Crystallization behaviour of β-spodumene in the calcination of Li2O-Al2O3-SiO2-ZrO2 gels

This work was carried out in order to prepare precursor powders with a spodumene composition (Li₂O·Al₂O₃·4SiO₂, LAS) and to investigate their crystallization behaviours during calcination. A fine β-spodumene type amorphous powder was obtained through sol-gel techniques using LiOCH₃, Al(OC₂H₅)₃, Si(OC₂H₅)₄ and Zr(OC₂H₅)₄ as the starting metal alkoxides. The process included well controlled hydrolysis polycondensation of the raw alkoxides. Differential thermal analysis (DTA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electron diffraction (ED) analyses were utilized to study the crystallization behaviour of the gels. The activation energy of β-spodumene crystallization was 192 kJ mol⁻¹ for LAS gels with 4 wt% ZrO₂, being much smaller than those of LAS gel without ZrO₂, 382 kJmol⁻¹. For calcination at 800–1200°C, the crystallized phases comprised a major phase of β-spodumene and a minor phase of zirconia (ZrO₂).     

Preparation and photoluminescence of Er-doped Al2O3 films by sol-gel method

The 0-1.5 mol% Er³⁺-doped Al₂O₃ films have been prepared on the thermally oxidized SiO₂/Si(100) substrate in the dip-coating process by the sol-gel method, using the aluminium isopropoxide [Al(OC₃H₇)₃]-derived γ-AlOOH sols with the addition of erbium nitrate [Er(NO₃)₃·5H₂O]. The continuous Er³⁺-doped Al₂O₃ films with the thickness of about 1.2 μm were obtained for nine coating cycles at a sintering temperature of 900 °C. The aggregate size for the Er³⁺-doped Al₂O₃ films increased with increasing the Er³⁺ doping concentration from 0 to 1.5 mol%. The root-mean-square roughness of the films was independent on the Er³⁺ doping, which was about 1.8 nm for the 0-1.5 mol% Er³⁺-doped Al₂O₃ films. The γ-Al₂O₃ phase with a (110) preferred orientation was produced for the Al₂O₃ film. The photoluminescence (PL) spectra of 0.1-1.5 mol% Er³⁺-doped Al₂O₃ films were observed at the measurement temperature of 10 K. There was no significant change for the PL peak intensity with the increase of Er³⁺ doping concentration from 0.1 to 1.5 mol%, and similar full width at half maximum of about 40 nm was detected for the 0.1-1.5 mol% Er³⁺-doped Al₂O₃ thin films. The Er³⁺-doped Al₂O₃ films possess the available PL properties for use in planar optical waveguides.     

Crystal Structure of (H3O)6[(UO2)5(SeO4)8(H2O)5](H2O)5

Crystals of (H₃O)₆[(UO₂)₅(SeO₄)₈(H₂O)₅](H₂O)₅ were prepared from aqueous solutions by evaporation. The crystal structure [monoclinic system, space group P2₁/m, a = 13.835(2), b = 13.4374(16), c = 14.310(3) Å, β = 108.004(14)°, V = 2530.1(7) Å ³] was solved by the direct method and refined to R ₁ = 0.090 for 4409 reflections with |F _hkl ≥ 4σ|F _hkl |. The structure is based on [(UO₂)₅(SeO₄)₈(H₂O)₅]⁶⁻ layers arranged parallel to the (101) plane; these layers have a unique topological structure. The U(1)O₆(H₂O) and U(3)O₆(H₂O) linked through selenate groups form chains running along [ [`1]\bar 1 01] direction. The chains are combined in layers by U(2)O₆(H₂O) bipyramids. The layers are linked with each other by hydrogen bonds through the H₂O and H₃O⁺ groups located between the layers.     

