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本文基于新型的磁过滤沉积技术(FCVA)研究了TiAlCN/TiAlN/TiAl多元复合涂层结构及不同C含量对其防腐耐磨性能的影响. 同时使用SEM, XRD, XPS, 电化学测试和摩擦磨损设备对其宏/微观性能进行了系统表征. 实验结果表明: 随C含量增加, C元素的存在形式从TiAlCN固溶相转化为TiAlCN固溶/非晶碳共存. 典型的TiAlCN固溶/非晶碳纳米复合结构TiAlCN/TiAlN/TiAl涂层不仅具有超高硬度和高韧性, 而且涂层中均匀无特征结构的非晶碳具有优异的自润滑效果, 通过结合各层的优势, 该结构涂层在3.5%NaCl电化学腐蚀试验中, Ecorr提高了5.6倍, 为0.271V, Icorr降低为原来的1/52, 为8.092 × 10–9 A·cm–2; 在干摩擦实验中, 摩擦系数降低了1/3, 为0.43, 磨损率降低了1/1.4, 为1.13 × 10–5 mm3·N–1·m–1.
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关键词:
- TiAlCN/TiAlN/TiAl多元复合涂层 /
- TiAlCN固溶/非晶碳复合结构 /
- 干摩擦 /
- 腐蚀
The experiment is based on novel magnetic filtered cathodic vacuum arc (FCVA) technology, the effects of the structure and C contents of TiAlCN/TiAlN/TiAl composite coating on anticorrosion and wear resistance were studied. The macro/micro properties of the coatings were systematically characterized by SEM, XRD, XPS, electrochemical tests and friction equipment. The results show that, with the increase of C content,the form of C element in the coatings transforms from the TiAlCN solid solution to the coexistence of crystallized TiAlCN/amorphous carbon. The TiAlCN/TiAlN/TiAl coating with TiAlCNcrystallized/amorphous carbon nanocomposite structure demonstrated excellent performanceby combining the advantages of each layer, which the hardness reaches an ultrahigh leveland the amorphous carbonwith excellent self-lubricating effect exists in the coating structure. In 3.5% NaCl electrochemical corrosion test, Ecorr increased by 5.6 times to 0.271 V, Icorr decreased by 1/52 to 8.092 ×10–9 A·cm–2. During the dry sliding, friction coefficient decreased by 1/3 to 0.43, and wear rate decreased by 1/1.4 to 1.13×10–5 mm3·N–1·m–1.-
Keywords:
- TiAlCN/TiAlN/TiAlmultilayer composite coatings /
- crystallized TiAlCN/amorphous carbon /
- friction /
- corrosion
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Wang H 2002 Ph. D. Dissertation (Xian: Northwestern Polytechnical University) (in Chinese)
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图 3 不同C2H2流量沉积的TiAlCN/TiAlN/TiAl涂层的截面形貌 (a) 0 sccm; (b) 10 sccm; (c) 15 sccm
Fig. 3. Thecrosssection of TiAlCN/TiAlN/TiAl coatings deposited at various C2H2:(a) 0 sccm; (b) 10 sccm; (c) 15 sccm
图 4 不同C2H2流量沉积的TiAlCN/TiAlN/TiAl涂层的XRD图谱
Fig. 4. XRD diffractogram of TiAlCN/TiAlN/TiAl coatings deposited at various C2H2.
图 5 不同C2H2流量沉积的TiAlCN/TiAlN/TiAl涂层的拉曼谱图
Fig. 5. Raman spectra of TiAlCN/TiAlN/TiAl coatings deposited at various C2H2.
图 6 S3(15 sccm, 12.39 at.%C)的XPS图谱 (a) N 1s; (b) C 1s; (c) Ti 2p; (d) Al 2p
Fig. 6. XPS analysis of S3: (a) N 1s;(b) C 1s;(c) Ti 2p; (d) Al 2p.
图 7 不同C2H2流量沉积的TiAlCN/TiAlN/TiAl涂层在3.5 wt-% NaCl溶液中的动电位极化曲线
Fig. 7. Potentiodynamic polarization curves of TiAlCN/TiAlN/TiAl coatings in 3.5 wt-% NaCl solution.
图 8 不同C2H2流量沉积的TiAlCN/TiAlN/TiAl涂层电化学腐蚀的数据结果
Fig. 8. Results of Electrochemical corrosion characterization activities for TiAlCN/TiAlN/TiAl coatings deposited at various C2H2.
图 9 不同C2H2流量沉积的TiAlCN/TiAlN/TiAl涂层电化学阻抗谱
Fig. 9. Electrochemical impedance spectroscopy of TiAlCN/TiAlN/TiAl coatings deposited at various C2H2.
