CN101365824A - 用包含四面体碳涂层的多层结构涂覆的基底 - Google Patents
用包含四面体碳涂层的多层结构涂覆的基底 Download PDFInfo
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Abstract
本发明涉及至少部分涂覆有多层结构的金属基底(11)。多层结构包括沉积于所述基底(11)上的中间层(14)和沉积于所述中间层上的四面体碳层(16)。该中间层包括至少一层杨氏模量低于200GPa的无定形碳层,并且四面体碳层具有高于200GPa的杨氏模量。本发明还涉及一种改善四面体碳层对基底的附着的方法以及涉及弥合金属基底的杨氏模量和沉积于所述金属基底上的四面体碳涂层的杨氏模量之间差距的方法。
Description
技术领域
本发明涉及用包含沉积于基底上的中间层和沉积于中间层上的四面体碳层的多层结构涂覆的金属基底。所述中间层包括无定形碳层。
背景技术
术语类金刚石碳(DLC)描述了包含具有类似于金刚石的结构和性能的碳的一组材料。类金刚石碳涂层的一些例子为a-C、a-C:H、i-C、ta-C和ta-C:H涂层。
由于DLC具有许多吸引人的性能,包括高硬度、化学惰性、高热导率、良好的电和光性能、生物适应性以及优异的摩擦学行为,DLC作为涂层材料已经吸引了相当大的关注。
通过sp3键合的分数给出了DLC涂层的大致分类方法。四面体碳涂层具有高的sp3键合碳分数,而诸如a-C或a-C:H的无定形碳涂层具有较低的sp3键合分数以及较高的sp2键合分数。
氢含量给出了第二分类方法。DLC涂层可以分为无氢化涂层(ta-C和a-C)以及氢化涂层(ta-C:H和a-C:H)。
四面体碳涂层的组显示了许多有益的性能,例如高硬度(类似于金刚石的硬度)和高杨氏模量。这些性能使得四面体碳涂层对许多要求耐磨的应用很理想。然而,由于压应力和sp3键合成正比,四面体碳涂层中的压应力很高。
涂层中巨大的压应力限制了涂层对基底的附着并且限制了涂层的总体膜厚度。
发明概要
本发明的一个目的是避免现有技术的缺陷。
本发明的另一个目的是提供用包含硬的四面体碳层并且对金属基底有良好附着的多层结构涂覆的金属基底。
本发明的再一个目的是提供一种用包含中间层和四面体碳层的多层结构涂覆的金属基底,其中中间层弥合了金属基底和四面体碳层之间杨氏模量上的差距。
根据本发明的第一方面,提供了至少部分用多层结构涂覆的金属基底。多层结构包括中间层和四面体碳层。中间层沉积于基底上,四面体碳层沉积于中间层上。中间层包括至少一层杨氏模量低于200GPa的无定形碳层以及具有高于200GPa的杨氏模量的四面体碳层。
多层结构可以包括许多周期,每一周期包括包含至少一层杨氏模量低于200GPa的无定形碳层的中间层和杨氏模量高于200GPa的四面体碳层。周期的数目可以在2和100之间,例如在2和30之间,比如10或15。
四面体碳层
四面体碳层的杨氏模量范围优选在200和800GPa之间。更优选四面体碳层具有至少300GPa的杨氏模量,例如400GPa、500GPa或600GPa。
四面体碳层的硬度优选高于20GPa。四面体碳层的硬度的优选范围在20GPa和80GPa之间。更优选,四面体碳层的硬度为至少30GPa,例如40GPa、50GPa或60GPa。
四面体碳的sp3键合的碳的分数优选高于50%,例如在50%和90%之间,比如80%。
四面体碳层可以包括非氢化四面体碳(ta-C)或氢化四面体碳(ta-C:H)。在氢化四面体碳的情况下,氢浓度优选低于20at%,例如10at%。
优选的四面体碳层包括具有高的sp3键合碳分数的无氢化四面体碳(ta-C),例如80%的sp3键合碳分数。
可以通过多种不同技术沉积四面体碳层。
优选的沉积技术包括离子束沉积、脉冲激光沉积、诸如过滤的或未过滤的电弧沉积的电弧沉积、诸如增强等离子体辅助化学气相沉积的化学气相沉积以及激光电弧沉积。
为了影响根据本发明的多层结构的诸如电导性的性能,可以用金属掺杂四面体碳层。原则上任何金属都可考虑用作掺杂剂。
优选掺杂剂包含一种或多种过渡金属,例如Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Mn、Re、Fe、Co、Ir、Ni、Pd和Pt。别的掺杂剂可以包含B、Li、Na、Si、Ge、Te、O、Mg、Cu、Al、Ag和Au。
优选的掺杂剂是W、Zr和Ti。
