CN112218976A - 金属基底上的硬材料层 - Google Patents

金属基底上的硬材料层 Download PDF

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CN112218976A
CN112218976A CN201980019734.5A CN201980019734A CN112218976A CN 112218976 A CN112218976 A CN 112218976A CN 201980019734 A CN201980019734 A CN 201980019734A CN 112218976 A CN112218976 A CN 112218976A
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hard material
material layer
mass concentration
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power transmission
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B·瓦辛格
M·布格尔
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Evis Engine Systems Co ltd
Iwis Motorsystem GmbH and Co KG
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Abstract

本发明涉及涂覆有硬材料层的用于动力传输的链的链部件，其包括基于钢的基底和在基于钢的基底的外表面上的硬材料层，该硬材料层包含金属氮化物并且硬材料层中的C质量浓度在朝向硬材料层的外表面的方向上降低。

Description

金属基底上的硬材料层
本发明涉及一种生产涂覆有硬材料层的金属部件的方法，该方法包括以下加工步骤：制备脱模剂，将所制备的脱模剂添加到粉末混合物中，制备粉末混合物，制备金属基底，在加热装置中加热该粉末和基底，在基底上沉积一层，该层具有比基底更高的硬度，并冷却基底以及具有硬材料层的金属部件。
技术现状
具有通过链接头彼此连接的链节的链条以各种方式使用。当用作传动链或输送链时，链接头的区域尤其要承受如此大的应力，使得需要耐磨支承表面。特别有利的是，特别是由于工件数量大，用经济的涂覆程序和工艺代替昂贵的解决方案来解决这个问题。
DE 10 2005 047 449 A1提出了一种更加耐磨的连接链，其链销和/或链套筒设有硬材料涂层。这些涂层是通过PVD(PVD：物理气相沉积)施加的。硬材料层的厚度为1至10μm，并且此外可以被减摩擦层例如PTFE覆盖。
文献DE 10 2006 052 869 A1描述了一种连接链，其销和套筒的链接面设有PVD硬材料层。
销和套筒由具有高碳含量且碳含量在0.4wt.％至1.2wt.％之间的钢组成。
DE 10 2011 006 294 A1公开了一种用于生产硬化的涂覆的金属部件的方法。为了富集碳和/或氮含量，对金属部件的表面层进行热处理，然后将其淬火至低于马氏体形成的温度。然后在比随后的涂覆过程发生的温度更高的温度下对金属部件进行退火。涂覆本身通过CVD或PVD方法进行(CVD：化学气相沉积)。
DE 10 2013 222 244 A1描述了一种用于设有减摩擦摩擦涂层的链的链节。通过PVD或PACVD方法施加涂层。
DE 10 2016 215 709 A1示出了链部件，诸如钢套筒、链节、销和线圈，这些链部件均设有减磨CrN层。CrN层是通过CVD程序生产的。在这种情况下，氮是从处理前已被硝化的钢中获得的。
WO 2014019699 A1公开了一种用于滚子或套筒链的接头。硬材料的氮化物或碳化物层通过PVD或CVD程序施加到接头上。
