CN1086742C - 镍－基超合金 - Google Patents

镍－基超合金 Download PDF

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CN1086742C
CN1086742C CN97195550A CN97195550A CN1086742C CN 1086742 C CN1086742 C CN 1086742C CN 97195550 A CN97195550 A CN 97195550A CN 97195550 A CN97195550 A CN 97195550A CN 1086742 C CN1086742 C CN 1086742C
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alloy
nickel
base superalloy
low angle
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CN1222199A (zh
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M·肯特
M·纽纳姆
C·特内斯
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General Electric Technology GmbH
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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
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/52—Alloys

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Abstract

本发明涉及一种镍-基超合金，该合金特别适于制造大型单晶部件，其基本组成(以%(重量)计)为：6.0-6.8%Cr、8.0-10.0%Co、0.5-0.7%Mo、6.2-6.6%W、2.7-3.2%Re、5.4-5.8%Al、0.6-1.2%Ti、6.3-7.0%Ta、0.15-0.3%Hf、0.02-0.04%C、40-100ppm B、15-50ppmMg，其余为镍及杂质。

Description

镍-基超合金
发明领域
本发明涉及一种镍-基超合金，该合金特别适于制造单晶-部件。
发明背景
镍-基超合金用于制造单晶-部件或定向结晶部件，特别是气轮机的涡轮叶片。采用这种单晶部件可使高温下的材料强度达最高。由此可提高气轮机的入口温度，从而提高气轮机的效率。
单晶-合金含有混晶增强元素，诸如，Re、W、Mo、Co、Cr以及γ’相(即L10型Ni3Al基金属间相)组成元素，诸如Al、Ta、和Ti。无缺陷的单晶-超合金铸件之特点在于其较高的蠕变强度、疲劳强度及抗氧化能力。另一方面，制造无缺陷的单晶部件，特别是气轮机的叶片，甚为困难，特别是在部件大，几何形状复杂的情况下尤为困难。因此，形成小角度晶界是大型单晶-部件的特征性缺陷。
通常的单晶-超合金，诸如公布于US 4,459,160、US 4,643,782和EP 076 360的超合金，选择了尽可能小的碳和硼含量(C≤150ppm，B≤30ppm)，避免使用另一些晶界硬化元素，诸如Zr、Ce等，以便使单晶-超合金具有大的热处理窗(Wrmebehandlungsfenster)。在这种合金中小角晶界甚弱，因而不可接受。用C和B含量低的合金制成之大型单晶-部件的横向力学性能甚差，因此，甚至在铸造时部件可能发生断裂。小角晶界在此起了氧化和腐蚀过程中扩散途径的作用。
这种合金曾为飞机用涡轮机研制的，因而只对短期和中期性能进行优化，即其使用寿命设计为20000小时。为对该合金在高温和高压力下的蠕变压力进行最优化，应使其具有正的热处理窗，即无需合金的局部初熔就可使初级γ’相完全溶解。
与前言所述之合金相反，诸如GB 2 234 521，EP 240 451和EP 208645所公开的，C-，B-和Hf-含量较高的单晶-超合金明显有较高的横向断裂物性。小角晶界的抗氧化和抗腐蚀性仍然是低的。此外，纵向LCF(低荷载循环次数疲劳)性能比前述合金低10％，其原因在于生成条状碳化物的有害影响。
WO-A-93/24683描述了一种镍-基超合金，该合金选择性地含有达0.1％(重量)C，和达0.5％(重量)Hf和5-200ppm Mg，但不含B。添加Mg以改善抗氧化能力。
发明概述
本发明之目的在于，在镍-基超合金情况下，特别是用于制造前言中所提及类型的大型单晶-部件以及在大铸件时，提高纵向和横向疲劳强度，同时得到良好的抗氧化和抗腐蚀能力。
本发明通过第一权利要求的特征部分达到上述目的。
