CN1031147C - 具有保护性双涂层的钢制品及其生产方法 - Google Patents
具有保护性双涂层的钢制品及其生产方法 Download PDFInfo
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Abstract
本发明涉及一种保护性金属底涂层，它形成于燃气轮机不锈钢压气机叶片表面和陶瓷材料保护外涂层之间。
Description
一般说来，本发明涉及冶金技术的防腐蚀领域，更具体地说，涉及具有保护性双涂层钢燃气轮机部件之类的新型耐腐蚀复合制品。
工业和航海燃气轮机的钢部件通常用于各种操作条件下，特别是周围的大气条件下。在某些情况下，抽入发动机的空气具有对压气机叶片和其它部件有腐蚀和磨蚀作用的成分，尽管这些部件有比较高的铬含量旦一般具有耐腐蚀性质。
因此，业已建议提供保护性涂层以防止腐蚀破坏，同时还提出并试验了各种金属涂层，它们皆因技术和经济原因而不合格。还提出陶瓷涂层，但是都没有解决问题，因为在通常的燃气轮机操作条件下，即使它们十分坚固也会碎裂，露出底层钢表面受到腐蚀破坏。
按照本发明，基于下述新概念和发现，则可解决在严酷环境中操作的燃气轮机压气机叶片和其它马氏体钢部件的腐蚀问题。因此，据我所知，目前首次有可能提供在严酷的腐蚀性的周围的空气操作条件下长期工作的这些部件所需要的耐腐蚀。而且是以合理的成本并不会带来明显不利的情况下获得这种成果。
实质上，本发明基于我们的新概念，使用一种陶瓷涂层并通过提供一种粘合在基体制品表面并同样与陶瓷外涂层粘合的金属材料保护性底涂层而解决了劈裂和破碎的问题。用这种方法保护的压气机叶片和其它不锈钢部件的表面，由于陶瓷外涂层而不会一开始就曝露在环境空气中，并且尽管陶瓷外涂层劈裂和破碎，只要保护性金属层保持完整无损，就会受到屏蔽。
我们已发现由于陶瓷外涂层破裂使保护性底涂层曝露时，在整个金属底涂层发生腐蚀作用的时间意想不到的长。我们还意外地发现，即使底涂层贯穿之后，其紧邻区的保护性金属材料有助于保护钢基体的曝露表面不受腐蚀损坏。
而且，我们发现这种外延保护的效果是通过使用保护性金属涂层而获得的，该涂层可为极薄的并且甚至可有在制造或工作过程中造成的缺陷或宽度大至1.59毫米的孔。
我们的另一概念是，将电动势序中位于铁上面的任何合适的金属或金属的合金用作保护性底涂层。当然，这不包括高活性金属，例如钠和钾，但包括铝、锌、镉和镁以及它们的合金中那些电势序比铁更活泼的，且必将符合本发明用作保护目的的合金。
我们还发现可用各种方法提供保护性底涂层而都能获得好的结果。因此，镍一镉和镍—锌底涂层已以最低成本电镀形成并提供了具有优良涂覆和粘附性的底涂层。质量同样好的铝底涂层也已制成，其制法是，使用铝涂料，经过浸涂、喷涂或刷涂，随后干燥、热处理和喷砂处理或其它抛光处理以便压实金属粒子沉积物，从而得到与金属基底表面呈电导接触的粘合铝体。用于本发明目的的其它沉积技术包括等离子和火焰喷射、溅射、离子蒸汽沉积(IVD)、物理蒸汽沉积(PVD)和化学蒸汽沉积(CVD)。
保护性金属涂层的厚度一般说来并不是关键性的，因为用约0.005毫米薄的和可能希望厚得多的涂层都可以得到本发明的新结果和优点。
此外，我们还发现，可以用1966年4月16日颁发给Allen的美国专利№3,248,251中描述的方法形成陶瓷外涂层。然后如果需要可再将初始形成的陶瓷外涂层用第2和第3涂层封闭和密封，且每一涂覆步骤后进行干燥和固化步骤。
最后，我们还发现陶瓷涂层形成所需的温度(一般为538℃或更高)与不锈钢抗疲劳保持力所需温度(低于约316℃)的不同温度要求可以由始终如一的好结果而克服。特别是，我们发现通过限制Allen专利方法中干燥和固化步骤的温度低于约316℃，最好是260-288℃，则可得到好的陶瓷外涂层并且不会牺牲喷砂或其它合适的冷加工处理过程中所形成的不锈钢基体的耐疲劳性。
