0000000000140358
AUTHOR
Francisco Jose Torres
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 …
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…
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…
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…
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…
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…
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.
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 …
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…
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 …
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…
Los otros trabajadores agrícolas transnacionales: una red de injertadores mexicanos
La globalización del régimen agroalimentario ha detonado una serie de flujos migratorios transnacionales. Los más estudiados han sido los de los jornaleros de temporada que realizan los trabajos más arduos, precarios y estacionales. Los trabajadores transnacionales especializados tanto en el campo como en las diversas actividades requeridas para una industria vitivinícola globalizada no han sido estudiados. Este artículo aborda el estudio de una red de trabajadores agrícolas especializados, los injertadores. Se estudia el origen de la red en el condado de Napa y su ampliación y consolidación que ha llevado a estos trabajadores a diferentes países y continentes. Se analizan las característic…
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…
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 …
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…
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…
Urban Development and Cultural Policy “White Elephants”: Barcelona and Valencia
AbstractThe importance of culture in defining new models of local development has been increasingly emphasized. However, less attention has been paid to the influence of local development models on local cultural policy. This article will focus on analysing two cities that have used culture as a central element in their economic and urban development. In both cases, they have followed different strategies but the two have finally finished generating two “white elephants”: the Universal Forum of Cultures in the case of Barcelona and the City of Arts and Sciences in the case of Valencia. From a comparison of the two cases, the paper analyses the causes of this urban phenomenon, which combines…