CN1474732B - 焊接材料及以此所制得的产品 - Google Patents

焊接材料及以此所制得的产品 Download PDF

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CN1474732B
CN1474732B CN018187366A CN01818736A CN1474732B CN 1474732 B CN1474732 B CN 1474732B CN 018187366 A CN018187366 A CN 018187366A CN 01818736 A CN01818736 A CN 01818736A CN 1474732 B CN1474732 B CN 1474732B
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P·E·斯杰丁
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Alfa Laval AB
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
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Abstract

一种铁基钎焊料，其中包括至少50％Fe；0-30％Cr，优选9-30％Cr；最大5％Mn；0-25％Ni；最大7％Mo；0-1％N；6-20％Si，所有百分比以重量百分率表示，该Si的加入量足以有效降低此钎焊料完全熔化的温度；以及条件是，若B存在，则其量为小于2％。一种包括由一种用本发明钎焊料钎焊在一起的铁基材料制成的部件的钎焊制品。

Description

焊接材料及以此所制得的产品
技术领域
本发明涉及一种供通过钎焊连接物件用的铁基钎焊料。本发明还包括以一种本发明的铁基钎焊料将铁基材料物件钎焊在一起而制得的钎焊产品。 
背景技术
一般通过以Ni或Cu钎焊料来钎焊使不同的钢或铁基材料焊接。在一些应用中，该钎焊料可包括Ag或Co。 
钎焊为一种固定/连接方法，在钎焊时其温度低于该基体材料(将加以连接/固定的构件)原本的固相线温度。 
钎焊料系指连接或加固材料，它在钎焊过程中完全或部分地熔化。 
US4135656描述了一种Ni基合金，按重量百分数计，除了较小量的其它成分外，它含有19-23％Mn、5-8％Si、4-6％Cu、0.6-1.8％B和Ni。US4314661描述了另一类Ni基合金；按原子百分数计，它含有0-4％Fe、0-21％Cr、0-19％B、0-12％Si、0-22％P；而其余则为Ni。 
US4516716描述了一种钎焊方法，所用的铁基合金包括约为2-6％重量的硼和约为5-12％的硅。 
当以Cu钎焊时，人们通常使用纯的或近乎纯的Cu。纯铜钎焊料有完全确定的熔点，而镍钎焊料则视其构成合金的情况往往具有一个熔化区间。 
如果焊接平板热交换器中的不锈钢板，那么经常使用的是铜钎焊料。然而铜并非适合于所有种类的应用。例如铜钎焊料不可用于食品应用，但却用于区域加热和自来水装置。 
以镍钎焊料焊接成的热交换器可用于许多连接之中，并且也可在数目有限的食品应用中加以使用。 
若用含镍合金的钎焊料来焊接铁或非镍基材料物件，则其钎焊缝的组成与被焊接在一起之材料的组成非常不同。这能导致所不希望的化学和机械特性上的差别。 
发明内容
本发明借助使用与用来制做其产品之基体材料成分大抵相同的钎焊料进行钎焊，而提供焊接物件的可能性，其中该钎焊料含有降低其液相线温度的添加成分。因此本发明提供制造如同平板热交换器那样的装置的可能性，通过使用本发明的钎焊料，该装置便适合于食品 应用的要求。本发明的主要特征在于钎焊料由一合金构成，它含有至少50％Fe并包括0-30％Cr，最好9-30％Cr，最大5％Mn，0-25％Ni，最大7％Mo，0-1％N和6-20％Si，均以百分重量表示，这里Si的加入降低了其液相线温度，即使该钎焊料完全熔化的温度。 
除了Si以外，此钎焊料也可含有B，它起补充Si之降低熔点成分的作用，其中B的总量低于2％，最好低于1.5％。B的加入还提高该钎焊料的湿润度。 
附图说明
图1给出第2号熔料的DTA曲线，图2给出第3号熔料的同样曲线，而图3则为第5号熔料的曲线。 
具体实施方式
在一优选实施方案中，其铁基钎焊料含有7-16％Si，最好为8-12％。为了获得预定的熔点降低，活性融化的Si总量应在所述的范围之内。然而分析的Si总量也许要高得多，因为倘若己同氧键合或按某一其它方式在化学上键合，Si就可以碳化硅或硼化硅之形式存在。 
