CN1519991B - 用于制备电接点的复合材料 - Google Patents

用于制备电接点的复合材料 Download PDF

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CN1519991B
CN1519991B CN2003101215089A CN200310121508A CN1519991B CN 1519991 B CN1519991 B CN 1519991B CN 2003101215089 A CN2003101215089 A CN 2003101215089A CN 200310121508 A CN200310121508 A CN 200310121508A CN 1519991 B CN1519991 B CN 1519991B
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composite material
additive
diameter
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phi
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伊莎贝尔·布雷施
赫尔曼斯·斯特鲁姆
罗兰·宾德尔
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Wieland Werke AG
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Abstract

本发明涉及用于制备电接触元件的导电的复合材料，所述的电接触元件由金属带和至少一侧涂覆的由银或锡-接触材料组成的接触涂层组成，其中该接触材料包含0.5至60重量％的以直径Φ1＝5至200纳米的细颗粒形式存在的碳粉作为第一添加剂和0.5至60重量％的以直径Φ2＝5至200纳米的细颗粒形式存在的第二粉状添加剂。此外还涉及由可流动的或呈液态的材料组成的射流的气体雾化的装置和制备导电的复合材料的方法以及其应用。

Description

用于制备电接点的复合材料
技术领域
本申请涉及制备电接触元件的导电的复合材料，所述的接触元件由金属带和至少一侧涂覆的由银-或锡-接点材料(Kontaktwerkstoff)组成的接触涂层(Kontaktschicht)组成。此外涉及用于将由可流动的或者液态的材料组成的射流气体雾化的装置和制备该导电复合材料的方法以及其应用。 
这种导电接触元件例如作为插头接点在汽车工业的插塞连接器或者在插塞连接器-接头中使用。 
背景技术
对于插塞连接器的可靠性来说，接触元件的结构形式扮演着重要角色。在工作中，所使用的接点支承材料与所使用的接点表面一起决定老化状态和寿命。 
已知的用于这些目的的电接点通常由基体(金属带)，特别是由铜合金和以电镀方式通过热浸镀法(例如热镀锡)或者通过轧制涂覆的接点材料组成。对此特别地使用金、银或者锡涂层。在插塞连接器-特别是插座的情况下，接触点(其是焊接在接触区域上的)的粉末金属制备方法是不可能的，因为接触区域变形，并因此是不能自由进入的。 
因此在设计的寿命期间，在迄今为止所要求的边界条件下，仅对于最高达14伏的工作电压才能使插塞连接器体系获得足够的耐磨性和低的接触电阻。 
然而，当对插头接点提出更高的要求时，例如鉴于在汽车工业中在42V的机载电网下可能形成电弧的危险或者鉴于在邻近发动机附近由于高的温度插头接点的破裂，这不再是切合实际的。产生电弧的问题对于连接接点例如继电器已经是已知的。在连接接点的情况下，通过附加的工序在支承材料上通过钎焊或者通过焊接涂覆特定的接触涂层。接点材料本身是在之前的工序中通过烧结或者挤压机制备的。 
在汽车领域中通常使用的插塞连接中，这种现象仅在电压超过16伏时才出现。在42V-机载电网下，在插塞连接器接头插塞或者拔出时存在形成电弧和接头弹跳的危险。由于电弧在局部出现材料被加热至1000℃以上，这导致插塞连接器的接触表面分离。同样不完全插塞的连接通过在运行时产生的震动招致这种电弧，这导致插 塞连接缓慢的烧损并最终导致完全中断。 
