Effect of [MnO6] Octahedra to the Coloring Mechanism of (Li1-x Na x )2MnO3.

Abstract

(Li1–xNax)2MnO3 (0 ≤ x ≤ 0.10) solid solutions were synthesized by a conventional solid-state reaction technique to investigate the relationship between the steric structure of the [MnO6] octahedra and coloration mechanisms. The color, optical properties, and crystal structure of the solid solutions were characterized. The (Li1–xNax)2MnO3 (0 ≤ x ≤ 0.10) solid solutions absorbed the visible light at wavelengths shorter than 550 nm and around 680 nm. The former and latter optical absorption bands were attributed to the spin-allowed (4A2g → 4T1g, 4T2g) and spin-forbidden (4A2g → 2Eg, 2T1g) d–d transitions of tetravalent manganese ions, respectively. The absorption band assigned to the 4A2g → 4T2g transition shifted toward longer wavelengths with the enlargement of the average [Mn(2)O6] bond distance by doping Na+. In contrast, the latter absorption bands did not shift but the absorption intensities increased due to the distortion of the [Mn(2)O6] octahedra. Consequently, the red color purity of the sample gradually increased with the increase in the Na+ concentration. Among the (Li1–xNax)2MnO3 (0 ≤ x ≤ 0.10) samples synthesized in this study, the highest red color purity was obtained in the (Li0.93Na0.07)2MnO3 (hue angle: h° = 39.1) sample. The results of this study provide important insights for the development of environment-friendly inorganic red pigments containing Mn4+ ions as a coloring source.