四面体碳层优选具有高于0.5μm,例如1μm的厚度。
无定形碳层
无定形碳层具有低于200GPa的杨氏模量。
无定形碳层可以包括无定形氢化碳(a-C:H)层或类金刚石纳米复合物(DLN)层。
无定形氢化碳层(a-C:H)优选具有低于40%的sp3键合碳分数。更优选sp3键合碳分数低于30%。
氢含量优选在20和40%之间,例如30%。
无定形氢化碳层(a-C:H)的硬度优选在15GPa和25GPa之间。更优选无定形氢化碳层(a-C:H)的硬度在18GPa和25GPa之间。
类金刚石纳米复合层的硬度优选在10GPa和20GPa之间。
优选纳米复合组合物包含在C、Si和O的总量中所占比例为:40-90at%的C、5-40at%的Si以及5-25at%的O。
优选类金刚石纳米复合组合物包含a-C:H和a-Si:O的两个互穿网络。
可以进一步用诸如过渡金属的金属掺杂无定形碳层(a-C:H层或DLN层),例如Ti、Zr、Hf、V、Nb、Ta、Cr、Mo、W、Mn、Re、Fe、Co、Ir、Ni、Pd和Pt。
其它掺杂剂可以包括B、Li、Na、Si、Ge、Te、O、Mg、Cu、Al、Ag和Au。
优选的掺杂剂是W、Zr和Ti。
无定形碳层优选具有高于0.5μm,例如高于1μm的厚度。
多层结构的厚度优选高于0.5μm或高于1μm,例如2μm或3μm。
基底
基底可以包括任何金属基底,是挠性的或是刚性的。基底的例子包括钢基底、硬质合金基底、铝或铝合金基底、钛或钛合金基底或铜和铜合金基底。
根据本发明的多层涂层特别适于应用于气阀机构元件,例如梃杆、活塞销、指状件、指状随动件、凸轮轴、摇臂、活塞、活塞环、齿轮、阀、阀簧和升降机构。
附着促进层
为了进一步增强四面体碳层对金属基底和/或多层结构对金属基底的附着力,在中间层沉积之前,可以把附加的附着促进层沉积于金属基底上。
附着促进层可以包含任何金属。
优选附着促进层包含至少一种选自硅和周期表IVB族元素、VB族元素和VIB族元素的元素。
优选的中间层包含Ti和/或Cr。
或者,附着促进层包含多于一层,例如两层或更多层金属层,每一层包含选自硅、周期表IVB族元素、VB族元素以及VIB族元素的金属,例如Ti或Cr层。
可选地,附着促进层可以包含一层或多层选自硅、周期表IVB族元素、VB族元素以及VIB族元素的金属的碳化物、氮化物、碳氮化物、碳氧化物、氧氮化物、氧碳氮化物(oxycarbonitride)的层。
一些例子是TiN、CrN、TiC、Cr2C3、TiON、TiCN和CrCN。
而且,附着促进层可以包含一层或更多层选自硅、周期表IVB族元素、VB族元素以及VIB族元素的金属的金属层与一层或多层选自硅、周期表IVB族元素、VB族元素以及VIB族元素的金属的碳化物、氮化物、碳氮化物、碳氧化物、氧氮化物、氧碳氮化物的层的任何组合。
中间层的一些例子包括金属层与金属碳化物的组合,金属层与金属氮化物的组合,金属层与金属碳氮化物的组合,金属层、金属碳化物层与金属层的组合以及金属层、金属氮化物层与金属层的组合。
附着促进层的厚度优选在1nm和1000nm之间,例如在10和500nm之间。
可以通过本领域已知的任何技术来沉积附着促进层,例如通过诸如溅射和蒸发的物理气相沉积。
顶层
根据本发明的另一个实施方式,多层结构可以进一步包括沉积于四面体碳层上的顶层。
可以根据人们想要获得的多层结构的性能以及取决于用途来选择多层结构的顶层。
由于四面体碳涂层具有高硬度和高粗糙度,它们可能导致相对物体增加的磨损速率。因此,期望在四面体碳涂层的顶部沉积具有低粗糙度的顶层。该顶层可以对四面体碳涂层的磨合磨损行为产生积极的影响。
顶层的例子包括无定形氢化碳(a-C:H)层、类金刚石纳米复合物(DLN)层、用元素O、N和/或F中的一种或多种掺杂的无定形氢化碳层(a-C:H)、用元素O、N和/或F中的一种或多种掺杂的类金刚石纳米复合物(DLN)层、金属掺杂的氢化碳层或金属掺杂的类金刚石纳米复合物层。
当无定形氢化碳(a-C:H)层沉积于多层结构的顶部时,将会获得对该层来说是典型的硬度和低磨损特征。
当沉积类金刚石纳米复合物(DLN)层作为顶层时,多层结构的特征在于低表面能和低摩擦系数。这种多层结构特别适于作为不粘涂层。
根据本发明的沉积在金属基底上的多层结构的一个优选实施方式包括沉积在金属基底上的无定形碳层(例如a-C:H)、沉积在该无定形碳层顶部的类金刚石纳米复合物(DLN)以及沉积在该类金刚石纳米复合物(DLN)顶部的四面体碳层。
