Crystal growth and thermodynamic investigation of Bi2M2+O4 (M = Pd, Cu)

Phase equilibria that are relevant for the growth of Bi2MO4 have been studied experimentally, and the ternary phase diagrams of Bi2O3–PdO2–Pd and Bi2O3–Cu2O–CuO and its isopleth section Bi2O3–CuO were redetermined. It is shown that every melting and crystallization process is always accompanied by a...

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Published inCrystEngComm Vol. 23; no. 17; pp. 3230 - 3238
Main Authors Wolff, Nora, Klimm, Detlef, Habicht, Klaus, Fritsch, Katharina
Format Journal Article
LanguageEnglish
Published Cambridge Royal Society of Chemistry 01.01.2021
Subjects
Bismuth oxides
Bismuth trioxide
Copper oxides
Crystal growth
Crystallization
Crystals
Diameters
Magnetic properties
Nomograms
Palladium
Phase boundaries
Phase diagrams
Phase equilibria
Single crystals
Ternary systems
Transition metals
Transport properties
X ray powder diffraction
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Summary:Phase equilibria that are relevant for the growth of Bi2MO4 have been studied experimentally, and the ternary phase diagrams of Bi2O3–PdO2–Pd and Bi2O3–Cu2O–CuO and its isopleth section Bi2O3–CuO were redetermined. It is shown that every melting and crystallization process is always accompanied by a redox process at the phase boundary and that for both title compounds, the valence of the transition metal is lowered during melting. Vice versa, during crystal growth, O2 must be transported through the melt to the phase boundary. Based on these new insights provided by our thermodynamic studies, Bi2CuO4 single crystals with a length of up to 7 cm and a diameter of 6 mm were grown by the OFZ technique to be used for investigations of magnetic, electronic and thermal transport properties. The grown crystals were characterized by powder X-ray diffraction, Laue, magnetization and specific heat measurements.
ISSN:1466-8033
DOI:10.1039/d1ce00220a