Synthesis and crystal structure of new U(VI) and Np(VI) benzoates, K11(AnO2)23(OOCC6H5)57(H2O)18+x

The structure of new double benzoates of hexavalent actinides, K₁₁(AnO₂)₂₃(O₂C₇H₅)₅₇(H₂O)_18+x (An = U, Np), was studied. There are five crystallographically independent actinide atoms in the crystals. The coordination polyhedra of An(1), An(3), An(4), and An(5) are distorted hexagonal bipyramids, and that of An(2) is a distorted pentagonal bipyramid. Ten crystallographically independent benzoate ions have been found in the crystals. All but one anions are bidentate chelating and form with AnO₂²⁺ cations either electrically neutral [AnO₂(O₂C₇H₅)₂(H₂O)₂][An(1)O₂²⁺ cations] or negatively charged [AnO₂(O₂C₇H₅)₃]⁻[An(3)O₂²⁺, An(4)O₂²⁺, An(5)O₂²⁺ cations] complexes. The bidentate bridging benzoate ion links two adjacent An(2)O₂²⁺ cations with the formation of peculiar electrically neutral cyclic fragments [AnO₂(O₂C₇H₅)₂(H₂O)]₆ arranged perpendicular to the c-axis. There are three independent K⁺ cations in the structure. The coordination surrounding of K(1)⁺ (coordination number CN 6) is formed by oxygen atoms of two electrically neutral [AnO₂(O₂C₇H₅)₂(H₂O)₂] fragments and of the complex anion [AnO₂(O₂C₇H₅)₃]⁻. The coordination surrounding of K(2)⁺ (CN 6) consists of oxygen atoms of three complex anions [AnO₂(O₂C₇H₅)₃]⁻. The disordered K(3)⁺ cation is arranged near the sixfold axis between the cyclic fragments [AnO₂(O₂C₇H₅)₂(H₂O)]₆. An important structure-forming factor in the crystals is hydrogen bonding involving coordinated water molecules. In the coordination polyhedra of actinides, the An-O bond lengths regularly decrease in going from U to Np owing to actinide contraction.     

Synthesis of SiO2 glass fibres from Si(OC2H5)4-H2O-C2H5OH-HCl solutions through sol-gel method

Various factors affecting the spinnability of the Si(OC₂H₅)₄-H₂O-C₂H₅OH-HCl solutions have been investigated in order to find appropriate experimental conditions for making gel-derived SiO₂ glass fibres. The molar ratios of H₂O, C₂H₅OH and HCl to Si(OC₂H₅)₄ were changed in the range from 0.5 to 10.0, 0.5 to 7.0 and 0.001 to 0.1, respectively. The solutions were reacted at 30 and 80° C. It has been reconfirmed that the most important factor determining the spinnability of the solution in the course of the hydrolysis reaction is the molar ratio of water to Si(OC₂H₅)₄ in the solution. The rise of the reaction temperature led to the remarkable shortening of the time required for drawing fibres. The increase of the amount of HCl decreased the upper limit of the H₂O/Si(OC₂H₅)₄ molar ratio range where the spinnability is found as well as reaction temperature. The solutions with a H₂O/Si(OC₂H₅)₄ ratio larger than 2.0 gave often fibres having a circular cross-section, while other solutions gave fibres with a non-circular one. The tensile strength of the gel-derived SiO₂ glass fibres was also reported.     

Bioactivity and mechanical properties of polydimethylsiloxane (PDMS)–CaO–SiO2 hybrids with different calcium contents

Polydimethylsiloxane (PDMS)–CaO–SiO₂ hybrids with starting compositions containing PDMS/(Si(OC₂H₅)₄+PDMS) weight ratio=0.30, H₂O/Si(OC₂H₅)₄ molar ratio=2, and Ca(NO₃)₂/Si(OC₂H₅)₄ molar ratios=0–0.2, were prepared by the sol–gel method. The apatite-forming ability of the hybrids increased with increasing calcium content in the Ca(NO₃)₂/Si(OC₂H₅)₄ molar ratio range 0–0.1. The hybrids with a Ca(NO₃)₂/Si(OC₂H₅)₄ molar ratio range 0.1–0.2 formed apatite on their surfaces in a simulated body fluid (SBF) within 12 h. The hybrid with a Ca(NO₃)₂/Si(OC₂H₅)₄ molar ratio of 0.10 showed an excellent apatite-forming ability in SBF with a low release of silicon into SBF. It also showed mechanical properties analogous to those of human cancellous bones. This hybrid is expected to be useful as a new type of bioactive material.     

