Low-temperature Ti-containing 3:2 and 2:1 mullite nanocrystals from single-phase gels

Abstract TiO 2 -containig single-phase gels with (Al 2 O 3  + TiO 2 )/(SiO 2 ) molar ratios 3/2 and 2/1 were prepared by gelling mixtures of aluminium nitrate, tetraethylorthosilicate and titanium isopropoxide. Gels were fast heated at several temperatures up to 1100 °C. Dried and heated gels were characterized by differential thermal analysis (DTA), magic angle spinning nuclear magnetic resonance (MAS-NMR), X-ray powder diffraction (XRD), and scanning and transmission electron microscopies (SEM and TEM). Coupled DTA and XRD results of gels fast heated at 900 °C showed the crystallisation of two mullites as well as a small amount of alumina-silica spinel. 27 Al NMR spectra showed the format…

Improvement of boehmite nanoparticles' aqueous dispersability by controlling their size, shape and crystallinity

In this work, results on the control of size, shape, crystallinity and aqueous dispersability of boehmite prepared by a hydrothermal process are reported. The two step synthetic procedure entailed the precipitation of a xerogel by adding NaOH until pH 10 to a solution of aluminum nitrate at 100 °C without or with additives such as tartaric acid and maltitol, and a subsequent hydrothermal treatment at 150 and 200 °C for different periods of time. The final materials were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and elemental analysis. The stability and other characteristics of the boehmite nanoparticle aqueous dispersions were determined by measuring t…

Cr- and Sb-containing TiO 2 inorganic orange nano-pigments prepared by a relative long hydrocarbon chain polyol

Abstract We report the preparation of a series of orange Cr- and Sb-containing TiO 2 nano-pigments by the polyol via using triethylenglycol (TEG). Poorly crystallized anatase nanopowders with nominal stoichiometric compositions Cr x Sb x Ti 1−2x O 2 , with 0 ≤ x ≤ 0.2, were obtained by heating at 180 °C a solution of antimony acetate, chromium acetylacetone and titanium butoxide in TEG. The transition temperature of the chromium- and antimonium-containing anatase nanoparticles into the rutile crystalline form occurred over the range of temperature between 500 and 650 °C, depending on the dopant amount. After annealing at 800 °C for short time the series of samples displaying the rutile stru…

Crystallization behaviour and microstructural development in ZrSiO 4 and V-ZrSiO 4 solid solutions from colloidal gels

Abstract Zircon and vanadium-doped zircon blue pigments were prepared by heat treatment of gel precursors. Gels with nominal compositions Vx-ZrSiO4 with x=0.0, 0.002, 0.004, 0.02 and 0.2 were prepared by formation of a silica coating on zirconia colloidal particles previously obtained. The crystallization behavior and microstructural evolution were studied using X-ray powder diffraction (XRD), energy dispersive X-rays microanalysis (EDX), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and selected area electron diffraction (SAED). The results indicated that the vanadia loading in the precursor gels speeds up the crystallization of the vanadium-co…

Effect of some additives on the development of spinel-based glass-ceramic glazes for floor-tiles

Abstract The feasibility of developing spinel-based glass-ceramic glazes from a glass with composition in the system ZnO–MgO–B 2 O 3 –Al 2 O 3 –SiO 2 was examined. To do it additional fluxes and/or nucleants were added to a parent glass before melting. Pressed pellets of powdered glasses were submitted to standard thermal treatments up to 1200 °C. The crystallization path and the microstructural development at several temperatures were followed by several experimental techniques. The results showed that additions of TiO 2 as nucleant or additional B 2 O 3 as flux to the chosen glass favored the crystallization of cordierite or mullite as main crystalline phase. Glasses which also contained …

Microheterogeneous electrocatalytic chiral recognition at monoclinic vanadium-doped zirconias: enantioselective detection of glucose.

Synthetic tetragonal and monoclinic vanadium-doped zirconias (t- and m-VxZr1-xO2, 0.005x0.150) exert an effective catalytic effect toward the electrochemical oxidation of glucose in aqueous alkaline media. The catalytic effect of monoclinic specimens attached to carbon and fluorine-doped tin oxide electrodes exhibits a remarkable enantioselectivity, so that catalytic currents for the oxidation of L-glucose at +0.92 V vs AgCl/Ag are considerably larger than those obtained for the oxidation of D-glucose. This enantioselectivity can be associated with the existence of a noncentrosymmetric coordination of vanadium centers in the monoclinic crystalline form of zirconia. From the electrochemical …

One-pot preparation of surface modified boehmite nanoparticles with rare-earth cyclen complexes.

We report on the one-pot synthetic procedure of cyclen derivatives bearing three acetate groups attached on boehmite nanoparticles, the complexing capabilities of these inorganic–organic hybrid materials with rare earth cations, and the behaviour as contrast agents or fluorescence probes. Delgado Pinar, Estefania, Estefania.Delgado@uv.es ; Frias Martinez, Juan Carlos, Juan.Frias@uv.es ; Albelda Gimeno, Maria Teresa, Teresa.Albelda@uv.es ; Alarcon Navarro, Javier, Javier.Alarcon@uv.es ; Garcia-España Monsonis, Enrique, Enrique.Garcia-Es@uv.es

Electrochemistry of vanadium-doped ZrSiO4Site-selective electrocatalytic effect on nitrite oxidation

The electrochemistry of vanadium-doped zircon (VxZrSiO4, 0 < x < 0.10) has been studied using abrasive-conditioned paraffin-impregnated graphite electrodes. It is compared with that of ZrSiO4, ZrO2, and vanadium-doped tetragonal and monoclinic zirconias. In contact with acetic/acetate and HCl + NaCl electrolytes, zirconium materials are reduced to Zr(III) at potentials near to −0.5 versus AgCl/Ag and to Zr metal at potentials more negative than −1.2 V, via proton-assisted reductive processes, influenced by the complexing action of chloride ions. Vanadium-centred oxidation processes appear at potentials from +0.2 to +0.7 V enabling for a distinction between different coordinative arrangement…

Crystal structure and microstructure of synthetic hexagonal magnesium–cobalt cordierite solid solutions (Mg2−2xCo2xAl4Si5O18)

Co2+-containing cordierite glasses, of nominal compositions (Mg1−xCox)2Al4Si5O18(withx= 0, 0.2, 0.4, 0.6, 0.8 and 1), were prepared by melting colloidal gel precursors. After isothermal heating at 1273 K for around 28 h, a single-phase α-cordierite (high-temperature hexagonal polymorph) was synthesized. All materials were investigated using X-ray powder diffraction and field-emission scanning electron microscopy. The crystal structure and microstructure were determined from X-ray diffraction patterns. Rietveld refinement confirmed the formation of magnesium–cobalt cordierite solid solutions. The unit-cell volume increased with the increase of cobalt content in the starting glass. The crysta…

Crystallization and microstructural development of nickel-containing aluminosilicate glasses with cordierite stoichiometry

