CN117845166A - 滑动构件及其用途 - Google Patents

滑动构件及其用途 Download PDF

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CN117845166A
CN117845166A CN202311259459.9A CN202311259459A CN117845166A CN 117845166 A CN117845166 A CN 117845166A CN 202311259459 A CN202311259459 A CN 202311259459A CN 117845166 A CN117845166 A CN 117845166A
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layer
sliding member
craln
protective coating
thickness
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朱利亚诺·阿韦拉阿罗约
拉斐尔·拉贝洛
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Mahle International GmbH
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Mahle International GmbH
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Abstract

本发明涉及一种滑动构件及其用途。一种滑动构件(1)，包含：金属基材(2)；至少一个中间结合层(3)，所述中间结合层(3)由至少一种金属构成并且以覆盖所述金属基材(2)的至少一部分表面的方式存在于所述金属基材(2)上；以及存在于中间结合层(3)上的多层保护涂层(4)，其中所述多层保护涂层(4)具有CrAlN(4a)和Cr(Al)N(4b)的交替层，其中每两个CrAlN(4a)和Cr(Al)N(4b)的交替层形成周期性层组(4c)，CrAlN层(4a)具有比Cr(Al)N层(4b)更高的Al含量，在每个周期性层组(4c)中CrAlN层(4a)对Cr(Al)N层(4b)的厚度比为1<(CrAlN层的厚度)/(Cr(Al)N层的厚度)≤10，并且所述多层保护涂层(4)的总Al含量为15至40原子％。

