CN115803306A - 一种环境屏障的制造方法 - Google Patents

一种环境屏障的制造方法 Download PDF

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CN115803306A
CN115803306A CN202180046902.7A CN202180046902A CN115803306A CN 115803306 A CN115803306 A CN 115803306A CN 202180046902 A CN202180046902 A CN 202180046902A CN 115803306 A CN115803306 A CN 115803306A
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environmental barrier
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L·平
L·P·毕央彻
S·O·M·鲍迪特
J·J·玛斯
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Safran Ceramics SA
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Abstract

一种制造(100)环境屏障的方法，包括以下步骤：用致密化剂前体涂覆(102)稀土硅酸盐粉末，以形成涂覆有致密化剂前体的稀土硅酸盐粉末；将涂覆的粉末热喷涂(104)到基材上，从而在基材上获得至少部分非结晶的环境屏障；对环境屏障进行热处理(106)，以使环境屏障结晶化和致密化。

Description

一种环境屏障的制造方法
技术领域
本公开内容涉及环境屏障(根据"环境屏障涂层"的首字母缩写也称为"EBC")，及其制造方法。
背景技术
在FR3059323中已知用于涡轮机的CMC(陶瓷基质复合材料)部件的环境屏障。
例如，该CMC部件可以是涡轮机的涡轮部件。例如，该涡轮机可以是涡轮喷气发动机。
在航空涡轮机的工作条件下，例如高温和腐蚀性环境，CMC通常对腐蚀很敏感。CMC的腐蚀通常会导致碳化硅氧化成二氧化硅。在水蒸气存在的情况下，二氧化硅会以Si(OH)4氢氧化物的形式挥发出来。这些腐蚀现象导致了CMC的过早降解。此外，为了保证CMC的使用寿命，CMC要通过环境屏障(EBC)来防止湿腐蚀。
EBC通常是通过热喷涂制备的。然而，这种方法通常会产生包含一系列缺陷的涂层，这些缺陷会产生对EBC性能有不利影响的多孔/裂纹3D网络。
另一方面，已经证明EBC的有效性与其气密性密切相关，其气密性是为了阻止氧化性和腐蚀性物质的分子扩散。
有多种解决方案可以改善EBC的一层或多层的密封性，如添加烧结剂或愈合剂。然而，要获得烧结剂和/或愈合剂的均匀分布可能是复杂的。
发明内容
本公开旨在至少部分地克服这些缺点。
本公开涉及一种制造环境屏障的方法，该方法包括以下步骤：
用致密化剂前体涂覆稀土硅酸盐粉末，以形成涂覆有致密化剂前体的稀土硅酸盐粉末；
将涂覆的粉末热喷涂到基材上，从而在基材上获得至少部分非结晶的环境屏障；以及
对环境屏障进行热处理，以使环境屏障结晶化和致密化。
由于用致密化剂前体涂覆稀土硅酸盐粉末，致密化剂前体以及因此的致密化剂得以均匀分布。
应理解，与常规的混合/研磨方法相比，用致密化剂前体涂覆稀土硅酸盐粉末可以获得更好的分布以及更好地控制致密化剂的用量。该方法可以使致密化剂在稀土硅酸盐粉末的基质中获得均匀的分布和非常细密的分散形式。
在热喷涂过程中，致密化剂的前体会在稀土硅酸盐粉末上反应形成致密化剂，并促进环境屏障的致密化。因此，与将两种粉末混合/研磨在一起得到的混合物相比，可以考虑减少致密化剂的质量含量。
作为非限制性的示例，在热喷涂涂覆的粉末过程中得到的致密化剂可以是氧化镁、氧化钙、氧化铁、氧化钇、莫来石、二氧化硅。
在一些实施方式中，热喷涂可以是空气等离子喷涂、真空等离子喷涂或HVOF(根据"高速氧燃料"的首字母缩写)。
在一些实施方式中，可以通过湿法进行涂覆。
在一些实施方式中，可以将稀土硅酸盐粉末浸入包含溶剂和致密化剂前体的溶液中，将溶剂蒸发以形成团聚的涂覆粉末，并将团聚的涂覆粉末解聚以形成涂覆的粉末。
在一些实施方式中，团聚粉末的解聚可以包括在250℃(摄氏度)至600℃的温度下对团聚粉末进行1h(小时)至4h的热处理的步骤。
在一些实施方式中，可以在包含溶剂和致密化剂前体的溶液中流化稀土硅酸盐粉末。
在一些实施方式中，可以通过气体法进行涂覆。
在一些实施方式中，致密化剂的前体可以是有机金属前体。
作为非限制性的例子，有机金属前体可以是金属硝酸盐、金属乙酸盐、金属氯化物、金属醇盐或金属磷。
作为非限制性的例子，有机金属前体可以是镁、铁、铝的金属盐和/或硅和/或磷酸铝和/或氧化镁溶胶、氧化铁、勃姆石、二氧化硅。
