CN1416377A - 钎焊板产品及使用钎焊板产品制造组件的方法 - Google Patents

钎焊板产品及使用钎焊板产品制造组件的方法 Download PDF

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CN1416377A
CN1416377A CN01806329A CN01806329A CN1416377A CN 1416377 A CN1416377 A CN 1416377A CN 01806329 A CN01806329 A CN 01806329A CN 01806329 A CN01806329 A CN 01806329A CN 1416377 A CN1416377 A CN 1416377A
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aluminium
brazing sheet
sheet product
covering
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CN1207125C (zh
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A·J·维特布鲁德
J·H·O·J·维金伯格
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Dana Canada Corp
Novelis Koblenz GmbH
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/001Interlayers, transition pieces for metallurgical bonding of workpieces
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    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10Electroplating with more than one layer of the same or of different metals
    • C25D5/12Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
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    • C22C21/00Alloys based on aluminium
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    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
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    • B23K35/0233Sheets, foils
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/28Selection of soldering or welding materials proper with the principal constituent melting at less than 950 degrees C
    • B23K35/286Al as the principal constituent
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    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34Pretreatment of metallic surfaces to be electroplated
    • C25D5/42Pretreatment of metallic surfaces to be electroplated of light metals
    • C25D5/44Aluminium
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    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60Electroplating characterised by the structure or texture of the layers
