GCr15轴承钢等离子体基C、N、Ta多元共注组织及性能
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摘要
本文采用等离子体基离子注入的方法,通过改变C、N、Ta三种元素的注入剂量和注入顺序在GCr15轴承钢基体上制备了表面改性层,以提高材料表面的硬度和耐磨性能。
利用X射线光电子能谱(XPS)分析了表面注入层的成分和原子百分含量;用激光拉曼光谱(Raman)分析了表面注入层的性质;并通过XRD测试分析了表面注入层的相结构。利用美国Nano Indenter XP型纳米压痕仪测量硬度和弹性模量;通过球-盘式摩擦磨损试验机研究了在干摩擦、常规实验室条件下表面改性层的摩擦学行为,并根据磨痕轮廓采用积分的方法计算粘着和磨损量,也对试样摩擦表面进行了金相和扫描电子显微镜(SEM)观察分析。
研究结果表明:等离子体基离子注入C、N后,在试样表面形成DLC膜。先注氮后注碳试样表面注入层的DLC膜性质优于先注碳后注氮的试样;无论是先注碳后注氮还是先注氮后注碳,硬度变化规律都是先增加后降低,并且在C和N的注入剂量都是3E17ions/cm2时,表面注入层硬度最高。先注氮后注碳试样表面耐磨性好于先注碳后注氮试样,并且随着碳注入剂量的增加,耐磨性逐渐提高。摩擦副为GCr15钢球,先注碳后注氮试样的磨损机制以粘着磨损为主,先注氮后注碳试样的磨损机制以磨粒磨损为主;摩擦副为Si3N4陶瓷球,随着氮离子注入剂量的增加,磨损机制由两种机制并存变为粘着磨损,随着碳离子注入剂量的增加,磨损机制由两种机制并存转变为磨粒磨损。
等离子体基离子注入C、N、Ta后,试样表面注入层形成TaC,Ta2C相。摩擦系数由于Ta的注入显著降低。先注金属Ta后注气体试样的耐磨性好于先注气体后注金属Ta的。摩擦副GCr15球,前者的磨损机制是磨粒磨损,后者的磨损机制是粘着磨损和磨粒磨损两种机制并存;摩擦副Si3N4陶瓷球,前者的磨损机制由两种机制并存转变为磨粒磨损,后者的磨损机制是粘着磨损和磨粒磨损两种机制并存。
The strengthening effects and wear resistance of carbon, nitrogen and tantalum ions implantation of Gr15 steel are discussed by studying the evolution of nano-hardness and wear mechanism of the samples with different implantation sequence and dose.
The composition and chemical structure of implanted layers were studied by X-ray photoelectron spectroscopy(XPS) and laser Raman spectroscopy respectively. The phases exist in the implanted layers were determined by grasing angle X-ray diffraction(GXRD). The Nano-impression apparatus were used to determine the nano-hardness and modulus of the implanted layers. The tribologocial behavior of the implanted layers was investigated by ball-disk friction wear testing machine under the condition of dry friction and laboratory ambient, and scanning electron microscopy(SEM) and metallographical were also used to investigate the wear machining.
The results show that the properties of the DLC films for the sample with implantation sequence of nitrogen-carbon are better than the samples with implantation sequence of carbon-nitrogen. The highest hardness is with the nitrogen and carbon implantation dose of 3E17ions/cm2 whatever the implantation sequence, respectively. The adhesion abrasion resistance of samples with implantation sequence of nitrogen-carbon is better than the samples with implantation sequence of carbon-nitrogen during the friction tests without lubrication and the wear resistance increases with the increasing of carbon implantation dose. With friction pair GCr15 steel ball for the sample with implantation sequence of carbon-nitrogen, the wear machine is adhesive; for the sample with implantation sequence of nitrogen-carbon, the wear machine is abrasive. With friction pair Si3N4 ceramic ball at the beginning the wear machine is adhesive and abrasive one, then transisting into the adhesive or abrasive machine with the increasing of carbon and nitrogen implantation dose, respectively.
