CN1994656A - 钎焊合金组合物 - Google Patents

钎焊合金组合物 Download PDF

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CN1994656A
CN1994656A CNA2006100641307A CN200610064130A CN1994656A CN 1994656 A CN1994656 A CN 1994656A CN A2006100641307 A CNA2006100641307 A CN A2006100641307A CN 200610064130 A CN200610064130 A CN 200610064130A CN 1994656 A CN1994656 A CN 1994656A
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braze
nickel
cobalt
hafnium
braze alloy
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CN1994656B (zh
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L·蒋
L·克雷特尼
W·米利蒂
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General Electric Co
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/06—Alloys based on chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • 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
    • 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
    • B23K35/3033—Ni as the principal constituent
    • 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
    • B23K35/3033—Ni as the principal constituent
    • B23K35/304—Ni as the principal constituent with Cr as the next major constituent
    • 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
    • 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
    • B23K35/32—Selection of soldering or welding materials proper with the principal constituent melting at more than 1550 degrees C
    • 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
    • C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
    • 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
    • C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
    • 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
    • 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
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
    • 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
    • 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

Abstract

镍基高温钎焊合金组合物含有Cr、Hf和B。此外，钴基高温钎焊合金组合物含有Cr、Hf和B。例如该钎焊合金可以以单种均质钎焊合金的形式使用。该钎焊合金也可以例如在使用较高或较低熔点的高温合金和/或钎焊粉末的宽口钎焊混合物中用作为一种成分。该钎焊合金能够连接/修补具有复杂形状的高温合金制品，并可以在高温应用中使用。

