电弧离子镀氮化钛、氮化铬薄膜制备及特性研究
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摘要
在过去的二十几年里,物理气相沉积(PVD)过渡族金属氮化物涂层的研究得到了迅速的发展,其中最早应用于金属表面的涂层是TiN,其次是CrN_x薄膜。由于它们具有高硬度,高耐磨,良好的抗腐蚀性能,较高的高温稳定性等优点,而被广泛用作工模具的保护涂层,材料的装饰涂层,微电子领域的扩散阻挡层以及生物领域等。
本文采用直流叠加脉冲偏压电弧离子镀技术在不锈钢和45钢基体上制备了TiN和CrN_x薄膜。对比分析了两种薄膜的基本特性,比如:显微硬度,表面粗糙度和膜基结合强度。对比研究了摩擦过程中摩擦参数(速度,载荷,摩擦副)对两种薄膜耐磨性等的影响,并对薄膜的摩擦磨损机理进行了分析。探讨了三种不同环境介质(干摩擦,水润滑,油润滑)条件下,两种薄膜的摩擦学特性及磨损机理。
研究结果表明:TiN薄膜的摩擦学特性受摩擦速度,载荷和摩擦副的影响均较大,而CrNx薄膜的摩擦学特性受速度和载荷的影响较大,受摩擦副的影响不明显。干摩擦条件下,TiN薄膜主要表现为磨粒磨损和氧化磨损;水润滑条件下,薄膜主要表现为疲劳磨损;油润滑条件下,薄膜几乎无磨损。水和油分别起到边界润滑和流体润滑作用,与薄膜无化学反应,仅物理吸附在薄膜表面。CrN_x薄膜在干摩擦条件下,主要表现为磨粒磨损;水润滑条件下,主要表现为腐蚀磨损;而油润滑条件下,油分子与摩擦表面相互作用,在表面形成保护膜或改性层,使薄膜表面几乎无磨损。相对于千摩擦条件下,水润滑和油润滑条件下TiN和CrN_x薄膜的摩擦系数和磨痕深度都降低。在相同的介质条件下,CrN_x薄膜的摩擦系数和磨痕深度始终小于TiN薄膜。因此,在一定的应用领域CrN_x薄膜很有潜力替代TiN薄膜。
Transition metal nitride cluster have developed rapidly in the last twenty decades. TiN film was the earliest horniess film,and the second one was CrN_x film.Due to their excellent properties,such as their high hardness,wear-resisting,chemical inertness with corrosive resistance and thermal stability.TiN films and CrN_x films have found several important applications in cutting tools,die mold,decoration,microelectronics, biotechnology field and so on.
For this study,TiN films and CrN_x films were prepared by Arc Ion Plating method on stainless steel and 45 steel substrates.Micro-hardness,surface roughness and adehesion strength of TiN films were compared with those of CrN_x films.Effect of parameter including velocity,load and Counterpart on tribological properties of TiN films and CrN_x films.The wear resistance of TiN films and CrN_x films were studied in different tribological conditions(in dry,water and oil lubricated) by the ball—disk wear tester.
The results showed that tribological properties of TiN films were effected obviously by the friction velocity,load and Counterpart.But the tribological properties of CrN_x films were little effected by courterpart.It was verified that TiN films present abrasive pxidized wear under dry friction,fatigue wear with water's boundery lubrication under water lubricating condition and almost no wear because of oil's fluidic lubricability under oil lubricating condition.Tribological mechanism of CrN_x films were abrasion in dry、corrosion in water and little wear in oil.both the grinding crack depth and friction coefficient of TiN films and CrN_x films clearly tend to decrease under water/oil lubricating conditions in comparison under dry friction.But CrN_x films possess much better wear ressistance than TiN films under all conditions.So CrN_x films is thus a potential candidate for replacing TiN in certain applications.
本文采用直流叠加脉冲偏压电弧离子镀技术在不锈钢和45钢基体上制备了TiN和CrN_x薄膜。对比分析了两种薄膜的基本特性,比如:显微硬度,表面粗糙度和膜基结合强度。对比研究了摩擦过程中摩擦参数(速度,载荷,摩擦副)对两种薄膜耐磨性等的影响,并对薄膜的摩擦磨损机理进行了分析。探讨了三种不同环境介质(干摩擦,水润滑,油润滑)条件下,两种薄膜的摩擦学特性及磨损机理。
研究结果表明:TiN薄膜的摩擦学特性受摩擦速度,载荷和摩擦副的影响均较大,而CrNx薄膜的摩擦学特性受速度和载荷的影响较大,受摩擦副的影响不明显。干摩擦条件下,TiN薄膜主要表现为磨粒磨损和氧化磨损;水润滑条件下,薄膜主要表现为疲劳磨损;油润滑条件下,薄膜几乎无磨损。水和油分别起到边界润滑和流体润滑作用,与薄膜无化学反应,仅物理吸附在薄膜表面。CrN_x薄膜在干摩擦条件下,主要表现为磨粒磨损;水润滑条件下,主要表现为腐蚀磨损;而油润滑条件下,油分子与摩擦表面相互作用,在表面形成保护膜或改性层,使薄膜表面几乎无磨损。相对于千摩擦条件下,水润滑和油润滑条件下TiN和CrN_x薄膜的摩擦系数和磨痕深度都降低。在相同的介质条件下,CrN_x薄膜的摩擦系数和磨痕深度始终小于TiN薄膜。因此,在一定的应用领域CrN_x薄膜很有潜力替代TiN薄膜。
Transition metal nitride cluster have developed rapidly in the last twenty decades. TiN film was the earliest horniess film,and the second one was CrN_x film.Due to their excellent properties,such as their high hardness,wear-resisting,chemical inertness with corrosive resistance and thermal stability.TiN films and CrN_x films have found several important applications in cutting tools,die mold,decoration,microelectronics, biotechnology field and so on.