因此，本发明的核心在于，该镍-基超合金的基本组成(以％(重量)计)如下：6.0-6.8％ Cr、8.0-10.0％ Co、0.5-0.7％ Mo、6.2-6.6％ W、2.7-3.2％ Re、5.4-5.8％ Al、0.6-1.2％ Ti、6.3-7.0％ Ta、0.15-0.3％ Hf、0.02-0.04％ C、40-100ppm B、15-50ppm Mg、0-400ppm Y，其余为镍及杂质。
在本发明的优点中值得指出，合金所含诸如C、B、Hf等晶界-元素的量对小角晶界具有有利的影响，所生成的碳化物非常精细并呈岛形。而且碳化物主要分布在小角晶界，从而使单晶-部件的纵向和横向力学性能和疲劳强度得到有效的改进。
添加Mg与B，C和Hf相组合，会阻碍沿小角晶界的扩散，从而提高小角晶界的抗氧化能力。
特别适宜的是使Hf＝(8-12)×C，B＝(0.18-0.25)×C，Mg＝(0.08-0.2)×C或Hf∶C∶B∶Mg＝100∶10∶2∶1(以重量％计)。从而对合金的纵向和横向力学性能、疲劳强度、小角晶界的抗氧化能力产生有利的影响。
本发明的其它有利特点列于各从属权利要求。发明的实施途径
与前言提及的US 4,459,160、US 4,643,782和EP 076 360的合金相反，设计寿命为75000小时的工业气轮机部件的只进行部分固溶液处理，这样可保留部分初级γ’相，这对于阻碍单晶-结构的再结晶是必要的。因此采用一种热处理，它使初级γ’相溶解90-97％，这就可能采用晶界-元素，而这些元素通常基于其具有降低局部初熔温度的倾向而在单晶-超合金中不采用。这些晶界元素，诸如C、B、Hf和Mg对小角晶界具有利影响。
与前言中提及的GB 2 234 541、EP 240 451和EP 208 645的合金相反，本发明不仅使横向力学性能，而且还使小角晶界的抗腐蚀和抗氧化能力以及疲劳强度得到改善。
本发明的合金是为铸造定向结晶的大型单晶-部件研制的，其基本组成(以％(重量)计)为：
Cr  6.0-6.8
Co  8.0-10.0
Mo  0.5-0.7
W   6.2-6.6
Re  2.7-3.2
Al  5.4-5.8
Ti  0.6-1.2
Ta  6.3-7.0
Hf  0.15-0.3
C   0.02-0.04
B   40-100ppm
Mg  15-50ppm
Ni余量，以及不可避免的杂质
其中Hf＝(8-12)×C，优选10×C；
    B＝(0.18-0.25)×C，优选0.2×C；
    Mg＝(0.08-0.2)×C，优选0.1×C；
或  Hf∶C∶B∶Mg＝100∶10∶2∶1
表1将从本发明范围内选出的合金L1和L2与几种参比合金VL10-VL17进行对比。参比合金的化学组成在本发明的化学组成范围之外。参比合金VL16和VL17是市售的合金“CMSX-4”和“René N5”，它取自表1中所列出版文件US 4,643,782和US 5,270,123。
表2将本发明的合金L1和L2的LCF-性质与某些参比合金进行对比。表2列出了对称LCF循环R＝-1、总拉伸Δεtot＝1.2％下直至失效的循环数Nf。
表3将本发明的合金L1和L2的循环抗氧化能力与某些参比合金进行对比。
参比合金VL10是GB 2 234 521、EP 240 451和EP 208 645所公布合金的典型例子，该合金的C-、B-、和Hf-含量较高。由于沿小角晶界生成碳-硼化物，VL10的横向力学性能有所改善。对用参比合金VL10制造的大型涡轮叶片进行的金属学研究表明，生成的碳化物为条状结构并几乎均匀分布在体积中。因此，只有结合在小角晶界的碳-硼化物中的少量碳对其力学行为具有有利作用。其余份额的C在合金中形成条状碳化物，从表2可以看出，这种碳化物使其纵向疲劳强度降低。
少量合金元素Mg，约为碳含量的10-20％，与双倍量的B和Hf相组合，可大大改变单晶-超合金中的碳化物生成过程。本发明合金L1和L2中的碳化物极为精细并呈岛状，与之相反，在参比合金VL10中碳化物呈薄片状。碳化物在合金体积中的分布是不均匀地集中在小角晶界处。强烈地向晶界偏析的Mg影响碳化物形成元素Hf，Ta和Ti的偏析，并且Mg与这些元素进行相互作用。Mg的较大原子半径大使小角晶界的晶格发生强烈的畸变，从而使C在小角晶界上的偏析容易进行。由此沿晶界生成的精细和密集的碳-硼化物结构使单晶-部件的横向性能和疲劳强度同时得到改善。与此相反，参比合金VL10中由于形成薄片状碳化物而使疲劳强度降低。
从表2的参比例VL11可以看出，当Mg的含量超过50ppm，其横向力学性能急剧下降。其原因在于沿晶界形成了粗粒碳化物和Ni-Mg化合物。
在B含量(相当于参比合金VL12)或Hf含量(相当于参比合金VL13)，不足的情况下，析出有害的粗粒碳化物。它导致表2中VL12和VL13的低劣LCF-性能。
如果B-和Hf-含量过高，则生成低熔点共晶，参比合金VL14就是这种情况，它导致低劣的LCF性能。
如果C的含量过高(相当于参比合金VL15)，在横向强度方面无任何改善，还使其纵向性能变坏。
小角晶界的存在亦有害于单晶-部件的抗氧能力。小角晶界对于氧化产物起扩散途径的作用，沿小角晶界的氧化比无缺陷单晶-超合金更为剧烈。从表3可以看出，相当于VL10添加B、C和Hf只稍微提高小角晶界的抗氧化能力。
