CN101291775A - 铁及镍基纤焊箔以及纤焊方法 - Google Patents
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Abstract
一种非晶态延性钎焊箔,其由FeaNibCrcSidBeMofPg和任意杂质的组合物制备,其中25≤a≤50at%;30≤b≤45at%;5<c≤15at%;4≤d≤15at%;4≤e≤15at%;0≤f≤5at%;0≤g≤6at%;其中10≤d+e+g≤28at%,并且a+b+c+d+e+f+g=100。利用该钎焊箔可以制成优良的钎焊接头。
Description
本发明涉及一种铁及镍基钎焊箔、以及钎焊两个或多个金属部件的方法。
铁基钎焊合金已公开于例如US4402742中。铁基钎焊合金因原材料成本较低而具有比镍基钎焊合金更为廉价的优点。此外,铁基合金更易结合,因为其焊缝组成能更精确地与待焊接部件的成分相匹配。
然而,已知的铁基钎焊合金为晶体,并被制成粉末或糊状物。粉末一般通过对熔体进行雾化处理制成。糊状物则通过将金属粉末与有机粘结剂和溶剂混合而制成。事实上其不利之处在于,当加热到钎焊温度时该有机成分发生分解,这会影响熔融钎焊合金的流动性和浸润性。
此外还存在一个风险,即接头可能无法完全被该钎焊合金填充,这将导致不再能够可靠地确保待焊接部件的机械稳定性。当钎焊热交换器或类似产品时,这种结合缺陷对于其防漏性是极其危险的,并有可能使得该热交换器无法使用。
这些问题可以通过使用均质延性箔形式的钎焊合金而得以避免。但迄今为止仍不可能制造延性箔形式的铁及镍基钎焊合金。
因此,基于上述问题,本发明提供一种延性箔形式的铁基钎焊合金,其具有良好的流动性和浸润性,从而能保证无缺陷的钎焊接头(brazingjoint),本发明还制定了一种使用这类延性钎焊箔的钎焊方法。此外,该钎焊合金应当能够被制成具有很宽的厚度和宽度范围的快速凝固的箔,从而使其能够满足多种用途的技术需要。
根据本发明,上述问题是通过一种非晶态延性钎焊箔解决的,其组成主要由FeaNibCrcSidBeMofPg和任意杂质组成,其中25≤a≤50at%;25≤b≤50at%;5<c≤15at%;4≤d≤15at%;4≤e≤15at%;0≤f≤5at%;0≤g≤6at%;其中10≤d+e+g≤28at%,并且a+b+c+d+e+f+g=100。
与镍基钎焊合金相比,铁含量较高和镍含量较低使得原材料成本有所降低。因而根据本发明的钎焊箔不但经济而且适合工业用途。该钎焊合金的Ni含量优选为30≤b≤45at%。
铬含量提供优良的耐蚀性,因此该钎焊接头能够在腐蚀性介质中工作。镍基钎焊合金的延性会随铬含量的增加而变差。但在根据本发明的的钎焊箔中可以加入5-15at%的铬含量而不明显降低延性。
根据本发明的钎焊合金的组成经过进一步选择后使得该合金能被制成延性的非晶态箔。该箔优选通过快速凝固工艺制成。
元素硼、硅和磷是类金属和产气元素(gas-forming element)。这些元素的含量较高会导致熔化温度或液相线温度降低。一方面,如果产气元素的含量过低,该箔会凝固形成晶体并且极脆。而另一方面,如果产气元素的含量过高,该箔在极薄条情况下是脆性的,不再能用于生产工艺。
进一步选择类金属的含量,使得由该钎焊箔制成的焊缝具有适当的机械性能。B含量高会导致在该焊缝和基底材料中析出B硬质相,这会影响钎焊复合物的机械性能。在该工艺中,硼与铬发生反应,这同样导致耐蚀性明显降低。Si含量较高导致在焊缝中形成不希望的Si硬质相,这会降低焊缝的强度。
因此根据本发明的钎焊箔所具有的成分中,产气元素的含量总计占该合金的10-28at%。具有这种组成的钎焊合金可以通过快速凝固法被制成延性的非晶态箔。
基于上述原因,B含量为4-15at%,优选4-12at%,而Si含量为4-15at%,优选5-13at%。
根据本发明的钎焊合金具有低于1200℃的液相线温度。这是理想的,因为许多工业钎焊工艺特别是结合不锈钢基底材料的最高温度限于约1200℃。按照惯例,该钎焊温度应尽可能低,这是因为基底材料倾向于从1000℃开始生成不利的粗晶。生成这种不希望产生的粗晶会降低该基底材料的机械强度,这在诸如热交换器的许多工业应用中是十分危险的。在根据本发明的钎焊合金中,这一问题明显减少了。
