CN105026530B - 用于具有摩擦应力的高温应用的涂层 - Google Patents
用于具有摩擦应力的高温应用的涂层 Download PDFInfo
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Abstract
本发明涉及用于具有摩擦应力的高温应用的涂层。该涂层包含多层层体系和顶部润滑层,其中该顶部润滑层含有钼作为主要组分。
Description
本发明涉及用于组件、部件和工具的承受于高温应用中的磨损保护涂层。组件、部件和工具以下共同称为基材。
发明目的
在“高”温下的应用对于部件、组件和工具的表面功能性就机械、结构和化学稳定性而言提出极限要求。为了确保长期稳定的表面功能性和因此保障工业过程生产率,本发明为部件、可活动的组件和模制工具和切削工具提供了硬材料层体系,其以令人满意的方式改善该组件和工具在具有明显较高的热负荷的各种工业应用(即大于400℃的温度,以下称为高温应用)中的磨损。这些高温稳定的硬材料层体系的基本性能如下:i)足够的研磨-磨损保护、ii)足够的粘附-磨损保护、iii)足够的层附着和iv)足够的温度稳定性(相稳定性和耐氧化性)。
发明内容
根据本发明,建议基本上包含多层层体系作为基础的涂层体系。在该多层层体系上,设置具有至少一个层的顶部润滑层体系。该顶部润滑层体系向外终结涂层体系。该顶部润滑层体系含有钼作为主要成分,并且根据占优势的高温摩擦接触和由此产生的表面的机械和化学应力,可以具有合适的建造结构/微结构以及合适的组成。
以下给出对于优选的建造结构/微结构和组成的进一步阐述。以下简化地将顶部润滑层体系也称为顶部润滑层。
图1展示了根据本发明的涂层
图2展示了根据本发明的涂层的局部(纳米层)
图3展示了根据本发明的涂层的局部(纳米层)
图4展示了氮化铁
图5展示了AlCrN和ZnO
图6展示了类型1。
所述顶部润滑层的建造结构的特征可以在于i)单层结构、ii)双层结构、iii)多层结构或者iv)纳米层压的结构,其中在情况ii)-iv)中通过该结构改变所述微结构或者化学机理。然而,该微结构和/或组成的分级(Gradierungen)在所有情况i)-iv)中是可行的,并且设置其以对于各种应用确保润滑性能与所需的机械性能相协调。在所有情况中,所述层原则上是纳米级性质的。
该顶部润滑层的化学组成的特征基本上如下:Moa-Xb-Yc,其中a、b和c给出各个成分的原子浓度,和a+b+c=l,并且钼实现为占优势的成分,即0≤b<a和0≤c<a,其中优选为b+c>0,其中作为可变的金属成分的X:B、Si、V、W、Zr、Cu和Ag或者它们的组合,其中作为可变的非金属成分的Y:C、O和N或者它们的组合。
在高于500℃的高温应用中,特别优选为具有以下组成的顶部润滑层:
o Mo和/或Mo-Cu
o Mo-N和/或Mo-Cu-N
o Mo-O-N和/或Mo-Cu-O-N
o Mo-Si-B和/或Mo-Si-B-N
o Mo-Si-B-O-N。
该顶部润滑层优选地含有至少95原子%的钼。该顶部润滑层特别优选地不含有铝。该顶部润滑层的层厚度优选为0.25至1.5 μm,特别优选为0.5至1.0 μm。
优选地,对于特定的高温应用(温度、摩擦接触、环境气氛和持续时间)评定顶部润滑层和位于其下的层体系的合适配对。
以下应例如阐述Mo-X-Y顶部润滑层与位于其下的多层层体系的相互配合。该顶部润滑层与位于其下的多层层体系的组合的作用机理可以鉴于各种高温应用中的机械、结构和化学稳定性大致如下来描述:虽然仅在摩擦接触的最初阶段中使用顶部润滑层,其中在升高的温度下连续地施涂该润滑层并形成固体润滑相(尤其金属氧化物),并且因此优化摩擦运转(Einlauf)性能(即因此对于进一步进程最佳地调理最初摩擦接触),所述位于其下的多层层体系(在通过该顶部润滑层的发生了的表面调理之后)负责维持持久和高温稳定的(研磨和粘附的)磨损保护。认为在超过约400℃的温度下,顶部润滑层开始氧化(根据确切的微结构和组成)。包含于顶部润滑层中的金属,例如B、V、W、Zr、Cu、Ag和Mo的氧化可能导致形成所谓的“马格涅利相”。已知这样的马格涅利相具有出色的润滑性能(固体润滑)。相反地,位于其下的多层层体系通过其与层化学机理相协调的建造结构,不仅提供所需的机械、结构和化学的高温稳定性,而且还在最高1000℃的高温下在稳定的长时间使用中,依照希望地和在本情况中可控地形成固体润滑相(尤其金属氧化物;可能形成所谓的“马格涅利相”)。
