AlF3掺杂氧化铝陶瓷的高灵敏辐照诱导相分离行为

doi:10.15541/jim20190564

摘要/Abstract

摘要：

放电等离子体烧结的AlF₃掺杂氧化铝陶瓷在透射电镜(TEM)常规观察条件下发现了一种电子辐照诱导快速相分离行为。在透射电镜的电子辐照下, 球形纳米晶Al颗粒在几秒钟内从原始氧化铝晶粒表面析出。高分辨TEM观察结合衍射花样分析发现原始的F掺杂氧化铝晶粒表面为高度缺陷态, 电子辐照后, 随着Al纳米颗粒析出, 氧化铝晶粒表面的缺陷消失。通过对掺杂过程缺陷反应及氧化铝阳离子亚晶格的深入分析, 提出了一种缺陷辅助间隙原子偏析机理来解释这一现象。即掺杂F离子首先占据氧空位的同时Al离子占据间隙位, 当氧空位被全部占据时, F和Al离子同时占据基体八面体间隙位, 并形成了亚稳定的掺杂态。在氧化铝基体1/3 [11ˉ00]不全位错的作用下, 畸变的阳离子亚晶格产生双聚八面体间隙位。当这些双聚八面体空位被外来Al离子占据时, 正如高分辨图像所观察的, 形成了包含有三个原子层左右的堆垛层错。同时, 沿着层错偏聚在双聚八面体位的掺杂Al离子扮演了析出物早期的角色, 在电子辐照下随着F离子的烧蚀, 不稳定的偏聚Al离子析出成为纳米颗粒并伴随着基体氧化铝的晶格重构。

关键词: AlF₃, Al₂O₃, TEM, 电子辐照, 相分离

Abstract:

An electron irradiation induced fast phase-separation behavior was observed under convention Transmission electron microscopy (TEM) observation of spark plasma sintered AlF₃ doped alumina ceramic. Spherical nanocrystalline Al precipitates separated out from original alumina grain surface within several seconds under transmission electron microscopy electron irradiation. By high resolution TEM observation combined with diffraction patterns analysis, it was found that the original alumina grain surface was in highly defected state. After electron irradiation under TEM, the defects on original alumina surface vanished accompanied by the precipitation of nanocrystalline Al particles. By thoroughly analysis of the defect reaction during doping process and the feature of cation sub-lattice of alumina, a defect assisted interstitial atom segregation mechanism was proposed to explain this behavior. According to this mechanism, doped F ions first occupied oxygen vacancy sites with corresponding Al ions at intrinsic interstitial sites. After oxygen vacancies being fully occupied, both F and Al ions tended to settle down at intrinsic octahedron interstitial sites, which resulted in a metastable doping state. Under the act of 1/3 [11ˉ00] partial dislocation of alumina matrix, distorted cation sub-lattice generated double aggregated vacant octahedron sites. When these doublets vacant octahedron sites were occupied by foreign Al ions, stacking faults composed of about three sequences were generated as that observed in high resolution TEM. Meanwhile, the segregated doping Al ions at double aggregated octahedron sites along the stacking faults worked as early stage precipitations. Under electron irradiation, with the ablation of F ions, the unstable segregated Al ions separated out as nano precipitation with the reconstruction of alumina lattice.

Key words: AlF₃, Al₂O₃, TEM, electron irradiation, phase-separation

中图分类号:

TQ174

申璐, 汪德文, 黄荣, 都时禹, 黄庆. AlF₃掺杂氧化铝陶瓷的高灵敏辐照诱导相分离行为[J]. 无机材料学报, 2021, 36(1): 95-100.

SHEN Lu, WANG Dewen, HUANG Rong, DU Shiyu, HUANG Qing. Electron Irradiation Induced Phase-separation Behavior in AlF₃ Doped Alumina Ceramic with Superior Sensitivity[J]. Journal of Inorganic Materials, 2021, 36(1): 95-100.

图/表 4

Fig. 1 TEM observations of a grain surface of 0.1wt% AlF3 doped sample (a) Original surface before high magnification observation; (b) Surface after high magnification observation, where sphere precipitates separated out; (c-d) Black arrow shows the growing of a new precipitate under irradiation; (e) Lattice fringes of a precipitated crystal

Fig. 2 EELS of the precipitation and its reference

Fig. 3 HRTEM images and selected area diffraction of AlF3 doped alumina grain (a) HRTEM images of AlF3 doped alumina grain before Al precipitation. White arrows points to the planer defects; (b) The same grain after Al precipitation; (c, d) Diffraction patterns correspond to the grain before and after Al precipitation, respectively. The zone axis is along [0001] direction; (e) Magnification of area i in (a). The dotted box traces a dislocation core and the parallel lines show the distortion contrast composed of three or four layers; (f) Inversed FFT of the area ii in (a) from (21¯1¯0)/(2¯110) diffraction spots

Fig. 4 (a) Schematic diagram of cation sub-lattice in α-alumina. The open and closed circles are the unoccupied and occupied octahedron sites respectively. Half-filled circles represent octahedron sites occupied by extrinsic Al3+ ions; (b) Real alumina structure in [112¯0] projection. The red box selects an Al layer between two oxygen layers; (c, d) Structures of the selected Al ions layer repainted in [0001] projection, before and after the act of a 1/3 [11¯00] partial dislocation, respectively. The open circles indicate unoccupied octahedron sites in the same layer

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AlF₃掺杂氧化铝陶瓷的高灵敏辐照诱导相分离行为

Electron Irradiation Induced Phase-separation Behavior in AlF₃ Doped Alumina Ceramic with Superior Sensitivity

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