电弧离子镀CrAlN-DLC硬质复合薄膜的成分、结构与性能

doi:10.15541/jim20210616

无机材料学报 ›› 2022, Vol. 37 ›› Issue (7): 764-772.DOI: 10.15541/jim20210616 CSTR: 32189.14.10.15541/jim20210616

电弧离子镀CrAlN-DLC硬质复合薄膜的成分、结构与性能

程玮杰¹^,²(), 王明磊¹^,², 林国强¹^,²()

1.大连理工大学1. 材料科学与工程学院
2.三束材料改性教育部重点实验室, 大连 116024

收稿日期:2021-10-08 修回日期:2021-11-10 出版日期:2022-07-20 网络出版日期:2021-11-18
通讯作者: 林国强, 教授. E-mail: gqlin@dlut.edu.cn
作者简介:程玮杰(1997-), 男, 硕士研究生. E-mail: 737289840@qq.com
基金资助:
国家重点研发计划(2016YFB0101318)

Composition, Structure and Properties of CrAlN-DLC Hard Composite Films Deposited by Arc Ion Plating

CHENG Weijie¹^,²(), WANG Minglei¹^,², LIN Guoqiang¹^,²()

1. Material Science and Engineering School, Dalian University of Technology, Dalian 116024, China
2. Key Laboratory for Material Modification by Laser, Ion and Electron Beams, Ministry of Education, Dalian University of Technology, Dalian 116024, China

Received:2021-10-08 Revised:2021-11-10 Published:2022-07-20 Online:2021-11-18
Contact: LIN Guoqiang, professor. E-mail: gqlin@dlut.edu.cn
About author:CHENG Weijie (1997-), male, Master candidate. E-mail: 737289840@qq.com
Supported by:
National Key R&D Program of China(2016YFB0101318)

摘要/Abstract

摘要：

为了改善CrAlN薄膜的摩擦性能, 本研究在增强磁过滤脉冲偏压电弧离子镀设备上, 用分离靶弧流调控技术在硬质合金基体上分别制备了不同成分的CrAlN-DLC硬质复合薄膜, 并采用不同手段表征了薄膜的表面形貌、成分、相结构以及力学和摩擦性能。结果表明, 不同成分薄膜表面均平整致密, 膜厚均在1.05 μm左右。随着靶弧流比I_C/I_CrAl的升高, 薄膜中碳的原子分数由33.1%升至74.6%。薄膜的相结构主要由晶体相和非晶相复合组成, 其晶体相主要为c-(Cr,Al)N相, 且随着碳含量增大晶体相减少、晶粒尺寸减小, 其非晶相主要为DLC, 其中sp²/sp³的比值随碳含量增大而减小。相应地, 薄膜的硬度随着碳含量增大而提高, 当碳的原子分数为74.6%时, 达到最大值(26.2±1.4) GPa, 且该成分点处薄膜摩擦系数也降至最小值0.107, 磨损率仅为3.3×10^-9mm³/Nm。综合而言, 当非晶DLC相最多时, CrAlN-DLC复合薄膜的综合性能达到最佳, 较之CrAlN薄膜, 摩擦性能显著提高。

关键词: 电弧离子镀, 硬质复合薄膜, CrAlN-DLC, 成分, 相结构, 硬度, 摩擦性能

Abstract:

To improve the friction performance of CrAlN film, CrAlN-DLC hard composite films with different compositions were prepared on the cemented carbide substrates using separation target arc current control technology of the enhanced magnetic filter pulsed bias arc ion plating equipment, and their surface morphology, composition, phase structure, mechanical, and friction properties were investigated. The results revealed that the surfaces of different films were flat and dense, and the film thicknesses were all about 1.05 μm. With the increase of target arc current ratio (I_C/I_CrAl), the carbon atomic content of the film increased from 33.1% to 74.6%. Phase structure of the film was mainly composed of crystal phase and amorphous phase. With the increase of carbon content, the crystal phase of c-(Cr,Al)N decreased and the crystal grain size reduced, besides, the ratio of sp²/sp³ in DLC amorphous phase decreased. Correspondingly, the hardness of the film increased with the increase of carbon content. When the carbon atomic content is 74.6%, the hardness reaches the maximum of (26.2±1.4) GPa, which results in the friction coefficient at this point attaining the minimum value of 0.107, and the wear rate is only 3.3×10^-9 mm³/Nm. In summary, the comprehensive performance of the CrAlN-DLC composite film reaches the best when the content of amorphous DLC phase get the maxium, and the friction performance is significantly improved as compared to the CrAlN film.

Key words: arc ion plating, hard composite films, CrAlN-DLC, composition, phase structure, hardness, friction performance

中图分类号:

TQ174

程玮杰, 王明磊, 林国强. 电弧离子镀CrAlN-DLC硬质复合薄膜的成分、结构与性能[J]. 无机材料学报, 2022, 37(7): 764-772.

CHENG Weijie, WANG Minglei, LIN Guoqiang. Composition, Structure and Properties of CrAlN-DLC Hard Composite Films Deposited by Arc Ion Plating[J]. Journal of Inorganic Materials, 2022, 37(7): 764-772.

图/表 13

图1 增强磁过滤脉冲负偏压电弧离子镀膜机结构示意图

Fig.1 Schematic diagram of enhanced magnetic filtered pulse bias arc ion plating apparatus

表1 CrAlN-DLC薄膜的沉积参数

Table 1 Deposition parameters of CrAlN-DLC films

Sample	Arc current/A		Arc current ratio, I_C/I_CrAl	Gas flow/sccm		Pulsed bias			Deposition time/min
Sample	CrAl	C	Arc current ratio, I_C/I_CrAl	N₂	Ar	Frequency/Hz	Amplitude/V	Duty cycle/%	Deposition time/min
CrAlN-DLC 1#	90	30	0.33	10	90	30	-200	40	90
CrAlN-DLC 2#	80	40	0.5	10	90	30	-200	40	90
CrAlN-DLC 3#	70	50	0.71	10	90	30	-200	40	90
CrAlN-DLC 4#	55	65	1.18	10	90	30	-200	40	90
CrAlN-DLC 5#	50	70	1.4	10	90	30	-200	40	90
CrAlN-DLC 6#	40	80	2	10	90	30	-200	40	90

图2 CrAlN-DLC薄膜的表面SEM照片

Fig.2 SEM surface images of CrAlN-DLC films (a) 1#; (b) 2#; (c) 3#; (d) 4#; (e) 5#; (f) 6#

图3 CrAlN-DLC 1#薄膜的表面形貌及元素的面分布图

Fig. 3 SEM surface image and element mappings of CrAlN-DLC 1# film

表2 不同弧流比下CrAlN-DLC薄膜的厚度

Table 2 Thickness of CrAlN-DLC films with different arc current ratios

Sample	I_C/I_CrAl	Thickness/μm
CrAlN-DLC 1#	0.33	(0.99±0.03)
CrAlN-DLC 2#	0.50	(1.09±0.02)
CrAlN-DLC 3#	0.71	(1.09±0.02)
CrAlN-DLC 4#	1.18	(1.08±0.01)
CrAlN-DLC 5#	1.40	(1.02±0.02)
CrAlN-DLC 6#	2.00	(1.04±0.02)

图4 不同弧流比下制备CrAlN-DLC薄膜的成分

Fig. 4 Compositions of CrAlN-DLC films deposited at different arc current ratios

图5 CrAlN-DLC薄膜的GI-XRD图谱

Fig. 5 GI-XRD patterns of CrAlN-DLC films

图6 (a) CrAlN-DLC薄膜的Raman谱图和(b)薄膜中ID/IG、G峰峰位以及GFWHM随碳含量的变化曲线

Fig. 6 (a) Raman spectra of CrAlN-DLC films and (b) ID/IG, G peak position and gFWHM changed with C content in the films

