本研究目的為探討於碳基鍍膜中摻入少量鋯元素時，對鍍層之結構、機械性質以及磨潤效果之改變。碳基鍍膜即是以碳元素為主的鍍膜，在碳基鍍膜中，最常見者屬純碳鍍層,譬如類鑽碳鍍層及類石墨鍍層,以及碳氮鍍膜兩種鍍層，此兩種在本實驗中會探討。實驗上採用封閉式非平衡磁控濺鍍法製備一系列鍍層，碳靶作為碳源，氮氣為氮源，摻入少量鋯元素於兩種鍍膜中，並利用SEM, Raman, XPS,奈米硬度機以及迴轉式磨耗系統等多種方式對鍍層之成份、組織、結構、基本機械性質、磨潤性質等性質之影響。
實驗結果中發現到添加鋯元素會使得鍍層中單鍵比例上升。添加鋯會使得純碳鍍層硬度下降，而碳氮鍍層反而會提升硬度。同時在奈米硬度試驗中發現到碳氮鍍層添加鋯元素有助於提升鍍層的回彈率，因此在磨耗試驗中獲得相較於碳氮鍍層有更好的抗磨耗性以及更長的磨耗壽命。在熱處理實驗中，發現添加鋯元素會使得鍍層硬度下降的程度上升，其中以不添加鋯的碳氮鍍層有最佳的穩定性。在電化學實驗中，添加適量鋯元素可有效改善鍍層的抗純碳鍍層及碳氮鍍層的抗腐蝕性。

This study was aim on the change of doped Zirconium in the amorphous carbon-nitride coatings. The SEM, Raman, XPS and hardness indenter were used to investigate the composition, structure, structure, and basic mechanical properties of the coating.
The result showed that doped Zirconium in the carbon-nitride coatings will improve the tribological resistance. The result was due to the increasing of the hardness and improving of the recovery ratio. The result of XPS also showed that the carbon-nitride coating doped Zirconium had higher single bond than the undoped one.
Keywords: amorphous carbon-nitride coating、doped Zirconium、tribological property
INTRODUCTION
Carbon-nitride coatings have many excellent mechanical properties, such as low coefficient of friction, good anti-corrosion, high wear resistance, good corrosion resistance, and good adhesion. It is a coating that has gradually attracted attention in recent years.
Doped Zirconium in coatings is regularly discussed in recent years. Many study about doped Zirconium found that it can increase the hardness and get more excellent corrosion resistance comparing with the undoped coatings .
MATERIALS AND METHODS
The high-speed steel, which model was SKH51 and with hardness HRC65, was used for substrate. The coatings were prepared using a closed-field unbalanced DC magnetron sputtering system (CFUBMS KD-550U, MIRDC, Taiwan), which features four vertical orthogonally mounted magnetron cathodes surrounding a rotational substrate holder. For growth of the coatings, four targets were used, with two carbon targets next to each other and two metal targets, one was Titanium for making interlayer and the other was Zirconium for doping in the coating, in the chamber. The distance between the substrate and the target was 130mm.
The coating had three steps. The first is interlayer for improving the adhesion between substrate and coating. It was made by the pure Titanium. The second was called translayer, which was course from the pure Titanium to the carbon-nitride. In this process, the composition gradually changed which the Titanium course decrease and carbon, nitrogen and Zirconium were increased.
There were two samples: a-CN and a-CN:Zr; a- meant that the microstructure of coatings was the amorphous; C and N meant Carbon or Nitrogen was mine composition in the coatings; :Zr meant that there was Zirconium doped into the coatings.
The wear performance of the coatings was evaluated using a pin-on-disk(POD) rotating-sliding wear tester (Jun-Yan Precision Machine Co., Taiwan). The Alumina ball with 2.38mm diameter and 27GPa hardness was used as the against abrasive material. The testing conditions were as follows: applied load, 10N; line speed, 0.2 m/s; rotating radius, 6 mm; and sliding distance, 350m (9300cycles). The resulting wear track was measured by scanning four cross sections at an interval of 90° using a roughness indenter. Coefficient of friction (COF) was detected by 10N load cell during the process. The wear rate was calculated by the formula as below.

Where r(mm) was radius, A(mm2) was cross-section area, L(N) was load and D(m) was sliding distance
RESULTS AND DISCUSSION
The results of the tribological experiment was showed in Table 1. As it showed, doped Zirconium in the carbon-nitride coatings could reduce the wear rate and the track depth. It is because that the hardness increased from 13.3Gpa to 15.7Gpa and the recover ratio increased from 93.2% to 96.0% by doped Zirconium.
