CN101612823A - 多层热障涂层 - Google Patents

多层热障涂层 Download PDF

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CN101612823A
CN101612823A CN200910149755A CN200910149755A CN101612823A CN 101612823 A CN101612823 A CN 101612823A CN 200910149755 A CN200910149755 A CN 200910149755A CN 200910149755 A CN200910149755 A CN 200910149755A CN 101612823 A CN101612823 A CN 101612823A
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zirconic
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G·E·威茨
H·-P·博斯曼
V·施克洛弗
S·巴彻戈达
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Eidgenoessische Technische Hochschule Zurich ETHZ
Ansaldo Energia IP UK Ltd
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Alstom Technology AG
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Abstract

本发明涉及多层热障涂层及在其表面上具有热障涂层(2－6)的组件(1)，其中热障涂层包含至少一个包括化学稳定氧化锆的层(3)，其中至少间接与该包括化学稳定氧化锆的层(3)相临，且在面向其表面侧，提供与包含氧化钙的周围环境污染物组合物不反应，且不与包括化学稳定氧化锆的层(3)中的材料反应的保护层(4)和/或渗入区域(5)。本发明还涉及制备上述组件的方法和使用该特殊系统用来镀覆避免CMAS侵害的热障涂层。

Description

多层热障涂层
技术领域
本发明涉及氧化钇基热障涂层及其避免钙-铝-镁硅酸盐(CMAS)侵蚀的保护作用的技术领域。
技术背景
热障涂层会被周围环境的污染物不稳定化，大多数是被钙-铝-镁硅酸盐(Ca-Mg-Al-SiO，也称为CMAS，其中S代表SiO而不是硫)不稳定化，形成沉积物，该沉积物能够与氧化钇稳定的氧化锆反应，从而导致TBC剥落。对于现有技术中认识到的相应机制的一般的描述，例如请参考US5660885的介绍部分。近年来，在这一方面已经提出了多个解决方案。
US5560885-通过牺牲性表面层保护热障涂层：公开了一种以有效量置于热障涂层上的牺牲性氧化物涂层，从而在热障涂层的工作温度下，通过升高污染物组分的融化温度或粘度，氧化物层发生化学反应，被污染物组分消耗掉，其中牺牲性涂层选自氧化铝，氧化镁，氧化铬，氧化钙，锆酸钙，氧化钪，二氧化硅，氧化铝镁及其混合。
US5773141-被保护的热障涂层复合材料：公开了一种邻近热障涂层的外表面的连续牺牲性氧化物层，其中该热障涂层是化学稳定的氧化锆，选自氧化钇稳定氧化锆，氧化钪稳定氧化锆，氧化钙稳定氧化锆，和氧化镁稳定氧化锆，其中牺牲性氧化物层约0.2-250微米厚，且牺牲性氧化物层不与氧化锆混合，所述牺牲性涂层和污染物组分反应，从而避免污染物渗入热障涂层。
