CN100581700C - 用于硬钎焊的铝合金带 - Google Patents

用于硬钎焊的铝合金带 Download PDF

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CN100581700C
CN100581700C CN200480033570A CN200480033570A CN100581700C CN 100581700 C CN100581700 C CN 100581700C CN 200480033570 A CN200480033570 A CN 200480033570A CN 200480033570 A CN200480033570 A CN 200480033570A CN 100581700 C CN100581700 C CN 100581700C
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alloy
band
solder brazing
hard soldering
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CN1882407A (zh
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S·迪拉克
S·亨利
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Constellium Issoire SAS
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Alcan Rolled Products Ravenswood LLC
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Abstract

本发明涉及铝合金带或片，包括至少80重量%铝和0.01-0.5%的钇和/或0.05-0.5%的铋，该带或片在至少一个面涂覆有硬钎焊合金。所述带或片用于无焊剂焊接的产品的生产。

Description

用于硬钎焊的铝合金带
发明领域
发明涉及铝合金带，可能的是在一个或两个面上包覆有硬钎焊合金并用于硬钎焊零件生产的铝合金带，具体是用于汽车或建筑物的热交换器，和更为具体的是在受控气氛下通过无焊剂硬钎焊装配的零件。
现有技术
用于汽车热交换器装配的最常用的方法是硬钎焊。这是基于使用由所谓“芯”合金组成的包覆带材，所谓“芯”合金的一个或两个面上涂覆有所谓“硬钎焊”合金，至少用于要装配的部件之一。这所谓“硬钎焊”合金特征在于，液相线温度低于芯合金固相线温度约30℃。通过应用适当的热处理，可以只熔化包覆层，该包覆层然后润湿接触的表面，在组件冷却后允许好的装配。
目前存在三种不同的硬钎焊技术：
最为广泛使用的是在要装配的零件上涂覆非腐蚀性的“焊剂”后，在受控的氮气气氛下的硬钎焊，最为常用的是
Figure C20048003357000041
焊剂。这种用来溶解铝上的表面氧化物层，并进而提高表面润湿性的产品是氟铝酸钾类型。当其使用时会产生一些问题；显而易见的，产品具有固有的成本；它的沉积需要特殊的设备，该设备经常会防碍交换器生产线的完全自动化；最后必须安排废液处理。
另一种较老的、但特别是在北美仍然使用的技术是真空硬钎焊。这种方法必须使用包含镁的包覆层；这种元素在表面偏析，在真空中蒸发，捕获残留的痕量氧。这就避免了最初由不一致膨胀破坏的氧化物层的重新形成。焊剂不是必须的，但真空产生设备是非常复杂的，连带的维护费用是非常高的。出于经济的原因，逐渐地放弃了现有的生产线并由
Figure C20048003357000042
生产线取代。
最后，更少使用的第三种方法是，沉积镍层而不是焊剂。然后在氮气下进行硬钎焊。在硬钎焊周期中通过在包覆层表面上Al-Ni相的产生而释放的能量足以破坏氧化物层。
主要的问题是在现有的生产线上实施硬钎焊操作(由于这些是最为广泛使用的和最为经济的)，不使用焊剂或其它任何复杂的表面制备且不会引起使用这种技术装配的交换器最终性能的退化。
在这个领域中已经被广泛开发的解决方法是镍沉积硬钎焊方法的适用。尽管已经获得和使用日益简化的沉积技术，如专利申请WO02/07928(Corus)所描述的，但也从未提供解决问题的更为全面的方法。如果生产者实施这种操作，交换器或铝带的生产者就必须增加用于在硬钎焊前的表面制备的特殊设备，并必须继续处理此时由镍镀槽产生的废液。此外，尽管就耐腐蚀而言已经取得了进步，如专利申请WO02/060639(Corus)提到的，但显示的性能并没有总是达到
Figure C20048003357000052
硬焊产品所要求的性能(例如参见Pechiney Rhenalu的专利申请WO02/40729)。
其它的解决方法涉及包覆合金和/或在硬钎焊炉中气氛条件的适用，例如专利US 3811177(VAW)，该专利提及在硬钎焊合金中Bi、Sr、Ba或Sb元素的添加以调节它的表面张力。铋对表面张力的作用在专利EP0004096(Ford)中也有提及。最近，在Kaiser Aluminum的申请WO01/98019提及添加钠，可能的伴随添加钾或铋的优点。最后在EP1306207(Sky Aluminium)中，含有Mg和Bi的硬钎焊被一层由铝合金形成的薄层覆盖，该铝合金当开始熔融时仍保持固态；铝合金薄层仅在硬钎焊周期的后期破裂，释放出液体包覆物，该包覆物然后润湿其上表面；通过在气氛下短时间的工作，避免了液体硬钎焊合金的氧化。当薄层上存在的氧化物被液体环绕时会破裂。
发明的目的
本发明的目的是能够在良好的经济条件下，通过由铝合金制成零件的无焊剂硬钎焊进行生产，并具体的是使用与在受控气氛下采用焊剂的硬钎焊中相同的设备。
