摘要
本研究采用热丝CVD法在YG3硬质合金(WC-3%Co)和YG6硬质合金(WC-6%Co)基体上沉积了金刚石薄膜。在对硬膜-软基体体系的附着机理进行综合分析的基础上,通过考察基体含Co量、基体预处理和CVD工艺(温度、浓度和压强等参数)对表面层去Co、金刚石薄膜形核和长大的影响,研究了改善膜/基附着性能的途径。得到如下结论:
1.硬质合金基体经一步或两步浸蚀法都能不同程度地去除基体表面的钻,抑制金刚石沉积过程中表面Co的不利影响。较之一步法,二步法处理的效果更明显。基体浸蚀层达10μm左右,有效地防止了金刚石沉积过程中钴的迁移和挥发,可以沉积出质量高、附着力好的金刚石薄膜。
2.二步浸蚀法采用浸蚀剂B腐蚀30min,再用浸蚀剂C浸泡30s最佳,YG6样品表面Co含量减少到0.82%,YG3样品降低到1.36%。基体上成核密度大,形成连续的金刚石薄膜,组织结构具有{110}面取向,薄膜附着性较好。
3.硬质合金基体上金刚石薄膜的附着性能主要与基体表面钴含量、基体表面特性、金刚石的形核密度以及金刚石膜的质量等因素有关。基体钴含量的降低对改善膜/基附着性能有利。采用相同的处理工艺,YG6系列比YG3系列钴含量下降的幅度大,薄膜晶形完整,膜/基结合效果更理想。
4.硬质合金基体上金刚石薄膜的沉积工艺对金刚石形核密度、薄膜形貌和结构以及膜/基界面上非金刚石相的含量有重要影响,从而影响薄膜与基体间的附着性能。在其它沉积条件相同的情况下,基体温度为750℃左右,沉积气压为20Torr,甲烷浓度为1%时,硬质合金基体上金刚石薄膜的晶粒大小、生长取向和附着性能较好。
In the present work, diamond thin films were deposited on the cobalt-cemented tungsten carbide (WC-6%Co and WC-3%Co) by Hot Filament Chemical Vapor Deposition (HFCVD). After sythetically analysing the mechanism of adhesion on the system of hard film and soft substrate, an investigation had been made on the methods of improving the adhesion by studying the effects of Co content, surface etching treatment and process parameter in diamond nucleation and growth. Conclusion can be drawn as following:
(1) One-step and Two-step chemical etching methods can remove the Co contents on the cemented carbides substrate and prevent Co negative effects in the process of deposition. Compared with one-step method, two-step etching is a more effective method for removing cobalt from WC-Co. This role can decrease the diffusion of Co to substrate surface and guarantee the deposition of good qualitative and adhesive diamond films.
(2) Among two-step etching, firstly using etching reagent B to attack WC grain 30 minute and then with etching reagent C 30 second removing Co is the most effective way consequently. The Co content of surface area can be reduced to 0.82% and 1.36% for YG6 and YG3 sample, respectively. The nucleation density can increase remarkably, at the same time, the purity of diamond thin films can improve greatly. A slight preference towards {110} oriented texture can be observed by XRD analysis.
(3) The adhesion between the diamond thin films and the cemented carbides substrates is dependent on the content of cobalt at the surface, the WC-Co substrate properties, the nucleation density and the quality of diamond films. Especially, the content of cobalt is a more important factor. The decreasing of Co content is easy for improving the adhesion between substrate and thin film. Of the two types of substrate used, WC-6%Co and WC-3%Co, it was easier to remove the Co from the former 6% samples.
(4) The conditions of diamond film deposition evidently affect on the nucleation density, the morphology, the structure, the purity of diamond film and lastly its adhesion strength. Our experiments show that the adhesion between diamond thin films and cemented carbide substrates is strong when substrate temperature is 750, chamber pressure is 20Torr and methane concentration is 1%.