相当于合金L1和L2添加Mg与B、C和Hf相组合，导致非常有利的小角晶界的抗氧化能力。这可通过镁“俘获”氧-和硫-原子，生成Mg-O-S化合物来解释，该化合物阻碍了沿小角晶界的扩散。
还可添加另一元素钇。含量达400ppm，特别是含量为10-400ppm的钇能改善抗氧化和抗腐蚀能力。提高Y含量使延展性降低。但掺杂Y的合金要求专门的铸造技术以防止铸模和金属之间发生反应。
本发明之合金特别适于热处理，其处理工序如下：在850-1100℃下退火，特别是在930-970℃处理1-4小时和在1030-1070℃下处理2-20小时；再加热到1200℃；以小于或等于1℃/min的加热速度加热到1200℃＜T≤1300℃，特别是以约0.5℃/min的加热速度；在1300℃≤T≤1315℃的温度下进行多级匀质化和固溶过程，特别是在约1300℃下处理约2小时，再在1310℃下处理6-12小时。
在热处理的优点中值得指出，通过本方法排除了位错源，从而阻碍另一位错的产生。另外，避免了加热过程中的再结晶及促使位错网络的湮灭。通过多级匀质化和固溶过程可使材料工件具有很高的匀质度。残留的1-4％(体积)的共晶足以牵制再结晶晶粒的晶界。
当然，本发明不限于所列举和所描述的实施例。本发明之合金亦可用于制造在高温下需要保持稳定的结构和良好力学性能的其它机器的大型部件。
      元素含量％(重量)合金    Cr    Co    Mo    W    Re    Al    Ti    Ta     Hf   C，ppm   Bppm  Mg，ppm
    L1  6.3  9.5  0.6  6.6   3   5.7   0.8   6.7   0.25   250   50   25
    L2  6.3  9.5  0.6  6.6   3   5.7   0.8   6.7   0.3   300   60   40
    VL10  6.3  9.5  0.6  6.6   3   5.7   0.8   6.7   0.2   330   50   -
    VL11  6.3  9.5  0.6  6.6   3   5.7   0.8   6.7   0.25   250   50   60
    VL12  6.5  9.5  0.6  6.6   3   5.7   0.8   6.7   0.25   250   25   40
    VL13  6.5  9.5  0.6  6.5   3   5.6   0.9   6.7   0.1   250   40   40
    VL14  6.5  9.5  0.6  6.5   3   5.6   0.9   6.7   0.35   250   80   40
    VL15  6.3  9.5  0.6  6.6   3   5.7   0.8   6.7   0.3   500   60   40
  VL16(CMSX-4，US 4,643,782)  6.4  9.7  0.6  6.4   2.9   5.65   1.0   6.5   0.1   30   -   -
  VL17(RenéN5，US 5,270,123)  7  7.5  1.5  5   3   6.2   -   6.5   0.15   500   40   -
表1：合金的化学组成，其余为Ni
   合金      1000℃，6％/min.，R＝-1，Δεtot＝1.2％时的循环次数Nf
  纵向<001>                 横向<010>，小角晶界7-8°
    L1    1442                 1261
    L2    1430                 1338
   VL10    1160                 1020
   VL11     -                 575
   VL12     -                 545
   VL13     -                 877
   VL14     -                 766
   VL15    1197                 1108
   VL16    1494                 387
表2：单晶-超合金的LCF-性质
        合金 1000循环、RT/1000℃、1循环/小时后，含小角晶界7-8°的合金中受损区域的深度
         L1             150(沿小角晶界)
         L2             130(沿小角晶界)
        VL10             290(沿小角晶界)
        VL16             380(沿小角晶界)
        VL16(小部件无小角晶界)                   60(无小角晶界)
表3：单晶-超合金直循环下的抗氧化能力