概括说来，新型马氏体不锈钢制品，例如本发明之压气机叶片，具有保护性金属底涂层和防护性陶瓷外涂层的双涂层，两涂层彼此粘结在一起，而且底涂层粘附在叶片的表面上以形成一个整体复合制品。
同样，一般说来，本发明方法包括提供燃气轮机压气机叶片，在叶片上形成最小厚度的连续保护性金属涂层，并在保护性金属涂层外形成陶瓷涂层并与其粘结在一起的步骤。
熟悉本领域的技术人员研究附属并构成本说明书一部分的附图则可进一步和更好地了解本发明。
图1是本发明之燃气轮机压气机叶片复合件的部分横截面显微放大图(100x)，示出粘附在叶片表面的铝—陶瓷双保护涂层系统；
图2是类似于图1的另一压气机叶片的显微放大图(500x)，它具有用陶瓷涂层包覆的镍—镉底涂层的双涂层。
图3是图2之压气机叶片的照片图，曝露在ASTM B117盐雾试验中227小时后，示出无锈斑划痕。
图4是具有陶瓷层但没有金属底涂层的燃气轮机压气机叶片的放大(放大倍率约1.6)图，曝露在图3试验条件之后显示出划痕和锈斑；
图5是图4照片图中划痕区的放大图(约12x)，显示出没有本发明之底涂层时的锈斑发展程度。
本发明目前的最佳实施形式，是在403不锈钢燃气轮机压气机叶片的清洁表面上最先形成无间断的较薄的保护性金属涂层。如上所指，镍—镉涂层被用于此目的，而且被电镀至厚度约0.005-0.010毫米，最好是0.0076毫米。然后用1966年4月26日颁发给Charlotte Allen的美国专利№3,248,251(本文的参考文献)所述方法，将所得之坚硬的底涂层用陶瓷包覆。
按另一种方法，可使用常用的等离子和火焰喷射技术形成保护性金属底涂层，或者更好是将金属涂料涂敷于，最初已进行喷砂处理的基底表面，然后干燥，加热至固化，随后用喷砂的玻璃珠使接触金属表面的金属粉适当地压实，从而形成保护性金属底涂层。一般说来，一次涂敷足以形成符合本发明目的的厚度至少约0.076毫米的足够的金属涂层。
本发明提供了一种钢燃气轮机压气机叶片的制造方法，该叶片上有保护性双涂层，从而使该叶片可用于腐蚀的环境中，本发明的制法包括以下的步骤：用铝颗粒在液体载体中的浆料涂覆叶片；对所得涂层进行干燥；对该涂层进行抛光，从而将铝颗粒压实成为与叶片表面呈电导性接触的粘合体；然后用陶瓷涂层包覆叶片上所得的铝的底涂层。其中所述浆料主要由铬酸和磷酸加上铝颗粒组成。而抛光则是用颗粒铝或喷砂的玻璃珠进行。本发明方法还包括涂覆陶瓷的若干步骤，即在铝底涂层上形成一种多孔的骨架陶瓷体；用加热时可转化成氧化物的铬化合物溶液浸渍所述多孔体；干燥并固化所得之浸渍过的陶瓷体；以及重复浸渍和固化步骤，以使所述陶瓷体硬化和密实。上述每一固化步骤的进行是通过加热已浸渍的多孔体至260℃与316℃之间的一个温度，直到基本上完成了铬化合物转化为氧化物为止。
当按上述和以下详述方法形成外涂层时，保护性金属涂层和陶瓷材料防护外涂层粘合在一起是没有问题的。因此，由于涂敷有陶瓷并借助互连联作用粘合，底涂层将承受陶瓷而将外涂层牢固地保持在复合制品的上面。按照牢固粘合陶瓷外涂层的要求准备保护性金属涂层表面，最好是通过喷砂使金属表面粗糙。
通过以下实践的实施例进一步说明本发明以及本发明与先有技术的区别，但本发明不限于这些实施例。
实施例1
将AlSl 403不锈钢燃气轮机叶片试样净化处理，然后提供约0.0076毫米均匀厚度的镍—镉合金电镀层，喷砂处理使电镀层表面粗糙，随后外涂覆约0.076毫米均匀厚度的陶瓷体。该陶瓷外涂层是将试样浸渍在表1所示组分的浆料中，并将浆料外涂层在316℃干燥、烧制1小时而制得的。在这种情况下，用磷—铬酸溶液(50％的浓磷酸和50％的饱和三氧化铬)浸渍8次使陶瓷硬化。试样每次浸渍后在316℃干燥或烧制1小时。生成的双涂层，在多次浸渍之间稍加抛光以达到表面精整要求，使其具有光洁度为Ra＝0.2微米(用光洁度仪测)的褐色玻璃质的光滑涂层。试样经过ASTM B117盐雾试验200小时后没出现表面锈斑。
表1
