CN108689725A - 复合涂层及其制造方法 - Google Patents

复合涂层及其制造方法 Download PDF

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CN108689725A
CN108689725A CN201810648474.5A CN201810648474A CN108689725A CN 108689725 A CN108689725 A CN 108689725A CN 201810648474 A CN201810648474 A CN 201810648474A CN 108689725 A CN108689725 A CN 108689725A
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coating
mosi
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metal silicide
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J.万
M.K.布伦
P.J.梅施特
R.萨拉菲-诺尔
D.M.利普金
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General Electric Co
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Abstract

一种制品，包括基材和设置在基材表面上的涂层。该涂层包括至少一个基本上由MoSi2或WSi2或(Mo,W)Si2或铂族金属硅化物构成的金属硅化物层，和至少一个基本上由Si3N4构成的层。

Description

复合涂层及其制造方法
本申请是申请日为2014年3月11日，申请号为201480016254.0，发明名称为“复合涂层及其制造方法”的发明专利申请的分案申请。
技术领域
本发明技术总体上涉及涂层系统和方法，该涂层系统和方法适用于保护暴露在高温环境下的制品或部件，如涡轮发动机的不利热环境。更具体地，本发明技术涉及一种涂层，该涂层可用作抗氧化涂层和/或对于环境和/或热屏障涂层的结合涂层。
背景技术
陶瓷和耐高温金属间材料和复合材料是目前被认为用于这种高温应用中，如燃烧器衬里、叶片、护罩、叶片和涡轮发动机的其它热区段部件，以及用于设计为在高温下工作的结构中，如换热器和内燃机等应用。复合材料的一些实例包括含硅复合材料，例如其中硅、碳化硅(SiC)、氮化硅(Si3N4)和/或耐高温金属硅化物作为增强相和/或基体相的复合材料。然而，这些应用的环境特点经常含有水蒸汽，已知这在高温下会导致含硅材料的显著表面凹陷和质量损失。水蒸汽在高温下与结构材料反应形成挥发性含硅物类，这经常导致无法接受的高凹陷率。
发明内容
本发明技术提供了复合涂层和在由含硅材料制成的制品或部件上制备复合涂层的方法，该含硅材料如陶瓷基体复合材料(CMC)。复合涂层保护暴露于高温的含硅制品，该高温包括涡轮发动机的不利热环境。
根据该技术的一个实例，制品包括基材和设置在基材表面上的涂层。该涂层包括至少一个基本上由MoSi2、WSi2、或Mo和W的硅化物的组合((Mo,W)Si2)或铂族金属硅化物构成的金属硅化物层，和至少一个基本上由Si3N4构成的层。
根据本发明技术的另一个实例，一种制品包括基材，该基材包括含硅的区域，该含硅的区域包括在金属基体或非金属基体中的SiC、Si3N4和/或过渡金属硅化物作为增强材料；和设置在基材表面上的涂层，该涂层包括MoSi2和Si3N4，其中Si3N4的百分比按体积计大于涂层的约55％。
根据本技术的另一个实例，一种涂覆制品的方法包括：在基材的表面涂敷涂层，该涂层包括至少一个基本上由MoSi2或WSi2或(Mo,W)Si2或铂族金属硅化物构成的金属硅化物层和至少一个基本上由Si3N4构成的层。
根据本技术的另一个方面，提供了一种涂覆包括基材的制品的方法，该基材包括含硅的区域，该含硅的区域包括在金属基体或非金属基体中的SiC、Si3N4和/或过渡金属硅化物作为增强材料；该方法包括：在基材表面上涂敷涂层，该涂层包括MoSi2和Si3N4，其中Si3N4按体积计的百分比大于涂层的约55％。
附图说明
通过下面的详细说明并参考附图，可以更好地理解本技术的其它方面和优点，其中相似的附图标记所指的是本发明技术的相似特征，并且其中：
图1示意性地表示一种制品，该制品包括根据本发明技术的一个实例的涂层系统；
图2示意性地表示一种制品，该制品包括根据本发明技术的另一个实例的涂层系统；
图3示意性地表示一种制品，该制品包括根据本发明技术的另一个实例的涂层系统；
图4示意性地表示根据本发明技术的一个实例的一种方法；
图5示意性地表示根据本发明技术的另一个实例的一种方法；
图6示意性地表示根据本发明技术的另一个实例的一种方法；
图7示意性地表示根据本发明技术的另一个实例的一种方法；
图8示意性地表示多层膨胀与厚度比的关系；和
图9示意性地表示多层膨胀与体积分数的关系。
具体实施方式
本发明技术通常适用于在以相对高的温度、严酷的热循环和应力、氧化和腐蚀为特点的环境中工作的部件或制品。这种部件的例子包括高压和低压涡轮机轮叶(喷嘴)和叶片(叶片(bucket))、护罩、燃烧器衬里、推力增强装置硬件和涡轮发动机的其它热区段部件，然而该技术也已应用到其它部件上。
参考图1，部件或制品10包括具有涂层或涂层系统30的基材20。制品10还可以包括环境屏障涂层(EBC)和/或热屏障涂层(TBC)40，其设置在涂层系统30上。EBC和/或TBC可以是例如多层涂层系统。基材20可包括含硅区域。含硅材料的例子包括含硅、碳化硅、氮化硅、硅化物，例如过渡金属硅化物的那些材料，其中过渡金属是耐高温金属，例如钼或钨或其组合，铂族金属如铂、铱或铑，例如在基体和/或增强体中。进一步的例子包括含有碳化硅作为增强和基体相的陶瓷基体复合材料(CMC)。
涂层系统30可以包括两个主要相，二硅化钼(MoSi2)和氮化硅(Si3N4)。出于加工和/或性质的原因，涂层系统30还可以包括次要相，例如Mo5Si3、Si、Mo5Si3C、SiC和/或SiNx。次要相可能占涂层系统30的少于50％。在涂层系统中，Si3N4的体积百分比可能大于约55％。
