CN1268696C - 一种防护涂层 - Google Patents
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Abstract
现有技术中已知的防护涂层或者具有良好的抗腐蚀性能，或是具有良好的机械性能。一种在中高温下具有抗腐蚀性能有创造性的防护涂层能够显示出良好的抗腐蚀性能，同时具有良好的机械性能，它基本上由以下元素组成(以重量百分比计)：26-30%的镍、20-28%的铬、8-12%的铝、0.1%-3%的至少一种反应性稀土元素，余量的钴。
Description
本发明涉及一种防护涂层。
已经开发和试验了多种合金的防护涂层的组分，这些合金主要包括镍、铬、钴、铝和一种反应性稀土元素。迄今为止，这些涂层可以从，如美国专利US4005989或US5401307中获知。
从美国专利US4034142中，还可以知道一种额外的成分，硅，可以进一步改进这些防护涂层的性能。
尽管这些文献中披露的较宽范围的各种元素，事实上，定性地提示了一种制备耐高温腐蚀的防护涂层的方法，但是，这些披露的组合物不足以定量地满足所有目的。
德国专利2355674进一步披露了一些防护涂层的组分，但是它们并不适用于具有高进气温度的固定式燃气涡轮机的情形。
这些防护涂层显示出高度的内部氧化，从而产生导致上层涂层脱落的裂缝。
本发明的目的是提供一种施加在部件上的防护涂层，它至少可以减少导致机械性能和与其它上层涂层的粘合力降低的裂缝的产生。
为了实现上述以及其它目的，本发明提供了一种施加在由镍基或钴基合金形成的部件上的耐中高温腐蚀的防护涂层，该防护涂层基本上由以下元素组成(以重量百分比计)：
26-30％的镍，
20-28％的铬，
8-12％的铝，
0.1％-3％的至少一种反应性稀土元素，
余量的钴
和杂质
以及选择性地含有0-15％的至少一种选自铼、铂、钯、锆、锰、钨、钛、钼、铌、铁和铪的元素。其中可含有0.1％-3％的铼。
具体地，本发明提供了
1.一种施加在由镍基或钴基超耐热合金形成的部件上的抗氧化防护涂层，防护涂层基本上由以下元素组成，以重量百分比计：
26-30％的镍
20-28％的铬
8-12％的铝
0.1％-3％的稀土元素
余量的钴。
2.项1所述的防护涂层，其中防护涂层基本上由以下元素组成，以重量百分比计：
28％的镍
24％的铬
10％的铝
0.1％-3％的稀土元素
余量的钴。
3.项1所述的防护涂层，其中：
添加0.1wt％-3wt％的铼。
4.项1所述的防护涂层，其中：
添加0.08wt％-0.1wt％的碳。
5.项1所述的防护涂层，其中：
添加1.5wt％-2wt％的钼。
6.项1所述的防护涂层，其中：
添加2.5wt％-4wt％的钨。
7.项1所述的防护涂层，其中，以重量百分数计：
添加0-1％的钛
0-0.1％的锆
0-1％的铪
0-0.5％的硼。
8.项1-7中任一项所述的防护涂层，其中：混合有铼、铂、钯、锆、锰、钨、钛、钼、铌、铁和铪的元素，其总掺入量小于15％。
优选的钼的用量范围是1.5wt％-2wt％，优选的钨的用量范围是2.5wt％-4wt％，优选的钛的用量范围最多为1wt％，优选的锆的用量范围最多为0.1wt％，优选的铪的用量范围最多为1wt％，优选的硼的用量范围最多为0.5wt％。
还可以添加0.08wt％-0.1wt％的碳。
该防护涂层不会在涂层中以及基材与涂层间的界面中产生脆性相。
抗氧化性得到了改善。
富铝相的量和结构足以生成良好的锚固层(anchoring layer)：一种分别位于MCrAlY顶部和MCrAlY陶瓷间的TGO(热成长氧化物)层。
在这方面，选择性地包括上述元素组中的特定元素是基于这种认识：这些元素不会破坏防护涂层的性能，相反，实际上至少在某些环境下能够改善防护涂层的性能。
下列的特性或重要性可以归因于防护涂层中的不同组成：
钴，作为一种组成，在高温下可以实现良好的防腐蚀特性。
镍可以改善涂层的延展性，并减少与镍基基材的相互扩散。优选的镍的用量范围是26-30％，优选约为28％。
铬可以改善高达约900℃的中温下的防腐蚀性能，并能促进氧化铝覆盖膜的形成。优选的铬的用量范围是20-28％，特别是约为24％。
铝可以改善高达1150℃高温下的防腐蚀性能。铝的含量应该在8-12％之间，特别是约为10％。
反应性元素，尤其是钇的作用，本身是已知的。其优选的用量范围是0.1-3％，特别是约为0.6％。
在给定的优选用量范围内，实验表明，应用于进气温度高于1200℃的燃气涡轮机时，防护涂层具有特别优良的防腐蚀性能。
从现有文献，已经知道有各种元素，它们不会损害防护涂层的性能，相反地，当它们的掺入总量小于15％，特别是仅占很少百分比时，实际上在某些方面能够改善涂层的性能。本申请的发明也将包括有这些掺合物的防护涂层。
一种很少被考虑用于防护涂层的元素即铼，如果其掺入量为0.1-3％，优选0.1-2％或0.1-1％时，能够显著改善防腐蚀性能。
尽管铼不像大多数贵金属一样昂贵，但是作为防护涂层的一种组成，它能够产生像那些贵金属例如，铂，一样好的性能，并且即使其在防护涂层中的构成量很少时也是有效的。
因此铼含量为1％-2％，优选1.2％-1.7％时能产生良好的效果。
本发明的涂层可通过等离子喷雾或等离子蒸发沉积(PVD)进行施加，它们特别适用于由镍基或钴基超耐热合金形成的燃气涡轮机叶片。其它涡轮机部件，特别是进气温度高于1200℃的燃气涡轮机中的部件，也同样适用这些防护涂层。实验证明本发明涂层的特定组成对具有高进气温度的固定式燃气涡轮机而言是特别合适的选择。这些实验将在下面讨论。
实施例
涂有上述涂层的部件最好是由镍基或钴基超耐热合金生产的。这些部件可以由以下材料形成：
1.基本上由下列组成的锻造合金(以重量百分比计)：0.03-0.05％的碳、18-19％的铬、12-15％的钴、3-6％的钼、1-1.5％的钨、2-2.5％的铝、3-5％的钛，任选的选自钽、铌、硼和/或锆的少量添加物，余量的镍。这种合金已知称为Udimet 520和Udimet 720。
2.基本上由下列组成的铸造合金(以重量百分比计)：0.1-0.15％的碳、18-22％的铬、18-9％的钴、0-2％的钨、0-4％的钼、0-1.5％的钽、0-1％的铌、1-3％的铝、2-4％的钛、0-0.75％的铪，任选的选自硼和/或锆的少量添加物，余量的镍。这种合金已知称为GTD 222、IN 939、IN 6203和Udimet 500。
