溅射沉积WS_x/Ni/a-C/Ni多层膜的微结构及大气环境摩擦学性能
|
摘要
采用磁控溅射技术在硅基体上交替沉积WS2、Ni及非晶碳(a-C)层制备出不同Ni层厚度的WSx/Ni/a-C/Ni多层膜.利用扫描电子显微镜、X射线衍射仪、拉曼光谱仪、X射线光电子能谱仪等研究了多层膜的成分及微观结构;通过纳米压痕仪、划痕仪和球盘式摩擦磨损试验机等评价了薄膜的力学及大气环境中的摩擦学性能.结果表明:随着Ni层厚度的增加,WSx/Ni/a-C/Ni多层膜的致密度下降,ns/nw值(S与W原子百分数之比)由0.84降至0.73,WSx层以微晶或非晶的形式存在.多层膜的硬度和磨损率均随Ni层厚度的增加先降低后升高,但摩擦系数由0.22升至0.38,结合力先增大后减小. Ni层厚度为6 nm的多层膜的硬度可达13.4 GPa,抗氧化性能和耐磨性最优,磨损率仅为9.47×10–14 m3/(Nm).
WS_x/Ni/a-C/Ni multilayer films with different Ni layer thicknesses were successfully prepared by alternate depositing WS2, Ni and amorphous carbon(a-C) layer on silicon substrate with magnetron sputtering technique. The composition and microstructure of the films were investigated by using scanning electron microscopy, X-ray diffractometry, Raman spectroscopy and X-ray photoelectron spectroscopy. The mechanical and tribological properties of the films in air were evaluated by using nano-indentation tester, scratch tester and ball-on-disc tribotester. The results show that the density of WSx/Ni/a-C/Ni multilayer films decreased and the value of ns/nw(the atomic fraction ratio of S to W) dropped from 0.84 to 0.73 as increasing the Ni layer thickness, the WS2 layer was microcrystalline or amorphous.With the increase of Ni layer thickness, the hardness and wear rate of the multilayer film decreased first and then increased, but the friction coefficient increased from 0.22 to 0.38, the adhesion increased first and then decreased. The multilayer film with Ni layer thickness of 6 nm exhibited the hardness of 13.4 GPa, the excellent antioxidant properties and the best wear resistance,wear rate is 9.47×10–14 m3/(Nm).
WS_x/Ni/a-C/Ni multilayer films with different Ni layer thicknesses were successfully prepared by alternate depositing WS2, Ni and amorphous carbon(a-C) layer on silicon substrate with magnetron sputtering technique. The composition and microstructure of the films were investigated by using scanning electron microscopy, X-ray diffractometry, Raman spectroscopy and X-ray photoelectron spectroscopy. The mechanical and tribological properties of the films in air were evaluated by using nano-indentation tester, scratch tester and ball-on-disc tribotester. The results show that the density of WSx/Ni/a-C/Ni multilayer films decreased and the value of ns/nw(the atomic fraction ratio of S to W) dropped from 0.84 to 0.73 as increasing the Ni layer thickness, the WS2 layer was microcrystalline or amorphous.With the increase of Ni layer thickness, the hardness and wear rate of the multilayer film decreased first and then increased, but the friction coefficient increased from 0.22 to 0.38, the adhesion increased first and then decreased. The multilayer film with Ni layer thickness of 6 nm exhibited the hardness of 13.4 GPa, the excellent antioxidant properties and the best wear resistance,wear rate is 9.47×10–14 m3/(Nm).
引文
[1]Zhu L N,Wang C B,Wang H D,et al.Tribological properties of WS2 composite film prepared by a two-step method[J].Vacuum,2010,85(1):16-21.doi:10.1016/j.vacuum.2010.03.003.
[2]Pimentel J V,Danek M,Polcar T,et al.Effect of rough surface patterning on the tribology of W-S-C-Cr self-lubricant coatings[J].Tribology International,2014,69:77-83.doi:10.1016/j.triboint.2013.09.004.
[3]Zheng X H,Tu J P,Lai D M,et al.Microstructure and tribological behavior of WS2-Ag composite films deposited by RF magnetron sputtering[J].Thin Solid Films,2008,516(16):5404-5408.doi:10.1016/j.tsf.2007.07.102.
