放电等离子烧结制备ZrB<sub>2</sub>-SiC超高温陶瓷的力学性能及氧化行为

何慧娟; 闫晓杰; 树学峰; 肖革胜; 郝鑫; 李志刚

doi:10.11858/gywlxb.20200623

放电等离子烧结制备ZrB₂-SiC超高温陶瓷的力学性能及氧化行为

doi: 10.11858/gywlxb.20200623

太原理工大学机械与运载工程学院应用力学研究所，山西太原　030024

基金项目: 国家自然科学基金（11772217，11802198）

详细信息

作者简介:
何慧娟（1995－），女，硕士研究生，主要从事弹塑性力学研究. E-mail：1945106146@qq.com

通讯作者:
李志刚（1975－），男，副教授，主要从事弹塑性力学研究. E-mail：254970134@qq.com

中图分类号: O347.3
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出版历程
- 收稿日期: 2020-10-09
- 修回日期: 2020-11-06

Mechanical Properties and Oxidation Behavior of ZrB₂-SiC Ultra-High Temperature Ceramics Prepared by Spark Plasma Sintering

Institute of Applied Mechanics, College of Mechanical and Vehicle Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China

摘要

摘要: 在服役环境中，超高声速飞行器表面与空气剧烈摩擦导致温度极高。超高温陶瓷相较于一般陶瓷而言具有高熔点和良好的抗氧化烧蚀性能，是目前极具前景的热防护材料之一。采用放电等离子两步烧结工艺将ZrB₂纳米粉末和SiC粉末在1 700 ℃下制备超高温陶瓷材料ZrB₂-20%SiC，通过纳米压痕微观实验、三点弯实验研究其力学性能及其在高温环境下的氧化行为，着重分析1 000、1 200、1 400和1 600 ℃ 4种不同氧化温度下ZrB₂-20%SiC超高温陶瓷的氧化表面、氧化截面和氧化层厚度。结果表明：ZrB₂-20%SiC超高温陶瓷的硬度为18 GPa，弹性模量为541 GPa，断裂韧性为5.7 MPa·m^1/2；当氧化温度为1600 ℃时，超高温陶瓷内部的SiC由被动氧化转变为主动氧化，并且随着氧化温度升高，超高温陶瓷氧化层厚度与氧化温度呈正相关。
- ZrB₂-SiC /
- 超高温陶瓷 /
- 放电等离子烧结 /
- 力学性能 /
- 氧化行为
Abstract: In the application environment, the surface of the ultra-high-speed aircraft is violently rubbed with the air to make the temperature extremely high. Compared with ordinary ceramics, ultra-high temperature ceramics possess a higher melting point with good oxidation and ablation resistance performance. Therefore, it is particularly interested to be used as thermal protection materials. In this paper, ZrB₂-20%SiC ultra-high temperature ceramic materials are prepared by using the spark plasma two-step sintering process of ZrB₂ nanopowder and SiC powder at 1700 ℃. The mechanical properties of ZrB₂-20%SiC are studied through nanoindentation experiment and three-point bending experiment. The oxidation behavior of ZrB₂-20%SiC ultra-high temperature ceramics at four different oxidation temperatures of 1000, 1200, 1400 and 1600 ℃ is analyzed in this paper. The results show that the hardness of the ZrB2-20%SiC ultra-high temperature is 18 GPa, and the elastic modulus is 541 GPa with the fracture toughness of 5.7 MPa·m^1/2. When the oxidation temperature is 1600 ℃, the SiC inside the ultra-high temperature ceramic would transform from passive oxidation to active oxidation. As the oxidation temperature increases, the thickness of the ultra-high temperature ceramic oxide layer and the oxidation temperature demonstrate a positive correlation trend.
- ZrB₂-SiC /
- ultra-high temperature ceramics /
- spark plasma sintering /
- mechanical properties /
- oxidationbehavior

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图 1 放电等离子烧结曲线

Figure 1. Curves of spark plasma sintering

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图 2 未抛光烧结试件

Figure 2. Unpolished sintered sample

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图 3 三点弯单边切口试验 (a)及试件断口形貌(b)

