金属过渡层类型对非晶碳膜结构性能的影响

doi:10.15541/jim20170217

无机材料学报 ›› 2018, Vol. 33 ›› Issue (3): 331-338.DOI: 10.15541/jim20170217

金属过渡层类型对非晶碳膜结构性能的影响

李蕾^{1, 2}, 郭鹏¹, 刘林林¹, 孙丽丽¹, 柯培玲¹, 汪爱英¹

1. 中国科学院宁波材料技术与工程研究所, 中国科学院海洋新材料与应用技术重点实验室, 浙江省海洋材料与防护技术重点实验室, 宁波 315201;
2. 中国科学院大学, 北京 100049

收稿日期:2017-05-03 修回日期:2017-06-23 出版日期:2018-03-20 网络出版日期:2018-03-12
作者简介:李蕾(1991-), 女, 博士研究生. E-mail: llei@nimte.ac.cn
基金资助:
国家自然科学基金(51522106, 51375475);浙江省公益项目(2016C31121);宁波市自然科学基金(2015A610089)

Metal Buffer Layer on Structure, Mechanical and Tribological Property of GLC films

LI Lei^{1, 2}, GUO Peng¹, LIU Lin-Lin¹, SUN Li-Li¹, KE Pei-Ling¹, WANG Ai-Ying¹

1. Key Laboratory of Marine Materials and Related Technologies, Zhejiang Key Laboratory of Marine Materials and Protective Technologies, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China;
2. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2017-05-03 Revised:2017-06-23 Published:2018-03-20 Online:2018-03-12
About author:LI Lei. E-mail: llei@nimte.ac.cn
Supported by:
National Natural Science Foundation of China (51522106, 51375475);Pubic Project of Zhejiang Province (2016C31121);Ningbo Municipal Natural Science Foundation (2015A610089)

摘要/Abstract

摘要：

采用直流磁控溅射技术制备不同金属过渡层(Cr, Ti, W)的类石墨非晶碳膜(GLC), 研究过渡层类型对非晶碳膜微结构的影响, 并考察其在人工海水中摩擦性能的变化。研究结果表明: Cr/GLC薄膜sp²杂化键含量最高, 沿GLC表面到铬碳界面方向, sp²杂化键含量逐渐增大, Ti过渡层和W过渡层的sp²杂化键含量变化不明显。Cr/GLC薄膜较高的sp²杂化键含量有助于其在摩擦过程中产生可以充当润滑相的石墨化转化摩擦转移膜。在三种涂层中, Cr/GLC薄膜表现出最高的腐蚀电位-0.16 V和最低的腐蚀电流密度4.42×10^-9 A/cm²。因此相较于Ti, W作过渡层的GLC薄膜, Cr/GLC薄膜在海水环境下表现出优异的摩擦学特性。

关键词: 海水, 类石墨非晶碳膜(GLC), 金属过渡层, 电子能量损失谱(EELS)

Abstract:

Graphite-like carbon films (GLC) with different metal buffer layers (Cr, Ti, W) were fabricated by direct current magnetron sputtering technique. The effect of metal buffer layer on structure and tribological properties in artificial seawater were carefully investigated. The results show that, in contrast to Ti/GLC and W/GLC film, Cr/GLC film has the highest sp² hybridization content, which increases from the top layer to Cr/C interface. The highest sp² hybridization content promotes graphitization degree of the tribo-film which acts as lubrication phase in the sliding process. The results of potentiodynamic polarization tests show that, in all of three GLC films, Cr/GLC film shows superior corrosion resistance with the highest corrosion voltage (E_corr) of -0.16 V and the lowest corrosion current (i_corr) of 4.42×10^-9 A/cm². As a result, Cr/GLC film presents the best tribological properties in artificial seawater in contrast to Ti/GLC and W/GLC films.

Key words: seawater, GLC, metal buffer layer, EELS

中图分类号:

TH117

李蕾, 郭鹏, 刘林林, 孙丽丽, 柯培玲, 汪爱英. 金属过渡层类型对非晶碳膜结构性能的影响[J]. 无机材料学报, 2018, 33(3): 331-338.