图 10 不同C2H2流量沉积的TiAlCN/TiAlN/TiAl涂层的阻抗-频率图
Fig. 10. Bode plots ofTiAlCN/TiAlN/TiAl coatings deposited at various C2H2.
图 11 不同C2H2流量沉积的TiAlCN/TiAlN/TiAl涂层的相角-频率图
Fig. 11. Bode phase angle plots ofTiAlCN/TiAlN/TiAl coatings deposited at various C2H2.
图 12 不同C2H2流量沉积的TiAlCN/TiAlN/TiAl涂层表面SEM形貌(a)0 sccm; (b)10 sccm; (c)15 sccm
Fig. 12. SEM surface micrographs of TiAlCN/TiAlN/TiAl coatings deposited at various C2H2: (a)0 sccm; (b)10 sccm; (c)15 sccm.
图 13 不同C2H2流量沉积的TiAlCN/TiAlN/TiAl涂层的摩擦系数
Fig. 13. Friction coefficient curves of TiAlCN/TiAlN/TiAl coatings deposited at various C2H2.
图 14 不同C2H2流量沉积的TiAlCN/TiAlN/TiAl涂层的摩擦系数和磨损率
Fig. 14. Friction coefficientand wear rate of TiAlCN/TiAlN/TiAl coatings deposited at various C2H2.
图 15 不同C2H2流量沉积的TiAlCN/TiAlN/TiAl涂层磨痕区的SEM图像和EDS能谱分析 (a), (b) 0 sccm; (c), (d) 10 sccm; (e), (f) 15 sccm
Fig. 15. SEM micrographs of the wear track and EDS results of TiAlCN/TiAlN/TiAl coatings deposited at various C2H2: (a), (b) 0 sccm; (c), (d) 10 sccm; (e), (f) 15 sccm.
图 16 不同C2H2流量沉积的TiAlCN/TiAlN/TiAl涂层磨痕处的拉曼谱图
Fig. 16. Raman spectra of wear track of TiAlCN/TiAlN/TiAl coatings deposited at various C2H2.
表 1 不同C2H2流量沉积的TiAlCN/TiAlN/TiAl涂层的元素相对含量
Table 1. Chemical composition of TiAlCN/TiAlN/TiAl coatings deposited at various C2H2.
Sample C2H2/sccm Ti/at.% Al/at.% N/at.% C/at.% TiAlN/TiAl S1 0 30.87 22.85 46.28 — TiAlCN/TiAlN/TiAl S2 10 28.64 21.52 41.23 8.61 TiAlCN/TiAlN/TiAl S3 15 27.60 22.95 37.07 12.39 
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表 2 不同C2H2流量沉积的TiAlCN/TiAlN/TiAl涂层的显微硬度、杨氏模量和H/E比值
Table 2. Microhardness、Modules and ratio of H/E of TiAlCN/TiAlN/TiAl coatings deposited at various C2H2.
Sample C2H2/sccm E/GPa H/GPa H/E TiAlN/TiAl S1 0 290.20 30.53 0.105 TiAlCN/TiAlN/TiAl S2 10 310.65 41.16 0.133 TiAlCN/TiAlN/TiAl S3 15 316.14 44.36 0.140
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[1] 王均涛, 刘平, 李伟, 郑康培 2010 热加工工艺 20 104
Google Scholar
Wang J T, Liu P, Li W, Zheng K P 2010 Hot Working Technology 20 104
Google Scholar
[2] PalDey S, Deevi S C 2003 Sci. Eng. A 342 58
Google Scholar
[3] Hsu C H, Lee C Y, Lee C C 2009 Thin Solid Films 17 5212
[4] Brogren M, Harding G L, Karmhag R, Ribbing C G, Niklasson G A, Stenmark L 2000 Thin Solid Films 370 268
Google Scholar
[5] Hovsepian PEh, Münz W D, Medlock A, Gregory G 2000 Surf. Coat. Technol. 133–134 508
[6] Warcholinski B, Gilewicz A 2011 Wear 271 2812
Google Scholar
[7] Zheng J Y, Hao J Y, Li u X, Gong Q Y, Liu W M 2012 Surf. Coat. Technol. 209 110
Google Scholar
[8] Agudelo L C, Ospina R, Castillo H A, Devia A 2008 Phys. Scr. T131 014006
Google Scholar
[9] Kamath G, Ehiasarian A P, Purandare Y, Hovsepian PEh 2011 Surf. Coat. Technol. 205 2823
Google Scholar
[10] Hovsepian PEh, Ehiasarian A P, Deeming A, Schimpf C 2008 Vacuum 82 1312
Google Scholar
[11] Yang L J, Zhang Z H, Dang X A, Li L 2014 Mater. Sci. Forum 789 449
Google Scholar