    • C25D5/605Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611Smooth layers
    • EFIXED CONSTRUCTIONS
    • E04BUILDING
    • E04CSTRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C2/00Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
    • E04C2/30Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by the shape or structure
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    • E04C2/34Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by the shape or structure composed of two or more spaced sheet-like parts
    • E04C2/3405Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by the shape or structure composed of two or more spaced sheet-like parts spaced apart by profiled spacer sheets
    • E04C2002/3444Corrugated sheets
    • E04C2002/3455Corrugated sheets with trapezoidal corrugations
    • EFIXED CONSTRUCTIONS
    • E04BUILDING
    • E04CSTRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C2/00Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
    • E04C2/30Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by the shape or structure
    • E04C2/34Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by the shape or structure composed of two or more spaced sheet-like parts
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    • E04BUILDING
    • E04CSTRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C2/00Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
    • E04C2/30Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by the shape or structure
    • E04C2/34Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by the shape or structure composed of two or more spaced sheet-like parts
    • E04C2/3405Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by the shape or structure composed of two or more spaced sheet-like parts spaced apart by profiled spacer sheets
    • E04C2002/3472Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by the shape or structure composed of two or more spaced sheet-like parts spaced apart by profiled spacer sheets with multiple layers of profiled spacer sheets
    • YGENERAL 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
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    • Y10S428/922Static electricity metal bleed-off metallic stock
    • Y10S428/9335Product by special process
    • Y10S428/934Electrical process
    • Y10S428/935Electroplating
    • YGENERAL 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
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    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
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Abstract

本发明涉及具有由铝合金制成的芯板(1)的钎焊板产品,其具有在所述芯板的至少一个表面上包覆的铝包层(2)、和在所述一层或多层铝包层(2)的每一层的一个或两个外表面上的含镍层(3),其特征在于在所述一层或多层铝包层(2)的所述外表面与所述含镍层(3)之间存在作为连接层的含锌或锡层(4),且其中铝包层包含重量百分比如下的成分:Si2至18;Mg至多8.0;Zn至多5.0;Cu至多5.0;Mn至多0.30;In至多0.30;Fe至多0.8;Sr至多0.20;至少一种选自由以下成分组成的组中的元素:Bi 0.01至1.0;Pb 0.01至1.0;Li 0.01至1.0;Sb 0.01至1.0;Mg 0.2至2.0;杂质各至多0.05,总共至多0.20;余量为铝。

Description

钎焊板产品及使用钎焊板产品制造组件的方法
发明领域
本发明涉及一种钎焊板产品,其中在由含2至18wt%Si的Al-Si合金制备的包层表面上镀覆含镍层。本发明还涉及包含至少一种由钎焊板产品制备的部件的硬钎焊组件以及制备硬钎焊部件组件的方法。
相关现有技术的说明
对本发明来说,钎焊板应理解为是芯板,例如铝或铝合金芯板,在其一面上具有可钎焊的铝合金。适用于作为这种包层的典型的可钎焊的铝合金是铝业协会(Aluminium Association)(AA)4xxx-系列合金,通常含有2至18wt%的Si。可钎焊的铝合金可以经现有技术公知的各种途径来连接到芯板合金上,例如通过辊压接合、包层、或半连续或连续铸造。
可控气氛钎焊(CAB)和真空钎焊(VB)是工业规模铝钎焊所使用的两种主要方法。自1950年代起就已使用工业真空钎焊了,而在引入Nocolok(商标)钎焊焊剂后CAB在1980年代早期开始普遍应用。真空钎焊基本上是不连续的方法,并且对材料的清洁性有很高的要求。发生氧化层破坏主要是由包层合金中镁的蒸发所造成。在包层合金中总是存在超出需要的镁。过量的镁凝结在炉中的冷点上,并需要时常清除。适当设备的投资费用较高。
与VB相比,由于在钎焊之前要涂覆钎焊焊剂,在钎焊之前,CAB需要附加的加工步骤。CAB基本上是连续的方法,其中,如使用适当的钎焊焊剂,可制造出大体积的钎焊组件。在钎焊温度下钎焊焊剂溶解氧化物层,使得包层合金适当地流动。当使用Nocolok焊剂时,在涂覆焊剂之前表面要彻底地清洁。为得到良好的钎焊效果,钎焊焊剂应涂覆在钎焊组件的全部表面上。对某些类型的组件来说,由于它们的设计,这可能会产生困难。例如,由于蒸发器型的热交换器具有大的内表面,由于不易达到内部而产生问题。为得到良好的钎焊效果,在钎焊之前,焊剂应粘合到铝表面上。不利的是,在干燥后由小的机械振动易于使钎焊焊剂脱落。在钎焊循环中,产生腐蚀性烟雾如HF。这对在炉上涂覆材料的耐蚀性提出了很高的要求。
理想的是,应得到可用于CAB但没有应用钎焊焊剂那样的需求和缺陷的材料。这种材料可提供给钎焊组件的制造者,并可在装配部件成型后直接使用。不必进行附加的钎焊焊剂处理操作。目前,只有一种无焊剂(flux-less)的钎焊方法以工业规模来使用。用于这种方法的材料例如可是标准钎焊板,其由AA3xxx-系列芯板合金制备并在其两侧上包覆有AA4xxx-系列合金包层。在钎焊板可使用之前,表面必须进行改性以使得天然存在的氧化物层不影响钎焊循环。实现良好钎焊的方法是在包层合金表面上沉积特定数量的镍。如涂覆恰当,镍与底层铝进行反应。可在要连接的两部件之间使用镍垫片或可通过电镀进行沉积来镀覆镍。当使用电镀方法时,镍的结合力应足以耐受例如热交换器制造中所使用的典型的成型操作。