Abstract The crystallization behaviour of two glasses with chemical compositions MAl2O4/SiO2=1/2.5, being MNi and equimolar mixtures of Mg and Ni, was investigated. Glasses were prepared by cooling samples melted at 1650 °C. During thermal treatment over the range of temperature up to 1200 °C both glasses were first crystallized to form a β-quartz solid solution, then transformed to α-cordierite or spinel depending on the amount of nickel. The temperatures of both the crystallization of β-quartz solid solution and its further transformation were also dependent on the nominal amount of nickel. Lower temperatures were found for glasses with a large amount of nickel. UV–Vis diffuse reflectanc…

Microstructural Evolution in Fast-Heated Cordierite-Based Glass-Ceramic Glazes for Ceramic Tile

The crystallization mechanism of α-cordierite from a B 2 O 3 -and TiO 2 -containing glass submitted to fast heating in the cordierite primary phase field of the CaO-MgO-Al 2 O 3 -SiO 2 quaternary system was investigated. Addition of B 2 O 3 to a SiO 2 -rich glass suppressed the formation of μ-cordierite. This suppression facilitated densification by viscous flow before crystallization. Powder X-ray diffractometry, field-emission electron scanning microscopy, and energy-dispersive X-ray analysis revealed that α-cordierite nucleated directly from glass on the boundaries of original particles and was probably favored by TiO 2 , which acted as a nucleant. The growth kinetics of α-cordierite cry…

Preparation of Hg2+ selective fluorescent chemosensors based on surface modified core–shell aluminosilicate nanoparticles

A synthetic procedure for the preparation of functional structured inorganic–organic hybrid materials consisting of boehmite-silica core–shell nanoparticles and anthracene-containing amines covalently attached to the nanoparticles surface is reported. The system functionalised with the monoamine chain shows a very high sensing performance for Hg2+ detection in pure water reaching a detection limit of 0.2 ppb. Two additional advantages of these systems are their stability over a wide pH window and the feasibility to be recovered by a simple procedure.

Microstructural evolution of mullites produced from single-phase gels

The crystalline microstructure of mullites obtained by heating monophasic gels has been investigated. Gels with alumina to silica molar ratio of 3:2 (as in secondary mullite) and 2:1 (as in primary mullite) were prepared by gelling mixtures of aluminium nitrate and tetraethylorthosilicate. Phase transformations were induced by heating the gel precursors, with different final treatment temperatures between 1173 and 1873 K. The mullites formed as a result of thermal treatment were studied by means of X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The crystalline structure (unit-cell parameters) and microstructure were determined from X-ray diffraction pa…

Different kinds of solid solutions in the V2O5-ZrSiO4-NaF system by sol-gel processes and their characterization

Abstract In the V2O5-ZrSiO4-NaF system, three kinds of substances have been identified by sol-gel methods depending on the V2O5 amounts in the composition. Their characterization by X-ray diffraction, measurements of unit cell parameters, UV-visible (UV-V) spectroscopy, differential thermal analysis and lab colour parameter determination allow the consideration of three kinds of solid solution in the zircon lattice: (a) V+5,V+4-ZrSiO4, thermally stable and with a deep green colour; (b) V+4-ZrSiO4, thermally stable and blue coloured, made by the sol-gel method and with V2O5 amounts lower than 0·03 mol per formula weight; and (c) Na+,F−,V+4-ZrSiO4, a solid solution with a deep blue-turquoise …

Effect of boron oxide on the microstructure of mullite-based glass-ceramic glazes for floor-tiles in the CaO–MgO–Al2O3–SiO2 system

Abstract The effect of increasing replacement of Al2O3 by B2O3 in a parent glass on the sintering and further crystallization of mullite was investigated. The composition of the parent glass was chosen in the mullite primary phase field of the CaO–MgO–Al2O3–SiO2 quaternary system. Glass powder pellets were heated under standard (10 °C/min and 2 h of hold time) and fast heatings (25 °C/min and 5 min of hold time) at different temperatures from 700 to 1190 °C. Sintering of B2O3-containing glasses took place in the range between 850 and 1050 °C. X-ray diffraction results showed that mullite formed as unique crystalline phase for glasses containing amounts of B2O3 larger than 6 wt%. For lower a…

Synthesis and reactivity of cristobalite obtained from the SiO2-V2O5 system

On etudie par diffraction RX l'evolution des phases cristallines lors de la cuisson a 650-1250 o C de compositions du systeme ZrO 2 −V 2 O 5 −SiO 2 et la reactivite de la cristobalite preparee avec la phase ZrO 2 monoclinique

Cobalt aluminate spinel-mullite composites synthesized by sol-gel method

Abstract CoAl 2 O 4 spinel-mullite composites were prepared by double substitution of Al by Ti and Ni in stoichiometric 3:2 mullite. Gels with compositions 3(Al 2 − 2 x Co x Ti x O 3 )·2SiO 2 (x = 0.025, 0.05 and 0.2) and 3(Al 2 − 2 x M x O 3 )·2SiO 2 (x = 0.05; M = Co 2+ or Ti 4+ ) were synthesized by sol-gel techniques. The structure of the gels was investigated by infra-red spectroscopy. Heating gels at 750 °C produced an amorphous silicoaluminate network. The reaction sequence was investigated by differential thermal analysis, X-ray diffraction and ultraviolet-visible spectroscopy. All samples crystallized at temperatures lower than 1000 °C from the amorphous state. Al-Si spinel and/or …

A step forward in the development of superoxide dismutase mimetic nanozymes: the effect of the charge of the surface on antioxidant activity

Two binucleating hezaaza macrocycles containing a pyridinol spacer have been prepared and characterised. Protonation studies indicate the deprotonation of the phenol group at relatively low pH values with the concomitant occurrence of a keto-enolic equilibrium. These ligands readily form binuclear Cu2+ and Zn2+ complexes as denoted by potentiometric and spectroscopic studies. The binding of the metals yields to the ready deprotonation of the phenol with the stabilisation of the keto form that results in complexes of greater stabilities than the analogous ones containing pyridine as spacer instead of pyridine. Mixed Cu2+–Zn2+-complexes were also detected in aqueous solutions containing equim…

Effect of MgO/CaO ratio on the microstructure of cordierite-based glass-ceramic glazes for floor tiles

Abstract The effect of the MgO/CaO ratio on the microstructure and microhardness of cordierite-based glass-ceramic glazes was studied. For this purpose glasses, with compositions in the cordierite primary phase field of the CaO–MgO–Al 2 O 3 –SiO 2 quaternary system and, with different MgO/CaO ratios, were prepared by melting. Glass powder pellets pressed under low pressure were fast heated at several temperatures simulating industrial floor-tile processing, and characterized by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM) and energy dispersive X-ray emission spectroscopy (EDX). The studied glasses crystallized α-cordierite as the only crystalline phase…

Phase evolution by thermal treatment of equimolar cobalt–magnesium cordierite glass powders

Abstract The structural evolution with annealing time at temperatures between 900 and 1100 °C of loosely compacted equimolar cobalt–magnesium cordierite glass powder was reported. The glass, with composition MgCoAl4Si5O18, was prepared by melting a glass precursor, previously synthesized by a semiwet method, at 1650 °C. Field emission scanning electron microscopy (FESEM) of isothermally heated glasses at 900 and 950 °C revealed increased phase separation with thermal treatment. X-ray diffraction (XRD) results of these powders indicated that the first crystalline phase formed was μ cobalt-containing cordierite which transformed to α cordierite with longer annealing. At the beginning of the μ…

