B-C-N-Ti四元超硬复合材料的高压烧结

黄鸿东; 于晓辉; 贺端威

doi:10.11858/gywlxb.20240769

B-C-N-Ti四元超硬复合材料的高压烧结

doi: 10.11858/gywlxb.20240769

黄鸿东^1,,
于晓辉^2,*, ,,
贺端威^1,*, ,

1.
四川大学原子与分子物理研究所, 四川成都　610065
2.
中国科学院物理研究所, 北京　100190

基金项目: 国家重点研发计划（2023YFA1406200）

详细信息

作者简介:
黄鸿东（1997－），男，硕士研究生，主要从事高压下超硬材料的合成研究. E-mail：hongdonghuangsss@163.com

通讯作者:
于晓辉（1981－），男，博士，研究员，主要从事高压物理及材料研究. E-mail：yuxh@iphy.ac.cn

贺端威（1969－），男，博士，教授，主要从事高压物理、大腔体静高压技术以及超硬材料研究. E-mail：duanweihe@scu.edu.cn

中图分类号: O521.3; O521.2
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出版历程
- 收稿日期: 2024-03-29
- 修回日期: 2024-04-25
- 网络出版日期: 2024-07-08
- 刊出日期: 2024-07-25

High Pressure Sintering of B-C-N-Ti Quaternary Superhard Composites

HUANG Hongdong^1
,,
YU Xiaohui^{2,*
, ,},
HE Duanwei^{1,*
, ,}

1.
Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065, Sichuan, China
2.
Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China

摘要

摘要: 以金刚石、立方氮化硼（cBN）和钛（Ti）为初始材料，通过高温高压反应烧结制备了B-C-N-Ti四元超硬复合材料。结果表明：在高温高压下，Ti与金刚石及cBN反应生成TiC_0.7N_0.3和TiB₂；TiC_0.7N_0.3作为黏结相以键合金刚石和cBN晶粒，适量Ti的加入可以有效地提高烧结体的韧性；反应生成的TiC_0.7N_0.3和TiB₂等陶瓷相以及cBN对金刚石晶粒的包裹提高了烧结体的抗氧化性。当金刚石、cBN和Ti的摩尔比为2∶1∶0.10时，在压力为12 GPa、温度为2000℃、保温5 min的条件下得到的烧结样品性能较好，其维氏硬度达到 (49.0±1.2) GPa，韧性为(14.2±0.6) MPa·m^1/2，空气氛围下的起始氧化温度为921 ℃。
- 金刚石 /
- 立方氮化硼 /
- 钛 /
- 超硬复合材料 /
- 高温高压 /
- 烧结
Abstract: In this work, the B-C-N-Ti quaternary superhard composite was prepared by high pressure and high temperature sintering with diamond, cubic boron nitride (cBN) and titanium (Ti) as starting materials. The characterization results show that Ti reacts with diamond and cBN to form TiC_0.7N_0.3 and TiB₂ under high pressure and high temperature, which acts as the binding additives for diamond and cBN grains. The addition of appropriate amount of Ti can effectively improve the toughness of the sintered composite specimen. The formation of TiC_0.7N_0.3 and TiB₂ ceramics and cBN coated the diamond grains and greatly enhanced the oxidation ability. When the molar ratio of diamond, cBN and Ti is 2∶1∶0.10 and sintered at 12 GPa and 2000 ℃ for 5 min, the specimen exhibits the best performance with Vickers hardness of (49.0±1.2) GPa, fracture toughness of (14.2±0.6) MPa·m^1/2 and oxidation temperature of 921 ℃ under air condition.
- diamond /
- cBN /
- titanium /
- superhard composites /
- high pressure and high temperature /
- sintering

HTML全文

图 1 不同Ti含量下金刚石-Ti-cBN烧结样品（12 GPa、2000 ℃）的XRD谱

Figure 1. XRD patterns of diamond-Ti-cBN composites sintered at 12 GPa and 2000 ℃ with different contents of Ti

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图 2 金刚石-Ti-cBN烧结样品断裂面的SEM图像

Figure 2. SEM images of the fracture surfaces of diamond-Ti-cBN sintered composites

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图 3 BND₂Ti_0.10 的SEM图像以及B、C、N和 Ti 元素的EDS图谱

Figure 3. SEM image and the corresponding EDS mapping of B, C, N, and Ti element for BND₂Ti_0.10 specimen