Description

钎焊合金组合物
技术领域
本发明通常涉及钎焊合金组合物。更具体地，本发明涉及镍基和钴基钎焊合金组合物。
背景技术
为了有效地在高温环境下发挥作用，通常加入重合金组分以强化高温合金。这可导致极端环境下使用的高温合金部件(如燃气轮机中的热气通道的螺旋浆)焊接连接/修补的困难。由于其降低的成本与周期，钎焊成为高温合金部件连接/修补的更优的选择。然而，使钎焊接头/修补具有接近高温合金基材材料的某些性能，特别是延展性可能是有挑战性的。通常，首要障碍可能是在钎焊接头中形成了脆性相。
硼已经广泛应用于钎焊合金，但通常脆性硼化物导致钎焊接头的低劣的机械性能。提高钎焊接头/修补区域的机械完整性的方法通常需要采用延长的扩散周期。通过与基材高温合金或钎焊粉末混合物均化，这种方法可以降低脆性硼化物相的量。但是这种方法可能需要延长的周期时间，更高的成本并令基材高温合金遭受热劣化。
在Smith等人的美国专利No.4,414,178；Budinger等人的美国专利No.5,240,491；Draghi等人的美国专利No.5,735,448；Biondo等人的美国专利No.5,783,318；Pietruska等人的美国专利No.6,503,349；Miglietti的美国专利No.6,520,401；Cohen等人的美国专利No.6,530,971；Rabinkin的美国专利No.6,165,290；和Huang等人的美国专利申请公开No.20050067061中描述了钎焊合金组合物及相关的方法和制品。其中铪以低重量百分比存在，其通常作为晶界增强剂，而不是作为钎焊合金组合物熔点的降低剂。
发明内容
在本发明的范围内，通常有两种钎焊合金组合物的示范性实施方案。一种示范性实施方案涉及含有铬(Cr)、铪(Hf)和硼(B)的镍基高温钎焊合金组合物。另一种示范性实施方案涉及含有Cr、Hf和B的钴基高温钎焊合金组合物。
在一种实施方案中，镍基钎焊合金组合物含有：9-25wt％及其全部子区间的铬；5-45wt％及其全部子区间的铪；和0.05-6wt％及其全部子区间的硼。
在另一种实施方案中，钴基钎焊合金组合物含有：9-25wt％及其全部子区间的铬；5-56wt％及其全部子区间的铪；和0.05-6wt％及其全部子区间的硼。
附图说明
图1举例说明了镍基钎焊合金的典型微观结构；和
图2举例说明了钴基钎焊合金的典型微观结构。
具体实施方式
该钎焊合金组合物可以以单种均质钎焊合金(braze)的形式使用。或者，该钎焊合金组合物可以例如在使用较高或较低熔点的高温合金和/或钎焊粉末的宽口钎焊混合物中用作为一种成分。例如，这些钎焊合金组合物能够连接或修补具有复杂形状和高温应用的高温合金制品。此外，钎焊合金组合物可以提供更高的延展性。
一般来说，硼和铪偶合以抑制固相线温度，而且铬、铪和硼偶合以抑制液相线温度。此外，加入的铬可以提供，例如，钎焊合金的抗氧化和耐腐蚀性。含硼、含铬和含铪的金属间化合物可以比含铬、含钨和含镍的硼化物更易延展。
本文中公开并请求保护的钎焊合金组合物能够在不使高温合金劣化的情况下在高温下钎焊，可以降低在钎焊过程中生成的硼化物或金属间化合物的脆性，并可以提高钎焊接头的机械性能(包括例如，延展性)。
根据本发明的一种示范实施方案，镍基钎焊合金组合物含有：9-25wt％及其全部子区间的铬；5-45wt％及其全部子区间的铪；和0.05-6wt％及其全部子区间的硼。
根据本发明的一种示范实施方案，铬优选为9-15wt％。更优选铬为13wt％。铪优选为10-30wt％。更优选铪为15-25wt％。更加优选地，铪为15wt％、20wt％或25wt％。硼优选为0.05-3.6wt％。更优选硼为1wt％。
根据本发明的另一种实施方案，该镍基钎焊合金组合物中一部分剩余镍被至少一种通常存在于高温合金中的元素，如铝、钛、钼、钨、钴、铁、锆、铌、铼、碳和硅替代。优选高至60％的剩余镍被至少一种通常存在于高温合金中的元素替代。更优选高至50％的剩余镍被至少一种通常存在于高温合金中的元素替代。
根据本发明的另一种示范实施方案，该镍基钎焊合金组合物具有低于2175的固相线温度。更优选该镍基钎焊合金组合物具有低于2100的固相线温度。更加优选该镍基钎焊合金组合物具有低于2025的固相线温度。
根据本发明的另一种示范实施方案，该镍基钎焊合金组合物基本上由9-25wt％的铬；5-45wt％的铪；0.05-6wt％的硼；和镍组成。更优选该镍基钎焊合金组合物基本上由9-25wt％的铬；10-30wt％的铪；0.05-3.6wt％的硼；和镍组成。
根据本发明的另一种示范实施方案，钴基钎焊合金组合物含有：9-25wt％及其全部子区间的铬；5-56wt％及其全部子区间的铪；和0.05-6wt％及其全部子区间的硼。
根据本发明的另一种示范实施方案，铬为15-25wt％。更优选铬为20wt％。优选铪为10-30wt％。更优选铪为10-26wt％。更加优选地，铪为15wt％、20wt％或25wt％。优选硼为0.05-4wt％。更优选硼为1wt％。
根据本发明的另一种示范实施方案，该钴基钎焊合金组合物具有低于2175的固相线温度。更优选该钴基钎焊合金组合物具有低于2100的固相线温度。更加优选地，该钴基合金组合物具有低于2025的固相线温度。
根据本发明的另一种示范实施方案，该钴基钎焊合金组合物基本上由9-25wt％的铬；5-56wt％的铪；和0.05-6wt％的硼；和钴组成。更优选该钴基钎焊合金组合物基本上由9-25wt％的铬；10-26wt％的铪；0.05-4wt％的硼；和钴组成。
根据本发明的另一种实施方案，该钴基钎焊合金组合物中一部分剩余钴被至少一种通常存在于高温合金中的元素，例如，铝、钛、钼、钨、镍、铁、锆、铌、铼、碳和硅替代。优选高至60％的剩余钴被至少一种通常存在于高温合金中的元素替代。更优选高至50％的剩余钴被至少一种通常存在于高温合金中的元素替代。
本领域的普通技术人员应理解并认可所有公开的和要求保护的百分数是近似的。
图1描述了四种镍基钎焊合金组合物。图2描述了四种钴基钎焊合金组合物。
下表(表1)显示了特定钎焊合金组合物中不同相的硬度测量值：
                       显微硬度(HV)
    γ       共晶体 硼化物
钎焊合金 平均值 标准偏差 平均值 标准偏差 平均值 标准偏差
 Ni-13Cr-15Hf-1B  215  17  576  76  N/A  N/A
 Ni-13Cr-15Hf  242  19  294  56  /  /
 Ni-13Cr-20Hf  309  19  322  72  /  /
 Ni-13Cr-25Hf  398  32  324  30  /  /
 Ni-13Cr-25Hf-1B  326  93  746  108  1150  240
 Co-20Cr-15Hf-1B  433  18  917  53  1229  84
 Co-20Cr-15Hf  477  46  658  89  /  /
 Co-20Cr-20Hf  565  21  612  61  /  /
 Co-20Cr-25Hf  /  /  1104  197  /  /
 Co-20Cr-25Hf-1B  538  59  N/A  N/A
表1：含铪钎焊合金的显微硬度结果
表1举例说明了硼化物通常比含有铪的化合物更硬。
下表(表2)显示了特定钎焊合金组合物的熔点温度测量值：
 钎焊合金 固相线() 液相线()
 Ni-13Cr-15Hf-1B  2013  2352
 Ni-13Cr-15Hf  2201  2438
 Ni-13Cr-20Hf  2228  2380
 Ni-13Cr-25Hf  2248  2355
 Ni-13Cr-25Hf-1B  2010  2322
 Co-20Cr-15Hf-1B  2008  2340
 Co-20Cr-15Hf  2286  2493
 Co-20Cr-20Hf  2324  2381
 Co-20Cr-25Hf  2307  2408
 Co-20Cr-25Hf-1B  2012  2205
表2：含铪钎焊合金的DSC结果
表2中的温度基于差示扫描量热法(DSC)加热曲线分析。表2举例说明了具有硼的含铪钎焊合金具有有益的性能。
虽然本发明是连同目前认为最具实用性的和优选的实施方案公开的，但应理解本发明不仅限于所公开的实施方案，而是相反，意图涵盖包括在所附权利要求的宗旨和范围内的各种修改和等同方案。

