微米晶单斜氧化锆高压相变制备亚微米四方多晶氧化锆

董丙舜; 王海阔; 仝斐斐; 侯志强; 李振; 刘童; 臧金浩; 杨西贵

doi:10.11858/gywlxb.20190709

微米晶单斜氧化锆高压相变制备亚微米四方多晶氧化锆

doi: 10.11858/gywlxb.20190709

董丙舜^{1, 2,},
王海阔^2,*, ,,
仝斐斐²,
侯志强²,
李振¹,
刘童¹,
臧金浩¹,
杨西贵^1,*, ,

1.
郑州大学物理工程学院，河南郑州　450001
2.
河南工业大学材料科学与工程学院材料压处理研究所，河南郑州　450001

基金项目: 国家自然科学基金青年科学基金（11504087，11804307）；郑州市科技重大专项（174PZDZX567）

详细信息

作者简介:
董丙舜（1992－），男，硕士研究生，主要从事高压下陶瓷材料的合成和物性研究. E-mail: bingshun219@163.com

通讯作者:
王海阔（1984－），男，博士，副教授，主要从事超硬材料合成、大腔体静高压技术和高压下材料物性研究. E-mail: haikuo_wang@haut.edu.cn

杨西贵（1990－），男，博士，主要从事高压下碳材料的新结构和新性质研究. E-mail: yangxg@zzu.edu.cn

中图分类号: O521.2
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出版历程
- 收稿日期: 2019-01-10
- 修回日期: 2019-03-11

Fabrication of Submicron Tetragonal Polycrystalline ZrO₂ by the Transformation of Micro Monoclinic ZrO₂ under High Pressure

DONG Bingshun^{1, 2
,},
WANG Haikuo^{2,*
, ,},
TONG Feifei²,
HOU Zhiqiang²,
LI Zhen¹,
LIU Tong¹,
ZANG Jinhao¹,
YANG Xigui^{1,*
, ,}

1.
School of Physics and Engineering, Zhengzhou University, Zhengzhou 450001, China
2.
Institute of Materials Press-Treatment, School of Materials Science and Engineering, Henan University of Technology, Zhengzhou 450001, China

摘要

摘要: 高压相变已逐渐发展成为一种制备纳米/亚微米多晶陶瓷块体材料的有效方法。高压可以抑制原子的长程扩散进而抑制晶粒长大，高压下截获的新相不受初始材料晶粒尺寸的制约，通过热力学调控可以得到晶粒尺寸更小的多晶块体材料。陶瓷材料在特定热力学条件下通常会发生相变，新相的形成要经历形核、生长的过程。采用晶粒尺寸为2 $ {\text{μ}} $m的单斜ZrO₂与晶粒尺寸为50 nm的Y₂O₃以97 : 3的摩尔比混合，在5.5 GPa、800～1700 ℃温压区间内对初始材料进行烧结，采用X射线衍射、扫描电镜、透射电镜对所得样品进行表征。研究结果表明：高压下截获了单斜相和亚微米四方相复合的多晶ZrO₂块体材料，1200、1400、1600和1700 ℃温度下获得的四方相的平均晶粒尺寸为(145±62) nm、(246±165) nm、(183±62) nm和(245±107) nm。利用高压相变以微米晶制备细晶粒多晶块体材料，可以避免常规方法中以纳米粉末为初始材料制备细晶粒多晶块体材料存在的团聚、吸附及晶粒长大的问题，进而发展一种以微米晶为初始材料通过高压相变制备高性能细晶粒多晶块体材料的方法。
- 高压 /
- 相变 /
- 微米晶 /
- 亚微米晶 /
- 氧化锆
Abstract: The transformation-assisted consolidation under pressure has been demonstrated to be a promising method to fabricate the nano or submicron polycrystalline ceramic materials. The high pressure suppresses the long-range diffusion of the atoms and, consequently, restrains the grain coarsening. The new phases produced at high pressure could show finer grains under the appropriate thermodynamic conditions, which are not subject to the grain size of the raw materials. Ceramic materials exhibit the existence of the transformations under certain thermodynamic conditions and the formation of new phases generally undergoes the nucleation and growth. In the present work, monoclinic microcrystal ZrO₂ with average grain size of 2 µm and Y₂O₃ with average grain size of 50 nm were mixed in molar ratio of 97∶3. The preparation of the samples was carried out by sintering at 5.5 GPa and temperatures of 800–1700 °C using the high pressure cubic cell, and the sample characterization was performed via the X-ray diffraction, scanning electron microscope and transmission electron microscopy. It was found that the monoclinic and submicron tetragonal composite polycrystalline ZrO₂ in bulk is obtained under high pressure and high temperature. The average grain size of tetragonal ZrO₂ fabricated at 1200, 1400, 1600 and 1700 °C is (145±62) nm, (246±165) nm, (183±62) nm and (245±107) nm, respectively. The synthesis of the fine-grained polycrystalline materials by the transformation under high pressure can solve the problems of agglomeration, adsorption and grain coarsening caused by the nanopowders as the starting materials in the conventional approach, which would be an alternative route to fabricate the fine-grained polycrystalline materials with the enhanced performances.
- high pressure /
- phase transformation /
- micro crystal /
- submicron crystal /
- ZrO₂