引文
[1]戴达煌,周克崧等.金刚石薄膜沉积制备工艺与应用.北京,冶金工业出版社,2001:1-7
[2]Spitsyn B V, Bouilov L L, Derjaguin B V. Journal of Crystal Growth, 1981,52:219
[3]王和熙、张建军.金刚石薄膜的性质及其应用.新技术新工艺,1994,4:27-28
[4]唐伟忠.薄膜材料制备原理、技术及应用.北京,冶金工业出版社,1998:199-200
[5]A.Backon, A.Szymanski. Practical Uses of Diamond, in polish, translated in to English by EDaniel, pp.29-31
[6]陈会身、温绍国、韩秀丽.气相沉积法金刚石薄膜的性能和应用.金刚石与磨料磨具工程,1998,6(108):13-15
[7]Lu G. 1993 Application of Diamond Films and Related Materials. 2nd Int.Conf.ed A Feldmann et al p: 269
[8]黄永臣,扬志芬编译.国外金刚石薄膜工具的应用研究.磨料磨具与磨削 1994,79(1):36-37
[9]R.E. Clausing. in: Handbook of Industrial Diamonds and Diamond films. M. Prelas, G.Popovici, L.K. Bigelow (Eds.), Marcel Dekker. Inc., New York. 1998, p.19
[10]叶毅,叶伟昌.金刚石切削刀具及其应用.机械制造,1997,8:4-6
[11]叶伟昌,严卫平,叶毅.涂层硬质合金刀具的发展与应用.硬质合金,1998,15(1):54-57
[12]匡同春,王晓初,王成勇等.CVD金刚石厚膜刀具的研究进展与应用现状.金刚石与磨料磨具工程,2000,2(116):27-30
[13]方啸虎.超硬材料科学与技术(下卷).中国建材工业出版社,1998,
[14]郭志猛等.超硬材料与工具.冶金工业出版社,1996
[15]刘沙,易丹青,余志明等.金刚石涂层硬质合金的研究动态(Ⅰ).稀有金属与硬质合金,2000,2(141):53-57
[16]刘沙,易丹青,余志明等.金刚石涂层硬质合金的研究动态(Ⅱ).稀有金属与硬质合金,2000,3(142):36-44
[17]Saijo K., Yagi M., Shibuki K. et al. Deposition of diamond for cutting tool applications. Materials and Manufacturing Processes, 1993,8(1): 59-73
[18]Takalsu, Sokichi. Recent developments in hard cutting tool materials. High Temperature Materials and Processes, 1990,9 (2-4): 175-193
[19]刘志平,韩毅松,于启勤等.CVD金刚石膜刀具的制造技术及其应用.机械工艺师,2001,3:27-28
[20]郑良红,叶伟昌,汪通悦.刀具技术的发展动向(上).机械工程师,1998,9:34-35
[21]郑良红,叶伟昌,汪通悦.刀具技术的发展动向(下).机械工程师,1998,10:26
[22]F.Robert, Davis. Diamond Films and Coatings: development, properties and applications (Park Ridge, N. J.: Noyes, 1993)
[23]I. Reineck, M.E. Sjostrand, J.Karner. , et al.Diamond coated cutting tools. International Journal of Refractory Metals & Hard Materials, 1996:187-193
[24]C. Faure, W. Hanni, C. Julia Schmutz., et al. Diamond-coated tools. Diamond and Related Materials, 1999, 8:830-833
[25]Shibuki K., Sasaki K., Yagi M., et al. Diamond coating on WC-Co and WC for cutting tools. Surface & Coatings Technology, 1994, 68 (69): 369-373
[26]Zalavutdinov R.K., Gorodetsky A.E., Zakharov A.P., et al. Diamond-coated cemented carbide cutting inserts. Diamond and Related Materials, 1998,7 (7): 1014-1016
[27]Trava-Airoldi, Vladimir J., Corat, Evaldo J.,et al. Diamond chemical vapor deposition: Emerging technology for tooling applications. Key Engineering Materials, 1998,138-140: 195-244
[28]C. Faure, W. Hanni,C. Julia Schmutz, et al. Diamond-coated tools. Diamond and Related Materials, 1999, 8:830-833
[29]S. Silva, V. P. Mammana, M. C. Salvadori, et al. WC-Co cutting tool inserts with diamond coatings. Diamond and Related Materials, 1999, 8:1913-1918