The results also show that the new phase of TaC and Ta2C exited in the implanted layers for the samples with implated carbon, nitrogen and tantalum. Friction cofficient is also obvious decreased. The adhesion abrasion resistance of samples with implantation sequence of Ta-gas is better than the samples with implantation sequence of gas-Ta during the friction tests without lubrication. With friction pair GCr15 steel ball for the sample with implantation sequence of Ta-gas, the wear machine is abrasive. With friction pair Si3N4 ceramic ball its wear mechine is both abrasive and adhesive one at the beginning, then trasisting into abrasive one. The other is both abrasive and adhesive machine with whatwver friction pair.
利用X射线光电子能谱(XPS)分析了表面注入层的成分和原子百分含量;用激光拉曼光谱(Raman)分析了表面注入层的性质;并通过XRD测试分析了表面注入层的相结构。利用美国Nano Indenter XP型纳米压痕仪测量硬度和弹性模量;通过球-盘式摩擦磨损试验机研究了在干摩擦、常规实验室条件下表面改性层的摩擦学行为,并根据磨痕轮廓采用积分的方法计算粘着和磨损量,也对试样摩擦表面进行了金相和扫描电子显微镜(SEM)观察分析。
研究结果表明:等离子体基离子注入C、N后,在试样表面形成DLC膜。先注氮后注碳试样表面注入层的DLC膜性质优于先注碳后注氮的试样;无论是先注碳后注氮还是先注氮后注碳,硬度变化规律都是先增加后降低,并且在C和N的注入剂量都是3E17ions/cm2时,表面注入层硬度最高。先注氮后注碳试样表面耐磨性好于先注碳后注氮试样,并且随着碳注入剂量的增加,耐磨性逐渐提高。摩擦副为GCr15钢球,先注碳后注氮试样的磨损机制以粘着磨损为主,先注氮后注碳试样的磨损机制以磨粒磨损为主;摩擦副为Si3N4陶瓷球,随着氮离子注入剂量的增加,磨损机制由两种机制并存变为粘着磨损,随着碳离子注入剂量的增加,磨损机制由两种机制并存转变为磨粒磨损。
等离子体基离子注入C、N、Ta后,试样表面注入层形成TaC,Ta2C相。摩擦系数由于Ta的注入显著降低。先注金属Ta后注气体试样的耐磨性好于先注气体后注金属Ta的。摩擦副GCr15球,前者的磨损机制是磨粒磨损,后者的磨损机制是粘着磨损和磨粒磨损两种机制并存;摩擦副Si3N4陶瓷球,前者的磨损机制由两种机制并存转变为磨粒磨损,后者的磨损机制是粘着磨损和磨粒磨损两种机制并存。
The strengthening effects and wear resistance of carbon, nitrogen and tantalum ions implantation of Gr15 steel are discussed by studying the evolution of nano-hardness and wear mechanism of the samples with different implantation sequence and dose.
The composition and chemical structure of implanted layers were studied by X-ray photoelectron spectroscopy(XPS) and laser Raman spectroscopy respectively. The phases exist in the implanted layers were determined by grasing angle X-ray diffraction(GXRD). The Nano-impression apparatus were used to determine the nano-hardness and modulus of the implanted layers. The tribologocial behavior of the implanted layers was investigated by ball-disk friction wear testing machine under the condition of dry friction and laboratory ambient, and scanning electron microscopy(SEM) and metallographical were also used to investigate the wear machining.
The results show that the properties of the DLC films for the sample with implantation sequence of nitrogen-carbon are better than the samples with implantation sequence of carbon-nitrogen. The highest hardness is with the nitrogen and carbon implantation dose of 3E17ions/cm2 whatever the implantation sequence, respectively. The adhesion abrasion resistance of samples with implantation sequence of nitrogen-carbon is better than the samples with implantation sequence of carbon-nitrogen during the friction tests without lubrication and the wear resistance increases with the increasing of carbon implantation dose. With friction pair GCr15 steel ball for the sample with implantation sequence of carbon-nitrogen, the wear machine is adhesive; for the sample with implantation sequence of nitrogen-carbon, the wear machine is abrasive. With friction pair Si3N4 ceramic ball at the beginning the wear machine is adhesive and abrasive one, then transisting into the adhesive or abrasive machine with the increasing of carbon and nitrogen implantation dose, respectively.