[12] AL-Bukhaiti M A, Al-hatab K A, Tillmann W, Hoffmann F, Sprute T 2014 Appl. Surf. Sci. 318 180
Google Scholar
[13] Kawata K, Sugimura H, Takai O 2001 Thin Solid Films 390 64
Google Scholar
[14] 单磊, 王永欣, 李金龙 2013 中国表面工程 26 86
Google Scholar
Shan L, Wang Y X, Li J L 2013 China Surface Engineering 26 86
Google Scholar
[15] Kuptsov K A, Kiryukhantsev-Korneev P V, Sheveryko A N, ShtanskyDV 2013 Surf. Coat. Technol. 216 273
Google Scholar
[16] 李刘合, 张海泉, 崔旭明 2001 08 1549
Google Scholar
Li L H, Zhang H Q, Cui X M 2001 Acta Phys. Sin. 08 1549
Google Scholar
[17] Ferrari A C, Kleinsorge B, Morrison N A, Hart A 1999 J. Appl. Phys. 857 191
[18] Zhang X H, Jiang J Q, Zeng Y Q, Lin J L, Wang F L, Moore J J 2008 Surf. Coat. Technol. 203 594
Google Scholar
[19] Zeng Y Q, Qiu Y D, Mao X Y, Tan X Y, Tan Z, Zhang X H, Chen J, Jiang J Q 2015 Thin Solid Films 584 283
Google Scholar
[20] Dreiling I, Stiens D, Chasse T 2010 Surf. Coat. Technol. 205 1339
Google Scholar
[21] Rodríguez R J, García J A, Medrano A, Rico M, Sánchez R, Martínez R, Labrugère C, Lahaye M, Guette A 2002 Vacuum 67 559
Google Scholar
[22] 段晋辉, 梁银, 裴旺, 杨喜昆 2016 金属热处理 41 139
Du J H, Liang Y, Pei W, Yang X K 2016 Heat Treatment of Metals 41 139
[23] Jang C S, Jeon J H, Song P K, Kang M C, Kim K H 2005 Surf. Coat. Technol. 200 1501
Google Scholar
[24] Zehnder T, Schwaller P, Munnik F, Mikhailov S, Patscheider J 2004 J. Appl. Phys 95 4327
Google Scholar
[25] Matthews A, Franklin S, Holmberg K 2007 J. Phys. D: Appl. Phys. 40 5463
Google Scholar
[26] Musil J, Jirout M 2007 Surf. Coat. Technol. 201 5148
Google Scholar
[27] Massiani Y, Medjahed A, Crousier J P, Gravier P, Rebatel I 1991 Surf. Coat. Technol. 45 115
Google Scholar
[28] 陈淑年, 廖斌, 吴先映, 陈琳, 黄杰, 何光宇 2019 中国表面工程 3 49
Google Scholar
Chen S N, Liao B, Wu X Y, Chen L, Huang J, He G Y 2019 China Surface Engineering 3 49
Google Scholar
[29] Vacandio F, Massiani Y, Gravier P, Rossi S, Bonora P L, Fedrizzi L 2001 Electrochim. Acta 46 3827
Google Scholar
[30] 郑建云, 郝俊英, 刘小强, 龚秋雨, 刘维民 2013 摩擦学学报 33 87
Zheng J Y, Hao J Y, Liu X Q, Gong Q Y, Liu W M 2013 Tribology 33 87
[31] Eriksson A O, Ghafoor N, Jensen J, Näslund L Å, Johansson M P, Sjölen J, Odén M, Hultman L, Rosen J 2012 Surf. Coat. Technol. 213 145
Google Scholar
[32] Chen L, Yang B, Xu Y X, Pei F, Zhou L C, Du Y 2014 Thin Solid Films 556369
[33] HoörlingA, Hultman L, Odén M, Sjölén J, Karlsson L 2002 J. Vac. Sci. Technol. A 20 1815
[34] Cheng H H, Lee C Y, Lee C C 2009 ThinSolid Films 517 5212
Google Scholar
[35] Xie Z W, Wang L P, Wang X F, Huang L, Lu Y, Yan J C 2011 Trans. Nonferrous Met. Soc. China 21 470
Google Scholar
[36] Sampath Kumar T, Balasivanandha Prabu S, Manivasagam G 2014 J. Mater. Eng. Perform 23 2877
Google Scholar
[37] 王泓 2002 博士学位论文 (西安: 西北工业大学)
Wang H 2002 Ph. D. Dissertation (Xian: Northwestern Polytechnical University) (in Chinese)
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