CN101481800A - 抗侵蚀及腐蚀的覆层系统及其工艺 - Google Patents

抗侵蚀及腐蚀的覆层系统及其工艺 Download PDF

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CN101481800A
CN101481800A CNA2009100016846A CN200910001684A CN101481800A CN 101481800 A CN101481800 A CN 101481800A CN A2009100016846 A CNA2009100016846 A CN A2009100016846A CN 200910001684 A CN200910001684 A CN 200910001684A CN 101481800 A CN101481800 A CN 101481800A
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coating
coating system
mixture
covering layer
titanium dioxide
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S·S·帕布拉
J·C·谢菲尔
V·K·帕里克
D·V·布奇
T·穆尔斯
J·M·利普金
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General Electric Co
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    • F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
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    • F01D5/288—Protective coatings for blades
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Abstract

本发明涉及抗侵蚀及腐蚀的覆层系统及其工艺。一种覆层系统(10)及工艺，其能够为部件，特别是工业燃气轮机钢质压缩机叶片(18)提供抗侵蚀和腐蚀性。该覆层系统(10)包括该部件基底(16)表面上的金属牺牲底覆层(12)，以及通过热喷涂而沉积在该底覆层(12)上的陶瓷外覆层(14)。该底覆层(12)包含在电势序方面比铁更活泼的金属或金属合金，且可导电地接触该基底(16)的表面。该陶瓷外覆层(14)主要包括陶瓷材料，该陶瓷材料选自包括下列混合物的组：氧化铝和二氧化钛的混合物，氧化铬和二氧化硅的混合物，氧化铬和二氧化钛的混合物，氧化铬、二氧化硅和二氧化钛的混合物，以及二氧化锆、二氧化钛和氧化钇的混合物。

Description

抗侵蚀及腐蚀的覆层系统及其工艺
技术领域
本发明大体涉及用于涡轮机部件的保护性覆层和覆层工艺。更具体地讲，本发明涉及一种覆层系统，该系统适用于燃气轮机的钢质压缩机叶片以提高该叶片的抗水滴侵蚀与腐蚀性。
背景技术
在线水洗、雾化以及蒸发冷却器系统已被用来改进大型工业燃气轮机(例如用以发电的设施所使用的那些)的压缩机性能。这些系统通常必然会在压缩机入口处引入水滴，导致该压缩机第一级的叶片受到高速下水滴的冲击。由铁基合金(包括400系列不锈钢)制成的压缩机叶片易于在其前缘处(包括其根部，叶片翼型件(airfoil)在该根部处附连到叶片平台上)受到水滴侵蚀。该叶片还容易受到沿着该叶片前缘表面的腐蚀麻点的影响，其是由引起电流侵袭(galvanic attack)的污塞颗粒的积聚所产生的。如果该涡轮机在腐蚀性环境中或腐蚀性环境附近运行，例如在化学或石油工厂附近或者在盐性水体附近运行，腐蚀将加剧。