Synthesis and characterization of praseodymium-containing ZrSiO4 solid solutions from gels

Abstract The preparation and characterization of a series of praseodymium–zircon solid solution (Prx–ZrSiO4) materials with increasing nominal amounts of Pr is reported. Pr-doped zircon gels were prepared by gelling mixtures of zirconium n-propoxide, praseodymium acetylacetonate and tetraethylorthosilicate, and annealed over the range of temperature up to the formation of Pr–zircon solid solutions. The reaction sequence was followed by X-ray powder diffraction (XRD), ultraviolet–visible diffuse reflectance (DR) and infrared spectroscopy (IR). The first crystalline phase detected on annealing gels was a tetragonal praseodymium-containing ZrO2 phase (t-Pr–ZrO2). On further annealing, the subs…

Naphthalene-containing polyamines supported in nanosized boehmite particles

Boehmite nanoparticles with covalently linked polyamine chains functionalized with naphthalene fluorophores have been prepared and characterized. The characterization of the materials by elemental microanalysis, X-ray powder diffraction, MAS 29Si NMR and electron microscopy unambiguously prove that the covalent anchorage had occurred. Steady-state fluorescence emission studies show that the luminescent properties of the modified nanoparticles are sensitive to changes in concentration of hydrogen ions, metal ions and anionic nucleotides such as ATP. The behaviour of the attached materials in aqueous solution is parallel to the behaviour of the single fluorophoric polyamines. Comparisons are …

Electrochemical characterization of cobalt cordierites attached to paraffin-impregnated graphite electrodes

The electrochemistry of α, β and μ cobalt-containing cordierites (Co2Al4Si5O18) attached to paraffin-impregnated graphite electrodes has been studied by linear scan and cyclic voltammetries in HCl+NaCl and NaOH electrolytes. This electrochemistry is compared with that of vitreous cobalt cordierite, cobalt(II) oxide and cobalt spinel aluminate (CoAl2O4), the two last taken as reference materials. Electrochemical processes involve the site-characteristic reduction of Co(II) species to cobalt metal near to −0.5 V vs. SCE and their oxidative dissolution near +0.3 V, accompanied by solid state interconversion between Co(II) and Co(III) at potentials above +0.45 V. Cordierite-modified electrodes …

Ni-containing spinel aluminates glass-ceramic materials obtained from cordieritic bulk glasses

Monolithic glasses with compositions 2MO � 2Al2O3 � 5SiO2, being M ¼ Ni and equimolar mixtures of Ni and Mg, were prepared at 1650 C by melting mixtures of raw materials. The crystallization of monoliths was produced by heattreatment at several temperatures up to 1200 C. The crystallization sequence was followed by differential thermal analysis (DTA), X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM) and energy dispersive X-ray (EDX) and diffuse reflectance spectroscopies. Surprisingly, the only crystalline phase formed after heating up to 1100 C was a nickel-containing aluminate spinel for both compositions. The microstructural characterization indicated t…

Synthesis and characterization of V2O5SiO2ZrO2 pigments by sol-gel method

Abstract Polymeric gels in the V2O5 SiO2 ZrO2 system were prepared from tetraethylorthosilicate (TEOS), zirconium(IV)-n-propoxide and vanadium(IV) oxyacetylacetonate, precursors. The effects of prehydrolysis time of TEOS and drying gel method on the stabilization of tetragonal zirconia in the silica amorphous matrix, nucleation and growth of the zircon (ZrSiO4) phase, and stabilization of the blue and green stains of vanadium zircon were studied. Results provide evidence that long time of prehydrolysis and fast drying do not favour zircon crystallization but stabilize the tetragonal zirconia in the amorphous matrix.

Grafted squaramide monoamine nanoparticles as simple systems for sulfate recognition in pure water.

New simple systems formed by a chain containing a squaramide function and a quaternised amine group attached to boehmite or silica-coated boehmite nanoparticles are able to discriminate anions in pure water.

Mechanism of crystallization of Co-cordierites from stoichiometric powdered glasses

Abstract The influence of cobalt, as a divalent cation, on the crystallization behaviour of the cordierite based glasses was studied. Powdered glass specimens of stoichiometric composition 2MO 2Al 2 O 3 5SiO 2 (M=Co and/or Mg) were obtained and thermally treated at several temperatures and times, and the sequence of crystallization and their microstructural evolution were analysed by X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). Results on the crystallization sequence showed that the steps in the crystallization path are independent of the nature of the divalent cation. The first crystalline phase detected displayed the μ-cordierite structure, i.e. a solid…

Electrochemical characterization of praseodymia doped zircon. Catalytic effect on the electrochemical reduction of molecular oxygen in polar organic solvents

The voltammetry of microparticles and scanning electrochemical microscopy methodologies are applied to characterize praseodymium centers in praseodymia-doped zircon (PrxZr(1−y)Si(1−z)O4; y + z = x; 0.02 < x < 0.10) specimens prepared via sol–gel synthetic routes. In contact with aqueous electrolytes, two overlapping Pr-centered cathodic processes, attributable to the Pr (IV) to Pr (III) reduction of Pr centers in different sites are obtained. In water-containing, air-saturated acetone and DMSO solutions as solvent, PrxZr(1−y)Si(1−z)O4 materials produce a significant catalytic effect on the electrochemical reduction of peroxide radical anion electrochemically generated. These electrochemical…

Spinel-mullite composites with optical properties

The aim of this paper was to study the synthesis and characterization of spinel-containing mullite based materials, using sol-gel techniques. Several gels were prepared, with nominal compositions 3(Al2−2xMx TixO3)·2SiO2 and 3(Al2−xMxO3)·2SiO2, with M=Ni+2 or Co+2 and 0.0≤x≤0.2, by hydrolysis and condensation of mixtures of aluminum, silicon and titanium alkoxides and nickel chloride. Dried gels were homogeneous and displayed a glass transition at around 750°C, which indicated that the system could be described as an amorphous silicoaluminate network.

Synthesis, Characterization of FexZr1-xO2Solid Solution Nanoparticles and Bulk Powders Prepared Using a Sol-Gel Technique

Vanadium‐Doped Zircon and Zirconia Materials Prepared from Gel Precursors as Site‐Selective Electrochemical Sensors

Abstract Polymer film electrodes incorporating vanadium‐doped zircon (V x ZrSiO4, 0.00 < x < 0.10) and vanadium‐doped monoclinic and tetragonal zirconias (V x ZrO2, 0.00 < x < 0.15), prepared by heat treatment of gel precursors, exhibit a significant site‐selective electrocatalytic activity towards the oxidation of amino acids, polyalcohols, and polyhydroxycarboxylic acids in alkaline media. Catalysis of the oxidation of carboxylate and alcohol groups involves a relatively slow chemical reaction between the substrate and vanadium centers, while the oxidation of thiolate in cysteine can be attributed to the oxidation of an adduct formed by vanadium centers and the substrate.