本发明的目的是含有0.01-0.5％的钇和/或0.05-0.5％的铋，至少一个面上涂覆有硬钎焊合金的铝合金带或片。涂层可以是通过共轧包覆的层，例如含有4-15％硅的铝合金。它也可以是包括硬钎焊合金颗粒的层，具体的是Al-Si合金颗粒，可能的包覆在树脂中。
本发明的另一个目的是硬钎焊的零件，具体的是使用含有0.01-0.5％钇和/或0.05-0.5％铋的铝合金带或片制成的热交换器。
附图描述
图1a和1b分别表示在实施例中使用的以评价可硬钎焊性的V测试片的顶视和侧视图。
图2表示实施例中描述的可硬钎焊性测试中使用的硬钎焊接头宽度的定义。
发明描述
和上述提及的技术不同，本发明用来改进芯合金的组成，使得硬钎焊能在没有任何沉积物下、在标准的受控气氛条件下进行，并使得能在无需改变设备生产者使用的硬钎焊装置的条件下完成。
令人惊讶的是，对于在氮气下的无焊剂硬钎焊，在芯中一些元素如0.05％含量的钇或约0.15％含量的铋的添加能导致令人满意的硬钎焊接头质量。
本方法适用于所有含有至少80重量％铝的铝合金类型，具体的是在添加具体用于使之能够无焊剂硬钎焊的元素之前的组成满足下面条件(重量％)的合金：
Si＜1.0；Fe＜1.0；Cu＜1.0；Mn＜2.0；Mg＜3.0；Zn＜6.0；Ti＜0.3；Zr＜0.3；Cr＜0.3；Hf＜0.6；V＜0.3；Ni＜2.0；Co＜2.0；In＜0.3；其它元素每种＜0.05，总量＜0.15，剩余铝。
片或带可通过在一个或两个面上共轧用硬钎焊铝合金包覆，通常合金包含4-15％的硅。硬钎焊合金可包含其它添加剂如铜、镁或锌。也可包含用来调整合金表面张力的元素如Ag、Be、Bi、Ce、La、Pb、Pd、Sb、Y或混合稀土合金，换言之是无法分离的稀土的混合物。在硬钎焊合金单面被包覆的情况下，另一面可用本身已知的方式涂覆牺牲合金，通常是Al-Zn类型，旨在提高芯合金的耐腐蚀性。
硬钎焊合金也可以颗粒的形式沉积，具体的是Al-Si颗粒，例如专利EP0565568(Alcan International)所描述的。对于在受控气氛条件下的硬钎焊，硬钎焊合金颗粒通常与焊剂颗粒相联系，特别是基于氟化物如氟铝酸钾的焊剂，和如聚合物树脂的粘结剂。在这种情况下发明的一个特别的好处在于可避免涂层中焊剂的存在。
当用于硬焊零件的生产并与其它涂覆有硬钎焊合金的片相联系时时，添加铋和/或钇的合金片也可不涂覆的使用。
实施例
实施例1
铸造4个具有下面组成的芯合金的板：
  合金   Si   Fe   Cu   Mn   Mg   Ti   Y   Bi   Ca
  M   0.40   0.22   0.63   0.57   0.47   0.08
  M+Y   0.39   0.24   0.61   0.57   0.47   0.09   0.06
  M+Bi   0.39   0.22   0.62   0.59   0.49   0.09   0.15
  M+Ca   0.40   0.22   0.63   0.57   0.47   0.08   0.05
和4047包覆合金板(Al-12％Si)。由这些板制得的组件使得包覆合金的厚度是总厚度的10％。热轧这些组件，然后冷轧以生产0.3mm厚的包覆带材。然后这些带在260℃进行回复处理10h。
如图1描述的测试件用于评价这些材料的可硬钎焊性。“V”由0.3mm厚的由在H24状态的3003合金制得的裸带组成。对要硬钎焊的金属在250℃脱脂处理15分钟。无需其它的表面准备，尤其不需沉积焊剂。在双层玻璃炉中进行硬钎焊，在炉中可观察处理中的液体硬钎焊合金的运动和接头的形成。热周期的组成是：以约20℃/min的速度升温到610℃，在610℃保温2分钟，然后以约30℃/min的速度降温。整个过程在持续的以81/min速度的氮气吹扫下进行。
结果按下面的比例标记为A-E：
  标记   A   B   C   D   E
  形成的接头长度占全部长度的百分比   100％   90％   75％   50％   0％
在表1中给出结果：
表1
  芯   包覆层   可硬钎焊性
  M   4047   E
  M+Y   4047   A
  M+Bi   4047   A
  M+Ca   4047   E
可以看出由于在芯合金中Y和Bi的添加而获得的可硬焊接性的提高。
实施例2
用同样的方式铸造2个具有下面组成的板：
  合金   Si   Fe   Cu   Mn   Mg   Ti   Y
  N   0.17   0.18   0.64   1.37   0.08
  N+Y   0.19   0.17   0.67   1.32   0.09   0.06
和4045包覆合金板(Al-10％Si)。进行的相变过程和测试与实施例1完全相同。
表2中给出结果：
表2
  芯   包覆层   可硬钎焊性
  N   4045   E
  N+Y   4045   A
可以看出，向合金N中加入钇明显改善了可硬钎焊性。
实施例3
用同样的方式铸造2个具有下面组成的板：
  合金   Si   Fe   Cu   Mn   Mg   Ti   Y
  P   0.15   0.35   0.1   0.1   0.8   0.125
  P+Y   0.15   0.35   0.1   0.1   0.8   0.125   0.06
和4045包覆合金板(Al-10％Si)。进行的相变过程和测试与实施例1完全相同。
表3中给出结果：
表3
  芯   包覆层   可硬钎焊性
  P   4045   E
  P+Y   4045   A
可以看出钇在合金P中的添加显著的提高了可硬钎焊性。