陶瓷外涂层浆料组成
CrO3 48g
SiO2(发烟的) 155g
Al2O 132g
H3PO4(次) 35cc
H2O(去离子的) 164cc
实施例2
类似于实施例1的另一个AlSl不锈钢燃气轮机压气机叶片试样，提供厚度约0.0076毫米的镍—镉电镀层，经过喷砂，然后用均匀厚度约0.076毫米的陶瓷体外涂覆。使用的方法除了使用含氧化锆而不是含氧化铝的浆料，而且用喷射而不是用浸浴外，其它均与实施例1相同。用硬质合金刀具切刮双涂层试样，然后经受ASTM B117盐雾试验227小时，其结果示于图3。表明叶片没有被腐蚀。
实施例3
将实施例1和2之压气机叶片样品的对照物进行同样的试验，其试样被腐蚀的结果示于表4和5。该试样不同于实施例1和2，没有提供金属底涂层而仅有陶瓷涂层，其厚度、组成和实施方法与实施例2相同。
实施例4
近来，在本发明作为燃气轮机进口导向叶片方面已获得经验，该叶片具有实施例2中所叙述的镍—镉底涂层和陶瓷外涂层，并且用于两个不同位置的发动机中。尽管进口导向叶片的损坏一般是压气机所有叶片中最严重的，但体现本发明的这些叶片具有超过1000小时操作记录而没有显示出任何腐蚀的迹象。
实施例5
同实施例1的试样，在样品表面喷涂含铝涂料(市售AlsealT 518Coatings of Industry，Souderton，Pa)使之形成铝的基底涂层。然后将样品加热至260-288℃1小时，其后用氧化铝或用喷砂的玻璃珠进行抛光，以便压实涂料沉积物的铝颗粒成为一块无间断的片，从而提供一层电导性复盖层，与马氏体钢基底相接触。然后将带有有机载体的磷酸盐—铬酸盐混合物按Alseal制品数据说明书涂敷在底涂层上，其后，样品在约260-288℃干燥和加热几小时。然后，按实施例2的方法和浆料配方涂敷陶瓷外涂层。其结果示于图1。
按照标准程序进行上述ASTM B117盐雾试验，每个试样都经受5％氯化钠水溶液液滴构成的雾气试验，雾气的释放率是80平方厘米上每小时散出1-2立方厘米，整个试验期间227小时内温度保持在35℃。选择这个试验是因为它特别有利于判明无保护层的AlSl403不锈钢在快速腐蚀，产生锈蚀的结果。
本说明书和附属的权利要求中所列举的百分率、比例或比率，除有其它说明，均是以重量为基础。
Claims (7)
1.一种耐腐蚀复合制品，它包括抗疲劳钢基体和粘合于该基体上的保护性双涂层，所述涂层包括在所述基体上的保护性金属底涂层和所述底涂层上的陶瓷材料外涂层，所述金属底涂层的厚度基本上均匀，在大约0.005毫米与约0.05毫米之间，而且是电动势序中比铁的活性更强的金属。
2.根据权利要求1的制品，其中，所述基体是燃气轮机压气机叶片，所述保护性金属底涂层是选自于铝、锌、镉、镁及其合金的金属。
3.根据权利要求2所述的制品，其中，所述叶片的保护性底涂层是铝。
4.根据权利要求3所述的制品，其中，所述已涂层叶片的精整表面是光滑的和玻璃质的，其光洁度用表面光洁度仪测定为大约Ra＝0.2毫米。
5.根据权利要求2所述的制品，其中，所述叶片的陶瓷材料外涂层是厚度基本上均匀的氧化锆，其厚度约为0.076毫米。
6.一种抗疲劳钢燃气轮机压气机叶片的制造方法，所述叶片具有使该叶片能在腐蚀环境中使用的双涂层，所述方法包括以下的步骤：
用浆料涂复所述经过热处理的叶片，所述浆料主要由在铬酸和磷酸的液体载体中的铝颗料组成，
对所述铝涂层进行干燥，使所述铝涂层固化，
用喷砂的玻璃球或铝颗粒对所述铝涂层进行抛光，使之成为一种与该叶片的钢表面呈电导性接触的粘合体，所述粘合体的厚度基本上均匀，其厚度在0.005毫米与0.05毫米之间，
在所述铝涂层的上面形成一种多孔的骨架陶瓷，借此提供一种陶瓷的包复面，
用一种在加热时能转化为氧化物的铬化合物的溶液浸渍所述多孔陶瓷，
对所得的已浸渍的陶瓷进行干燥和固化，以及，
反复进行浸渍和固化的步骤，直至使所述陶瓷硬化和密实为止。
