Kohara Shinji, Akola Jaakko, Patrikeev Leonid, Ropo Matti, Ohara Koji, Itou Masayoshi, Fujiwara Akihiko, Yahiro Jumpei, Okada Junpei T, Ishikawa Takehiko, Mizuno Akitoshi, Masuno Atsunobu, Watanabe Yasuhiro, Usuki Takeshi
1] Research and Utilization Division, Japan Synchrotron Radiation Research Institute/SPring-8, 1-1-1 Kouto, Sayo-cho, Sayo, Hyogo 679-5198, Japan [2] Schools of Materials Science, Japan Advanced Institute of Science and Technology, Nomi, Ishikawa 923-1291, Japan.
1] Department of Physics, Tampere University of Technology, PO Box 692, FI-33101 Tampere, Finland [2] COMP Centre of Excellence, Department of Applied Physics, Aalto University, FI-00076 Aalto, Finland [3] Peter-Grünberg-Institut PGI-1, Forschungszentrum Jülich, D-52425 Jülich, Germany.
Nat Commun. 2014 Dec 18;5:5892. doi: 10.1038/ncomms6892.
The structure of high-temperature liquids is an important topic for understanding the fragility of liquids. Here we report the structure of a high-temperature non-glass-forming oxide liquid, ZrO2, at an atomistic and electronic level. The Bhatia-Thornton number-number structure factor of ZrO2 does not show a first sharp diffraction peak. The atomic structure comprises ZrO5, ZrO6 and ZrO7 polyhedra with a significant contribution of edge sharing of oxygen in addition to corner sharing. The variety of large oxygen coordination and polyhedral connections with short Zr-O bond lifetimes, induced by the relatively large ionic radius of zirconium, disturbs the evolution of intermediate-range ordering, which leads to a reduced electronic band gap and increased delocalization in the ionic Zr-O bonding. The details of the chemical bonding explain the extremely low viscosity of the liquid and the absence of a first sharp diffraction peak, and indicate that liquid ZrO2 is an extremely fragile liquid.
高温液体的结构是理解液体脆性的一个重要课题。在此，我们在原子和电子层面上报告了一种高温非玻璃形成氧化物液体ZrO₂的结构。ZrO₂的Bhatia-Thornton数-数结构因子未显示出第一个尖锐衍射峰。原子结构由ZrO₅、ZrO₆和ZrO₇多面体组成，除了顶角共享外，氧的边共享也有显著贡献。锆相对较大的离子半径导致了多种大的氧配位和具有短Zr-O键寿命的多面体连接，扰乱了中程有序的演化，这导致离子Zr-O键合中电子带隙减小和离域增加。化学键合的细节解释了该液体极低的粘度以及第一个尖锐衍射峰的缺失，并表明液态ZrO₂是一种极其脆弱的液体。
