Spectroscopic studies of the Eu3+ and Er3+ ions in the fluorozirconate LaZr2F11 matrix

An investigation by optical spectroscopy of the Eu3 + and Er3 + active ions in the crystallized fluorozirconate matrix LaZr2F11 is presented. The D-5(1) --> F-7(0-5) emission lines of Eu3 + are used to extract the F-7(0-5) energy scheme and the observed extinctions permit the deduction of irreducible representations (IRREPS) associated with corresponding sub-levels in the D-2 symmetry. The crystal field analysis was carried out on a 387 x 387 basis set, comprising the F-7, D-5(1,2,3) F-5(1,2), (5)G(1,2,3) and P-3(1,2,3,4,5,6) terms of the Eu-3 (+) 4f(6) configuration. The deviation and rms are 6.8 and 7.9 cm (-1), respectively for 38 levels and ten parameters. The experimental crystal field parameters are in good agreement with the ab-initio ones. Moreover, the relative intensities of the D-5(0) --> F-7(2,3,4) emissions are well reproduced by an 'ab-initio' calculation, except for three lines. The Er3 + ions introduced in LaZr2F11, microcrystals also lie in an unique crystallographic site. A total of 31 energy levels were recorded and the crystal field analysis led to 6.6 and 7.8 cm (-1) for the deviation and rms, respectively, for nine variable parameters taken into account. The experimental CF parameters for Er3 + and Eu3 + are very similar, which seems to show that the host lattice contracts around the smaller Er3 + ion. The informations given by both Eu3 + and Eu3 + optical probes in LaZr2F11 are very consistent with the structure previously determined for the isotypic PrZr2F11 fluoride. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Montmorillonite (MMT) effect on the structure of poly(oxyethylene) (PEO)-MMT nanocomposites and silica-PEO-MMT hybrid materials

In this work we report the effects of incorporation of variable amounts (0.5-25%w/w) of montmorillonite in poly(oxyethylene) based materials in order to decrease the polymer crystallinity. Two different classes of materials were studied: silica-poly(oxyethylene)-montmorillonite hybrids prepared by the sol-gel route and poly(oxyethylene)-montmorillonite nanocomposites prepared by mixing the dry clay or the clay aqueous suspension into the melt poly(oxyethylene). The effects of monternorillonite loading on the poly(oxyethylene) crystallization control and on the nanostructural features were investigated by X-ray powder diffraction, small-angle X-ray scattering and differential scanning calorimetry. Experimental results show that free montmorillonite layers coexist with open aggregates and tactoids in the poly(oxyethylene)-montmorillonite nanocomposites, with different features depending on the filler proportion and preparation route. The intercalation of polymer chains in montmorillonite galleries markedly hinders the crystallization of the poly(oxyethylene) matrix. For hybrids materials the silica phase favors the exfoliation of montmorillonite tactoids, so that samples are predominantly constituted by dispersed platelets. (c) 2006 Elsevier B.V. All rights reserved.

Structure of magnetic poly(oxyethylene)-siloxane nanohybrids doped with Fe-II and Fe-III

Hybrid organic - inorganic nanocomposites doped with Fe-II and Fe-III ions and exhibiting interesting magnetic properties have been obtained by the sol - gel process. The hybrid matrix of these ormosils ( organically modified silicates), classed as di-ureasils and termed U( 2000), is composed of poly( oxyethylene) chains of variable length grafted to siloxane groups by means of urea crosslinkages. Iron perchlorate and iron nitrate were incorporated in the diureasil matrices, leading to compositions within the range 80 greater than or equal to n greater than or equal to 10, n being the molar ratio of ether-type O atoms per cation. The structure of the doped diureasils was investigated by small-angle X-ray scattering (SAXS). For Fe-II-doped samples, SAXS results suggest the existence of a two-level hierarchical structure. The primary level is composed of spatially correlated siloxane clusters embedded in the polymeric matrix and the secondary, coarser level consists of domains where the siloxane clusters are segregated. The structure of Fe-III-doped hybrids is different, revealing the existence of iron oxide based nanoclusters, identified as ferrihydrite by wide-angle X-ray diffraction, dispersed in the hybrid matrix. The magnetic susceptibility of these materials was determined by zero-field-cooling and field-cooling procedures as functions of both temperature and field. The different magnetic features between Fe-II- and Fe-III-doped samples are consistent with the structural differences revealed by SAXS. While Fe-II-doped composites exhibit a paramagnetic Curie-type behaviour, hybrids containing Fe-III ions show thermal and field irreversibilities.