Chromium oxide nanoparticles with controlled size prepared from hydrothermal chromium oxyhydroxide precursors

Abstract This work reports the preparation of morphologically well-defined chromium oxide nanoparticles with controlled sizes of 20–30 nm. The synthetic procedure encompass two stages, the first one refers to the preparation of chromium oxyhydroxide nanoparticles by a hydrothermal approach of previously precipitated xerogels, followed by a thermal transformation of CrOOH nanoparticles to Cr2O3. The series of chromium oxyhydroxide particles sized over the range 15–50 nm were prepared through the control of the pH of precipitation of the xerogels and the water/xerogel ratio of the hydrothermal aging. Results showed the formation of non-aggregated oxyhydroxide nanoparticles with two different …

Comparative X-ray diffraction study of the crystalline microstructure of tetragonal and monoclinic vanadium–zirconium dioxide solid solutions produced from gel precursors

The microstructural characteristics of solid solutions, prepared by heating dried gel precursors with nominal compositions VxZr1−xO2(0 ≤x≤ 0.1) at 723 and 1573 K, were determined from X-ray diffraction patterns. The crystalline microstructure of the resulting specimens, characterized by a prevalent crystallite shape, a volume-weighted crystallite size distribution and a second-order lattice strain distribution, was found to depend on the vanadium content. A characteristic feature of all size distributions was their bimodality, explained as a result of transformations between tetragonal and monoclinic phases during thermal treatment. A comparative study of the microstructure of both zirconia…

Synthesis of Uvarovite Garnet

A garnet with interesting optical properties is synthesized by means of the ceramic method and the formation of gels. Colloidal silica or tetraethoxysilane (TEOS) is used as a starting reagent in the latter method of synthesis, together with nitrate and chloride salts of the remaining components. Use is made of ultraviolet-visible and infrared spectroscopy techniques and X-ray diffraction in studying the evolution of the system. Formation of the garnet phase at lower temperatures is observed when using the gel methods, as well as the absence of chromates during the process in the samples which contained chlorides.

Effect of TiO2 on the mullite formation and mechanical properties of alumina porcelain

Abstract The effect of adding TiO 2 to standard alumina porcelain on its microstructure and flexural strength was investigated. A series of alumina porcelain bodies containing increasing amounts of TiO 2 were prepared by extruding mixtures of raw materials and TiO 2 . Porcelain rods were fired under industrial scheduling in a manufacturing kiln. The overall degree of crystalline and amorphous phase content within the porcelain bodies was quantitatively determined using a Rietveld analysis. Results indicated a higher amount of mullite formation in porcelain bodies containing TiO 2 . Examination of the product materials using field emission scanning electron microscopy showed a high density o…

Synthesis of V-ZrSiO4 solid solutions

This letter describes the results of the preparation of V-ZrSiO 4 solid solutions from a sol or alkoxide and solute salts. This technique allows a greater degree of product formation to be achieved at lower temperatures, as well as the possibility of studying the characteristics of possible solid solutions

Lanthanide complexes as imaging agents anchored on nano-sized particles of boehmite

International audience; The synthesis of boehmite nanoparticles modified with lanthanides (Eu, Tb and Gd) is described. Their synthesis, characterization and in vitro assays with HeLa cells were performed. The nuclear magnetic relaxation dispersion (NMRD) profiles of the two chelating moieties were studied. Imaging data from laser scanning confocal fluorescence microscopy and flow cytometry revealed that the nanoscaffolds were taken up by the cells, distributed throughout the cytoplasm and showed no toxicity. This platform could represent an alternative to silica-based inert matrices as imaging vehicles.

Study of solid state kinetics using voltammetry of immobilized particles. Application to tetragonal to monoclinic transition in nanoparticulate zirconia and praseodymia-doped zirconia

Abstract The voltammetry of immobilized particles methodology is applied to study solid state reaction kinetics on the basis of the electrocatalytic ability of solids toward selected electrochemical processes. Measurement of the time variation of catalytic current for oxygen evolution reaction in aqueous alkaline media provides a direct estimate of fractional conversion of the reactant in the course of the reaction for testing different reaction kinetic models. This methodology is applied to analyze the formation of monoclinic zirconia and praseodymia-doped zirconia from tetragonal precursors. Discrimination between competing and successive reactions mechanisms is obtained for reactions inv…

Rietveld refinement study of vanadium distribution in V+4–ZrSiO4 solid solutions obtained from gels

Abstract Vanadium-containing zircon gel precursors with nominal compositions Vx–ZrSiO4 with x=0.0, 0.004, 0.01, 0.04 and 0.2 were prepared by a previously reported colloidal sol-gel technique and annealed for 30 h at 1400 °C. The Rietveld refinement of the structures by X-ray powder diffraction confirms previous results concerning the limit of solubility of V+4 in the zircon structure. The new finding regarding with the entry of V+4 in the Zr+4 site for zircon doped with high contents of vanadium is in accordance with reported results.

Mesocrystalline Cr and Sb-codoped anatase visible-light-driven photocatalyst

Abstract We report on the synthesis, characterization and visible-light-driven photocatalytic activity of mesocrystalline Cr- and Sb-codoped anatase nanoparticles. Discrete and morphologically well-defined assemblies of anatase nanoparticles sized below 100 nm × 50 nm were prepared by hydrothermal aging of aqueous solutions containing titanium alkoxide, chromium acetylacetonate, antimony acetate and triethanolamine (TEOA) as stabilizer. The as-prepared and TEOA-free doped nanoparticles showed similar crystallographic parameters and spectroscopic features. The incorporation of Cr and Sb dopant cations into the anatase nanoparticles was evaluated by Rietveld refinement of X-ray diffraction pa…

Evolution of the structural and optical properties from cobalt cordierite glass to glass-ceramic based on spinel crystalline phase materials

Co 2+ -containing cordierite stoichiometric glasses have been prepared by melting colloidal gel precursors. After controlled thermal processing in the range of temperatures between 900 and 1300 C different polycrystalline, almost single phase materials displaying l-, a-, and b-cordierite crystalline forms were synthesized. In addition, spinel glass-ceramic materials were also prepared from the base glasses. All these materials were characterized by X-ray powder diffraction and infrared spectroscopy. Room temperature (RT) absorption and emission spectra of Co 2+ – cordierites and – spinel-glass material have allowed determining the local environment of the Co 2+ in the crystalline structure …

Hydrothermal-mediated synthesis of orange Cr, Sb-containing TiO 2 nano-pigments with improved microstructure

Abstract A hydrothermal-mediated via was developed to prepare discrete, non-aggregated Cr,Sb-doped rutile nano-pigments. After annealing the Cr- and Sb-containing TiO2 anatase nanocrystals obtained by hydrothermal aging the nano-pigments Cr,Sb-TiO2 were characterized with the aid of X-ray diffraction (XRD) including lattice parameter and crystallite size determination, Raman spectroscopy, field emission scanning and transmission electron microscopies (FESEM and TEM, respectively) including energy-dispersive X-ray (FESEM/EDX) spectroscopy, high resolution transmission electron microscopy (HRTEM) including selected area electron diffraction (SAED), ultraviolet–visible diffuse reflectance (UV–…

Mesocrystalline anatase nanoparticles synthesized using a simple hydrothermal approach with enhanced light harvesting for gas-phase reaction