[4]Banerjee T,Chattopadhyay A K.Structural,mechanical and tribological properties of WS2-Ti composite coating with and without hard under layer of TiN[J].Surface and Coatings Technology,2014,258:849-860.doi:10.1016/j.surfcoat.2014.07.072.
[5]Xu S,Gao X,Ming H,et al.Microstructure evolution and enhanced tribological properties of Cu-doped WS2 films[J].Tribology Letters,2014,55(1):1-13.doi:10.1007/s11249-014-0322-3.
[6]Nossa A,Cavaleiro A.The influence of the addition of C and N on the wear behaviour of W-S-C/N coatings[J].Surface and Coatings Technology,2001,142:984-991.
[7]Yin Guilin,Huang Pinghua,Yu Zhen,et al.Microstructure and tribological properties of co-sputtered MoS2/WS2 composite films[J].Tribology,2007,27(1):41-44(in Chinese)[尹桂林,黄平华,余震,等.MoS2/WS2共溅射复合薄膜的微结构及其摩擦磨损性能研究[J].摩擦学学报,2007,27(1):41-44].doi:10.3321/j.issn:1004-0595.2007.01.009.
[8]Matthews A,Eskildsen S S.Engineering applications for diamondlike carbon[J].Diamond and Related Materials,1994,3(4):902-911.
[9]Yang Fanger,Lu Ye,Li Ang,et al.Effects of modulation ratio on microstructure and tribological properties of WSx/a-C multilayer films[J].Tribology,2017,37(3):387-394(in Chinese)[杨芳儿,鲁叶,李昂,等.调制比对WSx/a-C多层膜微观组织及摩擦学性能的影响[J].摩擦学学报,2017,37(3):387-394].doi:10.16078/j.tribology.2017.03.015.
[10]Zheng Xiaohua,Zhang Rong,Shi Yulong,et al.Microstructure and tribological properties of WSx/a-C multilayered films with various layer thickness ratio[J].Journal of Vacuum Science and Technology,2016,36(6):659-665(in Chinese)[郑晓华,章荣,史玉龙,等.不同层厚比WSx/a-C多层膜的组织结构与摩擦学特性[J].真空科学与技术学报,2016,36(6):659-665].
[11]Yang F E,Lu Y,Zhang R,et al.Microstructure and tribological properties of WSx/a-C multilayer films with various layer thickness ratios in different environments[J].Surface and Coatings Technology,2017,309:187-194.doi:10.1016/j.surfcoat.2016.11.071.
[12]Wang D Y,Chang C L,Ho W Y.Microstructure analysis of MoS2deposited on diamond-like carbon films for wear improvement[J].Surface and Coatings Technology,1999,111(2):123-127.
[13]Wu Y,Li H,Ji L,et al.A long-lifetime MoS2/a-C:H nanoscale multilayer film with extremely low internal stress[J].Surface and Coatings Technology,2013,236:438-443.doi:10.1016/j.surfcoat.2013.10.021.
[14]He Tengfei,Wu Youzhi,Xu Jiao,et al.Structure and tribological properties of MoS2/DLC multilayer films with different modulation periods[J].Tribology,2017,37(1):35-43(in Chinese)[贺腾飞,吴有智,许佼,等.不同调制周期MoS2/DLC多层薄膜结构及摩擦学性能[J].摩擦学学报,2017,37(1):35-43].doi:10.16078/j.tribology.2017.01.005.
[15]Xu S S,Gao X M,Hu M,et al.Nanostructured WS2-Ni composite films for improved oxidation,resistance and tribological performance[J].Applied Surface Science,2014,288(2):15-25.
[16]Du Guangyu,Ba Dechun,Wang Xiaoguang.Effects of Ti/Ni transition layers on frictional behavior of tungsten disulfide thin film[J].Tribology,2009,29(2):146-151(in Chinese)[杜广煜,巴德纯,王晓光.Ti/Ni过渡层对WS2薄膜摩擦学性能影响[J].摩擦学学报,2009,29(2):146-151].doi:10.3321/j.issn:1004-0595.2009.02.009.