Claims (11)

1.铝芯合金带或片，用于受控气氛下的无焊剂硬钎焊，其包括至少80重量％铝、0.01-0.5％钇和/或0.05-0.5％铋，和具有下面含量的元素：
Si＜1.0；Fe＜1.0；Cu＜1.0；Mn＜2.0；Mg＜3.0；Zn＜6.0；Ti＜0.3；Zr＜0.3；Cr＜0.3；Hf＜0.6；V＜0.3；Ni＜2.0；Co＜2.0；In＜0.3；Sn＜0.3，其它元素每种＜0.05和总量＜0.15，余量为铝，
在所述带或片至少一个面上涂覆有硬钎焊铝合金，作为单个涂层，
并且，当仅有一个面涂覆有硬钎焊合金时，则另一面要么是未涂覆的，要么涂覆有Al-Zn类型的牺牲合金。
2.根据权利要求1的带或片，其特征在于该硬钎焊合金是含有4-15重量％硅的合金。
3.根据权利要求1的带或片，特征在于该硬钎焊合金包含至少一种用于改变合金的表面张力的元素。
4.根据权利要求3的带或片，特征在于所述至少一种用于改变合金的表面张力的元素选自Ag、Be、Bi、Ce、La、Pb、Pd、Sb、Y或混合稀土合金。
5.根据权利要求1-4之一的带或片，其特征在于该硬钎焊合金涂层是通过与基质铝合金共轧获得的包覆层。
6.根据权利要求1-4之一的带或片，其特征在于该硬钎焊合金涂层由颗粒组成。
7.根据权利要求6的带或片，其特征在于所述颗粒被包覆在树脂层中。
8.使用铝合金带或片制得的硬钎焊零件，该铝合金带或片包括0.01-0.5％钇和/或0.05-0.5％铋，和具有下面含量的元素：
Si＜1.0；Fe＜1.0；Cu＜1.0；Mn＜2.0；Mg＜3.0；Zn＜6.0；Ti＜0.3；Zr＜0.3；Cr＜0.3；Hf＜0.6；V＜0.3；Ni＜2.0；Co＜2.0；In＜0.3；Sn＜0.3，其它元素每种＜0.05和总量＜0.15，余量为铝。
9.根据权利要求8的硬钎焊零件，其特征在于所用的带或片涂覆有硬钎焊合金。
10.根据权利要求9的硬钎焊零件，其特征在于所用的带或片涂覆有硬钎焊合金颗粒。
11.根据权利要求10的硬钎焊零件，其特征在于所述硬钎焊合金颗粒被包覆在树脂层中。
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