此铁基钎焊料可含有微量成合金成分，如V、Ti、W、Al、Nb、Ta等。组成的不同也可能是少量不可避免的掺杂成分的结果，如C、O和S。 
代之以将B加入该钎焊料，也可以在本发明的范围内加入P作为降低熔点的成分。在此情况下P的总量最大为15％。 
此铁基钎焊料B通过气体雾化或水雾化来有效地加以制备。如该合金含有硼，则也可通过融熔旋压来制备此钎焊料。 
本发明还包括借助将铁基物件钎焊在一起而制得的钎焊产品，这样该产品的特征就是以一为具有上述组成合金的铁基钎焊料来对其物件进行焊接。 
有优势的钎焊产品为欲用作至少两个热交换介质的平板热交换器，它包括至少一组板，乃通过用铁基钎焊料将若干薄壁铁基材料热交换器板钎焊在一起而制得。此热交换器板限定它们之间的供其热交换介质所用的板间间隙。其钎焊缝具有接近于该铣基板材的冶金组成，唯在钎焊缝内及其周围局部的Si量较之铁基板材为高。 
当连系平板热交换器使用薄壁这一表述时，它用于厚度小于1mm的板。为了得到充分的热转换，这样的薄板是必须的。 
此钎焊产品可有效地以含有B或P的铁基钎焊料来钎焊。 
对于如平板热交换器的薄壁产品，重要的是要使该钎焊料中硼的总量同待钎焊板的重量之间有精确的关系。在这样一种情况下，硼的 百分率含量将为最大1.5％，以避免过多的硼化铬的形成，下面将对此加以描述。 
为钎焊铁基材料，人们习惯上使用早先提到的Cu或Ni钎焊料。现在出乎意外地发现，人们可以一种与人们想要连接在一起之物件材料有相同组成的基体材料开始。通过以硅使这样一种材料合金化，人们便可得到功能不错的钎焊料。借助研究纯铁和Si、B以及P的二元相图人们可发现，Fe-Si合金在约19％Si时为1212℃的熔点最小值。对于Fe-B合金在约4％B时有约为1174℃的熔点最小值。在Fe-P体系中，在约10％P时有约为1048℃的熔点最小值。 
在大多数情况下，并非使用纯铁材料而是使用合金，它除Fe之外还含有相对大量的Cr和Ni。在许多合金中还有Mo、Mn、Cu和N。试图从理论上确定不同用量硅加入这些合金中的效果几乎是不可能的，因为其变数将同该合金中的成分数一样大。 
为达到钎焊连接，其钎焊料的液相线温度应低于1220℃。 
足以令人惊奇的是，已发现加入相对少量硅可引起这样的液相线温度降低，因此可以得到适合的钎焊料。 
美国专利4516718描述了一种含有硅和硼的钎焊料。在这一专利中硼的总量据说约为2-6％，以便达到所希望的液相线温度的降低。 
根据本发明，硼的百分率含量应低于2％。这点的理由是，与硅不同，硼非常迅速地扩散进入待钎焊的铁基材料中。这样一来就影响该钎焊产品的性能。如果使待连接部件间的空隙尽可能地小，那么最好的钎焊连接便达到。由于钎焊料在该空隙中的厚度，因此所用的钎焊料在待连接部件间形成一个间隙。当钎焊时，钎焊料熔化并被挤压向旁边，使该空隙能缩小。在许多情况下，当钎焊物件比如平板热交换器时，该物件的外围较之该物件的内心将被更快地加热。钎焊料必然也在其外围开始熔化。硼开始扩散；同时由于组成的变化，在内心处钎焊料已熔化之前，在外围此钎焊料便开始固化。按照本发明，硅是用以降低其熔点的成分，而硼则为次要的熔点降低成分。因为硅扩散比硼慢，所以要增长扩散时间，使得在内部的钎焊料能于其外部的固化之前熔化。硼的功用主要是增加该钎焊料的湿润度。 
避免使用高含量硼的另一个理由，是在钎焊含铬合金的时候。许多不锈钢含有约17％Cr。此铬含量很大程度上支配不锈钢的腐蚀特性。 如果在待钎焊物件中有铬以及在钎焊料中有硼，那么就存在形成硼化铬的风险。若此硼化物的分子式为Cr23B6，则每一硼原子便结合3.8个铬原子。Cr和B间的分子重量关系为52.0/10.8＝4.8还表明，甚至小百分率含量如2-3％的B可使铬的含量减少至这样的程度，使之将对其抗腐蚀性有严重的影响。钢的抗腐蚀将随着每一硼化物的形成而下降。硼化铬比基体材料要硬，并且还有形成针状结晶之形状。其形状可引起应力的集中并因此而引起裂纹的形成。 
本发明对钎焊不同种类钢物件有很大的价值。作为一个例子可以提到不锈钢合金316。这一合金的化学组成为最大2.0％Mn、16.5-18％Cr、10.0-13.0％Ni、2.0-2.5Mo，剩余部分是Fe。根据本发明，以与该合金相同的成分制备钎焊料；不过要按重量以合适总量的Si代替同量的Fe。经钎焊作业后，该钎焊的产品，像在钎焊缝中一样，将具有被钎焊物件中大抵相同的组成。 
在下表中给出钎焊料组成的不同实例，它们乃通过于小真空炉中熔化而制得。该铸锭此后可其模中固化。 
表1.一些实验熔料的分析结果 
  
