Formation enthalpies of rare earth titanate pyrochlores

High-temperature oxide melt solution calorimetry and Rietveld refinements of powder X-ray diffraction data were used to investigate the structure (Fd3m; Z=8) and energetics of a series of RE₂Ti₂O₇ (RE=Sm-Lu) compounds with the pyrochlore structure as well as La₂Ti₂O₇ with a layered perovskite-type structure. All of the RE-titanates were found to be stable in enthalpy with respect to their oxides. In the pyrochlore series, Lu₂Ti₂O₇ was least stable in enthalpy (ΔHf-ox at 298 K=−56.0±4.0 kJ/mol); the most stable materials were Gd-, Eu-, and Sm₂Ti₂O₇ with ΔHf-ox at 298 K=−113.4±2.7, −106.1±4.2, −115.4±4.2 kJ/mol, respectively. In general, as the radius ratio of the A- to B-site cations, R_A/R_B, decreases, the pyrochlore structure becomes less stable. The trend of ionic radius of the RE³⁺ cation vs. ΔHf-ox at 298 K is non-linear and approximately parallels the increasing “resistance” to ion-beam-induced amorphization as R_A/R_B decreases.     

Effect of structure and thermodynamic stability on the response of lanthanide stannate pyrochlores to ion beam irradiation

The lanthanide stannates, Ln2Sn2O7, Ln=La-Lu and Y, have the isometric pyrochlore structure, A2B2O7, and their structural properties have been refined by Rietveld analysis of powder neutron and synchrotron X-ray diffraction data. In this study, the enthalpies of formation of selected stannate pyrochlores, Ln=La, Nd, Sm, Eu, Dy, and Yb, were measured by high-temperature oxide melt solution calorimetry. Their radiation response was determined by 1 MeV Kr2+ ion irradiation combined with in situ TEM observation over the temperature range of 25 to 1000 K. The enthalpy of formation from binary oxides of stannate pyrochlores became more endothermic (from -145 to -40 kJ/mol) as the size of the lanthanide in the A-site decreases. A more exothermic trend of the enthalpy of formation was observed in stannate pyrochlores with larger lanthanide ions, particularly La, possibly as a result of increased covalency in the Sn-O bond. In contrast to lanthanide titanate pyrochlores, Ln2Ti2O7, that are generally susceptible to radiation-induced amorphization and zirconate pyrochlores, Ln2Zr2O7, that are generally resistant to radiation-induced amorphization, the lanthanide stannate pyrochlores show a much greater variation in their response to ion irradiation. La, Nd, and Gd stannates experience the radiation-induced transformation to the aperiodic state, and the critical amorphization temperatures are approximately 960, 700, and 350 K, respectively. Y and Er stannate pyrochlores cannot be amorphized by ion beam irradiation, even at 25 K, and instead disorder to a defect fluorite structure. Comparison of the calorimetric and ion irradiation data for titanate, zirconate, and stannate pyrochlores reveals a strong correlation among subtle changes in crystal structure with changing composition, the energetics of the disordering process, and the temperature above which the material can no longer be amorphized. In summary, as the structure approaches the ideal, ordered pyrochlore structure, radiation-induced amorphization is more easily attained. This is consistent with an increasingly exothermic trend in the enthalpies of formation of pyrochlores from the oxides, that is, the greater the thermochemical stability of the pyrochlore structure, the more likely it will be amorphized upon radiation damage rather than recover to a disordered fluorite structure.     

Oxide melt solution calorimetry of rare earth oxides

Key to the evaluation of the long-term durability and reactivity of REE-materials is the accurate determination of their thermodynamic properties. High-temperature oxide melt solution calorimetry offers an effective methodology for the determination of enthalpies of formation for REE-materials. Calorimetric techniques and crosschecks are summarized that demonstrate that consistent and correct thermodynamic data can be generated using lead borate and sodium molybdate solvents. A summary of recent calorimetric studies of REE-orthophosphates and REE-oxyapatites illustrates the successful application of our techniques in quantifying formation enthalpies and elucidating energetic trends. This revised version was published online in August 2006 with corrections to the Cover Date.     

Short-term changes in delta(13)C and delta(15)N signatures of water discharged from grazed grasslands

The composition of dissolved organic matter (DOM) in a soil is the product of a variety of soil processes. Changes in the composition of DOM in water discharged from soil should, therefore, give an important insight into modifications in these soil processes. We hypothesise that these processes in soils, under different grassland management regimes, would be affected to different extents by the short-term disturbance of a storm event and that evidence of this could be detected in delta(13)C and delta(15)N signatures in drainage and surface runoff waters. During a storm event we collected discharge waters from 1 ha grassland lysimeters, with or without artificial drainage, which received contrasting fertiliser inputs, and delta(13)C and delta(15)N signatures were determined. Changes in (13)C enrichment during the storm event were clearly identifiable, as were differences between plots for (13)C and (15)N, illustrating that this technique has potential to be a useful tool for identifying and investigating short- and long-term changes in soil organic matter dynamics. Copyright 1999 John Wiley & Sons, Ltd.     

Magnetic behavior of the oxide spinels: Li0.5Fe2.5−2x Al x Cr x O4

In order to study the effect of substitution of Fe³⁺ by Al³⁺ and Cr³⁺ in Li_0.5Fe_2.5O₄ on its structural and magnetic properties, the spinel system Li_0.5Al _x Cr _x Fe_2.5?2x O₄ (x=0.0, 0.2, 0.4, 0.5, 0.6 and 0.8) has been characterized by X-ray diffraction, high field magnetization, low field ac susceptibility and ⁵⁷Fe Mossbauer spectroscopy. Contrary to the earlier reports, about 50% of Al³⁺ is found to occupy the tetrahedral sites. The system exhibits canted spin structure and a central paramagnetic doublet was found superimposed on magnetic sextet in the Mössbauer spectra (x>0.5).