CN100482866C - 钎焊性能优异的表面处理a1薄板、使用该薄板的散热器以及制备钎焊性能优异的表面处理a1薄板的方法 - Google Patents

钎焊性能优异的表面处理a1薄板、使用该薄板的散热器以及制备钎焊性能优异的表面处理a1薄板的方法 Download PDF

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CN100482866C
CN100482866C CNB2004800053484A CN200480005348A CN100482866C CN 100482866 C CN100482866 C CN 100482866C CN B2004800053484 A CNB2004800053484 A CN B2004800053484A CN 200480005348 A CN200480005348 A CN 200480005348A CN 100482866 C CN100482866 C CN 100482866C
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林田贵裕
鹤田知之
驹井正雄
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Toyo Kohan Co Ltd
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Abstract

目的是提供一种具有优异的与镀层结合性能、钎料润湿性和钎焊强度，并且可以优选用于具有优异热辐射性能并且能够加以钎焊的散热器的表面处理Al薄板；一种使用所述Al薄板的散热器；以及一种低成本制备所述表面处理Al薄板的方法。在Al基体表面上形成Zn层，并且在其上通过置换镀覆形成Ni层和Sn层，或者，在表面处理Al薄板上，进一步形成一个具有钎焊焊剂性能和改善散热性能的涂层。