[30]高志栋,曾效舒,梁吉等.金刚石薄膜涂层刀具的应用现状及前景.工具技术,1997,32(2):33-35
[31]杨仕娥.硬质合金刀具基体上金刚石涂层的制备及其附着性能的研究:[博士学位论文].郑州:郑州大学,2002
[32]K. V. Pavi, L. S. Plano et al. Proceeding of 1st International Conference of Science and Technology of New Diamond, Tokyo, Japan, 1990, P.29
[33]王伊卿,吕反修.金刚石气相沉积硬膜在工具表面的应用与发展.金刚石与磨料磨具工程,2002,1,(127):29-34
[34]赵建敏,丁波海,陈德才.高精度、超高精度气相沉积金刚石厚膜刀具的特性及其应用.航空制造技术,2002,1:30-33
[35] 匡同春,成晓玲,白晓军等.CVD金刚石涂层硬质合金刀片的基体预处理方法进展.硬质合金,2001,18(1):50-54
[36] 杨仕娥,马丙现,李会军等.金刚石涂层刀具的研究进展.真空与低温,2001,2,(7):68-71
[37] B. Sahoo, A. K. Chattopadhyay. On effectiveness of various surface treatments on adhesion of HF-CVD diamond coating to tungsten carbide inserts. Diamond and Related Materials, 2002, 11:1660-1669
[38] Tang, W., Wang, S., Lu, F. Preparation and performance of diamond coatings on cemented carbide inserts with cobalt boride interlayers. Diamond and Related Materials, 2000, 9:1744-1748
[39] Nesladek M, Vandierendonck K, Quaeyhaegens C, et al. Adhesion of diamond coatings on cemented carbides. Thin Solid Films, 1995,270:184-188
[40] Sun, F.H., Chen, M., Zhang, ZM., et al. Improvement of adhesive strength and surface roughness of diamond-coated thin film tools. Key Engineering Materials, 2001,202-203:159-164
[41] 匡同春,成晓玲,白晓军等.硬质合金基体上金刚石膜粘附性能的影响因素探讨.稀有金属,2001,25(2):108-113
[42] 曾效舒,高志栋,梁吉等.硬质合金上沉积金刚石膜提高粘结力的研究.人工晶体学报,1997,26(1):52-54
[43] Geng, Dongsheng, Zhang, Guifeng, Li, Xingwu, et al. Investigation on the adhesion between diamond films and WC-Co cemented carbides. Mechanical Science andTechnology, 1997, 16(6): 1050-1054
[44] 黄树涛,姚英学,袁哲俊.基体表现粗糙度对金刚石膜涂导层刀具附着强度的影响.制造技术与机床,2000,2:44-45
[45] 刘沙,易丹青,余志明等.金刚石涂层用硬质合金基体表面预处理研究进展.稀有金属材料与工程,2001,30(5):392-395
[46] 黄元盛,刘正义,邱万奇,CVD金刚石薄膜衬底表面预处理技术进展.中国表面工程,2001(3):18-20
[47] Katsumura, Yuji, Yagi, Masaru, Suzuki, Hisashi. Effects of cobalt content and surface state of substrate on cutting performance of diamond deposited cemented carbide tool for Al-18% Si alloy. Journal of Japan Institute of Light Metals, 1989, 39 (9): 634-638
[48] Mehlmann, A.K., Berger, S., Fayer, A., et al. Investigation of cobalt behaviour during diamond deposition on cemented carbides. Diamond and Related
Materials, 1994, 3 (4-6): 805-809
[49] Yu, Shift, Wu, Qinchong, Zhang, Zhiming, et al. Study of etching-Co pre-treatment on MW-PCVD diamond-coated WC-Co cemented carbide surface. High Technology Letters, 1998, 8 (4): 35-38
[50] Soderberg S, Gerendas A, Sjostrand M,, et al. Factors influencing the adhesion of diamond coating on cutting tools. Vacuum, 1990, 41(4-6): 1327-1321
[51] Matsumumoto S, Sato Y, Tsumi M, et al. Growth of Diamond particles from methane-hydrogen gas. Journal of Material Science, 1982, 17:3106