US5851678-具有非渗透性涂层的复合热障涂层：公开了一种邻近热障涂层外表面的连续非渗透性阻挡层，其中该非渗透性阻挡层是致密的、非多孔的，且该非渗透性阻挡层的厚度大约0.2-250微米厚，所述非渗透性阻挡层选自：氧化钽，氧化钪，氧化铪，氧化铝镁，锆酸钙，碳化硅，碳化钽，碳化钛，碳化钨，碳氧化硅，氮化硅，氮化锆，氮化钽，氮化硼，硅化铬，硅化钼，硅化钽，硅化钛，硅化钨，硅化锆，银，金和它们的合金。
US5871820-用非渗透性阻挡层保护热障涂层：公开了一种保护TBC(热障涂层)免受液体污染物的污染的非渗透性涂层，其中该非渗透性涂层选自金属氧化物，金属碳化物，金属氮化物，金属硅化物和其混合物，其中金属氧化物涂层选自氧化硅，氧化钽，氧化钪，氧化铪，氧化铝镁和其混合物；其中金属碳化物涂层选自碳化硅，碳化钽，碳化钛，碳化钨，碳氧化硅和其混合物；其中金属氮化物涂层选自氮化硅，氮化锆，氮化钽，氮化硼，和其混合物；其中金属硅化物涂层选自硅化铬，硅化钼，硅化钽，硅化钛，硅化钨，硅化锆及其混合物。
US5914189-具有多层涂层的被保护的热障涂层复合材料：公开了热障涂层涂覆的零件，其至少有两个外部保护涂层降低熔融污染物低共熔混合物渗入热障层中的开孔中。
US6261643-具有多层涂层的被保护的热障涂层复合材料：公开了一种体系，其具有两个保护层，其通过在热障涂层上沉积非渗透性阻挡第一涂层或牺牲性氧化物第一涂层、然后在第一涂层上沉积至少一层其它的第二保护涂层来制备，该第二保护涂层是非润湿性的、牺牲性的或非渗透性的。
US6627323-抗沉积物的热障涂层及其涂覆方法：公开了“一种覆盖在热障涂层上的保护性涂层系统，该保护性涂层系统包括内氧化铝层和外氧化铝层，并有铂族金属层嵌入其之间”。
US6720038-形成抗沉积物的涂层的方法及该方法形成的涂层：公开了一种通过PVD形成含有氧化钇稳定氧化锆和氧化铝的混合物的涂层的方法，该涂层能够防止CMAS的渗入。
US6794059-多层热障涂层：公开了一种多孔非牺牲性表层涂层，用于防护抵抗周围环境污染物。表层涂层的材料选自carts稳定的氧化锆(CSZ)，钙稳定氧化锆(CaSZ)；氧化锆增韧氧化铝(ZTA)；包含两个或更多的化合物的复合氧化物，其中化合物选自铝，钴，铬，铁，钛和镍的氧化物及其两种或两种以上的混合物；表层涂层选自比热障涂层对周围环境污染物更具抵抗力的材料。
US7226668-包含反应性保护材料的热障涂层和制备方法：公开了一种多层体系，其具有保护避免CMAS的侵蚀的外层，包括“(1)一种CMAS反应性材料，最多为100％的量，并足够保护热障涂层至少部分地抵抗会沉积在暴露的外表面上的CMAS，该CMAS反应性材料包括碱土金属的铝酸盐、碱土金属的硅铝酸盐或其混合物，其中碱土金属选自钡，锶和其混合物；(2)可选地，一种陶瓷热障涂层材料。
US2006/280955公开了一种物品，包括含硅的基体，覆盖在基体上的环境阻挡层(EBC)，其中EBC包括一个外部碱土金属铝硅酸盐阻挡层，和用于该外阻挡层上的抗腐蚀的氧化铝/铝酸盐密封剂。还提供了一种用于在EBC的外阻挡层上形成抗腐蚀的氧化铝/硅酸铝密封剂层的方法；还提供了另一种处理多孔外阻挡层的方法，用包含抗腐蚀氧化铝/铝酸盐密封剂前体的液体组合物渗入多孔的外阻挡层，其中氧化铝/铝酸盐密封剂前体的量应当在转变成抗腐蚀的氧化铝/铝酸盐密封剂时，足以保护环境阻挡层抵抗周围环境的侵害；将渗入多孔外阻挡层内的氧化铝/铝酸盐密封剂前体转化为抗腐蚀氧化铝/铝酸盐密封剂。该文件清楚地阐述了硫酸盐是腐蚀性物质，在许多正文部分提到“钙、镁、钠等的硫酸盐和/或氯化物”，其中包括CaSO4作为腐蚀性物质。