Mesocrystalline TiO2 nanoparticles were synthesized using a hydrothermal approach. A simple two-step procedure at low temperature (<140 °C) allowed the nucleation of primary particles sized 2–4 nm and their subsequent assembly as almost spherical aggregates sized ≈20 nm. X-ray powder diffraction (XRD), Raman and X-ray photoelectron spectroscopy (XPS) studies, and HRTEM studies confirmed anatase as the unique TiO2 crystalline phase. The mesocrystalline structure of the anatase aggregates was clearly evidenced by HRTEM and SAED results. The mesocrystalline nanopowders exhibit a mesoporous structure with a surface area and pore volume of 63.5 m2 g−1 and 0.22 cm3 g−1, respectively. Ultraviolet …

Synthesis and Characterization of Iron-Doped ZrSiO4 Solid Solutions from Gels

The mechanism of formation and the structural features of tetragonal Fe–ZrO2-amorphous silica composites and particulated Fe-doped ZrSiO4 solid solutions were studied. A series of specimens with compositions Fex–ZrSiO4, 0 ≤ x ≤ 0.10 were prepared by sol–gel techniques and thermally annealed over the range of temperature between 400°C and 1600°C. Results confirmed the formation of tetragonal Fe–ZrO2 solid solution as first crystalline phase on the whole process leading to Fe-doped ZrSiO4 solid solution. The annealing temperature for the preparation of Fe-containing ZrSiO4 solid solutions was dependent on the nominal amount of iron. The Fex–ZrSiO4 solid solutions, with 0.02 < x < 0.08, were a…

Reaction Sequence in the Preparation of NiAl2O4 Spinel-Mullite Composites by Sol-Gel

NiAl 2 O 4 spinel-mullite composites were prepared by simultaneous replacement of Al by Ti and/or Ni in 3:2 stoichiometric mullite. Specimens having nominal compositions 3(Al 2-2x Ni x Ti x O 3 ).2SiO 2 (x = 0, 0.025, 0.05, 0.2) and 3(Al 2-x M x O 3) .2SiO 2 (M = Ni 2+ or Ti 4+ and x = 0.05) were synthesized by sol-gel techniques, which provide homogeneous gels in the SiO 2 -Al 2 O 3 system. Gel structures investigated by infrared (IR) spectroscopy revealed the formation of Al-O-Si bonds in dried gels. The reaction sequence of gel-derived glasses, previously obtained by preheating gels at 750°C for 3 h, was evaluated by X-ray powder diffraction (XRD) and ultraviolet-visible (UV-vis) spectro…

Boehmite Supported Pyrene Polyamine Systems as Probes for Iodide Recognition

New organic–inorganic fluorescent probes made by attaching the tripodal polyamine (tris(2-aminoethyl))amine (tren), propylamine, or diethylenetriamine functionalized with pyrene as a fluorophore to an γ-aluminum oxohydroxide matrix have been prepared and studied both in solution and supported on the surface of boehmite nanoparticles. Both kinds of systems have been revealed as sensitive and selective fluorescence turn-off chemosensors for iodide in aqueous solution with an estimated detection limit that reaches 36 ppb. The recognition characteristics and photophysical properties of these molecules are essentially preserved when they are grafted to the surface of the particles. Since the nan…

Tuning the size and shape of nano-boehmites by a free-additive hydrothermal method

A synthetic procedure allowing the control of boehmite micro and nanoparticles is presented. The proposed hydrothermal synthetic procedure is based on the control of three reaction parameters, the pH and temperature of precipitation of xerogels and the water/xerogel ratio for the hydrothermal process, carried out at 200 °C for 48 h. Results obtained by measurements on transmission electron microscopy (TEM) images indicate that at pH 5 micro or nanorods of controlled length between ca. 300 and 50 nm were obtained depending on the temperature of precipitation of the xerogel (25 or 100 °C) and the water/xerogel ratio used (1/1, 6/1, 15/1). On the contrary, at pH 10, nanoplatelets with major ba…

An X-ray powder diffraction study of the microstructural evolution on heating 3:2 and 2:1 mullite single-phase gels

Single-phase gels with compositions 3Al2O3·2SiO2 and 2Al2O3·SiO2 were prepared by gelling mixtures of aluminium nitrate and tetraethylorthosilicate. Gels were fast heated at different temperatures between 900°C and 1600°C. The phase transformation and microstructural changes of both mullite precursor gels over the temperature range were followed by X-ray powder diffraction (XRD), lattice parameter determination (LP), and scanning and transmission electron microscopies (SEM and TEM). The distribution of crystallite sizes and strains were determined by linewidth refinements of X-ray diffraction patterns using the integral breadth method of Langford and the Warren-Averbach analysis. XRD of bot…

Electrochemical Detection of High Oxidation States of Chromium( IV and V ) in Chromium‐Doped Cassiterite and Tin‐Sphene Ceramic Pigmenting Systems

Solid-state electrochemistry is applied to detect the presence of chromium centres with high oxidation states in chromium-doped cassiterite and tin-sphene ceramic pigmenting systems. Voltammetric data indicate that CrV and CrIV centres with different coordinative arrangements exist in the studied materials, and yield proton-assisted reduction processes at +0.95, +0.42 AgCl/Ag in contact with 0.50 M H2SO4. Electrochemical measurements are correlated with spectroscopic data. The CrIV and CrV metal ions display a significant light-driven electrocatalytic effect on the oxidation of 1,4-dihydrobenzoquinone and Fe(CN)64– ions that involves the formation of surface-confined adducts. (© Wiley-VCH V…

Structural Evolution and Vanadium Distribution in the Preparation of V4+-ZrSiO4 Solid Solutions from Gels

Vanadium-containing ZrSiO4-gel precursors with nominal compositions Vx-ZrSiO4 with x= 0.0, 0.002, 0.004, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.1, and 0.2 were prepared using a previously reported procedure and thermally treated over a range of temperature up to the formation of the V4+-ZrSiO4 solid solution. The structural evolution and the V4+ location and its homogenous distribution were followed using powder X-ray diffractometry and electron spin resonance spectroscopy (ESR). Our experiments showed that a tetragonal form of V4+-ZrO2 was the first crystalline phase obtained on heating the gels. On further heating, a phase transformation to the monoclinic form of V4+-ZrO2 took place. Final…

Thermal evolution and structural study of 2:1 mullite from monophasic gels

Abstract Single phase mullite gels with composition 2Al 2 O 3 ·SiO 2 (2:1) were prepared by the slow hydrolysis method using aluminium nitrate nonahydrate and tetraethylorthosilicate as reagents. The evolution to mullite from gels was studied by infrared (IR) spectroscopy and X-ray diffraction (XRD). Gels thermally treated under fast schedules showed mullite formation below 900 °C. Compositional and microstructural changes in 2:1 mullites through the range of temperature from 900 to 1600 °C were determined by the measurement of lattice parameters and field emission scanning electron microscopy. The alumina-rich mullites formed at low temperatures become almost the nominal 2:1 at 1600 °C. Th…

New sensing devices part 1: indole-containing polyamines supported in nanosized boehmite particles