[52] Vandierendonck K, et al. W/WC Diffusion Barrier Layers for CVD Diamond Coating Deposited on WC-Co. Microstructure and Properties. Surface and Coating Technology, 1998, 98:1060
[53] Chen J L, Huang T H, Pan F M,, et al. Diamond film growth on cemented tungsten carbides studied by SEM, AES and XPS. Surface and Coatings Technology. 1992, (54/55):392
[54] Hartnett T, Miller R, Montanari D, et al. Intermediate layers for the deposition of polycrystalline diamond films. Journal of Vacuum Science and Technology, 1990, A8:2129
[55] Belton D N, Badzian T. Stadies of Surface Carbon during Diamond Growth on Pt. Surface Science, 1990, 233:131-140
[56] 王丽军,王小平,李广庭.金刚石薄膜衬底表面不同预处理对薄膜表面形貌的影响.微细加工技术,1998,(2):18-22
[57] 唐壁玉,靳九成,陈宗璋.CVD金刚石成核的最新研究.材料开发与应用,1998,18(6):7-10
[58] Tonshoff H K, Mohlfeld A, Gey C, et aL Mechanical pretreatment for improved adhesion of diamond coatings. Surface and Coating Technology, 1999, 116-119: 440-446
[59] 李成明,王建明,徐重等.准分子激光预处理对硬质合金表面沉积金刚石薄膜结合强度的影响.金属学报,1996,32(9):966-970
[60] 李成明,王建明,徐重等.金刚石薄膜在硬质合金表面的沉积与结合强度.材料科学与工艺,1997,Vol.5,No.1:53-55
[61] Cappelli, E., Orlando, S., Pinzari, E, et al. Pulsed laser treatment of WC,Co tool substrates to improve Co removing and diamond nucleation. Materials Research Society Symposium - Proceedings 526 Apr 13-16 1998, 1998 Sponsored by: MRS MRS p 361-365
[62] Haubner, R.; Schubert, W.D.; Lux, B. Interactions of hard metal substrates during diamond deposition. International Journal of Refractory Metals and Hard Materials, 1998, 16 (3): 177-185
[63] 邵淑敏,吕向英,于剑.影响金刚石薄膜生长因素的研究.真空,1998,(4):17-22
[64] I.Endler; K. Bartsch; A. Leonhardt, et al. Preparation and wear behaviour of woodworking tools coated with superhard layers. Diamond and Related Materials, 1999, 8: 834-839
[65] Sato, Takayasu, Hosokawa, Yukio, Ito, Shigeru, et al. Plasma carbonitriding of cemented carbide substrate as an effective pretreatment process for diamond CVD. Surface and Coatings Technology, 1999, 112 (1): 189-193
[66] Dong-Gu Lee, et al. Novel Method for adherent diamond coatings on cemented carbide substrates. Surface and Coatings Technology, 1999, 112:189
[67] 王四根,唐伟忠,吕反修.硬质合金表面渗硼处理对CVD金刚石涂层形成的影响.金属热处理,1998,No.10:1-2
[68] 王四根,盖世英,吕反修等.硬质合金工具金刚石涂层渗硼预处理.北京科技大学学报,2000,22,(1):31-33
[69] Kalss W, Bohr S, Haubner R, et al. Influence of Boron on Diamond Growth on WC-Co ttardmetals. International Journal of Refractory Metals & Hard Materials, 1996, 14:137
[70] Meilunas R J, Chang R P, Liu S L, et al. Nucleation of diamond films on surfaces using carbon clusters. Applied Physics Letter, 1991, 59(26): 3461
[71] 代江明,余忠民,匡同春等.蒸镀C60对YG8硬质合金刀片上金刚石形核的影响.硬质合金,2000,7(1):1-5.