熔料 Fe ％Si ％Mn ％P ％B ％Cr ％Mo ％Ni
1 Bal 6 1 0 0 17 2.5 12
2 Bal 8 1 0 0 17 2.5 12
3 Bal 10 1 0 0 17 2.5 12
4 Bal 12 1 0 0 17 2.5 12
5 Bal 15 1 0 0 17 2.5 12
6 Bal 6 1 0 1.5 17 2.5 12
7 Bal 6 1 3 0 17 2.5 12
8 Bal 10 1.5     17 2.5 20
符号Bal(平衡量)表示该熔料中其余的材料是Fe。 
在浇铸后对熔料的实际组成进行了测量，其结果可见于表2。
表2.铸锭中所测得的百分率含量 
  
熔料 Fe ％Si ％Mn ％P ％B ％Cr ％Mo ％Ni ppm○·
1 Bal 5.86 1.43     17.1 2.45 11.9  
2 Bal 8.20 1.29     17.2 2.51 11.9  
3 Bal 10.0 1.25     17.1 2.46 12.0 (56∶57)
4 Bal 12.1 1.20     16.8 2.47 11.9 (31∶31)
5 Bal 14.7 1.81     16.6 2.54 11.9 (38∶42)
6 Bal 5.93 1.46   1.20 16.7 2.42 11.9  
7 Bal 6.37 1.60 3.09   17.2 2.51 11.6  
8 Bal 10.0 1.47     16.4 2.54 20.5 (27∶30)
·两次的测量值 
由这些实验熔料制得一种粉末，并于真空炉中进行一次试钎焊。在该炉中最高温度约为1190℃。用肉眼检验这些样品以确定：该合金是否已熔化，是否已达到并超越其固相线温度，或已完全熔化，是否已达到其液相线温度。 
表3.在1190℃于真空炉中试钎焊后对固相线和液相线特性的眼测结果 
  
熔料 >固相线 >液相线
1 是 否
2 是 接近
3 是 是或接近
4 是 是
5 是 是
6 是 否
7 是 否
8 是 接近
诚如在该表中可看出的，熔料2至5和8在低于1200℃的钎焊温度可适合于作为钎焊料。 
所附的图显示，为着用一DTA设备(差热分析)测量其熔化区间怎样对熔料2、3和5加以分析。此测量B通过分两步加热该材料来进行，从室温至900℃的温度以及此后达1300℃的最高温度。其后使该材料冷却至900℃的温度。使此加热和冷却重复两次。在该图中彼此重叠并指向下方的峰表示完成熔化所需的总热量。该峰的扩展范围形成对所研究合金之熔化区间的度量。
正如于图中可以看出的，具有约9％Si的一种合金其熔化区间为1154-1197℃(图1)，具有10％Si的一种合金为1145-1182℃(图2)以及具有15％Si的一种合金为1142-1177℃(图3)。 
此熔化区间的精确度或同已测值的偏差并非仅与其平均组成的差别有关。除了该材料的微结构之外，掺杂物的含量也是重要的。掺杂成分通常为C、O、S和N。在较高的O百分率含量时，硅在制备过程中便被化学结合，它意味着有效融化硅百分率含量的减少。这表示其液相线温度和固相线温度的增加。 
碳的百分率含量以这样一种方式影响其熔化温度，即较高的C含量一般产生较低的熔化区间(较低的固相线和液相线温度)，不过当钎焊像比如合金316那样的铁基材料时，例如其腐蚀特性就受到负面的影响。固相线和液相线温度在±10℃内变动并非不正常。 
该值的精确度也同用于分析的是哪一种仪器以及哪一种方法有关。对于通常以DTA方法分析的合金，其液相线和固相线温度具有±20℃的不确定性是正常的。 
本发明的钎焊料乃以粉末形式适当地制成。此粉末可借助形成铸锭并其后加以压碎和磨细来制造。该材料的易碎性倒为这一制造方法所利用。用铸锭的不利之处是，一定的结块风险可能产生具有难以确定的或宽的熔化区间之非均相材料。对于较小铸锭及/或快速冷却，此结块风险便减少。在铸锭浇注中，通过利用真空浇注或有保护气体的浇注，使得同空气接触减至最少最重要的。此机械处理的结果，该钎焊料的能量含量便增加，同时其反应性亦然。 
制得有均相组成粉末的另外的制造方法是水或气体雾化。该粉末的性质随着其制造方法而变化。压碎并磨细的颗粒为角状和尖状，水雾化的颗粒为节状，而气体雾化的颗粒则几乎为球状。这种颗粒形状的不同使此钎焊料在用于钎焊时有稍微不同的性质。通过选择不同雾化方法以及压碎/磨细程度，结合以对其颗粒类别的筛选，便可控制粒度。在水雾化中，氧含量一般将较高，因为水雾化是在比气体雾化要高的氧电位发生。较高的氧含量可引起Si氧化物的形成，它对钎焊缝的机械特性可能有负面影响。在该钎焊料中有效的Si百分率含量将因 此而更低，意味着其熔化区间将位移。 
表4.其它的改进的组成 
  
