高功率脉冲和脉冲直流磁控共溅射CrAlN薄膜的研究
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摘要
目的通过掺杂适量Al元素来固溶强化Cr N薄膜,从而提高薄膜的抗氧化性能和热稳定性。方法采用高功率脉冲磁控溅射和脉冲直流磁控溅射复合镀膜技术制备了Cr Al N薄膜,利用XRD、纳米压痕仪、应力仪、摩擦磨损试验机系统地研究了不同基体偏压对CrAlN涂层结构和力学性能的影响。结果所有CrAlN涂层均以fcc-(Cr,Al)N相为主,且随着基体偏压的增加,沿(111)晶面生长的衍射峰逐渐减弱,并向小角度偏移;薄膜压应力显著增加,最大值为-2.68GPa;薄膜硬度先上升后下降,在基体偏压为-30V时,硬度达到最大值22.3 GPa;H/E值和H~3/E~(*2)值随着基体偏压的增加,近似线性增大,当偏压为-120 V时,均达最大值0.11、0.21 GPa,同时摩擦系数和磨损率逐渐减小。结论当基体偏压为-120 V时,CrAlN薄膜具有最佳的耐磨性能,H/E和H~3/E~(*2)在一定程度上可评价涂层的耐磨性。
The work aims to strengthen CrN film through solid solution by doping appropriate amount of Al, so as to improve the oxidation resistance and thermal stability of the film. High power impulse magnetron sputtering and pulsed direct current magnetron sputtering were adopted to deposit Cr-Al-N films and the influence of different substrate biases on the structure and mechanical properties of the coating was studied by XRD, indentation tester, film stress tester and friction tests. All CrAlN coatings exhibited a face-centered cubic(Cr,Al)N solid solution phase. As the substrate bias increased, the diffraction peaks growing along the(111) plane gradually weakened and shifted toward a small angle; the compressive stress of the film increased remarkably; the hardness of the film rose first and then decreased, and the hardness reached a maximum value of 22.3 GPa when the substrate bias was -30 V. The H/E value and the H~3/E~(*2) value increased approximately linearly with the increase of the substrate bias voltage, and the maximum values were 0.11 and 0.21 at -120 V, respectively, and the friction coefficient and wear rate were gradually reduced. When the substrate bias is-120 V, the CrAlN film has the best wear resistance; H/E and H~3/E~(*2) can be used to evaluate the wear resistance of the coating.
The work aims to strengthen CrN film through solid solution by doping appropriate amount of Al, so as to improve the oxidation resistance and thermal stability of the film. High power impulse magnetron sputtering and pulsed direct current magnetron sputtering were adopted to deposit Cr-Al-N films and the influence of different substrate biases on the structure and mechanical properties of the coating was studied by XRD, indentation tester, film stress tester and friction tests. All CrAlN coatings exhibited a face-centered cubic(Cr,Al)N solid solution phase. As the substrate bias increased, the diffraction peaks growing along the(111) plane gradually weakened and shifted toward a small angle; the compressive stress of the film increased remarkably; the hardness of the film rose first and then decreased, and the hardness reached a maximum value of 22.3 GPa when the substrate bias was -30 V. The H/E value and the H~3/E~(*2) value increased approximately linearly with the increase of the substrate bias voltage, and the maximum values were 0.11 and 0.21 at -120 V, respectively, and the friction coefficient and wear rate were gradually reduced. When the substrate bias is-120 V, the CrAlN film has the best wear resistance; H/E and H~3/E~(*2) can be used to evaluate the wear resistance of the coating.
引文
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[24]SKORDARIS G,BOUZAKIS K D,KOTSANIS T,et al.Effect of PVD film's residual stresses on theirmechanical properties,brittleness,adhesion and cutting performance of coated tools[J].CIRP journal of manufacturing science and technology,2017,18:145-151.
[25]FANG X,JIN G,CUI X F,et al.Evolution characteristics of residual stress in metastable Ni-B alloy coatings identified by nanoindentation[J].Surface&coatings technology,2016,305:208-214.