Structure and electrical properties of potassium-doped siloxane-poly(oxypropylene) ormolytes

The structure and the ionic conduction properties of siloxane-poly(oxypropylene) (PPO) hybrids doped with different potassium salts (KCF3SO3, KI, KClO4 and KNO2) are reported for two polymer molecular weights (300 and 4000 g/mol), labelled PPO300 and PPO4000, respectively. The doping concentration, related to the concentration of the ether type oxygen of the PPO chain, is the same whatever the salt and verifies [O]/[K] = 20. Ionic room temperature conductivity shows the highest value for the KCF3SO3 doped PPO4000 hybrid (4 x 10(-7)Omega(-1).cm(-1)). The structure of these hybrids was investigated by X-ray powder diffraction (XRPD) and X-ray absorption spectroscopy (EXAFS and XANES) at the potassium K-edge (3607 eV). XRPD results show that the hybrid matrix is always amorphous and the formation of secondary potassium phases is observed for all the samples, except for the KCF3SO3 doped PPO4000 hybrid. EXAFS results evidence a good correlation between the ionic conductivity and the presence of oxygen atoms as first neighbours around potassium.

Structure and luminescence of Eu3+-doped class I siloxane-poly(ethylene glycol) hybrids

Transparent, flexible, and luminescent EU3+-doped siloxane-poly(ethylene glycol) (PEG) nanocomposites have been obtained by the sol-gel process. The inorganic (siloxane) and organic PEG phases are usually linked by weak bonds (hydrogen bonds or van der Waals forces), and small-angle X-ray scattering (SAXS) measurements suggest that the structure of these materials consists of fractal siloxane aggregates embedded in the PEG matrix. For low Eu3+ contents, n = 300 and n = 80, the aggregates are small and isolated and their fractal dimensions are 2.1 and 1.7, respectively. These values are close to those expected for gelation mechanisms consisting of reaction-limited cluster-cluster aggregation (RLCCA) and diffusion-limited cluster-cluster aggregation (DLCCA). For high Eu3+ content, SAYS results are consistent with a two-level structure: a primary level of siloxane aggregates and a second level, much larger, formed by the coalescence of the primary ones. The observed increase in the glass transition temperature for increasing Eu3+ content is consistent with the structural model derived from SAXS measurements. Extended X-ray absorption fine structure (EXAFS) and luminescence spectroscopy measurements indicate that under the experimental conditions utilized here Eu3+ ions do not strongly interact with the polymeric phase.

Small-angle X-ray scattering and X-ray absorption near-edge structure study of iron-doped siloxane-polyoxyethylene nanocomposites

The local and medium-range structures of siloxane-POE hybrids doped with Fe(III) ions and prepared by the sol-gel process were investigated by X-ray absorption near-edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) and small-angle X-ray scattering (SAXS), respectively. The experimental results show that the structure of these composites depends on the doping level. EXAFS data reveal that, for low doping levels ([O]/[Fe] > 40, oxygens being of the ether-type of the POE chains), Fe(III) ions are surrounded essentially by a shell of chlorine atoms, suggesting the formation of FeCl4- anions. At high doping levels ([O]/[Fe] < 20), Fe(III) ions interacts mainly with oxygen atoms and form FeOx species. The relative proportion of FeOx species increases with iron concentration, this result being consistent with the results of SAXS measurements showing that increasing iron doping induces the formation of iron-rich nanodomains embedded in the polymer matrix.

