CN1029133C - 一种钴基合金及其制品 - Google Patents
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- 229910052799 carbon Inorganic materials 0.000 claims description 9
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- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
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- 230000006698 induction Effects 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
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- 238000012423 maintenance Methods 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 235000002639 sodium chloride Nutrition 0.000 description 1
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- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3046—Co as the principal constituent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12931—Co-, Fe-, or Ni-base components, alternative to each other
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Abstract
一种新的钴基锻造合金,它具有独特的兼有高温强度,耐热腐蚀性、抗氧化性和抗热疲劳裂纹等性质,它适于焊接修补燃气轮机发动机喷嘴裂纹,作为这种发动机热段部件的保护涂层以及其它类似的用途。
Description
本发明涉及冶金技术的超耐热合金分支,更具体地说,涉及具有独特的兼有高温强度,耐氧化性,耐热腐蚀性和抗热疲劳裂纹等性质的新的钴基合金其制品。
燃气轮机热段部件必须能够在热腐蚀和侵蚀介质中,在应力和温度的苛刻条件下连续操作,迄今仅有高温钴基和镍基超耐热合金被证明可胜任此项任务。用于燃气轮机的几种铸造钴合金在市场上是可买得到的。然而,意想不到的是市场上买得到的锻造钴合金,其类号是十分有限的,尽管长期需要更好的产品。因此,用于生产制造或修补热段钴合金构件焊丝的锻造合金缺少若干种所需要的性质。目前,广泛使用的两种这样的锻造合金不能生产需长期经受热循环的修理用的零部件。因而,昂贵的热段零部件的寿命仍然是工业上的主要问题。
根据本发明,基于我们的新构思和下述的发现,避免了先有技术锻造合金的短处,并获得许多新优点和重要结果。而且是在没有明显弥补成本负担或其它损失下获得这些利益。
在完成本发明时,我们发现它可能符合和满足钴基锻造合金的长时期的要求,该合金需经受燃气轮机发动机热循环和长时期的热腐蚀破坏。另外,我们还发现获得这种新性质的同时还具有优良的焊接(以焊丝形式)特性,如流动性、润湿性,以及良好的机械性能。
另一发现是,按本发明制成的焊丝在维修铸造钴基合金燃气轮机部件时是特别有用的。事实上,用本发明焊丝维修的这些部件已被证明比用先有技术合金维修的相应部件性能改进近十倍,特别是在热疲
劳流化床试验中抗裂纹产生方面更是如此。
出乎意料的是,只要对至今已知的钴基锻造合金的组成作很小的,但是关键性地改变,即可获得上述新的结果和优点。因此,本发明合金含有与U.S.P.3,366,478中所公开之合金相类似比例的碳、镍、钽,稍多的铬和相应较少的钴。但是,作为本发明合金重要的添加组分还有小比例,却是有效的铈。
一般说来,本发明之新的合金除了钴之外还含有约0.03-0.10%(重量)的碳,约24-32%(重量)的铬,约14-22%(重量)镍,约2-8%(重量)钽,和约0.02-0.75%(重量)铈。此外,这些合金金还可能含有少量铝、铜、镁、硅、硼、钨、钼、铁和锆,其总量最高达1.38%(重量)。氧、氮及低温熔点金属元素如铋、砷和铅尽可能地保持在最低浓度水平。本发明最佳形式的合金含有29%铬,20%镍,6%钽,0.05%碳,0.25%铈,余量为钴。
作为生产的制品,本发明可采取各种形式。简单地说明,可以是本发明之新合金焊丝,或者是复合结构例如用所述新合金涂覆有防护层的热段燃气轮机部件。还可以是须用所述新合金焊接修补和填充裂纹的燃气轮机喷咀。
在构成说明书一部分的附图中,
图1是表示产生裂纹的时间和裂纹长度(毫米,密耳)对循环数的曲线图,用连接各有关的合金数据点的曲线表示实施本发明的样品以及两个选自先有技术填角焊缝的焊丝合金样品的热疲劳试验结果。
图2是表示1000小时断裂强度图,图中表示应力与温度之间的关系,用各数据点表示实施本发明的试样断裂强度试验结果和文献中报导的四种先有技术合金的相应试验的数据。图中“*”表示1003小时后没损坏。
图3是用连接试验数据点的曲线,表示在982℃(1800°F),天然
气中的抗氧化性图,该图表示平均侵透性(毫米,密耳)与时间(千小时)的关系;
图4是燃气轮发动机壳、挡板块及涡轮叶片个别的横截面图,其中的挡板,在其对着叶片尖的挡板块表面上是用本发明的合金涂覆的。