已经发现,镍含量为25-50at%且铁含量为25-50at%的合金的熔化温度低于1200℃。由于该镍含量,产气元素的含量能够得以降低。由于能够降低类金属含量,因而避免了形成B和Si的硬质相的缺点。
因此,根据本发明的钎焊合金适合最高钎焊温度限于1200℃的工业用途。该合金能提供可靠的钎焊接头。
根据本发明的钎焊合金优选制成均质、延性的非晶态钎焊箔,其一般50%、优选高于80%是非晶态的。
根据本发明的钎焊箔的特征在于优异的流动性和润湿性,能可靠地完成填角焊缝(fillet weld)和无缺陷接头。这保证了该钎焊缝的机械稳定性,并增加了根据本发明的钎焊箔的可能的用途数量。
在相同的类金属含量下,根据本发明的延性钎焊箔能够制成相当厚和相当宽的条带。因此根据本发明的钎焊合金非常适于铸造成厚度大于30μm、优选40μm≤D≤80μm,且宽度大于40mm、优选20mm≤B≤300mm,而采用现有技术中的合金仅能实现有限的范围。
在相同的类金属含量下,根据本发明的镍含量高于25at%的钎焊箔比镍含量低于20at%的钎焊合金具有更好的屈服点(ductility limit)。因此它能够制成更厚的钎焊箔,这样的钎焊箔容易满足多种用途的所有技术要求。采用根据本发明的钎焊合金,能制成大量工业用途所需的厚度至少为30μm的条带。
本发明进一步提供一种热交换器。该热交换器具有至少一个由下述钎焊箔制成的焊缝,该钎焊箔的组成主要由FeaNibCrcSidBeMofPg和任意杂质组成,其中25≤a≤50at%;25≤b≤50at%;5<c≤15at%;4≤d≤15at%;4≤e≤15at%;0≤f≤5at%;0≤g≤6at%;其中10≤d+e+g≤28at%,并且a+b+c+d+e+f+g=100。该钎焊缝由非晶态延性钎焊箔制成。在一个进一步的实施方案中,Ni含量为30≤b≤45at%。或者,该热交换器可以具有由前述任一实施方案所述非晶态延性钎焊箔制成的焊缝。
上述由非晶态延性钎焊箔制成的焊缝与由晶体粉末制成的焊缝的不同之处在于B和Si硬质相的尺寸。
本发明进一步提供一种通过附着力连接两个或多个金属部件的方法,该方法包括下述步骤。在两个或多个待连接的金属部件之间引入前述任一实施方案所述的非晶态延性钎焊箔。所述待连接的金属部件具有高于该钎焊箔的熔化温度,并可以由例如不锈钢、Ni或Co合金组成。将待钎焊的复合物加热至高于该钎焊箔的液相线温度的温度,随后冷却,从而在所述待连接的金属部件之间形成钎焊接头。
所述待连接的金属部件优选为热交换器部件、废气环流冷却器或燃料电池。这些产品需要可靠的钎焊接头,该钎焊接头完全防漏,在升高工作温度下耐腐蚀,机械上稳定因而可靠。根据本发明的钎焊箔使得能够获得这样的接头。
根据本发明的钎焊箔可以用于在物品中制成一个或多个焊缝。该经钎焊的物品可以用作例如热交换器、废气环流冷却器或燃料电池。
利用快速凝固工艺将根据本发明的钎焊箔制成非晶态、均质的、延性钎焊箔。为此,通过铸口将金属熔体喷射到高速浇铸轮或浇铸筒上,并以高于105℃/s的速率冷却。随后,一般在100℃-300℃之间的温度下将铸造的条带从该浇铸轮取下,直接卷绕成所谓的带材卷或卷绕在卷轴上。
根据本发明的非晶态钎焊箔用于通过附着力连接两个或多个部件,包括下述步骤:
-提供熔体,其由FeaNibCrcSidBeMofPg和任意杂质组成,其中25≤a≤50at%;25≤b≤50at%;5<c≤15at%;4≤d≤15at%;4≤e≤15at%;0≤f≤5at%;0≤g≤6at%;其中10≤d+e+g≤28at%,并且a+b+c+d+e+f+g=100;
-通过以高于约105℃/s的速率在移动冷却表面上快速凝固上述熔体,制造非晶态钎焊合金箔;
-通过在待连接的金属部件之间施加该钎焊合金箔,形成钎焊复合物;
-将该钎焊复合物加热至高于该钎焊合金箔的液相线温度的温度;
-冷却该钎焊复合物,从而在所述待连接的金属部件之间形成接头。
在一个进一步的实施方案中,提供熔体,其由FeaNibCrcSidBeMofPg和任意杂质组成,其中25≤a≤50at%;30≤b≤45at%;5<c≤15at%;4≤d≤15at%;4≤e≤15at%;0≤f≤5at%;0≤g≤6at%;其中10≤d+e+g≤28at%,并且a+b+c+d+e+f+g=100。