由DE 195 03 184C1已知一种用于电接点的材料，其由银和碳组成。其中涉及通过一定的含量的炭黑而具有改善的烧损性能的烧结材料。在其制备时在以炭黑形式存在的碳中加入初始颗粒尺寸小于150纳米的银，将该混合物冷静压压制，随后烧结。出于改善烧损性能和抗焊合性的相同的意图，DE41 11 683 C2公开了一种用于电接点的复合材料。该复合材料由银或者含有碳的银合金组成，该碳是以由碳粉和碳纤维以10∶1至1∶10的质量比的组合物形式与金属组分一起加工的。 
这种材料的缺陷是，其制备和再加工对于电接触元件的制备和金属带的变形是不适合的。 
此外，由EP 0 225 080 B1已知一种具有雾化器的装置，借助于该雾化器可以将由液态金属组成的射流通过气体射流雾化为由小液滴组成的喷雾。在这种情况下，该雾化器是围绕着固定的轴可倾斜地这样布置的，即该喷雾均匀地分布在运动的带状基体上或者分布在另一接受装置上。该装置用于制备薄的金属带或者用于涂覆金属带。 
采用这种制备方法尽管可以获得平面状的均匀分布的金属涂层，然而首先其允许仅单一地根据熔体组分选择材料。此外，相对于金属射流可移动的雾化器是附加的设备开支。 
发明内容
因此本发明赖以为基的任务是提供一种金属复合材料，其是借助于与现有技术相比改进的装置制备的，并且很大程度上满足本文开头提及的高的要求。 
本发明提供了一种导电的复合材料，其用于制备电接触元件，所述复合材料由金属带、接触涂层和位于金属带和接触涂层之间的中间涂层组成，该接触涂层由银或锡接点材料制成，该接点材料包含0.5至60重量％的以直径Φ1＝5至200纳米的细颗粒形式存在的碳粉作为第一添加剂和0.5至60重量％的以直径Φ2＝5至200纳米的细颗粒形式存在的第二添加剂，该添加剂改善了导电性、硬度和耐磨性，并且中间涂层(6)厚度D3＝0.1至1微米，由Ag或Sn制成。 
本发明在产品方面的任务是通过用于制备电接触元件的导电的复合材料解决的，所述的电接触元件由金属带和至少一侧涂覆的由银或锡-接点材料组成的接触涂层组成，其中该接点材料包含0.5至60重量％的以直径Φ＝5至200纳米的颗粒形 式存在的碳粉的第一添加剂和0.5至60重量％的以直径Φ＝5至200纳米的细颗粒形式存在的第二粉末状添加剂。 
本发明的复合材料特别适合于插塞连接器和插塞连接器接头和可开合的接点。 
在这种情况下，本发明是以这种考虑为出发点的，即该复合材料应该具有许多最佳的相互一致的性能。 
为了选择支承体材料上适合的接点材料，应该使下面的标准或性能最佳化： 
-抗电弧侵蚀性 
-高的导电性/导热性 
-所需的低的接点压力 
-耐磨性/耐用性 
-好的可加工性：可焊的。 
特别地，在这种情况下，对于在汽车行业42V机载电网下使用时，为了防止接点的烧损，抗电弧侵蚀性应该是很重要的。 
对此该导电复合材料中应该加入碳。在插塞连接器和接点的插塞或拔出时产生的电弧形成游离的碳化合物，通过该碳化合物可以进一步防止由于接点表面在环境中的氧化导致接触电阻的升高。 
所以接触层的主要组分是具有好的导电性的构成基体的金属，这二种添加剂根据它们小的直径特别细分散地填充在其中，并形成一种均匀的复合材料。这直接对其它的材料性能产生有利的影响。特别地，硬度不同的合金组分的细分布和因此获得的均匀性防止了表面的机械磨损。 
在制备插头时，必须成型为带状物。为了更好地加工，在成型时，接触涂层不能脱离支承体。在优选的实施方案中，通过在金属带和接触涂层之间布置由Ag和/或Sn组成的厚度D3＝0.1至1微米的中间涂层。在这种情况下该中间涂层沉积在清洁的并活化的带表面上。 
在优选的实施方案中，该接点材料包括作为第一添加剂的3至40质量％的碳粉，其是呈片状和/或球状和/或粒状的直径Φ＝20至150纳米的细颗粒。该碳具有与金属材料相比明显低的硬度。正是基于该原因，重要的是该添加剂处于纳米级的小的颗粒尺寸导致该复合材料在其表面由于金属组分而具有足够的硬度并因此具有抗机械应力的耐磨性。该软的碳粉填充在硬的金属骨架中。 
