CN114107965A - 一种聚酰亚胺表面金属层制备方法 - Google Patents

一种聚酰亚胺表面金属层制备方法 Download PDF

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CN114107965A
CN114107965A CN202111274806.6A CN202111274806A CN114107965A CN 114107965 A CN114107965 A CN 114107965A CN 202111274806 A CN202111274806 A CN 202111274806A CN 114107965 A CN114107965 A CN 114107965A
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layer
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王楠
白晶莹
冯立
李家峰
崔庆新
李思振
徐俊杰
张家强
文陈
王景润
王旭光
佟晓波
张立功
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Beijing Satellite Manufacturing Factory Co Ltd
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Abstract

本发明公开了一种聚酰亚胺表面金属层制备方法，依次对聚酰亚胺表面进行化学粗化、表面活化、烘烤、还原处理后，再进行表面化学镀铜或者化学镀银。本发明设计了化学粗化和表面活化过程中所使用溶液的配方，且对上述过程的工艺进行了相应的优化，在聚酰亚胺表面形成均匀的沉积点作为化学镀的活化中心。本发明制备方法可操作性强，得到的镀层外观均匀，镀层结合力好。

Description

一种聚酰亚胺表面金属层制备方法
技术领域
本发明属于非金属材料表面金属层制备领域，涉及一种聚酰亚胺表面金属层制备方法，特别涉及一种聚酰亚胺表面镀铜、镀银或者镀金的方法。
背景技术
聚酰亚胺(PI)材料是一类分子主链含有酰亚胺环(CO-NH-CO)结构的聚合物，使用温度可达-250℃～+450℃，具有优异的机械性能、化学稳定性、低介电常数和优异的抗辐射性能，可广泛应用于电子电器、航空航天、微电子、激光等领域。但是，PI的高绝缘性限制了其在导电要求比较高的电子电路等领域的应用，因此，对聚酰亚胺表面金属化是非常有必要的。目前常用的表面金属化方法中，化学镀技术具有操作简单、结构适应性强等优点。其中铜、银比其他金属材料电阻系数低，电荷迁移阻力小，导电性好且镀层致密、附着力良好，化学镀铜或者化学镀银可以作为优先考虑的化学镀种。由于聚酰亚胺表面极高的化学惰性和较差的表面吸附性，需要对其表面进行粗化活化处理。相比于机械粗化，化学粗化法具有良好的结构适应性，可满足复杂、大件产品的表面粗化需求，但现有的化学粗化工艺不成熟，使用现有的化学粗化液进行粗化处理时，会导致材料表面刻蚀不均匀，进而导致表面金属层不均匀，镀层结合强度不高。
发明内容
本发明的目的在于克服上述缺陷，提供一种聚酰亚胺表面金属层制备方法，依次对聚酰亚胺表面进行化学粗化、表面活化、烘烤、活化、还原处理后，再进行表面化学镀铜或者化学镀银。本发明设计了化学粗化和表面活化过程中所使用溶液的配方，且对上述过程的工艺进行了相应的优化，在聚酰亚胺表面形成均匀的沉积点作为化学镀的活化中心。本发明制备方法可操作性强，得到的镀层外观均匀，镀层结合力好。
为实现上述发明目的，本发明提供如下技术方案：
一种聚酰亚胺表面金属层制备方法，包括以下步骤：
(1)采用二次粗化法对聚酰亚胺表面进行粗化处理，所述粗化处理包括预粗化和第二次粗化两个步骤：
预粗化采用二甲苯作为处理液，处理温度为20～30℃，处理时间20～30min；第二次粗化采用的处理液包括以下浓度的组分：
碱 120～1000g/L；
高锰酸钾 82～100g/L；
二氧化锰 10～20g/L；
所述第二次粗化处理的温度为40～80℃，粗化时间为5～60min；
