CN1325689C - 锡-银涂层 - Google Patents
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Abstract
本发明涉及改进涂层,其用于电连接器或电子连接器,诸如用于汽车上的接触器或端子。本发明的涂层优选包含锡-银二元涂层,该涂层含有1.0wt%-约20wt%的银,优选2.0wt%-15wt%,更优选3.0wt%-10wt%,以及基本上余量的锡。所述涂层优选通过将所述基质材料浸没于熔融锡-银浴中来施加。
Description
相关申请参考
本发明要求优先权,其为美国未审定专利,题为锡-银涂层,序列号为No.60/312,331,递交于2001年8月14日。
技术背景
本发明涉及用于基质材料上的锡-银涂层,该材料用于电器或电子领域,诸如汽车上的连接器,并且涉及将所述锡-银涂层施加于所述基质材料的方法。
汽车中的电接触装置容易由于高温和其工作环境而产生各种危险。例如,汽车电接触装置经常产生有微小运动引起的震动和磨损腐蚀。由于磨损腐蚀提高了电接触装置表面的接触阻抗,因此其为一种损伤。此外,当两个电接触装置或端子结合时,将产生电弧。
为了解决这些问题,一些汽车电接触装置上涂敷金。由于金不会形成有害的氧化物,因此它是一种可利用的材料。但金的价格过高,并极大地增加了汽车电接触装置的成本。
为了消除金的高成本,一些电接触装置涂敷锡。虽然达到了降低成本的目的,纯锡涂层不具有很长的循环寿命,一般为约170次循环。
因此,现在仍需要一种涂层,其可用来形成电接触装置,该装置成本低且经受汽车工作时的环境压力。
发明简述
因此,本发明的目的是提供一种用于电连接器或电子连接器的改进涂层。
本发明的另一个目的是提供上述的改进涂层,其可用于汽车领域并具有长循环寿命。
本发明的另一个目的是提供上述的改进涂层,其可用于汽车电接触装置,成本低。
本发明的另一个目的是提供一种在基质材料上形成涂层的改进方法。
本发明的另一个目的是提供一种形成电连接器或电接触装置的改进方法。
前述目的可通过本发明的锡-银涂层和方法来实现。
根据本发明,可在被用作电接触装置的基质材料上施加锡-银涂层。所述基质材料可为任意适宜的具有理想导电性的金属。例如,所述基质材料可为铜、铜合金、碳钢材料或铝合金。本发明优选实施方式中的所述锡-银涂层含有1.0wt%-约20wt%的银,优选2.0wt%-15wt%,更优选3.0wt%-10wt%,以及基本上余量的锡。如以下所述,本发明的二元锡-银涂层是特别优良的涂层。例如,所述涂层不产生对涂层有害并增加所述涂层电阻的氧化物。
尽管本发明的涂层优选为二元锡-银涂层,所述涂层还可含有多达5.0wt%有效量至少一种硬化元素,其选自铋、硅、铜、镁、铁、镍、锰,锌、锑及其混合物。在涂层中所述至少一种硬化元素的含量,其应当为不会产生增加所述涂层电阻的氧化物为宜。
本发明的锡-银涂层的一个优点是其无须包含诸如脱氧剂的元素。
本发明的锡-银涂层的形成是通过一种方法,其大致包括步骤:提供被涂敷的基质材料;制备含有1.0wt%-约20wt%的银和余量的锡的浴;以及将所述基质材料浸入所述浴以在所述基质材料上形成涂层,所述涂层含有1.0wt%-约20wt%的银;以及基本上余量的锡。在本发明另一个实施例中,所述浴和涂层还可含有至少一种元素,其选自铋、硅、铜、镁、铁、镍、锰,锌、锑以及其混合物。所述至少一种硬化元素的含量,其应当为不会产生增加所述涂层电阻的氧化物为宜。
本发明锡-银涂层的其他细节和其制备方法,以及其他目的和优点,均描述于下述说明书和附图中。
附图简述
图中所示为,与本发明的锡-银涂层相比,纯锡涂层硬度实验比较结果。
优选实施例详述
如前所述,本发明涉及在作为电连接器或电子连接器(诸如汽车上的电接触装置)的基质材料上施加锡-银涂层。所述基质材料可为适宜已知导电性材料,诸如铁基材料,例如碳钢材料,或非铁基材料例如纯铜、铜基合金或铝合金。一种常用于汽车中的基质材料为代号为CDA ALLOY 14530的铜碲合金,其含有0.003-0.023的碲,0.003-0.023的锡,0.001-0.010的磷以及余量的铜。
