CN1191387C - 具有梯度组成的耐磨氮化铬镀层 - Google Patents

具有梯度组成的耐磨氮化铬镀层 Download PDF

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CN1191387C
CN1191387C CN94113832.1A CN94113832A CN1191387C CN 1191387 C CN1191387 C CN 1191387C CN 94113832 A CN94113832 A CN 94113832A CN 1191387 C CN1191387 C CN 1191387C
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coating
chromium
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nitrogen
wear resistance
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大矢正规
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Riken Corp
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Abstract

在滑动部件的滑动基材表面制成包括铬和氮的镀层。该镀层的铬浓度沿垂直方向由该基材表面至所述镀层表面连续且逐渐地增加。获得的镀层具有良好的耐磨性和初始适应性。

Description

具有梯度组成的耐磨氮化铬镀层
本发明涉及在滑动零件例如活塞环(piston ring)中的滑动基材的表面制成的具有良好的耐磨性、良好的加工适应性和良好的初始适应性的镀层。
作为要获得滑动零件例如用于内燃机的活塞环所必需的耐磨性而进行的典型的镀敷处理，由于需要高发动机功率、高发动机性能及排气调节，使活塞环所必需的性能变得更为严格，用镀铬法这种在先技术难以获得令人满意的耐热、耐磨和耐粘附性能。
有人提出表面处理例如镀复合材料、火焰喷涂工艺及氮化来改善这些问题。近年来，已开发出离子镀敷层(ion-plating coating)，并将其应用于例如活塞环的外滑动表面。其中的氮化铬镀层是通过使氮和铬以气相形式反应来制备的活塞环，其花费非常有效，并具有显著的耐磨性和耐粘附特性。然而，该镀层是陶瓷覆层(ceramiccoating)，并且若覆层与使用活塞环的气缸的材料的硬度差异大，则在开始操作后的老化期间由于气缸受损而产生强烈的漏气现象。正如所述，该活塞环本身的磨损较小。然而，由于在某些情况下会产生气缸磨损，因而人们认为无法获得具有令人满意的特性的环。因此，已能在陶瓷覆层的最外表面形成一软镀层例如镀锡或镀复合材料例如Cr-N和Ti-N镀层。但存在诸如昂贵和粘附性差的问题。
为解决上述问题，本发明的目的是提供用于滑动零件的表面的镀层，该镀层具有令人满意的耐磨性和初始适应性，并可用于滑动零件例如活塞环。该镀层使这样的零件能够在内燃机中的严酷条件下使用，在内燃机中，由于排气调节和大功率输出，热负荷很大。
在第一个实施方案中，本发明提供一种在可滑动部件的基材的表面形成的由铬和氮构成的镀层，其特征在于在与所述基材的表面接触的所述镀层的一部分是氮化铬，并且所述镀层中铬含量在与所述基材的表面垂直的方向上由所述氮化铬向所述镀层的表面连续增加。
在第二个实施方案中，与该基材的表面接触的氮化铬可以以恒定的铬含量存在于该镀层的部分厚度中。
在第三个实施方案中，所述镀层还包括中间层，其特征在于与基材的表面接触的该中间层的一部分是铬，而且所述中间层中的铬含量在与该基材的表面垂直的方向上由所述铬向所述氮化铬连续降低。
用来形成按照本发明的镀层的离子镀敷设备大致如图1所示。
由本发明获得的用于实施例的线性分析的镀层的剖面见图2所示。
图2中的镀层的线性分析结果见图3。
通过在各氮分压下离子镀敷制成的镀层的磨损试验的结果见图4。
本发明镀层中的硬度分布见图5所示。
本发明镀层老化后，在外表面中包括软氮化铬或铬，具有良好的适应性，并包括具有良好的耐磨性能的与该基材表面邻接的硬氮化铬。当用于活塞环时，滑动配合件例如气缸不会被损害，该陶瓷氮化铬的特性得以利用。但当该陶瓷接触在基材和镀层之间的界面的金属时，可能存在该镀层的粘附问题。在这样的情况下，按照本发明，不在该基材界面制备具有良好的耐磨性能的氮化铬，而是先在该基材表面制成中间层，然后形成具有梯度组成的氮化铬层。在该中间层中，与所述基材的表面接触的所述中间层的一部分是铬，不含氮，而且所述中间层中的氮含量在与所述基材的表面垂直的方向上由所述铬向所述具有梯度组成的氮化铬层连续增加。由于该铬层的热胀系数几乎不含氮的铬层与该基材的相同，因此该铬层几乎不受热应力的影响而牢固地粘附在所述基材上。此外，由于该镀层较软，可将其用作在严酷条件下工作的滑动零件的滑动表面。
用以下实施例具体解释本发明。
