Textural evolution and phase transformation in titania membranes: Part 1. -unsupported membranes

Textural evolution in sol–gel derived nanostructured unsupported titania membranes has been studied using differential scanning calorimetry (DSC), differential thermal analysis (DTA), thermal gravimetry (TG), X-ray diffraction (XRD) and N2 adsorption. The anatase-to-rutile phase transformation kinetics were studied using the Avrami model. The precursor gel had a surface area of ca. 165 m2 g–1, which after heat treatment at 600 °C for 8 h reduced to zero. Undoped titania-gel layers transformed to more than 95% rutile after calcination at 600 °C for 8 h. The causes of surface-area reduction and pore growth were anatase crystallite growth and the enhanced sintering of rutile during transformation. Lanthanum oxide was identified as a suitable dopant for shifting the transformation temperature to ca. 850 °C. Lanthanum oxide doped titania showed an improved stability of porous texture compared to that of the undoped titania membranes

Effect of sintering atmosphere on the pore-structure stability of cerium-doped nanostructured alumina

Pore-structure stability of pure and Ce-doped alumina in air and argon atmospheres was studied using DTA, TGA, N2 ads./des. and XRD with a view to understand the importance of the ionic size of the dopant cation on the pore-structure stability of alumina. The ionic size effect was studied by heat treating the Ce-alumina system in both oxidizing and reducing atmospheres to have Ce4+ (87 pm) and Ce3+ (106 pm) respectively. No compound formation between Ce and alumina was observed. In the case of pure alumina there is a drastic reduction in porosity during the transformation to α-alumina. Ce-doped alumina has a higher DSC transformation temperature corresponding to the α-alumina transformation compared to pure alumina. Ce-doped alumina showed higher pore-structure stability compared with pure alumina and the stability was relatively higher in reducing atmosphere (higher Ce3+/Ce4+ ratio, higher effective ionic size) compared with oxidizing conditions (lower Ce3+/Ce4+ ratio, lower effective ionic size)

Synthesis and textural properties of unsupported and supported rutile (TiO2) membranes

Two approaches were postulated for improving the stability of porous texture of titania membranes: (1) retarding the phase transformation and grain growth; (2) avoiding the phase transformation. Based on the second approach, rutile membranes were made directly from a rutile sol, prepared by the precipitation of titania on SnO2 nuclei. The rutile membranes were stable up to 800 °C, with a porosity of ca. 40%, whereas normal titania membranes (starting with anatase) show very little porosity above 600 °C. Alumina substitution retards grain growth and pore growth at 850 °C for unsupported as well as supported membranes. \u

Textural evolution and phase transformation in titania membranes: Part 2. - Supported membranes

Nanostructural evolution and phase transformation in supported and unsupported titania membranes have been studied using Raman spectroscopy, X-ray diffraction (XRD) and field-emission scanning electron microscopy (FE-SEM). Densification of unsupported membranes started at ca. 450 °C and reached more than 97% density at 600 °C, whereas the supported membranes had a density of only ca. 70–75% even at 700 °C when calcined for 8 h. At 700 °C the average crystallite size of supported and unsupported membranes was ca. 20 and 70 nm, respectively. This behaviour is primarily attributed to the decrease in the driving force for sintering due to the stress developed during the constrained sintering of a film attached to a rigid support and to the inhibition of the reorganization process within the film, resulting in lower coordination numbers in supported membranes. Supported membranes showed a higher transformation temperature (slower rate of transformation) than did the unsupported. Supported and unsupported membranes, calcined for 8 h, transformed to ca. 90% rutile (calculated from Raman spectrum) after calcination at 850 and 650 °C, respectively. This difference in phase transformation behaviour is attributed primarily to the large stress which is developed in a constrained environment owing to the negative volume change during the anatase–rutile transformation

Effect of peptization on densification and phase transformation behaviour of sol-gel-derived nanostructured titania

Porosity reduction, packing, pore-size distribution, and anatase to rutile phase transformation behavior of nanostructured titania ceramics prepared from both peptized and unpeptized sols were studied and compared using XRD, DSC, and nitrogen-gas physisorption techniques. Precursor gels prepared from the peptized sol had a green density of about 70% after drying at 40°C, whereas the samples prepared from the unpeptized sol had a green density of only 50%. Samples prepared from the peptized sol showed higher sintering and phase transformation rates compared to the unpeptized sols

Textural stability of titania-alumina composite membranes

Textural evolution (porosity reduction, pore and crystallite growth) in titania–alumina composite membranes has been studied using thermal analysis, X-ray diffraction, field emission scanning electron microscopy and N2 physisorption techniques. The presence of alumina in the membranes improved the thermal stability of the porous texture by retarding the anatase-to-rutile phase transformation and grain growth of the anatase phase. Pure unsupported titania membranes lose their porosity completely after calcination at 600 °C for 8 h, whereas the titania–50 wt.% alumina composite membranes retained a porosity of ca. 40% even after calcination for 30 h at 800 °C. The anatase-to-rutile phase transformation temperatures for pure unsupported titania and the titania phase of the unsupported titania–alumina composite membranes (50 wt.% alumina) were found to be 580 and 960 °C, respectively, as observed from the DSC data.From XRD results it was found that pure unsupported titania and the unsupported titania–alumina (50 wt.% alumina) composite membranes transformed to more than 95% of rutile after heat treatment for 8 h at 600 and 900 °C, respectively. The anatase to rutile phase transformation kinetics were studied using DSC data and applying a non-isothermal form of the Avrami equation