LI Lei, GUO Peng, LIU Lin-Lin, SUN Li-Li, KE Pei-Ling, WANG Ai-Ying. Metal Buffer Layer on Structure, Mechanical and Tribological Property of GLC films[J]. Journal of Inorganic Materials, 2018, 33(3): 331-338.

图/表 12

表1 人工海水配方/(g•L-1)

Table 1 Chemical composition of artificial seawater/(g•L-1)

Constituent	NaCl	MgCl₂	Na₂SO₄	CaCl₂	KCl	NaHCO₃	KBr	H₃BO₃	SrCl₂	NaF
Concentration	24.530	5.200	4.090	1.160	0.695	0.201	0.101	0.027	0.025	0.003

图1 不同金属过渡层GLC薄膜的表面和截面SEM照片

Fig. 1 Surface and cross-sectional morphologies of GLC films with different metal buffer layers(a, d) Cr/GLC; (b, e) Ti/GLC; (c, f) W/GLC

图2 不同金属过渡层GLC薄膜的截面HRTEM照片及对应的非晶碳层的SAED图案

Fig. 2 Cross-sectional high-resolution transmission electron microscopy (HRTEM) images and SAED patterns of the GLC films with different metal buffer layers(a) Cr/GLC; (b) Ti/GLC; (c) W/GLC

图3 不同金属过渡层GLC薄膜的(a)拉曼光谱, (b)G峰半峰宽和G峰位置ID/IG

Fig. 3 (a) Raman spectra and (b) fitted ID/IG, G peak position, GFWHM of the GLC films with different metal buffer layers

图4 不同金属过渡层GLC薄膜的电子能量损失谱(EELS)

Fig. 4 EELS spectra of the GLC films with different metal buffer layers(a) Cr/GLC; (b) Ti/GLC; (c) W/GLC; (d) Position schematic diagram of taking EELS spectra

图5 不同金属过渡层GLC薄膜的机械性能

Fig. 5 Mechanical properties of the GLC films with different metal buffer layers

图6 316L不锈钢基底与不同金属过渡层GLC薄膜在人工海水中的动电位极化曲线

Fig. 6 Potentiodynamic polarization curves of the 316LSS substrate and GLC films with different metal buffer layers in artificial seawater

图7 不同金属过渡层GLC薄膜在人工海水环境下的电化学阻抗图谱

Fig. 7 EIS results of the GLC films with different metal buffer layers in artificial seawater(a) Nyquist plots; (b) Bode plots; (c) Equivalent circuit

表2 不同金属过渡层GLC薄膜的EIS拟合数据

Table 2 Fitting data of EIS results for the GLC films with different metal buffer layers

Sample	R_S/(Ω•cm²)	Q₁/(Ω^-1•cm^-2•sⁿ)	n₁	R₁/(Ω•cm²)	Q₂/(Ω^-1•cm^-2•sⁿ)	n₂	R₂/(Ω•cm²)
Cr/GLC	85.1	1.3×10^-6	0.91	4.4×10⁴	1.4×10^-6	0.64	1.2×10⁶
Ti/GLC	110.1	1.2×10^-6	0.94	7.3×10³	3.4×10^-6	0.66	5.3×10⁵
W/GLC	74.9	6.2×10^-7	0.92	4.4×10³	1.9×10^-6	0.64	4.1×10⁵

图8 不同金属过渡层GLC薄膜在人工海水条件下的摩擦曲线(a)和平均摩擦系数和磨损率(b)

Fig. 8 (a) Friction coefficient curves of the GLC films with different metal buffer layers in artificial seawater and (b) average friction coefficients and wear rates of GLC films with different metal buffer layers

图9 不同薄膜在海水环境下磨痕的SEM照片

Fig. 9 SEM images of wear track of the GLC films in artificial seawater(a) Cr/GLC; (b) Ti/GLC; (c) W/GLC

图10 不同金属过渡层GLC薄膜Si3N4对偶球磨斑表面的拉曼光谱

Fig. 10 Raman spectra on wear scars of Si3N4 balls for the GLC films(a) Cr/GLC; (b) Ti/GLC; (c) W/GLC

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金属过渡层类型对非晶碳膜结构性能的影响

Metal Buffer Layer on Structure, Mechanical and Tribological Property of GLC films

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