Determination of Debye temperatures and Lamb-Mössbauer factors for LnFeO3 orthoferrite perovskites (Ln = La, Nd, Sm, Eu, Gd).

Lanthanide orthoferrites have wide-ranging industrial uses including solar, catalytic and electronic applications. Here a series of lanthanide orthoferrite perovskites, LnFeO3 (Ln = La; Nd; Sm; Eu; Gd), prepared through a standard stoichiometric wet ball milling route using oxide precursors, has been studied. Characterisation through x-ray diffraction and x-ray fluorescence confirmed the synthesis of phase-pure or near-pure LnFeO3 compounds. 57Fe Mössbauer spectroscopy was performed over a temperature range of 10 K-293 K to observe hyperfine structure and to enable calculation of the recoil-free fraction and Debye temperature (θ D) of each orthoferrite. Debye temperatures (Ln = La 474 K; Nd 459 K; Sm 457 K; Eu 452 K; Gd 473 K) and recoil-free fractions (Ln = La 0.827; Nd 0.817; Sm 0.816; Eu 0.812; Gd 0.826) were approximated through minimising the difference in the temperature dependent experimental centre shift and theoretical isomer shift, by allowing the Debye temperature and isomer shift values to vary. This method of minimising the difference between theoretical and actual values yields Debye temperatures consistent with results from other studies determined through thermal analysis methods. This displays the ability of variable-temperature Mössbauer spectroscopy to approximate Debye temperatures and recoil-free fractions, whilst observing temperature induced transitions over the temperature range observed. X-ray diffraction and Rietveld refinement show an inverse relationship between FeO6 octahedral volume and approximated Debye temperatures. Raman spectroscopy show an increase in the band positions attributed to soft modes of Ag symmetry, Ag(3) and Ag(5) from La to GdFeO3 corresponding to octahedral rotations and tilts in the [0 1 0] and [1 0 1] planes respectively.

Vitrified metal finishing wastes II. Thermal and structural characterisation.

Waste filter cakes from two metal finishing operations were heat treated and vitrified. Substantial weight loss during heating was due to emission of water, volatile sulphur-rich and chlorine-rich compounds, and the combustion of carbonaceous components. Estimations of CO(x), SO(x) and HCl emissions were based on chemical analyses. Upon cooling from molten, one sample remained amorphous but all others partially crystallised. Crystalline nature was dependent upon waste composition and the level of P(2)O(5) addition. Thermal stabilities of the waste forms were good, but less so than MW, a borosilicate glass developed for its high temperature stability. Mossbauer and FTIR analyses showed that iron environments in the different vitrified waste forms were very similar. Iron was present predominantly as Fe(3+), although the exact redox ratio varied slightly between waste forms. Iron in both redox states occupied distorted octahedral coordination polyhedra with similar levels of site distortion. Phosphate networks in the vitreous materials were highly de-polymerised, consisting largely of (PO(4))(3-) monomer and (P(2)O(7))(2-) dimer units. This explained the high chemical durability of these waste forms and their structural insensitivity to compositional change, underlining their suitability as hosts for the immobilisation of toxic and nuclear wastes.

The effects of heating and devitrification on the structure and biological activity of aluminosilicate refractory ceramic fibres.

Three grades of ceramic fibre have been examined for their composition, structures and biological effect in several in vitro assay systems. The fibres were examined in the 'as-manufactured' state and after heating at 1200 and 1400 degrees C. Devitrification of the fibres at 1200 degrees C probably gave mullite crystals on the surface and caused the formation of the high-temperature form of cristobalite and, in zirconia grade fibres, the high-temperature, tetragonal form of zirconia as well. Further heating changed surface structure and led to zircon production in the zirconia fibres. Heating reduced the affinity of the fibres for the surface of V79-4 cells and lowered fibre toxicity toward these cells and towards macrophage-like cells. These changes in toxicity were not due to a reduction in the fibrous nature of the materials although they did become more brittle and powders prepared from them contained more isometric particles than those from as-manufactured materials. This suggests that the devitrification occurring during the use of these materials in high-temperature environments will not necessarily enhance their adverse biological activities despite the production of one phase of crystalline silica.