高功率调制脉冲磁控溅射沉积TiAlSiN纳米复合涂层结构调控与性能研究

doi:10.15541/jim20150096

无机材料学报 ›› 2015, Vol. 30 ›› Issue (12): 1254-1260.DOI: 10.15541/jim20150096 CSTR: 32189.14.10.15541/jim20150096

高功率调制脉冲磁控溅射沉积TiAlSiN纳米复合涂层结构调控与性能研究

吴志立^{1, 2}, 李玉阁¹, 吴彼¹, 雷明凯¹

(1. 大连理工大学材料科学与工程学院表面工程实验室, 大连116024; 2. 湖南农业大学工学院, 南方粮油作物协同创新中心, 长沙410128)

收稿日期:2015-02-12 修回日期:2015-08-15 出版日期:2015-12-20 网络出版日期:2015-11-24
作者简介:吴志立(1979–), 男, 副教授. E-mail: zhiliwu@hunau.edu.cn; zlwu@dlut.edu.cn
基金资助:
国家自然科学基金(51102032);国家自然科学基金创新群体(51321004)

Microstructure Controlling and Properties of TiAlSiN Nanocomposite Coatings Deposited by Modulated Pulsed Power Magnetron Sputtering

WU Zhi-Li^{1, 2}, LI Yu-Ge¹, WU Bi¹, LEI Ming-Kai¹

(1. Surface Engineering Laboratory, School of Materials Science and Engineering, Dalian University of Technology, Dalian 116024, China; 2. College of Engineering, Hunan Agricultural University/Southern Regional Collaborative Innovation Center for Gain and Oil Crops in China, Changsha 410128, China)

Received:2015-02-12 Revised:2015-08-15 Published:2015-12-20 Online:2015-11-24
About author:WU Zhi-Li. E-mail: zhiliwu@hunau.edu.cn; zlwu@dlut.edu.cn
Supported by:
National Natural Science Foundation of China(51102032);The Foundation for Innovative Research Groups of the National Natural Science Foundation of China(51321004)

摘要/Abstract

摘要：

采用高功率调制脉冲磁控溅射Al/(Al+Ti)原子比(x)分别为0.25、0.5和0.67的TiAlSi合金靶, 溅射功率1~4 kW, 氮气分压25%, 工作气压0.3 Pa, 在Si(100)和AISI 304奥氏体不锈钢基片上沉积了TiAlSiN纳米复合涂层。TiAlSiN涂层中氮含量保持在52.0at%~56.7at%之间, 均形成了nc-TiAlN/a-Si₃N₄/AlN纳米晶/非晶复合结构。随着原子比x增加, 非晶含量增加, 涂层硬度先升高而后降低。当x=0.5时, 硬度最高可达28.7 GPa。溅射功率升高可提高溅射等离子体中金属离化程度, 促进涂层调幅分解的进行, 形成了界面清晰的非晶包裹纳米晶结构, 且晶粒尺寸基本保持不变。当x=0.67时, 溅射功率由1 kW上升到4 kW时, 硬度由16.4 GPa升至21.3 GPa。不同靶材成分和溅射功率条件下沉积的TiAlSiN涂层的磨损率为(0.13~6.25)×10^-5 mm³/(N·m), 具有优良的耐磨性能。当x=0.67, 溅射功率2 kW时, nc-TiAlN/a-Si₃N₄纳米复合涂层具有最优的耐磨性能。

关键词: 高功率调制脉冲磁控溅射, TiAlSiN纳米复合涂层, 微结构, 硬度, 磨损

Abstract:

TiAlSiN nanocomposite coatings were deposited by modulated pulsed power magnetron sputtering (MPPMS) from TiAlSi targets with the Al/(Al+Ti) atomic ratios (x) of 0.25, 0.5 and 0.67. The targets were powered by average sputtering power of 1-4 kW under work pressure of 0.3 Pa with a nitrogen addition of 25%. All of the TiAlSiN coatings with a nitrogen content of 52.0at%~56.7at% possessed an nc-TiAlN/a-Si₃N₄/AlN nanocomposite structure. As x increased, the percentage of amorphous phases was increased, meanwhile the hardness of the coatings firstly increased and then decreased. In the TiAlSiN coating with x =0.5, a highest hardness of 28.7 GPa was detected. Improvement in average sputtering power could prompt the formation of a complete phase separation nanocomposite coatings with a constant grain size. With x =0.67 under average sputtering power from 1 kW to 4 kW, the hardness of the coatings increased from 16.4 GPa to 21.3 GPa. A low wear rate of about (0.13-6.25) ×10^-5 mm³/(N·m) was detected in the TiAlSiN coatings with different Al contents as a function of the average sputtering power. An optimized wear resistance was identified in the TiAlSiN coatings deposited by MPPMS under average sputtering power of 2 kW at x =0.5.