[17]Hilton M R,Reinhold B,Stephen V D,et al.Structural and tribological studies of MoS2 solid lubricant films having tailored metal-multilayer nanostructures[J].Surface and Coatings Technology,1992,53:13-23.doi:10.1016/0257-8972(92)90099-V.
[18]Lince J R,Hilton M R,Bommannavar A S.Metal incorporation in sputter-deposited MoS2 films studied by extended X-ray absorption fine structure[J].Journal of Materials Research,1995,10(8):2091-2105.doi:10.1557/JMR.1995.2091.
[19]Mikhailov S,Savan A,Pflüger E,et al.Morphology and tribologicalproperties of metal(oxide)-MoS2 nanostructured multilayer coatings[J].Surface and Coatings Technology,1998,105:175-183.doi:10.1016/S0257-8972(98)00483-6.
[20]Feng Kai,Li Zhuguo,Zhang Chao.Corrosion and wear resistance of sputtered carbon film coated magnesium alloy with electroless plating nickel interlayer[J].Surface Technology,2017,46(3):28-33(in Chinese)[冯凯,李铸国,张超.镁合金表面Ni+C涂层的耐腐蚀与耐磨性能研究[J].表面技术,2017,46(3):28-33].
[21]Chung J W,Ohuchi F S.Deposition of AlN on WS2(0001)substrate by atomic layer growth process[J].Materials Research Society,1997,449:379-384.
[22]Liu X D,Zhang H Y,Lu K,et al.The lattice expansion in nanometre-sized Ni polycrystals[J].Journal of Physics Condensed Matter,1994,6:L497-L502.doi:10.1088/0953-8984/6/34/001.
[23]Hu X,Yasaei P,Jokisaari J,et al.Mapping thermal expansion coefficients in freestanding 2D materials at the nanometer scale[J].Physical Review Letters,2018,120:055902-055908.doi:10.1103/PhysRevLett.120.055902.
[24]Nix F C,Macnair D.The thermal expansion of pure metals:copper,gold,aluminum,nickel,and iron[J].Physical Review,1941,60:597-605.doi:10.1103/PhysRev.60.597.
[25]Cao H,Hosson J T M D,Pei Y T.Effect of carbon concentration and argon flow rate on the microstructure and triboperformance of magnetron sputtered WS2/a-C coatings[J].Surface and Coatings Technology,2017,332:141-152.
[26]S?rhammar E,Strandberg E,Sundberg J,et al.Mechanisms for compositional variations of coatings sputtered from a WS2 target[J].Surface and Coatings Technology,2014,252(9):186-190.
[27]Liu Jingjing,Li Wei,Meng Jia,et al.Study on microstructure and mechanical properties of CrAlN/WS2 nanomultilayered films[J].Journal of Functional Materials,2016,47(12):12118-12123(in Chinese)[刘京京,李伟,孟佳,等.CrAlN/WS2纳米多层膜的微观结构和力学性能研究[J].功能材料,2 0 1 6,4 7(1 2):12118-12123].
[28]Lao Jijun,Han Zenghu,Tian Jiawan,et al.Microstrcture and mechanical properties of PVD nickel thin film[C].China National Conference on Funtional Materials and Applications,Xiamen,2001,(10):1553-1572(in Chinese)[[劳技军,韩增虎,田家万,等.气相沉积Ni薄膜的微结构和力学性能[C].中国功能材料及其应用学术会议,厦门,2001,(10):1553-1572].].
[29]Goto Y,Taniguchi K,Omata T,et al.Formation of Ni3Cnanocrystals by thermolysis of nickel acetylacetonate in oleylamine:characterization using hard X-ray photoelectron spectroscopy[J].Chemistry of Materials,2008,20(12):4156-4160.doi:10.1021/cm703644x.
[30]Du D,Liu D,Ye Z,et al.Fretting wear and fretting fatigue behaviors of diamond-like carbon and graphite-like carbon films deposited on Ti-6Al-4V alloy[J].Applied Surface Science,2014,313(9):462-469.
[31]Xu S,Gao X,Sun J,et al.Comparative study of moisture corrosion to WS2 and WS2/Cu multilayer films[J].Surface and Coatings Technology,2014,247:30-38.doi:10.1016/j.surfcoat.2014.03.001.