使用金属盐可以减少稀土硅酸盐粉末热喷涂过程中二氧化硅的损失，因为置于颗粒外的金属盐被优先氧化。因此，等离子体的氧化物质将优先与金属盐反应，并在稀土硅酸盐粉末周围形成保护性的氧化脉石(oxide gangue)，从而限制二氧化硅的挥发。
在一些实施方式中，致密化剂的前体可以是致密化剂。
作为非限制性的例子，致密化剂的前体可以是氧化镁或二氧化硅，与前体相同的致密化剂。
当二氧化硅作为致密化剂前体时，存在于粉末颗粒外层的二氧化硅将使等离子体"饱和"，从而避免或减少存在于稀土硅酸盐粉末中的二氧化硅的挥发。
在一些实施方式中，涂覆的粉末可以具有核壳结构。
核壳结构是可获得的，其中粉末颗粒包含由致密化剂前体形成的外层(或壳)所包覆的稀土硅酸盐粉末核。壳的厚度可以达到纳米量级，并且烧结剂前体的分布以及烧结剂前体剂量的控制得到了改善。
在一些实施方式中，热处理可以在大于或等于1100℃，优选大于或等于1200℃并且小于或等于1350℃，优选小于或等于1300℃的温度下进行，温度平稳的时间大于或等于5h并且小于或等于50h。
在一些实施方式中，基材可以是陶瓷基质复合材料基材。
CMC材料基材一般由陶瓷纤维以2D或3D方式织成。然后，可以对这些陶瓷纤维进行气体致密化(根据"化学气体渗透"的首字母缩写，也称为"CVI")，单独或与另一种技术相结合，如熔体浸渗(也称为"MI")，以获得由CMC材料制成的基材。
在一些实施方式中，环境屏障可以包含结合层。
作为非限制性的例子，结合层可以由硅制成。
应理解，结合层沉积在基材上，并包含在基材和材料层之间。
附图说明
本公开对象的其他特征和优点将从以下以非限制性示例的方式给出的实施方式并参考附图的描述中示出。
[图1]图1是根据一个实施方式的基材和环境屏障的示意性剖视图。
[图2]图2是根据一个具体实施方式的基材和环境屏障的示意性剖视图。
[图3]图3是根据一个实施方式的涂覆的粉末的示意性剖视图。
[图4]图4是根据另一个实施方式的涂覆的粉末的示意性剖视图。
[图5]图5是表示制造环境屏障的方法的步骤的流程图。
在所有的附图中，共同的元素都使用相同的附图标记来标识。
具体实施方式
图1是覆盖有环境屏障10的基材12的示意图。
作为非限制性的例子，基材12可以是陶瓷基质复合材料基材。
如图2所示意，作为非限制性的例子，环境屏障10可以包含硅结合层14和二硅酸钇层16。
在结合层14和二硅酸钇层16之间的界面处存在二氧化硅层18。二氧化硅层18是硅结合层14氧化形成的氧化硅层。
二硅酸钇层16包含致密化剂。
作为非限制性的例子，致密化剂可以是烧结剂和/或愈合剂。
作为非限制性的例子，烧结剂可以是氧化镁、氧化铁。
作为非限制性的例子，愈合剂是莫来石、二氧化硅或磷酸铝。
作为非限制性的例子，二硅酸钇层16可以包含0.1至5质量％的烧结剂，例如0.4质量％的烧结剂。
可以通过图4的制造方法100获得环境屏障10。
制造环境屏障10的方法100包括用致密化剂的前体24涂覆102稀土硅酸盐粉末22的步骤，以形成涂覆有致密化剂前体的稀土硅酸盐粉末20。
如图3所示，涂覆的粉末20可以具有核壳结构，涂覆的粉末20包含由致密化剂前体24形成的外层(或壳)所包覆的稀土硅酸盐粉末22的核。
或者，如图4所示，涂覆的粉末20可以具有存在于稀土硅酸盐粉末22的表面上的由致密化剂前体24形成的颗粒。
这两种类型的结构可以通过湿法或气体法获得。
涂覆的实施例
稀土二硅酸盐粉末，乙酸镁和蒸馏水。
在1L(升)的蒸馏水中，溶解5质量％的乙酸镁(通常为0.1至10质量％)。
将1kg的稀土二硅酸盐粉末倒入乙酸镁水溶液中。
用磁力棒搅拌混合。
在90℃的烘箱中进行干燥。
在空气中对团聚粉末块进行1小时的400℃热处理，使粉末块变得易碎。
制得涂覆的粉末20。
通过热喷涂方法104将涂覆的粉末20喷涂到基材12上，从而在基材12上获得至少部分非结晶的环境屏障10；
在上述致密化剂的有机金属前体的例子中，致密化剂的有机金属前体，即乙酸镁，在热喷涂过程中会脱水和氧化，在稀土二硅酸盐粉末周围形成致密化剂，其浓度达到所需且受控。可以得到部分非结晶的环境屏障10，其中有稀土二硅酸盐的扁平颗粒(也称为"斑点(splat)")，致密化剂均匀地分布在稀土二硅酸盐的扁平颗粒周围。
然后，环境屏障10经过热处理步骤106，以使环境屏障结晶化和致密化。
作为非限制性的例子，结晶化和致密化热处理106可以包括以100℃/h(摄氏度每小时)的速度升温到1300℃，在1300℃下保持50小时的稳定时间，以100℃/h的速度降温到室温，即20℃左右。
作为非限制性的例子，结晶化和致密化热处理106可以包括以300℃/h(摄氏度每小时)的速度升温到1,350℃，在1,350℃下保持5小时的稳定时间，以100℃/h的速度降温到室温，即20℃左右。
尽管已经参考特定实施方式描述了本公开，但是显然可以在不脱离由权利要求书限定的本发明的一般范围的前提下对这些实施例进行各种修改和改变。此外，所讨论的各种实施方式的各个特征可以在其他的实施方式中组合。因此，说明书和附图应该被认为是说明性的而不是限制性的。