Table 1 Tribological properties of the coatings
Samples Coefficient of Friction
(μ) Track depth
(μm) Wear rate
(10-6mm3/Nm)
a-CN 0.17 0.70 0.51
a-CN:Zr 0.19 0.29 0.18

CONCLUSION
The effect of adding a small amount of zirconium element on the pure carbon coating and the carbon-nitrogen coating can be summarized as follows:
1. As a result of XPS analysis, it was found that the addition of zirconium increases the proportion of single bonds in the coating.
2. The addition of zirconium increases the thickness of the pure carbon coating, but the adhesion becomes worse and the hardness decreases.
3. The addition of zirconium has no significant effect on the thickness, adhesion and surface roughness of the carbonitride coating.
4. The addition of zirconium can help increase the hardness and elastic recovery rate of carbonitriding coatings to achieve better mechanical properties
5. In the abrasion test, a-C coating and a-CN:Zr coating have excellent wear resistance. The former has a very low friction coefficient while the latter has a higher hardness.
6. In the heat treatment experiment, the a-CN:Zr coating showed the highest hardness after heat treatment, and the decrease in hardness was smaller than that of the a-C coating.
7. In the electrochemical corrosion experiment, the a-CN:Zr coating showed the lowest corrosion current density, indicating that the addition of an appropriate amount of zirconium to the carbon-nitrogen coating can effectively improve the corrosion resistance of the coating.
In summary, because of the higher hardness, it can be expected that the addition of zirconium carbon nitride coating will have wider application, and can improve the wear resistance and corrosion resistance of the coating at the same time, which can be used for the future development of the coating industry.

[1] L.C. Chen, D.M. Bhusari, C.Y. Yang, et al., “Si-containing crystalline carbon nitride derived from microwave plasma-enhanced chemical vapor deposition” , Thin Solid Films, 303 (1997) 66.
[2] A. Leonhardt, H. Gruger, D. Selbmann, B. Arnold, J. Thomas, “Preparation of CNx phases using plasma-assisted and hot filament chemical vapor deposition” ,Thin Solid Films, 332 (1998) 69.
[3] J.Takadoum, J.Y. Rauch, J.M. Cattenot, N. Martin, “Comparative study of mechanical and tribological properties of CNx and DLC films deposited by PECVD technique” , Surf. Coat. Technol, 174-175 (2003) 427.
[4] Aisenberg, S. and R. Chabot, Ion‐beam deposition of thin films of diamondlike carbon. Journal of applied physics, 1971. 42(7): p. 2953-2958.
[5] Grill, A., Review of the tribology of diamond-like carbon. Wear, 1993. 168(1-2): p. 143-153.
[6] Butter, R.S. and A.H. Lettington, Diamond like carbon for biomedical applications. Review. Journal of Chemical Vapor Deposition(USA), 1995. 3(3): p. 182-192.
[7] Singh, A., et al., Glial cell and fibroblast cytotoxicity study on plasma-deposited diamond-like carbon coatings. Biomaterials, 2003. 24(28): p. 5083-5089.
[8] Zhang, D., B. Shen, and F. Sun, Study on tribological behavior and cutting performance of CVD diamond and DLC films on Co-cemented tungsten carbide substrates. Applied Surface Science, 2010. 256(8): p. 2479-2489.
[9] Huang, M.-S., et al., Effect of mold surface antistiction treatment on microinjection replication quality using Cr-N/Zr-DLC thin-layer coating. Journal of Polymer Engineering, 2012. 32(6-7): p. 389-399.
[10] Chou, C.-C., et al., Mechanical properties of fluorinated DLC and Si interlayer on a Ti biomedical alloy. Thin Solid Films, 2013. 528: p. 136-142.
