CN102341527A - 多层涂层 - Google Patents
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Abstract
本发明提供了涂层和在基材上形成所述涂层的方法。所述涂层设置有至少一个陶瓷材料层和至少一个金属材料层。所使用的材料中的至少一种是形状记忆合金,以在所述涂层中提供弹性,从而使所述涂层的任何变形都能够基本恢复。
Description
本发明涉及形成涂层的方法和所述涂层本身。现有涂层的问题在于虽然可以将它们形成以具有特定的性能,但是这可能不利于该涂层的其它性质,因此这将该涂层的用途限制在特定用途。
从美国专利4554201、4895770、4904542和5656364已知在基材上制备多层耐磨涂层,其中所述多层体系耐受与金属切割相关的磨损(US4554201和US 4895770)、耐受滑动磨损或侵蚀(US 4904542、US 5656364)。
从美国专利(US 5656364)和欧洲专利(EP0366289A、EP0289173A)已知使用金属材料和金属材料的氮化物、碳化物或氧化物材料的交替涂层在基材表面上制备多层耐磨涂层。特别在专利EP02089173A中,所述多层由钛和氮化钛构成。在专利US 4904542中,所述多层由钛、锆、铪或钽与所选材料的氮化物构成。在专利US 5656364中,所述多层由二硼化钛和具有高弹性模量的金属材料,如基于钨的合金构成。专利US 5656364排除使用低弹性模量材料如铝和钛用于其中所公开的耐侵蚀多层涂层体系中。
本发明的目的是提供弹性涂层,其特征在于所述涂层的变形基本恢复,并得到相对耐磨的性质。
本发明的第一方面提供了用于基材表面的耐磨涂层,所述涂层具有至少一个金属材料层和至少一个陶瓷材料层,并且其具有充分的弹性以耐冲击、侵蚀和/或循环负载磨损过程。
在一个实施方案中,所述涂层由多个金属材料层和陶瓷材料层构成。在一个实施方案中,所述涂层由至少四个层组成。通常所述陶瓷层与所述金属材料层交替。
在一个实施方案中,至少一个所述金属层由“形状记忆合金”形成,所述“形状记忆合金”通常提供所需的弹性性能。
在一个实施方案中,所述陶瓷层是第4、5或6族金属和/或铝或硅的硼化物、碳化物、氮化物或氧化物中的任意一种或任意组合。根据本发明的一个形式,提供了具有合金层和至少一个由硼化物、碳化物、氮化物或氧化物形成的陶瓷层的涂层。
通常,所述金属层包含NiTi合金和/或选自镍、钛、铬、铝、铂、铪、锆、钴、铜和/或钇元素以提供形状记忆合金性质,并且优选提供超弹性性能。
在一个实施方案中,在一定温度下沉积多层涂层以辅助所述“形状记忆合金”层的重结晶。
通常使用的陶瓷是所述“形状记忆合金”材料中包含的合金元素之一的硼化物、碳化物、氮化物或氧化物,以确保在各层之间良好的化学粘接。
在一个实施方案中,沉积界面陶瓷层。在一个实施方案中,所述界面层是所述“形状记忆合金”材料中包含的合金元素之一的硼化物、碳化物、氮化物或氧化物。
通常,所述陶瓷层的厚度在0.1-5.0μm的范围内,优选0.3-3.0μm。
在一个实施方案中,所述陶瓷层厚度小于如下定义的陶瓷脆性断裂的临界厚度:
其中E是陶瓷的弹性模量,γS是陶瓷的断裂表面能,σ是因冲击负载而在陶瓷层中产生的最大拉伸应力,以及f是与接触几何形状相关的几何因子,通常对于模量为300GPa的1μm厚度陶瓷层为16。
在一个实施方案中,所述陶瓷层本身是多个层,并且各层可以具有不同的具有不同的陶瓷组成,从而所述陶瓷层显示出超晶格结构,这改善了硬度和耐断裂性。
在本发明的另一个实施方案中,提供了在基材上形成弹性涂层的方法,所述方法包括涂覆多个陶瓷材料层和多个金属材料层的步骤,并且其中在形成所述涂层时,所述陶瓷材料层与金属材料层交替。
在一个实施方案中,至少一个所述金属层由形状记忆合金形成。
在一个实施方案中,使用溅射方法提供所述陶瓷层,并且优选使用闭合场非平衡磁控溅射离子镀(CFUBMSIP)以改善所述陶瓷层的粘合性和结构/性质。
在一个实施方案中,使用溅射方法以涂覆所述金属层,并且优选使用闭合场非平衡磁控溅射离子镀(CFUBMSIP)以改善所述金属层的结构/性质。
在一个实施方案中,通过粘合层将第一陶瓷层粘接在基材上,所述粘合层不是“形状记忆合金”,而是特别选择的金属或合金,以辅助所述陶瓷层和基材之间的粘接。在一个实施方案中,所述粘合层是钛和/或铬或基于钛或铬的合金。