因为压缩机叶片承受着由离心力和振动产生的巨大应力，位于叶片根部的麻点和裂缝可导致高周疲劳(HCF)破裂，如果该叶片没有被移除，将导致该叶片的最终丧失。因此，减少因水滴冲击引起的叶片侵蚀所导致的在压缩机叶片中形成裂缝的可能性，具有重大的意义。尽管由镍和钛合金制成的叶片能够呈现出改进的抗腐蚀性，但它们未必呈现出改进的抗水滴侵蚀性。减轻前缘应力的尝试已包括叶片根部处的设计特征，例如在共同转让的美国专利No.6,902,376和No.7,165,944中所公开的措施。备选地或作为补充，为了改进涡轮机部件的抗腐蚀性，已经提出了多种覆层系统。实例包括授予Allen的美国专利No.3,248,251和授予Mosser的美国专利No.4,537,632和No4,606,967中所记载的、在无机粘合剂(优选是磷酸盐和铬酸盐的混合物)中包含颗粒(例如铝粉)的覆层系统。该覆层系统可通过喷涂来涂敷，随后进行固化。
另一种防护性覆层系统在授予Haskell的共同转让的美国专利No.5,098,797中描述为使用金属牺牲底覆层和陶瓷上覆层。用于该牺牲底覆层的适当材料据说为电动势序高于铁的任何金属或金属合金，其实例包括铝，锌，镉，镁以及它们的合金，且所产生的牺牲底覆层据说是与该叶片表面处于导电性接触的粘结体。Haskell陶瓷外覆层被描述为优选与Allen的陶瓷上覆层具有相同的成分并且以同样的方式沉积，即磷酸盐/铬酸盐粘合剂中包含铝颗粒。
尽管有上述优点，仍希望对压缩机叶片抗水滴侵蚀和腐蚀的能力有进一步的改进。
发明内容
本发明提供了一种能够为部件，特别是工业燃气轮机的钢质压缩机叶片提供抗侵蚀和腐蚀性的覆层系统及工艺。
该覆层系统包括位于该部件表面上的金属牺牲底覆层，以及通过热喷涂而沉积在该底覆层上的陶瓷外覆层。该底覆层包含在电势序方面比铁更活泼的金属或金属合金，并且可导电地接触该部件的表面。该陶瓷外覆层主要包括陶瓷材料，该陶瓷材料选自包括以下混合物的组：氧化铝和二氧化钛的混合物；氧化铬和二氧化硅的混合物；氧化铬和二氧化钛的混合物；氧化铬、二氧化硅和二氧化钛的混合物；以及二氧化锆、二氧化钛和氧化钇的混合物。该覆层系统可选地包括聚合体封闭件以封闭其表面，从而提供保护以防止腐蚀介质的进入，并且还通过其弹性特性而改进了该覆层的固体颗粒和水滴侵蚀特性。
形成该覆层系统的工艺需要沉积金属牺牲底覆层，优选使得该底覆层的成分固结(consolidated)以确保与该部件表面的可导电接触。然后将陶瓷材料热喷涂在该底覆层上以产生陶瓷外覆层，该陶瓷外覆层比该底覆层以及该部件表面更坚硬且有更强的抗侵蚀性。
本发明的重要优点是该覆层系统提供抗腐蚀性和抗水滴侵蚀性的能力，从而增强了该被保护表面的抗腐蚀麻点和抗裂缝腐蚀性，在压缩机叶片的情况下，这具有极大地延长该叶片寿命的潜力。该覆层系统利用了如下事实：结合到压缩机叶片表面并且可导电地接触该表面的牺牲底覆层将提供极好的抗腐蚀性，而坚硬的外覆层将提供抵抗由水冲击所产生的侵蚀的屏蔽，且从而减少麻点腐蚀和裂缝腐蚀的发生。该覆层系统可以有策略地布置在压缩机叶片上，将该覆层的厚度调整为以便提供期望的优点，同时减小可由该覆层系统所引起的翼型件空气动力性能的任何损失。人们认为，该覆层系统另外的优点包括提高该叶片防污性能和旋转叶片损伤容限的能力。
通过下文的详细说明，本发明的其它目标和优点将更容易理解。
附图说明
图1表示了根据本发明的一个实施例的、工业燃气轮机压缩机叶片翼型件表面区域的局部剖视图。