Figure 3. Schematic diagram of three-point bending single-side notch test (a) and fracture morphology of the specimen (b)

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图 4 GSX-1600高温氧化炉

Figure 4. GSX-1600 high temperature oxidation furnace

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图 5 ZrB₂-SiC的纳米压入实验：（a）载荷-位移曲线，（b）弹性模量-位移曲线，（c）硬度-位移曲线

Figure 5. ZrB₂-SiC nanoindentation experiment：(a) load-displacement curves，(b) elastic modulus-displacement curves， (c) hardness-displacement curves

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图 6 ZrB₂-20%SiC超高温陶瓷抛光表面

Figure 6. Polished surface of ZrB₂-20%SiC ultra-high temperature ceramic

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图 7 ZrB₂-20%SiC超高温陶瓷断裂截面

Figure 7. Fracture section of ZrB₂-20%SiC ultra-high temperature ceramic

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图 8 不同氧化温度( 1 000 ～ 1 600 ℃)下ZrB₂-20%SiC超高温陶瓷的氧化表面

Figure 8. Oxidized surface of ZrB₂-20%SiC ultra-high temperature ceramic at different oxidation temperatures (1 000–1 600 ℃)

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图 9 在不同氧化温度下（1200、1400 和 1600 ℃）ZrB₂-20%SiC的超高温陶瓷的氧化截面

Figure 9. Oxidation cross-sections of ZrB₂-20%SiC ultra-high temperature ceramicsat different oxidation temperatures (1200, 1400 and 1600 ℃)

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图 10 ZrB₂-SiC超高温陶瓷在不同氧化温度下（1000～1600 ℃）的氧化层厚度

Figure 10. Oxide layer thickness of ZrB₂-SiC ultra-high temperature ceramic at different temperatures (1000–1600 ℃)

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表 1 ZrB₂基陶瓷材料的粒径尺寸、相对密度及力学性能

Table 1. Particle size, relative density and mechanical properties of ZrB₂-based ceramic materials

Material	ZrB₂ particle size/μm	SiC particle size/μm	Relative density/%	Elastic modulus/MPa	Hardness/ GPa	Fracture toughness/ (MPa·m^1/2)	Preparation method
ZrB₂-20%SiC^[22]	3.0	1.50	94.4		13.4	4.8	Hot press sintering
ZrB₂-20%SiC^[23]	3.9	2.00	97.5	446		5.5	Hot press sintering
ZrB₂-20%SiC^[24]	1.2	1.00	99.8	520	20.7	4.6	Hot press sintering
ZrB₂-20%SiC	0.4	0.05	98.1	541	18.0	5.7	Spark plasma sintering

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参考文献(27)