7.根据权利要求6所述的方法，其中，每一个陶瓷的固化步骤的进行是通过将已浸渍的多孔陶瓷加热至260℃与316℃之间，直到使所述铬化合物转化为氧化物基本上完成为止。
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| US4576874A (en) * | 1984-10-03 | 1986-03-18 | Westinghouse Electric Corp. | Spalling and corrosion resistant ceramic coating for land and marine combustion turbines |
| US4761346A (en) * | 1984-11-19 | 1988-08-02 | Avco Corporation | Erosion-resistant coating system |
| US4686155A (en) * | 1985-06-04 | 1987-08-11 | Armco Inc. | Oxidation resistant ferrous base foil and method therefor |
| JP2710944B2 (ja) * | 1987-03-31 | 1998-02-10 | キヤノン株式会社 | 液体噴射記録装置 |
-
1990
- 1990-04-30 US US07516450 patent/US5098797B1/en not_active Expired - Lifetime
-
1991
- 1991-04-25 JP JP3121938A patent/JPH0737674B2/ja not_active Expired - Lifetime
- 1991-04-25 DE DE69123631T patent/DE69123631T2/de not_active Expired - Lifetime
- 1991-04-25 EP EP91303741A patent/EP0455419B1/en not_active Expired - Lifetime
- 1991-04-26 NO NO91911666A patent/NO911666L/no unknown
- 1991-04-26 KR KR1019910006741A patent/KR930008927B1/ko not_active IP Right Cessation
- 1991-04-30 CN CN91102891A patent/CN1031147C/zh not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1056132A (zh) | 1991-11-13 |
| DE69123631D1 (de) | 1997-01-30 |
| NO911666L (no) | 1991-10-31 |
| NO911666D0 (no) | 1991-04-26 |
| JPH0737674B2 (ja) | 1995-04-26 |
| KR930008927B1 (ko) | 1993-09-17 |
| DE69123631T2 (de) | 1997-06-05 |
| KR910018577A (ko) | 1991-11-30 |
| EP0455419A1 (en) | 1991-11-06 |
| US5098797A (en) | 1992-03-24 |
| US5098797B1 (en) | 1997-07-01 |
| EP0455419B1 (en) | 1996-12-18 |
| JPH04228583A (ja) | 1992-08-18 |
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