参考图2，涂层系统50可包括交替的MoSi2层31,33和Si3N4层32,34。应当理解的是，虽然在图2中所示的与基材20接触的初始层31是MoSi2，但与基材20接触的初始层也可以是Si3N4。还应当认识到，尽管所示的是两层MoSi2与两层Si3N4交替，但MoSi2和Si3N4的层数可以是任何数字，包括各自单一的层。应进一步理解，虽然所示的MoSi2和Si3N4的层数是相等的，但各自的层数可以是不相等的。例如，涂层系统可包括四层MoSi2和3层Si3N4，反之亦然。
参考图3，涂层系统60可包括交替的MoSi2层31,33和Si3N4层32,34。过渡区域35可在交替层31,32；32,33；33,34之间设置。过渡区域35包括MoSi2和Si3N4二相的混合物。过渡区域35还可以包括如上所述的次要相。过渡区域35可以如下面的更加详细的描述地形成。如参考图2的上述讨论，虽然图3所示的涂层系统60包括与基材20接触的MoSi2第一层31，并且MoSi2和Si3N4的层数是相同的，但应当理解的是，涂层系统60可以是如上所述的图2的变体。
参考图4-7，示意性地示出了各种用于涂覆包括基材的制品或部件的方法。因为相似的附图标记指代实施例方法中的相似的特征，那些两个或更多的实施例方法所共有的特征将仅参考一个实施例方法说明。
参考图4，在涂覆制品的方法开始于S100。在S120中，在基材表面上沉积MoSi2，以在基材上形成一层MoSi2。
在形成MoSi2层后，在S150中在MoSi2层上形成Si3N4层。如果MoSi2层和Si3N4层的结合厚度t小于预定的厚度tp(S170：是)，则过程返回到S120，以形成MoSi2的附加层。当MoSi2层和Si3N4层的结合厚度t不小于预定的厚度tp(S170：否)时，在S180处结束过程。
参考图5，根据另一实施例，在涂覆制品的方法开始于S100。在S142中，在形成MoSi2层之后，形成MoSi2与Si3N4的过渡区域。两相的混合物在MoSi2与Si3N4的层之间提供过渡区域，例如如上面参考图3所描述。
参考图6，在S172中，交替的MoSi2和Si3N4层经热处理形成MoSi2与Si3N4的双相混合物。应当理解的是，热处理步骤也可以被图5的方法所包括。
参考图7，根据另一实施例，在S112中，可形成具有预定的体积比的MoSi2与Si3N4的双相混合物。确定工艺参数和/或条件以得到MoSi2与Si3N4的双相混合物，该双相混合物具有一定的体积比，以降低或最小化与基材的CTE失配。可以确定工艺参数和/或条件以控制次要相的物类和/或体积分数。工艺条件和/或参数可以在涂覆过程中进行调整，以实现在厚度上具有分级微结构和性质的涂层。
应当理解的是，本文描述的涂层可通过各种方法形成，包括例如CVD、离子等离子沉积和物理气相沉积(如蒸发或溅射)。
还应当理解的是，减少涂层与基材之间的CTE失配的机制在层-层涂层的实施例(例如图2和3)和包括MoSi2和Si3N4的相混合物的层的实施例之间不同地起作用。在层-层涂层的情况下，MoSi2与Si3N4厚度的期望比率可根据有效热膨胀系数αeff确定。对于MoSi2和Si3N4层的多层涂层，有效热膨胀系数可利用线性弹性分析根据以下公式计算：
αeff＝(tMoSi2E’MoSi2αMoSi2+tSi3N4E’Si3N4αSi3N4)/(tMoSi2E’MoSi2+tSi3N4E’Si3N4)
其中对于每种材料i，ti是堆叠的所有层的总厚度，E′i是双轴弹性模量，定义为E′i＝Ei/(1-vi)，vi是泊松比，αi是热膨胀系数。重排后，厚度比与有效热膨胀相关：
tMoSi2/tSi3N4＝-((αeff-αSi3N4)/(αeff-αMoSi2))(E’Si3N4/E’MoSi2)。
针对关注的材料取代表值：
Si3N4：αSi3N4＝3.3x10-6/C；ESi3N4＝310GPa；vsi3N4＝0.25→E’Si3N4＝413GPa；
MoSi2:αMoSi2＝8.25x10-6/C；EMoSi2＝432GPA；vMoSi2＝＝0.16→E’MoSi2＝514GPa.。
多层膨胀与厚度比之间的关系示于图8，多层膨胀与体积分数之间的关系示于图9。
在考虑的实施例中，例如，具有SiC基体和SiC增强体的基材，为了匹配SiC的CTE(αeff＝αSiC～4.5x10-6/C)，tMoSi2/tSi3N4～0.26。为了匹配SiC+25％的CTE(αeff＝1.25αSiC～6.9x10-6/C)，tMoSi2/tSi3N4～0.71。为了匹配SiC-25％的CTE(αeff＝0.75αSiC～3.4x10-6/C)，tMoSi2/tSi3N4～0.01。
由此，MoSi2:Si3N4厚度比可以是，例如约0.01-约0.75，或例如约0.01-约0.45。由此，相应的MoSi2体积分数(VMoSi2)，根据VMoSi2＝tMoSi2/(tSi3N4+tMoSi2)计算，可以是例如约1-约45vol％MoSi2，或例如约10-约30％vol％MoSi2。
应当理解的是，WSi2或(Mo,W)Si2或铂(Pt)族的硅化物可用于替换上述实施例中的MoSi2。
当MoSi2或WSi2或(Mo,W)Si2/Si3N4的混合物在含氧气氛如空气中被氧化时，Si优先氧化而Mo和/或W被拒绝进入涂层中。如果涂层相对于由氧化形成的SiO2层厚，则硅化物或硅化物/Si3N4混合物很大程度上保留在氧化物之下的基材中，并且过量的Mo和/或W拒绝进入涂层本体中，形成Mo5Si3和/或W5Si3颗粒。
另一方面，如果硅化物是与Si3N4交互成层的铂族硅化物，则在硅化物层中所有的硅已消耗掉时铂族金属将会留下，因为铂族金属的凝聚相氧化物在超过1400℃的温度下是不稳定的。硅化物层的最终状态很可能是具有第二相Pt族金属颗粒的无定形SiO2层。然后氧化将传递至硅化物层之下的Si3N4层中，诸如此类，负面后果很少或没有。
虽然已根据公开的实施例说明了本技术，但应当理解的是，本领域技术人员可以采用其它的形式。因此，本发明的范围由随后的权利要求唯一地限定。

