TiN<sub>0.3</sub>/AlN复合烧结界面扩散现象

邹芹; 孙俊绒; 李艳国; 罗永安

doi:10.13394/j.cnki.jgszz.2022.0222

TiN_0.3/AlN复合烧结界面扩散现象

doi: 10.13394/j.cnki.jgszz.2022.0222

邹芹^{1, 2},
孙俊绒²,
李艳国^2, ,,
罗永安²

1.
燕山大学机械工程学院, 河北秦皇岛 066004
2.
燕山大学，亚稳材料制备技术与科学国家重点实验室, 河北秦皇岛 066004

基金项目: 河北省高等学校科学技术研究项目资助项目(ZD2021099)

详细信息

通讯作者:
李艳国，男， 1978年生，副研究员。主要从事陶瓷及其复合材料研究。E-mail：lyg@ysu.edu.cn

中图分类号: TB383.3
计量
- 文章访问数: 243
- HTML全文浏览量: 110
- PDF下载量: 31
- 被引次数: 0
出版历程
- 收稿日期: 2022-12-19
- 修回日期: 2023-02-04
- 录用日期: 2023-02-09
- 网络出版日期: 2023-12-07
- 刊出日期: 2023-10-20

Interfacial diffusion in TiN_0.3/AlN composite

ZOU Qin^{1, 2},
SUN Junrong²,
LI Yanguo^{2
, ,},
LUO Yong`an²

1.
School of Mechanical Engineering, Yanshan University, Qinhuangdao 066004, Hebei, China
2.
Metastable Materials Science and Technology State Key Laboratory, Yanshan University, Qinhuangdao 066004, Hebei, China

Funds: Projects(ZD2021099) supported by the Science and Technology Project of Hebei Education Department

摘要

摘要: 为研究TiN_0.3/AlN复合烧结体中两相界面区域的N原子的扩散现象，通过机械合金化方法制备出非化学计量比TiN_0.3，采用放电等离子体烧结技术分层及复合烧结TiN_0.3/AlN复合材料，采用金相、XRD、SEM、EDS及TEM等分析表征TiN_0.3/AlN复合材料的物相组成、元素分布和组织形貌。结果表明： AlN中的N通过空位扩散机制向TiN_0.3中扩散，其扩散程度逐渐减弱；与AlN接触的TiN_0.3部分由于吸收了来自AlN中的N使成分接近正常比例的TiN，而远离界面处的部分则接近TiN_0.3的成分；在两相结合区域有宽度在1 nm以下的非晶层，其电子衍射斑点出现纵向伸长，产生共格，说明六方结构的AlN晶格向TiN晶格畸变，形成面心立方结构的TiN_0.3/AlN。
- TiN/AlN复合材料 /
- 放电等离子体烧结 /
- 界面扩散 /
- 共格
Abstract: In recent years, extensive research has been conducted on nano-multilayer films of TiN/AlN system. However, there are few reports on its bulk composites. In this study, non-stoichiometric TiN_0.3 was prepared by mechanical alloying, then TiN_0.3/AlN composites were fabricated through spark plasma sintering (SPS) utilizing both layered and mixed sintering techniques. The phase composition, element distribution and microstructure of TiN_0.3/AlN composites were characterized by metallography, XRD, SEM, EDS and TEM, to study the diffusion of N atoms in the interface region of TiN_0.3/AlN composites. The results show that N in AlN diffuses into TiN_0.3 through a vacancy diffusion mechanism, The area of TiN_0.3 in contact with AlN absorbs N from AlN to make the composition close to the normal proportion of TiN, while the area "far away" from the interface is close to the component of TiN_0.3, and its diffusion degree weakens gradually. In the two-phase bonding region, there is a thin amorphous layer whose width is less than 1 nm. The electron diffraction pattern elongates longitudinally and produces coherent lattice. The AlN lattice of hexagonal structure is distorted to TiN lattice, forming TiN_0.3/AlN with a face-centered cubic structure.
- TiN/AlN composite /
- SPS /
- interface diffusion /
- cohere