Key words: modulated pulsed power magnetron sputtering, TiAlSiN, microstructure, hardness, wear

中图分类号:

TG174

吴志立, 李玉阁, 吴彼, 雷明凯. 高功率调制脉冲磁控溅射沉积TiAlSiN纳米复合涂层结构调控与性能研究[J]. 无机材料学报, 2015, 30(12): 1254-1260.

WU Zhi-Li, LI Yu-Ge, WU Bi, LEI Ming-Kai. Microstructure Controlling and Properties of TiAlSiN Nanocomposite Coatings Deposited by Modulated Pulsed Power Magnetron Sputtering[J]. Journal of Inorganic Materials, 2015, 30(12): 1254-1260.

图/表 8

图1 MPPMS装置示意图

Fig. 1 Schematic drawing of MPPMS

图2 MPPMS溅射Ti47.5Al47.5Si5合金靶典型放电曲线

Fig. 2 Typical pulse waveform of MPPMS discharge on Ti47.5Al47.5Si5 target

表1 MPPMS沉积TiAlSiN涂层沉积工艺参数

Table 1 Deposition parameters for TiAlSiN coatings deposited by MPPMS

x	Pulsing parameters							Deposition conditions
	τ_total	τ_weak1	(τ_off/τ_on)	τ_weak2	(τ_off/τ_on)	τ_strong	(τ_off/τ_on)	P_a	P_p	I_p	V_p
	/μs	/μs	/μs	/μs	/μs	/μs	/μs	/kW	/kW	/A	/V
0.25	1000	200	54/6	300	34/6	500	10/10	2	58.78	135.73	411.83
0.50	1000	200	54/6	300	34/6	500	10/12	2	69.61	146.48	480.65
0.67	1000	200	54/6	300	34/6	500	10/10	2	58.11	127.12	430.66
0.67	1000	200	54/6	300	34/6	500	10/10	4	60.66	133.38	449.18
0.67	1000	200	54/6	300	34/6	500	10/10	1	65.30	143.81	445.07

表2 MPPMS沉积TiAlSiN涂层成分

Table 2 Composition of TiAlSiN coatings deposited by MPPMS

x	P_a/kW	Composition/at%
x	P_a/kW	N	Al	Si	Ti
0.25	2	52.0	10.7	8.5	28.8
0.50	2	56.7	22.7	2.3	18.3
0.67	2	53.4	22.7	12.7	11.2
0.67	4	53.5	22.6	12.6	11.2
0.67	1	53.4	22.7	13.6	10.3

图3 高功率调制脉冲磁控溅射TiAlSiN涂层XRD图谱, 氮气分压25%(a)溅射功率2 kW, x=0.25~0.67, (b)溅射功率1~4 kW, x=0.67

Fig. 3 XRD patterns of TiAlSiN coatings deposited by MPPMS at fN2= 25% (a) Pa=2 kW, depending on x in the range of 0.25-0.67, and (b) x=0.67, dependent on Pa in the range of 1-4 kW

图4 高功率调制脉冲磁控溅射沉积TiAlSiN涂层的高分辨透射电镜照片

Fig. 4 Planar view HRTEM images of TiAlSiN deposited by MPPMS at (a) x= 0.25; (a) x= 0.5; (c) x=0.67

图5 高功率调制脉冲磁控溅射TiAlSiN涂层表面扫描电镜照片

Fig. 5 FESEM images of TiAlSiN coatings deposited by MPPMS dependent on Pa (a) 1 kW, (b) 2 kW, and (c) 4 kW

表3 MPPMS沉积TiAlSiN涂层硬度与杨氏模量以及磨损率

Table 3 Nanohardness, Young’s Modulus, and wear rates of TiAlSiN coatings deposited by MPPMS

x	P_a/kW	Hardness/GPa	SD	Young’s modulus/GPa	SD	Wear rate /(×10^-5, mm³·N^-1·m^-1)
0.25	2	21.8	1.3	262.3	18.5	6.3
0.50	2	28.7	3.3	329.1	46.4	4.2
0.67	2	18.0	0.2	216.5	3.8	0.6
0.67	4	21.3	1.1	228.2	10.7	1.3
0.67	1	16.5	0.7	193.3	11.2	4.8

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高功率调制脉冲磁控溅射沉积TiAlSiN纳米复合涂层结构调控与性能研究

Microstructure Controlling and Properties of TiAlSiN Nanocomposite Coatings Deposited by Modulated Pulsed Power Magnetron Sputtering

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