可以考虑在第一添加剂中加入第二添加剂，该第二添加剂改善了抗电弧侵蚀 性、硬度和耐磨性。所以也可以加入金属颗粒。在优选的实施方案中，该第二添加剂是2至50重量％的选自Co、Cu、Mo、Ni、Ti、W的直径Φ＝10至200纳米细颗粒状的金属。 
另外也可以考虑使用硬质颗粒作为第二添加剂。有利地该硬质颗粒是2至40重量％的直径Φ2＝10至200纳米的细颗粒状的碳化物，优选是选自SiC、WC的碳化物。 
另外有利地该第二添加剂是0.5至40重量％的直径Φ2＝50至200纳米的细颗粒状的二硫化物，优选选自MoS2、WS2的二硫化物。 
在又一备择的实施方案中，该第二添加剂由2至40重量％的直径Φ2＝5至100纳米的细颗粒状的SnO2组成。 
在同样备择的实施方案中，该第二添加剂是2至40重量％的直径Φ2＝50至150纳米的细颗粒状的氧化物陶瓷颗粒，优选是选自Al2O3、ZrO2的。 
此外有利地是使用2至20重量％的直径Φ2＝50至200纳米的细颗粒状的PTFE(聚四氟乙烯)作为第二添加剂。 
对于接触涂层在支承体上的粘接性重要的是，除电性能外在插头制备时的成型也要达到预定的目的，而不会使接触涂层脱落。在优选的实施方案中，该金属带的厚度D1＝0.06至1.2毫米，接触涂层的厚度D2＝0.5至10微米。因此可以获得适合于成型的厚度比例，这可以防止涂层的剥落。 
对于适合的复合材料，相应地必须选择支承体。在这种情况下优选具有好至非常好的导电性的材料。有利地该金属带由Cu或者Cu合金组成、由Fe或Fe合金组成、由Al或者Al合金组成、由Ni或者Ni-合金组成。 
本发明在复合材料方面的优点特别地在于，在高的插塞和拔出速度下或者阻止电弧的形成或者只要一形成电弧，其立即熄灭，并不会导致接点表面的氧化。特别地，通过中间涂层可以保证接触涂层在支承体上的最佳粘接性。优于已经存在的复合材料，采用这种有创造性的解决办法可以使这种用于电子技术的复合材料的性能最佳化。 
用于使由可流动的或者呈液态的材料组成的射流例如由液态金属或金属合金组成的射流气体雾化的装置(该装置具有供给该射流雾化气体以便将该射流雾化为由小液滴组成的喷雾的雾化器单元)的任务是这样解决的，即该雾化器单元呈环状或者在长度上延伸，并且其具有连贯的雾化气体的流出口。该雾化器单元区域的上 方是用于粉末的具有涡流室的喷射器，该喷射器与固体给料单元相连。 
本发明在气体雾化装置方面的优点在于，在涡流室中将粉末组份均匀地引入喷雾中。对此雾化气体高的气体流速在涡流室的区域中形成低压，该低压使粉末颗粒恒定地离开该室。涡流室中颗粒的运动消除了细的粉末颗粒的附聚，并导致在沉积涂层中的均匀分布。特别地采用在长度上延伸形式的雾化器单元可以涂覆宽的带，而无需移动气体雾化装置或者其部分。对此该微长的部分应该垂直于带材的移动方向。 
根据粉末的特征，在向该喷雾供应粉末颗粒时对混合的方式提出不同的要求。在优选的实施方案中，该固体给料单元包括干燥粉末的储存容器或者用于随粉末供给的液体的带输入管线的容器。所以通过粉末预加工，特别地通过在适合的液体中的悬浮降低了颗粒的附聚。 
有利地，通过阀门控制和/或通过熔体储存容器的压力供料(Druckbeaufschlagung)装置来控制整个装置的射流量。根据相应的压力供给可以有针对性地控制材料的流量而无需阀门，因为熔体流仅通过相应的过压才能保持笔直。然而附加的阀门可以允许短的熔体流的接通和断开的转换时间。 
本发明的采用气体雾化装置制备复合材料的方法的任务是通过以下步骤解决的，将金属或金属合金在储存容器中加热至熔点以上，采用压力供料使该熔体以热射流的形式流出，并借助于气体流雾化为喷雾，与未熔化的颗粒状的添加剂混合，随后将雾化的小液滴沉积在支承体材料或者接受装置上。 
接受装置可以是在喷射流下面移动的冷却带，该喷射产物可以从该冷却带上剥离。 
在优选的实施方案中，将未熔化的添加剂供给来自涡流室的熔体流。 
该制备方法可以或者连续地或者间歇地进行，其中待涂覆的带或者连续或者以上下重叠放置的带的批料供应。将该设备安放在充满氮气或氮气/氢气混合气体的具有进料和出料闸门的壳体中。该进料闸门串接在带清洗和活化工段(经过这些工段可以在涂覆之前为涂覆的涂层的好的粘接性制备好带表面)的前面。 
