结构调制超硬Ti/TiN纳米多层膜的制备及其尺寸效应
|
摘要
使用多弧离子镀技术在高速钢基体上制备了调制周期为5～40 nm的Ti/TiN纳米多层膜,用扫描电子显微镜(SEM)、X射线能谱仪(EDS)、X射线衍射仪(XRD)、纳米压痕仪和划痕仪等手段表征薄膜的微观结构和性能,研究了调制周期对Ti/TiN纳米多层膜性能的影响,并讨论了在小调制周期条件下Ti/TiN纳米多层膜的超硬效应和多弧离子镀技术对纳米多层膜硬度的强化作用。结果表明,与单层TiN相比,本文制备的Ti/TiN纳米多层膜分层情况良好,薄膜均匀致密,没有明显的柱状晶结构,TiN以面心立方结构沿(111)方向择优生长。随着调制周期的减小薄膜的硬度呈现先增大后减小的趋势,并在调制周期为7.5 nm时具有最大的硬度42.9 GPa和H/E值。这表明,Ti/TiN在具有最大硬度的同时仍然具有良好的耐磨性和韧性。Ti/TiN纳米多层膜的附着力均比单层TiN薄膜的附着力高,调制周期为7.5 nm时多层膜的附着力为(58±0.9) N。
Multilayered films Ti/TiN with 5～40 nm modulation period were prepared on a high-speed steel substrate by multi-arc ion plating technology. The microstructure and mechanical property of the films were characterized by means of scanning electron microscopy(SEM), X-ray energy dispersive spectrometer(EDS), X-ray diffraction(XRD), nanoindentation and scratch test. The effect of modulation period on the performance of multilayered films Ti/TiN was investigated. Results show that the multilayered films Ti/TiN are uniform and dense with lamellar structure but without obvious features of columnar structure. TiN film is preferentially grown along the(111) direction. The film hardness increases firstly and then decreases with the decrease of the modulation period. The maximum hardness of 42.9 GPa and the maximum H/E value werer obtained when the modulation period is 7.5 nm, which indicates that the film possesses good combination of wear resistance and toughness. In addition, the adhesion of the multilayered films Ti/TiN is generally higher than that of the single-layered TiN film. When the modulation period is 7.5 nm, multilayered films Ti/TiN present a relatively high adhesion of(58±0.9) N.
Multilayered films Ti/TiN with 5～40 nm modulation period were prepared on a high-speed steel substrate by multi-arc ion plating technology. The microstructure and mechanical property of the films were characterized by means of scanning electron microscopy(SEM), X-ray energy dispersive spectrometer(EDS), X-ray diffraction(XRD), nanoindentation and scratch test. The effect of modulation period on the performance of multilayered films Ti/TiN was investigated. Results show that the multilayered films Ti/TiN are uniform and dense with lamellar structure but without obvious features of columnar structure. TiN film is preferentially grown along the(111) direction. The film hardness increases firstly and then decreases with the decrease of the modulation period. The maximum hardness of 42.9 GPa and the maximum H/E value werer obtained when the modulation period is 7.5 nm, which indicates that the film possesses good combination of wear resistance and toughness. In addition, the adhesion of the multilayered films Ti/TiN is generally higher than that of the single-layered TiN film. When the modulation period is 7.5 nm, multilayered films Ti/TiN present a relatively high adhesion of(58±0.9) N.
引文
[1]Sundgren J E.Structure and properties of TiN coatings[J].Thin Solid Films,1985,128:21
[2]Zhang X,Zhou Y W,Gao J B,et al.Effect of the filament discharge current on the microstructure and performance of plasma-enhanced magnetron sputtered TiN coatings[J].J.Alloys Compd.,2017,725:877
[3]Kashkarov E B,Nikitenkov N N,Sutygina A N,et al.Hydrogenation behavior of Ti-implanted Zr-1Nb alloy with Ti N films deposited using filtered vacuum arc and magnetron sputtering[J].Appl.Surf.Sci.,2018,432:207
[4]Song Y Z,Gao Y,Dong Z X,et al.Effects of multi-arc ion plating process parameters on binding force of TiN film[J].Hot Working Technol.,2016,45(14):133(宋沂泽,高原,董中新等.多弧离子镀工艺参数对氮化钛薄膜结合力的影响研究[J].热加工工艺,2016,45(14):133)
[5]Wen L S,Huang R F,Guo L P,et al.Microstructure and mechanical properties of metal/ceramic Ti/TiN multilayers[J].J.Magn.Magn.Mater.,1993,126:200