具体实施方式
本发明提供了抗侵蚀和腐蚀覆层系统，该系统特别适合于保护由铁基合金所形成的部件，特别是由马氏体不锈钢形成并且承受水滴侵蚀和腐蚀麻点的工业燃气轮机压缩机叶片。显著的实例包括由400系列马氏体不锈钢(例如AISI 403)和专有配方(例如GTD-450)沉淀硬化马氏体不锈钢形成的第一级压缩机叶片。尽管本发明将参考由不锈钢形成的压缩机叶片进行描述，但应当理解的是，本发明的教导将应用于由各种铁基合金形成的其它部件，并受益于对水滴侵蚀和腐蚀麻点的改进的抗性。
图1示意性地将本发明的覆层系统10表示为包括牺牲底覆层12和覆盖该牺牲底覆层12的坚硬的抗侵蚀的陶瓷外覆层14。底覆层12包括一种或多种在电势序(电极电位)方面高于铁的金属或金属合金，使得该底覆层12可作为对铁基叶片18的下层基底16的牺牲阳极。这样，该底覆层12和叶片基底16形成电偶，且底覆层12比该叶片18的任何未覆层的表面区域腐蚀得快得多。该抗侵蚀陶瓷外覆层14提供水滴和颗粒侵蚀保护，从而保护该牺牲底覆层12以及其提供抗腐蚀麻点和裂纹腐蚀的能力。该覆层系统10可以有策略地布置在该压缩机叶片18上，将该层覆层的单独的厚度调整为以便为压缩机翼型件应用提供特定的优势。
该牺牲底覆层12可以由能够满足上述以下要求的各种成分形成：即，包括足量的在电势序方面高于铁的一种或多种金属或金属合金以使得该底覆层12能够用作对下层的铁基叶片基底16的牺牲阳极。在坚硬的外覆层14侵蚀或剥落(尤其是处在高度腐蚀的盐性环境中)的情况下，用于该牺牲底覆层12的材料还优选能够保护叶片基底16。在损失了外覆层14的情况下，底覆层12还应当能够承受至少600℉至约1150℉(约320℃至约620℃)的温度。用于底覆层12的特别优选的成分由General Electric公司在商业上提供，其名为GECC1(公开于授予Haskell的美国专利No.5，098,797中)，并且在铬酸盐/磷酸盐无机粘合剂之中包括钴和铝颗粒。Haskell的涉及该GECC1材料、特别适用于该材料的成分以及适用于钴与铝颗粒的颗粒尺寸的内容通过引用而结合在本申请中。用于该牺牲底覆层12的其它候选材料包括镀镍和锌，该二者均已知可用作对于铁及其合金的牺牲阳极。根据特定的成分，适用于该牺牲底覆层12的厚度通常介于约五微米到约八微米的范围中。
图1示意性地将该覆层系统表示为还包括聚合体封闭件20，该封闭件20封闭了该外覆层14的表面。封闭件20优选提供保护以防腐蚀介质进入，并且还通过其弹性特性来改进外覆层14的固体颗粒和水滴侵蚀的特性。用于封闭件20的适当材料包括酚醛塑料，含氟聚合物，聚酯，橡胶，以及乙烯基物质，且适用于该封闭件20的厚度介于约1至50微米的范围内在适当的表面处理(例如喷砂处理)之后，该GECC1覆层材料优选通过使用标准喷涂器设备进行喷涂来涂覆，以获得最小约2密耳(约50微米)的总体干膜厚度。该沉积层优选可选地利用强制空气运动和/或高温(例如约100℉(约40℃))来干燥至少十五分钟。然后使该经干燥的层在至少约500℉(约260℃)下固化约三十分钟或更久。可以重复这些步骤，以沉积另外的层以产生所需厚度的底覆层12。然后例如通过用玻璃珠或铝氧化物(氧化铝)颗粒进行喷丸来抛光该底覆层12，以强化该覆层并确保其导电性。为了评定导电性，可将电阻表探针在底覆层12表面上间隔开约一英寸(约2.5厘米)放置，10欧姆或更小的读数表明导电性处于合适的水平。