Description

钎焊性能优异的表面处理Al薄板、使用该薄板的散热器以及制备钎焊性能优异的表面处理Al薄板的方法
技术领域
本发明涉及表面处理Al薄板，特别是涉及钎料润湿性或钎焊强度优异、导热率或散热率高，以及能够优选用于可以钎焊而成并且要求具有优异热辐射性能的散热器的表面处理Al薄板；使用该薄板的散热器；以及制备表面处理Al薄板的方法。
背景技术
随着电子器件尺寸的减小或者密度的提高，控制安装在底盘狭小内部或者基本不存在间隙的元件的温度上升变得更加必要。在印刷线路板中，为了抑止元件的温升，使用了安装有用于热辐射的散热器的基板。例如，如图1所示，散热器粘附在发热元件1例如印刷线路板的至少一侧上。粘附面积越大，热传导越大。至于散热器用材料，优选使用导热性优异的材料，以便能够将热量从发热元件快速吸收。如图1所示，由于散热器2位置可延伸至远离发热元件1的区域，而且热量由该延伸部分辐射出，因此，优选散热器表面具有优异的散热性能。在图1中，箭头3指的是热传导方向，箭头4指的是散热方向。
当散热器包含薄板-薄板基材料时，可以通过直接钎焊将散热器与印刷线路板结合一起。当要求进一步的热辐射时，优选使用热传导性能比钢薄板更优异的Al基材料作为散热器。但是，由于散热器难于通过直接钎焊与印刷线路板结合一起，因此，将一个特制销钉连接在Al基散热器上，并且，通过该销钉将散热器与印刷线路板钎焊一起。当散热器通过这种销钉连接时，在销钉与散热器之间不能获得可靠的结合，此外，由于散热器与印刷线路板直接粘附的面积减小，因此，热传导下降，而且，导热性高的Al的特性不能得到充分利用。因此，尝试进行了如下工作，以获得具有良好钎焊性能的Al薄板。
例如，JP-A-05-345969公开了一种钎焊性和镀层结合性均优异的Al基合金金属薄板，其中，Sn镀层通过Ni基镀层在Al薄板或Al基合金金属材料上形成。在Al基合金金属薄板中，采用真空沉积对基体例如热浸镀Al钢薄板进行镀Ni，随后进行镀Sn。根据该方法，真空沉积用于镀Ni和镀Sn，并且需要大规模设备如真空设备。此外，沉积速率小，因而生产率低。所以，难于低成本制造薄板。
JP-A-09-291394公开了一种采用锡或锡合金层镀覆的钎焊性能优异的铝材料，其特征在于：在铝基体上镀覆锡或锡合金层，在铝基体与所述锡或锡合金层之间的界面处形式锡浓度梯度层。在铝材料中，铝合金薄板进行电镀锡处理，之后加热，或者，铝合金薄板通过锡合金熔体，由此，薄板锡化处理之后，在铝基体与锡或锡合金层之间的界面处形成锡浓度梯度层。然而，该材料的缺点在于铝基体与锡化层之间的结合强度不足，而且，特别是，在实施弯曲时，镀锡膜很容易与铝基体分离。
本发明目的是提供表面处理Al薄板，该薄板具有优异的与镀层结合性能、钎料润湿性能和钎焊强度，以及高的热传导性或散热性，并且，能够优选用于可以钎焊而且散热性优异的散热器；还提供使用该薄板的散热器；以及低成本制备所述表面处理Al薄板的方法。
发明公开
用于实现上述目标的本发明表面处理Al薄板的特征在于：自Al基体表面一侧，在基体表面上顺序形成Zn层、Ni层和Sn层。Al基体不限于纯Al薄板，可以是Al合金薄板。在表面处理Al薄板中，希望的是zn层的镀覆量为5-500mg/m2，而且，在Sn层上进一步形成用于改善散热性的涂层。
用于实现上述目标的本发明散热器的特征在于：该散热器使用表面处理Al薄板形成，该薄板中，自Al基体表面一侧，在基体表面上顺序形成Zn层、Ni层和Sn层，或者，所述散热器使用这样的表面处理Al薄板，其中Zn层镀覆量为5-500mg/m2，其中，希望的是导热率为60W/m·k和更高。
或者，本发明的另一种散热器的特征在于：该散热器使用下述表面处理Al薄板形成，其中，在表面处理Al薄板的Sn层上进一步形成用于改善散热性的涂层，其中，希望的是散热率为0.2-0.9。
此外，本发明的表面处理Al薄板的制备方法特征在于：对Al基体置换镀覆Zn，然后镀覆Ni，之后镀覆Sn；其中，希望的是：在镀覆Sn之后，进一步形成用于改善散热性的涂层。用于改善散热性的涂层例如可以通过在表面处理Al薄板上涂覆含黑色颜料和水溶性松香的水性树脂并进行干燥处理形成。
附图简述
图1是展示散热器与发热元件间连接状况实施例的示意图。
实施本发明的最佳模式
此后，详细介绍本发明。
关于作为本发明表面处理Al薄板基体的Al薄板，可以使用纯Al薄板以及JIS标准中1000系列、2000系列、3000系列、5000系列、6000系列和7000系列的Al合金薄板。对Al合金薄板进行脱脂处理，然后进行酸腐蚀，之后，进行去酸洗泥，并且随后实施置换镀覆Zn。实施置换镀覆Zn的步骤如下：在硝酸中浸泡处理、第一次Zn置换处理、锌-硝酸盐分离处理和第二次锌置换处理。这种情况下，在每个步骤处理之后进行清洗。当在置换处理之后实施镀Ni时，由于通过第一次Zn置换处理和第二次Zn置换处理形成的Zn层会发生轻微溶解，因此，在镀Ni之后，Zn层的镀覆量优选为5-500mg/m2，更优选为30-300mg/m2。镀覆量通过适当选择第二次Zn置换处理时处理液体中Zn离子浓度和在处理液体中的浸泡时间来调整。当镀覆量低于5mg/m2时，与在Zn层上形成的Ni镀层的粘附性能不足，当实施弯曲时镀层容易分离。另一方面，当镀覆量高于500mg/m2时，Ni的镀覆变得不均匀，导致钎焊强度下降。