[6]Cheng Y Y,Pang X L,Gao K W,et al.Corrosion resistance and friction of sintered NdFeB coated with Ti/TiN multilayers[J].Thin Solid Films,2014,550:428
[7]Koehler J S.Attempt to design a strong solid[J].Phys.Rev.,1970,2B:547
[8]Dück A,Gamer N,Gesatzke W,et al.Ti/TiN multilayer coatings:deposition technique,characterization and mechanical properties[J].Surf.Coat.Technol.,2001,142-144:579
[9]Ghasemi S,Shanaghi A,Chu P K.Nano mechanical and wear properties of multi-layer Ti/TiN coatings deposited on Al 7075 by highvacuum magnetron sputtering[J].Thin Solid Films,2017,638:96
[10]Krysina O V,Koval N N,Ivanov Y F,et al.Arc plasma-assisted deposition of nanocrystalline coatings[A].2012 25th International Symposium on Discharges and Electrical Insulation in Vacuum[C].Tomsk,Russia:IEEE,2012:537
[11]Lang W C.Design and performance of the double dislocation perforated shielding plate used in vacuum arc deposition for high quality coating deposition[J].Adv.Mater.Res.,2012,340:130
[12]Li F Q,Lin S S,Lin K S.Development and current status of decorative ion-plated hard films[J].Electroplat.Finish.,2016,35:817(李福球,林松盛,林凯生.离子镀硬质装饰膜的发展与现状[J].电镀与涂饰,2016,35:817)
[13]Zhao Y H,Lin G Q,Li X N,et al.Effect of pulsed bias on microhardness of Ti/TiN multilayer films deposited by arc ion plating[J].Acta Metall.Sin.,2015,41:1106(赵彦辉,林国强,李晓娜等.脉冲偏压对电弧离子镀Ti/TiN纳米多层薄膜显微硬度的影响[J].金属学报,2015,41:1106)
[14]Krella A K.Cavitation erosion resistance of Ti/TiN multilayer coatings[J].Surf.Coat.Technol.,2013,228:115
[15]Xiao N,Du F F,Yang B.Effects of modulation periods on structure and adhesion strength of TiN/Ti multilayer films[J].China Surf.Eng.,2015,28(2):65(肖娜,杜菲菲,杨波.调制周期对TiN/Ti多层膜组织结构和结合力的影响[J].中国表面工程,2015,28(2):65)
[16]Zhao Y H,Lin G Q,Xiao J Q,et al.Ti/TiN multilayer thin films deposited by pulse biased arc ion plating[J].Appl.Surf.Sci.,2011,257:2683
[17]Chun S Y,Chayahara A,Posselt M.Limitations on ultra-thin multilayers:pulsed cathodic arc and computer simulation[J].Surf.Coat.Technol.,2004,182:171
[18]Kimblin C W.Erosion and ionization in the cathode spot regions of vacuum arcs[J].J.Appl.Phys.,1973,44:3074
[19]Langford J I,Wilson A J C.Scherrer after sixty years:a survey and some new results in the determination of crystallite size[J].J.Appl.Cryst.,1978,11:102
[20]Patterson A L.The Scherrer formula for X-ray particle size determination[J].Phys.Rev.,1939,56:978
[21]Peng Z J,Qi L H,Liu D P,et al.Study on the preparation of multicomponent superhard films with PVD method at low temperature[J].J.Mater.Sci.Eng.,2003,21:110(彭志坚,齐龙浩,刘大鹏等.低温PVD法制备多组分超硬薄膜研究[J].材料科学与工程学报,2003,21:110)
[22]Du H J,Tian Y J.Hardening mechanism for nano-multilayer films[J].J.Inorg.Mater.,2006,21:769(杜会静,田永君.超硬纳米多层膜致硬机理研究[J].无机材料学报,2006,21:769)
[23]Hall E O.The deformation and ageing of mild steel:III discussion of results[J].Proc.Phys.Soc.,1951,64B:747
[24]Petch N J.The cleavage strength of polycrystals[J].J.Iron Steel Inst.,1953,174:25
[25]Wiecinski P,Smolik J,Garbacz H,et al.Microstructure and properties of metal/ceramic and ceramic/ceramic multilayer coatings on titanium alloy Ti6Al4V[J].Surf.Coat.Technol.,2017,309:709
[26]Gong H F,Shao T M.Influence of toughness on tribological performance of TiN/Ti multilayer coatings[J].J.Mater.Eng.,2009,(10):26(龚海飞,邵天敏.TiN/Ti多层膜韧性对摩擦学性能的影响[J].材料工程,2009,(10):26)
[2]Zhang X,Zhou Y W,Gao J B,et al.Effect of the filament discharge current on the microstructure and performance of plasma-enhanced magnetron sputtered TiN coatings[J].J.Alloys Compd.,2017,725:877
[3]Kashkarov E B,Nikitenkov N N,Sutygina A N,et al.Hydrogenation behavior of Ti-implanted Zr-1Nb alloy with Ti N films deposited using filtered vacuum arc and magnetron sputtering[J].Appl.Surf.Sci.,2018,432:207
