Structural evolution of aerogels prepared from TEOS sono-hydrolysis upon heat treatment up to 1100 degrees C

The structural evolution of aerogels prepared from TEOS sono-hydrolysis was studied as a function of the temperature of heat treatment up to 1100 degreesC by means of small angle X-ray scattering (SAXS) and density measurements. The mass fractal structure of the original wet sonogel (with scattering exponent alpha similar to 2.2) apparently transforms to a surface fractal structure in a length scale lesser than similar to1.5 nm, upon the process resulting in aerogel. Such a structural transformation is interpreted by the formation of new particles with characteristic dimension of similar to1.5 nm, with rough boundaries or electronic density fluctuations (or ultra-micropores) in their interior. The structural arrangement of these particles seem to preserve part of mass fractal characteristics of the original wet sonogel, now in a length scale greater than similar to1.5 nm. The electronic density heterogeneities in the particles start to be eliminated at around 800 degreesC and, at 900 degreesC, the particles become perfectly homogeneous, so the structure can be described as a porous structure with a porosity of similar to68% with similar to9.0 nm mean size pores and similar to4.3 nm mean size solid particles. Above 900 degreesC, a vigorous viscous flux sintering process sets in, eliminating most of the porosity and increasing rapidly the bulk density in an aerogel-glass transformation. (C) 2003 Elsevier B.V. All rights reserved.

A relationship between structural and electronic order-disorder effects and optical properties in crystalline TiO2 nanomaterials

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

Habermas leitor de Rousseau

Pretendemos mostrar um aspecto pelo qual a leitura que Habermas faz de Rousseau, em Mudança estrutural da esfera pública (1962), é levemente revisada em Direito e democracia (1992). Essa pequena mudança, por sua vez, reestrutura toda a concepção habermasiana da política de Rousseau.

Drying study of siloxane-PPG nanocomposites

This is a study of the structural transformations occurring in hybrid siloxane-polypropyleneglycol (PPG) nanocomposites, with different PPG molecular weight, along the drying process. The starting materials are wet gels obtained by the sol-gel procedure using as precursor the 3-(trietoxysilyl)propylisocyanate (IsoTrEOS) and polypropylenglycol bis(2-amino-propyl-ether) (NH2-PPG-NH2). The shrinkage and mass loss measurements were performed using a temperature-controlled chamber at 50 degreesC. The nanostructural evolution of samples during drying was studied in situ by small angle x-ray scattering (SAXS). The experimental results demonstrate that the drying process is highly dependent on the molecular weight of polymer. After the initial drying stage, the progressive emptying of pores leads to the formation of a irregular drying front in gels prepared from PPG of high molecular weight, like 4000 g/mol. As a consequence, an increase of the SAXS intensity due to the increase of electronic density contrast between siloxane clusters and polymeric matrix is observed. For hybrids containing PPG of low molecular weight, the pore emptying process is fast, leading to a regular drying front, without isolated nanopockets of solvents. SAXS intensity curves exhibit a maximum, which was associated to the existence of spatial correlation of the silica clusters embedded in the polymeric matrix. The spatial correlation is preserved during drying. These results also reveal that the structural transformation during drying is governed by capillary forces and depends on the entanglement of polymer chains.

Um estudo genealófico das críticas proferidas à razão versus a esfera pública em Habermas

Pós-graduação em Filosofia - FFC

Rapid preparation of alpha-FeOOH and alpha-Fe2O3 nanostructures by microwave heating and their application in electrochemical sensors

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Oxygen mobility and structural phase transformation in Bi2Sr2CaCu2O8+delta measured by anelastic spectroscopy

One of the most studied ceramic superconductors for application has been, undoubtedly, Bi2Sr2CaCu2O8+delta. Although being a multiphasic material, it has proved to have great advantages compared to other ceramic systems. Measurements of the elastic energy loss and modulus (anelastic spectroscopy) as a function of temperature call distinguish among different atomic jumps that occur inside the various phases or at different local ordering. In this paper, mechanical loss spectra of Bi2Sr2CaCu2O8+delta bar shaped samples, made by a conventional method, have been measured between 80 and 600 K, using a torsion pendulum operating in frequencies below 50 Hz, for samples annealed in vacuum up to 600 K. Possible relaxation mechanisms are proposed to explain the origin of the mechanical-loss peaks observed 300 and 500 K. (C) 2004 Elsevier B.V. All rights reserved.

Structural and magnetic transformation of monodispersed iron oxide particles in a reducing atmosphere

Uniform metal iron ellipsoidal particles of around 200 nm in length were obtained by reduction and passivation of alumina-coated alpha-Fe2O3 (hematite) particles under different conditions of temperature and hydrogen flow rate. The monodispersed hematite particles were prepared by the controlled hydrolysis of ferric sulfate and further coated with a homogeneous thin layer of Al2O3 by careful selection of the experimental conditions, mainly pH and aluminum salt concentration. The reduction mechanism of alpha-Fe2O3 into alpha-Fe was followed by x-ray and electron diffraction, and also by the measurements of the irreversible magnetic susceptibility. The transformation was found to be topotactic with the [001] direction of hematite particles, which lies along the long axis of the particles, becoming the [111] direction of magnetite and finally the [111] direction of metal iron. Temperature and hydrogen flow rate during the reduction have been found to be important parameters, which determine not only the degree of reduction but also the crystallite size of the final particles. Magnetic characterization of the samples shows that the only parameters affected by the crystallite size are the saturation magnetization and magnetic time-dependence effect, i.e., activation volume. (C) 2002 American Institute of Physics.