通常,将第一金属层设计为粘合层以增强所述第一陶瓷层的粘合性,进而提供扩散阻隔作用。
通常,所述形状记忆合金层的厚度在所述陶瓷层的厚度的0.5倍-2.0倍之间。
在一个实施方案中,所述多个层扩展至25个重复的金属和陶瓷双层,其中之一是所述金属粘合层。
根据本发明的一个实施方案,由多层金属和陶瓷材料的交替层形成耐磨涂层。通常选择两种材料以提供与耐磨涂层互补的性能;一种材料硬度大但相对较脆,而另一种材料具有高延展性和超弹性性能。具有延展性的超弹性合金是已知的称为“形状记忆合金”的材料类。优选的层厚度应在0.3-3.0μm之间,并且在所述多层交替层中的任意一层的陶瓷厚度不大于陶瓷脆性断裂的临界缺陷尺寸。
以下参照附图描述本发明的具体实施方案;其中
图1显示了可使用的设备的平面示意图;和
图2显示了根据本发明形成的涂层的一组测试结果。
根据本发明提供了用于基材的耐磨涂层体系,其特别适用于所述涂层受动态、往复、负载和/或滚动循环的情况。所述涂层的弹性是指任何对涂层的冲击都可被吸收,所述冲击例如由物体推进到涂层上或穿过涂层带来的冲击,并且造成涂层变形,涂层的弹性确保一旦冲击物移去时,至少一些且优选所有造成的变形得以恢复。
在一个实施方案中,冲击负载循环可产生多次弹道冲击(ballisticimpact),其在常规表面或涂层上造成由冲击所述涂层基材体系的颗粒带来的侵蚀效果。但是在本发明产生的涂层中,提供了多层耐侵蚀体系。在一个实施方案中,所述涂层可用于通常遭受冲击负载的不利影响的燃气轮机和/或汽轮机组件,如燃气轮机中的压气机叶片和汽轮机中的涡轮叶片。具有相似循环负载的第二个领域是在所有轴承系统中经受的滚动接触性疲劳,所述轴承系统用于高负载的机械机器,包括汽车、航空、风力涡轮机中和制造应用中。
具有相似负载循环的第二个领域是在所有轴承系统中经受的滚动接触性疲劳,用于高负载的机械机器,包括汽车、航空、各种制造应用、发电、精密加工和工业制造过程。图2显示了经过多次循环和在30牛、40牛和50牛的负载下的重复磨损测试中所得的测试结果,并且其中摩擦系数值的结果表明所述涂层耐蒸汽疲劳,并且耐滚动接触性疲劳,因为随循环次数的增加,所述摩擦系数值基本保持不变。
第三个领域是耐受在油气工业、海上能源领域、采矿和矿石加工工业中与泵送负载颗粒的液体相关的三体磨耗(three body abrasion)。
根据本发明的所述涂层的可能应用不受以上所述所述应用的限制。所述涂层在任何往复的负载磨损情况下都可改善耐久性和功能性。
以下参照图1,其中显示了可用于形成根据本发明的涂层的设备。
提供闭合场非平衡磁控溅射离子镀设备,其设置有可产生真空的室2和可围绕轴6旋转的支架(holder)4。在其外部,支架的侧壁8设置有当支架旋转时待涂覆的基材。面向所述基材,在所述室的外周设置有多个磁控管10,其可以形成闭合场的形式构造,使得例如相邻磁控管的磁构造为一个磁控管的磁极与相邻磁控管的磁极相反,以便在所述室内产生磁场12,所述磁场12使从磁控管靶溅射的材料向支架4上的待涂覆的基材沉积。可选地或另外地,在相邻磁控管之间可插入磁阵列以提供所需的磁场构造。
所述磁控管的靶可由所需材料提供以在所述基质上形成涂层。通常磁控管以预设的顺序操作,从而在所需时间沉积所需材料,以形成所需的多层涂层。此外,在涂覆过程中和在涂覆特定材料的过程中,可将合适的气体引入所述室中以形成待涂覆的涂层材料。
根据本发明,先操作至少一个具有金属靶的磁控管,以将金属层沉积在所述基材表面上。其后,操作至少一个其他磁控管,并且引入气体以在所述金属层上沉积陶瓷材料层,然后沉积金属合金层,以此类推,直至形成由多个金属和陶瓷层形成的最终涂层。
使用“形状记忆合金(SMA)”材料作为多层涂层体系的一部分,这利用了“形状记忆合金”的超弹性性能以提供额外的在弹道冲击、侵蚀或循环疲劳负载过程中可观察到的耐动态、往复、负载的性质。
由此,通过加入“形状记忆合金”金属层,本发明可以使多层涂层在动态冲击条件下的可接受的耐磨损性增强,所述“形状记忆合金”金属层为多层体系提供超弹性性能。
Claims (32)
1.用于基材表面的耐磨涂层,所述涂层具有至少一个金属层和至少一个陶瓷材料层,并具有充分的弹性以耐冲击、侵蚀和/或循环负载磨损过程。
2.根据权利要求1所述的涂层,其中所述涂层由至少四个层组成。
3.根据权利要求1或2所述的涂层,其中所述涂层由多个金属材料层和陶瓷材料层组成。
4.根据权利要求3所述的涂层,其中陶瓷层与金属材料层交替。
5.根据权利要求3所述的涂层,其中至少一个所述金属层由“形状记忆合金”形成。