这些文件的大多数中公开的材料应能够与液体沉积物反应，形成一种不能渗入TBC的固体相。其他的文件描述了能够阻止液体渗入的非渗透性涂层。
发明内容
因而，本发明的目的是为暴露在热气流中的组件如燃气轮机中的组件提供一种改进的热障涂层。具体而言，热障涂层的改进应在于对含有钙的氧化物的周围环境污染物组合物的抵抗，即较少倾向于CMAS侵蚀的热障涂层。另外，本发明的目的还提供用于制备这种热障涂层的方法，和具体的体系作为阻挡层的保护层的应用。
因此，本发明涉及一种阻挡层结构，或更具体地说涉及在其表面具有热障涂层的组件，其中该热障涂层包括至少一层包含化学稳定氧化锆的层。根据本发明，该阻挡层结构的特征特别在于，至少间接与包含化学稳定氧化锆的层相邻并在其面向表面一侧(即在直接或间接面对热气流并因此而暴露于上述污染物的一侧)提供保护层。实际上，它可以是一个独立的真正的保护层，然而也可以是一个渗入区域，其中保护性材料渗入包含化学稳定氧化锆的层。该保护层、该渗入区域或一般而言该保护材料的特征在于不与含有钙的氧化物的周围环境污染物组合物反应，并且其不与包含化学稳定氧化锆的层的材料反应。
热障涂层能够被周围环境污染物去稳定化，大多数是被钙-铝-镁硅酸盐(CMAS)去稳定化，形成能够与氧化钇稳定氧化锆反应的沉积物，并导致TBC剥落。
CMAS的侵蚀机制已经被确认为通过Ca在YSZ中的扩散导致其不稳定而进行，甚至通过固态反应进行。如至今为止一向所认为的那样，TBC退化机制不需要涉及溶融沉积物，它能够通过气态污染物直接与YSZ反应从而导致Ca渗入YSZ而发生。Ca在YSZ层中的扩散改变了先前沉积的用6-8wt％氧化钇部分稳定的氧化锆的微结构，导致了全稳定氧化锆含量增加。该全稳定的氧化锆的含量的增加导致了在TBC中残余应力的增加、TBC层的去稳定作用及其剥落。
因此缓和机制不能够有效地依赖于现有技术已提出的解决方法，即非渗入或牺牲性涂层保护免受熔融沉积物污染的侵害。所需要的是一种不与周围环境污染物组合物反应、且也不与包含化学稳定氧化锆的层的材料反应的涂层或体系。因此，不必要求这种保护材料/层如在现有技术的体系中总是被描述为必要的和关键的是非渗透性或牺牲性的。恰恰相反，重要的是保护层/渗入区域的材料既不能与包含钙的氧化物、尤其是CMAS的周围环境污染物组合物反应，也不能与TBC材料反应。优选地，此外它还具有对来自燃烧环境的钙的低的扩散系数，优选地，它具有对来自燃烧环境的钙的基本上等于零的扩散系数。
钙被证明从燃烧环境通过固态过程扩散到氧化钇稳定氧化锆(YSZ)TBC层。在已被本发明提出的体系、例如硫酸钙(CaSO4)所涂覆的氧化钇稳定氧化锆层中，未观测到Ca扩散到TBC层中(扩散系数基本为0)，相应地，其下的TBC层被高度保护免受上述的CMAS的侵害。同样，含Ca的保护性组合物具有减小的对来自外部燃烧环境的钙的扩散系数，能够达到相同的功能。
因此，本发明提出的解决方案在于通过使用不和Ca反应的外层来减轻CMAS侵害。这可以通过使用具有高钙含量的外层实现，也可以是其他所知的与CaO不反应的材料。我们通过试验发现，当CaSO4存在时，它和YSZ不反应。
典型地，这样的保护性涂层具有10-2000微米的厚度范围，优选在10-100微米之间。优选地，该保护层和/或该渗入区域，将组件暴露于热气流/燃烧气流的整个表面覆盖。然而，也可以使保护层和/或渗入区域仅覆盖暴露程度最高的区域。