在大多数电子方面的用途中,最好是在基质材料的至少一部分上设有涂层,以防止表面氧化,所述氧化将导致磨损腐蚀以及电阻增加。所述涂层必须具有足够的硬度以耐受多次循环,并且其电阻值不会太大。已经发现一种作为涂层的特别有益的组合物,其可在用于电子领域诸如汽车领域的基质材料上施加,所述涂层为二元锡-银涂层,其含有1.0wt%-约20wt%的银,优选2.0wt%-15wt%,更优选3.0wt%-10wt%,以及基本上余量的锡。此类涂层具有大于225℃的熔点,这是有益的。
如果需要,所述至少一种硬化元素,其选自铋、硅、铜、镁、铁、镍、锰,锌、锑以及其混合物,其在本发明的锡-银涂层另一种实施方式中存在以增加涂层的硬度性质。若存在,所述至少一种硬化元素可以多达5.0wt%有效量,并且优选为0.1wt%-约5.0wt%。所述硬化元素经特别选定其含量不应产生有害的氧化物以使涂层的电阻增加。例如,应当避免在涂层中采用大量的氧化物产生元素诸如镁和铜。
本发明锡-银涂层可以现有技术中的适宜工艺施加在基质材料上。但是优选采用非电镀技术将锡-银涂层施加于基质材料上。例如,本发明的涂层可通过将所述基质材料浸没于锡-银浴,锡-银浴保持于至少500和优选500-约900的温度下。在优选的实施例中,所述浴含有熔融的锡和银,并且其组成为1.0wt%-约20wt%的银,优选2.0wt%-15wt%,更优选3.0wt%-10wt%,以及基本上余量的锡。浸没于浴中的基质材料可为经压制形成电连接器或电子连接器特定形状的连续带状金属或片状金属。或者,在它们从所述浴中移出后,该涂敷后的基质材料可加工成电连接器或电子连接器的特定形状。例如,在它们从所述浴中移出后,该涂敷后的基质材料可加工成电连接器或电子连接器的特定形状。
任选地,所述涂层浴还可含有多达约5.0wt%有效量,并且优选为0.1wt%-约5.0wt%的至少一种硬化元素,其选自铋、硅、铜、镁、铁、镍、锰,锌、锑以及其混合物。例如,所述浴可含有0.1wt%-1.5wt%的铜。
如前所述,浸没于浴中的基质材料可具有任意所需的形状诸如卷带状基质材料。所述基质材料可以公知的适宜系统连续地或非连续地通过所述浴。而且,在本发明的优选实施例中,所述被涂敷的基质材料保持于浴中0.2秒-10秒的时间以形成厚度为0.00001″-0.001″的所述涂层。
已经发现,通过以上述量向锡中加入银,可形成具有硬化涂层表面的涂层。因为涂层越硬,其循环寿命越长,所以这是优选的。如前所述,在接触电阻超过10毫欧标准值之前,纯锡涂层具有170循环的循环寿命。通过向锡中加入2.0wt%的银,可以发现在接触电阻超过上述标准值时,循环寿命增至250次循环。可以发现,向锡中加入5.0wt%的银,在接触电阻超过上述标准值时,循环寿命增至900次循环。
已经发现,向涂层中加入5.0wt%的银,所述涂层的涂敷过程中保持为均匀状态。换言之,所述银不会从锡中分离出来。这意味着所述涂层冷却后,银不会悬浮或分离出来。
虽然本发明的锡-银涂层价格要远高于纯锡涂层,它们均比金涂层的便宜。因此,本发明的涂层成本较低。
还发现,在锡-银涂层形成后,通过向基质材料表面施加润滑材料(诸如合成烃基润滑脂),本发明的涂层的循环寿命可进一步增加。当采用了润滑材料后,预计在锡涂层含有多达10wt%的银的涂层将具有一百万次循环寿命,这大大增加了电流循环寿命。
向所述涂层中加入上述量的银具有其他优点。例如,银的存在增加了表面熔点。而且,银的存在可消除涂敷的接触器或端子短路或击穿。由于汽车电源增加为42伏系统,这种效果是所需要的。
本发明中所形成的涂层还不含氨基磺酸银以及有害的氧化物。
本发明的涂层其他优点包括涂层中不含任何无机物,涂层与基质材料间存在的强金属键(增加润滑性提高了使用寿命)以及具有超过15.6% IACS的优异导电性,例如,一种95%锡-5%银涂层具有16.6% IACS的导电性以及90%锡-10%银涂层具有超过20% IACS的导电性。而且,无须向所述形成涂层的浴中加入抛光剂。