接下来，在以上述方式形成的Zn层上镀覆Ni层。Ni镀层可以采用电镀和化学镀中之任一种方法形成。当采用化学镀时，由于使用P化合物或B化合物作为脱氧剂，Ni镀膜作为含Ni-P合金或Ni-B合金的薄膜形成，但是，与通过电镀形成的含纯镍薄膜类似，也能够获得优异的镀膜与Al基体结合性能、优异的钎料润湿性和钎焊强度。以这种方式获得的Ni层镀覆量优选为0.2-50g/m2，更优选为1-10g/m2。当镀覆量低于0.2g/m2时，由于Ni层不能均匀覆盖Zn层整个表面，故不能获得足够的钎焊强度。另一方面，当镀覆量高于50g/m2时，改善钎料润湿性和钎焊强度的效果达到饱和，因而会产生成本升高的缺点。
接下来，在Ni层上镀覆Sn层。Sn镀层可以采用电镀和化学镀中之任一种镀覆方法形成。Sn层镀覆量优选为0.2-20g/m2，更优选1-10g/m2。当镀覆量低于0.2g/m2时，使用非活性焊剂时钎料难于被润湿。另一方面，当镀覆水平高于20g/m2时，改善钎料润湿性和钎焊强度的效果达到饱和，因而会产生成本升高的缺点。Zn层、Ni层和Sn层以上述方式在Al薄板上形成，由此获得了本发明的表面处理Al薄板。此外，表面处理Al薄板加热至使得Al薄板最外面的Sn层不会由于和下面的Ni层或Al基体发生合金化而完全损失掉，自由Sn仍会得到保留，结果，Al基体与Zn层、Zn层与Ni层、以及Ni层与Sn层相互扩散，或者，Al基体、Zn层、和Ni层、以及Zn层、Ni层、与Sn层相互扩散，从而能够改善Al基体与镀层之间的结合强度以及各个镀层之间的结合强度。
尽管本发明的表面处理Al薄板的导热率为60W/m·k或更高，并且能够优选吸收发热元件的热量和作为热传导性优异的散热器将此热量辐射出去，但是，在Sn层上仍可存在一个用于改善散热性的涂层，由此可以进一步改善热辐射性能。虽然本发明表面处理Al薄板的散热率为约0.05-0.1，但是，通过提供用于改善散热性的涂层，散热率可以提高至约0.2-0.9。在Sn层上形成用于改善散热性的涂层的过程如下。即：在其上顺序形成zn层、Ni层和Sn层的表面处理Al薄板上，或者在对上述表面处理Al薄板实施热扩散处理之后的表面处理Al薄板上，涂覆含黑色颜料和水溶性松香的水性丙烯酸树脂并且加以干燥，由此形成一种处理膜。该处理膜具有焊剂效果，能够改善钎料润湿性。水性树脂的浓度优选100-900g/L，黑色颜料优选占树脂中树脂固含量的50重量％或更低。当其含量高于50重量％时，钎料润湿性和钎焊强度均下降。干燥之后处理膜的厚度优选0.05-10μm。当其小于0.05μm时，改善热辐射效果很小，而当其大于10μm时，热导性下降，而且不能改善热辐射性能。这样，在Sn层上形成用于改善散热性的涂层，从而能够改善散热器的热辐射性。
实施例
(试验薄板的准备)
采用一种Al合金薄板(JIS 5052H19，厚度0.5mm)作为镀覆基体，在碱性溶液中对上述Al合金薄板进行脱脂，之后在硫酸中进行腐蚀，然后，在硝酸中去酸洗泥，并且然后通过在含有150g/L氢氧化钠、50g/L Rochelle盐、25g/L氧化锌和1.5g/L氯化亚铁的处理液中浸泡进行第一次Zn置换处理，之后，在400g/L硝酸溶液中浸泡，以除掉电解置换的Zn，然后，通过在与第一次Zn置换处理所用相同的处理液中浸泡来进行第二次Zn置换处理。在第二次Zn置换处理中，变化各种浸泡时间，获得其上Zn层镀覆量如表1所示的镀Zn的Al薄板。
下面，就镀Zn的Al薄板而言，通过化学镀在镀覆量如表1所示的Zn层上形成Ni-12重量％P合金镀膜。接下来，就其上形成Zn层和Ni层的镀覆Al薄板而言，通过电镀在镀覆量如表1所示的Ni层上形成Sn镀膜，由此形成了试验薄板。在一些试验薄板中，在上述镀覆之后进行了扩散热处理，其中，所述薄板被加热至280℃，由此，Sn层被熔化，而且，Al基体与镀层相互扩散，各个镀层相互扩散，但扩散程度以不丧失最外面的自由Sn为限。在其它一些试验薄板中，使用液体组成如表2所示的处理液形成了用于改善散热性能的涂层。
为了比较，还准备了一种Al合金薄板上直接形成Ni镀层和Sn镀层而无Zn置换镀层的试验薄板、一种Al合金薄板上只存在Sn镀层而无Zn置换镀层的试验薄板和一种低碳钢薄板(厚度0.5mm)上只存在Sn镀层的试验薄板。
(试验薄板的特性评价)
就上述获得的试验薄板而言，对下述特性进行了评价。
[钎料润湿性]