术语保护层应被理解为真正的基本上连续的层结构，其保护/覆盖暴露于热气流通道的重要部分(如果不是全部表面)，该保护层避免CMAS的侵害。优选地，保护层因此形成一个覆盖组件上全部化学稳定氧化锆层的连续层。
根据依照本发明的组件的第一个优选实施方案，保护层包括钙体系，该钙体系选自：硫酸钙，钙掺杂SrZrO3，锶掺杂CaZrO3。其他的体系也相当可行，例如钙稳定的氧化锆、SrZrO3、CaZrO3作为外层。然而，目前为止优选的体系是包含硫酸钙的体系，最优选的是该保护材料基本上由硫酸钙组成。实质上一个硫酸钙层或渗入区域对于钙扩散具有几乎完全的阻挡效果(基本上是0扩散系数)，尽管该层能够渗透其他成分。
如上所述，US200610280955A1指出硫酸盐是腐蚀性物质。US200710160859简要地提到SO2作为一种污染物气体，EP178122提到硫酸铝作为氧化铝生产的先驱物，但同样也提到了硫酸盐是腐蚀性物质。在其他文献中，也发现提到CaSO4为腐蚀性物质，例如水合CaSO4是众所周知的用作FVV炉渣的组分之一。显然CaSO4在现有技术里未被视为腐蚀保护材料。其同样也没有被提到是CMAS的组分，而硫只是在某些文献中被提到为可能的污染物，而作为腐蚀性物质，另一环境阻挡层应提供对它的防护作用。
根据本发明的另一个实施方案，保护层和包含化学稳定氧化锆的层是直接相邻的。
优选地，包含化学稳定氧化锆的层选自氧化钇稳定氧化锆，氧化钪稳定氧化锆，氧化钙稳定氧化锆，和氧化镁稳定氧化锆或他们的组合。优选的是，包含化学稳定氧化锆的层基本上是由氧化钇稳定氧化锆构成。
进一步可能的是，在包含化学稳定氧化锆的层面对保护层的一侧，有一个渗入区域，其中保护层的材料渗入到包含化学稳定氧化锆的层的孔中。如上所述，如果提供此类的渗入区域而没有实际的保护层，实际上有时甚至也是足够的，只要该渗入区域基本上覆盖该其下的热障涂层最上面的表面结构，保护其免受污染物质的侵害。典型地，这样的渗入区域，单独或与附加的保护层相组合，其厚度在10-100微米的范围之间。
保护层和/或渗入区域可以是热障层结构的终端层和暴露层。然而也可以在面对保护层侧的表面上提供另外的层结构。然而优选保护层和/或渗入区域直接与包含化学稳定氧化锆的层相邻，并且是暴露于热污染物空气流的热障涂层结构的最外层。
如上所述，所述组件可以例如是暴露于压缩/燃烧空气流的燃气轮机组件。也可以是例如外壳或引导组件或者是燃烧腔室瓦或者其零件或其组件。也可以是轮叶(blade)或其零件或其组件，或者叶片(vane)或其零件或其组件。
本发明进一步涉及一种方法，用来制备上述的组件。优选该方法的特征在于，具有至少一个包含化学稳定氧化锆(优选YSZ)的层的组件用保护层涂覆，使用的涂覆方法选自：浆料涂覆；热喷涂涂覆；物理气相沉积；化学气相沉积；沉积CaO并使其在炉中与含有10Pa到1000Pa之间的SO2和100Pa到25kPa之间的O2的控制气氛反应，反应温度范围在300℃到800℃之间。CaSO4或CaSO4-2H2O也可以反应以层的形式直接沉积在涂层上形成保护层。
需要注意的是，只有在特定的处理条件下，才能够实现由CaO形成这种有用的保护层。实际上，CaSO4只能够在这种特定条件下形成，即，如上述处理条件中所提供的那样当气氛中存在有非常高的硫含量时。在燃气轮机的常规操作条件下是不能达到如此高的硫含量的。
