NMR and ESR relaxation in Nd- and Gd-doped LaPO4 : towards the accurate determination of the doping concentration
Résumé
We present an original method based on the 31P solid-state NMR relaxation to determine low concentrations (< 1 at.%) of paramagnetic ions in monazite LaPO4 crystals with a high accuracy (~ 0.1 at.%). NMR experiments in static and MAS (15 kHz) conditions show that the 31P relaxation time T1 is strongly affected by the presence of paramagnetic ions in the vicinity of the phosphorous nuclei. A linear variation of 1/T1 as a function of Nd3+ or Gd3+ concentration is shown in the 0-10 at.% range for a homogeneous distribution of the doping ions in the matrix, which is the case when doped LaPO4 is synthesized by a soft chemistry route, i.e. by aqueous coprecipitation followed by thermal annealing. As a proof of concept for the use of this tool to study dopant homogeneity, we show that in the case of a solid-state synthesis at 1350 °C, relaxation measurements show that the homogeneous distribution of the doping ions is ensured when the mixing of the oxide precursors is performed mechanically, but not in the case of a manual grinding. The electronic relaxation times t1 of Gd3+ and Nd3+ ions are evaluated by ESR measurements under saturation conditions. This allows us to provide a semi-quantitative interpretation of the nuclear 31P relaxation measurements both in Nd and Gd doped LaPO4. In addition, the comparison between nuclear and electronic relaxation suggests that Nd-Gd codoping may improve the efficiency of the Gd3+ ion as relaxing agent in MRI (Magnetic Resonance Imaging) techniques.
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