The results also show that the new phase of TaC and Ta2C exited in the implanted layers for the samples with implated carbon, nitrogen and tantalum. Friction cofficient is also obvious decreased. The adhesion abrasion resistance of samples with implantation sequence of Ta-gas is better than the samples with implantation sequence of gas-Ta during the friction tests without lubrication. With friction pair GCr15 steel ball for the sample with implantation sequence of Ta-gas, the wear machine is abrasive. With friction pair Si3N4 ceramic ball its wear mechine is both abrasive and adhesive one at the beginning, then trasisting into abrasive one. The other is both abrasive and adhesive machine with whatwver friction pair.
引文
1韦泽洪.高碳铬轴承钢GCr15冶炼工艺探索及质量控制.新产品开发. 2007. 4~7
2刘新佳.《工程材料》.化学工业出版社. 2006. 144~146
3叶健熠.滚动轴承常用金属材料.工艺与装备. 2005, 8: 96~98
4 R. C. Tucker, Jr. H. Nitta, Detonation Gun coating characteristics and applications [C]. Proceeding of ATTAC 88, Osaka, Japan, 1988: 85~92
5周志谰,马纯民.航空发动机主轴轴承失效分析与预防[M ].北京:科学出版社, 1998. 78~81
6崔菎.钢铁材料及有色金属材料[M].北京:机械工业出版社出版, 1981. 112~115
7车仁超,杨孚标,张家春,马欣新,夏立方. GCr15钢等离子体基离子混合注入层摩擦特性研究.《金属热处理》1999, 3: 12~14
8孙明仁,夏立方,孙跃,马欣新,李光. GCr15钢等离子体基离子注入Ti和C混合层的XPS研究.真空科学与技术. 1999, 18(1): 74~78
9梁华.轴承钢氮离子注入层的显微组织分析.金属热处理. 2006(31), 5: 43~44.
10王钧石. GCr15钢等离子体源离子注入表面改性.机械工程材料. 2001, Vol. 25 No. 9: 22~24
11王和好, N+注入GCr15钢摩擦磨损性能研究,安徽机电报, 2000, 15(4): 35~40
12 F. M. Kustas, Implatation Parameters and Rolling contact Fatigue Improvement[J], Surface and Coatings Technologies, 2003, 37(1): 26~31
13 J. K. Hirvoen. Nitrogen implantation into steels[J]. J. Vac. Sci. technol., 1978(15): 1622~1663
14 A. Wittkewer, J. K. Hirvohen, ibid, 1979(12): 78~79
15张通和,吴瑜光.离子注入表面优化技术,冶金工业出版社, 1993, 251~256
16 Q. Y. Zhang, X. X. Mei, D.Z. Yang, Preparation, structure and properties of TaN and TaC films obtained by ion beam assisted deposition. NIMB 127/128 (1997) 664~668
17 S. S. Roy, R. McCann, P. Papakonstantinou, The structure of amorphous carbon nitride films using a combined study of NEXAFS, XPS and Raman spectroscopies. Thin Solid Films 482 (2005): 145~150
18 H. O. Pierson, Handbook of Refractory Carbides and Nitrides, Chap. 5, Noyes Publications, New Jersey, 1996: 166~170
19 T. B. Massalski, Binary, Alloy Phase Diagrams, 2nd ed, ASM International, Metal Park, OH, USA, 1990: 51~57
20 A. Rubinshtein, R. Shneck, A, Raveh, J.E. Klemberg-Sapieha, L. Martinu, J. Vac. Sci. Technol. A 18 (4) (2004): 2017~2018
21 G. R. Gruzalski, D. Z. Zehner, Phy. Rev. B 42(1990): 2768~2769
