Zirconate systems having the composition 3HfO₂·15SiO₂·xY₂O₃·(82 − x)ZrO₂, where x = 2, 7 and 12 mol% Y₂O₃, were synthesized by a sol‐gel method. The analysis of X‐ray diffraction data showed the presence of the t‐ZrO₂, m‐ZrO₂, m‐HfO₂, Y₂SiO₅ and Y₂Si₂O₇ crystalline phases in a ceramic nanomixture. Spectroscopic data show that the increase of the Y₂O₃ content of samples determines the increase of the t‐ZrO₂, m‐HfO₂ and silicate crystalline phases. Gap energy values decrease almost linearly with increasing Y₂O₃ content of samples. A detailed study of XANES data does not show a significant difference with increasing Y₂O₃ content of the samples suggesting an appreciable stability of the hafnium ions +4 oxidation state and their microvicinity. EXAFS results show that the local structure around the Hf cation is similar to that from the monoclinic crystalline HfO₂ where the Hf–O coordination number tends to 7. The bond lengths of Hf–O shells show small deviations from ∼2.12 Å and the Hf–metal paths become more structured by increasing the Y₂O₃ content of the samples.

中文翻译：

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silicate硅酸锆锆酸盐陶瓷纳米混合物的特征和局部结构

通过溶胶-凝胶法合成了组成为3HfO ₂ ·15SiO ₂ · x Y ₂ O ₃ ·（82- x）ZrO _2的锆酸盐体系，其中x = 2，7和12 mol％Y ₂ O ₃。X射线衍射数据分析表明，在陶瓷纳米混合物中存在t-ZrO ₂，m-ZrO ₂，m-HfO ₂，Y ₂ SiO ₅和Y ₂ Si ₂ O ₇结晶相。光谱数据表明，Y ₂ O的增加样品_3的含量决定了t-ZrO ₂，m-HfO ₂和硅酸盐结晶相的增加。随着样品中Y ₂ O ₃含量的增加，能隙值几乎呈线性下降。XANES数据的详细研究并未显示出随着样品中Y ₂ O ₃含量的增加而产生显着差异，这表明the离子+4氧化态及其微污染度具有明显的稳定性。EXAFS结果表明，Hf阳离子周围的局部结构与单斜晶体HfO ₂中的局部结构相似其中Hf–O的配位数趋于7。Hf–O壳的键长与〜2.12Å的偏差很小，并且通过增加样品的Y ₂ O ₃含量，Hf–金属的路径变得更加结构化。