图5是用于评价本发明合金和图1示有结果的先有技术用作填角焊缝的焊接材料的热疲劳试验样品的平面视图。
图6是图5所示样品中的线6-6处的截面图。
本发明合金的生产可由操作人员选择,但根据我们目前的实践是在真空下,即用真空感应熔化方法熔炼钴、铬、镍、钽和碳。在接近熔炼终了时添加铈或含铈的稀土元素合金。然后将铸块第二次再熔以促使均匀化和组织精炼,以便能成功地进行粗轧。得到的坯锭再加工成各种形式锻件;棒材和焊丝。另一方面可以将铸块变成粉末形式。
当这些新的合金用作燃气轮机挡板块之类的外涂层形式时,我们建议最好是采用低压(即真空)等离子喷镀,电子束物理汽相沉积(PVD),氩气保护的等离子喷镀。在Powell等人著的Vapor Deposition(John Wiley & Sons,Inc.Pages 242-246(1966)和Smith等人所著“Low PressurePlasma Spray Coatings for Hot Corrosion Resistance”(Trans、9th Int.Spraying Confernce,page 334(1980)]的教科书中,所述的各种合适的方法都是有效的。
在用本发明焊丝修补铸造合金物体的裂缝时,我们建议最好是使用气体钨极弧焊,但本技术领域的技术人员应理解,其它方法也可使用,只要提供焊接所必需的强度、韧性和完整性。
先有技术合金和本发明合金(29%Cr,20%Ni;6%Ta,0.25%Ce,0.05%C,余量为Co)的样品已进行了试验。通过使用的试验样品在一个试验中测定了一组焊缝热疲劳行为,如图5所示的10,是用于生产具有用焊接金属(如图6所示的14)充填的缺口11,12和13的燃气轮机发动机
喷嘴的钴基超耐热合金。图1中的裂纹产生和增长曲线A、B和C分别表示在模拟条件下进行这些热疲劳试验中收集到的数据,该模拟条件是喷嘴在正常操作状态下一般所承受的条件,具体地说,流化床温度-时间循环是864℃(1588°F)4分钟加上21℃(70°F)4分钟。在20,40,60,80,100,150,200和300循环时中断试验以检查裂纹产生和测量裂纹延展的程度,并在500循环后终止。由本发明合金、合金L-605和合金FSX-414 LC进行上述试验所得到的数据在图1中分别用曲线A、B和C表示。
紧接上述试验进行另一组试验,在816℃/172kPa(1500°F/25psi)测量本发明相同合金的断裂强度。所得数据在图2中以H点表示,而合金L-650,FSX-414-,HS-188和MM-918的文献的各数据点则分别表示为K、L、M和N。1003小时之后,本发明任一合金样品没有发现断裂迹象,随后终止试验。另一方面,代表其它各合金的数据点都显示试验样品已损坏。本发明合金在断裂强度方面的优势是很明显的。
从本发明之上述含29%铬合金样品所做的拉力试验中获得的数据列于下表Ⅰ中。由文献中获得的L-605,HS-188和MM-918合金的对比数据也示于表1中。
表1
合金 试验温度 极限抗拉强度 0.2%屈服强度 拉伸伸长
℃(°F) kPa(psi) kPa(psi) 率(%)
本发明 760(1400) 7,124,260(103,400) 494,702(71,800) 41.2
L605 760(1400) 454,740(66,000) 261,820(38,000) 12.0
HS188 760(1400) 633,800(92,000) 289,380(42,000) 43.0
MM918 760(1400) 558,779(81,100) 184,652(26,800) 52.8
本发明 871(1600) 414,089(60,100) 375,505(54,500) 48.8
L605 871(1600) 323,830(47,000) 241,150(35,000) 35.0
HS188 871(1600) 420,290(61,000) 261,820(38,000) 73.0
MM918 871(1600) 445,094(64,600) 163,293(23,700) 65.3
由表1可清楚地看出上述本发明之含29%铬合金在两种温度状况760℃(1400°F)和871℃(1600°F)下都具有优良的屈服强度。
对本发明合金和现有技术中最佳合金的热腐蚀/氧化已做了对比试验,其结果列于下表Ⅱ,该对比试验是使用普通的燃烧设备,将每一种合金的圆销样品置于732℃(1350°F),871℃(1600°F)和927℃(1700°F)温度下进行的。用于732℃(1350°F)和871℃(1600°F)试验的燃料是掺有叔丁基硫化物(提供1%硫)的#2柴油和约百万分之500的合成海盐。在燃烧空气中添加足够的SO2使硫的近似水平达到一般航海和工业燃气轮机操作时的含硫水平。927℃(1700°F)试验是在纯氧化条件下用天然气燃料进行。本发明合金在732℃(1350°F),在苛刻的类型Ⅱ的热腐蚀条件下,2000小时后的平均穿透深度为0.00381毫米(0.00015英寸),而作为对比的MM-918合金的穿透深度则为0.02286毫米(0.0009英寸)。
本发明合金在871℃(1600°F),也是在类型Ⅱ的条件下,2000小时后的平均穿透深度为0.12毫米(4.7密耳),而作为对比的MM-918合金的穿透深度则为0.17毫米(6.7密耳)。因此,本发明合金再次显示比MM-918合金优良。
表Ⅱ
合金 温度/燃料 小时 平均穿透深
度,毫米(密耳)
本发明 732℃(1350°F)/柴油 2000 0.0038(0.15)
MM-918 732℃(1350°F)/柴油 2000 0.023(0.90)