Design of Gaussian basis sets to the theoretical interpretation of IR-spectrum of hexaaquachromium (III) ion, tetraoxochromium (IV) ion, and tetraoxochromium (VI) ion

The Generator Coordinate Hartree-Fock (GCHF) method is employed to design 16s, 16s10p, 24s17p13d, 25s17p13d, and 26s17p Gaussian basis sets for the H ((2)S), O ((3)P), O(2-) ((1)S), Cr(3+) ((4)F), Cr(4+) ((3)F), and Cr(6+) ((1)S) atomic species. These basis sets are then contracted to (4s) for H ((2)S), (6s4p) for O ((3)P), and O(2-) ((1)S), (986p3d) for Cr(3+) ((4)F), (10s8p3d) for Cr(4+) ((3)F), and (13s7p) for Cr(6+) (1S) by a standard procedure. For evaluation of the quality of those basis sets in molecular calculations, we have accomplished studies of total and orbital (HOMO and HOMO-1) energies at the HF-Roothaan level for the molecular species of our interest. The results obtained with the contracted basis sets are compared to the values obtained with our extended basis sets and to the standard 6-311G basis set from literature. Finally, the contracted basis sets are enriched with polarization function and then utilized in the theoretical interpretation of IR-spectrum of hexaaquachromium (III) ion, [Cr(H(2)O)(6)](3+), tetraoxochromium (IV) ion, [CrO(4)](4-), and tetraoxochromium (VI) ion, [CrO(4)](2-). The respective theoretical harmonic frequencies and IR-intensities were computed at the density functional theory (DFT) level. In the DFT calculations we employed the Becke's 1988 functional using the LYP correlation functional. The comparison between the results obtained and the corresponding experimental values indicates a very good description of the IR-spectra of the molecular ions studied, and that the GCHF method is still a legitimate alternative for selection of Gaussian basis sets. (C) 2003 Elsevier B.V. All rights reserved.

Structure of luminescent mono and di-urethanesil nanocomposites doped with Eu3+ ions

A structure modeling of two families of sol-gel derived Eu3+-doped organic/inorganic hybrids based on the results of small-angle X-ray scattering experiments is reported. The materials are composed of poly(oxyethylene) chains grafted at one or both ends to siloxane groups and are called mono- and di-urethanesils, respectively. A theoretical function corresponding to a two-level hierarchical structure model fits well the experimental Scattering curves. The first level corresponds to small siloxane clusters embedded in a polymeric matrix. The secondary level is associated to the existence of siloxane cluster rich domains surrounded by a cluster-depleted polymeric matrix. Results show that increasing europium doping favors the growth of the secondary domains. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Variable structure controller and observer applied to induction machine

This work will propose the control of an induction machine in field coordinates with imposed stator current based on theory of variable structure control and sliding mode. We describe the model of an induction machine in field coordinates with imposed stator current and we show the design of variable structure control and sliding mode to get a desirable dynamic performance of that plant. To estimate the inaccessible states we will use a state observer (estimator) based on field coordinates induction machine. We will present the results of simulations in any operation condition (start, speed reversal and load) and with parameters variation of the machine compared to a PI control scheme.

A controller design used in Lorenz synchronization chaotic system for secure communication based on LMI fuzzy control system

This paper describes a mathematical study about chaotic system and about the unified approach of chaos control via fuzzy control system based in Linear Matrix Inequality to design a controller which synchronizes the transmission/reception system. This system, that was based in Lorenz chaotic circuit, can be used for transmit signals in secure way.

Local structure and near-infrared emission features of neodymium-based amine functionalized organic/inorganic hybrids

Nd3+-based organic/inorganic hybrids have potential application in the field of integrated optics. Attractive sol-gel derived di-urea and di-urethane cross-linked poly (oxyethylene) (POE)/siloxane hybrids (di-ureasils and di-urethanesils, respectively) doped with neodymium triflate (Nd(CF3SO3)(3)) were examined by Fourier transform mid-infrared (FT-IR), Raman (FT-Raman), Si-29 magic-angle spinning (MAS) nuclear magnetic resonance (NMR) and photoluminescence spectroscopies, and small-angle X-ray scattering (SAXS). The goals of this work were to determine which cation coordinating site of the host matrix (ether oxygen atoms or carbonyl oxygen atoms) is active in each of the materials analyzed, its influence on the nanostructure of the samples and its relation with the photoluminescence properties. The main conclusion derived from this study is that the hydrogen-bonded associations formed throughout the materials play a major role in the hybrids nanostructure and photoluminescence properties.