[1]	杜善义, 方岱宁, 孟松鹤, 等. “近空间飞行器的关键基础科学问题”重大研究计划结题综述 [J]. 中国科学基金, 2017, 31(2): 109–114. DU S Y, FANG D N, MENG S H, et al. Summary of the major research project of "Key Basic Scientific Issues of Near Space Vehicles" [J]. Chinese Science Foundation, 2017, 31(2): 109–114.
[2]	SZIROCZAK D, SMITH H. A review of design issues specific to hypersonic flight vehicles [J]. Progress in Aerospace Sciences, 2016, 84: 1–28. doi: 10.1016/j.paerosci.2016.04.001
[3]	TANG S F, HU C L. Design, preparation and properties of carbon fiber reinforced ultra-high temperature ceramic composites for aerospace applications: a review [J]. Journal of Materials Science & Technology, 2017, 33(2): 117–130.
[4]	韩洪涛, 王璐, 郑义. 2019年国外高超声速技术发展回顾 [J]. 飞航导弹, 2014(3): 16–20. HAN H T, WANG L, ZHENG Y. Review of the development of foreign hypersonic technology in 2019 [J]. Flying Missile, 2014(3): 16–20.
[5]	廖龙文, 曾鹏, 陈军燕, 等. 高超声速飞行器发展困境分析 [J]. 飞航导弹, 2019(12): 22–27. LIAO L W, ZENG P, CHEN J Y, et al. Analysis on the development dilemma of hypersonic vehicles [J]. Flying Missile, 2019(12): 22–27.
[6]	张幸红, 胡平, 韩杰才, 等. 超高温陶瓷复合材料的研究进展 [J]. 科学通报, 2015, 60(3): 257–266. ZHANG X H, HU P, HAN J C, et al. Research progress of ultra-high temperature ceramic composite materials [J]. Science Bulletin, 2015, 60(3): 257–266.
[7]	杨亚政, 杨嘉陵, 方岱宁. 高超声速飞行器热防护材料与结构的研究进展 [J]. 应用数学和力学, 2008, 29(1): 47–56. doi: 10.3879/j.issn.1000-0887.2008.01.007 YANG Y Z, YANG J L, FANG D N. Research progress on thermal protection materials and structures of hypersonic vehicles [J]. Applied Mathematics and Mechanics, 2008, 29(1): 47–56. doi: 10.3879/j.issn.1000-0887.2008.01.007
[8]	樊乾国, 郝志彪, 闫联生, 等. 超高温陶瓷改性C/SiC复合材料的研究进展 [J]. 材料导报, 2011, 25(S1): 539–542. FAN Q G, HAO Z B, YAN L S, et al. Research progress of C/SiC composites modified by ultra-high temperature ceramics [J]. Materials Review, 2011, 25(S1): 539–542.
[9]	向阳. C_f/SiC复合材料超高温陶瓷涂层的制备及性能研究 [D].长沙: 国防科学技术大学, 2008: 4−9. XIANG Y. Fabrication and properties investigation on ultra high temperature ceramics coatings of C_f/SiC composites [D]. Changsha: National University of Defense Technology, 2008: 4−9.
[10]	PADTURE N P. Advanced structural ceramics in aerospace propulsion [J]. Nature Materials, 2016, 15(8): 804–809. doi: 10.1038/nmat4687
[11]	史姣红, 李玉龙, 刘元镛, 等. 超高速碰撞C-SiC复合材料双层防护结构的力学特性 [J]. 高压物理学报, 2012, 26(1): 18–26. doi: 10.11858/gywlxb.2012.01.003 SHI J H, LI Y L, LIU Y Y, et al. Mechanical properties of C-SiC composite double-layer protection structure for hypervelocity impact [J]. Chinese Journal of High Pressure Physics, 2012, 26(1): 18–26. doi: 10.11858/gywlxb.2012.01.003
[12]	HU P, WANG G L, WANG Z. Oxidation mechanism and resistance of ZrB₂-SiC composites [J]. Corrosion Science, 2009, 51(11): 2724–2732. doi: 10.1016/j.corsci.2009.07.005
[13]	WILLIAM G F, GREG E H. Ultra-high temperature ceramics: materials for extreme environments [J]. Scripta Materialia, 2016, 129(1): 94–99.
[14]	JIN X C, LI P, HOU C, et al. Oxidation behaviors of ZrB₂ based ultra-high temperature ceramics under compressive stress [J]. Ceramics International, 2019, 45(6): 7278–7285. doi: 10.1016/j.ceramint.2019.01.009