上述通过附着力形成的接头涉及利用根据本发明的铁及镍基钎焊合金进行的钎焊工艺,借此可以获得无任何接合缺陷的完美的钎焊接头。
根据本发明的钎焊合金的液相线温度低于1200℃。根据本发明的钎焊方法特别适合通过附着力连接由不锈钢和/或镍和/或钴合金制成的金属部件。这些部件通常用于制造热交换器或类似产品(例如废气环流冷却器)。
在钎焊温度下,该熔融钎焊箔润湿所述待连接的金属部件,由于其具有根据本发明的组成因而完全填充该焊缝,因此避免了接合缺陷。
下面,参照实施方案和对比例详细说明本发明。
表1列出了具有不同Ni和类金属含量的Fe-Ni钎焊箔的固相线及液相线温度。
表1
- | Fe(at%) | Ni(at%) | Cr(at%) | Si(at%) | B(at%) | Mo(at%) | 固相线温度(℃) | 液相线温度(℃) |
1 | 68 | 10 | 10 | 5 | 7 | 0 | 1130 | 1280 |
2 | 66 | 10 | 10 | 5 | 9 | 0 | 1115 | 1225 |
3 | 66 | 10 | 10 | 9 | 5 | 0 | 1130 | 1280 |
4 | 64 | 10 | 10 | 9 | 7 | 0 | 1110 | 1230 |
5 | 62 | 10 | 19 | 5 | 13 | 0 | 1100 | 1215 |
6 | 51 | 25 | 19 | 5 | 9 | 0 | 1055 | 1200 |
7 | 49 | 25 | 10 | 9 | 7 | 0 | 1100 | 1200 |
8 | 49 | 25 | 10 | 5 | 13 | 0 | 1045 | 1195 |
9 | 44 | 30 | 10 | 9 | 7 | 0 | 1050 | 1185 |
10 | 42 | 30 | 10 | 9 | 9 | 0 | 980 | 1160 |
11 | 36 | 40 | 10 | 9 | 5 | 0 | 960 | 1195 |
12 | 34 | 40 | 10 | 9 | 7 | 0 | 970 | 1175 |
13 | 32 | 40 | 10 | 5 | 13 | 0 | 915 | 1140 |
14 | 27 | 40 | 14 | 9 | 9 | 1 | 955 | 1135 |
第1至5号的钎焊箔不是本发明的一部分,而第6至14号的则是根据本发明的钎焊箔。
这些钎焊箔的加工温度和钎焊温度通常比液相线温度高10-50℃。如表1所示,Ni含量低于25at%(表1中第1至5号)的Fe-Ni钎焊箔倾向于具有明显高于1200℃的液相线温度。这使得Ni含量低于25at%的Fe-Ni钎焊箔的加工温度高于1200℃。这样的加工温度是不能被接受的,因为该温度会导致形成粗晶,损害待连接部件的基底材料。
在相同的类金属含量下,即Si和B含量,具有25或40at%的较高Ni含量的Fe/Ni钎焊合金(表1中第6至14号)具有低于工业技术中可允许的最高温度1200℃的液相线温度。因此加工温度低于1200℃,这是可以接受的。而且这些合金可以被制成带厚大于30μm的非晶态延性箔,从而满足工业应用的要求。
第1实施方案
采用组成为Fe32-Ni40-Cr10-Si9-B9的延性非晶态钎焊箔制成焊缝。钎焊条件为在1190℃达30分钟。该合金流过并润湿该基底材料,形成理想地填充的填角焊缝。该焊缝无任何熔合不良的缺陷。
第2实施方案
采用组成为Fe62-Ni10-Cr10-Si5-B11的延性非晶态钎焊箔制成焊缝。钎焊条件为在1240℃达30分钟。该钎焊合金的流动性和浸润性极差,因此接头未被完全填充。接头的熔合情况极差。无法保证可靠的接头。
Claims (19)
1.非晶态延性钎焊箔,其组成主要由FeaNibCrcSidBeMofPg和任意杂质组成,其中25≤a≤50at%;25≤b≤50at%;5<c≤15at%;4≤d≤15at%;4≤e≤15at%;0≤f≤5at%;0≤g≤6at%;其中10≤d+e+g≤28at%,并且a+b+c+d+e+f+g=100。
