CN105673090A - 研磨涂覆基底及其制造方法 - Google Patents

研磨涂覆基底及其制造方法 Download PDF

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CN105673090A
CN105673090A CN201510886627.6A CN201510886627A CN105673090A CN 105673090 A CN105673090 A CN 105673090A CN 201510886627 A CN201510886627 A CN 201510886627A CN 105673090 A CN105673090 A CN 105673090A
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coating
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CN105673090B (zh
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W.M.巴巴奇
W.埃贝林
M.霍伊贝
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Energy Resources Switzerland AG
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Abstract

描述了一种涂覆基底，其包括基底材料，该基底材料至少部分地涂覆有抗氧化涂层，其中涂层由耐磨的研磨涂层构成或包括耐磨的研磨涂层，该耐磨的研磨涂层由嵌入在抗氧化基质材料中的涂覆的研磨颗粒构成，其中研磨颗粒中的至少一些由α-Al2O3构成，并且研磨颗粒涂覆有设置在研磨颗粒上的第一颗粒涂层，以及设置在第一颗粒涂层上的可选的第二颗粒涂层，其中基质材料由化合物MCrAlY构成或包括化合物MCrAlY，其中M为选自由Ni、Co和Fe构成的组的至少一种元素。还公开了一种用于制造此类涂覆基底的方法。

Description

研磨涂覆基底及其制造方法
技术领域
本发明涉及一种包括基底材料的涂覆基底，其至少部分地涂覆有抗氧化涂层，其中涂层由耐磨的研磨涂层构成或者包括该耐磨的研磨涂层，该耐磨的研磨涂层由嵌入在抗氧化基质材料中的涂覆的研磨颗粒构成。本发明还涉及一种制造其的方法。例如，此类基底材料可由单晶超级合金构成，其中基底材料为用于涡轮转子的沿径向延伸的涡轮叶片，并且其中涂层施加在径向外侧的叶片末端表面处。
背景技术
在瞬变过程，如，燃气涡轮和压缩机的启动、重启、停机或负载变化期间，转子叶片与静止构件如热障层之间的距离变化。通常，转子叶片的摩擦由转子叶片与定子构件之间的充分大的距离防止。该措施相当大地降低了效率。
作为备选方案，氧化和耐磨的研磨涂层施加在转子叶片末端处，以在与静止构件，尤其是与热障层接触时防止涡轮叶片的磨损。这些研磨涂层包含研磨颗粒，从而提高了耐磨性，使得即使静止构件设有热障涂层(TBC)，仍提供涡轮叶片的充分保护。经常地，研磨颗粒由立方氮化硼(cBN)构成，如例如DE102010049399A1中公开的。由于其形态和极高的硬度，故cBN具有优异的切削能力。然而，在高于800℃到850℃的操作温度下，cBN氧化，结果研磨涂层的保护效果仅可提供非常短的时间。研磨涂层中的cBN颗粒仅可在高于900℃的温度下保证大约1000操作小时的充分保护。在高于900℃时，cBN颗粒由于氧化过程而迅速退化。尤其是在燃气涡轮的第一涡轮级中，温度可在900℃到1300℃之间。
发明内容