镀镍方法或铝钎焊板的方法由US-A-3970237、US-A-4028200、US-A-4164454和B.E.Cheadle and K.F.Dockus的SAE-paper no.880446所公开。按照每个这些文献,镍优选与铅组合来沉积。还可将钴与铅组合来进行沉积。现有技术公知,还可使用铁来取代镍、钴或其结合。添加铅用来改进在钎焊循环中包层合金的润湿性。这些镀覆方法的一个重要特征是,镍优选沉积在包层合金的硅颗粒上。为在表面上得到足够的用于钎焊的镍,包层合金应含有较大数量的硅颗粒来用作镍沉积的核。据信,为在镀覆之前得到足够的成核部位应通过化学和/或机械预处理来除去其中嵌有硅颗粒的部分铝。相信这是得到足够镍覆盖率的必要条件,从而用作钎焊或包层合金的润湿作用的核。在微观尺度上,包覆钎焊板的含Si表面由镍球所覆盖。
以下将提到在现有技术文献中发现的一些其它镀镍的公开内容。Wernick和Pinner的通用教科书,“The Surface Treatment andFinishing of Aluminium and its Alloys”,第五版,卷2,1023-1071页。该教科书叙述了在铝上进行镀覆的一般的浸渍方法。
Bureau of Mines Technology的论文,“Soft-Solding”,2301 N.T.I.S.Tech Notes(manufacturing),1985,January,No.1G,Springfield,VA,USA.pp.12-13。该论文叙述了制备用于软钎焊的铝的方法,其中铝表面通过通用的锡铅焊剂来进行连接。该方法包括在涂覆锌之前首先仔细地清洗铝表面。其次,沉积薄的锌镀层,随后用镍-铜合金进行电镀。在电镀镍-铜结束后,可使用通常的步骤来实现焊接。
FR-A-2617868叙述了具有可钎焊的锡或锡铋合金表面镀层的铝产物的制备方法,其中所述产物提供有中间层。这一中间层是由第一层锌和第二层镍所组成,所述镍通过由中性电解液进行电解来沉积。这里,底层铝或铝合金在钎焊过程中未熔化。
发明简述
本发明的一个目的是提供一种在钎焊过程中要熔化的具有芯板和填料材料的钎焊板产品,所述填料材料包括Al-Si合金包层和在所述包层上的镍层,其中镍层与包层有良好的结合力。
本发明的再一目的是提供可用于真空钎焊方法以及无钎焊焊剂的可控气氛的钎焊方法中的钎焊板产品,但理想地适用于无钎焊焊剂的CAB方法。
本发明的另一目的是提供一种使用本发明的钎焊板产品制备钎焊部件的组件的方法。
按照本发明的一个方面,提供了由铝合金制成的芯板(1)的钎焊板产品,其具有在所述芯板的至少一个表面上包覆的铝包层(2)、和在所述一层或多层铝包层的每一层的至少一个外表面上的含镍层(3),其中在所述一层或多层铝包层的所述外表面与所述含镍层(3)之间存在作为连接层的含锌或锡层(4),且其中铝包层包含重量百分比如下的成分:
Si  2至18
Mg  至多8.0
Zn  至多5.0
Cu  至多5.0
Mn  至多0.30
In  至多0.30
Fe  至多0.8
Sr  至多0.20
至少一种选自以下成分的元素:
Bi    0.01至1.0
Pb    0.01至1.0
Li    0.01至1.0
Sb    0.01至1.0
Mg    0.2至2.0
其它成分/杂质各至多0.05,总共至多0.20
余量为铝。
通过含锌或锡连接层,在铝合金包层与含镍层之间形成很有效的连接,所述连接在随后的钎焊板的形变如弯曲过程中仍有效。镍层的覆盖不再取决于裸露包层的表面特性。所获得的钎焊板产品适用于在可控气氛条件下的无焊剂焊接。
本发明部分是基于一种观察事实,即,要在钎焊板产品的含Si铝包层上得到良好连接的镍层,使得所述连接在大的形变下仍有效,则包层的预处理是极重要的。现有技术方法显然着力于以分散形态来涂覆镍,主要是在包层表面的硅颗粒上,而不是试图达到均一的镍层。在本发明中,含Si包层合金的表面以这样的方式进行改变,即,使得镍的覆盖率与在其表面上的硅颗粒无关。镀镍不在硅颗粒上进行而是在涂覆的含锌或锡层上进行。由于镍沉积在铝包层的全部表面上,与现有技术方法相比,在钎焊之前必需的反应的进行容易的多。涂覆的锌或锡在钎焊过程中完全不发生影响,并可含有下述的辅助钎焊的组分。由于镍平滑且均一地沉积在表面上,可减少或避免使用铅来在钎焊过程中促进润湿,或可使用其它元素如铋来用于这种目的。在所述表面上平滑且均一地沉积镍或镍-铅的另一优点是可减少为实现良好的无焊剂焊接所要涂覆的镍的总量。再一优点是,表面完全覆盖避免了在包层表面上铝氧化物所引起的任何难题。