2.非晶态延性钎焊箔,其组成主要由FeaNibCrcSidBeMofPg和任意杂质组成,其中25≤a≤50at%;30≤b≤45at%;5<c≤15at%;4≤d≤15at%;4≤e≤15at%;0≤f≤5at%;0≤g≤6at%;其中12≤d+e+g≤24at%,并且a+b+c+d+e+f+g=100。
3.根据权利要求1或2所述的非晶态延性钎焊箔,其特征在于Si含量为5≤d≤13at%。
4.根据权利要求1或2所述的非晶态延性钎焊箔,其特征在于B含量为4≤e≤12at%。
5.根据权利要求1-4中任一项所述的非晶态延性钎焊箔,其特征在于液相线温度低于1200℃。
6.根据权利要求1-5中任一项所述的非晶态延性钎焊箔,其特征在于该钎焊箔至少80%为非晶态。
7.根据权利要求1-6中任一项所述的非晶态延性钎焊箔,其特征在于其厚度D大于30μm。
8.根据权利要求7所述的非晶态延性钎焊箔,其特征在于其厚度为40μm≤D≤80μm。
9.根据权利要求1-8中任一项所述的非晶态延性钎焊箔,其特征在于其宽度为20mm≤B≤300mm。
10.根据权利要求56所述的非晶态延性钎焊箔,其特征在于其宽度B≥40mm。
11.热交换器,该热交换器具有至少一个由下述非晶态延性钎焊箔制成的焊缝,该钎焊箔的组成主要由FeaNibCrcSidBeMofPg和任意杂质组成,其中25≤a≤50at%;25≤b≤50at%;5<c≤15at%;4≤d≤15at%;4≤e≤15at%;0≤f≤5at%;0≤g≤6at%;其中10≤d+e+g≤28at%,并且a+b+c+d+e+f+g=100。
12.具有至少一个由权利要求1-10任一项所述钎焊箔制成的焊缝的热交换器,其特征在于,该焊缝>30μm。
13.通过附着力连接两个或多个金属部件的方法,该方法包括下述步骤:
-在待连接的两个或多个金属部件之间引入权利要求1-10中任一项所述非晶态延性钎焊箔,其中所述待连接的金属部件的熔化温度高于该钎焊箔;
-将该钎焊复合物加热至高于该钎焊箔的液相线温度的温度;
-冷却该钎焊复合物,从而在所述待连接的金属部件之间形成钎焊接头。
14.根据权利要求13所述通过附着力连接两个或多个金属部件的方法,其特征在于所述待连接的金属部件为热交换器、废气环流冷却器或燃料电池的部件。
15.通过附着力连接两个或多个部件的方法,包括下述步骤:
-提供FeaNibCrcSidBeMofPg和任意杂质的熔体,其中25≤a≤50at%;25≤b≤50at%;5<c≤15at%;4≤d≤15at%;4≤e≤15at%;0≤f≤5at%;0≤g≤6at%;其中10≤d+e+g≤28at%,并且a+b+c+d+e+f+g=100;
-通过以高于约105℃/s的速率在移动冷却表面上快速凝固上述熔体,制成非晶态钎焊合金箔;
-通过在待连接的金属部件之间施加该钎焊合金箔,形成钎焊复合物;
-将该钎焊复合物加热至高于该钎焊合金箔的液相线温度的温度;
-冷却该钎焊复合物,从而在所述待连接的金属部件之间形成钎焊接头。
16.通过附着力连接两个或多个金属部件的方法,包括下述步骤:
-提供FeaNibCrcSidBeMofPg和任意杂质的熔体,其中25≤a≤50at%;30≤b≤45at%;5<c≤15at%;4≤d≤15at%;4≤e≤15at%;0≤f≤5at%;0≤g≤6at%;其中10≤d+e+g≤28at%,并且a+b+c+d+e+f+g=100;
-通过以高于约105℃/s的速率在移动冷却表面上快速凝固上述熔体,制成非晶态钎焊合金箔;
-通过在所述待连接的金属部件之间施加该钎焊合金箔,形成钎焊复合物;
-将该钎焊复合物加热至高于该钎焊合金箔的液相线温度的温度;
-冷却该钎焊复合物,从而在所述待连接的金属部件之间形成接头。
17.权利要求1-10中任一项所述非晶态延性钎焊箔用于钎焊热交换器、废气环流冷却器或燃料电池的两个或多个部件的用途。
18.经钎焊的物品,其特征在于,至少一个焊缝由权利要求1-10中任一项所述非晶态延性钎焊箔制成。
19.根据权利要求18所述经钎焊的物品,用作热交换器、废气环流冷却器或燃料电池。
