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Colored oxides with hibonite structure II: Structural and optical properties of CaAl 12 O 19 -type pigments with chromophores based on Fe, Mn, Cr and Cu
Progress in Solid State Chemistry ( IF 12.0 ) Pub Date : 2017-03-01 , DOI: 10.1016/j.progsolidstchem.2017.02.002
Elena A. Medina , Jun Li , M.A. Subramanian

Abstract Colored hibonite-type oxides with a general formula CaAl12-xMxO19 were prepared by solid state reactions through M-site substitution of aluminum with various di-, tri- and tetravalent cations (M = Fe, Mn, Cr, Cu, Ga, In, Ti, Ge, Sn or any combination thereof), where Fe, Mn, Cr and Cu are chromophore ions. Neutron Rietveld refinements of CaAl9.5Fe2.5O19, CaAl11.5Mn0.5O19 and CaAl10SnMnO19 compounds show that Fe3+ and Mn2+ ions prefer to occupy the tetrahedral site, while Mn3+ has an evident preference for both tetrahedral and octahedral sites and Sn4+ for octahedral site in the hibonite structure. No oxygen vacancies are found by structural analyses. Magnetic measurement confirms divalent Mn for CaAl11Sn0.5Mn0.5O19 and trivalent Mn for CaAl11.5Mn0.5O19. Diffuse reflectance spectra reveal that the d-d transitions occurring in transition metal chromophores are mainly responsible for the observed colors. The colored powders exhibit fairly high reflectance in the near-infrared region (750–2500 nm) which makes them potential candidates for cool pigment applications. Synthesis and characterization methods are briefly reviewed for hibonite type of oxides, especially those containing Fe, Mn, Cr and Cu.

中文翻译:

具有铁、锰、铬和铜基发色团的 CaAl 12 O 19 型颜料的结构和光学性质

摘要 通过固态反应,通过铝与各种二价、三价和四价阳离子(M = Fe、Mn、Cr、Cu、Ga、In 、Ti、Ge、Sn 或其任何组合),其中 Fe、Mn、Cr ​​和 Cu 是发色团离子。CaAl9.5Fe2.5O19、CaAl11.5Mn0.5O19 和 CaAl10SnMnO19 化合物的中子 Rietveld 精修表明 Fe3+ 和 Mn2+ 离子更喜欢占据四面体位点,而 Mn3+ 对八面体位点和 Sn4+ 位点有明显的四面体和八面体偏好黑曜石结构。通过结构分析没有发现氧空位。磁性测量确认 CaAl11Sn0.5Mn0.5O19 为二价 Mn,CaAl11.5Mn0.5O19 为三价 Mn。漫反射光谱显示过渡金属发色团中发生的 dd 跃迁是观察到的颜色的主要原因。有色粉末在近红外区域(750-2500 nm)表现出相当高的反射率,这使它们成为冷颜料应用的潜在候选者。简要回顾了黑铁矿型氧化物的合成和表征方法,特别是那些含有铁、锰、铬和铜的氧化物。
更新日期:2017-03-01
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