根据本发明,多层层体系包含至少一个高温稳定化的层(HT-层)。这样的层可以例如为符合(Mel, Me2, Mo)N的组成。
在本发明的一个特别优选的实施方案中,多层层体系含有至少两个层组,其中随着与基材的增大的距离,在HT-层上跟着润滑活性层。润滑活性层可以符合HT-层,但用提高的钼含量构成。与此相应地,贫钼层可能形成HT-层,而富钼层可以形成润滑活性层。优选地,富钼层中的最大钼浓度超过相邻的贫钼层的最小钼浓度至少10原子%,特别优选至少20原子%。例如既可以借助PVD-方法通过使用单组分材料源(靶),也可以借助PVD-方法通过使用多组分材料源,使该交替层体系的富钼层沉积。
为了进一步改善润滑,该交替层体系的富钼层可以含有一种或者多种来自通过C、O、B、Si、V、W、Zr、Cu和Ag构成的组的其它元素。
为了例如通过提高机械和化学性能而进一步提高高温稳定性,该交替层体系的贫钼层可以含有一种或者多种来自通过B、Si、W和Zr构成的组的其它元素及其混合物。
根据本发明,在该多层层体系上设置如上陈述的顶部润滑层。
根据本发明的基材,即用根据本发明的涂层体系涂覆的基材可以有利地用于在应用中出现高温和摩擦应力的各处。这例如在直接模压淬火(Presshaerten)中是该情况。作为实例可以在此提及:
o AlSi-涂覆的22MnB5 USSH-金属板的直接模压淬火
o 未涂覆的22MnB5 USSH-金属板的直接模压淬火
o 用基于Zn的层涂覆的类型22MnB5的超高强度的钢的直接模压淬火。
其它的应用实例是
o 高强度的金属板的锻造
o 特别是高强度的钛合金和镍合金的切削和变形
o 内燃机中和涡轮增压机领域中的部件和可活动的组件
o 铝压铸和镁压铸
o 特别是高强度的塑料或者铝的注塑和挤出。
根据本发明的第一实例,在模压淬火-模制工具上施涂2μm厚的(Ti0.5Al0.5)N层。紧随其后跟着5个层组,其中各个层组含有0.5 μm厚的(Ti0.3Al0.3Mo0.4)N层,在其上跟着0.5 μm厚的(Ti0.5Al0.5)N层。0.5 μm厚的(Ti0.3Al0.3Mo0.4)N层终结该多层层体系。相反地,整个层体系通过作为顶部润滑层的0.5 μm厚的Mo0.95Si0.03B0.02来终结。作为合适的顶部润滑层,在该具体情况中MoN和Mo0.95Cu0.05N也是特别重要的。
根据本发明的第二实例,在模压淬火-模制工具上施涂2μm厚的(Al0.65Cr0.25Si0.05)N层,其中也可以任选地略去Si。紧随其后跟着5个层组,其中各个层组含有0.5 μm厚的(Al0.42Cr0.18Mo0.35Cu0.05)N层,其上跟着0.5 μm厚的(Al0.7Cr0.3)N层。0.5 μm厚的(Al0.42Cr0.18Mo0.35Cu0.05)N层终结该多层层体系。相反地,整个层体系通过作为顶部润滑层的0.5 μm厚的MoN来终结。
此外优选的是具有多层层体系和具有顶部润滑层的涂层,该多层层体系一方面包含Al和B与IV和V副族元素的化合物(C和/或N和/或O)和另一方面包含Mo-化合物(C和/或B和/或N和/或O),并且该顶部润滑层含有以Mo作为主要组分的Mo-化合物,并且其厚度相比于多层中的含Mo的层而言是相同大的,优选更厚的。
特别优选的是具有如上的多层层体系的涂层,其中占金属总含量的Mo的总含量为小于50原子%。
对于本发明的特别优选的实施方案的以下特征,实施进一步实验:
- 润滑活性层(TiAlMoN)应有利地具有 20-60原子%,优选25-35原子%,特别优选30原子%的(平均的;当用EDX在l0kV下测量时)Mo-含量。
- 该(平均)Mo-含量也可以经由润滑活性层的建造结构(纳米层-结构)来控制(参见下图)。这可以使用2种靶-类型(Mo和TiAl)在技术上经由i)旋转速度的变化和/或经由ii)所有同时运转的靶的靶-参数的变化来实现。
- TiAlMoN(纳米层中的浅色层)中的富MoN层的厚度可以在10-60nm,优选20-50nm,特别优选30-40nm之间变化。TiAlMoN中的富MoN层的最佳厚度看似为约40nm。
- 在润滑活性层(TiAlMoN)中的约30原子%的Mo-含量可以在约800-900℃的温度下非常有利地促进表面氧化(而不负面地影响整个层结构),从而提供始终足够的(氧化物)润滑剂,以在长时间使用中防止涂抹AlSi。这被接近应用的测试(例如具有连续交替Usibor®-金属板的HT-SRV-测试,其中始终测试相同的层)所证实。
- 还非常有利的事实是,在润滑活性层(TiAlMoN)中在20-40原子%的范围中改变Mo-含量时,整个层的机械性能(硬度、E-模量、附着)、结构性能(相的持续)以及氧化性能(在800℃下在环境气氛下1小时的氧化物层生长)不明显地变化。这有针对性地实现,对于各种HT-应用就针对研磨磨损和粘附磨损的耐受性而言优化建造结构以及组成。
如上已展示,在用于汽车中的超高强度的钢(例如B-柱)的直接模压淬火的领域中,经Al-Si涂覆的类型22MnB5的钢板是现有技术。Al-Si钢涂层在奥氏体化(T > 900℃)时在环境气氛中防止钢表面起氧化皮(氧化铁形成),并且相比于未涂覆的钢板而言提供足够的腐蚀保护(钝化的边界层效应)。
然而为了在模压淬火时满足对于腐蚀保护的日益增长的要求,近期在进行的研发的焦点中出现了越来越多基于Zn的钢涂层。这些基于Zn的钢涂层除了避免高温起氧化皮以外,还提供非常有效的阴极腐蚀保护(Zn比Fe不昂贵,从而在原电池中的腐蚀条件下,Zn为阳极和Fe为阴极-人们称为阴极腐蚀保护)。然而存在明显的问题,其在例如基于Zn的超高强度的类型22MnB5的钢的直接模压淬火时出现:
- 由于形成氧化锌的研磨的工具磨损
- 由于氧化锌的强烈粘附的粘附的工具磨损
- 在直接模压淬火时由于变形的高机械负荷,基于Zn的钢涂层中直至钢板内的裂纹形成。
特别地,裂纹形成是一个主要问题。如今问题是,如果优化工具表面和钢板表面之间的界面摩擦,即如果减小界面摩擦,是否可以在直接模压淬火时防止裂纹形成。因此,目的是提供工具涂层,其能够一方面显著地减小工具磨损和另一方面显著减小摩擦系数。
基于上述背景,用基于Zn的钢涂层进行进一步实验。为此,在高温下进行接近应用的摩擦测试(例如HT-SRV测试),以得到关于层磨损和对于摩擦系数的结论。在约880℃下10分钟贮存(Auslagerung)涂覆Zn的钢板之后,使温度降至700℃,并且将(具有待测试的涂层的)经涂覆的SRV-测试样品用10N的负荷置于热的钢表面上。随后,在振荡模式中实施摩擦测试2.5分钟。直接测量摩擦系数,并且借助扫描电子显微镜和球形磨耗(Kalottenschliff)研究磨损痕迹的粘附和研磨磨损。主观地分级粘附磨损(1 = 无材料涂抹直至5 = 明显的材料涂抹),并且绝对地以%根据8 μm的层厚度归一化地测定研磨磨损。
在2个变型方案中相对于基准-涂层氮化铁(具有化合物层的氮化的钢表面)和AlCrN,测试根据本发明的层体系。
变型方案1(类型I)的描述:作为顶层的具有约0.5 μm的层厚度的(Mo0.95Cu0.05)N在多层层体系上,其如下构成:在2 μm厚的(Τi0.5Α10.5)Ν层上跟着5个层组,其中各个层组含有0.5 μm厚的(Τi0.3Α10.3Mo0.4)Ν层,其上跟着 0.5 μm厚的(Τi0.5Α10.5)Ν层。0.5 μm厚的(Ti0.3Al0.3Mo0.4)N层终结该多层层体系。