3.基本上由下列组成的铸造合金(以重量百分比计)：0.07-0.1％的碳、12-16％的铬、8-10％的钴、1.5-2％的钼、2.5-4％的钨、1.5-5％的钽、0-1％的铌、3-4％的铝、3.5-5％的钛、0-0.1的锆、0-1％的铪，任选的少量硼的添加物，余量的镍。这种合金已知称为PWA 1483SX、IN 738LC、GTD Ill、IN 792CC和IN 792DS；IN 738LC被认为在本发明中特别有用。
4.基本上由下列组成的铸造合金(以重量百分比计)：约0.25％的碳、24-30％的铬、10-11％的镍、7-8％的钨、0-4％的钽、0-0.3％的铝、0-0.3％的钛、0-0.6的锆，任选的少量硼的添加物，余量的钴。
采用厚度范围为200μm-300μm的涂层特别有利。
实验
实施了循环氧化实验。实验周期是1000℃、2小时、15分钟。使用压缩空气冷却。实验中新的涂层组合物表现出优越的循环氧化行为。损坏时间长于同类实验中其他实验涂层的2.5倍左右。
附图的简要说明
附图是条形图，它显示了不同涂层的对比实验结果。
附图的详细说明
根据说明实验结果的附图，样品1是现有技术中广泛应用的涂层，而样品2是本发明的涂层。
根据上面的分类，样品1和样品2的基材由PWA 1483 SX制得。
与现有技术中的样品1(11-13％Co、20-22％Cr、10.5-11.5％Al、0.3-0.5％Y、1.5-2.5％Re、余量Ni，由US 5154885、US 5273712或US 5268238可知)相比，本发明的样品2(本发明中以重量百分比计：28％Ni、24％Cr、0.6％Y、10％Al、余量Co)就其循环氧化性能方面具有特别明显的优势。
如附图中所示，现有技术中的样品1显示其损坏周期大约为1200个循环，根据本发明的样品显示其损坏循环大约为3200个循环。
样品1被广泛认为在相关技术中是最好的涂层，特别是在其抗循环氧化性能方面。
本发明的涂层可以不再需要在抗氧化性能和延展性(对于抗撕裂和粘合性能很重要)之间进行平衡。这些性能不但使相互之间的关系最佳化，而且他们大大超越了现有技术。
Claims (7)
1.一种施加在由镍基或钴基超耐热合金形成的部件上的抗氧化防护涂层，防护涂层基本上由以下元素组成，以重量百分比计：
28％的镍
24％的铬
10％的铝
0.1％-3％的稀土元素
余量的钴。
2.权利要求1所述的防护涂层，其中：
添加0.1wt％-3wt％的铼。
3.权利要求1所述的防护涂层，其中：
添加0.08wt％-0.1wt％的碳。
4.权利要求1所述的防护涂层，其中：
添加1.5wt％-2wt％的钼。
5.权利要求1所述的防护涂层，其中：
添加2.5wt％-4wt％的钨。
6.权利要求1所述的防护涂层，其中，以重量百分数计：
添加0-1％的钛；
0-0.1％的锆；
0-1％的铪；
0-0.5％的硼。
7.权利要求1-6中任一项所述的防护涂层，其中：混合有铼、铂、钯、锆、锰、钨、钛、钼、铌、铁和铪的元素，其总掺入量小于15％。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP0300183 | 2003-01-10 | ||
| WOPCT/EP03/00183 | 2003-01-10 |
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| Publication Number | Publication Date |
|---|---|
| CN1521221A CN1521221A (zh) | 2004-08-18 |
| CN1268696C true CN1268696C (zh) | 2006-08-09 |
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| CN200410003852.2A Expired - Fee Related CN1268696C (zh) | 2003-01-10 | 2004-01-10 | 一种防护涂层 |
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| Country | Link |
|---|---|
| US (1) | US6974638B2 (zh) |
| EP (2) | EP1621648B1 (zh) |
| JP (1) | JP3875973B2 (zh) |
| CN (1) | CN1268696C (zh) |
| DE (2) | DE60302425T2 (zh) |
| ES (2) | ES2250818T3 (zh) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1693473B1 (de) * | 2005-02-18 | 2008-05-07 | Siemens Aktiengesellschaft | MCrAIX-Legierung, Schutzschicht aus MCrAIX-Legierung und Verfahren zur Herstellung |
| EP1783236A1 (de) * | 2005-11-04 | 2007-05-09 | Siemens Aktiengesellschaft | Legierung, Schutzschicht zum Schutz eines Bauteils gegen Korrosion und/oder Oxidation bei hohen Temperaturen und Bauteil |
| EP1820883A1 (de) * | 2006-01-17 | 2007-08-22 | Siemens Aktiengesellschaft | Legierung, Schutzschicht und Bauteil |