[32]Turgut E,?mer?oban,Sar?ta?S,et al.Oxygen partial pressure effects on the RF sputtered p-type NiO hydrogen gas sensors[J].Applied Surface Science,2018,435:880-885.doi:10.1016/j.apsusc.2017.11.133.
[33]Mahata N,Cunha A F,órf?o J J M,et al.Highly selective hydrogenation of C=C double bond in unsaturated carbonyl compounds over NiC catalyst[J].Chemical Engineering Journal,2012,188:155-159.doi:10.1016/j.cej.2012.01.127.
[34]Sekine T,Nakashizu T,Toyoda K,et al.Raman scattering in layered compound 2H-WS2[J].Solid State Communications,1980,35(4):371-373.doi:10.1016/0038-1098(80)90518-9.
[35]Hong C F,Wang J Z,Yan W,et al.The Microstructure and tribological behavior of Ti/a-C and Ti/a-C:H films prepared by magnetron sputtering[J].Applied Mechanics and Materials,2013,420:123-128.doi:10.4028/www.scientific.net/AMM.420.
[36]Yang Fanger,Chang Xinxin,Lin Lingling,et al.Effects of single layer thickness of CNx on microstructure and mechanical properties of DLC/CNx multilayer films[J].China Surface Engineering,2018,31(2):66-74(in Chinese)[杨芳儿,常新新,林玲玲,等.CNx层厚度对DLC/CNx多层膜结构和力学性能的影响[J].中国表面工程,2018,31(2):66-74].
[37]Lackner J,Major L,Kot M.Microscale interpretation of tribological phenomena in Ti/TiN soft-hard multilayer coatings on soft austenite steel substrates[J].Bulletin of the Polish Academy of Sciences Technical Sciences,2011,59(3):343-355.doi:10.2478/v10175-011-0042-x.
[2]Pimentel J V,Danek M,Polcar T,et al.Effect of rough surface patterning on the tribology of W-S-C-Cr self-lubricant coatings[J].Tribology International,2014,69:77-83.doi:10.1016/j.triboint.2013.09.004.
[3]Zheng X H,Tu J P,Lai D M,et al.Microstructure and tribological behavior of WS2-Ag composite films deposited by RF magnetron sputtering[J].Thin Solid Films,2008,516(16):5404-5408.doi:10.1016/j.tsf.2007.07.102.
[4]Banerjee T,Chattopadhyay A K.Structural,mechanical and tribological properties of WS2-Ti composite coating with and without hard under layer of TiN[J].Surface and Coatings Technology,2014,258:849-860.doi:10.1016/j.surfcoat.2014.07.072.
[5]Xu S,Gao X,Ming H,et al.Microstructure evolution and enhanced tribological properties of Cu-doped WS2 films[J].Tribology Letters,2014,55(1):1-13.doi:10.1007/s11249-014-0322-3.
[6]Nossa A,Cavaleiro A.The influence of the addition of C and N on the wear behaviour of W-S-C/N coatings[J].Surface and Coatings Technology,2001,142:984-991.
[7]Yin Guilin,Huang Pinghua,Yu Zhen,et al.Microstructure and tribological properties of co-sputtered MoS2/WS2 composite films[J].Tribology,2007,27(1):41-44(in Chinese)[尹桂林,黄平华,余震,等.MoS2/WS2共溅射复合薄膜的微结构及其摩擦磨损性能研究[J].摩擦学学报,2007,27(1):41-44].doi:10.3321/j.issn:1004-0595.2007.01.009.
[8]Matthews A,Eskildsen S S.Engineering applications for diamondlike carbon[J].Diamond and Related Materials,1994,3(4):902-911.
[9]Yang Fanger,Lu Ye,Li Ang,et al.Effects of modulation ratio on microstructure and tribological properties of WSx/a-C multilayer films[J].Tribology,2017,37(3):387-394(in Chinese)[杨芳儿,鲁叶,李昂,等.调制比对WSx/a-C多层膜微观组织及摩擦学性能的影响[J].摩擦学学报,2017,37(3):387-394].doi:10.16078/j.tribology.2017.03.015.