[26]CHO I S,AMANOV A,KIM J D,et al.The effects of AlCrN coating,surface modification and their combination on the tribological properties of high speed steel under dry conditions[J].Tribology international,2015,81:61-72.
[27]HE C L,ZHANG J L,MA G F,et al.Influence of bias voltage on structure,mechanical and corrosion properties of reactively sputtered nanocrystalline TiN films[J]Journal of iron and steel research,international,2017,24(12):1223-1230.
[28]LAN Y P,SHI Y B,QI K J,et al.Fabrication and characterization of single-phase a-axis Al N ceramic films[J].Ceramics international,2018,44(7):8257-8262.
[29]WU Z L,LI Y G,WU B,et al.Effect of microstructure on mechanical and tribological properties of TiAlSiNnanocomposite coatings deposited by modulated pulsed power magnetron sputtering[J].Thin solid films,2015,597:197-205.
[30]BIROLA Y,ISLER D.Abrasive wear performance of AlCrN-coated hot work tool steel at elevated temperatures under three-body regime[J].Wear,2011,270(3/4):281-286.
[2]KOPF A,JOZEF K,TODT J,et al.Nanostructured coatings for tooling applications[J].International journal of refractory metals and hard materials,2017,62:219-224.
[3]ZHANG D B,ZHOU Z P,WANG H Y,et al.Structure and magnetic properties of Cr N thin films on La0.67Sr0.33Mn O3[J].Crrentapplied physics,2018,18(11):1320-1326.
[4]SHI P Z,WANG J,TIAN C X,et al.Structure and tribological properties deposited by circular combined tubular arc ion plating[J].Surface&coatings technology,2013,228:s534-s537.
[5]REN X R,ZHANG Q Y,HUANG Z,et al.Microstructure and tribological properties of crn films deposited by direct current magnetron sputtering[J].Rare metal materials and engineering,2018,47(8):2283-2289.
[6]齐东丽,宋健宇,沈龙海.基体温度对磁控溅射CrN涂层微观结构和性能的影响[J].热加工工艺,2018,47(8):158-161.QI Dong-li,SONG Jian-yu,SHEN Long-hai.Effect of substrate temperature on microstructure and properties of crn coating prepared by magnetron sputtering[J].Hot working technology,2018,47(8):158-161.
[7]梁进觉,陈诗敏,孔少于,等.关于CrN基涂层的研究进展[J].岭南师范学院学报,2017,38(6):44-50.LIANG Jin-jue,CHEN Shi-min,KONG Shao-yu,et al.The latest research about CrN base coating[J].Journal of Lingnan Normal University,2017,38(6):44-50.
[8]DA Y W,WU W.Deposition of CrN coatings by current-modulating cathodic arc evaporation[J].Surface&coatings technology,2001,137:31-37.
[9]余春燕,王社斌,尹小定,等.Cr AlN薄膜高温抗氧化性的研究[J].稀有金属材料与工程,2009,38(6):1015-1018.YU Chun-yan,WANG She-bin,YIN Xiao-ding,et al.Study on high-temperature oxidation resistance of CrAlNcoatings[J].Rare metal materials&engineering,2009,38(6):1015-1018.
[10]HOFMANN S,JEHN H A,HOFMANN S,et al.Oxidation behavior of CrNx and(Cr,Al)Nx hard coatings[J].Materials&corrosion,2015,41(12):756-760.
[11]WILLMANN H,MAYRHOFER P H,PERSSON P O?,et al.Thermal stability of Al-Cr-N hard coatings[J].Scriptamaterialia,2006,54:1847-1851.
[12]HOFMANN S,JEHN H A.Oxidation behavior of Cr Nand(Cr,Al)N hard coatings[J].Werkstoffekorros,1990,41(12):756-763.
[13]LIN J,MISHRA B,Moore J J,et al.A study of the oxidation behavior of CrN and CrAlN thin films in air using DSC and TGA analyses[J].Surface&coatings technology,2008,202:3272-3283.