用于生产硬化涂覆的金属部件的上述方法具有缺点。PVD方法需要10-4到10Pa的工作压力，并且根据涂层的性质，在数百℃的温度下运行。因此，PVD程序对涂覆室提出了很高的要求。此外，它们不适用于大体积材料。基底和将要沉积的材料(靶)在涂覆室中在空间上分开。PVD程序是所谓的视线工艺，即仅对目标可见的表面进行涂层。内表面或孔的涂层较薄。另一方面，粉末法存在碳扩散到硬材料层中而导致碳化物形成的问题。但是，由于氮化物，特别是氮化铬，在磨损方面保证了部件的使用寿命大大提高，因此有必要增强氮化物的形成，特别是在表面附近的区域。现有技术中提出的程序决不能满足该要求。
因此本发明的目的是提供一种硬化的氮化物涂覆的金属部件，该部件具有硬材料层的高品质和长寿命并且可以在批量生产过程中简单且经济地制造，这使得可以经济地每单位时间进行大量物品的涂覆。
本发明的目的通过根据权利要求1的装置来实现。
根据用于动力传输的链的本发明的链部件涂覆有硬材料层。链部件具有基于钢的基底以及在基底外部上的硬材料层。将硬材料层制作成包含金属氮化物。根据本发明，在硬材料层中的碳(C)质量浓度降低，特别是朝向硬材料层的外部的方向降低。
借助于CVD涂覆，在基底上沉积了含碳钢的硬层，该层具有高耐磨损性和耐磨性、高硬度和温度稳定性、低摩擦力以及良好的化学性能和低的附着趋势。除了提高耐磨性外，硬材料层还提高了耐腐蚀性。含碳钢可以适合用作基底，因为这些钢具有足够的强度和良好的回火抗性。硬材料层可以由金属和非金属硬材料组成。合适的金属硬材料是过渡金属(例如铬、钨、锆、钛)的所有碳化物、氮化物、碳氮化物、硼化物和硅化物。合适的非金属硬材料是例如金刚石和DLC(类金刚石碳)以及刚玉、碳化硼、立方氮化硼、碳化硅或氮化铝。已经发现金属氮化物形成物，特别是氮化铬(CrN)适合直接涂覆具有高碳含量的钢的基底表面。与其他金属和非金属硬材料相比，氮化铬具有多个优势。氮化铬可以另外通过CVD沉积，并且与基底具有良好的粘附性，从而以至少1至5μm的厚度产生具有高耐磨损性的硬材料薄层。与PVD程序相比，CVD程序在生产硬材料层方面具有优势。与PVD程序相反，CVD程序适用于大体积材料，并在设备技术、维修和工艺技术方面具有经济优势：例如，要涂覆的基底在转鼓中涂覆有含氮粉末。涂覆过程在一定的加工温度和环境压力下进行数小时。基底的所有可及表面(包括狭窄的孔)均被均匀涂覆。在涂覆过程结束时将涂覆的基底冷却。在PVD程序的情况下，基底和待沉积的材料在空间上不利地分开，通过在10-4至10Pa的工作压力下蒸发待沉积的材料来执行涂覆。
形成硬材料层，使其基本上由CrN组成。它在部件表面上具有一个向外的侧面(外表面)，以及与基底接触的一个向内侧面。当使用含碳钢作为基底时，碳在高加工温度下会从钢扩散到硬材料层中并形成CrNC和/或CrC。
有利地形成硬材料层，使得硬材料层的外表面上的C质量浓度小于内部中的C质量浓度。这显然增加了耐磨性，并因此增加了根据本发明的链部件的寿命。此外，硬材料层显然在其外部具有较高的金属氮化物含量，与由金属碳化物制成的硬材料层相比，这导致耐磨性的提高。
在从属权利要求2至15中描述了关于传感装置的本发明的其他实施方式。
在本发明的另一个实施方式中，在硬材料层的外表面处的氮的质量浓度大于碳的质量浓度。在优选的另一实施方式中，氮与碳的质量浓度之比大于3:1，最优选大于5:1。
在本发明的另一实施方式中，在基底附近的区域中的硬材料层中的C质量浓度朝着硬材料层的外侧增加。通过碳向由含碳钢组成的存在的基底的扩散，碳在基底的表面处积聚。因此，硬材料层的C质量浓度在基底表面附近增加。
在本发明的另一实施方式中，C质量浓度在硬材料层中达到最大值。通过碳向由含碳钢组成的基底表面扩散，碳在基底表面处积聚。因此，硬材料层的C质量浓度在基底表面附近最大。
在本发明的另一实施方式中，硬材料层中的C质量浓度的最大值与硬材料层的外表面的距离小于硬材料层中的C质量浓度的最大值与硬材料层和基底之间的边界的距离。通过碳向含由碳钢组成的基底表面扩散，碳在基底表面处积聚。因此，硬材料层中的C质量浓度最大值在基底附近。
在本发明的另一实施方式中，在基底附近的区域中，硬材料层中的C质量浓度增加的量大于在减小的C质量浓度的区域中增加的量。C质量浓度在基底附近的区域急剧上升。因此，硬材料层的大部分碳结合在硬材料层的相当大的深度处。
在本发明的另一个实施方式中，硬材料层中的氮(N)的质量浓度朝着硬材料层的外部增加。因此，硬材料层的外表面比较深的区域具有更高的CrN含量。
在本发明的另一实施方式中，靠近基底的区域中的硬材料层中的N质量浓度的增加大于靠近硬材料层的外表面的区域中的增加。因此，硬材料层的N质量浓度在基底表面附近达到最大值。
在本发明的另一实施方式中，硬材料层中的平均N质量浓度大于硬材料层中的平均C质量浓度。为了获得尽可能均匀的硬材料的CrN层，有利的是可以通过适当的工艺参数(例如，通过基底的硝化和/或使用含氮粉末)来增加N质量浓度。
在本发明的另一实施方式中，硬材料层中的平均N质量浓度是硬材料层中的平均C质量浓度的2倍，优选3倍，特别优选4倍。该实施方式确保了硬材料层主要由CrN组成。
在本发明的另一实施方式中，在每个深度处，硬材料层的表面附近的区域中的平均N质量浓度均大于硬材料层中的平均C质量浓度。在基底附近的硬材料层的更大深度处，由含碳钢组成的基底的碳积聚。这种碳富集导致形成碳化物，主要是铁和铬的碳化物。表面附近的区域的深度为层厚度的50％，优选为层厚度的65％，特别优选为层厚度的80％。
在本发明的另一实施方式中，硬材料层中的铬(Cr)的平均质量浓度大于硬材料层中的铁(Fe)的平均质量浓度。Cr主要通过涂覆工艺(例如在CVD工艺中通过包含Cr、Fe的粉末)内置入硬材料层。存在于硬材料层中的Fe改善了硬材料层对基底的附着性并防止剥落。
在本发明的另一个实施方式中，硬材料层中的平均Cr质量浓度为硬材料层中的平均Fe质量浓度的2倍，优选4倍，特别优选6倍。硬材料层和/或扩散层中的少量Fe足以改善硬材料层对基底的附着力。
在本发明的另一实施方式中，在每个深度处，硬材料层的表面附近的区域中的平均Cr质量浓度均大于硬材料层中的平均Fe质量浓度。在硬材料层的基底附近更深处，由钢组成的基底中的Fe含量增加。表面附近的区域的深度最高达层厚度的50％，优选层厚度的65％，特别优选层厚度的80％。
在附图中以示意性简化的方式示出了根据本发明的传感器和本发明的方法的示例性实施方式，并且在随后的描述中对其进行更详细的描述。
附图示出：
图1具有涂有硬材料的部件的链
图2样品1的元素Fe、Cr、N和C的深度分布分析
图3样品2的元素Fe、Cr、N和C的深度分布分析
图1示出了链10的两个链节，其例如可以用在链传动中。链10构造为具有分别通过链节互连的内链节和外链节的套筒链。内链节由平行布置的两个相应的内链板13和将内链板13彼此连接的两个套筒12组成，其中套筒12垂直于链板13。
外链节14由两个平行的外链板14组成，外链板通过两个销11彼此连接，并且销11设置在内链节13的套筒12中，以便它们可旋转。外链节14通过销11以可旋转的方式固定到相邻的内链节13上，并且通过外链板14将内链节13与第二内链节13连接，外链板14平行于内链板13布置。外链节14的销11以可旋转的方式设置在内链节13的套筒12中，每个连接构成链10的链节。链10的销11完全由含碳钢组成，销11的接合表面设有通过CVD工艺沉积的硬材料的CrN层。套筒12可以替代地或附加地也由含碳材料制成并且可以在其接合表面和/或支承表面上设有硬材料的CVD层。
下面给出了根据本发明的分别通过CVD工艺涂覆有硬材料层的两个不同链部件的两种浓度分布。样本是由氮化钢40CrMoV13-9制成的销11。这些层由铬氮化物和碳化物组成，层厚度为约10μm。通过辉光放电光发射光谱法(GD-OES)确定两个样品的浓度分布。此程序将金属样品用作DC等离子体中的阴极。从表面开始，通过用氩离子进行阴极溅射将样品从表面稳定地逐层移出。移出的原子通过扩散进入等离子体。在通过碰撞过程激发后，它们发出具有特征波长的光子，该光子由连接的光谱仪记录下来，然后进行量化。
图2示出了样品1的浓度分布。在分离过程中，首先将样品从0加热到960℃约1小时。保持时间为6小时，然后将样品缓慢冷却至200℃(约10小时)。在该过程中用氮气冲洗反应器。为了更好的可视化，水平轴以对数标度示出深度。垂直轴示出质量浓度，出于清楚的原因，也具有相对标度。垂直轴上的100％对应于元素Fe和Cr的100％质量浓度，20％N以及5％C。
在0至7.5μm范围内的Fe质量浓度始终接近于0％。自8μm时起，Fe的质量浓度上升至5％。在深度大于10μm的区域内，Fe质量浓度陡增至最高至深度27μm的90％。自深度大于27μm时起，Fe质量浓度以较低的梯度不断上升至50μm处的92％。
Cr质量浓度在0到7.5μm范围内从0μm处的86％不断增加到7.5μm处的88％。自深度7.5μm时起，Cr质量浓度急剧下降到10％的值，直到达到25μm的深度为止。自深度25μm时起，Cr质量浓度下降到50μm处的5％的值。
N质量浓度在0μm处为10.8％，并在7.5μm处降至6％。质量浓度的降低不是恒定的；在2.5μm的深度处观察到N质量浓度增加到9.4％。自深度7.5μm时起，N质量浓度急剧增加至在10μm处的最大值15.6％。在13μm的深度处，N质量浓度急剧下降至在25μm处的2％的值。因此，该层的厚度为约13μm。
C质量浓度在0μm处具有0.75％的值，并且增加至在2.5μm处的1.25％的值。自深度2.5μm时起，C质量浓度急剧增加至在8μm处的最大值2.75％。自深度8μm时起，C质量浓度急剧下降至在25μm处的0.5％的值。
对碳和氮的质量浓度变化的分析表明，硬材料层表面处的氮的质量浓度大于碳的质量浓度。该比率是大约14:1，因此大于10:1。
图3示出了样品2的浓度分布，其中在硬材料层中构建了基本上由CrC组成的中间层。在分离过程中，首先将样品加热到950℃约45分钟。保持时间为7小时，然后将样品缓慢冷却至200℃(约10小时)。在该过程中用氮气冲洗反应器。如图2所示，水平轴也以对数标度显示深度。垂直轴以相对标度显示质量浓度。垂直轴上的100％对应于元素Fe和Cr的100％质量浓度，20％N以及5％C。
Fe质量浓度在0至3μm的范围内恒定为0％。自3μm起，Fe质量浓度增加至5％。在深于8μm的区域中，Fe质量浓度陡增至27μm处的88％。自深度大于27μm时起，Fe质量浓度以低梯度不断增加到在50μm处的90％。
Cr质量浓度在0μm深度处为81％，然后在2μm深度处下降至78％的值。自2μm的深度起，Cr质量浓度增加到在3μm的深度处的最大值85％。自3μm的深度起，Cr质量浓度下降至在9μm的深度处的75％。自9μm的深度起，Cr质量浓度急剧下降至在25μm的深度处的5％。
N质量浓度在0μm处为9.8％的值，并在7.5μm处降至6％的值。质量浓度的降低不是恒定的；在2.5μm的深度处观察到N质量浓度增加到9.4％。自7.5μm的深度时起，N质量浓度急剧增加至在10μm处的最大值15.6％。在12μm的深度处，N质量浓度急剧下降至在25μm处的2％。因此，该层的厚度为约12μm。
C质量浓度在0μm的深度处为2.5％，在2μm处增加至2.6％。自2μm的深度时起，C质量浓度急剧增加至4μm处的最大值3.75％。自4μm的深度时起，C质量浓度急剧下降至15μm处的0.35％。
对碳和氮的质量浓度变化的分析表明，硬材料层表面上的氮的质量浓度大于碳的质量浓度。该比率为约4:1。
参考符号列表
1 脱模剂
2 活化剂
3 金属
4 金属氮化物
5 大体积材料
6 硬材料层
10 链
11 销
12 套筒
13 内链板
14 外链板
M 金属
N 氮

Claims (16)

1.涂覆有硬材料层的用于动力传输的链的链部件，具有
·基于钢的基底
·在所述基于钢的基底的外表面上的硬材料层，所述硬材料层包含金属氮化物，
其特征在于
所述硬材料层中的C质量浓度朝着所述硬材料层的外部降低。
2.根据权利要求1所述的涂覆有硬材料层的用于动力传输的链的链部件，
其特征在于
在靠近所述基底的区域中的所述硬材料层中的C质量浓度在位于内侧的所述硬材料层的一侧的方向上增加。
3.根据权利要求1或2所述的涂覆有硬材料层的用于动力传输的链的链部件，
其特征在于
所述硬材料层中的所述C质量浓度在所述硬材料层中具有局部最大值。
4.根据权利要求3所述的涂覆有硬材料层的用于动力传输的链的链部件，
其特征在于
所述硬材料层中的所述C质量浓度的最大值与所述硬材料层的外部的距离小于所述硬材料层中的所述C质量浓度的最大值与所述硬材料层和所述基底之间的边界的距离。
5.根据权利要求2至4中一项或多项所述的涂覆有硬材料层的用于动力传输的链的链部件，
其特征在于
所述硬材料层中的C质量浓度在所述基底附近的区域中的增加的幅度高于C质量浓度降低的区域中增加的幅度。
6.根据权利要求1至5中一项或多项所述的涂覆有硬材料层的用于动力传输的链的链部件，
其特征在于
所述硬材料层中的N质量浓度在所述硬材料层的外侧的方向上增加。
7.根据权利要求6所述的涂覆有硬材料层的用于动力传输的链的链部件，
其特征在于
在靠近所述基底的区域中的所述硬材料层中的N质量浓度的增加大于在靠近所述硬材料层的外侧的区域中的增加。
8.根据权利要求1至7中一项或多项所述的涂覆有硬材料层的用于动力传输的链的链部件，
其特征在于
所述硬材料层中的平均N质量浓度大于所述硬材料层中的平均C质量浓度。
9.根据权利要求8所述的涂覆有硬材料层的用于动力传输的链的链部件，
其特征在于
所述硬材料层中的平均N质量浓度是所述硬材料层中的平均C质量浓度的2倍，优选3倍，特别优选4倍。
10.根据权利要求1至9中一项或多项所述的涂覆有硬材料层的用于动力传输的链的链部件，
其特征在于
沉积在所述硬材料层表面附近的区域中的每层中的平均C质量浓度小于20wt.％，优选小于10wt.％，特别是小于5wt.％，所述表面附近的区域的厚度为所述硬材料层的总厚度的80％，优选为所述硬材料层的总厚度的90％，特别优选为所述硬材料层的总厚度的95％。
11.根据权利要求1至10中一项或多项所述的涂覆有硬材料层的用于动力传输的链的链部件，
其特征在于
所述硬材料层中的平均Cr质量浓度大于所述硬材料层中的平均Fe质量浓度。
12.根据权利要求11所述的涂覆有硬材料层的用于动力传输的链的链部件，
其特征在于
所述硬材料层中的平均Cr质量浓度为所述硬材料层中的平均Fe质量浓度的2倍，优选4倍，特别优选6倍。
13.根据权利要求1至12中一项或多项所述的涂覆有硬材料层的用于动力传输的链的链部件，
其特征在于
在所述硬材料层表面附近的区域中的平均N质量浓度在各处都比所述硬材料层中的平均C质量浓度大。
14.根据权利要求1至13中一项或多项所述的涂覆有硬材料层的用于动力传输的链的链部件，
其特征在于
在所述硬材料层表面附近的区域中的平均Cr质量浓度在各处都比所述硬材料层中的平均Fe质量浓度大。
15.根据权利要求13和/或14所述的涂覆有硬材料层的用于动力传输的链的链部件，
其特征在于
所述硬材料层的表面附近的区域的厚度为所述硬材料层的总厚度的50％，优选厚度为所述硬材料层的总厚度的65％，特别优选厚度为所述硬材料层的总厚度的80％。
16.根据权利要求1至15中一项或多项所述的涂覆有硬材料层的用于动力传输的链的链部件，
其特征在于
在所述硬材料层的表面处的N质量浓度大于在所述硬材料层的外表面处的C质量浓度。
CN201980019734.5A 2018-02-14 2019-02-14 金属基底上的硬材料层 Pending CN112218976A (zh)

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