Description

滑动构件及其用途
技术领域
本发明涉及一种滑动构件，特别是用于内燃机或压缩机中，所述滑动构件具有多个依次的由含铝氮化铬构成的涂层。由此产生的滑动构件实现了优异的耐磨和抗散裂(spalling)性能。
背景技术
按照奥托和狄塞尔循环(Otto and Diesel cycles)运行的内燃机用于牵引驱动绝大多数的汽车，并且基本上包含两个主要部件：汽缸体(一个或多个汽缸和曲轴位于其中)、与之相连的一个或多个汽缸盖。活塞和连杆与曲轴相连。
活塞顶面、气缸壁和气缸盖底部之间限定的空间对应于燃烧室，在柴油机中，燃烧室通常主要由设置在活塞头部上的一个以上的腔来限定。
在燃烧室内部，发动机将可燃混合物(燃料和空气)燃烧产生的化学能转化为能够将运动传递给车轮的机械能。
为了确保均匀燃烧且不会燃烧机油，并也为了避免过量气体从气缸去往曲轴箱，有必要使用环来为活塞和气缸壁之间的间隙提供良好的密封。
通常，现代四冲程发动机在每个活塞上使用三个环，两个压缩环和一个油环。压缩环的作用是防止燃烧气体去往曲轴箱，而油环的作用是从气缸壁刮掉多余的油并将其返回曲轴箱、控制油“膜”的厚度并防止它被过度燃烧。
所述环的另一个重要功能是充当桥梁将热量从活塞传递到气缸壁/套筒，在那里通过冷却系统使热量消散。
作为一般原则，活塞环、特别是压缩环，是由涂覆有至少一个涂层的金属基材形成的，所述涂层与气缸壁接触。
所述涂层的作用属于是最重要的，因为它寻求对所述环赋予低滑动磨耗性质、优异的抗散裂性、硬度和韧性。然而，这些性质中许多是对立的，其中之一的增加意味着另一者的性能受损，因此，基于发动机工作模式(working profile)的功能和所述环在其使用寿命期间所受的力来选择要使用的涂层类型。
本领域技术人员提出了一系列复杂的涂层，每一种都寻求增加期望的性质。然而，迄今为止提出的涂层，在同时提高内应力吸收性能、优异的硬度和低厚度、从而显著降低散裂上，均非有效。
第一种现有技术由美国专利No.5,718,437代表，该专利涉及一种刮油环，所述刮油环具有厚度约3μm至30μm的Cr2N单层涂层。
根据所述文献，Cr2N涂层提供了1300HV至2000HV之间的硬度，并通过本领域技术人员通常称为“离子镀”的工艺来施加。
第二种现有技术由日本专利JP 9196173代表，其公开的发明与美国专利No.5,718,437非常相似，即一种具有宽度约3μm至30μm的Cr2N单层涂层的刮油环。
此外，美国专利No.5,820,131涉及一种活塞环，所述活塞环具有由Cr2N单层或Cr2N和CrN混合物的单层形成的宽度为3μm至30μm的涂层并且氮的重量百分比在11％至17％之间。所述涂层通过一种被称为“物理气相沉积”(PVD)的工艺施加，其硬度范围从1300HV至2000HV。
美国专利No.5,743,536涉及一种具有至少由氮化铬形成的涂层的活塞环，所述涂层通过PVD施加。所述氮化铬以单相包含CrN、Cr2N、或CrN和Cr2N的混合物。该文献还指明了厚度和孔隙率的各种值，此外还公开了具有各种末端布置的涂层的产品的各种机械测试。根据该专利，所述涂层呈现出优异的耐磨损、散裂和燃烧的性质。
此外，WO 2005/121403 A1公开了一种活塞环，所述活塞环包含含有多个Cr/CrN(Cr2N)层的多层PVD涂层。
最后，美国专利No.6,631,907涉及一种活塞环，所述活塞环具有通过PVD施加的包含CrN或Cr2N、或氮化物混合物的涂层。该文献还公开了CrN与Cr2N和金属铬的混合物的应用，并公开了所述成分的重量百分比的细节。
因此，上述现有技术的所有解决方案都涉及使用CrN或Cr2N本身或混合物，来获得具有高等级的耐磨损、散裂和燃烧性的单层涂层。
然而，在现有技术的提议中存在关于进一步提高耐磨损、散裂和燃烧性的局限，这种局限取决于所述氮化物层的CrN或Cr2N的百分比以及所添加的任何其它元素而异。如果希望这些性能的更大改善，单层氮化涂层不是一个可行的解决方案。
发明内容
因此，本发明的目的是提供一种具有以氮化铬为基础的涂层的滑动构件，所述涂层提供了进一步改善的耐磨性和抗散裂性。
所述目的通过独立项1的主题实现。有利的实施方式是从属项的主题。
本发明基于在金属基材上使用多层保护涂层的总体思想，其中所述多层保护涂层具有CrAlN和Cr(Al)N的交替层，其中每个CrAlN层均具有比每个Cr(Al)N层更高的Al含量，并且每个CrAlN层的厚度均大于每个Cr(Al)N层的厚度。
CrAlN具有公认的由于间隙Al元素所致的钝化特性和高硬度。内燃机的滑动构件如活塞环需要低摩擦、耐磨损、散裂和擦伤性高的涂层。预期更高的涂层硬度达到的耐磨性更高。
本发明人发现了一种新的CrAlN/Cr(Al)N多层膜概念，其中所述交替层如上所述具有不同浓度的Al，使得所述多层的耐磨性显著改善。另外，由于所述多层概念，实现了高的抗散裂性，因为每个层都充当位错移动的屏障。此外，高的耐擦伤性是由Al量低的较薄的Cr(Al)N层实现的。