再有,本发明部分是基于一种观察事实,即,铝包层包含至少一种或多种选自铋、铅、锂和锑的元素,各种的范围为0.01至1.0%,两种或多种元素的组合优选不超过1.0%,且镁的含量范围为0.2至2.0%。镁与一或多种选自这些元素中的其它元素的组合优选不超过2.5%。因此,在铝包层中镁的含量可至多8.0%,优选范围在下面给出,以增强铝包层的尤其是机械性能,还发现范围为0.2至2.0%的镁还可起到与选自铋、铅、锂和锑的元素相似的作用。当存在的镁基本上仅是要促进钎焊合金与无铅镍层的润湿作用时,优选在包层中镁的含量不超过2.0%。可添加其它合金元素来改进包层的特定性能。在US-A-3970237中提到铝包层优选镀覆一层镍、镍-铅、钴、钴-铅或它们的组合。添加铅据信可改进钎焊过程中的润湿性。然而,按照本发明,已发现镍和/或钴层其本身不需包含铅来作为合金添加物。意外的是,已发现,如向铝包层本身中添加给定范围的Bi,Pb,Li和Sb和Mg中的一或多种元素,可得到相等或更好的效果。向铝包层中添加一或多种这些合金元素具有的优点是,镀液组成变得不复杂,这本身是一项大的收益,另外当制备包层时,向包层中添加合金是很简单的。结果,所镀覆的电镀镍层主要由镍和不可避免的杂质所构成。从操作角度来看,铋是添加到铝包层中的最优选的合金元素。再有,已发现元素铋是促进润湿的最优选的合金元素,因而达到与在镍层中添加铅相似的效果所需的这种元素的量减少。虽然在包层中在给定范围的作为合金元素的铅导致所需的效应,但优选避免添加这种元素,因为从环境角度来看它是极不利的元素。
虽公知在颗粒镀镍之前要涂覆锌层,据信在镀镍铝合金包层钎焊板产品中却未这样做,其中如以上所讨论的,人们一直认为需要直接在含Si包层上镀镍。
按照本发明的钎焊板可获得很好的结果,其中连接层应用了浸渍锌酸盐处理或浸渍锡酸盐处理,时常也称为置换镀覆。
在本发明钎焊板产品的一种实施方案中,含锌或锡的涂覆层的厚度仅至多0.5μm,更优选至多0.3μm(300nm),最优选范围为0.01至0.15μm(10-150nm)。在目前所得到的最佳结果中,使用的厚度为约30nm。镀层厚度大于0.5μm需要延长处理时间,例如对于置换镀覆,在改善结合力上认为没有进一步的优点。
在本发明钎焊板产品上涂覆的锌或锡层可基本上是纯锌或锡层或或主要是锌或锡(如至少50wt%)。可存在少量的杂质元素或有意添加的元素,如以下所详细讨论的那样。在锌或锡层中典型的杂质元素的含量小于10%,更通常小于5wt%。
含镍层优选是电镀层。在含锌或锡层上镀覆的含镍层的结合力是优异的,并可经受较剧烈的成型操作而不出现分层。
在这种钎焊板产品中优选含镍层层的厚度至多2.0μm,优选至多1.0μm,更优选至多0.5μm。镀层厚度大于2.0μm需要延长镀覆处理时间,可导致在钎焊过程中熔融填料材料起皱。这种含镍层的优选最小厚度为0.3μm。也可使用其它技术如辊压接合、热喷涂、化学气相沉积和物理气相沉积。
在这种钎焊板产品中优选各铝包层的厚度范围为钎焊板产品总厚度的约2至20%。
优选在钎焊板产品中钎焊时熔融、通称为填料材料的材料、尤其是镍层和/或锌或锡层包含在钎焊过程中减少熔融钎焊合金的表面张力的一或多种元素。在本发明中意外发现,与现有技术教导相反,不需要在镍层中作为合金元素来添加铅以促进钎焊合金的润湿作用。但铅及其它适用元素可添加到镍层或锌或锡层中或两者中,其中铋是优选的适用元素。从钎焊板的制备角度来看这具有各种各样的优点。
因而在整体填料材料中,可存在以wt%计的至少一种如下元素:
Bi  0.01至0.5,优选0.05至0.5
Mg  0.2至2.0
Li  0.01至0.5,优选0.05至0.5
Sb  0.01至0.5,优选0.05至0.5
锌或锡层自身可因而含一或多种选自铋、铅、锂和锑组成的附加元素。附加元素(一种或多种)的总量可至多50%,但优选少于25%,如范围为1至25%。
在本发明钎焊板产品的优选实施方案中,在铝包层中铋添加的上限为0.5%。铋添加的适当的下限为0.01%,更优选0.05%。
在本发明钎焊板产品的优选实施方案中,在铝包层中锂添加的上限为0.5%。锂添加的适用范围为0.01-0.3%。
在本发明钎焊板产品的优选实施方案中,在铝包层中锑添加的上限为0.5%。锑添加的适用范围为0.01-0.3%。
在一种实施方案中,铝包层包含作为合金元素以wt%计的Si范围为2至18%,优选7至18%,还包含的镁的范围至多8.0%,优选至多5.0%。优选镁的范围为0.5至5%,更优选0.5至2.5%。可添加其它合金元素例如但非仅限于适当范围的Cu,Zn,和Sr。已发现在使用钎焊板产品时,在包层存在镁对钎焊过程无有害影响。这对公知的钎焊板产品是一项大的改进。这使得铝包层的设计可对总体钎焊板产品的强度起作用或换言之钎焊板产品具有更薄的包层。再有,其使得含Mg钎焊板可应用于真空钎焊或无焊剂可控气氛钎焊两者中。后一种可能性具有许多经济和技术上的优点。另外已发现由于添加铋和镁两者作为合金元素而克服了对向依序电镀的镍层中添加促进润湿或连接的合金元素的强制需求。本发明的钎焊板产品可容易地在现有的工业钎焊生产线中使用。
