Structure, conductivity and magnetism of orthorhombic and fluorite polymorphs in MoO3-Ln(2)O(3) (Ln = Gd, Dy, Ho) systems

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Structure, conductivity and magnetism of orthorhombic and fluorite polymorphs in MoO3-Ln(2)O(3) (Ln = Gd, Dy, Ho) systems

机译：在MOO3-LN（2）O（3）（LN = Gd，Dy，HO）系统中的正交和萤石多晶型物的结构，电导率和磁性

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Phase-pure orthorhombic compositions at a Ln/Mo ratio similar to 5.2-5.7 (Ln = Gd, Dy, Ho) have been obtained for the first time by prolonged (40-160 h) heat treatment of mechanically activated 5Ln(2)O(3) + 2MoO(3) (Ln = Gd, Dy, Ho) oxide mixtures at 1200 degrees C. Although the starting Ln:Mo ratio was 5:1 (Ln(10)Mo(2)O(21) (Ln = Dy, Ho)), it changed slightly in the final product due to the volatility of molybdenum oxide at 1200 degrees C (40-160 h) (ICP-MS analysis). Brief high-temperature firing (1600 degrees C, 3 h) of 5Ln(2)O(3) + 2MoO(3) (Ln = Gd, Dy, Ho) oxide mixtures leads to the formation of phase-pure fluorites with compositions close to Ln(10)Mo(2)O(21) (Ln = Gd, Dy, Ho). Gd10Mo2O21 molybdate seems to undergo an order-disorder (orthorhombic-fluorite) phase transition in the range of 1200-1600 degrees C. For the first time, using the neutron diffraction method, it was shown that low-temperature phases with a Ln/Mo ratio similar to 5.2-5.7 (Ln = Gd, Dy, Ho) have an orthorhombic structure rather than a tetragonal structure. Proton contribution to the total conductivity of Ln(10)Mo(2)O(21) (Ln = Gd, Dy, Ho) fluorites and gadolinium and dysprosium orthorhombic phases in a wet atmosphere was observed for the first time. In both orthorhombic and fluorite phases, the total conductivity in wet air decreases with decreasing lanthanide ionic radii. In a wide temperature range, the compounds under study exhibit paramagnetic behaviour. However, the orthorhombic phases of Dy and Ho compounds reach the antiferromagnetic state at 2.4 K and 2.6 K, respectively.

机译：通过延长（40-160小时）的机械活化5LN（2）O的热处理，首次获得了类似于5.2-5.7（LN = Gd，Dy，Ho）的LN / Mo比的相纯正交组合物。（3）+ 2Moo（3）（LN = Gd，Dy，HO）氧化物混合物在1200℃下。尽管起始Ln：Mo比为5：1（Ln（10）Mo（2）O（21）（LN = Dy，HO）），由于1200℃（40-160小时）（ICP-MS分析）氧化钼的挥发性，它在最终产品中略微发生变化。简短的高温烧制（1600℃，3h）的5LN（2）O（3）+ 2mOO（3）（Ln = Gd，Dy，HO）氧化物混合物导致形成相纯氟的组合物关闭对于LN（10）Mo（2）O（21）（Ln = Gd，Dy，HO）。 Gd10MO2O21钼酸盐似乎在1200-1600摄氏度的范围内进行了命令障碍（正交 - 荧光）相转变。首次使用中子衍射方法，显示出具有LN / Mo的低温相与5.2-5.7（ln = gd，dy，ho）相似的比率具有正交结构而不是四边形结构。第一次观察到质子对LN（10）Mo（2）o（2）O（2）O（2）O（2）O（2）O（2）（LN = Gd，Dy，HO）氟化物和钆和镝和镝和镝的助糖鎓。在双晶状体和萤石相中，湿空气中的总电导率随着镧系元素离子半径的降低而降低。在宽温度范围内，研究的化合物表现出顺磁性行为。然而，Dy和HO化合物的正晶相分别在2.4k和2.6k处达到反铁磁性状态。

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《Dalton transactions: An international journal of inorganic chemistry》 |2020年第9期|共10页
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Structure, conductivity and magnetism of orthorhombic and fluorite polymorphs in MoO3-Ln(2)O(3) (Ln = Gd, Dy, Ho) systems

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