坚硬的陶瓷外覆层14必须比底覆层12和叶片基底16更坚硬，并且更能抵抗处于非常高的速度下的水滴的侵蚀。候选材料的抗侵蚀性可以使用矿物硬度的莫氏硬度表来初步评定。例如，在莫氏硬度表上金刚砂(天然氧化铝，Al2O3)具有约9的硬度，氧化铬(Cr2O3)具有约8.5的硬度，石英(二氧化硅，SiO2)具有约7的硬度，二氧化锆(ZrO2)具有约6.5的硬度，以及二氧化钛(TiO2)具有约5.5至6.5的硬度。据记载，氧化铝和二氧化钛的混合物具有约6的硬度，氧化铝和二氧化锆的混合物具有约5.7的硬度。基于提高硬度的期望，认为特别优选的成分是氧化铝和二氧化钛的混合物，例如，按重量分别约50/50，或60/40，或87/13，优选的是约70％至99％重量比的氧化铝，其余为二氧化钛。其它候选材料也是混合物，且包括：氧化铬和二氧化硅(例如，按重量分别约为95/5)的混合物；氧化铬和二氧化钛(例如，按重量分别为约45/55)的混合物；氧化铬、二氧化硅和二氧化钛(例如，按重量分别为约92/5/3)的混合物；以及二氧化锆、二氧化钛和氧化钇(Y2O3)的混合物(例如，按重量分别为约72/18/10)。针对这些成分所提到的特定比例是基于相信其抗侵蚀性在这些比例时被最大化。但是，应当理解的是这些成分是名义上的。抗磨性也受到关注，有文献报道氧化铬和二氧化钛均可改进颗粒侵蚀。
为了提高由上述坚硬陶瓷材料形成的覆层所提供的侵蚀防护，认为通过热喷涂，特别是通过等离子体喷涂以及高速等离子体喷涂进行沉积是优选的覆层技术，因为认为热喷涂工艺过程可增加用于形成该覆层的粉末颗粒的硬度。如本领域中已知的，通过热喷涂工艺而沉积的覆层材料最初通常是粉末形式的，然后在粉末颗粒离开喷枪时被熔融。该熔融颗粒以“泼溅(splats)”的形式沉积在该目标表面上，从而形成具有非柱状的、不规则展平的颗粒以及一定程度的不均匀性和多孔性的覆层。等离子体喷涂包括空气等离子体喷涂(APS)和低压等离子体喷涂(LPPS，也称作真空等离子体喷涂(VPS))，除了等离子体喷涂之外，另一种值得注意的热喷涂工艺过程是高速氧燃料(HVOF)沉积。
由于压缩机叶片的空气动力学要求，外覆层14的表面光洁度也很重要，并且该外覆层14的表面粗糙度优选是100微英寸(约2.5微米)Ra或更小。热喷涂工艺过程还使得陶瓷外覆层14能够选择性地沉积在压缩机叶片18上，使外覆层14的厚度调整为以便为压缩机翼型件应用提供特定的优势。特别的是，可应用陶瓷外覆层14，以使其厚度在叶片18的翼型件表面上沿空气流动方向逐渐减小(渐弱)，以减弱对空气动力效率的任何不良影响。不过，可预见的是可通过其它方法生成适当坚硬的陶瓷外覆层14，例如通过低温蒸镀工艺来生成。
在初步试验中，空气等离子体喷涂(APS)的氧化铝-二氧化钛外覆层已经在抗侵蚀性、抗腐蚀性以及与本发明的牺牲底覆层的相容性等方面呈现出良好的性能。在这些试验的其中各试验中，测试试样是通过空气等离子体喷涂而覆有氧化铝和二氧化钛混合物的GTD-450试件，其中氧化铝：二氧化钛的重量比约为55:45至97:3。所产生的覆层具有约五密耳(约130微米)的厚度。
水滴侵蚀测试在试验台上完成，该试验台构造成用于Dv90＝700微米的水滴(水容量的90％包含于700微米或更小的水滴中)，降水速度约为20英寸/小时(约50厘米/小时)。该喷涂由非空气辅助的雾化喷嘴产生，该雾化喷嘴产生了均匀地分散的全锥状流。试样以约777米/秒的速度移动经过该锥体。在该环境中对氧化铝-二氧化钛覆层的测试表明覆层裂口在约1.8小时后产生于裸露的GTD-450试件基底上。期望使用较小的液滴尺寸和封闭件20的测试可获得改进的结果。
固体颗粒侵蚀测试按照ASTM G76-2000标准使用约70℉(约20℃)下的试样来进行。使用笔状喷丸设备以约250英尺/秒(约76米/秒)的速度、且以约20和90度的角度在覆层基底上喷射50Tm角的白色氧化铝之后，测量重量损失。对氧化铝-二氧化钛覆层的侵蚀表明在20度时约有0.58立方厘米/1000小时的重量损失，在90度时约有2.23立方厘米/1000小时的重量损失。认为可以通过增加封闭件20来进一步降低这些侵蚀速率，特别是90度重量损失值。