[15]	ZOU J, ZHANG G J, VLEUGELS J, et al. High temperature strength of hot pressed ZrB₂-20vol%SiC ceramics based on ZrB₂ starting powders prepared by different carbo/boro-thermal reduction routes [J]. Journal of the European Ceramic Society, 2013, 33(10): 1609–1614. doi: 10.1016/j.jeurceramsoc.2013.03.001
[16]	陈小武. C_f/SiC-ZrC-ZrB₂超高温陶瓷基复合材料的制备及性能研究 [D]. 上海: 中国科学院上海硅酸盐研究所, 2018: 5−8. CHEN X W. Preparation and properties of C_f/SiC-ZrC-ZrB₂ ultra-high temperature ceramic matrix composites [D]. Shanghai: Shanghai Institute of Ceramics, Chinese Academy of Sciences, 2018: 5−8.
[17]	WILLIAMS P A, SAKIDJA R, PEREPEZKO J H, et al. Oxidation of ZrB₂-SiC ultra-high temperature composites over a wide range of SiC content [J]. Journal of the European Ceramic Society, 2012, 32(14): 3875–3883. doi: 10.1016/j.jeurceramsoc.2012.05.021
[18]	王秀芬, 周曦亚. 放电等离子烧结技术 [J]. 中国陶瓷, 2006, 42(7): 14–16. doi: 10.3969/j.issn.1001-9642.2006.07.005 WANG X F, ZHOU X Y. Spark plasma sintering technology [J]. Chinese Ceramics, 2006, 42(7): 14–16. doi: 10.3969/j.issn.1001-9642.2006.07.005
[19]	刘永红, 于丽丽, 徐玉龙, 等. 电火花放电通道蚀除绝缘工程陶瓷的热力学特性研究 [J]. 高压物理学报, 2009, 23(2): 91–97. doi: 10.3969/j.issn.1000-5773.2009.02.003 LIU Y H, YU L L, XU Y L, et al. Study on the thermodynamic characteristics of electrical spark discharge channel erosion of insulating engineering ceramics [J]. Chinese Journal of High Pressure Physics, 2009, 23(2): 91–97. doi: 10.3969/j.issn.1000-5773.2009.02.003
[20]	HU P, GUI K, HONG W, et al. Preparation of ZrB₂-SiC ceramics by single-step and optimized two-step hot pressing using nanosized ZrB₂ powders [J]. Materials Letters, 2017, 200(1): 14–17.
[21]	OLIVER W C, PHARR G M. An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments [J]. Journal of Materials Research, 1992, 7(6): 1564–1583. doi: 10.1557/JMR.1992.1564
[22]	万德田, 魏永金, 包亦望, 等. 陶瓷断裂韧性测试方法准确性和简便性比较分析 [J]. 硅酸盐学报, 2019, 47(8): 1080–1088. WAN D T, WEI Y J, BAO Y W, et al. Comparative analysis of accuracy and convenience of ceramic fracture toughness testing methods [J]. Journal of the Chinese Ceramic Society, 2019, 47(8): 1080–1088.
[23]	龚江宏, 关振铎. 陶瓷材料断裂韧性测试技术在中国的研究进展 [J]. 硅酸盐通报, 1996, 15(1): 53–57. GONG J H, GUAN Z D. Research progress of ceramic material fracture toughness testing technology in China [J]. Bulletin of the Chinese Ceramic Society, 1996, 15(1): 53–57.
[24]	ADAM L C, WILLIAM F G F, GREGORY E H, et al. High-strength zirconium diboride-based ceramics [J]. Journal of the American Ceramic Society, 2004, 87(6): 1170–1172. doi: 10.1111/j.1551-2916.2004.01170.x
[25]	PATEL M, REDDY J J, PRASAD V V B, et al. Strength of hot pressed ZrB₂-SiC composite after exposure to high temperatures (1 000-1 700 ℃) [J]. Journal of the European Ceramic Society, 2012, 32(16): 4455–4467. doi: 10.1016/j.jeurceramsoc.2012.06.025
[26]	ZHU S, WILLIAM G F, GREGORY E H. Influence of silicon carbide particle size on the microstructure and mechanical properties of zirconium diboride-silicon carbide ceramics [J]. Journal of the European Ceramic Society, 2007, 27(4): 2077–2083. doi: 10.1016/j.jeurceramsoc.2006.07.003
[27]	WU W W, SAKKA Y, SUZUKI T S, et al. Microstructure and anisotropic properties of textured ZrB₂ and ZrB₂-MoSi₂ ceramics prepared by strong magnetic field alignment [J]. International Journal of Applied Ceramic Technology, 2014, 11(2): 218–227. doi: 10.1111/ijac.12061