Modifications induced by acetylacetone in properties of sol-gel derived Y3Al5O12:Tb3+ - I: Structural and morphological organizations

Acetylacetone has been used as a chemical modifier for the synthesis of undoped and Tb3+-doped Y3Al5O12 powders. A systematic investigation concerning its influence on the structural and morphological properties of amorphous and crystallized samples has been carried out. These properties have been comparatively studied by means of X-ray diffraction, infrared spectroscopy, SEM, XAS and SAXS. 27Al NMR and EPR experiments have been performed to complete the study. The combined results have evidenced that acetylacetone promotes organic groups departure during calcination, entailing a better structural organization at lower temperatures compared with unmodified powders. Structuration has been proven to occur at short-scale range until a 600°C heating treatment before being extended by coalescence at higher temperatures. Finally, the presence of acac ligands on the alkoxides leads to a monomer-cluster aggregation process, and thus to a more open network. © 2010 The Royal Society of Chemistry.

Nonlinear dynamic model and simulation of morphing wing profile actuated by shape memory alloys

Morphing aircraft have the ability to actively adapt and change their shape to achieve different missions efficiently. The development of morphing structures is deeply related with the ability to model precisely different designs in order to evaluate its characteristics. This paper addresses the dynamic modeling of a sectioned wing profile (morphing airfoil) connected by rotational joints (hinges). In this proposal, a pair of shape memory alloy (SMA) wires are connected to subsequent sections providing torque by reducing its length (changing airfoil camber). The dynamic model of the structure is presented for one pair of sections considering the system with one degree of freedom. The motion equations are solved using numerical techniques due the nonlinearities of the model. The numerical results are compared with experimental data and a discussion of how good this approach captures the physical phenomena associated with this problem. © The Society for Experimental Mechanics, Inc. 2012.

Use of conventional electrochemical techniques to produce crystalline FeRh alloys induced by Ag seed layer

By combining galvanic displacement and electrodeposition techniques, an ordered Fe20Rh80 structure deposited onto brass was investigated by X-ray diffractometry, Mössbauer spectroscopy and magnetization measurements. Mössbauer and X-ray diffraction analyses suggest that the Fe-Rh alloy directly electrodeposited onto brass displays a nanocrystalline state while a similar alloy deposited onto Ag/brass shows a faced centered cubic-like structure, with dendrites-like features. These results directly indicate that the presence of Ag seed layer is responsible for the Fe-Rh alloy crystallization process. In addition, room temperature Mössbauer data indicate firstly paramagnetic states for two Fe-species. In the dominant Fe-species (major fraction of the Mössbauer spectra), Fe atoms are situated at a cubic environment and it can be attributed to the γ-Fe20Rh80 alloy based on their hyperfine parameters. In the second species, Fe atoms are placed in a non-local symmetry, which can be related to Fe atoms at the grain boundaries or/and Fe small clusters. These Fe-clusters are in superparamagnetic state at room temperature, but they may be ordered below 45 K, as suggested by magnetization data. © 2013 Elsevier B.V. All rights reserved.

Biomedical Ti-Mo Alloys with Surface Machined and Modified by Laser Beam: Biomechanical, Histological, and Histometric Analysis in Rabbits

Purpose: In vivo bone response was assessed by removal torque, hystological and histometrical analysis on a recently developed biomedical Ti-15Mo alloy, after surface modification by laser beam irradiation, installed in the tibia of rabbits. Materials and Methods: A total of 32 wide cylindrical Ti-15Mo dental implants were obtained (10mm × 3.75mm). The implants were divided into two groups: 1) control samples (Machined surface - MS) and 2) implants with their surface modified by Laser beam-irradiation (Test samples - LS). Six implants of each surface were used for removal torque test and 10 of each surface for histological and histometrical analysis. The implants were placed in the tibial metaphyses of rabbits. Results: Average removal torque was 51.5Ncm to MS and >90Ncm to LS. Bone-to-implant-contact percentage was significantly higher for LS implants both in the cortical and marrow regions. Conclusions: The present study demonstrated that laser treated Ti-15Mo alloys are promising materials for biomedical application. © 2011 Wiley Periodicals, Inc.

XAS/WAXS time-resolved phase speciation of chlorine LDH thermal transformation: Emerging roles of isovalent metal substitution

The XAS/WAXS time-resolved method was applied for unraveling the complex mechanisms arising from the evolution of several metastable intermediates during the degradation of chlorine layered double hydroxide (LDH) upon heating to 450 °C, i.e., Zn2Al(OH)6·nH2O, ZnCuAl(OH)6·nH2O, Zn2Al 0.75Fe0.25(OH)6·nH2O, and ZnCuAl0.5Fe0.5(OH)6·nH2O. After a contraction of the interlamellar distance, attributed to the loss of intracrystalline water molecules, this distance experiences an expansion (T > 175-225 °C) before the breakdown of the lamellar framework around 275-295 °C. Amorphous prenucleus clusters with crystallo-chemical local order of zinc-based oxide and zinc-based spinel phases, and if any of copper-based oxide, are formed at T > 175-225 °C well before the loss of stacking of LDH layers. This distance expansion has been ascribed to the migration of Zn II from octahedral layers to tetrahedral sites in the interlayer space, nucleating the nano-ZnO or nano-ZnM2O4 (M = Al or Fe) amorphous prenuclei. The transformation of these nano-ZnO clusters toward ZnO crystallites proceeds through an agglomeration process occurring before the complete loss of layer stacking for Zn2Al(OH)6· nH2O and Zn2Al0.75Fe0.25(OH) 6·nH2O. For ZnCuAl(OH)6·nH 2O and ZnCuAl0.5Fe0.5(OH)6· nH2O, a cooperative effect between the formation of nano-CuO and nano-ZnAl2O4 amorphous clusters facilitates the topochemical transformation of LDH to spinel due to the contribution of octahedral CuII vacancy to ZnII diffusion. © 2013 American Chemical Society.

Effect of the ZrO2 phase on the structure and behavior of supported Cu catalysts for ethanol conversion

The effect of amorphous (am-), monoclinic (m-), and tetragonal (t-) ZrO2 phase on the physicochemical and catalytic properties of supported Cu catalysts for ethanol conversion was studied. The electronic parameters of Cu/ZrO2 were determined by in situ XAS, and the surface properties of Cu/ZrO2 were defined by XPS and DRIFTS of CO-adsorbed. The results demonstrated that the kind of ZrO2 phase plays a key role in the determination of structure and catalytic properties of Cu/ZrO 2 catalysts predetermined by the interface at Cu/ZrO2. The electron transfer between support and Cu surface, caused by the oxygen vacancies at m-ZrO2 and am-ZrO2, is responsible for the active sites for acetaldehyde and ethyl acetate formation. The highest selectivity to ethyl acetate for Cu/m-ZrO2 catalyst up to 513 K was caused by the optimal ratio of Cu0/Cu+ species and the high density of basic sites (O2-) associated with the oxygen mobility from the bulk m-ZrO2. © 2013 Elsevier Inc. All rights reserved.

Influence of current density on crystalline structure and magnetic properties of electrodeposited Co-rich CoNiW alloys

The influence of current density, at the interval 5-100 mA cm-2, on the structural and magnetic properties of electrodeposited (Co 100-xNix)100-yWy alloys (x = 23-33.5 at. % Ni, y = 1.7-7.3 at. % W) was studied from a glycine-containing bath. W-content decreases with the increase of the current density magnitude. X-ray data have shown stabilization of hexagonal close packed, face centered cubic or a mixture of these structures by modulating the applied cathodic current density, for values lower than 50 mA cm-2. Two structural phase transitions were observed: one from hexagonal close packed to face centered cubic structural transition occurring for a current density of 20 mA cm -2, and another one, from cubic crystalline phase to amorphous state, which happens for values higher than 50 mA cm-2. These structural phase transitions seem to be associated with the W-content as well as average crystalline grain sizes that reduce with increasing the current density value. The grain size effect may explain the face centered cubic stabilization in Co-rich CoNiW alloys, which was initially assumed to be basically due to H-adsorption/incorporation. Magnetic properties of Co-rich CoNiW alloys are strongly modified by the current density value; as a result of the changes on the W-content and their structural properties© 2013 Elsevier B.V. All rights reserved.