还进行了使用盐雾的腐蚀测试，且表明结合氧化铝-二氧化钛外覆层和GECC1牺牲底覆层的覆层系统是抗腐蚀的。该腐蚀试验按照ASTM B117进行，该标准是该领域公认的标准化程序。试样被置于温度约95℉(约35℃)的包含约5％NaCl水溶液的雾中。该雾的沉降速度及其他规则依据ASTM B117标准。该测试通常进行约一千小时，之后对该测试试样进行腐蚀侵袭评估。该测试完成之后在该测试试件表面上未发现腐蚀。
从上述试验可以断定，氧化铝外覆层和金属牺牲底覆层能够呈现出足够的抗侵蚀性和抗腐蚀性，以提高不锈钢压缩机叶片的寿命。基于它们呈现更高硬度的能力，进一步断定含二氧化钛的混合物、且尤其是氧化铝-二氧化钛混合物可以呈现出同等的(如果不是更好的)抗侵蚀性和抗腐蚀性。前文所提及的另一外覆层成分也呈现出和氧化铝相似的或更高的硬度，因此也可作为本发明的坚硬陶瓷外覆层14的可行的候选成分。外覆层14的适当厚度通常介于约25至约250微米的范围中，更优选介于约50至约125微米的范围中。
尽管已根据具体的实施例描述了本发明，但很明显其它形式也可被本领域的技术人员采用。例如，覆层系统10可通过对陶瓷浆进行浸渍，喷涂等来包覆，该陶瓷浆被固化以形成能够提供对侵蚀的额外保护的外陶瓷覆层。因此，本发明的范畴将仅受到所附的权利要求的限制。

Claims (10)

1.一种位于部件的钢基底(16)上的覆层系统(10)，所述覆层系统(10)是抗腐蚀且抗水滴侵蚀的，其包括：
所述基底(16)的表面上的金属牺牲底覆层(12)，所述底覆层(12)包含在电势序方面比铁更活泼的金属或金属合金，所述底覆层(12)可导电地接触所述基底(16)的表面；和
通过在所述底覆层(12)上热喷涂而沉积的陶瓷外覆层(14)，所述陶瓷外覆层(14)主要包括陶瓷材料，所述陶瓷材料选自包括下列混合物的组：氧化铝和二氧化钛的混合物，氧化铬和二氧化硅的混合物，氧化铬和二氧化钛的混合物，氧化铬、二氧化硅和二氧化钛的混合物，以及二氧化锆、二氧化钛和氧化钇的混合物。
2.根据权利要求1所述的覆层系统(10)，其特征在于，所述陶瓷外覆层(14)主要包括氧化铝和二氧化钛的混合物。
3.根据权利要求2所述的覆层系统(10)，其特征在于，所述陶瓷外覆层(14)主要包括按重量约50％直至约99％的氧化铝，其余为二氧化钛。
4.根据权利要求1所述的覆层系统(10)，其特征在于，所述陶瓷外覆层(14)主要包括氧化铬和二氧化硅的混合物。
5.根据权利要求1所述的覆层系统(10)，其特征在于，所述陶瓷外覆层(14)主要包括氧化铬和二氧化钛的混合物。
6.根据权利要求1所述的覆层系统(10)，其特征在于，所述陶瓷外覆层(14)主要包括氧化铬、二氧化硅和二氧化钛的混合物。
7.根据权利要求1所述的覆层系统(10)，其特征在于，所述陶瓷外覆层(14)主要包括二氧化锆、二氧化钛和氧化钇的混合物。
8.根据权利要求1到7中任一项权利要求所述的覆层系统(10)，其特征在于，所述牺牲底覆层(12)的金属或金属合金包括固结在所述底覆层(12)内的铝和钴颗粒。
9.根据权利要求1到8中任一项权利要求所述的覆层系统(10)，其特征在于，所述牺牲底覆层(12)还包括包含有磷酸盐的无机粘合剂。
10.根据权利要求1到9中任一项权利要求所述的覆层系统(10)，其特征在于，所述部件是工业燃气轮机的压缩机叶片(18)，且所述基底(16)限定了所述叶片(18)的至少翼型件表面。
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