22 J. E. Holiday, J. Appl. Phys. 38(1997): 4720
23 M. Traving, I. Zienert, E. Zschech. Phase analysis of TaN/Ta barrier layers in sub-micrometer trench structures for Cu interconnects. Appl. Surf. Sci. 252(2005): 11~17
24 D. Gerstenberg and C.J. Calbick, J. Appl. Phys. 35(1964): 402~404
25 H. J. Coyne, Jr. and R. N. Rauber, J. Appl. Phys. 39(1968): 5585~5586
26 D. J. Willmott. J. Appl. Phys. 43(1972): 4865~4866
27 C. R. Aita and T. A. Myers, J. Vac. Sci.Techn. A 1(1983): 348~349
28 B.Mehrotra and J.stimmell, J. Vac. Sci.Techn. B 5(1987): 1736~1737
29 Q.Y. Zhang, B. Chen, G.B. Li, S. Jin, F.X. Chen. Surf. Coat. Techn. 66 (1994):
468~469
30 E. Benko, T. L.Barr, A. Bernasik, Experimental and calculated phase equlibria in the cubic BN-Ta-C system. CERAMICS 30(2004): 31~40
31赵青,任文静,耿漫.升温Ta+N双注入对硬质合金性能的影响.核聚变与等离子物理22(2002): 61~64
32娄燕雄,赵贵才译.钽铌译文[M].湖南:中南工业大学出版社,1984: 34~35
33张涛,侯君达,张孝吉.金属等离子体基浸没和离子注入.北京师范大学学报(自然科学版). 36(2006): 181~183.
34 W. Ensinger, J. Klein, P. Usedom and B. Rauschenbach. Characteristics of an Apparatus for Plasma Immersion Ion Implantation and Physical Vapour Deposition. Surface and Coatings Technology. 1997, 93: 175~180
35 S. Lo. Russo, Appl. Phys. Lett, 1984: 125~126
36 R. C. Richardson, Wear, 11(1968): 245~247
37 E. P. Bowden, The Friction and Lubrication of Solids, Part II, Oxford University Press, London, 1964: 365~367
38 N. E. W. Hartley, Ion Implantation in Semiconductors and Other Materials, ed. by B. L. Crowder, Plenum Press, 1976: 423~424
39 J. F. Arehard, Prog. Boy. Sec. A243(1957): 190~193
40 J. Halling, Principles of Tribology, Macmillam, London, 1957.1: 98~102
41 I. I. Banmvol, Phys. Stat. Sol. (a), 87(1981): 67~68
42杨雨时,王磊,沈江力.类金刚石膜(DLC)及应用.宇航材料工艺. 1996, 26(1): 13~16
43 D. J. Li, F. Z. cui, H. Q. Gu. Studies of Diamond-Like Carbon Films Coated on PMMA by Ion Beam Assisted Deposition. Applied Surface Science. 1999, 137: 30~37
44 X. D. Li, B. Bhushan. A Review of Nanoindentation Continuous Stiffness Measurement Technique and Its Applications. Materials Characterization. 2002, 48(1): 11~36
45 E. Atanassova, G. Tyuliev, A.Paskaleva. XPS study of annealing effect on thermal Ta2O5 layers on Si. Applied Surface Science 225(2004): 86~99.
46 E. Atanassova, D. Spassov. X-ray photoelectron spectroscopy of thermal Ta2O5 films on Si. Applied Surface Science 135(1998): 71~82.
47 J. Walter, W. Boonchuduang, S. Hara. XPS study on pristine and intercalated tantalum carbosulfide. Journal of Alloys and Compounds305 (2000): 259~263.
48黄卫东,詹如娟.表面波等离子体沉积类金刚石膜结构的Raman光谱和XPS分析.光谱学和光谱分析. 2003, 23(3): 512~514.