本发明的多层概念的另一个优点是减小了层界面处的元素相互扩散的体积，因为以上述的方式，具有不同Al浓度的层也具有不同的厚度。这种特定构造对弹性状态(elastic regime)、塑性变形、裂纹的萌生和扩展中的能量吸附和弛豫动力学有影响。
此外，所述多层概念是基于晶格参数的连续适应(adaptation)，由此是基于晶格的能量状态(尺寸)的连续适应。因此，例如，在CrAlN/Cr(Al)N的共格界面处计算的应力梯度低于纯CrN/CrAlN的。在本多层概念中，基于界面共格应力与位错的弹性应力场的相互作用，所述共格强化阻碍了位错移动。所述多层概念考虑了所述层内部的组成梯度和晶格参数变化。核心区的消除消除了自由裂纹扩展，因为核心区中没有应力梯度。
另外，所述多层概念能够通过对于具有不同Al浓度的层对(pairs of layers)的相同周期性厚度减小晶格参数的差异并因此减小最大残余应力值，从而降低所述涂层的总硬度并减轻在摩擦对应部分上的任何高磨损。此外，所述层之一(所述Cr(Al)N层)的厚度减小将增加表现为内在弹性应力(intrinsic elastic stress)的平均应力梯度，这被认为是由组成差异和相应的晶格参数变化所产生的。
应力幅度和应力梯度都能够影响硬度。因此，更陡的应力梯度可能导致位错移动更加困难。所述周期性厚度越小，则在所述界面附近产生的应力梯度越大，对位错移动造成的应力屏障越大。
Al并入CrN中促进了更高的硬度、热稳定性和化学稳定性。本多层概念还能够增加涂层的硬度和韧性。
最后，在作为整体的所述涂层中低浓度的Al能够在面心立方(fcc)CrN晶格内部形成Al的亚稳固溶体，这增加了硬度。所述CrAlN相形成致密且粘附的混合Al和Cr氧化物皮，其最终抑制氧扩散到所述涂层中，直至高达900℃的温度均提供优异的抗氧化性。此外，Al作为反应元素的加入被认为减少了在本体/皮界面(氧化物膜)处空隙的累积，从而通过改变所述涂层的结构来改善其机械性质或防止在升高的温度下的晶粒粗化。
鉴于上述效果，本发明的新的多层概念提供了一种滑动构件，所述滑动构件相比于现有技术概念具有大幅改善的耐磨性和抗散裂性。
特别是，本发明提供了一种滑动构件，所述滑动构件包含：金属基材；至少一个中间结合层，所述中间结合层由至少一种金属构成并且以覆盖所述金属基材的至少一部分表面的方式存在于所述金属基材上；以及存在于所述中间结合层上的多层保护涂层，其中所述多层保护涂层具有CrAlN和Cr(Al)N的交替层，其中每两个CrAlN和Cr(Al)N的交替层形成周期性层组，所述CrAlN层具有比所述Cr(Al)N层更高的Al含量，在每个周期性层组中所述CrAlN层对所述Cr(Al)N层的厚度比为1<(CrAlN层的厚度)/(Cr(Al)N层的厚度)≤10，并且所述多层保护涂层的总Al含量为15至40原子％。
根据本发明的一个优选实施方式，所述金属基材由具有10至17重量％Cr的钢、具有通常应用于内燃机或压缩机的滑动构件领域的组成的碳钢或铸铁制成。然而，本发明不限于所述用于金属基材的材料，而是可以使用其它材料。
根据本发明的一个优选实施方式，所述金属基材是氮化的。所述氮化可以通过已知的方法如气体氮化、盐浴氮化或等离子体氮化来进行，并且导致所述金属基材的表面硬化，改善其总体耐磨性。
根据本发明的一个优选实施方式，所述至少一个中间结合层由选自由Cr、Ni和Co组成的组中的至少一者、优选Cr制成。所述中间结合层改善了所述多层保护涂层的粘附力。施加于所述金属基材材料上的所述中间结合层以及所述功能性涂层是例如通过物理气相沉积(PVD)工艺产生的。
根据本发明的一个优选实施方式，所述至少一个中间结合层和所述多层保护涂层的总厚度为6μm至70μm、优选6μm至60μm、更优选10μm至50μm。本滑动构件的层厚度例如通过截面评价来测量。
根据本发明的一个优选实施方式，在每个周期性层组中，所述CrAlN层对所述Cr(Al)N层的厚度比为1.3至10、优选1.5至10、更优选1.7至10、还更优选为1.5至5、特别是1.7至5。
根据本发明的一个优选实施方式，所述CrAlN层含有20至40原子％的Al、优选25至35原子％的Al、更优选27至32原子％的Al，并且所述Cr(Al)N层含有10至25原子％的Al、优选15至22原子％的Al、更优选18至20原子％的Al。例如，所述化学组成可以通过EELS(电子能量损失谱)或EDS(能量色散谱)来测量。
根据本发明的一个优选实施方式，每个周期性层组的厚度小于20nm、优选小于18nm、更优选15nm以下、特别是5至15nm。
根据本发明的一个优选实施方式，所述多层保护涂层的硬度为1600至2600HV、优选1800至2400HV、更优选1900至2000HV。
根据本发明的一个优选实施方式，通过X射线分析进行测量，所述多层保护涂层的内部压缩应力为1000至2500MPa、优选1200至2300MPa、更优选1400至2000MPa。