[72] Guseva M B, et al. High quality diamond films on WC-Co surfaces. Diamond and Related Materials, 1997, 6:89-94
[73] Taher M A, Schmodt WE Brown W D, et al. Effect of Methane concentration on mechanical properties of HFCVD diamond-coated cemented carbide tool inserts. Surface and coating technology, 1996, (86/87): 678-685
[74] 黎向峰,左敦稳,王珉.硬质合金上金刚石膜的沉积.航空精密制造技术,1999,35(3):8-11
[75] 周灵平,靳九成等.热丝CVD法变压沉积金刚石薄膜.矿冶工程,1997,17,(3):72-74
[76] 陈明,孙方宏等.硬质合金刀具基体沉积低表面粗糙度金刚石薄膜的工艺研
究.工具技术,2000,34(3):9-13
[77]孙方宏,陈明,张志明.碳源浓度对金刚石薄膜涂层刀具性能的影响.金刚石与磨料磨具工程,2000,5:3-6
[78]王强,王四根,唐伟忠等.沉积温度对硬质合金金刚石涂层附着力影响的研究.金属热处理学报,2000,21(4):6-11
[79]马志斌,汪建华等.WC-C硬质合金上高质量金刚石薄膜的制备.武汉化工学院学报,2001,23(2):44-49
[80]Neslanek M, Vandierendonck L, Quaeyheagens C, et al. Adhesion of diamond coatings on cemented carbides. Thin Solid Films, 1995, 270:184-186
[81]Murakawa, M., Takeuchi, S., Quantitative adhesion strength measurement of diamond coatings. Thin Solid Films, 1989, 181:443-450
[82]J.Schultz, M.Nardin. Adhesion Promotion Technique, edited by K.L.Mittal, A.Pizzi (Marcel Dekker, Inc, 1999),p.1
[83]K.L.Mittal, Adhesion measurement of films and coatings (VSP, 1995), p.1
[84]J. W.McBain, D.G..Hopkins, Journal of Physics Chemistry, 1925, 29 (88)
[85]W.C.Wake. Adhesion and Formation of Adhesive. Applied Science, London: 1982
[86]简小刚,孙方宏,赵国伟等.金刚石薄膜膜基界面结合强度测量技术的研究进展.金刚石与磨料磨具工程,2002,3(129):3-7
[87]谢中维,郭薇,朱静等.金刚石薄膜结合强度的测量.金刚石与磨料磨具工程,2000,1(1):36-39
[88]王和照,张建军.金刚石薄膜的人工合成及其结合力的评估.微细加工技术,1994,2
[89]Polini R,D'antonio P, Lo Casto,et al. Cutting performance and indentation behavior of diamond films on Co-cemented tungsten carbide. Surface and Coating Technology, 2000, 123: 78
[90]吕反修,付一良,钟国仿等.CVD金刚石膜的断裂行为.金属热处理学报,1997,3:117-112
[91]何贤昶,沈挺,沈荷生等.用垂直拉伸法测定金刚石薄膜的附着强度.机械工程材料,1998,10(22):7-9
[92]高鹏,陶敏中,袁哲俊等.纳米压痕技术及其应用.中国机械工程,1996,7(5):58-59
[93]朱晓东,黄鹤,胡奈赛等.用球滚接触疲劳法评定硬质薄膜的结合强度.金属学报,1999,35(5):523-526
[94]谢中维,朱静.薄膜结合强度的刮剥式测量方式及其应用.94秋季中国材料研讨会论文集,Ⅱ,1994:123
[95]龚辉.新型金刚薄膜的制备和应用研究:[博士学位论文].上海:中科院上海光机所,2001
[96]刘沙.硬质合金基体表面预处理及其金刚石涂层的研究:[博士学位论文].长沙:中南大学,2003
[97]刘沙,易丹青,余志明等.金刚石涂层用低钴硬质合金基体表面二步浸蚀法的研究.稀有金属材料与工程,2002,31(4):106-109
[98]刘沙,余志明,易丹青.金刚石涂层用高钴硬质合金基体表面二步浸蚀法的研究.粉末冶金技术,2001,20(6):41-44
[99]刘泉,周健,余卫华等.WC-0.8%Co基底上微波等离子化学气相沉积金刚石膜.中国有色金属学报,2001,11(1):116-119
[100]杨莉,余志明,殷磊等.脱钴处理对金刚石/硬质合金附着性能的影响.中国表面工程,2003,6(16):16-20
[101]N. M. Everitt, R. F.Silva, J. Vieira, et al. Advances in New Diamond Science and Technology. In.. M. Yoshikawa (eds) , Proc. Fourth Int. Conf. on New Diamond Science and Technology, Kobe, July, 1994
[102]Makita H, Nishimura K, Jiang N, et al. Ultrahigh particle density seeding with nanocrystal diamond particles. Thin Solid Films, 1996, 281-282:279
[103]Xuanxiong Z, Jinxin W, Tiansheng S, et al. Proceedings of the International Conference on the Surface and Engineering. International Academic Publishers, 1995, p.590.
