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Tailoring structural properties of lanthanum orthoniobates through an isovalent substitution on the Nb-site

Abstract

Tetragonal polymorph of lanthanum orthoniobate can be stabilized to room temperature by the substitution of Nb with an isovalent element. LaNb1-xAsxO4 (0 < x ≤ 0.3), where As is an element stabilizing tetragonal structure, were successfully synthesized with combined co-precipitation and solid-state reaction method. The phase transition temperature, above which the material has tetragonal structure, decreases linearly with increasing As-content, and LaNb0.7As0.3O4 is tetragonal at room temperature. The analysis of the influence of different isovalent substituents, namely V, Sb and Ta, has shown that there is a relation between the properties of the chemical element and its effect on the structure. It was proposed that the electronegativity of the substituent determines the type of stabilization – the tetragonal/monoclinic structure is stabilized by chemical elements with electronegativity higher/lower than that of niobium. The slope of the phase transition temperature dependence on the substituent content has been proposed as a parameter determining the “quality” of the stabilization, since steeper function leads to a larger decrease of transition temperature for the same content of different substituents. The analysis has shown that the stabilization of tetragonal structure, apart from the electronegativity, depends also on ionic radius of a substituent. Arsenic has been found to be a better stabilizer of the tetragonal polymorph of lanthanum orthoniobate than Sb, but worse than V.

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Copyright (Chinese Chemical Society and the Royal Society of Chemistry 2018)

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Category:
Articles
Type:
artykuł w czasopiśmie wyróżnionym w JCR
Published in:
Inorganic Chemistry Frontiers no. 5, pages 2157 - 2166,
ISSN: 2052-1553
Language:
English
Publication year:
2018
Bibliographic description:
Wachowski S. L., Kamecki B., Winiarz P., Dzierzgowski K., Mielewczyk-Gryń A. D., Gazda M.: Tailoring structural properties of lanthanum orthoniobates through an isovalent substitution on the Nb-site// Inorganic Chemistry Frontiers. -Vol. 5, iss. 9 (2018), s.2157-2166
DOI:
Digital Object Identifier (open in new tab) 10.1039/c8qi00524a
Sources of funding:
Verified by:
Gdańsk University of Technology

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