| US20070231589A1 (en) * | 2006-04-04 | 2007-10-04 | United Technologies Corporation | Thermal barrier coatings and processes for applying same |
| EP1845171B1 (de) | 2006-04-10 | 2016-12-14 | Siemens Aktiengesellschaft | Verwendung metallischer Pulver mit unterschiedlichen Korngrössen zum Herstellen eines Schichtsystems |
| US8748008B2 (en) * | 2008-06-12 | 2014-06-10 | Exxonmobil Research And Engineering Company | High performance coatings and surfaces to mitigate corrosion and fouling in fired heater tubes |
| CN102115864A (zh) * | 2010-12-21 | 2011-07-06 | 苏州雅典娜科技有限公司 | 一种耐高温的防护涂层 |
| EP2474414A1 (de) * | 2011-01-06 | 2012-07-11 | Siemens Aktiengesellschaft | Legierung, Schutzschicht und Bauteil |
| US9441114B2 (en) | 2011-09-09 | 2016-09-13 | Siemens Aktiengesellschaft | High temperature bond coating with increased oxidation resistance |
| USH2292H1 (en) * | 2012-04-16 | 2014-06-03 | Invista North America S.A.R.L. | Materials of construction for a gas turbine |
| CN103966539B (zh) * | 2014-04-11 | 2016-08-17 | 北京航空航天大学 | 一种等离子蒸发沉积长寿命、高隔热具有复合结构的镧系热障涂层陶瓷层及其制备方法 |
| CN107201492A (zh) * | 2017-05-09 | 2017-09-26 | 中国科学院兰州化学物理研究所 | 一种等离子喷涂制备Mo‑Re涂层的方法 |
| CN109423067B (zh) * | 2017-06-21 | 2020-10-27 | 宝山钢铁股份有限公司 | 一种取向硅钢绝缘涂层溶液、其制备方法及应用 |
| CN108251781A (zh) * | 2018-02-08 | 2018-07-06 | 湖北鸿地重工股份有限公司 | 一种钢结构表面防腐工艺 |
| US11180847B2 (en) * | 2018-12-06 | 2021-11-23 | Applied Materials, Inc. | Atomic layer deposition coatings for high temperature ceramic components |
| CN109321785B (zh) * | 2018-12-12 | 2021-03-23 | 常州大学 | 一种在钴基合金表面制备钴基涂层的方法 |
| CN113846283B (zh) * | 2021-11-25 | 2022-04-05 | 潍柴动力股份有限公司 | 一种耐高温egr阀片及其制备方法 |
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| GB1426438A (en) * | 1972-11-08 | 1976-02-25 | Rolls Royce | Nickel or cobalt based alloy composition |
| US4034142A (en) * | 1975-12-31 | 1977-07-05 | United Technologies Corporation | Superalloy base having a coating containing silicon for corrosion/oxidation protection |
| US4005989A (en) * | 1976-01-13 | 1977-02-01 | United Technologies Corporation | Coated superalloy article |
| US5268238A (en) * | 1989-08-10 | 1993-12-07 | Siemens Aktiengesellschaft | Highly corrosion and/or oxidation-resistant protective coating containing rhenium applied to gas turbine component surface and method thereof |
| US5273712A (en) * | 1989-08-10 | 1993-12-28 | Siemens Aktiengesellschaft | Highly corrosion and/or oxidation-resistant protective coating containing rhenium |
| DE3926479A1 (de) | 1989-08-10 | 1991-02-14 | Siemens Ag | Rheniumhaltige schutzbeschichtung, mit grosser korrosions- und/oder oxidationsbestaendigkeit |