6.根据权利要求3所述的涂层,其中所述陶瓷层是第4、5或6族金属、和/或铝和/或硅的硼化物、碳化物、氮化物或氧化物中的任一种或任意组合。
7.根据权利要求3所述的涂层,其中提供了具有合金层和至少一个陶瓷层的涂层,所述陶瓷层由硼化物、碳化物、氮化物或氧化物形成。
8.根据权利要求3所述的涂层,其中所述金属材料层包含NiTi合金和/或选自镍、钛、铬、铝、铂、铪、锆、钴、铜和/或钇的元素。
9.根据权利要求8所述的涂层,其中至少所述金属材料层提供形状记忆合金的性能。
10.根据权利要求8所述的涂层,其中至少所述金属层显示出超弹性性能。
11.根据权利要求1所述的涂层,其中在一定温度下沉积多层涂层以辅助所述“形状记忆合金”层的重结晶。
12.根据权利要求3所述的涂层,其中所使用的陶瓷是所述金属层材料中包含的合金元素之一的硼化物、碳化物、氮化物或氧化物。
13.根据权利要求12所述的涂层,其中沉积界面陶瓷层,所述界面陶瓷层是所述金属层材料中包含的合金元素之一的硼化物、碳化物、氮化物或氧化物。
14.根据前述权利要求任一项所述的涂层,其中所述陶瓷层的厚度在0.1-5.0μm的范围内,优选0.3-3.0μm。
15.根据前述权利要求任一项所述的涂层,其中所述陶瓷层厚度小于如下定义的陶瓷脆性断裂临界厚度:
其中E是陶瓷的弹性模量,γS是陶瓷的断裂表面能,σ是因冲击负载而在陶瓷层中产生的最大拉伸应力,以及f是与接触几何形状相关的几何因子。
16.根据权利要求15所述的涂层,其中对于模量为300GPa的1μm厚度陶瓷层,所述几何因子f为16。
17.根据前述权利要求任一项所述的涂层,其中所述陶瓷层本身具有多个子层。
18.权利要求17所述的涂层,其中所述子层具有不同的具有不同的陶瓷组成,并且所述陶瓷层显示出超晶格结构,这改善了它的硬度和耐断裂性。
19.根据前述权利要求任一项所述的涂层,其中第一陶瓷层通过粘合层与所述基材材料粘接。
20.根据权利要求19所述的涂层,其中所述粘合层由特定选择的金属或合金形成,以辅助所述陶瓷层和所述基材之间的粘接。
21.根据权利要求20所述的涂层,其中所述粘合层是钛和/或铬或基于钛或铬的合金。
22.根据权利要求19所述的涂层,其中所述粘合层增强了所述第一陶瓷层的粘接,并提供扩散阻隔作用。
23.根据权利要求3所述的涂层,其中所述形状记忆合金层的厚度在所述陶瓷层的厚度的0.5倍-2.0倍之间。
24.根据权利要求3所述的涂层,其中所述多个层扩展为25个重复的金属和陶瓷双层,其中之一是所述金属粘合层。
25.具有多个交替的金属层和陶瓷材料层的耐磨涂层,所述金属层具有高延展性和超弹性性能。
26.根据权利要求25所述的涂层,其中所述金属层的厚度在0.3-3.0μm之间。
27.根据权利要求25所述的涂层,其中所述多个交替层中的任一陶瓷层的厚度不大于陶瓷脆性断裂的临界缺陷尺寸。
28.在基材上形成弹性涂层的方法,所述方法包括涂覆多个陶瓷材料层和多个金属材料层的步骤,并且其中在形成所述涂层时,所述陶瓷材料层与金属材料层交替。
29.根据权利要求28所述的形成涂层的方法,其中使用溅射过程以至少形成所述陶瓷层。
30.根据权利要求29所述的方法,其中使用闭合场非平衡磁控溅射离子镀(CFUBMSIP)方法。
31.根据权利要求28所述的形成涂层的方法,其中使用溅射过程以至少涂覆所述金属层。
32.根据权利要求31所述的方法,其中使用闭合场非平衡磁控溅射离子镀(CFUBMSIP)。
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Cited By (6)
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CN102580169A (zh) * | 2012-02-28 | 2012-07-18 | 淮阴工学院 | 提高不锈钢骨板和骨钉生物活性的涂层 |
CN103305801A (zh) * | 2013-06-05 | 2013-09-18 | 哈尔滨工程大学 | 一种TiNi基形状记忆合金多层薄膜及其制备方法 |
CN108611611A (zh) * | 2018-04-02 | 2018-10-02 | 苏州诺弘添恒材料科技有限公司 | 一种钛镍钴记忆合金膜的制备方法 |
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