H2S sensing properties of La-doped nanocrystalline In2O3

The nanocrystalline powders of pure and La³⁺-doped In₂O₃ with cubic structure were prepared by a simple hydrothermal decomposition route. The structure and crystal phase of the powders were characterized by X-ray diffraction (XRD) and microstructure by transmission electron microscopy (TEM). All the compositions exhibited a single phase, suggesting a formation of solid solution in the concentration of doping investigated. Gas-sensing properties of the sensor elements were tested by mixing a gas in air at static state, as a function of concentration of dopant, operating temperature and concentrations of the test gases. The pure In₂O₃ exhibited high response towards H₂S gas at an operating temperature 150 °C. Doping of In₂O₃ with La³⁺ increases its response towards H₂S and La³⁺ (5.0 wt.% La₂O₃)-doped In₂O₃ showed the maximum response at 125 °C. The selectivity of the sensor elements for H₂S against different reducing gases was studied. The results on response and recovery time were also discussed.     

Spectral analysis of RE (RE = Sm, Dy, and Tm): P2O5–Al2O3–Na2O glasses

Phosphate glasses in the compositions of 70P₂O₅–15Al₂O₃–14Na₂O–1RE³⁺ (RE = Sm, Dy, and Tm) (mol%) were prepared by melt-quenching technique and characterized optically. The differential thermal analysis (DTA) profile of the host glass was carried out to confirm its thermal stability. For all the glasses absorption, photoluminescence and decay measurements have also been carried out. These glasses have shown strong emission and absorption bands in visible and near-infrared (NIR) region. From the measured absorption spectra, Judd–Ofelt (J–O) intensity parameters (Ω₂, Ω₄ and Ω₆) have been calculated for all the studied ions. For Sm³⁺ doped glass, four emission bands centered at 562 nm (⁴G_5/2 → ⁶H_5/2), 598 nm (⁴G_5/2 → ⁶H_7/2), 644 nm (⁴G_5/2 → ⁶H_9/2), and 704 nm (⁴G_5/2 → ⁶H_11/2) have been observed with 402 nm (⁶H_5/2 → ⁴F_7/2) excitation wavelength. Of them, 598 nm (⁴G_5/2 → ⁶H_7/2) has shown a bright orange emission. With regard to Dy³⁺ doped glass, a blue emission band centered at 486 nm (⁴F_9/2 → ⁶H_15/2) and a bright yellow emission at 575 nm (⁴F_9/2 → ⁶H_13/2) have been observed, apart from 662 nm (⁴F_9/2 → ⁶H_11/2) emission transition with an excitation at 388 nm (⁶H_15/2 → ⁴I_13/2,⁴F_7/2) wavelength. Emission bands of 650 nm (¹G₄ → ³F₄) and 785 nm (¹G₄ → ³H₅) transitions for the Tm³⁺ doped glass, with an excitation wavelength at 466 nm (³H₆ → ¹G₄), have also been observed. The stimulated emission cross-sections of all the emission bands of RE³⁺ glasses (RE = Sm, Dy, and Tm) have been computed based on their measured full-width at half maximum (FWHM, Δλ) and measured lifetimes (τ_m).     