Effects of high temperature plasma immersion ion implantation on wear resistance of Ti-Si-B sintered alloys

Although titanium and its alloys own good mechanical properties and excellent corrosion resistance, these materials present poor tribological properties for specific applications that require wear resistance. In order to produce wear-resistant surfaces, this work is aimed at achieving improvement of wear characteristics in Ti-Si-B alloys by means of high temperature nitrogen plasma immersion ion implantation (PIII). These alloys were produced by powder metallurgy using high energy ball milling and hot pressing. Scanning electron microscopy (SEM) and X-ray diffraction identified the presence of α-titanium, Ti6Si2B, Ti5Si3, TiB and Ti3Si phases. Wear tests were carried out with a ball-on-disk tribometer to evaluate the friction coefficient and wear rate in treated and untreated samples. The worn profiles were measured by visible light microscopy and examined by SEM in order to determine the wear rates and wear mechanisms. Ti-7.5Si-22.5B alloy presented the highest wear resistance amongst the untreated alloys produced in this work. High temperature PIII was effective to reduce the wear rate and friction coefficient of all the Ti-Si-B sintered alloys. © 2013 Elsevier B.V.

Correlative light-electron fractography for fatigue striations characterization in metallic alloys

The correlative light-electron fractography technique combines correlative microscopy concepts to the extended depth-from-focus reconstruction method, associating the reliable topographic information of 3-D maps from light microscopy ordered Z-stacks to the finest lateral resolution and large focus depth from scanning electron microscopy. Fatigue striations spacing analysis can be precisely measured, by correcting the mean surface tilting with the knowledge of local elevation data from elevation maps. This new technique aims to improve the accuracy of quantitative fractography in fatigue fracture investigations. Microsc. Res. Tech. 76:909-913, 2013. © 2013 Wiley Periodicals, Inc.

The effect of the solute on the structure, selected mechanical properties, and biocompatibility of Ti-Zr system alloys for dental applications

New titanium alloys have been developed with the aim of utilizing materials with better properties for application as biomaterials, and Ti-Zr system alloys are among the more promising of these. In this paper, the influence of zirconium concentrations on the structure, microstructure, and selected mechanical properties of Ti-Zr alloys is analyzed. After melting and swaging, the samples were characterized through chemical analysis, density measurements, X-ray diffraction, optical microscopy, Vickers microhardness, and elasticity modulus. In-vitro cytotoxicity tests were performed on cultured osteogenic cells. The results showed the formation essentially of the α′ phase (with hcp structure) and microhardness values greater than cp-Ti. The elasticity modulus of the alloys was sensitive to the zirconium concentrations while remaining within the range of values of conventional titanium alloys. The alloys presented no cytotoxic effects on osteoblastic cells in the studied conditions. © 2013 Elsevier B.V. All rights reserved.

Local order of Pb1-xLaxZr0.40Ti 0.60O3 ferroelectric ceramic materials probed by X-ray absorption and Raman spectroscopies

This paper reports on the structural characterization of Pb 1-xLaxZr0.40Ti0.60O3 (PLZT) ferroelectric ceramic compositions prepared by the conventional solid state reaction method. X-ray absorption spectroscopy (XAS) and Raman spectroscopy were used to probe the local structure of PLZT samples that exhibits a normal and relaxor ferroelectric behavior. From the Zr K-edge and Pb LIII-edge EXAFS spectra, a considerable dissymmetry of Zr and Pb sites was observed in all samples, including those showing a long-range order cubic symmetry and a relaxor behavior. The Raman spectroscopy results confirmed the existence of a local disorder in all PLZT samples through the observation of Raman active vibrational modes. The variation in the intensity of the E(TO 3) mode in the PLZT relaxor samples indicates that the process of correlation between nanodomains stabilizes at temperatures lower than T m. © 2013 Elsevier B.V. All rights reserved.

Efeitos estruturais e ópticos da incorporação de Mn em filmes nanocristalinos de 'Ga IND. 1-x Mn IND. xAs' preparados por sputtering

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

The columnar to equiaxed transition of horizontal unsteady-state directionally solidified Al-Si alloys

Experiments were conducted to investigate the influence of thermal parameters on the columnar to equiaxed transition during the horizontal unsteady-state directional solidification of Al-Si alloys. The parameters analyzed include the heat transfer coefficients, growth rates, cooling rates, temperature gradients and composition. A combined theoretical and experimental approach is developed to determine the solidification thermal variables considered. The increasing solute content in Al-Si alloys was not found to affect significantly the experimental position of the CET which occurred for cooling rates in the range between 0.35 and 0.64 K/s for any of three alloy compositions examined. A comparative analysis between the results of this work and those from the literature proposed to analyze the CET during upward vertical solidification of Al-Si alloys is reported and the results have shown that the end of the columnar region during horizontal directional solidification is abbreviated as a result of about six times higher thermal gradient than that verified during upward unidirectional solidification of alloys investigated.

Interstitial oxygen's influence on the corrosion behavior of Ti-9Mo alloys

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)