Structure and properties of cation-deficient bismuth and vanadium containing CaMoO₄ — based solid solutions

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Abstract

The article is devoted to the synthesis, determination of structural features, electrical conductivity and pigment characteristics of cation-deficient scheelite-type Ca1−1.5x–yBix+yФ0.5xMo1–yVyO4 solid solutions. Complex oxides were studied with X-ray diffraction and Raman spectroscopy. The concentration ranges of existence of different types and distortion of structure were discussed via the element ordering in A sublattice. The total electrical conductivity of the compounds was studied by impedance spectroscopy in the temperature range of 400–650°C. Arrhenius plots of electrical conductivity on the inverse temperature were constructed and analyzed. According to the diffuse light scattering data of powders, functions of color coordinates of the solid solutions were calculated.

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About the authors

A. V. Klimova

Ural Federal University the first President of Russia B.N. Yeltsin; The Zavaritsky Institute of Geology and Geochemistry, Ural Branch of the Russian Academy of Sciences

Author for correspondence.
Email: bbgiyongchy@gmail.com
Russian Federation, Mira st., 19, Yekaterinburg, 620002; Academician Vonsovsky st., 15, Yekaterinburg, 620016

Z. A. Mikhaylovskaya

The Zavaritsky Institute of Geology and Geochemistry, Ural Branch of the Russian Academy of Sciences

Email: bbgiyongchy@gmail.com
Russian Federation, Academician Vonsovsky st., 15, Yekaterinburg, 620016

E. S. Buyanova

Ural Federal University the first President of Russia B.N. Yeltsin

Email: bbgiyongchy@gmail.com
Russian Federation, Mira st., 19, Yekaterinburg, 620002

E. A. Pankrushina

The Zavaritsky Institute of Geology and Geochemistry, Ural Branch of the Russian Academy of Sciences

Email: bbgiyongchy@gmail.com
Russian Federation, Academician Vonsovsky st., 15, Yekaterinburg, 620016

S. A. Petrova

Institute of Metallurgy, Ural Branch of the Russian Academy of Sciences

Email: bbgiyongchy@gmail.com
Russian Federation, Amundsen st., 101, Yekaterinburg, 620016

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Supplementary files

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2. Fig. 1. Concentration triangle illustrating the regions of existence of solid solutions with the structure of superordered scheelite (dark gray) and with the monoclinic-distorted structure of scheelite (gray) in the Ca1−1.5x–yBix+yФ0.5xMo1–yVyO4 system under standard conditions (25°C).

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3. Fig. 2. Fragments of typical X-ray diffraction patterns of samples of the Ca1−1.5x–yBix+yФ0.5xMo1–yVyO4 series using the example of the compositions Ca0.3Bi0.5167Mo0.85V0.15O4 (1) and Ca0.65Bi0.333Mo0.7V0.3O4 (2); arrows indicate reflections corresponding to superstructural ordering.

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4. Fig. 3. Dependences of the parameters and volume of the unit cell on the concentration of dopants in the Ca1−1.5x–yBix+yФ0.5xMo1–yVyO4 series.

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5. Fig. 4. Examples of Raman spectra of the solid solution Ca1−1.5x–yBix+yФ0.5xMo1–yVyO4.

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6. Fig. 5. Dependences of the position of the vibrational mode ν2(MoO4) on the vanadium content “y” (a), the content of bismuth introduced due to cation vacancies “x” (b); the total content of bismuth “x + y” (c).

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7. Fig. 6. Dependences of Δcorr values ​​on the vanadium content “y” (a, b), the content of bismuth introduced due to cation vacancies “x” (c, d); the total bismuth content “x + y” (d, e). The Δcorr values ​​were calculated in the range of deformation vibrations ν2 + ν4(MoO4) (a, c, d) and stretching vibrations ν1 + ν3(Mo/VO4) (b, d, e). Samples for which the presence of ordering is not characteristic are shown in black, those for which ordering is characteristic are shown in gray.

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8. Fig. 7. Impedance hodographs of the compositions Ca0.65Bi0.333Mo0.7V0.3O4 (1) and Ca0.35Bi0.45Mo0.95V0.05O4 (2) at 550°C.

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9. Fig. 8. Temperature dependences of electrical conductivity of selected compositions of the Ca1−1.5x–yBix+yФ0.5xMo1–yVyO4 system: 1 – Ca0.1Bi0.8Mo0.4V0.6O4; 2 – Ca0.25Bi0.7Mo0.4V0.6O4; 3 – Ca0.35Bi0.6333Mo0.4V0.6O4 (a); 1 – Ca0.45Bi0.5Mo0.6V0.4O4; 2 – Ca0.4Bi0.5Mo0.7V0.3O4; 3 – Ca0.35Bi0.5Mo0.6V0.4O4 (b).

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10. Fig. 9. Coordinates L*, a*, b* of powders of the Ca1−1.5x–yBix+yФ0.5xMo1–yVyO4 series depending on the chemical composition of the powder (x, y) for the standard radiation source ID65 (natural daylight with a correlated color temperature T = 6500 K).

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11. Additional materials
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