[10]Zheng Xiaohua,Zhang Rong,Shi Yulong,et al.Microstructure and tribological properties of WSx/a-C multilayered films with various layer thickness ratio[J].Journal of Vacuum Science and Technology,2016,36(6):659-665(in Chinese)[郑晓华,章荣,史玉龙,等.不同层厚比WSx/a-C多层膜的组织结构与摩擦学特性[J].真空科学与技术学报,2016,36(6):659-665].
[11]Yang F E,Lu Y,Zhang R,et al.Microstructure and tribological properties of WSx/a-C multilayer films with various layer thickness ratios in different environments[J].Surface and Coatings Technology,2017,309:187-194.doi:10.1016/j.surfcoat.2016.11.071.
[12]Wang D Y,Chang C L,Ho W Y.Microstructure analysis of MoS2deposited on diamond-like carbon films for wear improvement[J].Surface and Coatings Technology,1999,111(2):123-127.
[13]Wu Y,Li H,Ji L,et al.A long-lifetime MoS2/a-C:H nanoscale multilayer film with extremely low internal stress[J].Surface and Coatings Technology,2013,236:438-443.doi:10.1016/j.surfcoat.2013.10.021.
[14]He Tengfei,Wu Youzhi,Xu Jiao,et al.Structure and tribological properties of MoS2/DLC multilayer films with different modulation periods[J].Tribology,2017,37(1):35-43(in Chinese)[贺腾飞,吴有智,许佼,等.不同调制周期MoS2/DLC多层薄膜结构及摩擦学性能[J].摩擦学学报,2017,37(1):35-43].doi:10.16078/j.tribology.2017.01.005.
[15]Xu S S,Gao X M,Hu M,et al.Nanostructured WS2-Ni composite films for improved oxidation,resistance and tribological performance[J].Applied Surface Science,2014,288(2):15-25.
[16]Du Guangyu,Ba Dechun,Wang Xiaoguang.Effects of Ti/Ni transition layers on frictional behavior of tungsten disulfide thin film[J].Tribology,2009,29(2):146-151(in Chinese)[杜广煜,巴德纯,王晓光.Ti/Ni过渡层对WS2薄膜摩擦学性能影响[J].摩擦学学报,2009,29(2):146-151].doi:10.3321/j.issn:1004-0595.2009.02.009.
[17]Hilton M R,Reinhold B,Stephen V D,et al.Structural and tribological studies of MoS2 solid lubricant films having tailored metal-multilayer nanostructures[J].Surface and Coatings Technology,1992,53:13-23.doi:10.1016/0257-8972(92)90099-V.
[18]Lince J R,Hilton M R,Bommannavar A S.Metal incorporation in sputter-deposited MoS2 films studied by extended X-ray absorption fine structure[J].Journal of Materials Research,1995,10(8):2091-2105.doi:10.1557/JMR.1995.2091.
[19]Mikhailov S,Savan A,Pflüger E,et al.Morphology and tribologicalproperties of metal(oxide)-MoS2 nanostructured multilayer coatings[J].Surface and Coatings Technology,1998,105:175-183.doi:10.1016/S0257-8972(98)00483-6.
[20]Feng Kai,Li Zhuguo,Zhang Chao.Corrosion and wear resistance of sputtered carbon film coated magnesium alloy with electroless plating nickel interlayer[J].Surface Technology,2017,46(3):28-33(in Chinese)[冯凯,李铸国,张超.镁合金表面Ni+C涂层的耐腐蚀与耐磨性能研究[J].表面技术,2017,46(3):28-33].
[21]Chung J W,Ohuchi F S.Deposition of AlN on WS2(0001)substrate by atomic layer growth process[J].Materials Research Society,1997,449:379-384.
[22]Liu X D,Zhang H Y,Lu K,et al.The lattice expansion in nanometre-sized Ni polycrystals[J].Journal of Physics Condensed Matter,1994,6:L497-L502.doi:10.1088/0953-8984/6/34/001.
[23]Hu X,Yasaei P,Jokisaari J,et al.Mapping thermal expansion coefficients in freestanding 2D materials at the nanometer scale[J].Physical Review Letters,2018,120:055902-055908.doi:10.1103/PhysRevLett.120.055902.