图7 CrAlN-DLC薄膜的(a) C1s, (b) Cr2p, (c) Al2p, (d) N1s XPS图谱以及(Cr9.5Al8.5N7.4)-C74.6薄膜(e) C1s, (f) Cr2p, (g) Al2p, (h) N1s XPS峰的拟合结果

Fig. 7 (a) C1s, (b) Cr2p, (c) Al2p, and (d) N1s XPS spectra of CrAlN-DLC films, and fitting results of (e) C1s, (f) Cr2p, (g) Al2p, and (h) N1s XPS peaks for (Cr9.5Al8.5N7.4)-C74.6 film

表3 CrAlN-DLC薄膜C1s、Cr2p、Al2p以及N1s的XPS峰拟合结果(原子分数/%)

Table 3 Fitting results of C1s, Cr2p, Al2p and N1s XPS peak of CrAlN-DLC films (atomic percentage/%)

Area Sample	C1s				Cr2p				Al2p			N1s
	C-Cr	C-C		C-O	Cr-N	Cr-C	Cr-O	Cr-Cr	Al-N	Al-O	Al-Al	Cr	N-Al
	C-Cr	sp²	sp³	C-O	Cr-N	Cr-C	Cr-O	Cr-Cr	Al-N	Al-O	Al-Al	Cr	N-Al
(Cr₂₉Al_25.1N_12.8)-C_33.1	18.9	42.3	33.8	5.0	40.5	32.8	6.2	20.5	64.5	15.5	20.0	79.4	20.6
(Cr_24.7Al_21.9N_13.7)-C_39.7	15.4	43.3	36.0	5.3	42.6	35.5	6.9	16.0	70.9	14.8	14.3	73.9	26.1
(Cr_18.9Al₁₇N₁₅)-C_49.1	12.5	42.6	38.0	6.8	44.2	35.4	6.3	14.1	76.2	13.0	10.8	67.4	32.6
(Cr_15.3Al_14.4N_16.2)-C_53.9	9.8	42.7	40.0	7.5	47.7	34.6	6.1	11.6	78.3	14.2	7.5	62.8	37.2
(Cr_12.4Al_11.1N_6.2)-C_70.3	7.5	41.4	42.3	8.7	40.4	36.0	7.3	18.3	63.8	17.9	18.6	59.2	40.8
(Cr_9.5Al_8.5N_7.4)-C_74.6	4.3	39.0	47.0	10.0	45.0	31.6	7.7	15.7	71.7	17.3	11.0	55.5	44.5

图8 CrAlN-DLC薄膜的硬度(H)和弹性模量(E)

Fig. 8 Hardness (H), elastic modulus (E) of CrAlN-DLC films

图9 CrAlN-DLC薄膜的摩擦曲线

Fig. 9 Friction curves of CrAlN-DLC films Colorful figures are available on website

