AlCrN/VN多层涂层力学性能及其热稳定性
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摘要
目的制备高硬度自润滑AlCrN/VN纳米多层复合涂层,提升刀具耐磨性,增加刀具寿命。方法采用多弧离子镀技术在单晶硅(100)、不锈钢以及硬质合金基底上沉积不同调制周期的Al Cr N/VN纳米多层涂层,系统研究涂层力学性能、滑动摩擦性能及高温稳定性。涂层制备采用Al_(70)Cr_(30)合金和单质V靶材,EDS结果显示涂层Al/Cr比例接近靶材成分,V元素原子比约为30%。利用扫描电镜(SEM)、原子力显微镜(AFM)以及X射线衍射技术(XRD)表征涂层显微结构,采用显微硬度仪以及滑动摩擦试验研究涂层硬度以及摩擦性能随调制周期的变化。最后对调制周期为24nm的涂层进行氧化实验,并测试其硬度与摩擦系数。结果沉积涂层厚度以及相组成几乎不受调制周期的影响。沉积涂层硬度与调制周期紧密关联,摩擦系数随着调制周期的减小而逐渐降低。当调制周期为24 nm时,涂层获得最大硬度,为3970HV_(0.05),此时涂层表面最为光滑(Ra=33.6 nm)。对调制周期为24 nm的多层涂层进行不同温度下空气氧化并测定其硬度与摩擦系数,结果表明硬度随着氧化温度升高到400、500、700℃而下降至1474、1248、370HV_(0.05),摩擦系数随之大幅度升高。结论 VN涂层的加入使得AlCrN涂层硬度降低,摩擦系数降低,且其硬度以及摩擦系数受到调制周期的显著影响,涂层经400℃氧化后,硬度值大幅度降低,热稳定性不好。
The preparation of AlCrN/VN nano-multilayered coating with high hardness and self-lubricating properties aims to prolong the service life by improving the wear properties of cutting tools. AlCrN/VN nano multi-layer coatings with different bilayer thickness(deposited with different rpm) were deposited onto Si(100), stainless steel and cemented carbide substrates by cathodic arc ion-plating with Al_(70)Cr_(30) and V targets to study the mechanical properties, sliding friction and high thermal stability. The Al:Cr atomic ratios of AlCrN coatings measured by EDS were closed to the ratio of Al_(70)Cr_(30) target composition and V was about 30 at%. The microstructure of coatings was characterized by SEM, AFM, and XRD. The variation of hardness and friction properties along with the bilayer period was studied by micro-hardness test and sliding test. The oxidation test was carried out in samples with a bilayer thickness of 24 nm to investigate the hardness and friction coefficient. The compositions,thickness and phase structure were hardly affected by the bilayer thickness. The hardness was depended on the bilayer thickness and the friction coefficient decreased with increasing bilayer thickness. The maximum hardness 3970 HV_(0.05) was obtained when bilayer thickness was 24 nm. Meanwhile, the coating also showed the smoothest surface with roughness of 33.6 nm. After oxidation, the hardness of coating with a bilayer thickness of 24 nm decreased from 1474 to 1248, 370 HV_(0.05) as the temperature increased from 400 to 500, 700 ℃ and friction coefficient increased greatly. The addition of VN coating can reduce the hardness and friction coefficient of AlCrN coating which are affected obviously by the bilayer period. After oxidation at 400 ℃, the hardness of coating decreases dramatically, indicating the poor thermal stability.
The preparation of AlCrN/VN nano-multilayered coating with high hardness and self-lubricating properties aims to prolong the service life by improving the wear properties of cutting tools. AlCrN/VN nano multi-layer coatings with different bilayer thickness(deposited with different rpm) were deposited onto Si(100), stainless steel and cemented carbide substrates by cathodic arc ion-plating with Al_(70)Cr_(30) and V targets to study the mechanical properties, sliding friction and high thermal stability. The Al:Cr atomic ratios of AlCrN coatings measured by EDS were closed to the ratio of Al_(70)Cr_(30) target composition and V was about 30 at%. The microstructure of coatings was characterized by SEM, AFM, and XRD. The variation of hardness and friction properties along with the bilayer period was studied by micro-hardness test and sliding test. The oxidation test was carried out in samples with a bilayer thickness of 24 nm to investigate the hardness and friction coefficient. The compositions,thickness and phase structure were hardly affected by the bilayer thickness. The hardness was depended on the bilayer thickness and the friction coefficient decreased with increasing bilayer thickness. The maximum hardness 3970 HV_(0.05) was obtained when bilayer thickness was 24 nm. Meanwhile, the coating also showed the smoothest surface with roughness of 33.6 nm. After oxidation, the hardness of coating with a bilayer thickness of 24 nm decreased from 1474 to 1248, 370 HV_(0.05) as the temperature increased from 400 to 500, 700 ℃ and friction coefficient increased greatly. The addition of VN coating can reduce the hardness and friction coefficient of AlCrN coating which are affected obviously by the bilayer period. After oxidation at 400 ℃, the hardness of coating decreases dramatically, indicating the poor thermal stability.
引文
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[2]PODGORNIK B,HOGMARK S,SANDBERG O.Proper coating selection for improved galling performance of forming tool steel[J].Wear,2006,261(1):15-21.
[3]VEPREK S,VEPREK-HEIJMAN M J G.Industrial applications of superhard nanocomposite coatings[J].Surface&coatings technology,2008,202(21):5063-5073.
[4]ALLAM I M.Solid lubricants temperatures for applications at elevated temperature[J].Journal of material science,1991,26:3977-3984.