Claims (10)

1.一种镍基钎焊合金组合物，含有：
9-25wt％的铬；
5-45wt％的铪；和
0.05-6wt％的硼。
2.权利要求1所述的镍基钎焊合金组合物，含有9-15wt％的铬。
3.权利要求1所述的镍基钎焊合金组合物，含有10-30wt％的铪。
4.权利要求1所述的镍基钎焊合金组合物，含有0.05-3.6wt％的硼。
5.权利要求1所述的镍基钎焊合金组合物，其中高至60％的剩余镍内容物被至少一种选自铝、钛、钼、钨、钴、铁、锆、铌、铼、碳和硅的元素替代。
6.一种钴基钎焊合金组合物，含有：
9-25wt％的铬；
5-56wt％的铪；和
0.05-6wt％的硼。
7.权利要求6所述的钴基钎焊合金组合物，含有15-25wt％的铬。
8.权利要求6所述的钴基钎焊合金组合物，含有10-26wt％的铪。
9.权利要求6所述的钴基钎焊合金组合物，含有0.05-4wt％的硼。
10.权利要求6所述的钴基钎焊合金组合物，其中高至60％的剩余镍内容物被至少一种选自铝、钛、钼、钨、镍、铁、锆、铌、铼、碳和硅的元素替代。
CN2006100641307A 2005-12-15 2006-12-15 钎焊合金组合物 Expired - Fee Related CN1994656B (zh)

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US11/300394 2005-12-15
US11/300,394 US7156280B1 (en) 2005-12-15 2005-12-15 Braze alloy compositions

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CN1994656A true CN1994656A (zh) 2007-07-11
CN1994656B CN1994656B (zh) 2012-05-30

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CN102581517A (zh) * 2012-04-05 2012-07-18 郑州机械研究所 钎焊铝电解用惰性阳极与金属导电杆的高温钎料
CN102581517B (zh) * 2012-04-05 2015-02-11 郑州机械研究所 钎焊铝电解用惰性阳极与金属导电杆的高温钎料
CN105084713A (zh) * 2014-05-22 2015-11-25 赫罗伊斯石英玻璃股份有限两合公司 特别用于石英玻璃坩埚提拉法的组件及生产该组件的方法
CN105084713B (zh) * 2014-05-22 2018-11-13 赫罗伊斯石英玻璃股份有限两合公司 特别用于石英玻璃坩埚提拉法的组件及生产该组件的方法
CN104801891A (zh) * 2015-04-24 2015-07-29 柳州金茂机械有限公司 一种焊接工艺用焊丝的制造方法
CN104874938A (zh) * 2015-05-09 2015-09-02 芜湖鼎恒材料技术有限公司 一种Co-Ti-Mo-W纳米焊层及其制备方法

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NO20065799L (no) 2007-06-18
EP1818132B1 (en) 2014-07-23
CN1994656B (zh) 2012-05-30
EP2589460B1 (en) 2014-06-25
CA2572278C (en) 2015-06-23
US7156280B1 (en) 2007-01-02
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