Claims (9)

1.一种制造(100)环境屏障(10)的方法，所述方法包括以下步骤：
用致密化剂前体(24)涂覆(102)稀土硅酸盐粉末(22)，以形成涂覆有致密化剂前体的稀土硅酸盐粉末(20)；
将涂覆的粉末(20)热喷涂(104)到基材(12)上，从而在基材(12)上获得至少部分非结晶的环境屏障(10)；以及
对环境屏障(10)进行热处理(106)，以使环境屏障结晶化和致密化。
2.如权利要求1所述的制造方法(100)，其中涂覆(102)是通过湿法进行的。
3.如权利要求2所述的制造方法(100)，其中将稀土硅酸盐粉末(22)浸入包含溶剂和致密化剂前体(24)的溶液中，将溶剂蒸发以形成团聚的涂覆粉末，并将团聚的涂覆粉末解聚以形成涂覆的粉末(20)。
4.如权利要求2所述的制造方法(100)，其中稀土硅酸盐粉末(22)在包含溶剂和致密化剂前体(24)的溶液中流化。
5.如权利要求1所述的制造方法(100)，其中涂覆(102)是通过气体法进行的。
6.如权利要求1至5中任一项所述的制造方法(100)，其中致密化剂前体(24)是有机金属前体。
7.如权利要求1至6中任一项所述的制造方法(100)，其中所述涂覆的粉末(20)具有核壳结构。
8.权利要求1至7中任一项所述的制造方法，其中所述基材(12)是陶瓷基质复合材料基材。
9.如权利要求1至8中任一项所述的制造方法，其中所述环境屏障(10)包含结合层(14)。
CN202180046902.7A 2020-07-02 2021-06-22 一种环境屏障的制造方法 Pending CN115803306A (zh)

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