为了说明本发明涂层所产生的改进,根据本发明的方法制备了样品,其包括由涂敷有纯锡的代号为Alloy 4252的商购铜合金制成的基质,由相同材料涂敷98wt%的锡和2wt%的银制成的基质,由相同材料涂敷95wt%的锡和5wt%的银制成的基质,以及由相同材料涂敷90wt%的锡和10wt%的银制成的基质。所述样品经过测试,以确定(在电阻增加为10毫欧之前)循环次数和电阻值。所述测试表明,在到达10毫欧之前所述纯锡涂敷的基质平均具有289次循环,并且其电阻值为10.09-10.88。所述测试还表明所述98-2涂层平均循环寿命为452次循环,并且其电阻值为10.16-10.74;所述95-5涂层平均循环寿命为399次循环,并且其电阻值为10.11-10.82;以及所述90-10涂层平均循环寿命为157次循环,并且其电阻值为10.09-10.83。还发现,随涂层中银含量增加,所述涂层熔点提高。例如,纯锡涂层的熔点为231℃,所述95-5锡-银涂层的熔点为245℃-253℃,并且所述90-10锡-银涂层熔点为310℃。
所进行的另一个实验来确定本发明的锡-银涂层相对于纯锡涂层的硬度。所述测试采用微压痕(nanoidentation)来测定是否所述锡基薄膜的压痕硬度受所添加银的影响。为了进行实验,以纯锡涂敷铜合金基质,铜合金上涂敷98wt%的锡和2wt%的银,铜合金上涂敷95wt%的锡和5wt%的银,以及铜合金上涂敷90wt%的锡和10wt%的银来制备样品。每一个锡基涂层为约3000nm厚。为了消除从基质上分层,锡基涂层上最大压痕深度小于33%的涂层厚度。至少在每一个具有锡基涂层的样品上进行三次压痕实验。
锡基薄膜的硬度实验表明,硬度随涂层中银含量增加而增加。纯锡涂层的压痕硬度为0.3GPa,而98-2锡涂层、95-5锡涂层和90-10锡涂层的硬度为0.32GPa-0.41GPa。附图表明,每种锡-银涂层的硬度范围。所述测试清楚表明采用本发明锡-银涂层后硬度得以改进。
尽管本发明的涂层以汽车为例进行描述,对于本领域的普通技术人员而言,所述涂层可用于其他电接触装置或电器端子。
显而易见,所述锡-银涂层完全可实现前述的目的、方法以及优点。尽管本发明以实施例形式进行了详述,本领域普通技术人员在阅读了本发明之后,其他的替代、修改以及变换是显而易见的。因此所述的替代、修改和变换均落在本发明权利要求的保护范围之内。
Claims (19)
1.一种接合电连接器,其包括:
导电材料;以及
施加于至少一部分导电材料上的涂层,所述涂层含有3.0wt%-20wt%的银和余量的锡,并且其熔点大于225℃,所述涂层厚度为0.00001英寸-0.001英寸。
2.如权利要求1所述的接合电连接器,其中所述涂层中银含量为3.0wt%-15wt%。
3.如权利要求2所述的接合电连接器,其中所述涂层中银含量为3.0wt%-10wt%。
4.如权利要求1所述的接合电连接器,其中所述涂层硬度为0.32-0.41GPa。
5.如权利要求1所述的接合电连接器,其中所述涂层为非电镀涂层。
6.如权利要求1所述的接合电连接器,所述涂层含有3.0wt%-20wt%的银;5.0wt%以下有效量的至少一种任选元素,所述任选元素选自铋、硅、铜、镁、铁、镍、锰,锌、锑;以及余量的锡。
7.如权利要求6所述的接合电连接器,其中所述至少一种元素的含量为0.1wt%到不致于形成有害氧化物的量。
8.如权利要求1所述的接合电连接器,其中所述导电材料含有铁基材料、非铁基材料或铜-碲合金。
9.接合电连接器的制备方法,其包括步骤:
提供被涂敷的导电材料;
制备含有3.0wt%-20wt%银和余量锡的浴;以及
将基质材料浸入所述浴以在所述基质材料上形成涂层,所述涂层具有0.00001英寸-0.001英寸的厚度并含有3.0wt%-20wt%的银,以及
将所述经涂敷的基质材料制成电连接器。