Local and nanoscopic structure of potassium triflate-doped siloxane-polyoxyethylene ormolytes

Siloxane-poly(oxyethylene) hybrids obtained by the sol-gel process and containing short polymer chain have been doped with potassium triflate (KCF3SO3). The local structure of these hybrids was investigated by X-ray absorption spectroscopy near the potassium K-edge. Small angle X-ray scattering was used to determine the structure at the nanometer scale. Results revealed that at low and medium potassium concentration (n = [O][K] >= 8, where n represents the molar ratio of ether-type oxygen atoms per alkaline cation) the cations interact mainly with the polymer chains, while at larger doping level (n < 8) the formation of a polyehter:KCF3SO3 Complex is observed. The nanoscopic structure of the hybrids is also affected by doping. By increasing the doping level, decreasing trends in the electronic density contrast between siloxane nanoparticles and polyether matrix and in the siloxane interparticle distance are observed. At high doping level the small angle X-ray scattering patterns are strongly modified, showing the disappearance of the correlation peak and the formation of a potassium-containing nanophase. (c) 2006 Elsevier B.V. All rights reserved.

Structure of weakly bonded PPG-silica nanocomposites

The structure of silica-polypropyleneglycol (PPG) nanocomposites with weak physical bonds between the organic (PPG) and inorganic (silica) phase, prepared by the sol-gel process, was investigated by small angle X-ray scattering (SAXS). These nanocomposite materials are transparent, flexible, have good chemical stability and exhibit high ionic conductivity when doped with lithium salt. Their structure was studied as a function of silica weight fraction x (0.06 less than or equal to x less than or equal to 0.29) and [O]/[Li] ratio (oxygens being of ether-type). The shape of the experimental SAXS curves agrees with that expected for scattering intensity produced by fractal aggregates sized between 30 and 90 Angstrom. This result suggests that the structure of the studied hybrids consists of silica fractal aggregates embedded in a matrix of PPG. The correlation length of the fractal aggregates decreases and the fractal dimension increases for increasing silica content. The variations in structural parameters for increasing Li+ doping indicate that lithium ions favor the growth of fractal silica aggregates without modifying their internal structure and promote the densification of the oligomeric PPG matrix.

H-2 and H-infinity - norm control of intelligent structures using LMI techniques

Linear Matrix Inequalities (LMIs) is a powerful too] that has been used in many areas ranging from control engineering to system identification and structural design. There are many factors that make LMI appealing. One is the fact that a lot of design specifications and constrains can be formulated as LMIs [1]. Once formulated in terms of LMIs a problem can be solved efficiently by convex optimization algorithms. The basic idea of the LMI method is to formulate a given problem as an optimization problem with linear objective function and linear matrix inequalities constrains. An intelligent structure involves distributed sensors and actuators and a control law to apply localized actions, in order to minimize or reduce the response at selected conditions. The objective of this work is to implement techniques of control based on LMIs applied to smart structures.

Extracellular matrix of porcine pericardium: Biochemistry and collagen architecture

Pericardial tissue has been used to construct bioprostheses employed in the repair of different kinds of injuries, mostly cardiac. However, calcification and mechanical failure have been the main causes of the limited durability of cardiac bioprostheses constructed with bovine pericardium. In the course of this work, a study was conducted on porcine fibrous pericardium, its microscopic structure and biochemical nature. The general morphology and architecture of collagen were studied under conventional light and polarized light microscopy. The biochemical study of the pericardial matrix was conducted according to the following procedures: swelling test, hydroxyproline and collagen dosage, quantification of amino acids in soluble collagen, component extraction of the extracellular matrix of the right and left ventral regions of pericardium with different molarities of guanidine chloride, protein and glycosaminoglycan (GAG) dosage, sodium dodecyl sulfate-polyacrylamide gel electrophoresis and total GAG analysis. Microscopic analysis showed collagen fibers arranged in multidirectionally oriented layers forming a closely knit web, with a larger number of fibers obliquely oriented, initiating at the lower central region toward the upper left lateral relative to the heart. No qualitative differences were found between proteins extracted from the right and left regions. Likewise, no differences were found between fresh and frozen material. Protein dosages from left frontal and right frontal pericardium regions showed no significant differences. The quantities of extracted GAGs were too small for detection by the method used. Enzymatic digestion and electrophoretic analysis showed that the GAG found is possibly dermatan sulfate. The proteoglycan showed a running standard very similar to the small proteoglycan decorin.