所用的离子镀敷设备见图1。将固定在基材架2上的基材1用加热器3加热，并将基材1用热调节器(未在图中示出)维持在指定的温度。将水冷却的钢坩埚6置于容器9中的基材1的下方，在钢坩埚6中的金属5被用作汽化源。管道11将氮气引入容器9中。用来使金属5汽化的电子枪8被置于容器9的侧壁中。聚焦线圈7位于坩埚6的周围以使电子由电子枪8射向待汽化的金属5。容器9中的压力用真空泵(未示出)来降低。挡板10位于坩埚6和基材架2之间。在将SUS 440C不锈钢板(尺寸为50×50×10mm)作为基材放入该设备中并使容器9成为真空后，将氩气从管道11引入容器9，并将容器9的压力减至1×10-1乇。然后将基材1的表面通过用基材1作阴极放电来清洁。然后将该基材加热至400℃并将容器9的压力减至5×10-5乇。此后，将金属铬5通过使电子束由电子枪8射向置于坩埚6中的金属铬5而汽化。通过由引入管道11引入氮气使容器9中氮分压达到2×10-3乇，并通过打开挡板10进行汽相淀积。将这样的条件维持2分钟。将氮气用20分钟时间连续降至1×10-4乇，其中氮的分压为零，并将这样的分压维持2分钟。将挡板关闭。此后，将在表面形成汽相淀积镀层的基材1从容器9中取出。然后用如此形成的汽相淀积镀层进行下列试验。
(1)用X射线微量分析仪分析氮和铬含量的变异
为检测镀层中铬和氮的含量即量的平均变异，将样品沿与该表面垂直的方向切割并由表至里进行线性分析(图2和图3)。镀层中铬的含量在与基材接触的内区中较低，而在靠近该表面的区域较高。而且，镀层中氮的含量在与基材接触的内区中最高，而在靠近该表面的区域较低。
(2)用X射线衍射法分析最外表面的组成
根据X射线衍射结果和ASTM卡片的分析得出结论：在该汽相淀积镀层的最外表面的组成是Cr+Cr2N。
(3)用X射线衍射法分析剖面组成
如上所述，本发明镀层的化学组成由内部向表面连续变化。因此预计，该镀层的相构成(phase constituting)的形式必然是由内向表面变化。为检测镀层的相构成，用由在0.3-2.0×10-3乇范围内的固定氮分压制成的镀层进行X射线衍射分析(所用的条件除氮分压外均与上述试验的相同)。分析结果见表1。
                            表 1
  样品  氮分压   镀层组成   镀层剖面的硬度
    A  2.0×10-3乇   CrN，Cr2N     Hv 1895
    B  1.5×10-3乇   CrN，Cr2N     Hv 1832
    C  1.0×10-3乇   Cr2N     Hv 1722
    D  0.7×10-3乇   Cr，Cr2N     Hv 1507
    E  0.3×10-3乇   Cr     Hv 1291
本发明镀层在下述条件下形成：其中开始时氮分压为2×10-3乇，然后逐渐降低，包含氮化铬和铬的汽相淀积层在仅含有氮化铬的汽相淀积层上形成，再在其上形成单纯的铬层。由该表得出结论：铬浓度由该镀层的内部至表面连续增加。该分析与上述的X射线微量分析仪的线性分析结果一致。
(4)镀层剖面的硬度分析
本发明镀层的剖面的硬度分布见图5。在上述实施例中的镀层的A至E剖面的硬度见表1。经鉴定，该硬度由基材至表面层逐渐降低，还鉴定出，镀层的硬度从内至表面连续降低而且镀层逐渐变软，因为该硬度大致与表1中所示的样品A至E的硬度一致。
(5)磨损试验
用pH2.5的硫酸作润滑剂并用FC-25材料(按照JIS具有25kgf/cm3抗张强度的生铁)作配合的气缸在下列条件下进行磨损试验：负荷2kg，磨擦速度为0.2m/秒，使用纹钉滚筒设备(pin drum apparatus)，其中将在上述X射线衍射分析中所用的样品用作纹钉。关于对比试验，用具有硬镀铬的纹钉进行同样的试验。试验结果见图4。
可以理解的是，若与硬镀铬层相比，本发明镀层在离开镀层表面的区域具有良好的耐磨性。而且，与样品A和C相比，当氮分压如同样品E的情况一样变低时，可以断定，自磨损变大，而配合的气缸的磨损量变小。对于样品A和C来说，自磨损变得较小，但与E相比，气缸的磨损较大。因此，若将本发明用于活塞环和其它的滑动零件，可以认为，镀层形成，其中，配合的材料不受损害，并且在老化后，由于具有较小自磨损的A和C的镀层而保持了耐磨性，但当形成其组成不是逐渐变化而是突变的镀层时(例如E层突然在A层上形成)，硬度变异变大，且该配合件的磨损增加。
在滑动零件或组件的滑动基材表面制成的包含铬和氮的本发明镀层中，铬的浓度由该基材表面沿垂直的方向逐渐增加，且该镀层的表面由铬制成。这样，配合的材料就不会被磨损，由于该镀层里面的硬氮化物而使该镀层本身具有良好的耐磨性。当用于需要高电动机性能的滑动零件例如活塞环时，能获得具有良好耐磨性和良好的初始适应性的镀层。

Claims (2)

1.一种在可滑动部件的基材的表面形成的含铬和氮的耐磨镀层，其特征在于在与所述基材的表面接触的所述镀层部分是氮化铬，并且所述镀层中铬含量在与所述基材的表面垂直的方向上由所述氮化铬向所述镀层的表面连续增加。
2.根据权利要求1的耐磨镀层，其表面主要由铬组成。
CN94113832.1A 1994-10-27 1994-11-10 具有梯度组成的耐磨氮化铬镀层 Expired - Fee Related CN1191387C (zh)

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