因此，本发明的目的在于提供一种涂覆基底，其在升高温度下针对磨损和氧化提供基底材料的长期保护，并且其可相对容易且快速地产生。
该任务由权利要求1的主题解决。因此，研磨颗粒中的至少一些，有利的是所有研磨颗粒，由α-Al2O3构成，其中研磨颗粒涂覆有设置在研磨颗粒上的第一颗粒涂层。可选地，第二颗粒涂层设置在第一颗粒涂层上。此外，研磨涂层的基质材料由抗氧化化合物MCrAlY构成或包括抗氧化化合物MCrAlY，其中M为选自由Ni、Co和Fe构成的组的至少一种元素。
称为矿物刚玉或蓝宝石的α-Al2O3相对于氧化极为稳定，自身已经是氧化物。尽管其硬度低于cBN并且拥有较低的切削效率，但α-Al2O3仍具有足够的硬度(莫氏硬度9)。
为了加强基质材料MCrAlY中的研磨颗粒的固持，颗粒涂覆有第一和可选还有第二颗粒涂层。第一涂层防止颗粒与颗粒涂层分离。因此，优选地，第一颗粒涂层由允许层与化学表面的化学连结的技术形成在颗粒上。第二颗粒涂层防止涂覆颗粒与基质分离。因此，选择相对好地粘结于第一颗粒涂层和基质材料的材料。
因此，关于本发明，涂覆基底可设有相比于现有技术水平在升高温度下的研磨涂层的延长的寿命。这实现了在整个操作时段期间的900℃到1300℃之间的温度下相对于磨损和氧化的涡轮叶片的保护，该整个操作时段通常取决于除氧化外的其它损坏机制在24,000到36,000操作小时之间。
优选地，研磨颗粒为单晶的。这导致了颗粒的提高的硬度和耐久性。研磨涂层中的研磨颗粒的厚度和/或量可宽泛地变化，由此，平均粒径可在0.1到1.000微米的范围中。优选地，研磨颗粒具有20到150μm之间的平均尺寸。
第一颗粒涂层可由Ti,Zr,Hf,V,Nb,Ta,Cr,Co,Mo,Ni、它们的合金或其碳化物、硼化物、氮化物或氧化物构成，或包括它们。因此，可实现颗粒表面与颗粒涂层之间的充分连结。此外，这些材料允许了第一颗粒涂层化学连结于颗粒表面，因为它们可在常规沉积条件下形成金属碳化物或氮化物的填隙层。第一颗粒涂层的厚度可宽泛地变化。可使用小于0.1μm的厚度以及远高于五μm的厚度。
第二颗粒涂层可由与可用于第一颗粒涂层的相同材料构成或包括该相同材料。优选地，第二颗粒涂层的厚度比第一颗粒涂层的厚度更厚。
如果选择两层涂层，则颗粒涂层的总质量优选地处于相当于涂覆之前的研磨颗粒的40wt%到95wt%的量。对于单层涂层，颗粒涂层的质量通常较小，并且典型地在从1wt%到30wt%的范围中。
如果基底为单晶超级合金，则根据本发明的有利方面，中间涂层设置在基底材料与研磨涂层之间。该中间涂层可外延地连结于基底材料。中间层也可由MCrAlY合金构成或包括MCrAlY合金。该中间缓冲涂层较好地粘结于基底材料。如果外延地形成在单晶基底材料上，则中间缓冲层具有像基底的类似各向异性材料性质(例如，杨氏模量)。因此，其热物理性质与基底匹配，导致了较高的循环寿命。中间缓冲层的外延沉积还防止了形成晶粒边界和缺陷。此外，缓冲层的MCrAlY材料提高基底材料的抗氧化性，因为可形成无裂缝的、稳定且致密的保护层。
优选地，基质材料和/或中间涂层由具有小于50K的固相线温度与液线温度之间的凝固间隔ΔT0的MCrAlY合金构成。有利的是，其小于40K。这降低了在凝固期间开裂的风险。这可通过选择接近共晶成分的MCrAlY合金来实现。
根据本发明的又一个有利方面，基质材料和/或中间涂层由抗氧化γ/β或γ/γ'类型的MCrAlY合金构成，其中合金的化学成分选定成使得在凝固时，γ相首先形成，并且接着形成β或γ'相。由于首先形成γ相，故在基底材料上凝固时，外延连结的中间涂层可设在基底材料上。特别有利的γ/β类型的MCrAlY合金具有以下化学成分：35-40wt%Co,18-24wt%Cr,7-9wt%Al,0.3-0.8wt%Y,0.1-1wt%Si,0-2wt%的其它成分，余量的Ni。该合金具有大约1370℃的液线温度。