在另一种实施方案中,铝包层以wt%计包含作为合金元素的范围为2至18%的Si,优选7至18%,还包含范围至多5%的锌。优选锌的范围为0.5至3%。可添加其它合金元素例如但非仅限于适当范围的Mg和Cu。按照本发明,已发现,当使用这种钎焊板产品时,在包层中存在锌对钎焊过程没有有害影响。这对公知钎焊板产品是一项大的改进。其使得包层的设计可对总体钎焊板产品的强度起作用。另外,其中包层含有作为有意添加的合金元素的锌的钎焊板产品可应用于真空钎焊或无焊剂可控气氛钎焊两者中,两种方法均以工业规模来使用。
在另一种实施方案中,铝包层以wt%计包含作为合金元素的范围为2至18%的Si,优选7至18%,还包含范围至多5%的铜。优选铜的范围为3.2至4.5%。可添加其它合金元素例如但非仅限于适当范围的Mg和Zn。按照本发明,已发现,当使用这种钎焊板产品时,在包层中存在铜对钎焊过程没有有害影响。这对公知钎焊板产品是一项大的改进。其使得包层的设计可对总体钎焊板产品的强度起作用。另外,其中包层含有作为有意添加的合金元素的铜的钎焊板产品可应用于真空钎焊或无焊剂可控气氛钎焊两者中,两种方法均以工业规模来使用。
在所有铝包层实施方案中,可存在范围至多0.30%的铟(“In”)作为合金元素以达到与铝芯合金相比更电负性的铝包层合金腐蚀电位。已发现,对于减少合金的腐蚀电位来说,铟比添加锌更有效。通常0.1%的In与2.5%的Zn同样有效。
在所有铝包层实施方案中,在铝包层中作为杂质元素可存在范围至多0.30%的各种镁和锆,优选仅至多0.10%,更优选至多0.05%。
在所有铝包层实施方案中,在铝包层中可存在作为典型杂质元素的范围至多0.8%的铁,优选范围至多0.4%。
在所有铝包层实施方案中,可添加范围至多0.20%的锶来对当包层合金铸造时固化过程中存在的硅进行改性。锶添加量的更优选的最大值为至多0.05%。
在本发明的钎焊板产品的实施方案中,芯板是含镁范围至多8.0%的铝合金。在优选实施方案中,镁的范围为0.5至5.0%。可添加其它合金元素例如但非仅限于适当范围的Cu,Zn,Bi,V,Fe,Zr,Ag,Si,Ni,Co和Mn。已发现,当使用本发明的钎焊板产品时,在铝包层中存在镁对钎焊过程没有有害影响。这对公知钎焊板产品是一项大的改进。在钎焊板产品自身的制备过程中及其在后续钎焊方法中应用中,镁自芯向包层的扩散看起来对本发明的钎焊板产品的可钎焊性(brazeability)没有有害影响。这使得可设计出具有铝芯板的高强度的钎焊板产品,所述芯板具有作为强化元素的在给定范围的镁。所述产物可应用于真空钎焊(VB)或无焊剂可控气氛钎焊(CAB)两者中,两种方法均以工业规模广泛使用。
在本发明的钎焊板产品中,芯板可经中间层与铝包层连接。具有这种中间层或夹层的益处例如在US-A-2821014中进行了叙述,其内容引入本文作为参考。
本发明还提供了包含至少一种由钎焊板产品制成的部件的钎焊组件,所述钎焊板产品按上述及权利要求书中所述本发明来制备。
在本发明的另一方面中,提供了一种使用本发明钎焊板产品制备钎焊组件的方法,其包含如下顺序的加工步骤:
(a)对部件进行成型,所述部件中的至少一种是由如上所述的本发明的钎焊板产品来制备
(b)将所述部件装配成组件;
(c)在升高温度下且不存在钎焊焊剂的条件下在真空或在惰性气氛下对所述组件进行钎焊,所述钎焊时间足够长以使得填料合金熔化并铺展,由此填料合金至少由包层合金(2)、连接层(4)和镍层(3)形成;
(d)冷却钎焊组件。所述冷却速率的范围可为通常的钎焊炉冷却速率。通常的冷却速率是为至少10℃/分钟或更快的冷却速率,通常为40℃/分钟或更多。
根据芯板的铝合金,所述方法还可包括加工步骤(e)对钎焊并冷却过的组件进行时效处理(ageing)以使所得到的组件的机械和/或腐蚀性能最佳化。
已发现使用本发明的钎焊板产品使钎焊温度降低约10℃。这种降低的钎焊温度使得对钎焊循环整体来说可显著减少工业规模加工时间,已发现通常时间减少20%或更多。
在本发明的再一方面中,提供了一种在以无钎焊焊剂的惰性气氛钎焊(CAB)工艺制备钎焊组件的方法中,将上述和在权利要求书中所述的铝包层合金用于钎焊板产品的方法。
附图简要说明
现在参照附图通过若干个非限制性实施例来对本发明进行说明,其中:
图1是表明现有技术钎焊板产品结构的纵向断面示意图;
图2是表明本发明钎焊板产品结构的纵向断面示意图;
图3是表明本发明钎焊板产品结构的纵向断面示意图;
优选实施方案的说明
图1示意性图示了按照例如US-A-3970237的方法所得到的现有技术钎焊板。所述钎焊板产品由芯板1构成,在所述芯板一或两侧上包覆有含Al-Si-合金的铝包层6。在包层6之上通过电镀镀覆一薄的镍层3,优选镍-铅层。