根据本发明的一个优选实施方式，通过分析软件对涂层截面图像进行测量，所述多层保护涂层的孔隙率低于6％、优选低于5％、更优选低于4％、特别是低于3％。
根据本发明的一个优选实施方式，所述多层保护涂层通过阴极电弧沉积制成。阴极电弧沉积的方法和装置是技术人员公知的。具体的阴极电弧沉积方法和相应的装置在下面进一步讨论。
此外，本发明提供了滑动构件在内燃机或压缩机中的用途，其中所述滑动构件优选是活塞环、挺杆、阀或凸轮。所要求保护的所述滑动构件的用途的其它具体实例是刮油环、二冲程发动机的压缩环、和活塞式压缩机的环。
本发明的其它重要特征和优点由从属项、附图和附图的相应描述得出。
应当注意，上述的和下面讨论的特征不仅可以用在相应的给定组合中，而且也可以用在不同的组合中或不超出本发明的范围的此类组合中。
附图说明
本发明的优选实施方式示于附图中，并在下面的描述中进一步讨论，其中相同的参考数字是指相似或功能相同的部件。
在图中示意性显示的是：
图1本发明的滑动构件(1)的截面图，包含金属基材(2)、中间结合层(3)、以及形成多层保护涂层(4)的多个CrAlN和Cr(Al)N层(4a，4b)，
图2适合于制造本发明的多层保护涂层(4)的阴极电弧沉积装置的示意性俯视图，
图3活塞环形式的本发明的滑动构件(1)，和
图4用于将现有技术保护涂层和根据本发明的多层保护涂层的相对磨损进行比较的条形图。
具体实施方式
根据图1，本发明的滑动构件(1)的截面图包含金属基材(2)、存在于所述金属基材(2)上的中间结合层(3)、以及在所述中间结合层(3)上形成多层保护涂层(4)的多个CrAlN和Cr(Al)N层(4a，4b)。所述多个CrAlN和Cr(Al)N层(4a，4b)交替排列在所述中间结合层(3)上，其中紧挨在所述中间结合层(3)之上的层是CrAlN层(4a)。然而，以CrAlN层(4a)起始不是强制性的，即，在所述中间结合层(3)上的第一层也可以是Cr(Al)N层(4b)。根据本发明并且如图1中示意性地显示的，如上所述，所述CrAlN层(4a)的厚度被设置为大于所述Cr(Al)N层(4b)的厚度。此外，根据本发明，如上所述，所述CrAlN层(4a)中的Al浓度被设置为大于所述Cr(Al)N层(4b)中的Al浓度。每两个CrAlN和Cr(Al)N交替层(4a，4b)形成周期性层组(4c)，如对图1中最底下的两个CrAlN和Cr(Al)N层(4a，4b)示例性指示的那样。
图2显示了适合于制造本发明的多层保护涂层(4)的阴极电弧沉积装置的示意性俯视图。
氮化物多层，如本发明中使用的CrAlN/Cr(Al)N，是同构的且相互可混相的(miscible)。所述成分的混合通过PVD(物理气相沉积)室构造而限定为在沉积期间发生，导致组成梯度。混合的程度随沉积条件而变，特别是关于在所述过程期间靶之间的交叉污染，并且主要是由于自身靶组成所致(例如，在本情况下，靶的一半具有50至75原子％范围内的高Al量，而靶的另一半具有3至10原子％范围内的Al)。
根据图2，作为制造本发明的滑动构件的示例，在工业尺寸的室(6)中，通过“阴极电弧物理气相沉积(Cathodic Arc Physical Vapour Deposition)”(CAPVD)在气体氮化的马氏体不锈钢(AISI 440B)试片(5)上沉积CrAlN/Cr(Al)N纳米结构的多层保护涂层。处于交替位置的两种阴极[Al含量为3至10原子％的一套Cr(Al)(7b)，Al含量为50至75原子％的一套CrAl(7a)]用自己的电源供电。通过改变位于所述室(6)中央的台(8)的旋转速度，获得了30μm厚的涂层，其周期性层组(4c)的厚度小于15nm。所述旋转速度以实现控制所述周期性厚度的方式来控制基底在每个CrAl或Cr(Al)靶(7a，7b)前面通过的时间，确保了大大减少所述靶之间的交叉污染。所有沉积的平均沉积速率为5μm/h。
图3显示了活塞环形式的本发明的滑动构件(1)，所述活塞环可以通过上文讨论的CAPVD制造。图3的活塞环包含金属基材(2)(仅显示了活塞环的环片段)、存在于所述金属基材(2)的外环表面上的中间结合层(3)、以及存在于所述中间结合层(3)上的多层保护涂层(4)。
最后，图4显示了用于将现有技术保护涂层和根据本发明的多层保护涂层的相对磨损进行比较的条形图。所有发动机测试都在HDD平台上进行，内径(bore diameter)为128mm，功率为320至370kW，持续时间为250小时直至1,000小时。第一个条显示了由周期性为20nm的NbN/CrN(比例为1:1，10nm NbN和10nm CrN)构成的现有技术多层涂层结构的结果，而第二个条显示了CrAlN单层涂层(没有多层)，最后的第三个条显示了周期性为20nm并且比例也为1:1的多层CrAlN/Cr(Al)N的结果。
如图4中由长方形包围的其余四个条所示，测试了根据本发明的CrAlN/Cr(AlN)的变体。结果发现，涂层总磨损显著降低。