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图 1 组装示意图

Figure 1. Schematic diagram of assembly

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图 2 亚微米原料和微晶ZrO₂的XRD图谱（插图为ZrO₂单斜相特征峰XRD图谱）

Figure 2. XRD pattern of submicron and microcrystalline ZrO₂ (Inset: XRD pattern of the characteristic diffraction peaks of monoclinic ZrO₂)

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图 3 亚微米晶ZrO₂(a)和微米晶ZrO₂(b)的SEM照片

Figure 3. SEM images of submicron (a) and microcrystalline ZrO₂ (b)

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图 4 5.5 GPa不同温度条件下样品的XRD图谱（a）、单斜相和四方相的特征峰放大图谱（b）以及（a）中方框标记的800和1000 ℃条件下合成样品的XRD图谱（c）

Figure 4. (a) XRD pattern of samples sintered at 5.5 GPa and different temperatures; (b) magnified range of the characteristic diffraction peaks of monoclinic and tetragonal phases from (a); (c) XRD patterns of samples sintered at 800 and 1000 ℃ marked with dotted line in (a)

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图 5 (a) 1400 ℃温度条件下样品中亚微米晶粒的SEM照片，(b) (a)中箭头所指亚微米晶粒的EDS能谱，(c) 1700 ℃温度条件下样品中亚微米晶粒的SEM照片，(d) (c)中箭头所指亚微米晶粒的EDS能谱

Figure 5. (a) SEM images of submicron grains in the sample sintered at 1400 ℃; (b) EDS spectra of the submicron grain directed by the arrow; (c) SEM images of submicron grains in the sample sintered at 1700 ℃; (d) EDS spectra of the submicron grain directed by the arrow

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图 6 5.5 GPa、不同温度下合成样品的SEM照片

Figure 6. SEM images of samples sintered at the condition of 5.5 GPa and different temperatures

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图 7 5.5 GPa不同温度下合成样品中亚微米晶粒的晶粒尺寸分布

Figure 7. Grain size distribution of submicron grains in samples sintered at 5.5 GPa and different temperatures

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图 8 5.5 GPa、1700 ℃合成样品的TEM照片（（a）样品中亚微米晶粒的低倍TEM照片；（b）样品中亚微米晶粒的HRTEM照片，插图为虚线椭圆部位的放大图）

Figure 8. TEM images of the sample sintered at 5.5 GPa and 1700 ℃ ((a) Low-magnification TEM image of submicron grains in the sample; (b) HRTEM image of submicron grains in the sample. Inset: Magnified HRTEM image marked with the dotted ellipse in (b))

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表 1 室温下稳定四方相氧化锆的晶胞参数

Table 1. Unit-cell parameters of tetragonal zirconia stabilized at room temperature

Sample	Processing temperature/℃	a/nm	c/nm	Test method
Tetragonal zirconia	1400	0.3607(6)	0.5219(8)	XRD
Tetragonal zirconia	1700	0.3615(5)	0.5168(3)	XRD
ZrO₂^[42]		0.3591(1)	0.5169(1)	Neutron diffraction
Zr_0.94Y_0.06O_1.97^[43]		0.3610	0.5168	XRD

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