基底材料可由可沉淀硬化的单晶超级合金构成。通常，镍基超级合金用于涡轮叶片。超级合金如IN713LC,IN738LC,MARM247,CM247LC,CMSX-4,MK4或MD2为待使用的适合的选择物。
通常，涂层施加在径向外侧的叶片末端表面处，由此研磨涂层中的研磨颗粒的重量内容物可朝径向外侧方向增大。
本发明的任务还通过一种用于制造根据本发明的涂覆基底的方法来解决。因此，研磨涂层由激光金属成型来形成。该方法在EP1476272B1中详细公开，其内容通过引用如完整阐述那样并入。因此，涂覆的研磨颗粒和基质材料颗粒在粉末喷嘴中混合，由载体气体输送，并且接着围绕激光束同心地喷射作为粉末的聚焦射流来进入由激光束在叶片末端上产生的熔池中。激光金属成型过程为焊接方法，并且相比于常用的涂覆方法，其产生与基底材料的稳定的冶金连结，而没有附加的扩散热处理。
如果涂层还包括中间层，则中间层首先由适合的涂覆方法形成。优选地，也使用激光金属成型，因为其提供用于产生涂层的廉价且简单的方法。此外，激光金属成型可控制成使得有可能在单晶基底上实现外延沉积。
根据本发明的另一个有利方面，在熔池中的温度或温度分布在激光金属成型过程期间另外连线记录，并且该信息由控制系统使用，以控制激光效率，以及因此激光金属成型期间的熔池的温度，使得研磨涂层的形成期间的熔池的温度处于基底材料的液线温度与研磨颗粒的熔化温度或者第一或第二颗粒涂层的熔化或液线温度之间。因此，可实现具有研磨颗粒的良好嵌入的涂层的完全受控的增长。
如果涂层还包括中间层，则熔池的温度可控制成使得在形成研磨涂层期间，温度处于基质材料的液线温度与研磨颗粒的熔化温度或者第一或第二涂层的熔化或液线温度之间。
根据本发明的又一个有利方面，在形成涂层之前，涂覆研磨颗粒。在第一步骤中，第一颗粒涂层形成在研磨颗粒上。优选地，使用一种方法，使得第一颗粒涂层化学地连结于基底材料。适合的方法为盐浴沉积。在以下可选步骤中，第二层可沉积在第一颗粒涂层上。一定数量的技术如无电极、电解和汽相沉积技术可用于允许形成厚的第二颗粒涂层。有利的是，使用无电极沉积，因为厚涂层可迅速且廉价地产生。涂层还可包括两个以上的涂层。涂覆这些研磨颗粒的过程称为金属喷镀。
附图说明
基于示例性实施例并且基于图1至4来更详细阐释本发明。
附图示出了：
图1为用于燃气涡轮的转子的涡轮叶片的示意性透视图；
图2为根据本发明的实施例的涂覆基底的沿图1中的线II-II的示意性侧视图；
图3为根据本发明的另一实施例的涂覆基底的沿图1中的线II-II的示意性侧视图；
图4为涂覆的研磨颗粒的示意性侧视图；
图5为涂覆设备和激光金属成型方法的原理。
部件列表
1叶片
2转子
3叶片末端
4基体
5研磨涂层
6基质材料
7研磨颗粒
8中间层
9涂层(总)
10激光束
11基质粉末颗粒
12基底材料
13涂覆设备
14镜
15载体气体
16熔池
17温度信号
18涂覆基底
19第一颗粒涂层
20第二颗粒涂层
L位置1的长度
r径向方向。
具体实施方式
图1示出了用于燃气涡轮的转子2(示意性示出)的涡轮叶片1。涡轮叶片1可具有定向凝固或单晶基体4，其沿径向方向r(关于转子)延伸，具有长度L和在径向外侧叶片末端3处的端部。
根据图2，由基体4表示的基底材料12涂覆有研磨涂层5。因此，产生了涂覆基底18。根据本申请的涂覆基底18可为新的或修整的涡轮叶片。
研磨涂层5由基质材料6和研磨颗粒7构成，基质材料6由化合物MCrAlY构成，而研磨颗粒7由单晶α-Al2O3构成，其嵌入在基质材料6中。