本发明 871℃(1600°F)/柴油 2000 0.12(4.7)
MM-918 871℃(1600°F)/柴油 2000 0.17(6.7)
最后,用所述含29%铬的本发明合金进行一组抗高温氧化试验。该试验是按上述热腐蚀/氧化试验,使用燃烧设备和圆销样品进行的。在这些试验中使用了天然气。所得数据在图3中表示为用曲线R连接的数据点。
上述实验中所选用的商品合金如下:
合金L-605-一种最早期的Co基锻造合金;
合金FSX-414 LC-低碳焊丝型的GE专利铸造Co基合金;
合金HS-188-改进的L-605,含有少量的La;
合金MM-918-美国专利No.3,366,478的权利要求9。
如图4所示,本发明采取的复合物体形式,具体为用本发明合金涂覆的燃气轮机发动机挡板块15。因此,正对着涡轮叶片尖17的挡板块15的表面具有本发明合金涂层16。由于挡板块15是固定在涡轮壳18上,通过抗热腐蚀和裂纹的涂层16保护关键性位置上免受热疲劳的氧化和腐蚀作用。涂层16合适的厚度约0.2-0.25毫米(约8-10密耳),该涂层是由空气等离子喷镀或真空等离子喷镀方法涂覆的。
在本申请说明书和附上的权利要求书中所说的比例、份或百分数,若没有其它说明,均以重量为基础。
Claims (4)
1、一种具有优良高温强度、抗氧化性、耐热腐蚀性、抗热疲劳的综合性能、特别适用于982℃(1800°F)的燃气轮机环境的钴基锻造合金,其特征在于其化学成分(重量%)为:Cr24-32%,Ni14-22%,Ta2-8%,Ce0.02-0.75%,C0.03-0.1%,余量为Co。
2、权利要求1所述的钴基合金,其特征在于其化学成分(重量%)为:Cr 29%,Ni 20%,Ta 6%,C 0.05%,Ce 0.25%,余量为Co。
3、一种局部涂覆权利要求1所述的钴基合金的燃气轮机部件的复合物制品,其特征在于所述钴基合金的化学成分(重量%)为:Cr 24-32%,Ni 14-22%,Ta 2-8%,Ce 0.02-0.75%,C 0.03-0.1%,余量为Co。
4、权利要求3所述的复合物制品,该制品是挡板块,其特征在于所述钴基合金的化学成分(重量%)为:Cr 29%,Ni 20%,Ta 6%,C 0.05%,Ce 0.25%,余量为Co。
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Application Number | Priority Date | Filing Date | Title |
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US486,531 | 1990-02-28 | ||
US07/486,531 US5192625A (en) | 1990-02-28 | 1990-02-28 | Cobalt-base wrought alloy compositions and articles |
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CN1054448A CN1054448A (zh) | 1991-09-11 |
CN1029133C true CN1029133C (zh) | 1995-06-28 |
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CN91101324A Expired - Lifetime CN1029133C (zh) | 1990-02-28 | 1991-02-28 | 一种钴基合金及其制品 |
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US (1) | US5192625A (zh) |
EP (1) | EP0444483B1 (zh) |
JP (1) | JP3241745B2 (zh) |
KR (1) | KR100195659B1 (zh) |
CN (1) | CN1029133C (zh) |
DE (1) | DE69114543T2 (zh) |
NO (1) | NO910773L (zh) |
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US5525429A (en) * | 1995-03-06 | 1996-06-11 | General Electric Company | Laser shock peening surface enhancement for gas turbine engine high strength rotor alloy repair |
WO1997010368A1 (fr) * | 1995-09-11 | 1997-03-20 | Hitachi, Ltd. | Alliage a base de cobalt, buse de turbine a gaz et materiau de soudure fabriques avec cet alliage |
US5735044A (en) * | 1995-12-12 | 1998-04-07 | General Electric Company | Laser shock peening for gas turbine engine weld repair |
JP3629920B2 (ja) * | 1997-10-20 | 2005-03-16 | 株式会社日立製作所 | ガスタービン用ノズル,発電用ガスタービン,Co基合金及び溶接材料 |