图2示意图示了本发明的钎焊板,其中在包含Al-Si-Bi合金的包层2与Ni层3之间还镀覆有锌或锡层4,其优点已在前面提及。在图2中,仅图示了在钎焊板一侧上的层4和3,但对技术人员显而易见它们可镀覆在钎焊板产品的两侧上。各种层的组成及它们的优点已在前面提及。
图3示意图示了本发明的另一种钎焊板,其具有图2的层和在芯板1与在两侧上的包层2之间的中间层5。在图3中,只在钎焊板的一侧图示了层4和3,但技术人员显而易见它们可镀覆在钎焊板产品的两侧上。另外,中间层5也可应用于钎焊板的一侧,优选在包含层4和3的那侧。各种层的组成及它们的优点已在前面提及。
实施例
按照表2所述对实验室规模的试验铝钎焊板进行处理,所述钎焊板由Aluminium Association(AA)3003芯板合金制备,在所述芯板合金的一侧包覆四种不同组成(见表1)的AA4000-系列铝包层合金,其总厚度为0.5mm,包层厚度为约50μm。
所述处理由如下顺序进行的加工步骤组成:
-通过在ChemTec 30014(一种市售除油剂和碱性浸蚀清洗剂)中浸渍180秒来进行清洗,随后进行漂洗;
-在室温下在ChemTec 30203(一种市售碱性浸蚀清洗剂)中刻蚀20秒,随后进行漂洗;
-任选地,在室温下在含ChemTec 11093(一种市售酸洗活化剂)的酸性氧化浴(通常为25-50vol%的硝酸)中进行4秒的去酸洗泥(desmutting),随后进行漂洗;
-使用ChemTec 024202在室温下进行12秒的锌酸盐浸渍,随后进行漂洗;
-电镀镍,并进行漂洗。
对于电镀镍,使用不含铅的碱性镀液,在表2中由“L-”表示。无铅碱性镀液包含50g/1的硫酸镍,50g/l的氯化镍,30g/l的柠檬酸钠,和75ml/l的氢氧化铵(30%)。在26℃下的电镀条件是,使用3A/dm2的电流密度电镀50秒,得到0.5μm厚的镍镀层。
使用Erichsen dome test(屋顶试验)、和T弯曲试验测试镀镍试件的结合力。然后给出对结合力的量值评价,其中:(-)=不良,(±)=适中,(+)=良好。按下述来进行钎焊性的评价。在实验室规模的测试中,在小型石英炉中来进行钎焊试验。从镀镍板上切下25mm×25mm的小试样。将尺寸为30mm×7mm×1mm的小条AA3003合金在中心处弯曲至45℃角度并放置在所述试样上。在所述试样上的所述合金条在氮气流下进行加热,在约10分钟的时间由室温加热至580℃的温度,在580℃下保持时间为1分钟,从580℃冷却至室温。对钎焊方法评价其形成折皱、毛细下降和形成圆角(fillet)的可能性。给出总体评价,其中:(-)=不良钎焊性,(-/±)=适中钎焊性,(±)=良好钎焊性,(+)=极好的钎焊性。所得结果列于表2中。
从表2结果可见,施用锌酸盐处理对镀镍层具有良好结合力是必要的。从包层合金no.1的结果可见,省略去酸洗泥(desmutting)步骤仍导致镀镍层良好的结合力。包层no.2的结果证实,向包层中添加Bi导致极好的钎焊性。相应的,按照本发明,可省去向镍层添加铅。包层no.3的结果证实,向包层中添加Bi与镁结合仍导致极好的钎焊性。包层no.4的结果证实,向包层中添加Bi与锌结合仍导致极好的钎焊性。而如在包层中不含铋也不含铅或在镍层不含铅则导致不良的钎焊性(参见包层合金no.1)。
表1.铝包层合金组成,以wt%计。余量为A1和不可避免的杂质(各<0.05%,总共<0.20%)。
  合金     Si     Fe     Cu     Mn     Mg     Zn     Ti     Bi
    1     10.0     0.3     <0.01     <0.02     <0.02     <0.02     0.003      +
    2     8.5     0.2     <0.01     <0.02     <0.02     <0.02     0.003     0.09
    3     9.6     0.25     <0.01     <0.02     1.35     <0.02     0.003     0.13
    4     7.6     0.35     <0.01     <0.02     <0.02     1.02     0.003     0.11
表2.应用预处理及测试结果。
  包层合金no.   清洗 刻蚀 去酸洗泥 锌酸盐 镀镍   结合力   钎焊性
    1   是   是     是     是     L-     +     -
    1   是   是     否     是     L-     +     -
    2/3/4   是   是     是     是     L-     +     +