49 T. B. Massalski, Binary, Alloy Phase Diagrams, 2nd ed, ASM International, Metal Park, OH, USA, 1990: 105~111
50 A. Rubinshtein, R. Shneck, A, Raveh, J.E. Klemberg-Sapieha, L. Martinu, J. Vac. Sci. Technol. A 18 (4) (2005): 2017~2018
51刘纶,鲁光浣,刘富润.小角度掠射X-Ray Diffraction用于离子注入后金属材料的物相鉴定.天津师大学报. 1999, (19): 2~4
52徐淑艳. M50钢等离子体基升温注入氮层的组织结构及耐磨性.哈尔滨工业大学. 2002: 13~48
2刘新佳.《工程材料》.化学工业出版社. 2006. 144~146
3叶健熠.滚动轴承常用金属材料.工艺与装备. 2005, 8: 96~98
4 R. C. Tucker, Jr. H. Nitta, Detonation Gun coating characteristics and applications [C]. Proceeding of ATTAC 88, Osaka, Japan, 1988: 85~92
5周志谰,马纯民.航空发动机主轴轴承失效分析与预防[M ].北京:科学出版社, 1998. 78~81
6崔菎.钢铁材料及有色金属材料[M].北京:机械工业出版社出版, 1981. 112~115
7车仁超,杨孚标,张家春,马欣新,夏立方. GCr15钢等离子体基离子混合注入层摩擦特性研究.《金属热处理》1999, 3: 12~14
8孙明仁,夏立方,孙跃,马欣新,李光. GCr15钢等离子体基离子注入Ti和C混合层的XPS研究.真空科学与技术. 1999, 18(1): 74~78
9梁华.轴承钢氮离子注入层的显微组织分析.金属热处理. 2006(31), 5: 43~44.
10王钧石. GCr15钢等离子体源离子注入表面改性.机械工程材料. 2001, Vol. 25 No. 9: 22~24
11王和好, N+注入GCr15钢摩擦磨损性能研究,安徽机电报, 2000, 15(4): 35~40
12 F. M. Kustas, Implatation Parameters and Rolling contact Fatigue Improvement[J], Surface and Coatings Technologies, 2003, 37(1): 26~31
13 J. K. Hirvoen. Nitrogen implantation into steels[J]. J. Vac. Sci. technol., 1978(15): 1622~1663
14 A. Wittkewer, J. K. Hirvohen, ibid, 1979(12): 78~79
15张通和,吴瑜光.离子注入表面优化技术,冶金工业出版社, 1993, 251~256
16 Q. Y. Zhang, X. X. Mei, D.Z. Yang, Preparation, structure and properties of TaN and TaC films obtained by ion beam assisted deposition. NIMB 127/128 (1997) 664~668
17 S. S. Roy, R. McCann, P. Papakonstantinou, The structure of amorphous carbon nitride films using a combined study of NEXAFS, XPS and Raman spectroscopies. Thin Solid Films 482 (2005): 145~150
18 H. O. Pierson, Handbook of Refractory Carbides and Nitrides, Chap. 5, Noyes Publications, New Jersey, 1996: 166~170
19 T. B. Massalski, Binary, Alloy Phase Diagrams, 2nd ed, ASM International, Metal Park, OH, USA, 1990: 51~57
20 A. Rubinshtein, R. Shneck, A, Raveh, J.E. Klemberg-Sapieha, L. Martinu, J. Vac. Sci. Technol. A 18 (4) (2004): 2017~2018
21 G. R. Gruzalski, D. Z. Zehner, Phy. Rev. B 42(1990): 2768~2769
22 J. E. Holiday, J. Appl. Phys. 38(1997): 4720
23 M. Traving, I. Zienert, E. Zschech. Phase analysis of TaN/Ta barrier layers in sub-micrometer trench structures for Cu interconnects. Appl. Surf. Sci. 252(2005): 11~17
24 D. Gerstenberg and C.J. Calbick, J. Appl. Phys. 35(1964): 402~404
25 H. J. Coyne, Jr. and R. N. Rauber, J. Appl. Phys. 39(1968): 5585~5586
26 D. J. Willmott. J. Appl. Phys. 43(1972): 4865~4866
27 C. R. Aita and T. A. Myers, J. Vac. Sci.Techn. A 1(1983): 348~349
28 B.Mehrotra and J.stimmell, J. Vac. Sci.Techn. B 5(1987): 1736~1737
29 Q.Y. Zhang, B. Chen, G.B. Li, S. Jin, F.X. Chen. Surf. Coat. Techn. 66 (1994):
468~469
30 E. Benko, T. L.Barr, A. Bernasik, Experimental and calculated phase equlibria in the cubic BN-Ta-C system. CERAMICS 30(2004): 31~40
31赵青,任文静,耿漫.升温Ta+N双注入对硬质合金性能的影响.核聚变与等离子物理22(2002): 61~64
32娄燕雄,赵贵才译.钽铌译文[M].湖南:中南工业大学出版社,1984: 34~35
33张涛,侯君达,张孝吉.金属等离子体基浸没和离子注入.北京师范大学学报(自然科学版). 36(2006): 181~183.