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图 4 不同Ti含量的金刚石-Ti-cBN烧结样品的维氏硬度和韧性

Figure 4. Vickers hardness and fracture toughness of diamond-Ti-cBN specimens with different contents of Ti

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图 5 BND₂Ti_0.10 样品在49 N加载下的压痕SEM图像

Figure 5. SEM images of the Vickers hardness indentation for BND₂Ti_0.10 specimens at the applied load of 49 N

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图 6 空气氛围下加热至1400 ℃的BND₂Ti_0.10烧结样品的TG-DSC曲线

Figure 6. TG-DSC curve of BND₂Ti_0.10 specimen to 1400 ℃ under air condition

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参考文献(31)

[1]	VEPŘEK S. The search for novel, superhard materials [J]. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, 1999, 17(5): 2401–2420.
[2]	IRIFUNE T, KURIO A, SAKAMOTO S, et al. Ultrahard polycrystalline diamond from graphite [J]. Nature, 2003, 421(6923): 599–600. doi: 10.1038/421599b
[3]	MONTEIRO S N, SKURY A L D, DE AZEVEDO M G, et al. Cubic boron nitride competing with diamond as a superhard engineering material: an overview [J]. Journal of Materials Research and Technology, 2013, 2(1): 68–74. doi: 10.1016/j.jmrt.2013.03.004
[4]	SOLOZHENKO V L, ANDRAULT D, FIQUET G, et al. Synthesis of superhard cubic BC₂N [J]. Applied Physics Letters, 2001, 78(10): 1385–1387. doi: 10.1063/1.1337623
[5]	ZHAO Y, HE D W, DAEMEN L L, et al. Superhard B-C-N materials synthesized in nanostructured bulks [J]. Journal of Materials Research, 2002, 17(12): 3139–3145. doi: 10.1557/JMR.2002.0454
[6]	DONG H N, HE D W, DUFFY T S, et al. Elastic moduli and strength of nanocrystalline cubic BC₂N from X-ray diffraction under nonhydrostatic compression [J]. Physical Review B, 2009, 79(1): 014105. doi: 10.1103/PhysRevB.79.014105
[7]	TANG M J, HE D W, WANG W D, et al. Superhard solid solutions of diamond and cubic boron nitride [J]. Scripta Materialia, 2012, 66(10): 781–784. doi: 10.1016/j.scriptamat.2012.02.006
[8]	WANG P, HE D W, WANG L P, et al. Diamond-cBN alloy: a universal cutting material [J]. Applied Physics Letters, 2015, 107(10): 101901. doi: 10.1063/1.4929728
[9]	LIU Y J, HE D W, KOU Z L, et al. Hardness and thermal stability enhancement of polycrystalline diamond compact through additive hexagonal boron nitride [J]. Scripta Materialia, 2018, 149: 1–5. doi: 10.1016/j.scriptamat.2018.01.034
[10]	LI B Z, YING P, GAO Y F, et al. Heterogeneous diamond-cBN composites with superb toughness and hardness [J]. Nano Letters, 2022, 22(12): 4979–4984. doi: 10.1021/acs.nanolett.2c01716
[11]	DRORY M D, DAUSKARDT R H, KANT A, et al. Fracture of synthetic diamond [J]. Journal of Applied Physics, 1995, 78(5): 3083–3088. doi: 10.1063/1.360060
[12]	DUB S, LYTVYN P, STRELCHUK V, et al. Vickers hardness of diamond and cBN single crystals: AFM approach [J]. Crystals, 2017, 7(12): 369. doi: 10.3390/cryst7120369
[13]	TIAN Y J, XU B, YU D L, et al. Ultrahard nanotwinned cubic boron nitride [J]. Nature, 2013, 493(7432): 385–388. doi: 10.1038/nature11728
[14]	HUANG Q, YU D L, XU B, et al. Nanotwinned diamond with unprecedented hardness and stability [J]. Nature, 2014, 510(7504): 250–253. doi: 10.1038/nature13381
[15]	LI J, SHAO G, MA Y, et al. Processing and properties of polycrystalline cubic boron nitride reinforced by SiC whiskers [J]. International Journal of Applied Ceramic Technology, 2019, 16(1): 32–38. doi: 10.1111/ijac.13077
[16]	ZHAO Y S, QIAN J, DAEMEN L L, et al. Enhancement of fracture toughness in nanostructured diamond-SiC composites [J]. Applied Physics Letters, 2004, 84(8): 1356–1358. doi: 10.1063/1.1650556