组成 ％Fe ％si ％Mn ％P ％B ％N ％Cr ％Mo ％Ni >固相线 >固相线
9 bal 12.2 1.5       18 0.3 8 是 是
10 bal 18.1 1.2       0 0 0 是 是
11 bal 8 1.5   0.5   17 2.2 11 是 是
12 bal 5 1.5 5     17 2.2 11 是 是
13 bal 7.8 0.45     0.2 20 6.1 18 是 是
14 bal 13 0.7       13 0 0 是 是
组成为9-12的合金在1190℃的温度加以钎焊，组成为13-14的合金在1215℃的温度加以钎焊。 
本发明的钎焊料可用于人们想要借助不同方法进行钎焊连接的地方。由任一所述方法制得的钎焊料粉末可分散于某一粘结剂中，以便按某种合适的方式加以应用。

Claims (8)

1.一种铁基钎焊料，其中此钎焊料由一合金组成，该合金含有下列组分，
(i)至少50重量％Fe；
(ii)9-30重量％Cr；
(iii)最大5重量％Mn；
(iv)0-13重量％Ni；
(v)最大7重量％Mo；
(vi)0-1重量％N；
(vii)6-20重量％Si，该Si的加入量足以有效降低此钎焊料完全熔化的温度；以及
(viii)任选的微量成合金成分，选自V、Ti、W、Nb和Ta；和
(ix)B，其量为小于1.5重量％，或者P，其量为小于15重量％；以及
(x)少量作为不可避免的掺杂成分的C、O和S。
2.权利要求1的钎焊料，其中所述合金包括7-16重量％的Si。
3.权利要求1或2的钎焊料，其中所述合金包括8-12重量％的Si。
4.权利要求1或2的钎焊料，其中所述合金通过气体雾化或水雾化或者熔融旋压作用而制得。
5.一种包括由一种用铁基钎焊料钎焊在一起的铁基材料制成的部件的制品，其中所述钎焊料为含有下列组分的合金，
(i)至少50重量％Fe；
(ii)9-30重量％Cr；
(iii)最大5重量％Mn；
(iv)0-13重量％Ni；
(v)最大7重量％Mo；
(vi)0-1重量％N；
(vii)6-20重量％Si，该Si的加入量足以有效降低此钎焊料完全熔化的温度；以及
(viii)任选的微量成合金成分，选自V、Ti、W、Nb和Ta；和
(ix)B，其量为小于1.5重量％，或者P，其量为小于15重量％；以及
(x)少量作为不可避免的掺杂成分的C、O和S。
6.权利要求5的制品，其中使用铁基钎焊料钎焊在一起的铁基材料包括最大2.0重量％Mn、16.5-18重量％Cr、10.0-13.0重量％Ni、2.0-2.5重量％Mo，剩余部分是Fe和少量作为不可避免的掺杂成分的C、O和S。
7.权利要求5或6的制品，其中的部件是热交换器板，所述制品是欲用作至少两种热交换介质的板式热交换器，并包括至少一组板，该组板包括由用所述钎焊料焊在一起的几块铁基材料薄壁热交换器板，其钎焊缝具有接近于该铁基板材的冶金组成，唯在该钎焊缝内及其周围局部的Si量较之铁基板材为高。
8.一种用铁基钎焊料钎焊铁基材料制成的部件的方法，其中所述钎焊料由一合金组成，该合金含有下列组分
(i)至少50重量％Fe；
(ii)9-30重量％Cr；
(iii)最大5重量％Mn；
(iv)0-13重量％Ni；
(v)最大7重量％Mo；
(vi)0-1重量％N；
(vii)6-20重量％Si，该Si的加入量足以有效降低此钎焊料完全熔化的温度；以及
(viii)任选的微量成合金成分，选自V、Ti、W、Nb和Ta；和
(ix)B，其量为小于1.5重量％，或者P，其量为小于15重量％；以及
(x)少量作为不可避免的掺杂成分的C、O和S。
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