在优选的实施方案中，粉末颗粒的喷射(Verdusen)在使用N2下进行。对此在0.15至1.5MPa下将添加剂吹进喷射流中。通过该过压，氮气以非常高的速度通过流出口进入混合室中，以便使进入该混合室的细的粉末颗粒涡流，并且获得最佳的混合。此外借助于处于超音速区的气体速度来有效地防止纳米粉末的附聚。对此为 了更好地混合可以相应地控制粉末组份的压力供料。 
为了能够在制备过程中以可变的组成沉积添加剂，有利地添加剂的吹入是相互独立的。 
在选择沉积条件时，力求获得均匀的具有细分散的添加剂的接触涂层。对此有利地，将金属带加热至(0.6至0.9)×接点材料Sn或Ag的Ts的温度。因此可以沉积这种同时具有低的孔隙率和高的粘接性的涂层。 
为了改善涂层在支承体材料上的粘接性，在涂层沉积之前有利地用助熔剂对金属带进行表面处理以使其活化。 
通过其它的沉积参数调节涂层厚度。对此在优选的实施方案中，接触涂层的厚度D2由喷射流密度和待涂覆的金属带的移动速度控制。优选喷射流密度由针形阀等控制。如果在这种情况下针形阀是持续打开的，那么也可以进行完全平面的单侧涂覆。为了制备相同的涂层可以使该金属带以恒定的速度从喷射流下方通过。或者也可以无需阀装置仅通过熔体的压力供料来控制喷射头中的材料流量。 
在选择适当的沉积条件下，也可以有针对性地调节接触涂层的厚度和/或孔隙率。在特别有利的实施方案中，通过选择的喷射参数可以将接触涂层的开口孔隙率调节为70至85％。最终为了自动润滑使油渗入多孔的接触涂层中。 
在另一工艺步骤中，通过在至少0.8×涂层基体材料的Ts的温度下对该喷射的金属带精轧而对该多孔涂层进行后处理，以便获得100％的密度。 
在特别优选的实施方案中，该金属带仅部分地被涂覆。因此例如在插头的尖端上形成部分电阻涂层。 
在部分电阻涂层的情况下，在拔出过程期间连续地降低电流，所以根据材料和电压从一定的临界电阻起不再形成电弧。在这种自动断开的接点情况下以这种方式使烧损最低化。 
为了制备部分电阻涂层，有利地将该金属带用掩模覆盖。或者可以保护该金属带以阻挡喷射流。对此不用将该掩模覆盖在支承体上，而是以一定的距离布置在射流中。 
现场电子学一方面意味着升高的温度另一方面意味着升高的振荡负荷。这特别有利于多阀门技术(Mehrventiltechnik)。对于在汽车中的应用，需要电导性接头例如插塞连接器、冲压屏栅接头、继电器接头以及耐磨损和抗振荡的高温稳定的涂层。以这种方式发现了导电复合材料在汽车领域以及特别是在电子接触元件例如插塞连 接器和插塞连接器接头中的应用。 
通过本发明获得的方法方面的优点在于，给作为支承体材料的金属带部分地涂覆接触涂层，以便获得具有低的烧损性能的可自动断开的接点。特别地，通过选择适合的参数可以在工艺过程中在支承体材料上产生接触涂层，该涂层可以直接进一步加工成带材。优于已经存在的制备方法，该涂覆方法可以毫无困难地内连为合理的批量生产形式。 
借助于附图进一步详细地说明本发明的实施方案。 
附图说明
附图1表示具有支承体和接触涂层的复合材料， 
和 
附图2是气体雾化装置的示意图。 
其中图号： 
1复合材料 
2金属带 
4接触涂层 
6中间涂层 
8掩模 
10气体雾化装置 
12熔体容器 
14熔体的进料管道 
16压力供料的接头 
18针形阀 
20液体和混合物的容器 
22进料管道 
24压力供料的接头 
26涡流室 
28喷嘴 
30出口漏斗/喷射流控制 
32具有涡流室的喷射器单元 
34 N2-雾化器单元 
36 N2-室 
38 N2-流出口 
40 加热的容器 
42 其它熔体容器的接头 
44 粉末容器 
46 间歇操作时的批料 
47 清洗和活化单元 
具体实施方式
在所有的附图中彼此相同的部件用相同的附图标记表示。 
根据附图1用于制备电接触元件的复合材料由作为支承体的金属带2和至少一侧涂覆的由银或锡接触材料制成的接触涂层4构成。该接触材料包含0.5至60重量％作为第一添加剂的直径 
Figure S031C1508920070702D000081
至200纳米的细颗粒状的碳粉和0.5至60重量％的直径 
Figure S031C1508920070702D000082
至200纳米的细颗粒状的不同材料的第二粉状添加剂。 