[104]Z.Yu, A.Flodstrm. Orientation of (1 × 1)-surface free energies of crystals. Surface Science, 1998, 401: 236-247
[105]Z.Yu, T. Rogelet, A.Flodstrm. Diamond growth on turbostratic carbon by HFCVD. Applied Physics, 1993, 74 (12): 7235-7240
[106]Z.Yu, A.Flodstrm. Pressure dependence of growth mode of HFCVD diamond. Diamond and Related Materials, 1997, (6): 81-84
[107]Saijo K, Yagi M, Shibuki K, et al. Improvements in adhesive strength and cutting performance of diamond coated tools[J]. Surface and Coating Technology, 1991,47: 646-653.
[108]W.Tang, Q.Wang, S.Wang, F.Lu, Adherent diamond coating on cemented carbide substrates with different cobalt contents[J].Diamond and Related Materials,2001,10:1700-1704.
[109]杨国伟,廖静.化学气相沉积金刚石薄膜生长动力学模型.人工晶体学报,1997,26(1):72-77
[110]赵南方,杨巧勤,赵立华等.金刚石薄膜显微结构研究.炭素,1998,1:40-43
[111]LIU Sha, YI Dan-qing, YU Zhi-ming, et al. Chemical pretreatments at surface of WC-6%Co for diamond coatings. Transactions of Nonferrous Metals Society of China, 2002, 12 (3): 396-399
[112]刘雄飞,李晨辉.镀膜对金刚石与结合剂之间结合性能的影响.中国有色金属学报,2001,11(3):445-448
[113]Nesladek M, Vandierendonck K, Quaeyhaegens C, et al. Adhesion of diamond coatings on cemented carbides. Thin Solid Films, 1995,270 : 184-188
[114]Polini, Riccardo, Marcheselli, et al. Nucleation and growth of diamond films on Ni-cemented tungsten carbide: Effects of substrate pretreatments. Journal of the American Ceramic Society, 1994, 77(8): 2043-2048
[115]Polini, Riccardo, Marcheselli, et a. Nucleation and growth of diamond films on Ni-cemented tungsten carbide: Ⅱ, effects of deposition conditions. Journal of the American Ceramic Society ,1995,78 (9): 2431-2436
[116]马志斌.在铜及硬质合金基体上金刚石薄膜的沉积研究:[博士学位论文].合肥:中科院等离子体物理研究所,2001
[117]Frenklach M. The role of hydrogen in vapor deposition of diamond. Journal of Applied Physics, 1989, 65(12):5142-5145
[118]Shah S I, Walls D J. Plasma assisted conversion of carbon fibers to diamond. Applied Physics Letter, 1995, 67(22):3355-3358
[119]俞世吉,丁振峰,马腾才等.基体位置对MWPCVD制备金刚石薄膜的影响.真空科学与技术,2000,20(2):131-133