Claims (10)

1.一种制品，其包括：
基材包括含有碳化硅作为增强和基体相的陶瓷基体复合材料 （CMC）；和
设置在所述基材表面上的涂层，该涂层包括：
至少一个基本上由MoSi2或WSi2或(Mo, W)Si2或铂族金属硅化物构成的
金属硅化物层，和
至少一个基本上由Si3N4构成的层，其中所述至少一个金属硅化物层和所述至少一个Si3N4层的厚度比为所述涂层提供基本上等于基材热膨胀系数的热膨胀系数。
2.权利要求1的制品，其还包括：
在所述至少一个金属硅化物层和所述至少一个Si3N4层之间的至少一个过渡区域，该过渡区域包括金属硅化物层和Si3N4二者的混合物。
3.权利要求1的制品，其中Si3N4按涂层体积计的百分比大于约55％，并且其中至少一个基本上由MoSi2构成的金属硅化物层以体积计是所述涂层的约1％-约45％，优选地，是所述涂层的约1％-约30％。
4.权利要求1的制品，其中所述至少一个金属硅化物层基本上由MoSi2构成，并且至少一个MoSi2层的厚度与至少一个Si3N4层的厚度之比是约0.01-约0.75，优选地是约0.01-约0.45。
5.权利要求1的制品，其还包括：
多个基本上由MoSi2或WSi2或(Mo, W)Si2或铂族金属硅化物构成的金属硅化物层；和
多个基本上由Si3N4构成的层，其中金属硅化物和Si3N4的层是交替的。
6.一种制品，其包括：
基材包括含有碳化硅作为增强和基体相的陶瓷基体复合材料 （CMC）；和
设置在所述基材表面上的涂层，该涂层包括MoSi2和Si3N4，其中按体积计，Si3N4的百分比大于所述涂层的约55％。
7.权利要求6的制品，其中MoSi2和Si3N4在混合物中。
8.权利要求7的制品，其中该混合物是功能分级的。
9.权利要求7的制品，其中该混合物进一步包括：
Mo5Si3、Si和/或SiNx。
10.权利要求1或6的制品，其还包括：
在所述涂层上施敷环境屏障涂层和热屏障涂层中的至少一个。
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