[14]GENG D S,LI H X,ZHANG Q,et al.Effect of incorporating oxygen on microstructure and mechanical properties of AlCrSiON coatings deposited by arc ion plating[J].Surface and coatings technology,2017,310:223-230.
[15]BOBZIN K,BAGCIVAN N,IMMICH P,et al.Advantages of nanocomposite coatings deposited by high power pulse magnetron sputtering technology[J].Journal of materials processing technology,2009,209:165-170.
[16]FAGA M G,GIOVANNA G,FEDERICO C,et al.AlSiTiN and AlSiCrN multilayer coatings:Effects of structure and surface composition on tribological behavior under dry and lubricated conditions[J].Applied surface science,2016,365:218-226.
[17]SUN S Q,YE Y W,WANG Y X,et al.Structure and tribological performances of CrAlSiN coatings with different Si percentages in seawater[J].Tribology international,2017,115:591-599.
[18]CHEN M H,CHEN W L,CAI F,et al.Structural evolution and electrochemical behaviors of multilayer Al-Cr-Si-Ncoatings[J].Surface&coatings technology,2016,296:33-39.
[19]CHEN X,XI Y T,MENG J,et al.Effects of substrate bias voltage on mechanical properties and tribological behaviors of RF sputtered multilayer TiN/CrAlN films[J].Journal of alloys and compounds,2016,665:210-217.
[20]GONG M F,CHEN J,DENG X,et al.Sliding wear behavior of TiAlN and AlCrN coatings on a unique cemented carbide substrate[J].International journal of refractory metals and hard materials,2017,69:209-214.
[21]耿东森,吴正涛,聂志伟,等.基体偏压对电弧离子镀Al Cr Si ON涂层结构和热稳定性的影响[J].中国表面工程,2016,12(6):60-66.GENG Dong-sen,WU Zheng-tao,NIE Zhi-wei,et al.Influence of Substrate bias on microstructure and thermal stability of AlCrSiON coatings deposited by arc ion plating[J].China surface egineering,2016,12(6):60-66.
[22]GUO J,WANG H Y,MENG F P,et al.The H/E*ratio and E*of AlN coatings by copper addition[J].Surface&coatings technology,2013,228:68-75.
[23]XI Y T,GAO K W,PANG X L,et al.Film thickness effect on texture and residual stress sign transition insputtered TiN thin films[J].Ceramics international,2017,43(15):11992-11997.
[24]SKORDARIS G,BOUZAKIS K D,KOTSANIS T,et al.Effect of PVD film's residual stresses on theirmechanical properties,brittleness,adhesion and cutting performance of coated tools[J].CIRP journal of manufacturing science and technology,2017,18:145-151.
[25]FANG X,JIN G,CUI X F,et al.Evolution characteristics of residual stress in metastable Ni-B alloy coatings identified by nanoindentation[J].Surface&coatings technology,2016,305:208-214.
[26]CHO I S,AMANOV A,KIM J D,et al.The effects of AlCrN coating,surface modification and their combination on the tribological properties of high speed steel under dry conditions[J].Tribology international,2015,81:61-72.
[27]HE C L,ZHANG J L,MA G F,et al.Influence of bias voltage on structure,mechanical and corrosion properties of reactively sputtered nanocrystalline TiN films[J]Journal of iron and steel research,international,2017,24(12):1223-1230.
[28]LAN Y P,SHI Y B,QI K J,et al.Fabrication and characterization of single-phase a-axis Al N ceramic films[J].Ceramics international,2018,44(7):8257-8262.
[29]WU Z L,LI Y G,WU B,et al.Effect of microstructure on mechanical and tribological properties of TiAlSiNnanocomposite coatings deposited by modulated pulsed power magnetron sputtering[J].Thin solid films,2015,597:197-205.
[30]BIROLA Y,ISLER D.Abrasive wear performance of AlCrN-coated hot work tool steel at elevated temperatures under three-body regime[J].Wear,2011,270(3/4):281-286.