变型方案2(类型II)的描述:作为顶层的具有约0.5 μm的层厚度的MoN在多层层体系上,其如下构成:在2 μm厚的(Τi0.5Α10.5)Ν层上跟着5个层组,其中各个层组含有0.5 μm厚的(Τi0.3Α10.3Mo0.4)Ν层,其上跟着 0.5 μm厚的(Τi0.5Α10.5)Ν层。0.5 μm厚的(Ti0.3Al0.3Mo0.4)N层终结该多层层体系。
相比于基准涂层而言,根据本发明的涂层体系的两个变型方案显示了非常小的粘附磨损以及明显减小的摩擦系数。在所述2.5分钟-测试之后,仅在氮化铁的情况下可以看出一定的研磨磨损。还非常令人惊奇的事实是,根据本发明的涂层体系的变型方案2在10个彼此相接的2.5分钟-测试之后显示未变化的优越性能。这些结果明显表明,根据本发明的涂层体系对于工业长时间使用而言也具有非常大的潜力。
Claims (12)
1.具有顶部润滑层以及位于其下的多层层体系的涂层,所述顶部润滑层具有Mo-Si-B或Mo-Si-B-N或(Mo-Si-B和Mo-Si-B-N)或Mo-Si-B-O-N的组成,所述多层层体系包含至少一个高温稳定化的组成为(Mel,Me2,Mo)N的层。
2.根据权利要求1的涂层,其特征在于,所述顶部润滑层的建造结构具有单层或者双层或者多层或者纳米层压结构。
3.根据权利要求2的涂层,其特征在于,所述顶部润滑层的建造结构具有双层或者多层或者纳米层压结构,并且通过所述结构来改变微结构。
4.根据权利要求1的涂层,其特征在于,所述顶部润滑层的建造结构具有双层或者多层或者纳米层压结构,并且通过所述结构来改变化学机理。
5.根据权利要求1至4任一项的涂层,其特征在于,所述顶部润滑层含有至少95原子%的钼。
6.根据权利要求1至4任一项的涂层,其特征在于,所述顶部润滑层的层厚度为0.25μm至1.5μm。
7.基材,其至少部分地用根据前述权利要求1至6任一项的涂层涂覆。
8.根据权利要求7的经涂覆的基材,其特征在于,所述基材为工具。
9.根据权利要求8的经涂覆的工具,其特征在于,所述工具为模压淬火-模制工具。
10.根据权利要求9的经涂覆的模压淬火-模制工具,其特征在于,在所述涂层的顶部润滑层下设置至少一个氮化钛铝层。
11.根据权利要求10的经涂覆的模压淬火-模制工具,其特征在于,所述顶部润滑层基本上具有化学组成Mo0.95Si0.03B0.02和/或所述氮化钛铝层基本上具有化学组成Ti0.5Al0.5N。
12.根据前述权利要求9至11任一项的模压淬火-模制工具用于使以下材料直接模压淬火的用途:
·AlSi-涂覆的22MnB5USSH-金属板,或者
·未涂覆的22MnB5USSH-金属板,或者
·用基于Zn的层涂覆的类型22MnB5的超高强度的钢。
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KR20150084049A (ko) | 2015-07-21 |
BR112015010860A2 (pt) | 2017-07-11 |
AR092945A1 (es) | 2015-05-06 |
US20150291800A1 (en) | 2015-10-15 |
CN104995287A (zh) | 2015-10-21 |
JP2016500752A (ja) | 2016-01-14 |
US9623468B2 (en) | 2017-04-18 |
EP2906668B1 (de) | 2017-01-04 |
WO2014056605A1 (de) | 2014-04-17 |
JP2016501280A (ja) | 2016-01-18 |
US9586252B2 (en) | 2017-03-07 |
MX2015004645A (es) | 2016-03-04 |
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