Crystal Structure of (H3O)2[(UO2)2(SeO4)3(H2O)2](H2O)3.5

Crystals of (H₃O)₂[(UO₂)₂(SeO₄)₃(H₂O)₂](H₂O)_3.5 were prepared from aqueous solutions by evaporation. The crystal structure [monoclinic system, space group P2₁/m, a = 11.9402(11), b = 13.6452(14), c = 13.7271(12) Å, β = 109.436(7)°, V = 2109.1(3) ų] was solved by the direct method and refined to R ₁ = 0. 048 (wR ₂ = 0. 082) for 3677 reflections with |F _hkl |F _hkl |. The structure consists of [(UO₂)₂(SeO₄)₃(H₂O)₂]₂₋ layers arranged parallel to the (010) plane. The layers are formed by uranium and selenium coordination polyhedra sharing common vertices and are linked with each other by hydrogen bonds through the H₂O and H₃O⁺ groups arranged between the layers. __________ Translated from Radiokhimiya, Vol. 47, No. 5, 2005, pp. 412–414. Original Russian Text Copyright ? 2005 by Krivovichev, Kahlenberg.     

Role of bismuth and titanium in Na2O-Bi2O3-TiO2-P2O5 glasses and a model of structural units

0.60Na₂O-0.40P₂O₅ and (0.55−z)Na₂O-0.05Bi₂O₃-zTiO₂-0.40P₂O₅ glasses (0≤z≤0.15) were prepared by melting at 1000°C mixtures of Na₂CO₃, Bi₂O₃, TiO₂ and (NH₄)₂HPO₄. Differential Scanning Calorimetry (DSC) measurements give the variation of glass transition temperature (T_g) from 269°C (for 0.60Na₂O-0.40P₂O₅) to 440°C (for z=0.15). The density measurements increases from 2.25 to 3.01 g/cm³. FTIR spectroscopy shows the evolution of the phosphate skeleton: (PO₃)_∞ chains for 0.60Na₂O-0.40P₂O₅ to P₂O₇⁴⁻ groups in the glasses containing Bi₂O₃ or both Bi₂O₃ and TiO₂. When bismuth oxide and titania are added to sodium phosphate glass, phosphate chains are depolymerized by the incorporation of distorted Bi(6) and Ti(6) units through POBi and POTi bonds. Bi₂O₃ and TiO₂ are assumed to be present as six co-ordinated octahedral [BiO_6/2]³⁻and [TiO_6/2]²⁻ units again with shared corners. This is accompanied by the simultaneous conversion of [POO_3/2] into [PO_4/2]⁺ units which achieves charge neutrality in the glasses.     

L'oxynitrure de silicium: Si2N2O I. Attribution des absorptions du spectre infrarouge aux vibrations fondamentales

Infrared absorption frequencies (4000 ? 200 cm^?1) are assigned to stretching and bending normal vibrations of the various inter-atomic bonds in silicon oxinitride. The two kinds of atoms linked to the silicon with different force constants as well as numerous results on the Si1bO1bSi bridge in materials with quite the same symmetry make Si₂N₂O a suitable material for such an investigation. The study of silicon oxygen bonds is more particulary supported by the analysis of vibrations in a “pseudo-molecule” (N₃Si1bO1bSiN₃), with a simplified computation of valence force field, and by their correlation with normal modes in the primitive cell. The assigment is also supported by a study using internal coordinates of the reduced representation of the degrees of freedom and by the behavior of the absorption bands at low temperature.     

Formation and properties of glasses in the CaF2AlF3P2O5 system

Glasses from the system CaF₂AlF₃P₂O₅ have been synthesized. Glass formation characteristics, thermal expansion, and optical transmission of these glasses in the visible and infrared regions are described. Incorporation of P₂O₅ in the system greatly suppressed the spontaneous crystallization tendencies of the CaF₂AlF₃ binary system. The glasses obtained from the system transmit in the mid-infrared range. A strong absorption band centerd at 4.8 microns is a characteristic of these glasses. The absorption band is related to the presence of P₂O₅ in the glass.     

