三元过渡金属硼化物Os1-xRuxB2的制备及其结构和性能研究

doi:10.15541/jim20170392

摘要/Abstract

摘要：

以高纯锇(Os)、钌(Ru)、硼(B)粉为原料, 在常温常压下采用机械化学法制备了三元过渡金属硼化物Os_1-_xRu_xB₂粉末, 并对合成的粉末进行无压烧结使其致密化。研究了机械化学法合成Os_1-_xRu_xB₂的反应过程、Ru含量对OsB₂相结构的影响、合成粉末的热稳定性及烧结后块体材料的力学性能。采用X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对Os_1-_xRu_xB₂粉末及块体的相成分、表面形貌和微观结构进行表征, 并通过维氏硬度计测得其烧结后块体材料的显微硬度。实验结果表明: 合成过程中生成了中间产物Os_1-_xRu_xB_1.1, 随着球磨时间的延长有少量Os_1-_xRu_xB₂生成, 球磨24 h后合成粉末的主相为Os_1-_xRu_xB₂, 继续球磨到40 h, 粉末中相成分不再发生变化。当x≤0.1时, 合成粉末的主相为六方结构Os_1-_xRu_xB₂; 而当x≥0.15时,合成粉末的主相为正交结构的Os_1-_xRu_xB₂。经1450℃(保温1 h)热处理后的粉末中有部分六方结构的Os_1-_xRu_xB₂向正交结构发生相变, 并生成了低硼化物 (Os_1-_xRu_x)₂B₃。合成的OsB₂和Os_0.85Ru_0.15B₂粉末经1700℃无压烧结后颗粒呈板条状, 其致密度均为85%左右, 在0.49 N载荷下测得其硬度分别(27±2) GPa和(21±1) GPa。

关键词: 超硬材料, 机械化学法, 过渡金属硼化物, 固溶

Abstract:

Ternary Os_1-_xRu_xB₂ powders were synthesized by using mechanical alloying (MA) technique with Os (Osmium), Ru (Ruthenium) and B (Boron) powders as raw materials. The synthesis process and effect of Ru content on phase composition, and thermal stability of the as-milled powders, and mechanical properties of the samples were studied. X-Ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed to study chemical composition and microstructure of the as-synthesized powders and the as-sintered bulk samples. Result showed that Os_1-_xRu_xB_1.1was formed as an intermediate product during the formation process of solid-state reaction of Os_1-_xRu_xB₂from Os, Ru and B powders. After milled for 24 h, the main phase mixture powders were Os_1-_xRu_xB₂ which kept unchanged till milled for 40 h. When x≤0.1, the main phase of the mixture powders was ReB₂-type Os_1-_xRu_xB₂ with hexagonal structure; when x≥0.15, the main phase of the as-milled powders was RuB₂-type Os_1-_xRu_xB₂ with orthogonal structure. After heat treatment at 1450℃ for 1 h, the ReB₂-type Os_1-_xRu_xB₂ partially converted to the orthorhombic phase, while the structure of RuB₂-type Os_1-_xRu_xB₂kept unchanged. The as-sintered OsB₂ and Os_0.85Ru_0.15B₂samples by pressure-less sintering at 1700℃ showed rod-like particles with small pores, the density of the two samples was about 85%, and the micro hardness under a load of 0.49 N was (27±2) GPa and (21±1) GPa, respectively.

Key words: super-hard materials, mechanical alloying, transition metal boride, solid solution

中图分类号:

TQ174

邹灿辉, 龙莹, 郑鑫, 张锦阳, 林华泰. 三元过渡金属硼化物Os_1-_xRu_xB₂的制备及其结构和性能研究[J]. 无机材料学报, 2018, 33(7): 787-792.

ZOU Can-Hui, LONG Ying, ZHENG Xin, ZHANG Jin-Yang, LIN Hua-Tai. Preparation, Microstructure and Property of Ternary Transition Metal Boride Os_1-_xRu_xB₂[J]. Journal of Inorganic Materials, 2018, 33(7): 787-792.

图/表 8

图1 不同高能球磨时间得到的Os-Ru-B复合粉末的XRD图谱

Fig. 1 XRD patterns of Os-Ru-B system after high energy ball milling for different time(a) From 4 h to 40 h; (b) 4 h; (c) 40 h

表1 正交结构RuB2和OsB2的晶格参数

Table 1 Lattice parameters of orthorhombic RuB2 and OsB2

Lattice parameters	a/nm	b/nm	c/nm
RuB₂PDF#15-0213	0.46410	0.28630	0.40440
OsB₂ PDF#17-0370	0.46788	0.28693	0.40724

图2 球磨40 h得到的Os0.8Ru0.2B2粉末颗粒的SEM照片和EDS图谱

Fig. 2 SEM image and EDS pattern of Os0.8Ru0.2B2 powders produced by ball milling for 40 h

图3 球磨40 h后生成的Os0.8Ru0.2B2粉末颗粒的TEM照片

Fig. 3 TEM images of Os0.8Ru0.2B2 powders produced by ball milling for 40 h

图4 球磨40 h得到的Os0.8Ru0.2B2粉末颗粒的HRTEM照片

Fig. 4 HRTEM image of Os0.8Ru0.2B2 powders produced by ball milling for 40 h

图5 不同Ru含量, 球磨40 h后Os-Ru-B复合粉末的XRD图谱

Fig. 5 XRD patterns of Os-Ru-B system with different contents of Ru after ball milling for 40 h

图6 1450℃热处理后Os1-xRuxB2(x=0、0.1、0.2和0.3)粉末的XRD图谱

Fig. 6 XRD patterns of Os1-xRuxB2(x=0, 0.1, 0.2, 0.3) powders after heat-treatement at 1450℃ for 1 h

图7 1700℃无压气氛烧结后OsB2(a)~(b)和Os0.85Ru0.15B2(c)~(d)断面SEM照片

Fig. 7 SEM images of fractural surface of the OsB2 (a)-(b) and Os0.85Ru0.15B2 (c)-(d) samples after pressureless sintering at 1700℃

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三元过渡金属硼化物Os_1-_xRu_xB₂的制备及其结构和性能研究

Preparation, Microstructure and Property of Ternary Transition Metal Boride Os_1-_xRu_xB₂

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