在金属带2和接触涂层4之间是由Ag和/或Sn组成的厚度D3＝0.1至1微米的中间涂层6。 
金属带2的厚度总计优选是D1＝0.06至1.2毫米，接触涂层4的厚度D2＝0.5至10微米。金属带2可以用助熔剂进行表面处理以使其活化。 
在附图2中示意性描述的气体雾化装置10包括布置在加热壳体40中的具有注入导管和进料管道14熔体容器12，其用于将熔体输送到带有针型阀18的喷嘴28中，由液态金属或者金属合金组成的射流从该喷嘴喷出。通过安装在熔体容器12上的用于压力供料的接头来控制流出量。为了压力供料，熔体容器12上的注入导管是用软木塞或者螺旋连接气密性密封的。 
此外，在加热的壳体40中还布置有带有注入导管的容器20，其用于液体或者随粉末供给的液体组成的混合物。其经具有围绕针形阀18布置的喷射器单元32的进料管道22与涡流室26连通。同样来自该容器的流出量经安装在容器20上的用于压力供料的接头24控制。备择地或者附加地可以把具有干燥粉末用的粉末容器44的固体进料单元接在加热的壳体40上，其经过该示意图中未示出的管道与喷射器单 元32连通。另一熔体容器(如果需要具有单独的加热装置)可以对接在接头单元42上。 
通过针形阀18流出的熔体与来自涡流室的固体混合，并且通过N2-雾化单元34被雾化气体这样加负荷，即由该射流产生一种由小液滴组成的喷雾，该喷雾沉积在带2上。直接在N2-流出口38之前的N2-室36用于恒定地供给气体。 
具有预先规定的出口锥体(其保证在整个带宽度上的沉积)的出口漏斗30用于控制喷射流。为了选择性地沉积，将掩模8布置在射流中或者涂覆在该基体上。 
雾化器单元34是环状的或者如附图2的平面图所示在长度上延伸的，这里其具有用于N2-雾化气体的连贯的流出口38。通过清洗和活化单元48可以对金属带进行预处理以便用助熔剂活化其表面。该金属带可以在工艺过程中连续地或者在间歇操作中以批量堆叠的形式被涂覆。 

Claims (11)

1.导电的复合材料，其用于制备电接触元件，所述复合材料由金属带(2)、接触涂层(4)和位于金属带和接触涂层之间的中间涂层(6)组成，该接触涂层由银或锡接点材料制成，该接点材料包含0.5至60重量％的以直径Φ1＝5至200纳米的细颗粒形式存在的碳粉作为第一添加剂和0.5至60重量％的以直径Φ2＝5至200纳米的细颗粒形式存在的第二添加剂，所述第二添加剂改善了抗电弧侵蚀性、硬度和耐磨性，并且中间涂层(6)厚度D3＝0.1至1微米，由Ag或Sn制成。
2.根据权利要求1所述的复合材料，其特征在于，所述的接点材料包括作为第一添加剂的3至40重量％的碳粉，其是呈片状和/或球状和/或粒状的直径Φ＝20至150纳米的细颗粒。
3.根据权利要求1所述的复合材料，其特征在于，该第二添加剂是2至50重量％的选自Co、Cu、Mo、Ni、Ti、W的直径Φ＝10至200纳米的细颗粒状的金属。
4.根据权利要求1所述的复合材料，其特征在于，该第二添加剂是2至40重量％的直径Φ＝10至200纳米的细颗粒状的碳化物。
5.根据权利要求1所述的复合材料，其特征在于，该第二添加剂是0.5至40重量％的直径Φ＝50至200纳米的细颗粒状的选自MoS2、WS2的二硫化物。
6.根据权利要求1所述的复合材料，其特征在于，该第二添加剂是2至40重量％的直径Φ＝5至100纳米的细颗粒状的SnO2。
7.根据权利要求1所述的复合材料，其特征在于，该第二添加剂是2至40重量％的直径Φ＝50至150纳米的细颗粒状的选自Al2O3、ZrO2的氧化物陶瓷颗粒。
8.根据权利要求1所述的复合材料，其特征在于，该第二添加剂是2至20重量％的直径Φ＝50至200纳米的细颗粒状的PTFE。
9.根据权利要求1所述的复合材料，其特征在于，所述金属带(2)的厚度D1＝0.06至1.2毫米，接触涂层(4)的厚度D2＝0.5至10微米。
10.根据权利要求1所述的复合材料，其特征在于，金属带(2)由Cu或者Cu合金、由Fe或Fe合金、由Al或者Al合金、由Ni或者Ni-合金组成。
11.根据权利要求1至10的导电复合材料在汽车领域中作为插塞连接器和插塞连接器接头的应用。
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