因此在CMAS侵害下的燃气轮机中，CaSO4不是常规的产物。当CMAS侵害出现时，S的量不足以与所有现存的CaO发生反应。所以，即使燃气轮机用沙土操作，石英(SiO2)是沙的主要成分，还有石灰石(大多数是CaCO3)，长石，绿泥石，海绿石(三者都是硅酸盐)，而所有上述材料都不含硫(或者仅含硫作为少量的杂质)。由上述这些材料构成的沙子不能生产出能够形成具有保护作用的层的程度的CaSO4。
从上面引用的现有技术的专利文件可以看出，CaSO4不被认为是在CMAS侵害下能够在燃气轮机中形成的常规产物。只有US2006/0280955提到了CaSO4，其中它只作为污染物被提及，并且未提及硫酸盐和CMAS的混合物，当然也不是作为CMAS的成分或保护层。
因此，对于本领域技术人员而言，CaSO4不被视为在CMAS侵害下在燃气轮机中的产物，更不会形成保护层。实际上，只在非常特定的情形下才可以由CaO形成CaSO4。
优选地，该具有至少一个包含化学稳定氧化锆的层的组件是如下制备的，即，典型地由高温合金制备的组件优选地被喷砂，例如通过大气等离子喷涂或高速氧燃料热喷涂而沉积粘合层，然后通过等离子喷涂沉积化学稳定氧化锆、优选氧化钇稳定氧化锆热障涂层。
本发明进一步涉及一些用于阻止钙扩散到包含化学稳定氧化锆的热障涂层中的体系的应用。建议的体系选自：钙稳定氧化锆，CaSO4，SrZrO3，CaZrO3，钙掺杂SrZrO3，锶掺杂CaZrO3，用于组件的包含化学稳定氧化锆的热障涂层的外部区域的外部和/或作为包含化学稳定氧化锆的热障涂层的保护层。优选地，只在基本上由氧化钇稳定氧化锆构成的热障涂层上使用硫酸钙作为基本上由硫酸钙构成的保护层。
本发明的其他实施方案在从属权利要求中概括。
附图说明
本发明的优选实施方案由如下附图所示：
图1具有根据本发明的热障涂层的组件的切面示意图；
图2根据图1的组件的切面示意图，显示出了渗入区域；
图3根据图1的组件的切面示意图，在保护层顶部具有附加层；
图4退役的TBC中的YSZ-CMAS界面的横截面，显示了在界面处的反应层；和
图5在退役的TBC中的在YSZ(左下方)和CaSO4(深色层)之间的界面层，显示了在界面处无反应层。
具体实施方式
对于附图，其用于描述本发明的优选实施方案，而不用于限制本发明，图1显示了一个可能的组件结构的部分切面区域。
该结构包括组件1的基体金属。在基体金属上通常会有一个粘合涂层2用来粘接随后的由YSZ或类似体系制备的陶瓷热障涂层3。根据本发明，作为顶层，此处提供硫酸钙层4作为保护层。需要注意的是，热障涂层3可能是包含有几个单独的相同的或不同的热障涂层材料的材料层的结构。
如图2中所示意性显示的，通常地，特别是当使用液体渗入或浸镀涂覆来施加保护层4时，会形成一个渗入区域5，其为热障涂层3内的的区域，其中保护层4的材料渗入热障涂层表面的孔中。这样的渗入区域5厚度可以在10-100微米之间。如上已讨论的，实际的保护层4可能甚至只由这种渗入区域构成，只要该渗入区域确实能够提供本发明的屏蔽，避免钙扩散到热障涂层3中。
如图3中进一步示意性显示的，保护层4(具有或不具有渗入区域)不必一定是直接暴露至例如在燃气轮机中的燃烧空气的最顶层。在保护层4的上面可以提供附加层6。
为了完整起见，进一步指出，保护层4的构思是为了防止钙扩散进入热障涂层材料(优选YSZ)构成的层中。相应地，因而优选此类的保护层(或者渗入区域)是直接与热障涂层2相邻的，然而，这不是必需的。也可以在热障涂层2和保护层4之间提供一个或多个附加层。
基于上述考虑，本发明提出的避免CMAS侵害的解决方案是：
(1)将氧化钙稳定氧化锆应用于TBC的外层中，代替氧化钇稳定氧化锆