Structural phase transition study of FePt alloys using ab initio calculation

The FePt alloy undergoes the cubic to tetragonal lattice transformation in the ferromagnetic state. We calculated the electronic structure for both cubic and tetragonal structures using the FPLAPW method with APW + lo. Comparing the density of states of the cubic and tetragonal structures, it is expected that the lattice transformation is caused by the band Jahn-Teller effect. (C) 2009 Elsevier B.V. All rights reserved.

Effects of strontium and calcium simultaneous substitution on electrical and structural properties of Pb1-x-y Ca (x) Sr (y) TiO3 thin films

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

Thermal stability of the martensitic transformation of Cu-Al-Ni-Mn-Ti

The development of new shape memory alloys with high martensitic transformation temperature increases the potential for applications. The development and use of these new alloys depends on the stability of the structure during cycling at high temperatures. If it is possible to guarantee that on alloys keeps the structure during cycling, then the alloy can be used because of the shape memory properties. The aim of this work is to obtain a kinetic model of the forward and backward martensitic transformation of two Cu-Al-Ni-Mn-Ti alloys. Differential scanning calorimetry has been performed in order to establish the kinetic stability of the martensite and the beta transformation. (c) 2006 Elsevier B.V. All rights reserved.

On non-ideal simple portal frame structural model: Experimental results under a non-ideal excitation

We present measurements of the non-linear oscillations of a portal frame foundation for a non-ideal motor. We consider a three-time redundant structure with two columns, clamped in their bases and a horizontal beam. An electrical unbalanced motor is mounted at mid span of the beam. Two non-linear phenomena are studied: a) mode saturation and energy transfer between modes; b) interaction between high amplitude motions of the structure and the rotation regime of a real limited power motor. The dynamic characteristics of the structure were chosen to have one-to-two internal resonance between the anti-symmetrical mode (sway motions) and the first symmetrical mode natural frequencies. As the excitation frequency reaches near resonance conditions with the 2nd natural frequency, the amplitude of this mode grows up to a certain level and then it saturates. The surplus energy pumped into the system is transferred to the sway mode, which experiences a sudden increase in its amplitude. Energy is transformed from low amplitude high frequency motion into high amplitude low frequency motion. Such a transformation is potentially dangerous.We consider the fact that real motors, such as the one used in this study, have limited power output. In this case, this energy source is said to be non-ideal, in contrast to the ideal source whose amplitude and frequency are independent of the motion of the structure. Our experimental research detected the Sommerfeld Effect: as the motor accelerates to reach near resonant conditions, a considerable part of its output energy is consumed to generate large amplitude motions of the structure and not to increase its own angular speed. For certain parameters of the system, the motor can get stuck at resonance not having enough power to reach higher rotation regimes. If some more power is available, jump phenomena may occur from near resonance to considerably higher motor speed regimes, no stable motions being possible between these two.

Structural features of phosphate and sulfate modified zirconia prepared by sol-gel route

This paper describes the effect of sulfate, phosphate and nitrate complexing ligands on the structural features of amorphous xerogels and on the crystallization of metastable zirconia phases during the xerogel-ceramic conversion. Powdered samples were prepared by a sol-gel route using zirconyl chloride precursors chemically modified by complexing ligands. The structural evolution of ZrO2 phases as function of firing temperature was analyzed by XRPD, EXAFS and P-13 NMR/MAS. The experimental results show the formation of metastable t-ZrO2 during the low firing temperature of xerogels modified by sulfate or phosphate groups. The martensitic tetragonal-monoclinic transformation occurs during desorption of sulfate groups. The largest temperature interval of stability of metastable tetragonal zirconia was observed for phosphate-modified xerogels.

Structural and phenomenological characterization of the thermoreversible sol-gel transition of a zirconyl aqueous precursor modified by sulfuric acid

The thermoreversible sol-gel transition is well-known in biological and organic polymeric systems but has not been reported for inorganic systems. In this paper we put in evidence a thermoreversible sol-gel transition for zirconyl chloride aqueous solutions modified by sulfuric acid in the ratio 3:1 Zr:SO4. The synthesis conditions are detailed and a variety of experimental techniques (turbidimetry, dynamic rheology, and EXAFS) have been employed for investigating the thermal reversibility and the chemical structure of this new material. Turbidimetric measurements performed for solutions containing different concentrations of precursor have evidenced that the sol-gel transformation temperature increases from 50 to 80 degrees C as the concentration of zirconyl chloride decreases from 0.22 to 0.018 mol L-1. A more detailed study has been done for the sample with [Zr] = 0.156 mol L-1, in which the sol-gel-sol transformation has been repeated several times by a cyclic variation of the temperature. The mechanical properties of this sample, evaluated by measuring the storage and the loss moduli, show a change from liquid like to viscoelastic to elastic behavior during the sol-gel transition and vice versa during the gel-sol one. In situ EXAFS measurements performed at the Zr K-edge show that no change of the local order around Zr occurs during the sol-gel-sol transition, in agreement with the concept of physical gel formation. We have proposed for the structure of the precursor an inner core made of hydroxyl and oxo groups bridging together zirconium atoms surrounded in surface by complexing sulfate ligands, the sulfate groups act as a protective layer, playing a key role in the linking propagation among primary particles during sol-gel-sol transition.

Effect of lithium doping on the evolution of rheological and structural properties during gelation of siloxane-poly(oxypropylene) nanocomposites

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