[5]DONNET C,ERDEMIR A.Solid lubricant coatings:recent developments and future trends[J].Tribology letter,2004,17(3):389-397.
[6]FRANZ R,NEIDHARDT J,SARTORY B,et al.Hightemperature low-friction properties of vanadium-alloyed AlCrN coatings[J].Tribology letter,2006,23(2):101-107.
[7]耿东森,曾琨,黄健,等.电弧离子镀AlCrN涂层结构和摩擦性能的研究[J].真空科学与技术学报,2016,36(12):1387-1393.GENG Dong-sen,ZENG Kun,HUANG Jian,et al.Microstructures and tribological behavior of arc ion plated AlCrN coatings[J].Chinese journal of vacuum science&technology,2016,36(12):1387-1393.
[8]黄玲,张进,孙才沅,等.VN复合渗层的制备及对45#耐磨性能的影响[J].表面技术,2018,47(6):57-62.HUANG Ling,ZHANG Jin,SUN Cai-yuan,et al.Preparation of VN composite layer and its influence on wear resistance of 45#steel[J].Surface technology,2018,47(6):57-62.
[9]李淼磊,王恩青,岳建岭,等.TiAlN/VN纳米多层膜的微结构与力学和摩擦学性能[J].无机材料学报,2017,32(12):1280-1284.LI Miao-Lei,WANG En-qing,YUE Jian-ling,et al.Microstructure,mechanical and tribological property of TiAlN/VN nano-multilayer films[J].Journal of inorganic materials,2017,32(12):1280-1284.
[10]OUYANG J H,SASAKI S.Tribo-oxidation of cathodic arc ion-plated(V,Ti)N coatings sliding against a steel ball under both unlubricated and boundary-lubricated conditions[J].Surface&coatings technology,2004,187(2):343-357.
[11]PARK J K,BAIK Y J.Increase of hardness and oxidation resistance of VN coating by nanoscale multilayered structurization with AlN[J].Materials letter,2008,62(16):2528-2530.
[12]QIU Y,ZHANG S,LI B,et al.Improvement of tribological performance of CrN coating via multilayering with VN[J].Surface&coatings technology,2013,231:357-363.
[13]MAYRHOFER P H,HOVSEPIAN P E,MITTERER C,et al.Calorimetric evidence for frictional self-adaptation of TiAlN/VN superlattice coatings[J].Surface&coatings technology,2004,177:341-347.
[14]LUO Q.Temperature dependent friction and wear of magnetron sputtered coating Ti AlN/VN[J].Wear,2011,271(9):2058-2066.
[15]YOUSAF M I,PELENOVICH V O,YANG B,et al.Influence of substrate rotation speed on the structure and mechanical properties of nanocrystalline AlTiN/MoNcoatings synthesized by cathodic arc ion-plating[J].Surface&coatings technology,2015,265:117-124.
[16]SHI X,TAY B K,FlYNN D I,et al.Characterization of filtered cathodic vacuum arc system[J].Surface&coatings technology,1997,94:195-200.
[17]WITKE T,SIEMROTH P.Deposition of droplet-free films by vacuum arc evaporation-results and applications[J].IEEE Transactions on plasma science,1999,27(4):1039-1044.
[18]WU M K,LEE J W,CHAN Y C,et al.Influence of bilayer period and thickness ratio on the mechanical and tribological properties of CrSiN/TiAlN multilayer coatings[J].Surface&coatings technology,2011,206(7):1886-1892.
[19]KIM Y J,BYUN T J,HAN J G.Bilayer period dependence of CrN/CrAlN nanoscale multilayer thin films[J].Superlattice microstructure,2009,45(2):73-79.
[20]XU J,HATTORI K,SEINO Y,et al.Microstructure and properties of CrN/Si3N4 nano-structured multilayer films[J].Thin solid films,2002,414(2):239-245.
[21]KOEHLER J S.Attempt to design a strong solid[J].Physic review B,1970,2(2):547.
[22]MAYRHOFER P H,MUSIC D,REESWINKEL T,et al.Structure,elastic properties and phase stability of Cr1-xAlxN[J].Acta materialia,2008,56(11):2469-2475.
[23]KIM J O,ACHENBACH J D,MIRKARIMI P B,et al.Elastic constants of single-crystal transition-metal nitride films measured by line-focus acoustic microscopy[J].Journal of applied physics,1992,72(5):1805-1811.
[24]GAHN J W.Hardening by spinodal decomposition[J].Acta materialia,1963,11(12):1275-1282.
[25]QIU Y,ZHANG S,LEE J W,et al.Self-lubricating CrAlN/VN multilayer coatings at room temperature[J].Appllied surface science,2013,279:189-196.
[26]SERGEJEV F,PEETSALU P,SIVITSKI A,et al.Surface fatigue and wear of PVD coated punches during fine blanking operation[J].Engineering failure analysis,2011,18(7):1689-1697.
[27]KUTSCHEJ K,RASHKOVA B,SHEN J,et al.Experimental studies on epitaxially grown TiN and VN films[J].Thin solid films,2007,516(2):369-373.
[28]PANDE C S,COOPER K P.Nanomechanics of HallPetch relationship in nanocrystalline materials[J].Progress in materials science,2009,54(6):689-706.
[29]LIDE D R.CRC handbook of chemistry and physics[M].Boca Raton,FL:CRC Press,2003.
[30]FRANZ R,NEIDHARDT J,MITTERER C,et al.Oxidation and diffusion processes during annealing of AlCrVNhard coatings[J].Journal of vacuum science&technology A,2008,26(2):302-308.