以上对本发明进行了全面的叙述,对本领域普通技术人员显而易见,在不偏离这里所述的本发明的实质范围的条件下可对其进行许多改变和改进。

Claims (16)

1.具有由铝合金制成的芯板(1)的钎焊板产品,其具有在所述芯板的至少一个表面上包覆的铝包层(2)、和在所述一层或多层铝包层(2)的每一层的一个或两个外表面上的含镍层(3),其特征在于在所述一层或多层铝包层的所述外表面与所述含镍层(3)之间存在作为连接层的含锌或锡层(4),且其中铝包层包含重量百分比如下的成分:
Si  2至18
Mg  至多8.0
Zn  至多5.0
Cu  至多5.0
Mn  至多0.30
In  至多0.30
Fe  至多0.80
Sr  至多0.20
至少一种选自以下成分的元素:
Bi    0.01至1.0
Pb    0.01至1.0
Li    0.01至1.0
Sb    0.01至1.0
Mg    0.2至2.0
杂质各至多0.05,总共至多0.20
余量为铝。
2.如权利要求1的钎焊板产品,其中所述连接层(4)是电镀层。
3.如权利要求1或2的钎焊板产品,上所述连接层(4)的厚度不超过0.5μm,优选不超过0.3μm。
4.如权利要求3的钎焊板产品,其中所述连接层(4)的厚度范围为20至150nm。
5.如权利要求1至4任一项的钎焊板产品,其中所述含镍层(3)的厚度不超过2.0μm,优选不超过1.0μm。
6.如权利要求1至5任一项的钎焊板产品,其中所述铝包层(2)含Mg的量以重量计范围为0.5至5.0。
7.如权利要求1至6任一项的钎焊板产品,其中所述铝包层(2)含Zn的量以重量计范围为0.5至3.0。
8.如权利要求1至7任一项的的钎焊板产品,其中所述铝包层(2)含Bi量以重量计范围为0.01至0.5。
9.如权利要求1至8任一项的钎焊板产品,其中所述芯板(1)经中间层(5)与所述铝包层(2)连接。
10.如权利要求1至9任一项的钎焊板产品,其中所述芯板是含镁量范围至多8.0的铝合金。
11.通过钎焊连接的部件组件,至少一种所述部件是权利要求1至10任一项的钎焊板产品。
12.制造钎焊部件组件的方法,包括顺序进行的如下加工步骤:
(a)对所述部件进行成型,所述部件中的至少一种是由权利要求1至10任一项的钎焊板产品来制备;
(b)将所述部件装配成组件;
(c)在升高温度下且不存在钎焊焊剂的条件下在真空或在惰性气氛下对所述组件进行钎焊,所述钎焊时间足够长以使得包层熔化并铺展;
(d)冷却钎焊组件。
13.将铝包层合金用于权利要求1至10任一项的钎焊板中的方法。
14.在无钎焊焊剂的惰性气氛钎焊方法中使用权利要求1至10任一项的铝包层合金的方法。
15.如权利要求14的方法,其中所述铝包层合金包含以wt%计的如下成分:Si  2至18,优选7至18Bi  0.01至1.0,优选0.01至0.5其它各至多0.05%,总共至多0.20%余量为铝。
16.如权利要求14的方法,其中所述铝包层合金包含以wt%计的如下成分:Si  2至18,优选7至18Mg  0.5至8.0,优选0.5至2.5Bi  0.01至1.0,优选0.01至0.5其它各至多0.05%,总共至多0.20%余量为铝。
17.如权利要求14的方法,其中所述铝包层合金包含以wt%计的如下成分:Si  2至18,优选7至18Zn  至多5.0,优选0.5至3.0Bi  0.01至1.0,优选0.01至0.5其它各至多0.05%,总共至多0.20%余量为铝。
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WO2001068312A3 (en) 2002-02-28
US6391476B2 (en) 2002-05-21
EP1265725A1 (en) 2002-12-18
AU2001231737B2 (en) 2004-06-24
KR20020079980A (ko) 2002-10-21
DE60129416T2 (de) 2008-04-17
CA2402205A1 (en) 2001-09-20
EP1265725B1 (en) 2007-07-18
JP2003526519A (ja) 2003-09-09
ATE367238T1 (de) 2007-08-15
CA2402205C (en) 2005-07-26
US20010040180A1 (en) 2001-11-15
AU3173701A (en) 2001-09-24
CN1207125C (zh) 2005-06-22
MXPA02008389A (es) 2003-01-28
KR100756752B1 (ko) 2007-09-07

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