多层结构也可以包括多个周期,每个周期包括无定形碳层(例如a-C:H)、类金刚石纳米复合物(DLN)层以及四面体碳层。
周期的数目在2和100之间,例如在2和30之间,比如10或15。
包含杨氏模量低于200GPa的中间层和沉积于该中间层上的四面体碳层的根据本发明的多层结构特别适于作为用于诸如气阀机构元件的在润滑条件下使用的元件的涂层。
根据本发明的第二方面,提供一种改善四面体碳层对基底的附着力的方法。
该方法包括在沉积四面体碳层前应用杨氏模量低于200GPa的无定形碳层。
根据本发明的第三方面,提供一种弥合金属基底的杨氏模量和沉积于金属基底上的四面体碳涂层的杨氏模量之间差距的方法。
该方法包括在沉积四面体碳层前在金属基底上应用中间层。所述中间层包括至少一层杨氏模量低于四面体碳层的杨氏模量的无定形碳层。优选该中间层的杨氏模量高于金属基底的杨氏模量而低于四面体碳层的杨氏模量。
所述中间层的杨氏模量优选在100和200GPa之间,例如150GPa或者170GPa;然而四面体碳层的杨氏模量优选在200和800GPa之间。
附图简要说明
现在参照附图对发明进行更详细的描述,其中:
-图1-3以截面图显示了根据本发明的多层结构的不同实施方式。
发明优选实施方式的说明
图1给出了根据本发明的涂覆的金属基底10的第一实施方式的截面图。基底11涂覆有多层结构12。
多层结构包括:
-沉积于金属基底10上的中间层14。中间层14包括无定形氢化碳层,a-C:H。
-沉积于中间层14上的四面体碳层16。
中间层14具有1μm的厚度和170GPa的杨氏模量。
四面体碳层16具有1μm的厚度和400GPa的杨氏模量。
在本发明一个可选实施方式中,中间层14包括包含两个互穿网络a-C:H和a-Si:O的类金刚石纳米复合物层。
中间层14具有1μm的厚度和150GPa的杨氏模量。
图2显示了根据本发明的涂覆的基底20的第二实施方式的截面图。金属基底21涂覆有多层结构22。
多层结构包括:
-沉积于金属基底上的附着促进层23。附着促进层23包括例如铬或铬基的层或者钛或钛基的层;
-沉积于附着促进层23上的中间层24。中间层24包括无定形碳层;
-沉积于中间层24上的四面体碳层26。
附着促进层23具有0.2μm的厚度;中间层24具有1μm的厚度和170GPa的杨氏模量以及四面体碳层26具有1μm的厚度和400GPa的杨氏模量。
或者,多层结构22进一步包括沉积于四面体碳层26上的顶层27。顶层27包括例如包含两个互穿网络a-C:H和a-Si:O的类金刚石纳米复合物层。顶层27具有例如0.1μm的厚度和150GPa的杨氏模量。
对本领域技术人员来说,显然可以想到包含附着促进层或者顶层的可替换的实施方式。
图3显示了根据本发明的涂覆的基底30的第三实施方式的截面图。
金属基底31涂覆有包括许多周期33的多层结构32。每个周期包括中间层34和四面体碳层36。周期的数目例如为10。
或者,多层结构32进一步包括顶层37。
Claims (19)
1.至少部分涂覆有多层结构的金属基底,所述多层结构包括沉积于所述基底上的中间层和沉积于所述中间层上的四面体碳层,所述中间层包含至少一层杨氏模量低于200GPa的无定形碳层,所述四面体碳层具有高于200GPa的杨氏模量。
2.根据权利要求1的基底,其中所述多层结构包括多个周期,每一周期包括包含至少一层杨氏模量低于200GPa的无定形碳层的中间层和杨氏模量高于200GPa的四面体碳层,其中所述周期的数目在2和100之间。
3.根据权利要求1或2的基底,其中所述四面体碳层的杨氏模量在200和800GPa之间。
4.根据前述权利要求任一项的基底,其中所述四面体碳层具有高于20GPa的硬度。
5.根据前述权利要求任一项的基底,其中所述四面体碳层具有高于30%的sp3键合碳分数。
6.根据前述权利要求任一项的基底,其中所述四面体碳层选自非氢化四面体碳(ta-C)和氢化四面体碳(ta-C:H)。
7.根据前述权利要求任一项的基底,其中用金属掺杂所述四面体碳层。
8.根据前述权利要求任一项的基底,其中所述无定形碳层选自无定形氢化碳(a-C:H)和另外包含Si和O的无定形氢化碳(a-C:H)。
9.根据权利要求8的基底,其中所述另外包含Si和O的无定形碳层包含两个互穿网络:通过氢稳定的类金刚石碳网络中主要为sp3键合碳的第一网络以及通过氧稳定的硅的第二网络。
10.根据前述权利要求任一项的基底,其中用至少一种金属掺杂所述无定形碳层。