The synthesis, characterisation and optical properties of new sensing systems made by attaching different polyamine chains functionalised with an indole fluorophore to a boehmite matrix is reported for the first time. Firstly, a family of tri(alkoxy)alkylpolyaminosilanes have been reacted with indole-3-carboxaldehyde to form the corresponding Schiff bases which were reduced with sodium borohydride. The anchoring to the surface of the boehmite nanoparticles was carried out by reacting the precursors with the hydroxyl groups available in the surface of the support. The characterisation of the materials by elemental microanalysis, X-ray powder diffraction, CP-MAS 29Si NMR and electron microsco…

Microstructure of Fe–ZrSiO4 solid solutions prepared from gels

Abstract Microstructural changes associated with chemical and structural evolution from gels to Fe x –ZrSiO 4 solid solutions are reported. Mineralizer-free Fe x –ZrSiO 4 gels in the compositional range 0 ≤  x  ≤ 0.15 were prepared by sol–gel liquid-phase route from mixtures of alkoxides of silicon and zirconium, and iron (III) acetylacetonate, and annealed at different temperatures and/or times. The first step on the whole process to the final Fe x –ZrSiO 4 solid solutions was the formation of aggregated of tetragonal Fe-doped ZrO 2 nanocrystals with diameters smaller than 50 nm. At this stage the tetragonal Fe–ZrO 2 were embedded in amorphous silica resulting nanocomposite materials. The …

Synthesis and photophysical properties of dansyl-based polyamine ligands and their Zn(II) complexes

The synthesis, potentiometric studies and photophysical properties of two new polyamine ligands (L1 and L2) possessing the dansyl chromophore were studied in aqueous 0.15 M NaCl. The compounds show the absorption and emissions bands characteristic of the dansylamide fluorophore and both present intramolecular excited state proton transfer at intermediate pH ranges. One of the ligands (L2) strongly coordinates Zn(II) leading to fluorescence quenching. A model compound (L3) of the dansyl moiety was also investigated. http://www.sciencedirect.com/science/article/B6TG5-4MB4DV1-2/1/45cafbcee9a8df7daddd765512437ca3

V-containing ZrO2 inorganic yellow nano-pigments

In this work we report new results on the preparation, characterization and color properties of the inorganic yellow nano-pigmenting system based on monoclinic V–ZrO2 solid solution nanoparticles. The series of solid solution nanopowders were obtained by a polyol technique where the precipitates, obtained after heating at 180 °C ethylene glycol solutions of vanadyl acetonate and zirconium n-propoxide, were annealed at different temperatures up to 1300 °C for a short duration, in order to improve their crystallinity and control the crystalline form of the final nanoparticles. On annealing at around 450 °C highly crystalline tetragonal V-containing zirconia particles were developed, which tra…

The stoichiometry of blue vanadium doped zircon obtained by sol-gel methods

Abstract In this study, Sol-Gel processes in aqueous solution were used to investigate the stoichiometry of the V/1bZrSiO 4 solid solutions achieved by this method. Compositions with a formal stoichiometric defect in: (a) ZrO 2 ([ZrO 2 ] 1−2x [SiO 2 ] [V 2 O 5 ] x ), and (b) in SiO 2 ([ZrO 2 ] [SiO 2 ] 1−2x [V 2 O 5 ] x ), x=0.02, 0.04, 0.05 and 0.10 have been prepared. X Ray Diffraction analyses in fired samples (1200°/3 days) showed that cristobalite and monoclinic zirconia appear as residual crystalline phase in (a) and (b) compositions respectively, except in sample (a) with x=0.02 in which no residual phase was detected and therefore is considered stoichiometric. This sample and sample…

V-containing ZrO 2 inorganic yellow nano-pigments prepared by hydrothermal approach

Abstract Recent results on the preparation, characterization and color properties of the V-containing ZrO 2 inorganic yellow nano-pigment are reported. A series of monoclinic V-ZrO 2 solid solution nanocrystals (V x Zr 1-x O 2 , being x = 0, 0.1, 0.02, 0.03, 0.04, 0.05, 0.065, 0.08 and 0.1) were prepared straightforward by hydrothermal processing of mixtures of zirconyl nitrate and ammonium metavanadate in water. Interestingly, the crystalline precipitated obtained by hydrothermal processing at 140 °C for 3 d was almost entirely V-containing ZrO 2 nanocrystals with the structure of monoclinic zirconia for the whole range of compositions. Lattice parameters changes along the series of prepar…

Fluorescent Type II Materials from Naphthylmethyl Polyamine Precursors

Speciation studies in aqueous solution on the interaction of Cu2+ and Zn2+ with a series of polyaminic ligands N-naphthalen-1-ylmethyl-N′-{2-[(naphthalen-1-ylmethyl)-amino]-ethyl}-ethane-1,2-diamine (Ll), N-naphthalen-1-ylmethyl-N′-(2-{2-[(naphthalen-1-ylmethyl)-amino]-ethylamino}-ethyl)-ethane-1,2-diamine (L2) and N-naphthalen-1-ylmethyl-N′-[2-(2-{2-[(naphthalen-1-ylmethyl)-amino]-ethylamino}-ethylamino)-ethyl]-ethane-1,2-diamine (L3) containing two naphthylmethyl groups at their termini and N 1-(2-{2-[(naphthalen-1-ylmethyl)-amino]-ethylamino}-ethyl)-ethane-1,2-diamine (L4) containing just one naphthylmethyl group have been carried out at 298.1 K in 0.15 mol dm−3 NaCl. In the case of the …

Thermal stability of transition alumina nanocrystals with different microstructures

Abstract The preparation of well-crystallized boehmite nanoparticles with different morphologies, encompassing from aciculae or rods of 320, 150 and 70 nm of length to platelets of 50 nm in diameter, allowed a comparative study of their respective thermal evolutions as alumina precursors. Static thermal treatments of boehmite nanocrystals at 600, 1000 and 1200 °C and a dynamic, in situ synchrotron study between 100 and 1000 °C revealed that original boehmite microstructures, i.e. size and shape of the nanoparticles, were kept not only in γ-Al 2 O 3 but also in transitional aluminas up to 1000 °C. Specifically, at that temperature, acicular samples presented θ-Al 2 O 3 structure, while in pl…

Effect of thermal treatment on the structural evolution of 3:2 and 2:1 mullite monophasic gels

Abstract Single phase mullite gels with composition 3Al2O3 · 2SiO2 (3:2) and 2Al2O3 · SiO2 (2:1) were prepared by the semialkoxide method using aluminum nitrate nonahydrate and tetraethylorthosilicate as reagents. The influence of the thermal processing conditions on the reaction sequence was investigated. Both 3:2 and 2:1 mullite gels formed orthorhombic mullite under fast heating (40 °C/min) at 900 °C. Slow heatings delayed the formation of mullite in both gel compositions but no formation of spinel was detected between 1000 °C and 1100 °C. The slow transformation of pentacoordinated aluminum to octahedral and tetrahedral arrangements probably depends on the larger size and extent of the …