Claims (10)

1.一种镍-基超合金，该合金特别适于制造单晶部件，该合金包含(以％(重量)计)：
6.0-6.8％ Cr、8.0-10.0％ Co、0.5-0.7％ Mo、6.2-6.6％ W、2.7-3.2％Re、5.4-5.8％ Al、0.6-1.2％ Ti、6.3-7.0％ Ta、0.15-0.3％ Hf、0.02-0.04％C、40-100ppm B、15-50ppm Mg、0-400ppm Y，其余为镍和杂质。
2.权利要求1的镍-基超合金，其特征在于，其组成为(以％(重量)计)：
6.2-6.4％ Cr、9.4-9.6％ Co、0.6％ Mo、6.5-6.7％ W、2.9-3.1％ Re、5.7％ Al、0.7-0.9％ Ti、6.6-6.8％ Ta、0.25-0.3％ Hf、0.02-0.03％ C、50-60ppm B、25-40ppm Mg，其余为镍及杂质。
3.权利要求1的镍-基超合金，其特征在于，Hf＝(8-12)×C、B＝(0.18-0.25)×C、Mg＝(0.08-0.2)×C、或Hf∶C∶B∶Mg＝100∶10∶2∶1(以％(重量)计)。
4.权利要求3的镍-基超合金，其特征在于，Hf＝10×C和/或B＝0.2×C和/或Mg＝0.1×C。
5.权利要求1-4中任一项的镍-基超合金，其特征在于，Y的含量为10-400ppm。
6.一种镍-基超合金-单晶部件，其组成为(以％(重量)计)：
6.0-6.8％ Cr、8.0-10.0％ Co、0.5-0.7％ Mo、6.2-6.6％ W、2.7-3.2％Re、5.4-5.8％ Al、0.6-1.2％ Ti、6.3-7.0％ Ta、0.15-0.3％ Hf、0.02-0.04％C、40-100ppm B、15-50ppm Mg、0-400ppm Y，其余为镍及杂质。
7.权利要求6的镍-基超合金-单晶部件，其特征在于，其组成为(以％(重量)计)：
6.2-6.4％ Cr、9.4-9.6％ Co、0.6％ Mo、6.5-6.7％ W、2.9-3.1％ Re、5.7％ Al、0.7-0.9％ Ti、6.6-6.8％ Ta、0.25-0.3％ Hf、0.02-0.03％ C、50-60ppm B、25-40ppm Mg，其余为镍及杂质。
8.权利要求6的镍-基超合金-单晶部件，其特征在于，Hf＝(8-12)×C、B＝(0.18-0.25)×C、Mg＝(0.08-0.2)×C、或Hf∶C∶B∶Mg＝100∶10∶2∶1(以％(重量)计)。
9.权利要求8的镍-基超合金-单晶部件，其特征在于，Hf＝10×C和/或B＝0.2×C和/或Mg＝0.1×C。
10.权利要求6-9中任一项的镍-基超合金-单晶部件，其特征在于，该单晶部件为气轮机的叶片。
CN97195550A 1996-06-17 1997-06-09 镍－基超合金 Expired - Lifetime CN1086742C (zh)

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