11.根据前述权利要求任一项的基底,其中所述多层结构包括在所述中间层沉积之前沉积于所述基底上的附着促进层。
12.根据权利要求11的基底,其中所述附着促进层包括至少一层,所述层包含至少一种选自硅和周期表IVB族元素、VB族元素以及VIB族元素的元素。
13.根据权利要求11或12的基底,其中所述附着促进层包含至少一层金属层,
所述金属层包含至少一种选自硅和周期表IVB族元素、VB族元素以及VIB族元素的元素。
14.根据权利要求11或12的基底,其中所述附着促进层包含选自至少一种选自硅、周期表IVB族元素、VB族元素以及VIB族元素的元素的碳化物、氮化物、碳氮化物、碳氧化物、氧氮化物、氧碳氮化物的至少一个层。
15.根据权利要求11-14的任一项的基底,其中所述附着促进层包含至少一层选自硅、周期表IVB族元素、VB族元素以及VIB族元素的金属的金属层与至少一层选自硅、周期表IVB族元素、VB族元素以及VIB族元素的金属的碳化物、氮化物、碳氮化物、碳氧化物、氧氮化物、氧碳氮化物的层的组合。
16.根据前述权利要求任一项的基底,其中所述多层结构进一步包括顶层,所述顶层沉积于所述四面体碳层上。
17.根据权利要求16的基底,其中所述顶层选自无定形氢化碳(a-C:H)、用元素O、N和/或F中的一种或多种掺杂的无定形氢化碳(a-C:H)、进一步包含Si和O且或许用金属掺杂或者用元素O、N和/或F中的一种或多种掺杂的无定形氢化碳(a-C:H)以及金属掺杂的氢化碳。
18.一种通过在沉积四面体碳层前在基底上施用中间层来改善四面体碳层对基底的附着的方法,所述中间层包含杨氏模量低于200GPa的无定形碳层。
19.一种通过在沉积四面体碳层前在基底上施用中间层来弥合基底的杨氏模量和沉积于所述基底上的四面体碳涂层的杨氏模量之间差距的方法,所述中间层包含杨氏模量高于所述基底的杨氏模量而低于所述四面体碳层的杨氏模量的无定形碳层。
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2006
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- 2006-07-13 EP EP06777754.0A patent/EP1937873B8/en not_active Not-in-force
- 2006-07-13 WO PCT/EP2006/064195 patent/WO2007020138A1/en active Application Filing
- 2006-07-13 CN CN2006800299676A patent/CN101365824B/zh not_active Expired - Fee Related
- 2006-07-13 US US12/063,927 patent/US7820293B2/en active Active
- 2006-07-13 ES ES06777754.0T patent/ES2695024T3/es active Active
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2010
- 2010-10-01 US US12/896,438 patent/US20110020551A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
---|---|
JP5755830B2 (ja) | 2015-07-29 |
US20110020551A1 (en) | 2011-01-27 |
EP1937873B8 (en) | 2018-10-31 |
US20080233425A1 (en) | 2008-09-25 |
JP2009504919A (ja) | 2009-02-05 |
ES2695024T3 (es) | 2018-12-28 |
EP1937873B1 (en) | 2018-09-05 |
CN101365824B (zh) | 2010-09-01 |
US7820293B2 (en) | 2010-10-26 |
EP1937873A1 (en) | 2008-07-02 |
WO2007020138A1 (en) | 2007-02-22 |
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