Synthesis and structural characterization of mesoporous V2O5 thin films for electrochromic applications

Mesoporous vanadium pentoxide (V₂O₅) films have been synthesized by hydrolysis of vanadium tri-isopropoxide (VO(OC₃H₇)₃) in the presence of polyethylene glycol (PEG) as a structure-directing agent. The structure, the stoichiometry and the morphology of the films have been studied as a function of the thermal annealing by X-ray diffraction (XRD), micro-Raman spectroscopy, optical microscopy, scanning electron microscopy and atomic force microscopy. XRD patterns and Raman spectra show the presence of two previously unreported crystalline phases. The PEG:V₂O₅ molar ratio affects the temperature of phase formation, the amount and even the order in which the phases appear. The morphological characterization underlines the role of the surfactant to promote porous networks, formed by micrometric clusters of controlled shapes and patterns embedded in a homogeneous host matrix.     

Synthesis of New Crystalline Pu(V) Compounds from Solutions: V. Crystal Structure of [Co(NH3)6][PuO2(C2O4)2] · 3H2O

The compound [Co(NH₃)₆][PuO₂(C₂O₄)₂] · 3H₂O was studied by single crystal X-ray diffraction. The structure contains dimeric complex anions [PuO₂(C₂O₄)₂] ₂ ⁶⁻ in which the coordination polyhedra of the Pu atoms are distorted pentagonal bipyramids sharing a common equatorial edge. In going from [Co(NH₃)₆] · [NpO₂(C₂O₄)₂] · 3H₂O to [Co(NH₃)₆][PuO₂(C₂O₄)₂] · 3H₂O, the An-O distances, both axial (in the actinyl group) and equatorial, decrease virtually isotropically. __________ Translated from Radiokhimiya, Vol. 47, No. 5, 2005, pp. 419–422. Original Russian Text Copyright ? 2005 by Grigor'ev, Antipin, Krot, Bessonov.     

Low temperature synthesis of glassy solids of the system Al2O3-P2O5-SiO2

Glassy solids of the system Al₂O₃-P₂O₅-SiO₂, which have not been obtainable because of the devitrification of glass during the cooling process after melting, were obtained by the gel method. After the gels of the system Al₂O₃-P₂O₅-SiO₂ were prepared from AlCl₃·6H₂O, H₃PO₄ and Si(OC₂H₅)₄, they were heat treated up to 800° C to obtain glassy solids. In SiO₂ concentrations ranging from 75 to 82 mol % in batch compositions, non-porous transparent solids were obtained, while in SiO₂ concentrations above 87 mol %, porous transparent solids were obtained. Tridymite was precipitated because of the crystallization of glassy solids during heat treatment above 800° C. It depended upon the microstructure of the gels whether non-porous glassy solids were obtained or not. The thermal expansion coefficients of the glassy solids were greatly dependent upon the concentration of P₂O₅, ranging from 1.7×10⁻⁶ to 4.2×10⁻⁶ (1/° C).     

Coating of polymethylmethacrylate with transparent SiO2 thin films by a sol-gel method

In order to improve the surface characteristics of polymethylmethacrylate (PMMA), oxide thin-film coatings were applied using the sol-gel dip-coating technique. The Si(OC₂H₅)₄ (TEOS), CH₃Si(OC₂H₅)₃ (MTES) or Ti(O-i-C₃H₇)₄ (TIP) was used as a starting material for SiO₂ or TiO₂ coating. The hardness of the alkoxy-derived oxide-coated PMMA was increased from 200 MPa for non-coated PMMA with increasing film thickness. By optimizing the heating conditions and the hydrolysis conditions, and by repeating the dip-coating/heating processes, a hardness as high as 325 MPa was achieved in the PMMA triply coated with the TEOS-derived SiO₂ film using the withdrawal velocity of 0.30 mms^–1 and heat treatment at 80°C. The increase in hardness with the thickness of coating film was saturated before reaching that of bulk silica-dried gel (ca. 500 MPa), which may be due to the increased porous nature of the thick films.     