34 W. Ensinger, J. Klein, P. Usedom and B. Rauschenbach. Characteristics of an Apparatus for Plasma Immersion Ion Implantation and Physical Vapour Deposition. Surface and Coatings Technology. 1997, 93: 175~180
35 S. Lo. Russo, Appl. Phys. Lett, 1984: 125~126
36 R. C. Richardson, Wear, 11(1968): 245~247
37 E. P. Bowden, The Friction and Lubrication of Solids, Part II, Oxford University Press, London, 1964: 365~367
38 N. E. W. Hartley, Ion Implantation in Semiconductors and Other Materials, ed. by B. L. Crowder, Plenum Press, 1976: 423~424
39 J. F. Arehard, Prog. Boy. Sec. A243(1957): 190~193
40 J. Halling, Principles of Tribology, Macmillam, London, 1957.1: 98~102
41 I. I. Banmvol, Phys. Stat. Sol. (a), 87(1981): 67~68
42杨雨时,王磊,沈江力.类金刚石膜(DLC)及应用.宇航材料工艺. 1996, 26(1): 13~16
43 D. J. Li, F. Z. cui, H. Q. Gu. Studies of Diamond-Like Carbon Films Coated on PMMA by Ion Beam Assisted Deposition. Applied Surface Science. 1999, 137: 30~37
44 X. D. Li, B. Bhushan. A Review of Nanoindentation Continuous Stiffness Measurement Technique and Its Applications. Materials Characterization. 2002, 48(1): 11~36
45 E. Atanassova, G. Tyuliev, A.Paskaleva. XPS study of annealing effect on thermal Ta2O5 layers on Si. Applied Surface Science 225(2004): 86~99.
46 E. Atanassova, D. Spassov. X-ray photoelectron spectroscopy of thermal Ta2O5 films on Si. Applied Surface Science 135(1998): 71~82.
47 J. Walter, W. Boonchuduang, S. Hara. XPS study on pristine and intercalated tantalum carbosulfide. Journal of Alloys and Compounds305 (2000): 259~263.
48黄卫东,詹如娟.表面波等离子体沉积类金刚石膜结构的Raman光谱和XPS分析.光谱学和光谱分析. 2003, 23(3): 512~514.
49 T. B. Massalski, Binary, Alloy Phase Diagrams, 2nd ed, ASM International, Metal Park, OH, USA, 1990: 105~111
50 A. Rubinshtein, R. Shneck, A, Raveh, J.E. Klemberg-Sapieha, L. Martinu, J. Vac. Sci. Technol. A 18 (4) (2005): 2017~2018
51刘纶,鲁光浣,刘富润.小角度掠射X-Ray Diffraction用于离子注入后金属材料的物相鉴定.天津师大学报. 1999, (19): 2~4
52徐淑艳. M50钢等离子体基升温注入氮层的组织结构及耐磨性.哈尔滨工业大学. 2002: 13~48