Effect of NiO and/or TiO2 mullite formation and microstructure from gels

Polymeric and colloidal gels with a constant molar ratio of (Al+Ni and/or Ti)/Si=3/1 and various (Al/Ni and/or Ti) ratios (up to 21.42 mol% NiO+TiO2) were prepared and used to study the effect of the precursor chemical homogeneity on mullite formation processes and the resulting microstructure. Both kinds of gel precursors were preheated at 750°C for 3 h in order to obtain appropriate gel-derived glasses for further thermal processing. After annealing for several time periods at temperatures between 750 and 1500°C, differences in crystallization pathways were observed. Polymeric gels crystallized Al–Si and NiAl2O4 spinels from the amorphous form at temperatures in the range between 900 and …

Electrochemistry of Iron-Doped Zircon and Zirconia Materials and Electrocatalytic Effects on Nitrite Oxidation and Reduction

Crystalline microstructure of boehmites studied by multi-peak analysis of powder X-ray diffraction patterns

Nanocrystalline boehmite (gamma-aluminium-oxyhydroxide) is a material of industrial importance, the functionality of which follows from its crystalline microstructure. A procedure for preparing boehmite nanoparticles, comprising the formation of a precipitate by the alkalization of an aqueous solution of aluminium nitrate and subsequent hydrothermal aging, was previously elaborated. The application of an additive (maltitol or tartaric acid) to control the sizes and shapes of crystallites in the produced polycrystalline powder of boehmite was developed. The aim of this work is a study of the effect of the hydrothermal treatment time on nanocrystalline characteristics of boehmite, both in abs…

X-ray powder diffraction study of monoclinic V4+-ZrO2 solid solutions obtained from gels

Abstract Rietveld refinement of six monoclinic V x Zr 1− x O 2 solid solutions, with x =0, 0.01, 0.02, 0.05, 0.075 and 0.1, prepared by heating dried gel precursors at 1300°C in air atmosphere, has been characterized using X-ray powder diffractometer data. The present results confirm that crystal structure of these solid solutions contain V 4+ (Zr 4+ ) cations surrounded by seven oxygens, four at a distance between 2.13 and 2.28 A (referred as to O(2) in the tetrahedrally coordinated oxygens) and other three at a distance between 2.03 and 2.20 A (denoted as O(1) in the triangularly coordinated oxygens). The trends in the lattice parameter variation of V x Zr 1− x O 2 solid solutions specime…

Mechanism of Formation of TiO2-Doped Mullites from Heated Single-Phase Gels Investigated by Structural and Microstructural Parameters

An analysis of the microstructure of TiO 2 -doped mullites prepared from monophasic gels thermally treated in the temperature range 900°-1600°C is reported. Two series of gels with nominal compositions 3(Al 2-x Ti x O 3 ) ·2(SiO 2 ) and 2(Al 2-x Ti x O 3 )·(SiO 2 ), in the range 0≤x≤0.15, were prepared. X-ray powder diffraction (XRD) and scanning electron microscopy (SEM) were used to follow the structural and textural evolution from gels to the final doped mullites. The crystallite sizes and microstrains were determined by linewidth refinements of XRD patterns using the integral breadth method of Langford and the Warren-Averbach analysis. XRD patterns showed the formation of Al 2 TiO 5 and…

Electrocatalysis of the oxidation of methylenedioxyamphetamines at electrodes modified with cerium-doped zirconias

The catalytic effect of monoclinic and tetragonal cerium-doped zirconias (m-CexZr1−xO2 and t-CexZr1−xO2, 0<x<0.10, respectively), prepared from gel precursors, on the oxidation of methylenedioxyamphetamine (MDA) and methylenedioxymetamphetamine (MDMA) at pH 7.0 has been studied. Upon attachment of synthetic specimens to polymer film electrodes, an oxidation peak near to +1.05 V vs AgCl/Ag appears that is unaffected by chloride ions and common interfering compounds, namely, dopamine, norepinephrine and ascorbic acid. The catalytic effect appears to be strongly influenced by crystallinity of specimens and coordination of cerium, increasing from the amorphous starting material to t-CexZr1−xO2 …

Microstructural Evolution from Praseodymium-Containing Zircon Gels to Prx-ZrSiO4 Solid Solutions

Structural evolution and coupled microstructural transformations occurred on annealing mineralizer-free Pr-containing ZrSiO4 gels up to final praseodymium-doped zircon yellow pigments are reported. Gels with nominal compositions Prx-ZrSiO4, 0 ≤ x ≤ 0.125, were prepared from mixtures of zirconium and silicon alkoxides and praseodymium acetylacetonate. Crystallization pathway and microstructural changes of thermally treated dried gels were followed by infrared spectroscopy, X-ray diffraction, field emission scanning and transmission electron microscopies, respectively. Results indicated that the crystallization pathway through the whole process of final Prx-ZrSiO4 solid solutions formation di…

Mechanism of crystallization of pyroxene-based glass-ceramic glazes

Abstract The mechanism of crystallization of a powdered glass with composition in the pyroxene crystallization primary field within the CaO–MgO–Al 2 O 3 –SiO 2 quaternary system and containing some additives was studied. The crystallization sequence was compared with that from the same base glass without additives. After a short thermal anneal both powdered glasses showed phase separation. Further thermal treatment gave rise to the crystallization of pyroxene. Anorthite as secondary crystalline phase was also detected in the quaternary glass (without additives). The starting crystallization in the glass with additives took place in the outer surface of glass particles probably in the immisc…

Solubility and microstructural development of TiO2-containing 3Al2O3·2SiO2 and 2Al2O3·SiO2 mullites obtained from single-phase gels

Abstract The interdependence of the titanium oxide amount and the anisotropic growth of mullites prepared from single-phase gels were investigated. Gels with stoichiometries 3(Al2−xTixO3)·2(SiO2) and 2(Al2−xTixO3)·(SiO2), with 0 ≤ x ≤ 0.15 were prepared by the semialkoxide method. Gels and specimens heated at temperatures between 1200 and 1600 °C were characterized by using infrared spectroscopy (IR), X-ray diffraction (XRD) and transmission and field emission scanning electron microscopies (TEM and FESEM). Al2TiO5 as minor impurity was detected in both series of mullites for gel precursor compositions x = 0.10 and x = 0.15, obtained at temperatures between 1200 and 1600 °C. Variations of l…

Mechanism of crystallization of fast fired mullite-based glass–ceramic glazes for floor-tiles

Abstract The mechanism of crystallization from a B 2 O 3 -containing glass, with composition based in the CaO–MgO–Al 2 O 3 –SiO 2 system, to a glass–ceramic glaze was studied by different techniques. Glass powder pellets were fast heated, simulating current industrial tile processing methods, at several temperatures from 700 to 1200 °C with a 5 min hold. Microstructural study by field emission scanning electron microscopy revealed that a phase separation phenomenon occurred in the glass, which promoted the onset of mullite crystallization at 900 °C. The amount of mullite in the glass heated between 1100 and 1200 °C was around 20 wt%, as determined by Rietveld refinement. The microstructure …

Low-temperature metastabilization of tetragonal V+4-containing ZrO2 solid solutions