10.如权利要求9所述的方法,其中所述制备步骤包括,制备一种浴,其含有3.0wt%-20wt%的银;5.0wt%以下有效量的至少一种任选元素,其选自铋、硅、铜、镁、铁、镍、锰,锌、锑;以及余量的锡。
11.如权利要求9所述的方法,其中所述制备步骤包括制备含有3.0wt%-15wt%银的浴。
12.如权利要求11所述的方法,其中所述涂层中的银含量为3.0wt%-10wt%。
13.如权利要求9所述的方法,进一步包括在浸入步骤中使所述浴保持于大于260℃的温度下的步骤。
14.如权利要求13所述的方法,其中所述保持步骤包括在浸入步骤中使所述浴保持于260℃-482℃的温度下的步骤。
15.如权利要求9所述的方法,其中所述浸入步骤包括使所述基质材料连续通过所述浴的步骤。
16.如权利要求9所述的方法,其中所述浸入步骤包括使所述基质材料不连续通过所述浴的步骤。
17.如权利要求9所述的方法,其中所述浸入步骤包括将批量的所述基质材料浸到所述浴中,并保持该批量基质材料在浴中足够长的时间以形成所述涂层的步骤。
18.如权利要求9所述的方法,所述浸入步骤包括保持所述基质材料在浴中0.2秒-10秒的时间。
19.如权利要求9所述的方法,进一步包括在所述浸入步骤后向所述基质材料的表面上施加润滑材料。
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US09/991,287 | 2001-11-14 | ||
US09/991,287 US6924044B2 (en) | 2001-08-14 | 2001-11-14 | Tin-silver coatings |
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CN1325689C true CN1325689C (zh) | 2007-07-11 |
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EP (1) | EP1284301B2 (zh) |
JP (2) | JP4226858B2 (zh) |
KR (1) | KR100519673B1 (zh) |
CN (1) | CN1325689C (zh) |
AT (1) | ATE366830T1 (zh) |
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DE60221079D1 (de) | 2007-08-23 |
DE60221079T2 (de) | 2008-03-20 |
US20090197115A1 (en) | 2009-08-06 |
US20070148489A1 (en) | 2007-06-28 |
EP1284301A1 (en) | 2003-02-19 |
US20030035976A1 (en) | 2003-02-20 |
KR100519673B1 (ko) | 2005-10-11 |
ATE366830T1 (de) | 2007-08-15 |
JP2006299416A (ja) | 2006-11-02 |
EP1284301B1 (en) | 2007-07-11 |
JP2003160851A (ja) | 2003-06-06 |
US7147933B2 (en) | 2006-12-12 |
CN1401813A (zh) | 2003-03-12 |
JP4226858B2 (ja) | 2009-02-18 |
DE60221079T3 (de) | 2015-10-22 |
US6924044B2 (en) | 2005-08-02 |
US20050158529A1 (en) | 2005-07-21 |
EP1284301B2 (en) | 2015-07-01 |
KR20030015120A (ko) | 2003-02-20 |
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