电弧离子镀Cr1-xAlxN硬质薄膜的成分、结构与性能

doi:10.15541/jim20190353

摘要/Abstract

摘要：

采用电弧离子镀的分离靶弧流调控技术在硬质合金基体上制备了4组不同Al含量的Cr_1-_xAl_xN硬质薄膜, 采用SEM、XPS、GIXRD、Nanoindenter及划痕仪分别表征了薄膜的形貌、成分、相结构和力学性能。结果表明: 4组薄膜厚度分别为1.28、1.42、1.64和1.79 μm; 成分x随着Al靶的弧流相对增大而增大, 分别为x=0.41、0.53、0.64和0.73; 相结构与成分密切相关, 当x=0.41时, 薄膜呈单一的c-(Cr,Al)N相, 而当x≥0.53时, 则由c-(Cr,Al)N相和hcp-AlN相混相构成; 随着Al含量增加, 晶粒尺寸先减小后增大, 在x=0.64时达到最小值8.9 nm; 相应地硬度则先增大后减小, 在x=0.64时达到峰值35.3 GPa; 4组Cr_1-_xAl_xN薄膜的膜基结合良好, 结合力均在60 N以上。综合测试结果发现, 当x=0.53时, Cr_1-_xAl_xN薄膜的韧性最佳, 弹性恢复系数最高为57.4%, 同时兼具较高的硬度34.7 GPa, 此时薄膜具有最佳的综合性能。

关键词: 电弧离子镀, CrAlN, 硬质薄膜, 成分, 相结构, 力学性能

Abstract:

Four groups of Cr_1-_xAl_xN films with different Al contents were deposited on ultrafine cemented carbide substrates by arc ion plating, their morphology, composition, phase structure and mechanical property were investigated via field emission scanning electron microscope, X-ray photo electron spectrometry, grazing incidence X-ray diffraction, nanoindenter and scratch tests. The results revealed that the thickness of the films is 1.28, 1.42, 1.64 and 1.79 μm and the aluminum concentration x is 0.41, 0.53, 0.64 and 0.73, respectively, increased with incremental current of Al target. There is a close relationship between phase structure and composition. Films performed single centered cubic B1 structure when x is 0.41, however, demostrated mixed structure of c-(Cr,Al)N and hcp-AlN when x≥0.53. The dimensions of grains obtained a minimum value of 8.9 nm near x=0.64, as Al content increasing, while the variation in hardness followed an increase-decrease pattern, reaching peak values of 35.3 GPa at x=0.64. The films performed pretty adhesion strength and their critical loads were all over 60 N. Based on all test results, the Cr_1-_xAl_xN films exhibited the best combination properties including high hardness of 34.7 GPa, the highest elastic recovery coefficient of 57.4% and the best toughness while x is 0.53.

Key words: arc ion plating, Cr_1-_xAl_xN hard films, composition, phase structure, mechauical properties

中图分类号:

TQ174

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.

MO Yajie,WANG Minglei,CHEN Weijie,LIN Guoqiang. Composition, Structure and Properties of the Cr_1-_xAl_xN Hard Films Deposited by Arc Ion Plating[J]. Journal of Inorganic Materials, 2020, 35(6): 675-681.

图/表 12

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 Cr1-xAlxN薄膜的沉积参数

Table 1 Deposition parameters of Cr1-xAlxN films

Sample	N₂ flow/ sccm	Working pressure/Pa	Arc current/A		Pulsed bias			Deposition time/min
Sample	N₂ flow/ sccm	Working pressure/Pa	I_Cr	I_Al	Frequency/kHz	Amplitude/V	Duty cycle/%	Deposition time/min
CrAlN 1#	80	0.8	110	50	30	-200	40	120
CrAlN 2#	80	0.8	95	65	30	-200	40	120
CrAlN 3#	80	0.8	80	80	30	-200	40	120
CrAlN 4#	80	0.8	65	95	30	-200	40	120

图2 Cr1-xAlxN薄膜的表面、截面SEM照片

Fig. 2 SEM surface and cross-sectional images of Cr1-xAlxN films (a,b) 1#; (c,d) 2#; (e,f) 3#; (g,h) 4#

图3 Cr1-xAlxN薄膜刻蚀600 s时的XPS全谱图

Fig. 3 XPS spectra of Cr1-xAlxN films obtained after argon ions sputtering for 600 s

表2 Cr1-xAlxN薄膜的表面化学成分

Table 2 Surface composition of Cr1-xAlxN films

Sample	Surface composition/at%				$\frac{{{C}_{\text{Al}}}}{({{C}_{Cr}}+{{C}_{\text{Al}}})}$	$\frac{{{C}_{\text{N}}}}{({{C}_{Cr}}+{{C}_{\text{Al}}})}$	Film composition (Cr_1-_xAl_xN_y)
Sample	Cr	Al	N	O	$\frac{{{C}_{\text{Al}}}}{({{C}_{Cr}}+{{C}_{\text{Al}}})}$	$\frac{{{C}_{\text{N}}}}{({{C}_{Cr}}+{{C}_{\text{Al}}})}$	Film composition (Cr_1-_xAl_xN_y)
CrAlN 1#	32.9	22.6	41.8	2.7	0.41	0.75	Cr_0.59Al_0.41N_0.75
CrAlN 2#	26.2	29.1	41.3	3.4	0.53	0.75	Cr_0.47Al_0.53N_0.75
CrAlN 3#	19.8	34.6	42.2	3.4	0.64	0.78	Cr_0.36Al_0.64N_0.78
CrAlN 4#	15.1	39.9	42.1	2.9	0.73	0.77	Cr_0.27Al_0.73N_0.77

图4 Cr1-xAlxN薄膜的XPS高分辨分峰拟合谱

Fig. 4 High resolution XPS spectra of Cr1-xAlxN films (a) Cr2p; (b) N1s; (c) Al2p

图5 Cr1-xAlxN薄膜的XRD图谱

Fig. 5 XRD patterns of Cr1-xAlxN films

图6 Cr1-xAlxN薄膜的硬度(H)、弹性模量(E)和H/E*

Fig. 6 Hardness (H), elastic modulus (E) and H/E* of Cr1-xAlxN films

图7 Cr1-xAlxN薄膜的典型加载卸载曲线

Fig. 7 Typical load-displacement curves of Cr1-xAlxN films

图8 Cr1-xAlxN薄膜划痕测试的法向载荷-摩擦力曲线

Fig. 8 Frictional force vs normal force curves for Cr1-xAlxN films during scratch test

图9 Cr1-xAlxN薄膜的划痕形貌图

Fig. 9 Micrographs of scratch of Cr1-xAlxN films

表3 Cr1-xAlxN薄膜的临界载荷及CPRS

Table 3 Critical load and CPRS of Cr1-xAlxN films

Sample	L_C1/N	L_C2/N	CPR_S
CrAlN 1#	75.4	83.8	633.36
CrAlN 2#	64.6	87.3	1466.42
CrAlN 3#	60.2	80.4	1216.14
CrAlN 4#	61.3	82.5	1299.56

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