根据meniscograph方法(MIL-STD-883B)，采用SOLDERCHECKER(MODEL SAT-5000，制造商：RHESCA)，将自上述各实验材料切制出的7mm宽试样浸泡在焊剂(NA-200，制造商：TAMURA KAKENCORPORATION)中，将涂覆有焊剂的试样，以2mm/秒的浸渍速度，浸入温度保持在250℃的焊料池(JIS Z 3282：H60A)中2mm深处，并且测量被焊料润湿时的时间，或零交叉时间(Zero Cross Time)，然后，根据如下标准评价焊料润湿性。标准表明时间越短，焊料润湿性越好。
00：小于5秒
0：5秒或更长但小于7秒
Δ：7秒或更长但小于10秒
×：10秒或更长
表1 试验薄板的制备条件
Figure C200480005348D00091
表2 用于改善热辐射的处理液体组成
Figure C200480005348D00092
[钎焊强度]
通过将每种实验材料切制出的7mm宽、50mm长的两个试样折叠成L形状形成两个切出试件，将此两个试件叠放，其中评价表面相对放置，形成一个T形件，并且将一个0.5mm厚钢薄板插入T形件的垂直棒材部分，结果，制备出在T形件垂直棒材部分的下部形成有0.5mm空隙部分的试样。将在钎料润湿性评价中所用相同的焊剂涂覆在试样的空隙部分，然后，使用SOLDERCHECKER(SAT-5000，制造商：RHESCA)，将试样的空隙部分浸入温度保持在250℃的焊料池(JIS Z 3282：H60A)中10mm深处，并且保持5秒，以使空隙部分充满焊料，之后取出，由此形成了T形剥离试样。接下来，采用TENSILON，用夹具将T形剥离试样T形件水平棒材部分夹紧并拉拔，由此，将T形件垂直棒材部分之间的钎料填充部分撕裂开，并且根据如下标准测量和评价钎焊强度。
00：4kgf/7mm或更高
0：3kgf/7mm或更高但低于4kgf/7mm
Δ：1kgf/7mm或更高但低于3kgf/7mm
×：低于1kgf/7mm
[镀膜结合性能]
自每种实验材料切制出宽15mm、长50mm的试样，并进行90°弯折，将一种透明胶带(scotch tape)粘贴在弯折部分，然后剥去。之后，用肉眼观察镀膜的分离情况，并且根据如下标准评价镀膜的结合性能。
0：未观察到分离
×：观察到分离
[热辐射]
自每种实验材料切制出宽5mm、长10mm的试样，并且采用光学AC处理热常数测量系统(PIT-R2，制造商：ULVAC-RIKO，Inc)测量导热率。此外，使用散热计(D and S ARED散热计，制造商：KYOTOELECTRONICS MANUFACTURING CO.，LTD.)测量散热率，并且根据如下标准评价热辐射。
O0：导热率60W/m·k或更高，且散热率0.20或更高
0：导热率60W/m·k或更高，且散热率0.05或更高但低于0.20
Δ：导热率40W/m·k或更高但低于60W/m·k
×：导热率低于40W/m·k
结果，如表3所示，在Al薄板上形成有Zn层、Ni层和Sn层的本发明表面处理Al薄板具有优异的钎料润湿性、高的钎焊强度，并且具有高的导热率和优异的热辐射性。而且，已证实：在表面处理Al薄板的Sn层上存在用于改善散热性的涂层，能够进一步改善热辐射性。因此，本发明可以优选用于能够加以钎焊并且具有优异热辐射性能的散热器。
表3 特性评价结果
Figure C200480005348D00111
工业应用性
在本发明的表面处理Al薄板中，由于在Al基体表面上通过置换镀覆形成Zn层，并且在其上通过镀覆形成Ni层和Sn层，因此，Al基体与镀层之间的结合性能优异。而且，由于Sn层作为最外层表面存在，故能够获得优异的钎料润湿性和高的钎焊强度。此外，由于基体是Al薄板，故导热率高，热辐射性能优异。再有，在本发明的表面处理Al薄板上，存在具有钎焊焊剂性能和改善散热性能的涂层，因而钎焊性得到进一步改善，并且能够改善热辐射性能。因此，本发明的表面处理Al薄板可以优选用于能够加以钎焊并且具有优异热辐射性能的散热器。

Claims (6)

1.一种表面处理Al薄板，其中，自Al基体表面侧，在基体表面上顺序形成Zn层、Ni层和Sn层，其中，在Sn层上进一步形成用于改善散热性的涂层，所述用于改善散热性的涂层是含黑色颜料和水溶性松香的水性树脂的涂层。
2.根据权利要求1的表面处理Al薄板，其中，Zn层的镀覆水平为5-500mg/m2。
3.一种使用根据权利要求1或2的表面处理Al薄板的散热器。
4.根据权利要求3的散热器，其中，导热率为60W/m·k或更高。
5.一种使用根据权利要求1的表面处理Al薄板的散热器。
6.一种表面处理Al薄板的制备方法，其特征在于：对Al基体置换镀覆Zn，然后镀覆Ni，之后镀覆Sn；
在镀覆Sn之后，进一步形成用于改善散热性的涂层，其中，用于改善散热性的涂层通过在表面处理Al薄板上涂覆含黑色颜料和水溶性松香的水性树脂并进行干燥处理形成。
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