Structural and spectroscopic characterization of Yb doped Lu2O3 transparent ceramics

Yb³⁺ doped Lu₂O₃ transparent ceramics were fabricated by the solid-state reaction method and sintered in H₂ atmosphere. Structural and spectroscopic properties of Yb:Lu₂O₃ ceramics were studied. The Yb:Lu₂O₃ ceramic structure, and the lattice parameter are refined with the Rietveld method. Yb:Lu₂O₃ has broad absorption and emission bands with a long fluorescence lifetime (1.31 ms). The energy level diagram is calculated based on the absorption and emission spectra, Yb³⁺ in Lu₂O₃ ceramics exhibits a big splitting energy of the ²F_7/2 ground state (1023 cm⁻¹). Furthermore, the gain cross-section (σ_g) is estimated with different β values.     

Synthesis, characterization and photoluminescence properties of (Gd0.99,Pr0.01)2O2S sub-microphosphor by homogeneous precipitation method

Homogeneous precipitation method for synthesizing (Gd_0.99,Pr_0.01)₂O₂S sub-microphosphor was developed, using the commercially available Gd₂O₃, Pr₆O₁₁, H₂SO₄ and (NH₂)₂CO (urea) as the starting materials. It was found that the as-synthesized precursor is mainly composed of (Gd_0.99,Pr_0.01)₂(OH)₂(CO₃)(SO₄)·nH₂O. Pure quasi-spherical shaped (Gd_0.99,Pr_0.01)₂O₂S particles can be synthesized by calcining the precursor at a temperature higher than 700 °C for 1 h in flowing hydrogen. The (Gd_0.99,Pr_0.01)₂O₂S particles have a narrow size distribution with a mean grain size of about 300-400 nm. Photoluminescence spectra of (Gd_0.99,Pr_0.01)₂O₂S under 303 nm UV excitation show a green emission at 515 nm as the most prominent peak, which corresponds to the ³P₀ → ³H₄ transition of Pr³⁺ ions. Decay study reveals that the ³P₀ → ³H₄ transition of Pr³⁺ ions in Gd₂O₂S host lattice has a single exponential decay behavior.     

Diagramme d'equilibre du systeme binaire Ba(PO3)2  CsPO3; donnees cristallographiques sur BaCs4(PO3)6, Ba2Cs(PO3)5 et BaCsP3O9, H2O

Equilibrium diagram of Ba(PO₃)₂  CsPO₃ system is given. Two compounds are identified: BaCs₄(PO₃)₆, Ba₂Cs(PO³₃)₅  BaCsP₃O₉.H₂O was also prepared and characterized.     

Layered H2K2Nb6O17 exfoliation promoted by n-butylamine

We have been exploring experimental conditions to achieve the exfoliation of the layered niobate phase K₄Nb₆O₁₇ using alkyl amines. In this work, the exfoliation process of the niobate acidic form H₂K₂Nb₆O₁₇ was evaluated in aqueous solution media using n-butylamine. Different amine/H⁺-niobate molar ratios were used and for each one, two fractions were isolated: one that corresponds to the deposited solid (or sediment) and the second one that consists of an aqueous colloidal dispersion. Fractions were characterized by X-ray powder diffraction, electronic absorption spectroscopy and, scanning and transmission electron microscopies. It was observed that the hexaniobate exfoliation is very dependent on the amine/H⁺-niobate molar ratio utilized. The highest amount of exfoliated niobate particles was achieved by using a butylamine/H⁺-niobate molar ratio around 0.5. High molar ratios promote the intercalation preferred to the delamination, indicating that the interlayer region saturation precludes the hexaniobate sheets exfoliation. TEM images of delaminated sample showed nanosized particles with flat and tubular morphologies.