[17]	HONG S M, AKAISHI M, YAMAOKA S. High-pressure synthesis of heat-resistant diamond composite using a diamond-TiC_0.6 powder mixture [J]. Journal of the American Ceramic Society, 1999, 82(9): 2497–2501. doi: 10.1111/j.1151-2916.1999.tb02109.x
[18]	WANG H K, HE D W, XU C, et al. Nanostructured diamond-TiC composites with high fracture toughness [J]. Journal of Applied Physics, 2013, 113(4): 043505. doi: 10.1063/1.4789004
[19]	ZHOU L, LI Y Y, KOU Z L, et al. Heterogeneous diamond-TiC composites with high fracture toughness and electrical conductivity [J]. Journal of the European Ceramic Society, 2024, 44(8): 4887–4894. doi: 10.1016/J.JEURCERAMSOC.2024.02.042
[20]	LI K, MO P C, CHEN J R, et al. Phase composition, microstructure, and mechanical properties of PcBN composites with Ti and Ti-Al binders: effects of holding time and synthesis pressure [J]. International Journal of Refractory Metals and Hard Materials, 2024, 118: 106434. doi: 10.1016/j.ijrmhm.2023.106434
[21]	WU J H, ZHANG H L, ZHANG Y, et al. The role of Ti coating in enhancing tensile strength of Al/diamond composites [J]. Materials Science and Engineering: A, 2013, 565: 33–37. doi: 10.1016/j.msea.2012.11.124
[22]	SHA X H, YUE W, ZHANG H C, et al. Enhanced oxidation and graphitization resistance of polycrystalline diamond sintered with Ti-coated diamond powders [J]. Journal of Materials Science & Technology, 2020, 43: 64–73. doi: 10.1016/j.jmst.2020.01.031
[23]	SHA X H, FENG B, YUE W, et al. Comparison of tribological behaviors of polycrystalline diamonds synthesized by titanium- and boron-coated diamond particles [J]. Diamond and Related Materials, 2022, 128: 109242. doi: 10.1016/j.diamond.2022.109242
[24]	CHEN Z R, MA D J, WANG S M, et al. Wear resistance and thermal stability enhancement of PDC sintered with Ti-coated diamond and cBN [J]. International Journal of Refractory Metals and Hard Materials, 2020, 92: 105278. doi: 10.1016/j.ijrmhm.2020.105278
[25]	KLIMCZYK P, BENKO E, LAWNICZAK-JABLONSKA K, et al. Cubic boron nitride: Ti/TiN composites: hardness and phase equilibrium as function of temperature [J]. Journal of Alloys and Compounds, 2004, 382(1/2): 195–205. doi: 10.1016/j.jallcom.2004.04.140
[26]	CHEN C, MO P C, CHEN J R, et al. Effects of different binder systems on the reaction mechanism, microstructure and mechanical properties of PcBN composites [J]. Diamond and Related Materials, 2023, 134: 109797. doi: 10.1016/j.diamond.2023.109797
[27]	ARAMIAN A, SADEGHIAN Z, NARIMANI M, et al. A review on the microstructure and properties of TiC and Ti (C,N) based cermets [J]. International Journal of Refractory Metals and Hard Materials, 2023, 115: 106320. doi: 10.1016/J.IJRMHM.2023.106320
[28]	PENG Y, MIAO H Z, PENG Z J. Development of TiCN-based cermets: mechanical properties and wear mechanism [J]. International Journal of Refractory Metals and Hard Materials, 2013, 39: 78–89. doi: 10.1016/j.ijrmhm.2012.07.001
[29]	RITCHIE R O. The conflicts between strength and toughness [J]. Nature Materials, 2011, 10(11): 817–822. doi: 10.1038/nmat3115
[30]	SOLOZHENKO V L, KURAKEVYCH O O, LE GODEC Y. Creation of nanostuctures by extreme conditions: high-pressure synthesis of ultrahard nanocrystalline cubic boron nitride [J]. Advanced Materials, 2012, 24(12): 1540–1544. doi: 10.1002/adma.201104361
[31]	CHEN Z R, MA D J, WANG S M, et al. Enhanced thermal and mechanical performance of polycrystalline diamond compact by introducing polycrystalline cubic boron nitride at the grain boundaries [J]. International Journal of Refractory Metals and Hard Materials, 2021, 96: 105468. doi: 10.1016/j.ijrmhm.2020.105468