如图4中示意性所示，研磨颗粒7涂覆有第一涂层19，第一涂层19例如由设置在研磨颗粒7上的由盐浴沉淀形成的钛构成。可选的是，如图4中所示，第二颗粒涂层20可存在，例如，由设置在第一颗粒涂层19上的由无电极沉淀形成的镍构成。代表基底材料12的基体4例如由具有大约1330℃的液线温度和大约1670℃的研磨颗粒的钛涂层的熔化温度(其低于α-Al2O3研磨颗粒的熔化温度)的IN738C构成。用于激光金属成型过程的适合的熔池温度在该情况中为1500℃＋/-100℃。
根据图3中所示的另一个实施例，中间层8形成在单晶叶片基体4上，并且具有基质材料6中的研磨颗粒7的研磨涂层5形成在中间层8上。中间层8由化合物MCrAIY构成。代表基底材料12的基体4由单晶MD2超级合金(成分：5-5.25wt%Co,7.7-8.3wt%Cr,2.0-2.1wt%Mo,5.9-6.1wt%Ta,7.9-8.3wt%W,4.9-5.1wt%Al,1.2-1.4Ti,0.1-0.12wt%Si;0.11-0.13wt%Hf,200-250ppmwC,50-80ppmwB，余量的Ni)构成。具有与中间涂层相同成分的MCrAIY基质材料具有小于40K的凝固间隔，并且在凝固时，首先形成γ相。该材料具有大约1370℃的液线温度。在该情况下，α-Al2O3研磨颗粒涂覆有由盐浴沉积形成的钛构成的第一颗粒涂层19，以及由无电极沉积过程形成的镍/磷合金构成的可选的第二颗粒涂层20。在该情况下，研磨涂层的形成可在1550℃＋/-100℃的熔池温度下执行。
对于根据图2和3的涂层9的形成，使用了激光金属成型方法。该方法在EP1476272B1中详细公开。尽管外延的第一涂层是有益的，但这对于双层研磨涂层不是强制性要求。
图5示出了用于执行激光金属成型方法的涂覆设备13。因此，对于研磨涂层5的形成，研磨颗粒7连同基质粉末颗粒11经由粉末喷嘴(未示出)围绕聚焦的高强度激光束10同轴地喷射。分色镜14将高强度激光10偏转到叶片末端3上，并且将其聚焦在小瞄准点(熔池16)处。镜14可透过处理光，该处理光耦合于使熔池16的温度的连线控制可能的光学参数(未示出)。由研磨颗粒和基质材料颗粒构成的粉末颗粒7在粉末喷嘴中混合，由载体气体15输送，并且接着作为粉末的聚焦射流喷射到叶片末端3上的由激光束10产生的熔池16中，或如果存在中间层8，则喷射在中间层8上。此外，在激光金属成型期间连线记录熔池的温度或温度分布(可选温度信号17)，并且借助于控制系统(未示出)，使用该信息来在激光成型和/或激光束10和涡轮叶片1的相对移动的变化期间，以受控方式控制激光功率。通过将温度信号17反馈至激光控制器(未示出)，有可能借助于实时控制过程来自动地改变激光功率。
为了产生根据图3的涂层，在第一步骤中，中间层由激光金属成型方法形成，由此仅中间层粉末颗粒喷射到熔池16中。为了允许单晶基础材料上的中间层的外延凝固，激光功率通过温度控制改变，使得商Gn/vs处于定向单晶凝固所需的取决于材料的极限以上。这里，Gn表示局部梯度，vs表示凝固前部的速度，并且n表示又一材料参数。

Claims (17)

1.一种涂覆基底(18)，其包括基底材料(12)，所述基底材料(12)至少部分地涂覆有抗氧化涂层(9)，其中所述涂层(9)由耐磨的研磨涂层(5)构成或包括耐磨的研磨涂层(5)，所述耐磨的研磨涂层(5)由嵌入在抗氧化基质材料(6)中的涂覆的研磨颗粒(7)构成，其特征在于，所述研磨颗粒(7)中的至少一些由α-Al2O3构成，并且所述研磨颗粒(7)涂覆有设置在所述研磨颗粒(7)上的第一颗粒涂层(19)和设置在所述第一颗粒涂层(19)上的可选的第二颗粒涂层(20)，其中所述基质材料(6)由化合物MCrAlY构成或包括化合物MCrAlY，其中M为选自由Ni、Co和Fe构成的组的至少一种元素。
2.根据权利要求1所述的涂覆基底(18)，其特征在于，所述研磨颗粒(7)为单晶的。
