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Revealing Structural Detail in the High Temperature La 2 Si 2 O 7 –Y 2 Si 2 O 7 Phase Diagram by Synchrotron Powder Diffraction and Nuclear Magnetic Resonance Spectroscopy

2012; American Chemical Society; Volume: 116; Issue: 40 Linguagem: Inglês

10.1021/jp305777m

1932-7455

Alberto J. Fernández–Carrión, Mathieu Allix, Pierre Florian, Matthew R. Suchomel, Ana Isabel Becerro,

Glass properties and applications

High resolution synchrotron powder XRD, 89Y CPMG NMR, and 139La MAS NMR spectroscopy have been applied to eventually draw the phase diagram of the La2Si2O7–Y2Si2O7 system. The diagram presents a solid solubility region of G-(La,Y)2Si2O7, which extends to the La0.9Y1.1Si2O7 composition at any temperature of this study. Compositions richer in Y show two-phase domains, with G + α at T < 1450 °C and G + δ at T > 1450 °C. The Y-rich extreme is more complex, showing two solid solution regions of δ- and γ-(La,Y)2Si2O7 polymorphs which appear with increasing Y content, respectively. It is interesting to note that the La for Y substitution mechanism in the G-(La,Y)2Si2O7 polymorph is not homogeneous, but a preferential occupation of Y for the RE2 site is observed. Finally, the 89Y and 139La isotropic chemical shift values in G-(La,Y)2Si2O7 have been described here for the first time and assigned to the different RE crystallographic sites of the unit cell.