图10 薄膜样品的磨痕横截面轮廓

Fig. 10 Cross-sectional profiles of wear scars on samples

参考文献 21

[1]	SOROKA E, LYASHENKO B, QIAO S, et al. Tribological behaviour and cutting performance of PVD-TiN coating/substrate system with discontinuous surface architecture. Rare Metal Materials and Engineering, 2011, 40(4): 580-584. DOI URL
[2]	CHANG Z K, WAN X S, PEI Z L, et al. Microstructure and mechanical properties of CrN coating deposited by arc ion plating on Ti₆Al₄V substrate. Surface & Coatings Technology, 2011, 205(19): 4690-4696. DOI URL
[3]	BERTRAND G, SAVALL C, MEUNIER C, et al. Properties of reactively RF magnetron-sputtered chromium nitride coatings. Surface & Coatings Technology, 1997, 96(2): 323-329. DOI URL
[4]	WANG L, ZHANG G, WOOD R, et al. Fabrication of CrAlN nanocomposite films with high hardness and excellent anti-wear performance for gear application. Surface & Coatings Technology, 2010, 204(21): 3517-3524. DOI URL
[5]	KIM M W, KIM K H, KANG M C, et al. Mechanical properties and cutting performance of Cr-Al-N hybrid coated micro-tool for micro high-speed machining of flexible fine die. Current Applied Physics, 2012, 12: S14-S18.
[6]	REN X, ZHU H, LIU M, et al. Comparison of microstructure and tribological behaviors of CrAlN and CrN film deposited by DC magnetron sputtering. Rare Metal Materials and Engineering, 2018, 47(4): 1100-1106. DOI URL
[7]	DING X Z, ZENG X T, LIU Y C, et al. Cr_1-_xAl_xN coatings deposited by lateral rotating cathode arc for high speed machining applications. Thin Solid Films, 2007, 516(8): 1710-1715. DOI URL
[8]	MO J L, ZHU M H, LEI B, et al. Comparison of tribological behaviours of AlCrN and TiAlN coatings-deposited by physical vapor deposition. Wear, 2007, 263(7): 1423-1429. DOI URL
[9]	SCHEERER H, HOCHE H, BROSZEIT E, et al. Effects of the chromium to aluminum content on the tribology in dry machining using (Cr,Al)N coated tools. Surface & Coatings Technology, 2005, 200(1-4): 203-207. DOI URL
[10]	JFCA B, WA C, JCC A, et al. Structural, mechanical and tribological behavior of TiCN, CrAlN and BCN coatings in lubricated and non-lubricated environments in manufactured devices. Materials Chemistry and Physics, 2020, 252: 123164.
[11]	MO Y J, WANG M L, CHEN W J. Composition, structure and properties of the Cr_1-_xAl_xN hard films deposited by arc ion plating. Journl of Inorgamic Materials, 2020, 35(6): 675-681.
[12]	ROBERTSON J. Diamond-like amorphous carbon. Materials Science & Engineering R, 2002, 37(4): 129-281.
[13]	TILLMANN W, STANGIER D, SCHRDER P, et al. Investigation and optimization of the tribo-mechanical properties of CrAlCN coatings using design of experiments. Surface & Coatings Technology, 2016, 308: 147-157. DOI URL
[14]	ZHANG M, ZHOU F, FANG H, et al. Structure and tribological properties of CrTiAlCN coatings with various carbon contents. Journal of Materials Engineering and Performance, 2019, 28(3): 1509-1521. DOI URL
[15]	LIN G Q, ZHAO Y H, GUO H M, et al. Experiments and theoretical explanation of droplet elimination phenomenon in pulsed-bias arc deposition. Acta Ophthalmologica, 2004, 22(4): 288-303.
[16]	赵彦辉, 林国强, 董闯, 等. 脉冲工艺在薄膜制备中的应用. 中国真空学会. 薄膜技术学术研讨会论文集. 中国真空学会: 中国真空学会, 2003: 5.
[17]	DAI W, HE Z, WU G, et al. Effect of bias voltage on growth property of Cr-DLC film prepared by linear ion beam deposition technique. Vacuum, 2010, 85(2): 231-235. DOI URL
[18]	FERRARI A C. Determination of bonding in diamond-like carbon by Raman spectroscopy. Diam. Relat. Mater., 2002, 11: 1053-1061. DOI URL
[19]	ZHOU Y, GUO P, SUN L, et al. Microstructure and property evolution of diamond-like carbon films co-doped by Al and Ti with different ratios. Surface & Coatings Technology, 2019, 361: 83-90. DOI URL
[20]	CHOI J H, LEE S C, LEE K R. A first-principles study on the bond characteristics in carbon containing Mo, Ag, or Al impurity atoms. Carbon, 2007, 46(2): 185-188. DOI URL
[21]	WU D, REN S, PU J, et al. A comparative study of tribological characteristics of hydrogenated DLC film sliding against ceramic mating materials for helium applications. Applied Surface Science, 2018, 441: 884-894. DOI URL

