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Ni-doped Hibonite (CaAl12O19): A New Turquoise Blue Ceramic Pigment

机译:掺镍的Hibonite(CaAl12O19):一种新的绿松石蓝色陶瓷颜料

摘要

A new structure for ceramic pigments was synthesized by a conventional solid state reaction process. It is based on Ni-doped hibonite, CaAl12O19, which assumes a turquoise-like blue colour similar to that of V-doped zircon. Hibonite is associated with anorthite, CaAl2Si2O8, acting like a fluxing agent in order to lower the synthesis temperature, and with cassiterite, SnO2, acting as a tin buffer to promote coupled Ni2+ + Sn4+ -> Al3+ + Al3+ substitution, in order to ensure the electric neutrality of the hibonite lattice. Since relatively low chromophore contents are required, this new system constitutes an interesting alternative to the common blue ceramic pigments based on cobalt aluminate spinel or vanadium-doped zircon, implying lower cost and environmental advantages. The pigments characterization was performed by X-ray powder diffraction, diffuse reflectance spectroscopy, CIELAB colourimetric analysis, and testing in ceramic glazes and bodies. The substitution of Al3+ by bigger ions, like Ni2+ and Sn4+, increases the cell volume compared to undoped hibonite and is responsible of the turquoise blue colour, as verified by UV-Vis analysis. The chromatic mechanism is due to incorporation of Ni2+ in tetrahedral coordination, likely occurring at the site M3 of the hibonite lattice, where it partially substitutes the Al3+ ion. While this product shows a strong hue as a pigment, it is not stable after severe testing in glazes and attempts to improve its colouring performance are now under development.
机译:通过常规的固态反应过程合成了一种新型的陶瓷颜料结构。它基于掺Ni的锂白云石CaAl12O19,其呈现类似于V掺杂锆石的类似绿松石的蓝色。锂铁矿与钙长石CaAl2Si2O8起到助熔剂的作用以降低合成温度,锡石SnO2用作锡缓冲剂以促进Ni2 + + Sn4 +-> Al3 + + Al3 +的取代,从而确保堇青石晶格的电中性。由于需要相对较低的生色团含量,因此该新系统构成了基于铝酸钴尖晶石或钒掺杂锆石的普通蓝色陶瓷颜料的有趣替代品,这意味着更低的成本和环境优势。通过X射线粉末衍射,漫反射光谱,CIELAB比色分析以及在陶瓷釉料和陶瓷体中进行测试来表征颜料。 UV-Vis分析证实,与未掺杂的锂白云母相比,较大的离子(如Ni2 +和Sn4 +)替代Al3 +会增加晶胞体积,并导致蓝绿色。彩色机理是由于Ni2 +在四面体配位中的结合所致,可能发生在菱铁矿晶格的M3处,在那里它部分替代了Al3 +离子。尽管该产品显示出很强的色相,但经过在釉料中的严格测试后仍不稳定,目前正在努力改善其着色性能。

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