US6468367B1 (en) * | 1999-12-27 | 2002-10-22 | General Electric Company | Superalloy weld composition and repaired turbine engine component |
CN100430499C (zh) * | 2002-08-16 | 2008-11-05 | 阿尔斯托姆科技有限公司 | 金属间材料及该材料的应用 |
KR101709353B1 (ko) * | 2008-05-22 | 2017-02-22 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | 메시 층을 포함하는 다층 흡음 구조물 |
US9416671B2 (en) | 2012-10-04 | 2016-08-16 | General Electric Company | Bimetallic turbine shroud and method of fabricating |
DE102014202457A1 (de) * | 2014-02-11 | 2015-08-13 | Siemens Aktiengesellschaft | Verbesserte Verschleißbeständigkeit eines Hochtemperaturbauteils durch Kobaltbeschichtung |
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US1449338A (en) * | 1921-06-18 | 1923-03-20 | Haynes Stellite Co | Alloy and process of making the same |
US2763547A (en) * | 1955-06-09 | 1956-09-18 | Allegheny Ludlum Steel | Cast alloys |
US3366478A (en) * | 1965-07-21 | 1968-01-30 | Martin Marietta Corp | Cobalt-base sheet alloy |
DE2132022A1 (de) * | 1971-06-28 | 1973-01-11 | Battelle Institut E V | Hochwarmfeste legierung auf der basis von nickel und kobalt |
US3837838A (en) * | 1972-12-18 | 1974-09-24 | M Mohammed | High strength, ductile cobalt-base dental alloy |
US4124737A (en) * | 1976-12-30 | 1978-11-07 | Union Carbide Corporation | High temperature wear resistant coating composition |
-
1990
- 1990-02-28 US US07/486,531 patent/US5192625A/en not_active Expired - Fee Related
-
1991
- 1991-02-15 DE DE69114543T patent/DE69114543T2/de not_active Expired - Lifetime
- 1991-02-15 EP EP91102172A patent/EP0444483B1/en not_active Expired - Lifetime
- 1991-02-22 JP JP04858991A patent/JP3241745B2/ja not_active Expired - Fee Related
- 1991-02-27 NO NO91910773A patent/NO910773L/no unknown
- 1991-02-27 KR KR1019910003192A patent/KR100195659B1/ko not_active IP Right Cessation
- 1991-02-28 CN CN91101324A patent/CN1029133C/zh not_active Expired - Lifetime
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KR100195659B1 (ko) | 1999-06-15 |
EP0444483B1 (en) | 1995-11-15 |
NO910773L (no) | 1991-08-29 |
US5192625A (en) | 1993-03-09 |
DE69114543D1 (de) | 1995-12-21 |
DE69114543T2 (de) | 1996-06-20 |
NO910773D0 (no) | 1991-02-27 |
CN1054448A (zh) | 1991-09-11 |
JPH04221035A (ja) | 1992-08-11 |
KR910021493A (ko) | 1991-12-20 |
EP0444483A1 (en) | 1991-09-04 |
JP3241745B2 (ja) | 2001-12-25 |
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