| US5401307A (en) * | 1990-08-10 | 1995-03-28 | Siemens Aktiengesellschaft | High temperature-resistant corrosion protection coating on a component, in particular a gas turbine component |
| US5582635A (en) * | 1990-08-10 | 1996-12-10 | Siemens Aktiengesellschaft | High temperature-resistant corrosion protection coating for a component in particular a gas turbine component |
| EP0688885B1 (en) * | 1994-06-24 | 1999-12-29 | Praxair S.T. Technology, Inc. | A process for producing an oxide dispersed MCrAIY-based coating |
| DE59505454D1 (de) * | 1994-10-14 | 1999-04-29 | Siemens Ag | Schutzschicht zum schutz eines bauteils gegen korrosion, oxidation und thermische überbeanspruchung sowie verfahren zu ihrer herstellung |
| US6343134B1 (en) * | 1998-01-28 | 2002-01-29 | Euguene J. Czerwinski | Loudspeaker and horn with an additional transducer |
| EP1306454B1 (de) * | 2001-10-24 | 2004-10-06 | Siemens Aktiengesellschaft | Rhenium enthaltende Schutzschicht zum Schutz eines Bauteils gegen Korrosion und Oxidation bei hohen Temperaturen |
| US6346134B1 (en) * | 2000-03-27 | 2002-02-12 | Sulzer Metco (Us) Inc. | Superalloy HVOF powders with improved high temperature oxidation, corrosion and creep resistance |
| JP4166978B2 (ja) * | 2001-12-17 | 2008-10-15 | 三菱重工業株式会社 | 耐高温腐食合金材、遮熱コーティング材、タービン部材、及びガスタービン |
-
2003
- 2003-12-19 EP EP05019038A patent/EP1621648B1/en not_active Expired - Fee Related
- 2003-12-19 EP EP03029425A patent/EP1439245B1/en not_active Expired - Fee Related
- 2003-12-19 DE DE60302425T patent/DE60302425T2/de not_active Expired - Lifetime
- 2003-12-19 ES ES03029425T patent/ES2250818T3/es not_active Expired - Lifetime
- 2003-12-19 DE DE60311686T patent/DE60311686T2/de not_active Expired - Lifetime
- 2003-12-19 ES ES05019038T patent/ES2281048T3/es not_active Expired - Lifetime
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- 2004-01-07 JP JP2004001777A patent/JP3875973B2/ja not_active Expired - Fee Related
- 2004-01-09 US US10/754,949 patent/US6974638B2/en not_active Expired - Fee Related
- 2004-01-10 CN CN200410003852.2A patent/CN1268696C/zh not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| DE60302425T2 (de) | 2006-06-29 |
| US6974638B2 (en) | 2005-12-13 |
| JP2004218086A (ja) | 2004-08-05 |
| DE60302425D1 (de) | 2005-12-29 |
| ES2250818T3 (es) | 2006-04-16 |
| US20040170521A1 (en) | 2004-09-02 |
| EP1621648B1 (en) | 2007-02-07 |
| JP3875973B2 (ja) | 2007-01-31 |
| CN1521221A (zh) | 2004-08-18 |
| EP1621648A1 (en) | 2006-02-01 |
| DE60311686T2 (de) | 2007-06-06 |
| EP1439245B1 (en) | 2005-11-23 |
| ES2281048T3 (es) | 2007-09-16 |
| EP1439245A1 (en) | 2004-07-21 |
| DE60311686D1 (de) | 2007-03-22 |
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