Browse by author
Lookup NU author(s): Dr Terry Egerton
Full text for this publication is not currently held within this repository. Alternative links are provided below where available.
In situ high temperature EPR measurements of the growth of the signal of substitutional Fe(III) ions have been used to study the diffusion of Fe in the rutile form of titanium dioxide. Two preparations, characteristic of the two main processes employed for the production of titanium dioxide have been studied. The first preparation, designated TiO2(SO4), was made from precipitated TiO2. It was calcined at ca. 850 degreesC and cooled slowly to room temperature. The second preparation, designated TiO2(Cl), was from the gas phase oxidation of TiCl4 at above 1200 degreesC. The resulting TiO2 was rapidly quenched to room temperature. The surfaces of both samples were impregnated with 0.030% Fe and the development of an EPR signal at g = 8.11, characteristic of Fe(III) substituting for titanium ions in the rutile lattice was monitored in situ at temperatures up to 730 degreesC by using a high temperature EPR cavity. For both TiO2(SO4) and TiO2(Cl) the g = 8.11 signal showed a parabolic dependence of intensity with time typical of many diffusion processes. The temperature dependence of the slope of the intensity (I) vs. time(0.5) plots allows estimates of the activation energies for the diffusion to be made. Values of 110 +/- 30 kJ mol(-1) for TiO2(SO4) and 50 +/- 20 kJ mol(-1) for TiO2(Cl) are determined. The much lower value for the TiO2(Cl) is attributed to the presence of metastable defects which, because of the rapid cooling, persist in this rutile. This interpretation is supported by an observed increase in activation energies on heating the rapidly quenched TiO2(Cl) prior to the diffusion experiment. Pre-annealing at 700 degreesC to reduce the concentration of defects, increased the activation energy for diffusion in TiO2(Cl) to 90 +/- 30 kJ mol(-1). The activation energy for diffusion of Fe is significantly lower than that for Cr (150 kJ mol(-1)). Reasons for this are discussed.
Author(s): Egerton TA; Harris E; Lawson EJ; Mile B; Rowlands CC
Publication type: Article
Publication status: Published
Journal: Physical Chemistry Chemical Physics
Year: 2001
Volume: 3
Issue: 3
Pages: 497-504
Print publication date: 01/01/2001
ISSN (print): 1463-9076
ISSN (electronic): 1463-9084
Publisher: Royal Society of Chemistry
URL: http://dx.doi.org/10.1039/b007766f
DOI: 10.1039/b007766f
Altmetrics provided by Altmetric