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DE102005039803A DE102005039803A1 (de) | 2005-08-22 | 2005-08-22 | Hartlotfolie auf Eisen-Nickel-Basis sowie Verfahren zum Hartlöten |
PCT/DE2006/001242 WO2007022740A1 (de) | 2005-08-22 | 2006-07-18 | Amorphe hartlotfolie auf eisen-nickel-basis sowie verfahren zum hartlöten |
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CN109604861A (zh) * | 2018-11-16 | 2019-04-12 | 南京理工大学 | 用于连接TiAl合金与Ni基高温合金的铁基钎料 |
CN114514087A (zh) * | 2019-11-01 | 2022-05-17 | 欧瑞康美科(美国)公司 | 用于热交换器应用的低熔点铁基钎焊填料金属 |
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- 2005-08-22 DE DE102005039803A patent/DE102005039803A1/de not_active Ceased
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2006
- 2006-07-18 WO PCT/DE2006/001242 patent/WO2007022740A1/de active Application Filing
- 2006-07-18 CN CN2006800393907A patent/CN101291775B/zh not_active Expired - Fee Related
- 2006-07-18 EP EP06761819A patent/EP1917120A1/de not_active Ceased
- 2006-07-18 US US11/990,785 patent/US20090130483A1/en not_active Abandoned
- 2006-07-18 KR KR1020087006740A patent/KR20080043365A/ko not_active Application Discontinuation
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CN103492119A (zh) * | 2011-03-11 | 2014-01-01 | 真空融化股份有限公司 | 镍基硬钎焊箔、用于制造硬钎焊箔的方法、带焊缝的物品和用于硬钎焊的方法 |
CN109604861A (zh) * | 2018-11-16 | 2019-04-12 | 南京理工大学 | 用于连接TiAl合金与Ni基高温合金的铁基钎料 |
CN114514087A (zh) * | 2019-11-01 | 2022-05-17 | 欧瑞康美科(美国)公司 | 用于热交换器应用的低熔点铁基钎焊填料金属 |
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US20090130483A1 (en) | 2009-05-21 |
CN101291775B (zh) | 2011-11-30 |
EP1917120A1 (de) | 2008-05-07 |
DE102005039803A1 (de) | 2007-05-24 |
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US20130146184A1 (en) | 2013-06-13 |
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