were studied. The particle size distribution was estimated by transmission electron microscopy. Assuming that the maximum intensity photon energy of the photoluminescence spectra is related to the band gap energy of the system, the size dependence of the band gap energies of the quantum-confined SnO2 particles was studied. This dependence was observed to agree very well with the weak confinement regime predicted by the effective mass model. This might be an indication that photoluminescence occurs as a result of a free exciton decay process. (C) 2004 American Institute of Physics.

Effect of partial preferential orientation and distortions in octahedral clusters on the photoluminescence properties of FeWO4 nanocrystals

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

Interfacial photoluminescence emission properties of core/shell Al2O3/ZrO2

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Phase Transformation in Titania Nanocrystals by the Oriented Attachment Mechanism: The Role of the pH Value

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

Hyolith-dominated shell beds from the Lampazar Formation in NW Argentina: patterns and processes of origin in the Late Cambrian (Furongian) seas of western Gondwana.

Late Cambrian (Furongian) shell beds in the Salta Province of NW Argentina are unique because of the presence of abundant hyolith skeletal remains within them. Hyolith shell beds are located in the mid-upper part of the Lampazar Formation at the Angosto de La Quesera locality, and are the first recorded accumulations of this type in the lower Palaeozoic of the South American Andean Basin. The shell beds are of the order of several mm thick, and are laterally persistent within outcrop scale, with a few metres of lateral development. Two types of hyolith shell beds are recognised: Type 1 is a storm-dominated, event concentration, represented by dispersed to densely packed accumulations of well preserved hyolith and gastropod shells (Strepsodiscus austrinus). Hyolith conchs are current oriented with the long axes parallel to unidirectional flow on the sandstones surfaces. Type 2 shell beds are background, composite concentrations, of poorly preserved, comminuted debris of hyolith shells with associated gastropod and trilobite sclerites (dominated by Parabolina, Beltella and Leiostegium). The genesis of both shell beds was controlled primarily by physical processes, such as storms and current and/or wave agitation. The thickness, simple internal fabric and geometry shown by both accumulations are typical of Cambrian-style shell-beds.

Off-shell supersymmetry versus hermiticity in superstrings

We point out that off-shell four-dimensional spacetime supersymmetry implies strange Hermiticity properties for the N = 1 Ramond-Neveu-Schwarz superstring. However, these Hermiticity properties become natural when the N = 1 superstring is embedded into an N = 2 superstring.

Relativistic RPA for isobaric analogue and Gamow-Teller resonances in closed shell nuclei

We perform a self-consistent relativistic RPA calculation for the isobaric analogue and Gamow-Teller resonances based on relativistic mean field theory results for the ground states of 48Ca, 90Zr and 208Pb. We use the parameter set NL1 for the σ, ω and ρ mesons, and experimental values for the pion and nucleon. An extra parameter, related to the intensity of the contact term in the pion-exchange interaction, is crucial to reproduce the latter resonances. © 1998 Published by Elsevier Science B.V. All rights reserved.