Abstract The formation and characterization of tetragonal vanadium–zirconia solid solutions with different vanadium contents have been investigated. Vanadium–zirconia precursors were prepared by gelling mixtures of zirconium n-propoxide and vanadyl acetylacetonate, and studied over the range of temperature up to the tetragonal–monoclinic phase transformation. The formation of the tetragonal phase has been investigated by X-ray powder diffraction (XRD). It was found that it took place after annealing around 450°C for all specimens independently of the vanadium loading. In contrast, the temperature for the subsequent tetragonal to monoclinic transformation was dependent on the nominal vanadiu…

Pyroxene-based glass-ceramics as glazes for floor tiles

Abstract Crystallization of a glass with composition in the diopside primary crystallization field in the MgO–CaO–Al 2 O 3 –SiO 2 quaternary system was investigated. Also the action of some additives, nucleants and fluxes, in the pyroxene development was examined. Glasses were prepared by conventional melting of a mixture of raw materials and cooled by pouring in water. Pellets of glass powder specimens were thermally treated at several temperatures up to 1200 °C. The crystallization path was followed by X-ray diffraction powder (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDX). The results proved that, in addition to the effect of B 2 O 3 and TiO 2 in…

Synthesis and coordination properties of an azamacrocyclic Zn(II) chemosensor containing pendent methylnaphthyl groups

The synthesis of a polyazamacrocycle constituted by two diethylenetriamine bridges functionalized at their central nitrogen with naphth-2-ylmethyl units and interconnected through 2,6-dimethylpyridine spacers (L1) is reported. The protonation behaviour of the new macrocycle in water and in water-ethanol 70/30 v/v mixed solvent has been examined by means of pH-metric, UV-Vis and steady-state fluorescence techniques. The fluorescence emission is slightly quenched following the deprotonation of the central tertiary amines and more deeply quenched upon deprotonation of the secondary amino groups. pH-Metric titrations show that in water-ethanol 70/30 v/v L1 forms stable mononuclear complexes wit…

Effect of additives on the crystallization of cordierite-based glass-ceramics as glazes for floor tiles

Abstract The effect of several additives such as fluxes and/or nucleants on a parent glass with composition located in the primary field of cordierite within the quaternary system CaO–MgO–Al 2 O 3 –SiO 2 has been examined. Crystallization path of glasses was determined by differential thermal analysis (DTA) and X-ray powder diffraction (XRD). Pressed pellets of powdered glasses containing different additives were submitted at thermal treatments up to 1200 °C. The microstructural development at several temperatures was followed by field emission scanning electron microscopy and energy-dispersive X-ray analysis. The results shown that additions of TiO 2 as nucleant and/or B 2 O 3 as flux to a…

Effects of ZrO2 precursors on the synthesis of V-ZrSiO4 solid solutions by the sol-gel method

The preparation of V-ZrSiO4 solid solutions starting from different ZrO2 precursors by using sol-gel methods is reported. The starting materials were hydrolysed and the dried gels were fired at a temperature between 500 and 900 °C with soaking times of 12h. The organic character of zirconia precursors was stronger, i.e. the starting material had more carbon atoms, a higher temperature was necessary to make the first crystalline phase appear (ZrO2(tetragonal)) and the temperature range for the whole phase transformation was narrower. In all dried gel samples the presence of infrared bands which might be associated with either Si-O-Zr or Si-O-V was not observed. On the other hand, some bands …

Enhancement of SOD activity in boehmite supported nanoreceptors

The binuclear Cu2+ complex of a pyridinophane polyamine ligand ranking amongst the fastest SOD mimetics so far reported displays a remarkable SOD activity enhancement when grafted to the surface of boehmite (γ-AlO(OH)) nanoparticles (BNPs).

Preparation and characterization of gels with garnet structure: A3B2C3O12, using ‘non-classical’ solvents

Abstract Synthesis and characterization of some crystalline garnets by sol-gel techniques is described. The effects of emthanol, dimethyl sulfoxide (DMSO), CH2Cl2 and toluene solvents on gelation of TEOS are considered. Multicomponent gel formation in systems with stoichiometries 3CaO·Cr2O3·3SiO2 and 3CaO·Al2O2 was studied using DMSO, a polar solvent, and toluene, an apolar solvent. The dried gel was thermally treated and the powder was characterized by X-ray diffraction, differential thermal analysis/thermogravimetric analysis and scanning electron microscopy.

Determination of hydrogen peroxide using glassy carbon and graphite/polyester composite electrodes modified by vanadium-doped zirconias

Abstract Synthetic monoclinic and tetragonal vanadium-doped zirconias (VZrO2) with vanadium loading ranging from 0.5 to 15 mol% are used to modify glassy carbon and graphite/polyester composite electrodes able to detect oxygen and hydrogen peroxide in neutral aqueous media. Electrodes modified by monoclinic VZrO2 decrease the overpotential for the reduction of oxygen and hydrogen peroxide in neutral and alkaline media and enhance their reduction currents with respect to unmodified carbon electrodes. This is associated to seven-coordinated vanadium centers isomorphously substituting zirconium ones in the ZrO2 lattice. The catalytic effect shows site-selectivity, since it is almost entirely a…

A New ZnIITweezer Pyridine-Naphthalene System - An Off-On-Off System Working in a Biological pH Window

Their basic idea consisted of the connec-tion of an amine to a fluorophoric anthracene unit on oneside and to a pyridine moiety on the other. At acidic pHvalues the amino and the pyridine groups are protonatedand a photoinduced electron transfer (PET) occurs fromthe π-π* excited state of the anthracene to the protonatedpyridinium unit, leading to quenching of the fluorescence.However, at high pH values, where the amino group is notprotonated, PET alternatively takes place from the aminelone pair to the same excited state of the fluorophore, yield-ing the same inhibitory effect on the fluorescence. Betweenthese two pH values, there is a pH window where PET doesnot take place and fluorescence…

The preparation and thermal evolution of polymeric gels with garnet stoichiometry in the CaOAl2O3SiO2 and CaOCr2O3SiO2 systems

Abstract The synthesis of gels with garnet stoichiometry in the CaOAl 2 O 3 SiO 2 and CaOCr 2 O 3 SiO 2 systems and their evolution in thermal processing have been studied. Dried gels with the stoichiometry 3CaO.Al 2 O 3 .3SiO 2 show a homogeneous aspect without detectable crystalline phase. The thermal evolution of these gels indicates no formation of grossularite at temperatures up to 1000°C after 12 h. In the uvarovite garnet samples, 3CaO.Cr 2 O 3 .3SiO 2 , a small amount of crystalline phase was detected in the dried gels. The homogeneity of the gels was checked by scanning electron microscropy. The infrared study of these polymeric gels confirmed the presence of SiOMe (MeCr 3+ …

ChemInform Abstract: Synthesis of Uvarovite Garnet.

A garnet with interesting optical properties is synthesized by means of the ceramic method and the formation of gels. Colloidal silica or tetraethoxysilane (TEOS) is used as a starting reagent in the latter method of synthesis, together with nitrate and chloride salts of the remaining components. Use is made of ultraviolet-visible and infrared spectroscopy techniques and X-ray diffraction in studying the evolution of the system. Formation of the garnet phase at lower temperatures is observed when using the gel methods, as well as the absence of chromates during the process in the samples which contained chlorides.