[24]Nix F C,Macnair D.The thermal expansion of pure metals:copper,gold,aluminum,nickel,and iron[J].Physical Review,1941,60:597-605.doi:10.1103/PhysRev.60.597.
[25]Cao H,Hosson J T M D,Pei Y T.Effect of carbon concentration and argon flow rate on the microstructure and triboperformance of magnetron sputtered WS2/a-C coatings[J].Surface and Coatings Technology,2017,332:141-152.
[26]S?rhammar E,Strandberg E,Sundberg J,et al.Mechanisms for compositional variations of coatings sputtered from a WS2 target[J].Surface and Coatings Technology,2014,252(9):186-190.
[27]Liu Jingjing,Li Wei,Meng Jia,et al.Study on microstructure and mechanical properties of CrAlN/WS2 nanomultilayered films[J].Journal of Functional Materials,2016,47(12):12118-12123(in Chinese)[刘京京,李伟,孟佳,等.CrAlN/WS2纳米多层膜的微观结构和力学性能研究[J].功能材料,2 0 1 6,4 7(1 2):12118-12123].
[28]Lao Jijun,Han Zenghu,Tian Jiawan,et al.Microstrcture and mechanical properties of PVD nickel thin film[C].China National Conference on Funtional Materials and Applications,Xiamen,2001,(10):1553-1572(in Chinese)[[劳技军,韩增虎,田家万,等.气相沉积Ni薄膜的微结构和力学性能[C].中国功能材料及其应用学术会议,厦门,2001,(10):1553-1572].].
[29]Goto Y,Taniguchi K,Omata T,et al.Formation of Ni3Cnanocrystals by thermolysis of nickel acetylacetonate in oleylamine:characterization using hard X-ray photoelectron spectroscopy[J].Chemistry of Materials,2008,20(12):4156-4160.doi:10.1021/cm703644x.
[30]Du D,Liu D,Ye Z,et al.Fretting wear and fretting fatigue behaviors of diamond-like carbon and graphite-like carbon films deposited on Ti-6Al-4V alloy[J].Applied Surface Science,2014,313(9):462-469.
[31]Xu S,Gao X,Sun J,et al.Comparative study of moisture corrosion to WS2 and WS2/Cu multilayer films[J].Surface and Coatings Technology,2014,247:30-38.doi:10.1016/j.surfcoat.2014.03.001.
[32]Turgut E,?mer?oban,Sar?ta?S,et al.Oxygen partial pressure effects on the RF sputtered p-type NiO hydrogen gas sensors[J].Applied Surface Science,2018,435:880-885.doi:10.1016/j.apsusc.2017.11.133.
[33]Mahata N,Cunha A F,órf?o J J M,et al.Highly selective hydrogenation of C=C double bond in unsaturated carbonyl compounds over NiC catalyst[J].Chemical Engineering Journal,2012,188:155-159.doi:10.1016/j.cej.2012.01.127.
[34]Sekine T,Nakashizu T,Toyoda K,et al.Raman scattering in layered compound 2H-WS2[J].Solid State Communications,1980,35(4):371-373.doi:10.1016/0038-1098(80)90518-9.
[35]Hong C F,Wang J Z,Yan W,et al.The Microstructure and tribological behavior of Ti/a-C and Ti/a-C:H films prepared by magnetron sputtering[J].Applied Mechanics and Materials,2013,420:123-128.doi:10.4028/www.scientific.net/AMM.420.
[36]Yang Fanger,Chang Xinxin,Lin Lingling,et al.Effects of single layer thickness of CNx on microstructure and mechanical properties of DLC/CNx multilayer films[J].China Surface Engineering,2018,31(2):66-74(in Chinese)[杨芳儿,常新新,林玲玲,等.CNx层厚度对DLC/CNx多层膜结构和力学性能的影响[J].中国表面工程,2018,31(2):66-74].
[37]Lackner J,Major L,Kot M.Microscale interpretation of tribological phenomena in Ti/TiN soft-hard multilayer coatings on soft austenite steel substrates[J].Bulletin of the Polish Academy of Sciences Technical Sciences,2011,59(3):343-355.doi:10.2478/v10175-011-0042-x.