ISSN:
1600-5740
Source:
Crystallography Journals Online : IUCR Backfile Archive 1948-2001
Topics:
Chemistry and Pharmacology
,
Geosciences
,
Physics
Notes:
Neutron powder diffraction data, collected over the temperature range 10–770 K, have been analysed in order to make a detailed characterization of the sequence of phase transitions occurring in the Hf-rich ferroelectric PbHf0.8Ti0.2O3, titanium hafnium lead oxide. Over the whole temperature range this compound undergoes two phase transitions, which involve cationic displacements and octahedral deformations (tilt and/or distortion) leading to strongly distorted perovskite-type structures. The first transition appears around 415 K between two ferroelectric rhombohedral phases: a low-temperature nonzero-tilt phase FRL (space group R3c) and an intermediate zero-tilt phase FRH (space group R3m). The second one, detected around 520 K, is associated with a ferroelectric to-paraelectric transition between the FRH phase and the PC cubic phase (space group Pm3¯m). From high-resolution neutron powder diffraction data (diffractometer 3T2-LLB, Saclay, France, λ = 1.2251 Å), the crystallographic structure of the three successive phases has been accurately determined at the following temperatures: T = 10 K (FRL): space group R3c, Z = 6, ahex = 5.7827 (1), chex = 14.2702 (4) Å, Vhex = 413.26 (2) Å3; T = 150 K (FRL): space group R3c, Z = 6, ahex = 5.7871 (1), chex = 14.2735 (4) Å, Vhex = 413.98 (3) Å3; T = 290 K (FRL): space group R3c, Z = 6, ahex = 5.7943 (1), chex = 14.2742 (5) Å, Vhex = 415.04 (3) Å3; T = 440 K (FRH): space group R3c, Z = 6, ahex = 5.8025 (1), chex = 14.2648 (4) Å, Vhex = 415.94 (3) Å3; T = 520 K (PC): space group Pm3¯m, Z = 1, acub = 4.1072 (2) Å, Vcub = 69.29 (1) Å3. In addition, a neutron powder thermodiffractometry experiment, performed between 290 and 770 K (diffractometer D1B-ILL, Grenoble, France, λ = 2.533 Å), has been used to study in situ the temperature-induced phase transitions. From sequential Rietveld refinements, the temperature dependence of the cation displacements and the rotation and/or distortion of oxygen octahedra was derived.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1107/S0108768199011453
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