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Limits of solid solution and evolution of crystal morphology in (La1–xREx)FeO3 perovskites by low temperature hydrothermal crystallization
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Jia, Lu, Lloyd, Matthew D., Lees, Martin R., Huang, Limin and Walton, Richard I. (2023) Limits of solid solution and evolution of crystal morphology in (La1–xREx)FeO3 perovskites by low temperature hydrothermal crystallization. Inorganic Chemistry, 62 (11). pp. 4503-4513. doi:10.1021/acs.inorgchem.2c04325 ISSN 0020-1669.
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Official URL: https://doi.org/10.1021/acs.inorgchem.2c04325
Abstract
The crystallization of a new series of A-site substituted lanthanum ferrite materials (La1–xREx)FeO3 was explored by the hydrothermal method at 240 °C, for rare earth (RE) = Nd, Sm, Gd, Ho, Er, Yb, and Y, with 0 ≤ x ≤ 1. The effect of elemental substitution on the morphological, structural, and magnetic properties of the materials was studied using high-resolution powder X-ray diffraction, energy dispersive spectroscopy (EDS) on the scanning electron microscope, Raman spectroscopy, and SQUID magnetometry. If the radius of the La3+ and the substituent ions is similar, such as for Nd3+, Sm3+, and Gd3+, homogeneous solid solutions are formed, with the orthorhombic GdFeO3-type structure, and a continuous evolution of Raman spectra with composition and distinct magnetic behavior from the end members. When the radius difference between substituents and La3+ is large, such as for Ho3+, Er3+, Yb3+, and Y3+, then instead of forming solid solutions, crystallization in separate phases is found. However, low levels of element mixing are found and intergrowths of segregated regions give composite particles. In this case, the Raman spectra and magnetic behavior are characteristic of mixtures of phases, while EDS shows distinctive elemental segregation. A-site replacement induces an evolution in the crystallite shape with an increasing amount of substituent ions and this is most evident for RE = Y from cube-shaped crystals seen for LaFeO3 to multipodal crystals for (La1–xYx)FeO3, providing evidence for a phase-separation-driven evolution of morphology.
Item Type: | Journal Article | |||||||||||||||
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Subjects: | Q Science > QD Chemistry | |||||||||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | |||||||||||||||
Library of Congress Subject Headings (LCSH): | Lanthanum compounds, Iron oxides, Ferrites (Magnetic materials), Perovskite materials | |||||||||||||||
Journal or Publication Title: | Inorganic Chemistry | |||||||||||||||
Publisher: | American Chemical Society | |||||||||||||||
ISSN: | 0020-1669 | |||||||||||||||
Official Date: | 20 March 2023 | |||||||||||||||
Dates: |
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Volume: | 62 | |||||||||||||||
Number: | 11 | |||||||||||||||
Page Range: | pp. 4503-4513 | |||||||||||||||
DOI: | 10.1021/acs.inorgchem.2c04325 | |||||||||||||||
Status: | Peer Reviewed | |||||||||||||||
Publication Status: | Published | |||||||||||||||
Access rights to Published version: | Open Access (Creative Commons) | |||||||||||||||
Copyright Holders: | © 2023 The Authors. Published by American Chemical Society | |||||||||||||||
Date of first compliant deposit: | 17 March 2023 | |||||||||||||||
Date of first compliant Open Access: | 17 March 2023 | |||||||||||||||
RIOXX Funder/Project Grant: |
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