0000000000049213
AUTHOR
Esther Ruiz De Sola
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…
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 …
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…
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…
Protein Unfolding:1H-NMR Studies of Paramagnetic Ferricytochrome c-550 from Horse Heart
Electronic transfer protein cytochrome c-550 from horse heart is studied in the unfolded state by means of paramagnetic 1H NMR. The protein contains 104 aminoacid residues and a heme group with low spin FeIII ion in the oxidized form of protein. The global secondary structure is of the α-helix type as occurs in the case of very other cytochromes c investigated such as cyt c-550 from Thiobacillus versutus or cyt c-551 from Pseudomonas aeruginosa. We have studied the coordination characteristic and electronic properties of heme iron horse heart ferricytochrome c-550 at increasing denaturing conditions (up to 3.1 M GuHCl and 288-323 K). The 1H T1 values of the signals were measured and some re…
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…
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…
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…
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 …
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…
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 …