[11] Zhou Wang, Chengbing Wang, Qi Wang, Junyan Zhang, Journal of Applied Physics 104.7 (2008) 073306
[12] A.Y. Liu , M.L. Cohen, Science 245 (1989) 841-842
[13] R. Wäsche, M. Hartelt,U. Springborn, K. Bewilogua, M. Keunecke, Wear 269 (2010) 816-825
[14] J. Takadoum, J. Y.Rauch, J.M. Cattenot, N. Martin, Surf Coat Tech 174 (2003) 427–433
[15] Yong Seob Park, Hyun Sik Myung, Jeon Geon Han, Thin Solid Films 475 (2005) 298-302
[16] M. Camero, J. G. Buijnsters, C. Gómez-Aleixandre R. Gago, I. Caretti, I. Jiménez, Journal of Applied Physics 101.6 (2007) 063515
[17] Maisara Othman , Richard Ritikos, Noor Hamizah Khanis, Nur Maisarah Abdul Rashid, Siti Meriam AbGani, Saadah Abdul Rahman, Thin Solid Films 529 (2013) 439–443
[18] M. Marton , D. Kovalcík , M. Vojs , E. Zdravecká , M. Varga , L. Michalíková , M. Veselý ,R.Redhammer , P. Písecný, Vacuum 86 (2012) 696-698
[19] Catalin Iulian Pruncu, Mariana Braic, Karl D. Dearn, Cosmin Farcau, Robert Watson, Lidia Ruxandra Constantin, Mihai Balaceanu, Viorel Braic, Alina Vladescu, Arabian Journal of Chemistry (2016)
[20] 李正國、吳東益、賴敬華、譚安宏、張仁勇, Journal of Chinese Corrosion Engineering, Vol. 21, No. 4,pp. 299 ~ 306 (2007)
[21] Fei Zhou , Xiaolei Wang , Koshi Adachi , Koji Kato, Surface Coatings Technology 202 (2008) 3519–3528
[22] X.H. Zheng , J.P. Tu , R.G. Song, Applied Surface Science 256 (2010) 3211–3215
[23] Zhihong HUANG, Bing YANG, Xiangjun FAN and Dejun FU: Japanese Journal of Applied Physics Vol. 45, No. 22(2006) p. L562
[24] [5] P. Xu, J. J. Li, Q. Wang, Z. L. Wang, and C. Z. Gu: JOURNAL OF APPLIED PHYSICS Vol. 101, (2007) p. 014312
[25] Cosmin-Mihai Cotrut, Viorel Braic, Mihai Balaceanu, IrinaTitorencu, Mariana Braic , Anca Constantina Parau Thin Solid Films 538 (2013) 48–55
[26] L. Wang, X. Zhao, M.H. Ding, H. Zheng, H.S. Zhang, B. Zhang, X.Q. Li, G.Y. Wu , Applied Surface Science 340 (2015) 113-119.
[27] E. Grigore, C. Ruset, X. Li, H. Dong Surface & Coatings Technology 204 (2010) 1889–1892
[28] S.H. Yao, Y.L. Su, W.H. Kao, K.W. Cheng, Materials Letters 59 (2005) 3230 – 3233
[29] 汪建民, 材料分析. 1998: 中國材料科學學會發行
[30] N. Vidakis, A. Antoniadis, N. Bilalis, Journal of Materials Processing Technology 143–144 (2003) 481–485
[31] M.S. Srivastava, Methods of Multivariate Statistics, Wiley-Interscience, New York, 2004, p. 109.
[32] W. Yu, G.B. Ren, S.F. Wang, L. Han, X.W. Li, L.S. Zhang, G.S. Fu, Thin Solid Films 402 (2002) 55-59.
[33] S. Calderon V, A. Cavaleiro, S. Carvalho, Applied Surface Science 346 (2015) 240–247
[34] Fuzeng Zhou, Kaihu Fu, Bin Liao, Jingjing Yu, Chaolin Yang, Xu Zhang, Applied Surface Science 327 (2015) 350–357
[35] A. C. Ferrari and J. Robertson, “Interpretation of Raman spectra of disordered and amorphous carbon”, PHYSICAL REVIEW B 61(1999) 14095-14107
[36] Diesselberg, M., H.-R. Stock, and P. Mayr, Friction and wear behaviour of PVD chromium nitride supported carbon coatings. Surface and Coatings Technology 188(2004) 612-616.
[37] Stefan Makowski, Frank Schallera, Volker Weihnacht, Gregor Englberger, Michael Becker, Wear 392–393 (2017) 139–151
[38] M. K. Fung, K. H. Lai, C. Y. Chan, I. Bello, C. S. Lee, S. T. Lee, D.S. Mao and X. Wang, “Mechanical properties and corrosion studies of amorphous carbon on magnetic disks prepared by ECR plasma technique,” Thin Solid Films, 368(2000)198.