CN103547707B - 具有dlc涂层的零件和应用dlc涂层的方法 - Google Patents
具有dlc涂层的零件和应用dlc涂层的方法 Download PDFInfo
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Abstract
本发明涉及一种零件,该零件具有呈WC-C组成梯度、没有含金属的底漆且没有离子植入层的层和在划痕测试中具有粘合行为特征的DLC表面层。
Description
技术领域
本发明涉及DLC(类金刚石碳)涂层的技术领域,且尤其是用于摩擦零件的DLC涂层的技术领域。
本发明在降低如活塞杆、凸轮轴、气门挺杆、气缸、活塞环等以及更普遍地在负载下的摩擦的情况下的摩擦系数方面具有格外有利的应用。为了降低这种摩擦,本领域技术人员完全意识到可以应用DLC涂层到所述的零件。
本发明也可以具有在对由涂层提供的表面具有黑色存在需求方面的应用,这种应用不涉及任何降低摩擦的企图。
背景技术
本领域技术人员通常也已知部件上的DLC膜的低粘附在某些应用中能够带来实际的问题。为了改善粘附的一种技术方案包括使用基于例如硅或铬的含金属的粘附层。已经提出各种技术方案。
例如文件WO2011/018252描述了具有由粘附层、含金属的DLC涂层和无金属的DLC涂层组成的涂层的摩擦零件。粘附层优选为具有1μm最大厚度的铬涂层,而含金属的DLC涂层优选为由WCC碳化钨组成。各层和涂层的厚度比被限制在一定的数值范围,以便在这些范围外,如果DLC厚度太小,部件的使用寿命将被缩短,而如果DLC厚度太大,部件将呈现过早剥离或剥落的风险。
文件WO0179585公开了具有粘附层、过渡层和类金刚石碳层的多层系统。粘附层包括在第4、第5或第6副族元素和硅,而过渡层包括碳和在第4、第5或第6副族和硅中的至少一种元素。上层主要由类金刚石碳组成。该系统具有至少15GPa的硬度和至少HF3的粘附强度。
一般而言,观察到DLC膜与DLC膜中的内应力相关的此底漆分层并且这种分层增加这样的膜的厚度。在单独的步骤中形成此粘附的底漆也是明显的并且这增加了方法的成本并使这种方法更复杂。
发明内容
本发明自身设定了以简单的、可靠的、有效的和高效的方式克服这些缺点的目的。
本发明拟解决的问题是生产不使用基于现有技术教导的含金属的粘附底漆(例如硅或铬)的具有改善的粘附的DLC膜。
为了解决上述的问题,设计和完善了具有呈WC-C组成梯度且没有含金属的底漆的层和在划痕测试中具有粘合行为特征的DLC表面层的金属零件。
为了解决上述的问题,设计和完善了金属零件,所述金属零件具有呈WC-C组成梯度、没有含金属的底漆且没有离子植入层的层和在划痕测试中具有粘合行为特征的DLC表面层。
通过一种方法有利地解决指出的问题,其中:
-微波蚀刻零件;
-使零件承受WC-C组成梯度层;
-使用微波等离子体应用DLC涂层到WC-C涂层;
微波蚀刻可以比通过调节离子流使用二极管蚀刻获得更有效的蚀刻(不管待处理零件的几何形状)。也可以在低回火温度下蚀刻零件而不会使它们变劣。还观察到与传统的DLC涂层相比,使用微波DLC涂层可以使应用工艺时间降低大致50%。
有利地,产生氩等离子体,以便获得压力范围从0.05到0.5Pa的蚀刻。
根据另一方面,通过使用磁控管PVD技术产生WC-C组成梯度层。开始用第一纯WC层,接着是烃气例如C2H2的上升(rampe),最后是WC-C层。对于大多数应用,WC-C组成梯度层的厚度是0.3到10μm以及有利地为0.8μm,除了需要更大的厚度例如活塞环的那些应用之外。
根据另一方面,DLC涂层具有1到20μm的厚度。
本发明也涉及具有应用到微波蚀刻的零件所具有的WC-C组成梯度层上的DLC涂层的摩擦零件。
本发明还涉及使用前述的方法唯一获得的覆盖有DLC涂层的零件,其特征在于没有含金属的底漆和没有离子植入层并且具有WC-C组成梯度。
附图说明
下面参照附图更详细地解释本发明,其中:
图1为使用划痕测试方法的涂层的断裂轮廓的视图。
图2为在粘附剥落的情况下沿图1中的线A-A的横截面图。
图3为在粘合剥落的情况下沿图1中的线A-A的横截面图。
图4为在粘合/粘附剥落的情况下沿图1中的线A-A的横截面图。
具体实施方式
如上所述,现有技术描述了DLC涂层,其包括,在任何情况下,由例如纯Cr组成的粘附底漆,接着是基于碳化钨的层,其中碳含量逐渐增加直到获得具有确保没有掺杂金属的沉积的DLC粘附的目的的钨掺杂的DLC层。
在本发明的内容中,进行了测试以便比较通过产生具有一个或多个粘附底漆的DLC涂层和根据本发明各方面的没有使用粘附层的DLC涂层获得的结果。
沉积在含金属的衬底上的材料在之前已被离子蚀刻以便消除任何表面氧化物而增强涂层的粘附。本领域技术人员熟悉各种离子蚀刻技术,即,主要是二极管蚀刻、三极管等离子体蚀刻和ECR微波蚀刻。
二极管蚀刻涉及在氩气气氛中在1-10Pa的压力下施加几百伏的负电压(<-500V)到衬底。在这些条件下,零件周围发光放电并且等离子体中的正氩离子轰击衬底的表面,这允许表面溅射并且消除氧化物。
使用三极管等离子体技术,通过等离子体放大器在低压(0.1到1Pa)下产生密集的氩等离子体。正氩离子通过使衬底负偏压来加速并且它们蚀刻表面。关于这种类型的方法,负压必须在-250V到-500V之间以实现最大蚀刻效率。
ECR微波蚀刻使得可以在0.05到0.5Pa的压力范围内产生氩等离子体。通过最好是-50V到-250V的负压使零件偏压。
这些蚀刻技术中的每一种被用于这些测试。蚀刻之后,通过磁控管阴极溅射在一些测试试样上产生纯铬粘附底漆以获得大约0.1到0.2μm的铬厚度。然后通过磁控管阴极溅射在所有测试试样上沉积碳化钨,逐渐增加烃流量,使得可以使沉积的碳富集成超过50%的原子浓度,以便实现最终DLC涂层的粘附。含钨层具有大约0.5μm的厚度并且DLC是大约2μm厚,除了实施例9和10的含钨层的厚度被增加到1.5μm之外。
下表概括了测试条件。
蚀刻技术 | Cr粘附层的存在 |
二极管 | 是 |
二极管 | 否 |
三极管 | 是 |
三极管 | 否 |
ECR | 是 |
ECR | 否 |
以涂层的粘附来表征所有涂层。使用划痕测试方法。提醒读者的是这种方法涉及用例如那些用于HRC压痕测试的金刚石来划刻沉积的材料的表面。在测试试样以恒定速度在金刚石下面移动时施加逐渐增加的负载。这使得可以获得负载增加的划痕(图1),基于此可以确定剥落力(临界负载)以及剥落模式。剥落模式显示在涂层中破裂的位置。有两种主要类型的剥落:
-粘附剥落(图2)
-粘合剥落(图3)
存在兼具粘附断裂和粘合断裂的混合模式,这被称为粘合/粘附(图4)。
粘附剥落相当于裂纹沿着一个界面扩展并且因此平行于零件的表面,而粘合剥落以相对于界面的斜角穿过涂层扩展。粘附剥落的特征是缺乏涂层的粘附。当应力超过构成涂层的材料的断裂极限(机械强度)时发生粘合剥落。
在粘附面的情况下,临界负载表征粘附力。
在粘合断裂的情况下,表征涂层的断裂强度,而不是它的粘附。临界负载不仅是沉积的材料的特征,也是它的厚度和衬底硬度的特征。
使用第二种方法评估粘附。它涉及通过在2kg的负载下使用维氏(Vickers)金刚石压印沉积的材料。
下表概括了一系列实验,包括在实施例9和10的情况下,在由工具钢(硬度64HRC)制得的衬底上由没有铬底漆的2.5μm总沉积厚度和具有2.7μm铬底漆和3.5μm总厚度获得的划痕测试的结果。实施例11和12具有厚的堆,这证明本发明的稳固。实施例11包括4μm厚的基于钨的层,在其上沉积了8μm厚的DLC。在实施例12的情形中,钨层的厚度被增加到9.7μm并且DLC表面层的厚度被增加到19.2μm。
C=粘合
A=粘附
CA=粘合/粘附
NTR=没有沉积的材料脱离
上表显示,在二极管蚀刻的情况下以及根据现有技术的蚀刻,铬底漆使得可以获得强的粘附(实施例1)以及,在没有铬底漆的情况下,在WC和钢(实施例2)之间的界面出现断裂。
使用三极管蚀刻技术导致当划刻没有铬底漆的沉积的材料(实施例4和5)时沉积的材料的行为改变。与二极管蚀刻(实施例2)相比临界负载增加和剥落模式改变(实施例4和5)。
观察到的薄片显示中间的剥落模式。
根据本发明,使用ECR微波蚀刻技术证明了没有铬底漆可以获得非常类似于现有技术的机械行为(实施例8)。注意,与三极管蚀刻技术一样,降低压力导致提高的划痕测试性能(实施例7和8)。
实施例9和10显示如临界负载值所证明的,通过含钨底漆的厚度增强了对粘合剥落的抵抗力。在两个实施例中,碳化钨和梯度层的厚度为1.5μm。更具体地,在实施例9中,碳化钨的厚度被增加到1μm,该厚度相当于碳浓度梯度为0.5μm。在实施例10中,碳化钨厚度为0.2μm,然而碳浓度梯度层被增加到1.3μm。
实施例11和12说明方法的稳固。已知沉积在真空中的薄硬层的厚度的增加导致它们内部压应力的增大。然而,在划痕测试期间的行为保持粘合并且临界负载的增加是基于钨的层的厚度增加的结果。
在上述蚀刻技术中,结果趋向于显示当减小蚀刻压力时产生的没有铬底漆的层的粘附改进。在蚀刻过程中压力降低取决于实际技术本身。二极管技术通常在压力低至0.5Pa时不能产生等离子体。
因此,根据本发明,使用适当的蚀刻技术使得可以降低氩气压力并且产生没有铬底漆的DLC型粘附堆-得到了与本领域技术人员和先前的技术方案所普遍认为的事实完全不同的结果。
根据本发明的方法具有很多优势:
除了简化所需的装置和降低它的成本,消除粘附底漆还消除了一个界面并且因此改善涂层的可靠性和稳固性。
正如进行的测试所揭示的,也很明显的是,铬底漆趋向于掩饰某种类型的蚀刻的缺陷,与碳化钨形成对比,碳化钨似乎需要更有效蚀刻,以便就粘附而言表现得与沉积有铬底漆的材料一样好。
使用2kg负载的维氏压印也未能揭示沉积的材料的各种类型的粘附的任何不同。尽管施加的负载是2kg(20N),但是通过维氏金刚石引起的变形不足以引起沉积的材料的分离,如实施例2中的,其中通过划痕测试方法还是证明了粘附是有缺陷的。
Claims (10)
1.金属零件,所述金属零件具有呈WC-C组成梯度、没有含金属的底漆且没有离子植入层的层和在划痕测试中具有粘合行为特征的DLC表面层。
2.根据权利要求1所述的零件,覆盖有DLC涂层,所述DLC涂层被应用到微波蚀刻的零件所具有的WC-C组成梯度层。
3.应用DLC涂层到金属零件的方法,其特征在于所述方法包括以下步骤:
-微波蚀刻所述零件,
-使所述零件承受WC-C组成梯度层,
-使用微波等离子体应用所述DLC涂层到所述WC-C组成梯度层。
4.根据权利要求3所述的方法,其特征在于产生氩等离子体,以便在0.05到0.5Pa的压力范围内蚀刻。
5.根据权利要求3所述的方法,其特征在于通过磁控管PVD产生所述WC-C组成梯度层。
6.根据权利要求5所述的方法,其特征在于开始用第一纯WC层,接着是烃流量上升,最后是WC-C层。
7.根据权利要求5或6所述的方法,其特征在于所述WC-C组成梯度层的厚度为0.3到10μm。
8.根据权利要求7所述的方法,其特征在于所述WC-C组成梯度层的厚度为0.8μm。
9.根据权利要求3所述的方法,其特征在于所述DLC涂层具有1到20μm的厚度。
10.使用权利要求3-9中任一项所述的方法唯一获得的覆盖有DLC涂层的零件,其特征在于没有含金属的底漆和没有离子植入层并且具有WC-C组成梯度。
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