3.根据权利要求1或权利要求2所述的涂覆基底(18)，其特征在于，所述第一颗粒涂层(19)和/或所述第二颗粒涂层(20)由Ti,Zr,Hf,V,Nb,Ta,Cr,Co,Mo,Ni、其合金或其碳化物、硼化物、氮化物或氧化物构成，或包括它们。
4.根据前述权利要求中任一项所述的涂覆基底(18)，其特征在于，所述第一颗粒涂层(19)化学地连结于所述基底材料(12)。
5.根据前述权利要求中任一项所述的涂覆基底(18)，其特征在于，所述涂层包括设置在所述基底材料(12)与所述研磨涂层(5)之间的至少一个中间涂层(8)，其中所述研磨涂层(5)设置在所述中间涂层(8)的至少部分上。
6.根据权利要求5所述的涂覆基底(18)，其特征在于，所述中间涂层(8)外延地连结于所述基底材料(12)。
7.根据前述权利要求中任一项所述的涂覆基底(18)，其特征在于，所述基质材料(6)和/或所述中间涂层(8)由具有小于50K的固相线温度与液线温度之间的凝固间隔ΔT0的MCrAlY合金构成。
8.根据前述权利要求中任一项所述的涂覆基底(18)，其特征在于，所述基质材料(6)和/或所述中间涂层(8)由抗氧化的γ/β或γ/γ'类型的MCrAlY合金构成，其中所述合金的化学成分选定成使得在凝固时，所述γ相首先形成，并且接着仅形成所述β或γ'相。
9.根据前述权利要求中任一项所述的涂覆基底(18)，其特征在于，所述基质材料(6)和/或所述中间涂层(8)由具有以下化学成分的抗氧化γ/β类型的MCrAlY合金构成：35-40wt%Co,18-24wt%Cr,7-9wt%Al,0.3-0.8wt%Y,0.1-1wt%Si,0-2wt%的其它成分，余量的Ni。
10.根据前述权利要求中任一项所述的涂覆基底(18)，其特征在于，所述基底材料(12)由单晶超级合金构成。
11.根据前述权利要求中任一项所述的涂覆基底(18)，其特征在于，所述基底材料(12)为用于涡轮转子(2)的沿径向延伸的涡轮叶片(1)，其中所述涂层(9)施加在径向外侧的叶片末端表面处。
12.根据权利要求11所述的涂覆基底(18)，其特征在于，所述研磨涂层(5)中的研磨颗粒(7)的重量内容物沿径向方向(r)增大。
13.用于制造根据前述权利要求中任一项所述的涂覆基底(18)的方法，其特征在于，所述耐磨的研磨涂层(5)由激光金属成型形成。
14.根据权利要求13所述的方法，其特征在于，首先所述中间层(8)由适合的涂覆方法形成，并且其次所述研磨涂层(5)由激光金属成型形成。
15.根据权利要求13所述的方法，其特征在于，熔池(16)中的温度或温度分布在所述研磨涂层(5)的形成期间记录，以控制所述激光功率，使得所述研磨的涂层(5)的形成期间的所述熔池(16)的温度处于所述基底材料(12)的液线温度与所述研磨颗粒(7)的熔化温度或者所述第一或第二颗粒涂层(20)的熔化温度或液线温度之间。
16.根据权利要求14所述的方法，其特征在于，熔池(16)中的温度或温度分布在所述研磨涂层(5)的形成期间记录，以控制所述激光功率，使得所述研磨涂层(5)的形成期间的所述熔池(16)的温度处于所述基质材料(6)的液线温度与所述研磨颗粒(7)的熔化温度或者所述第一或第二颗粒涂层(20)的熔化温度或液线温度之间。
17.根据权利要求13至权利要求16中任一项所述的方法，其特征在于，在之前的步骤中，涂覆所述研磨颗粒(7)，其中所述步骤包括以下子步骤：
a)通过盐浴沉积将所述第一颗粒涂层(19)形成在所述研磨颗粒(7)上，以及可选地
b)由无电极沉积在所述第一颗粒涂层(19)上形成所述第二颗粒涂层(20)。
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