[4]Song Y Z,Gao Y,Dong Z X,et al.Effects of multi-arc ion plating process parameters on binding force of TiN film[J].Hot Working Technol.,2016,45(14):133(宋沂泽,高原,董中新等.多弧离子镀工艺参数对氮化钛薄膜结合力的影响研究[J].热加工工艺,2016,45(14):133)
[5]Wen L S,Huang R F,Guo L P,et al.Microstructure and mechanical properties of metal/ceramic Ti/TiN multilayers[J].J.Magn.Magn.Mater.,1993,126:200
[6]Cheng Y Y,Pang X L,Gao K W,et al.Corrosion resistance and friction of sintered NdFeB coated with Ti/TiN multilayers[J].Thin Solid Films,2014,550:428
[7]Koehler J S.Attempt to design a strong solid[J].Phys.Rev.,1970,2B:547
[8]Dück A,Gamer N,Gesatzke W,et al.Ti/TiN multilayer coatings:deposition technique,characterization and mechanical properties[J].Surf.Coat.Technol.,2001,142-144:579
[9]Ghasemi S,Shanaghi A,Chu P K.Nano mechanical and wear properties of multi-layer Ti/TiN coatings deposited on Al 7075 by highvacuum magnetron sputtering[J].Thin Solid Films,2017,638:96
[10]Krysina O V,Koval N N,Ivanov Y F,et al.Arc plasma-assisted deposition of nanocrystalline coatings[A].2012 25th International Symposium on Discharges and Electrical Insulation in Vacuum[C].Tomsk,Russia:IEEE,2012:537
[11]Lang W C.Design and performance of the double dislocation perforated shielding plate used in vacuum arc deposition for high quality coating deposition[J].Adv.Mater.Res.,2012,340:130
[12]Li F Q,Lin S S,Lin K S.Development and current status of decorative ion-plated hard films[J].Electroplat.Finish.,2016,35:817(李福球,林松盛,林凯生.离子镀硬质装饰膜的发展与现状[J].电镀与涂饰,2016,35:817)
[13]Zhao Y H,Lin G Q,Li X N,et al.Effect of pulsed bias on microhardness of Ti/TiN multilayer films deposited by arc ion plating[J].Acta Metall.Sin.,2015,41:1106(赵彦辉,林国强,李晓娜等.脉冲偏压对电弧离子镀Ti/TiN纳米多层薄膜显微硬度的影响[J].金属学报,2015,41:1106)
[14]Krella A K.Cavitation erosion resistance of Ti/TiN multilayer coatings[J].Surf.Coat.Technol.,2013,228:115
[15]Xiao N,Du F F,Yang B.Effects of modulation periods on structure and adhesion strength of TiN/Ti multilayer films[J].China Surf.Eng.,2015,28(2):65(肖娜,杜菲菲,杨波.调制周期对TiN/Ti多层膜组织结构和结合力的影响[J].中国表面工程,2015,28(2):65)
[16]Zhao Y H,Lin G Q,Xiao J Q,et al.Ti/TiN multilayer thin films deposited by pulse biased arc ion plating[J].Appl.Surf.Sci.,2011,257:2683
[17]Chun S Y,Chayahara A,Posselt M.Limitations on ultra-thin multilayers:pulsed cathodic arc and computer simulation[J].Surf.Coat.Technol.,2004,182:171
[18]Kimblin C W.Erosion and ionization in the cathode spot regions of vacuum arcs[J].J.Appl.Phys.,1973,44:3074
[19]Langford J I,Wilson A J C.Scherrer after sixty years:a survey and some new results in the determination of crystallite size[J].J.Appl.Cryst.,1978,11:102
[20]Patterson A L.The Scherrer formula for X-ray particle size determination[J].Phys.Rev.,1939,56:978
[21]Peng Z J,Qi L H,Liu D P,et al.Study on the preparation of multicomponent superhard films with PVD method at low temperature[J].J.Mater.Sci.Eng.,2003,21:110(彭志坚,齐龙浩,刘大鹏等.低温PVD法制备多组分超硬薄膜研究[J].材料科学与工程学报,2003,21:110)
[22]Du H J,Tian Y J.Hardening mechanism for nano-multilayer films[J].J.Inorg.Mater.,2006,21:769(杜会静,田永君.超硬纳米多层膜致硬机理研究[J].无机材料学报,2006,21:769)
[23]Hall E O.The deformation and ageing of mild steel:III discussion of results[J].Proc.Phys.Soc.,1951,64B:747
[24]Petch N J.The cleavage strength of polycrystals[J].J.Iron Steel Inst.,1953,174:25
[25]Wiecinski P,Smolik J,Garbacz H,et al.Microstructure and properties of metal/ceramic and ceramic/ceramic multilayer coatings on titanium alloy Ti6Al4V[J].Surf.Coat.Technol.,2017,309:709
[26]Gong H F,Shao T M.Influence of toughness on tribological performance of TiN/Ti multilayer coatings[J].J.Mater.Eng.,2009,(10):26(龚海飞,邵天敏.TiN/Ti多层膜韧性对摩擦学性能的影响[J].材料工程,2009,(10):26)
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |