Synthesis and characterization of Ti-doped ZrSiO4 at ambient and high-pressure conditions
- 47 Downloads
We have successfully synthesized for the first time a Ti-doped ZrSiO4 powder (stoichiometry Zr0.95Ti0.05SiO4) via a sol–gel route. The structural and vibrational properties have been characterized by X-ray diffraction, electron microscopy and Raman spectroscopy. Zr0.95Ti0.05SiO4 has a tetragonal zircon-type structure with a = 6.5981(2) Å and c = 5.9810(2) Å. Eight of its Raman-active modes have been measured and assigned. We also performed high-pressure synchrotron X-ray diffraction experiments. The structural behavior was studied up to 31 GPa. At this pressure, we found evidence of the onset of a phase transition, coexisting the low-pressure polymorphs (zircon) with the typical high-pressure polymorph of ZrSiO4 (reidite-type). From the analysis of unit-cell volume versus pressure using a Birch–Murnaghan equation of state, in the quasi-hydrostatic pressure regime (P < 10.5 GPa), we have determined a bulk modulus of 297 GPa. This magnitude represents an enhancement of a 30% in the value of this parameter if compared with un-doped zircon-type ZrSiO4 (bulk modulus < 227 GPa). The low compressibility of Zr0.95Ti0.05SiO4 converts this compound in a very good candidate for many technological applications. The effect of pressure on the linear compressibility of the lattice parameters is also analyzed.
SEM and Raman measurements were performed at Y-TEC S. A. S. Ferrari, F. Grinblat and L. G. Pampillo thank the financial support provided by the Agencia Nacional de PromociónCientífica y Tecnológica (ANPCyT) under Grant PICT-2012- 1730. D. E. thanks the support of Spanish MINECO and European FEDER under Grant No. MAT2016-75586-C4-1-P. The authors thank the partial support from LNLS with Project XDS-18856.
- 9.Marqués M, Flórez M, Recio JM, Gerward L, Olsen JS (2006) Structure and stability of ZrSiO4 under hydrostatic pressure. Phys Rev B 74:1–9Google Scholar
- 12.Hazen RM, Finger LW (1979) Crystal structure and compressibility of zircon at high pressure. Am Mineral 64:196–201Google Scholar
- 13.Flórez M, Contreras-García J, Recio JM (2009) Quantum-mechanical calculations of zircon to scheelite transition pathways in ZrSiO4. Phys Rev B 79:1–11Google Scholar
- 20.Klotz S, Chervin JC, Munsch P, Le Marchand G (2009) Hydrostatic limits of 11 pressure transmitting media. J Phys D 4:1–8Google Scholar
- 27.Heany PJ, Prewitt CT, Gibbs GV (1994) Silica: physical behaviour, geochemistry, and materials applications. Mineralogical Society of America, Washington, DCGoogle Scholar
- 28.Valigi M, Gazzoli D, Incocciati E, Dragone R (1997) Metastable phase formation in the TiO2–ZrO2 and CdO–ZrO2 systems. Solid State Ion 101:597–603Google Scholar
- 36.Garg AB, Errandonea D, Rodríguez-Hernández P, López-Moreno S, Muñoz A, Popescu C (2014) High-pressure structural behaviour of HoVO4: combined XRD experiments and ab initio calculations. J Phys: Condens Matter 26:265402Google Scholar
- 38.Lacomba-Perales R, Errandonea D, Meng Y, Bettinelli M (2010) High-pressure stability and compressibility of APO4 (A = La, Nd, Eu, Gd, Er, and Y) orthophosphates: an x-ray diffraction study using synchrotron radiation. Phys Rev 81:1–9Google Scholar