Claims (15)

1.一种滑动构件(1)，所述滑动构件(1)包含：
金属基材(2)；
至少一个中间结合层(3)，所述中间结合层(3)由至少一种金属构成并且以覆盖所述金属基材(2)的至少一部分表面的方式存在于所述金属基材(2)上；以及
存在于所述中间结合层(3)上的多层保护涂层(4)，其中
所述多层保护涂层(4)具有CrAlN(4a)和Cr(Al)N(4b)的交替层，其中每两个CrAlN(4a)和Cr(Al)N(4b)交替层形成周期性层组(4c)，
所述CrAlN层(4a)具有比所述Cr(Al)N层(4b)更高的Al含量，
在每个周期性层组(4c)中所述CrAlN层(4a)对所述Cr(Al)N层(4b)的厚度比为1<(CrAlN层的厚度)/(Cr(Al)N层的厚度)≤10，并且
所述多层保护涂层(4)的总Al含量为15至40原子％。
2.根据权利要求1所述的滑动构件(1)，其中所述金属基材(2)由具有10至17质量％Cr的钢、碳钢或铸铁制成。
3.根据权利要求2所述的滑动构件(1)，其中所述金属基材(2)是氮化的。
4.根据权利要求1至3中的任一项所述的滑动构件(1)，其中所述至少一个中间结合层(3)由选自由Cr、Ni和Co组成的组中的至少一者制成。
5.根据权利要求1至4中的任一项所述的滑动构件(1)，其中所述至少一个中间结合层(3)和所述多层保护涂层(4)的总厚度为6μm至70μm。
6.根据权利要求1至5中的任一项所述的滑动构件(1)，其中在每个周期性层组(4c)中，所述CrAlN层(4a)对所述Cr(Al)N层(4b)的厚度比为1.3至10。
7.根据权利要求1至6中的任一项所述的滑动构件(1)，其中所述CrAlN层(4a)含有20至40原子％的Al并且所述Cr(Al)N层(4b)含有10至25原子％的Al。
8.根据权利要求1至7中的任一项所述的滑动构件(1)，其中每个周期性层组(4c)的厚度小于20nm。
9.根据权利要求8所述的滑动构件(1)，其中每个周期性层组(4c)的厚度为4至15nm。
10.根据权利要求1至9中的任一项所述的滑动构件(1)，其中所述多层保护涂层(4)的硬度为1600至2600HV。
11.根据权利要求1至10中的任一项所述的滑动构件(1)，其中所述多层保护涂层(4)的内部压缩应力为1000至2500MPa。
12.根据权利要求1至11中的任一项所述的滑动构件(1)，其中所述多层保护涂层(4)的孔隙率低于6％。
13.根据权利要求1至12中的任一项所述的滑动构件(1)，其中所述多层保护涂层(4)通过阴极电弧沉积制成。
14.根据权利要求1至13中的任一项所述的滑动构件(1)在内燃机或压缩机中的用途。
15.根据权利要求14所述的用途，其中所述滑动构件(1)是活塞环、挺杆、阀或凸轮。
CN202311259459.9A 2022-10-04 2023-09-27 滑动构件及其用途 Pending CN117845166A (zh)

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Publication number Priority date Publication date Assignee Title
CN1068388C (zh) 1994-07-30 2001-07-11 株式会社理研 滑动部件
JP3766445B2 (ja) 1994-12-27 2006-04-12 日本ピストンリング株式会社 内燃機関用ピストンリング
JP2855419B2 (ja) 1995-12-19 1999-02-10 帝国ピストンリング株式会社 組合せオイルリングのスペーサエキスパンダおよび組合せオイルリング
JPH09196173A (ja) 1996-01-11 1997-07-29 Teikoku Piston Ring Co Ltd 組合せオイルリング
JP3228116B2 (ja) 1996-01-29 2001-11-12 帝国ピストンリング株式会社 組合せオイルリング
DE102004028486A1 (de) 2004-06-11 2005-12-29 Mahle Gmbh Gleitbauteil
DE102010052687A1 (de) * 2010-11-26 2012-05-31 GFE Gesellschaft für Fertigungstechnik u. Entwicklung Schmalkalden e.V. Hartstoff-Beschichtung für Maschinenteile und Werkzeuge zum Verschleißschutz und zur Wärmedämmung
BR102015008817B1 (pt) * 2015-04-17 2022-08-30 Mahle International Gmbh Anel de pistão para motores de combustão interna
BR102016015392A2 (pt) * 2016-06-30 2018-01-16 Mahle Metal Leve S.A. Sliding element for internal combustion engines
DE102018216658A1 (de) * 2018-09-27 2020-04-02 MTU Aero Engines AG Verfahren zur Herstellung einer mehrlagigen Erosions- und Korrosionsschutzschicht und Bauteil mit einer entsprechenden Schutzschicht

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