电弧离子镀CrAlN-DLC硬质复合薄膜的成分、结构与性能

Composition, Structure and Properties of CrAlN-DLC Hard Composite Films Deposited by Arc Ion Plating

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 13

参考文献 21

相关文章 15

编辑推荐

Metrics

本文评价

[1]	苏东良, 崔锦, 翟朋博, 郭向欣. 石榴石型Li_6.4La₃Zr_1.4Ta_0.6O₁₂对Si/C负极表面固体电解质中间相的调控机制研究[J]. 无机材料学报, 2022, 37(7): 802-808.
[2]	彭军辉, TIKHONOV Evgenii. 空位对Hf-Ta-C体系的结构、力学性质及电子性质影响的第一性原理研究[J]. 无机材料学报, 2022, 37(1): 51-57.
[3]	莫亚杰,王明磊,程玮杰,林国强. 电弧离子镀Cr_1-_xAl_xN硬质薄膜的成分、结构与性能[J]. 无机材料学报, 2020, 35(6): 675-681.
[4]	张丽艳, 李洪, 胡丽丽, 王亚杰. 玻璃成分-结构-性质的“基因结构”模拟法[J]. 无机材料学报, 2019, 34(8): 885-892.
[5]	郭胜强, 王皓, 涂兵田, 王斌, 徐鹏宇, 王为民, 傅正义. 细晶MgO·1.44Al₂O₃透明陶瓷的制备及其性能研究[J]. 无机材料学报, 2019, 34(10): 1067-1071.
[6]	崔凤单, 马天, 李伟萍, 吴国清. SiC和B₄C防弹插板抗多发弹打击损伤特性研[J]. 无机材料学报, 2017, 32(9): 967-972.
[7]	陈宇方, 李宇杰, 郑春满, 谢凯, 陈重学. 富锂层状氧化物正极材料研究进展[J]. 无机材料学报, 2017, 32(8): 792-800.
[8]	李淼磊, 王恩青, 岳建岭, 黄小忠. TiAlN/VN纳米多层膜的微结构与力学和摩擦学性能[J]. 无机材料学报, 2017, 32(12): 1280-1284.
[9]	马剑, 张波萍, 陈建银. Bi过量以及冷却方式对BiFeO₃-BaTiO₃陶瓷的相结构及电学性能的影响[J]. 无机材料学报, 2017, 32(10): 1035-1041.
[10]	鲁媛媛, 李贺军, 杨冠军. 氢稀释比对氢化硅薄膜两相结构和电学性能的影响[J]. 无机材料学报, 2015, 30(5): 474-478.
[11]	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.
[12]	梅兴志, 罗永春, 张国庆, 康龙. 稀土系A₂B₇型La_1-_xSc_xNi_2.6Co_0.3Mn_0.5Al_0.1(x = 0~0.5)储氢合金相结构和电化学性能研究[J]. 无机材料学报, 2015, 30(10): 1049-1055.
[13]	李戈扬. 评Veprek的nc-TiN/a-Si₃N₄模型和其“超过金刚石硬度”的实验基础[J]. 无机材料学报, 2015, 30(1): 1-8.
[14]	胡海龙, 曾宇平, 左开慧, 夏咏锋,姚冬旭. 烧结助剂种类对Si₃N₄/SiC陶瓷力学与摩擦性能的影响[J]. 无机材料学报, 2014, 29(8): 885-890.
[15]	王孝笑, 杨琳, 刘洪, 陈强, 肖定全, 朱建国. 低温水热法制备ZnS:Co+Cr纳米晶及其光学性能研究[J]. 无机材料学报, 2014, 29(10): 1049-1054.