(2)在TBC顶部沉积CaSO4层，从而保护其避免CMAS的侵害
(3)将SrZrO3、CaZrO3、钙掺杂SrZrO3或锶掺杂CaZrO3应用于TBC的外层中。
所有的解决方法都能够单独或共同使用，多层体系也能够在阶梯层体系中使用。外层能够用作顶层，也能够渗入最大100μm的TBC孔中，从而允许使用液体渗入或浸镀涂覆作为沉积方法。在解决方案1)、2)和3)中的材料也具有热膨胀系数接近氧化钇稳定氧化锆的热膨胀系数(10-6K-1)的优势，这使得可以形成一个在热循环时不会开裂的保护层。
可能的组件和涂有CaSO4的涂层的描述：
高温合金基体，通过APS(常压等离子喷涂)或HVOF(高速氧燃料热喷涂)沉积的粘合层，通过等离子喷涂沉积的氧化钇稳定氧化锆热障涂层，和以下述方法之一沉积的CaSO4环境阻挡层：
1)浆料涂覆
2)热喷涂
3)PVD(物理气相沉积)
4)CVD(化学气相沉积)
5)沉积CaO，在含SO2气氛中使其反应
可能的组件和涂层(CaZrO3或钙稳定氧化锆涂覆)的说明：
通过喷砂预备一个GT高温合金零件，通过APS(常压等离子喷涂)或HVOF(高速氧燃料热喷涂)沉积粘合涂层，通过等离子喷涂沉积氧化钇稳定氧化锆热障涂层，通过等离子喷涂沉积CaZrO3或Ca稳定氧化锆环境阻挡涂层。
根据本发明的镀覆有环境阻挡涂层的可能零件可以是：燃烧腔室瓦，叶片(vanes)，轮叶(blades)等等。
试验部分：
采用上述在热障涂层(YSZ)上面形成硫酸钙保护层的工艺过程，在标准气轮机组件YSZ热障涂层3上镀覆硫酸钙保护层4，然后投入测试条件。
在燃气轮机中在标准条件下，相应的保护效果在延续的操作中(在TBC平均表面温度高于1000℃，8000h)进行测试。
采用图4和5对标准CMAS层形成在YSZ热障涂层表面和形成在依照本发明所给出的保护层表面进行比较。
图4显示了一个退役的TBC中的YSZ-CMAS界面的横截面，显示了有反应层位于界面处。在该图中，在与CMAS沉积层7的界面处的TBC3显示出包含Zr、Y以及Ca、Mg和来自CMAS沉积物的一些其他化合物的反应层8。在以下的TBC中进行的元素分析显示，Ca的含量最高为10wt％，甚至在远离界面10-20微米的TBC中，也能够观测到几个重量％的Ca。
图5显示了在退役的TBC中在YSZ 3(左下方)和CaSO44(深色层)之间的界面层，显示了界面处没有反应层。在有CaSO4层的样品中，没有发现反应层8。远离界面10微米处，TBC中的钙含量低于1wt％，在EDX系统的检测限/噪音水平附近。
不局限于任何理论上的解释，相比于CMAS与TBC而减少的CaSO4与TBC的反应可以通过如下考虑来解释：
CMAS包含大量的CaO(而不是CaSO4！)，它的含量可以最高为35wt％甚至更高。CaO能够扩散到YSZ中，导致在YSZ结构中增加了稳定化元素的含量，从而导致YSZ的相组成向着立方氧化锆转变。增加的立方氧化锆含量可以通过X射线衍射在直接接触到CMAS的退役样品中观测到，清楚的显示了TBC比原始沉积的TBC包含更高含量的稳定化元素，从而导致在TBC层中残余应力的增加，和TBC层的非稳定化及其剥落。
CaSO4不能溶解在YSZ中，在YSZ中从CaSO4结合Ca，将不得不通过第一步的从CaSO4→CaO的转变，然后通过CaO结合入TBC中来进行。第一个反应在机器工作条件下不会发生，因为在高达1200℃的温度下，CaSO4的分解需要极端低的硫含量(SO2低于1ppm)。在机器中CMAS的进入发生的地方，SO2浓度另一方面不够高到将CaO转变成CaSO4，且SO2的浓度也不够低到允许现存的CaSO4分解成CaO。从X射线衍射能够观测到，被涂覆CaSO4的退役TBC样品未显示出任何其稳定元素的含量增加的迹象。