For this study,TiN films and CrN_x films were prepared by Arc Ion Plating method on stainless steel and 45 steel substrates.Micro-hardness,surface roughness and adehesion strength of TiN films were compared with those of CrN_x films.Effect of parameter including velocity,load and Counterpart on tribological properties of TiN films and CrN_x films.The wear resistance of TiN films and CrN_x films were studied in different tribological conditions(in dry,water and oil lubricated) by the ball—disk wear tester.
The results showed that tribological properties of TiN films were effected obviously by the friction velocity,load and Counterpart.But the tribological properties of CrN_x films were little effected by courterpart.It was verified that TiN films present abrasive pxidized wear under dry friction,fatigue wear with water's boundery lubrication under water lubricating condition and almost no wear because of oil's fluidic lubricability under oil lubricating condition.Tribological mechanism of CrN_x films were abrasion in dry、corrosion in water and little wear in oil.both the grinding crack depth and friction coefficient of TiN films and CrN_x films clearly tend to decrease under water/oil lubricating conditions in comparison under dry friction.But CrN_x films possess much better wear ressistance than TiN films under all conditions.So CrN_x films is thus a potential candidate for replacing TiN in certain applications.
引文
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[2]Xu Junhua,Lihua Yu,Kojima I,et al.Thermal stress hardening of α-Si_3N_4/nc-TiN nanostructureed multilayers[J].Applied Physics Letters,2002,81(22):4139-4141.
[3]Junhua Xu,Effect deposition parameters on composition,structure,density and t opography of CrNx films deposited by r.f magenetron sputtering[J],Applied Su rface Science,2002(201):201-218.
[4]Fan B W.The Property of CrN Films[J].Thin Solid Films,2000(4):377-378.
[5]Cunha L,Andritschky M.Multi-arc Ion Planting[J].Thin Solid Films,1999(5):355-356.
[6]Gunter B,Christoph F,Erhard B.Preparation and Properties of CrN Coating[J].Surface and Coatings Technology,1996(2):84-87.
[7].Cunha,M.Andritschky,K.Pischow et al.Microstructure of CrN coatings produce by PVD techniques.Thin Solid Films,1999(355/356):465-471.
[8]韩增虎,戴维嘉.磁控溅射CrN_x薄膜的制备与力学性能.功能材料.2002,33(5):500-502.
[9]周庆刚,白新德.CrN/Cr镀膜改性的H13钢摩擦学性能.清华大学学报(自然科学版)2003,43(6):762-765.
[10]Saki Krishnamurthy,Ivar Reimanis.Multiple cracking in CrN and Cr_2N films on brass。Surface and Coatings Technology,2005,(192):291-298.
[11]Guntere B,Christoph F,Erhard B,et al.Delopoment of chromium nitride coatings substituting titanium nitride.Surface and coatings Technology.1996(86/87):184-191.
[12]刘晓红,陈志勇,邓山江.气相沉积技术的现状与发展,2006,16:26
[13]扬烈宇,关文锋,顾卓明。材料表面薄膜技术。北京:人民交通出版社,1991
[14]顾培夫.薄膜技术。浙江大学出版社。1990,61
[15]郑伟涛.薄膜材料与薄膜技术.北京:化学工业出版社.2004,12-13.
[16]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
[17]Martin P J,Bendavid A.Surf Coat Tech.2002(163/164):245-250.
[18]郑伟涛.薄膜材与薄膜技术.北京:化学工业出版社.2004:100-101.
[19]Sathrum P,Coll B F.Plasma and deposition enhancement by modified arc evaporation source[J].Surface and Coating Technology,1992(50):103-109
[20]Vetter J.Vacuum arc coating for tools:potential and application[J].surf Coat Technol,1995(76/77):719-724.
[21]CUNHA L,ANDR ITSCHKYM,PISCHOW K.et al Microstructure of CrN coatings produced by PVD techniques[J].Thin Solid Films.1999,(355/356):465-471.
[22]NAV NSEK B,PANIAN P,CVELBAR A.Characterization of low temperature CrN and TiN(PVD) hard coatings[J].Surface and Coatings Technology,1995,74(1-3,part1):155-161.
[23]HOY R,SLOOF W G,JANSSEN G C A M.Hard dence CrN_X coatings on three-dimensional objects[J].Surface and coating Technology,2004,179(2-3):215-222
[24]PDTO,GAUTIER C,MACHET J.Comparative study of CrN coatings deposited by ion plating and vacuum arc evaporation influence of the nature and the energy of the layer-forming species on the structure and mechanical properties[J].Surface and caotings Technology.1997,94-95(1-3):409-415
[25]GAUTIER C,MOUSSAOU I H,ELSINER F.Comparative study of mechanical and structure properties of CrN films deposited by d c magnetron sputtering and vacuum arc evaporation[J].Surfce and coatings technology.1996,86-87(1-3,part1):254-262
[26]NAV NSEKB,PANJAN P.Oxidation of CrN_x hard coatings reactively sputtered at low temperature[J].Thin Solid Films,1993,223(1):4-6
[27]SU Y L,YAO S H,WU C T.Comparisons of characterization and tribological performance of TiN and CrN deposited by cathodic arc plasma deposition pro cess[J],Wear,1996,199(1):132-141
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