HTML全文

图 1 TiN_0.3/AlN分层烧结界面的金相图：(a)~(b) 未腐蚀；(c)~(d) 腐蚀

Figure 1. Metallurgical microscope images of TiN_0.3/AlN by layered sintering: (a)(b) no corrosion, (c)(d) after corrosion

下载: 全尺寸图片幻灯片

图 2 TiN_0.3/AlN分层烧结界面的SEM图

Figure 2. SEM images of TiN_0.3/AlN by layed sintering

下载: 全尺寸图片幻灯片

图 3 TiN_0.3/AlN分层烧结体界面各元素分布（a）分布范围；（b）Ti元素；（c）Al元素；（d）N元素

Figure 3. EDS mapping of TiN_0.3/AlN: (a) Distribution range; (b) Ti element; (c) Al element; (d) N element

下载: 全尺寸图片幻灯片

图 4 TiN_0.3/AlN分层烧结体界面各元素分布图：(a) 扫描范围；(b) Ti元素；(c)Al元素；(d) N元素

Figure 4. EDS mapping of TiN_0.3/AlN: (a) Scan range; (b) Ti element; (c) Al element; (d) N element

下载: 全尺寸图片幻灯片

图 5 TiN_0.3/AlN混合烧结前后的XRD图

Figure 5. XRD of mixed TiN_0.3/AlN before and after sintering

下载: 全尺寸图片幻灯片

图 6 TiN_0.3/AlN混合烧结体中垂直界面的线扫描结果

Figure 6. Line scanning results of vertical interface in sintered TiN_0.3/AlN mixture

下载: 全尺寸图片幻灯片

图 7 TiN_0.3/AlN混合烧结体界面的SEM图

Figure 7. SEM images of TiN_0.3/AlN

下载: 全尺寸图片幻灯片

图 8 TiN_0.3/AlN混合烧结体相界面EDS线扫描

Figure 8. EDS line scanning results of TiN_0.3/AlN

下载: 全尺寸图片幻灯片

图 9 TiN_0.3/AlN相界面处的高分辨电子显微像及电子衍射图

Figure 9. TEM and electron diffraction patterns at TiN_0.3/AlN interface

(a) TEM; (b) SED pattern of AlN; (c) SED pattern of TiN

下载: 全尺寸图片幻灯片

图 10 TiN_0.3/AlN复合材料高分辨电子显微像：(a)晶格条纹像；(b)傅里叶转换

Figure 10. High resolution electron microscopic images of TiN_0.3/AlN composites: (a) lattice fringe image; (b) Fourier transform

下载: 全尺寸图片幻灯片

表 1 TiN和AlN的晶面间距

Table 1. Space between crystal planes of TiN and AlN

类型	(hkl)	d / nm
TiN	100	0.424
	111	0.244
	200	0.213
	220	0.151
	211	0.173
	222	0.122
AlN	100	0.270
	002	0.249
	101	0.237
	102	0.183
	110	0.156
	103	0.141
	112	0.132

下载: 导出CSV

参考文献(37)

[1]	DRYGAŚ M, LEJDA K, JANIK J F, et al. Composite nitride nanoceramics in the system titanium nitride (TiN)-aluminum nitride (AlN) through high pressure and high temperature sintering of synthesis-mixed nanocrystalline powders [J]. Materials,2021,14(3):588. doi: 10.3390/ma14030588
[2]	陈俊云, 赵灼铮, 赵智胜, 等. 新型无粘结剂聚晶氮化硼材料的飞秒激光加工研究 [J]. 燕山大学学报,2020,44(6):7. doi: 10.3969/j.issn.1007-791X.2020.06.001 CHEN Junyun, ZHAO Zhuozheng, ZHAO Zhisheng, et al. Femtosecomd laser processing on new binderless polycrystalline boron nitride material [J]. Journal of Yanshan University,2020,44(6):7. doi: 10.3969/j.issn.1007-791X.2020.06.001
[3]	ZGALAT-LOZYNSKYY O B, APURBBA K S, YEHOROV I I, et al. cWear-resistant TiN-20wt.% Si₃N₄ and TiN-20wt.% TiB₂ composites produced by microwave sintering [J]. Powder Metallurgy and Metal Ceramics,2021,59(11):611-620. doi: 10.1007/s11106-021-00196-3
[4]	王佳程, 胡继林, 梁波, 等. AlN-Al₂O₃复合材料制备技术的研究进展 [J]. 中国陶瓷工业,2021,28(3):35-39. doi: 10.13958/j.cnki.ztcg.2021.03.008 WANG Jiacheng, HU Jilin, LIANG Bo, et al. Research progress in preparation technology of AlN-Al₂O₃ composite [J]. China Ceramic Industry,2021,28(3):35-39. doi: 10.13958/j.cnki.ztcg.2021.03.008
[5]	朱建斌, 李佳艳, 姜忆来, 等. 碳纤维增强氮化硅复合材料的制备及介电性能研究 [J]. 中国陶瓷,2021,57(10):35-42. ZHU Jianbin, LI Jiayan, JIANG Yilai, et al. Study on preparation and dielectric properties of carbon fiber reinforced silicon nitride composite [J]. China Ceramics,2021,57(10):35-42.
[6]	陈胜男, 林威豪, 汪建勋, 等. 阴极离子镀制备TiN薄膜及其光电性能的研究 [J]. 燕山大学学报,2017,41(4):371-376. doi: 10.3969/j.issn.1007-791X.2017.04.014 CHEN Shengnan, LIN Weihao, WANG Jianxun, et al. Study of optical and electrical properties of TiN thin films prepared by cathodic ion sputtering [J]. Journal of Yanshan University,2017,41(4):371-376. doi: 10.3969/j.issn.1007-791X.2017.04.014
[7]	SUN N, XU J, ZHOU D, et al. DC reactively sputtered TiN_x thin films for capacitor electrodes [J]. Journal of Materials Science: Materials in Electronics,2018,29(12):10170-10176. doi: 10.1007/s10854-018-9066-4
[8]	GRIGORIEV S, PRISTINSKIY Y, VOLOSOVA M, et al. Wire electrical discharge machining, mechanical and tribological performance of TiN reinforced multiscale SiAlON ceramic composites fabricated by spark plasma sintering [J]. Applied Sciences,2021,11(2):657. doi: 10.3390/app11020657
[9]	RAVI KUMAR K, PRIDHAR T, VETTIVEL S C. Influence on mechanical behaviour and characterization of A6063/Bagasse and titanium nitride hybrid composites [J]. Transactions of the Indian Institute of Metals,2021,74(2):473-486. doi: 10.1007/s12666-020-02143-z
[10]	MORTALO C, DEAMBROSIS S M, MONTAGNER F, et al. Production strategies of TiN_x coatings via reactive high power impulse magnetron sputtering for selective H₂ separation [J]. Membranes,2021,11(5):360. doi: 10.3390/membranes11050360
[11]	ZHAO S, ZHAO Y, RAN Y, et al. Surface enhanced Raman scattering on ion-beam-deposited TiN_x/Si substrates [J]. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms,2020,472:24-31. doi: 10.1016/j.nimb.2020.03.008
[12]	HE Z, ZHANG S, SUN D. Effect of bias on structure mechanical properties and corrosion resistance of TiN_x films prepared by ion source assisted magnetron sputtering [J]. Thin Solid Films,2019,676:60-67. doi: 10.1016/j.tsf.2019.02.037
[13]	BAIK Y, DREW R A L. Aluminum nitride: Processing and applications [J]. Key Engineering Materials,1996,122-124:553. doi: 10.4028/www.scientific.net/KEM.122-124.553
[14]	BEN J, LUO J, LIN Z, et al. Introducing voids around the interlayer of AlN by high temperature annealing [J]. Chinese Physics B,2022,31(7):517-522. doi: 10.1088/1674-1056/ac3d7f
[15]	JIANG M, SUN H, LIU R, et al. Fabrication and mechanical properties of Ti₂AlN/TiAl composite with continuous network structure [J]. Transactions of Nonferrous Metals Society of China,2023,33(5):1437-1451. doi: 10.1016/S1003-6326(23)66194-1
[16]	BASKUT S, CINAR A, TURAN S. Directional properties and microstructures of spark plasma sintered aluminum nitride containing graphene platelets. [J]. Journal of the European Ceramic Society,2017,37(12):3759. doi: 10.1016/j.jeurceramsoc.2017.03.032
[17]	KOUTNÁ N, LÖFLER L, HOLEC D, et al. Atomistic mechanisms underlying plasticity and crack growth in ceramics: A case study of AlN/TiN superlattices [J]. Acta Materialia,2022,229(1):117809. doi: 10.1016/j.actamat.2022.117809
[18]	MADAN A, KIM I W, CHENG S C, et al. Stabilization of cubic AlN in epitaxial AlN/TiN superlattices [J]. Physical Review Letters,1997,78(9):1743-1746. doi: 10.1103/PhysRevLett.78.1743
[19]	郑云西. AlN/TiN纳米多层涂层中c-AlN的生长及其热稳定性研究 [D]. 南京: 东南大学, 2020. ZHENG Yunxi. Growth and thermal stability research of cubic AlN in AlN/TiN nano-multilayers [D]. Nanjing: Southeast University, 2020.
[20]	CHEN Z, HOLEC D, BARTOSIK M, et al. Crystallographic orientation dependent maximum layer thickness of cuboc AlN in CrN/AlN multilayers [J]. Acta Materialia,2019,168:190-202. doi: 10.1016/j.actamat.2019.02.004
[21]	DÍAZ J H F, ESPITIA M J R, MARTÍNEZ J A R. Research of the structural and electronic properties of VN/AlN/VN and AlN/VN/AlN based on DFT calculation [J]. Journal of Physics Conference Series,2016,743(1):012004. doi: 10.1088/1742-6596/743/1/012004
[22]	LEITH S, VOGEL M, FAN J, et al. Superconducting NbN thin films for use in superconducting radio frequency cavities [J]. Superconductor Science and Technology,2021,34(2):025006. doi: 10.1088/1361-6668/abc73b
[23]	孙金峰. MA制备非化学计量比TiC_x和TiN_x及其烧结特性的研究 [D]. 秦皇岛: 燕山大学, 2010. SUN Jinfeng. Synthesized nonstoichiometric TiC_x and TiN_x powders by MA and study of the powers sintering property [D]. Qinhuangdao: Yanshan University, 2010.
[24]	叶亚男. TiN_0.3对难熔化合物烧结界面显微结构与性能的影响 [D]. 秦皇岛: 燕山大学, 2013. YE Ya’nan. The effects of non-stoichiometric TiN_0.3 on the interfacial microstructure and mechanical properties of refractory material [D]. Qinhuangda: Yanshan University, 2013.
[25]	陈俊云, 刘德辉, 张圣康, 等. 单晶金刚石微铣刀的飞秒激光制造研究 [J]. 燕山大学学报,2022,46(3):200-207. doi: 10.3969/j.issn.1007-791X.2022.03.002 CHEN Junfei, LIU Dehui, ZHANG Shengkang, et al. Research on micro-milling tools of single crystal diamond by femtosecond laser technique [J]. Journal of Yanshan University,2022,46(3):200-207. doi: 10.3969/j.issn.1007-791X.2022.03.002
[26]	李青, 王洪超, 屈年瑞, 等. 新型四方相I(4)2m-BCN力学性能的第一性原理研究 [J]. 燕山大学学报,2018,42(6):519-524. doi: 10.3969/j.issn.1007-791X.2018.06.007 LI Qing, WANG Hongchao, QU Nianrui, et al. First principle study on mechanical properties of new square phase I42m-BCN [J]. Journal of Yanshan University,2018,42(6):519-524. doi: 10.3969/j.issn.1007-791X.2018.06.007
[27]	邓华, 邢英, 王明智, 等. PCBN烧结体中TiN_0.3/AlN与CBN的界面关系研究 [J]. 金刚石与磨料磨具工程,2016,36(3):38-42. doi: 10.13394/j.cnki.jgszz.2016.3.0008 DENG Hua, XING Ying, WANG Mingzhi, et al. Research on the interface relation between TiN_0.3/AlN and CBN in PCBN sintering body [J]. Diamond & Abrasives Engineering,2016,36(3):38-42. doi: 10.13394/j.cnki.jgszz.2016.3.0008
[28]	罗涛, 江文清, 徐敏. TiN-Al体系结合剂配比对聚晶立方氮化硼复合材料性能的影响 [J]. 机械工程材料,2021,45(11):34-37. doi: 10.11973/jxgccl202111007 LUO Tao, JIANG Wenqing, XU Min. Effect of TiN-Al system binder ratio on properties of polycrystalline cubic boron nitride composite [J]. Materials for Mechanical Engineering,2021,45(11):34-37. doi: 10.11973/jxgccl202111007
[29]	叶大伦, 胡建华. 实用无机物热力学数据手册 [M]. 北京: 冶金工业出版社, 2002. YE Dalun, HU Jianhua. Practical handbook of inorganic thermodynamic data [M]. Beijing: Metallurgical Industry Press, 2002. (in Chinese)
[30]	耶红刚, 陈光德, 竹有章, 等. 六方AlN本征缺陷的第一性原理研究 [J]. 物理学报,2007,9:5376-5380. doi: 10.3321/j.issn:1000-3290.2007.09.065 YE Honggang, CHEN Guangde, ZHU Youzhang, et al. First-principles study of intrinsic defects in hexagonal aluminum nitride [J]. Journal of Physics,2007,9:5376-5380. doi: 10.3321/j.issn:1000-3290.2007.09.065
[31]	潘应君, 邓敏, 陈淑花, 等. 多弧离子镀制备TiN/AlN 纳米多层膜及其超硬效应 [J]. 武汉科技大学学报:自然科学版,2008,31(3):312-315. doi: 10.3969/j.issn.1674-3644.2008.03.022 PAN Yingjun, DENG Min, CHEN Shuhua, et al. Preparation and ultra micro-hardness of TiN/AlN nano-multilayer deposited by multi-arc ion plating [J]. Journal of Wuhan University of Science and Technology (Natural Science Edition),2008,31(3):312-315. doi: 10.3969/j.issn.1674-3644.2008.03.022
[32]	杨群, 王玉春, 李晓云, 等. 原位法制备AlN-TiN复相陶瓷性能的研究 [J]. 真空电子技术,2016(5):26-29. doi: 10.3969/j.issn.1002-8935.2016.05.007 YANG Qun, WANG Yuchun, LI Xiaoyun, et al. Research on AlN-TiN composite prepared by in-situ method [J]. Vacuum Electronics,2016(5):26-29. doi: 10.3969/j.issn.1002-8935.2016.05.007
[33]	SETOYAMA M, A. NAKAYAMA, M. TANAKA Formation of cubic-AlN in TiN/AlN superlattice [J]. Surface and Coatings Technology,1996,86-87(1-3):225-230. doi: 10.1016/S0257-8972(96)03033-2
[34]	LEE B T, PEZZOTTI G, HIRAGA K. Microstructure and fracture behavior of SiC-platelet-reinforced Si₃N₄ matrix composites [J]. Materials Science and Engineering A,1994,177(1-2):151-160. doi: 10.1016/0921-5093(94)90487-1
[35]	PEZZOTTI G, LEE B T, HIRAGA K, et al. Microscopy investigation on fracture mechanisms in hot-isostatically pressed Si₃N₄/SiC-platelet composites [J]. Journal of Materials Science,1994,29(7):1786-1794. doi: 10.1007/BF00351297
[36]	黄孝瑛. 电子衍射分析方法 [M]. 北京: 金属材料研究编辑部, 1976. HUANG Xiaoying. Electron diffraction analysis method [M]. Beijing: Editorial Office of Metal Materials Research, 1976.
[37]	进藤大辅, 平贺贤二. 材料评价的高分辨电子显微方法 [M]. 刘安生, 译. 北京: 冶金工业出版社, 1998. DAISUKE Shindo, HIRAGA Hyunji. High resolution electron microscopy for material evaluation [M]. Translated by Liu Ansheng. Beijing: Metallurgical Industry Press, 1998.