附图标记列表
1基体金属/组件
2粘合涂层
3热障涂层
4硫酸钙层
5渗入区域
6附加层
7CMAS沉积层
8反应层

Claims (15)

1、在其表面具有热障涂层(2-6)的组件(1)，其中热障涂层包含至少一层包含化学稳定氧化锆的层(3)，且其中至少间接与该包含化学稳定氧化锆的层(3)相邻并且在其面向表面一侧，提供不与包含氧化钙的周围环境污染物组合物反应，且不与所述包含化学稳定氧化锆的层(3)中的材料反应的保护层(4)和/或渗入区域(5)。
2、如权利要求1所述的组件(1)，其中保护层(4)包含选自硫酸钙、钙掺杂的SrZrO3、锶掺杂的CaZrO3的钙体系。
3、如权利要求1所述的组件(1)，其中保护层(4)基本上由硫酸钙组成。
4、如上述任一权利要求所述的组件(1)，其中保护层(4)与包含化学稳定氧化锆的层(3)直接相邻。
5、如上述任一权利要求所述的组件(1)，其中包含化学稳定氧化锆的层(3)选自氧化钇稳定的氧化锆、氧化钪稳定的氧化锆和氧化钙稳定的氧化锆或它们的组合。
6、如权利要求1-4中任一项所述的组件(1)，其中包含化学稳定氧化锆的层(3)基本上是由氧化钇稳定的氧化锆构成。
7、如上述任一权利要求所述的组件(1)，其中在包含化学稳定氧化锆的层(3)面对保护层(4)的一侧有渗入区域(5)，其中保护层(4)的材料渗入到包含化学稳定氧化锆的层(3)的孔隙中。
8、如权利要求7所述的组件(1)，其中渗入区域(5)厚度在10-100微米之间。
9、如上述任一权利要求所述的组件(1)，其中保护层(4)是渗透性的且非牺牲性的。
10、如上述任一权利要求所述的组件(1)，其中保护层(4)面对表面的一侧形成该组件的实际最终表面层。
11、如上述任一权利要求所述的组件(1)，其中该组件(1)是暴露于压缩/燃烧空气流中的燃气轮机组件，其选自外壳/导向组件/燃烧腔室瓦或它们的零件或组件、叶片或其零件或其组件、轮叶或其零件或其组件。
12、制造如上述任一权利要求所述的组件(1)的方法，其中通过沉积CaSO4或CaSO4-2H2O而用保护层(4)涂覆具有至少一层包含化学稳定氧化锆的层(3)的组件(1)，所述涂覆方法选自浆料涂覆、热喷涂涂覆、物理气相沉积、化学气相沉积，或者通过上述涂覆方法之一沉积CaO，并使其在炉中与含10Pa到1000Pa之间的SO2和100Pa到25kPa之间的O2的控制气氛在300℃到800℃之间的温度范围进行反应，从而用保护层(4)涂层组件(1)。
13、如权利要求12所述的方法，其中具有至少一层包含化学稳定氧化锆的层的(3)组件(1)是如下制备的：由高温合金制成的组件(1)经喷砂处理，通过大气等离子喷涂或高速氧燃料热喷涂沉积粘合涂层，然后通过等离子喷涂氧化钇稳定氧化锆热障涂层。
14、氧化钙稳定氧化锆、CaSO4、SrZrO3、CaZrO3、钙掺杂SrZrO3、锶掺杂CaZrO3的用途，用于组件的包含化学稳定氧化锆的热障涂层(2)的外部区域(5)和/或用作包含化学稳定氧化锆的热障涂层(2)的保护层(4)，以防止钙在包含化学稳定氧化锆的热障涂层(2)中扩散。
15、如权利要求14中的用途，其中只在基本上由氧化钇稳定氧化锆组成的热障层(2)上使用硫酸钙作为基本上由硫酸钙组成的保护层(4)。
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