(2)对粗化处理后的聚酰亚胺进行活化和烘烤处理；
(3)对步骤(2)所得产物再次进行活化处理，所述活化处理过程与步骤(2)中的活化处理过程相同；
(4)对步骤(3)所得产物进行还原处理；
(5)在步骤(4)所得产物表面进行化学镀铜或者化学镀银；
(6)在步骤(5)所得产物的铜层表面进行电镀铜，或在银层表面进行电镀银处理。
(7)在步骤(6)所得产物的铜层或银层表面进行电镀金或者化学镀金。
进一步的，所述步骤(1)中，第二次粗化采用的处理液中的碱为NaOH或KOH中的一种或一种以上组合。
进一步的，所述步骤(2)中，采用浓度为20～40g/L的AgNO3溶液对粗化处理后的聚酰亚胺进行活化处理，活化处理温度为20～60℃，活化处理时间为10～30min。
进一步的，所述步骤(2)中，采用活化处理溶液对粗化处理后的聚酰亚胺进行活化处理，所述活化处理溶液包括如下组分：
PdCl2 0.3～1.5g/L；
盐酸 2～10mL/L；
活化处理温度为20～40℃，活化处理时间为2～30min。
进一步的，所述步骤(2)中，烘烤处理的温度为120～150℃，烘烤时间为10～30min。
进一步的，所述步骤(4)中，采用浓度为10～30g/L的次亚磷酸钠溶液或体积分数为30％的过氧化氢溶液对步骤(3)所得产物进行还原处理，处理时间为1～20min。
进一步的，所述步骤(5)中，化学镀铜镀层或者化学镀银镀层的厚度为1～6微米。
进一步的，所述步骤(5)中，化学镀铜溶液含有以下组分：
Figure BDA0003329777130000031
化学镀铜时采用的溶液温度为30～40℃。
进一步的，所述步骤(6)中，电镀铜层或者电镀银层的厚度为1～10微米。
进一步的，所述步骤(6)中，电镀铜溶液含有以下组分：
Figure BDA0003329777130000032
电镀采用的电镀铜溶液温度为18～30℃，阴极电流密度为0.5～3A/dm2。
进一步的，所述步骤(6)中，记电镀铜层的预设厚度为d0，在步骤(5)所得产物的铜层表面进行电镀铜的具体步骤如下：
(61)在阴极电流密度为2～3A/dm2的条件下对步骤化学镀铜层表面冲击50～70s；
(62)在阴极电流密度为1～1.5A/dm2的条件下镀覆铜镀层，直至电镀铜层的厚度d1符合：
Figure BDA0003329777130000041
(63)在阴极电流密度为0.5～1A/dm2的条件下镀覆铜镀层，直至电镀铜层的厚度达到预设厚度d0。
进一步的，所述步骤(7)中，电镀金或者化学镀金层的厚度为0.2～3微米。
本发明与现有技术相比具有如下有益效果：
(1)本发明一种聚酰亚胺表面金属层制备方法，创新性的设计了二次粗化法，提高聚酰亚胺表面的粗化效果，改善可镀性，二次粗化方法中的预粗化可以使聚酰亚胺基材中结晶排列紧密的部分发生选择性溶解，使得第二次粗化容易发生，从而实现改善聚酰亚胺表面粗化的效果；
(2)本发明一种聚酰亚胺表面金属层制备方法，创新性的设计了二次粗化方法中第二次粗化的处理液的组分及配比，并对活化工艺进行了优化，能够对聚酰亚胺表面进行均匀刻蚀，有利于后续镀层的均匀附着，进而提高了镀层的耐冷热冲击性能；
(3)本发明一种聚酰亚胺表面金属层制备方法，设计了多种活化方案，可灵活应用于多种场景，且多种活化方案均能实现良好的活化效果；
(4)本发明一种聚酰亚胺表面金属层制备方法，设计了铜-金、铜-银、银等多种金属层，可实现聚酰亚胺表面导电、焊接、防腐等多种功能特性，灵活应用于多种场景，且镀层结合力高。
(5)本发明一种聚酰亚胺表面金属层制备方法，可操作性强，得到的镀层外观均匀，镀层结合力良好，聚酰亚胺工件工作温度范围为-100℃～+100℃，表面电阻≤20mΩ，可满足航天等领域中对工件工作温度范围和表面电阻率的需求，特别适用于需要轻量化、高导电等功能的产品。
附图说明
图1为本发明实施例1所制备的聚酰亚胺表面粗化后表面微观形貌；
图2为本发明实施例1所制备的聚酰亚胺表面镀银照片；
图3为本发明实施例2所制备的聚酰亚胺表面镀金照片；
图4为本发明实施例3所制备的聚酰亚胺表面镀铜照片；
图5为本发明对比例2所制备的聚酰亚胺表面镀镍经-100℃～+100℃冷热循环后的照片。
具体实施方式
下面通过对本发明进行详细说明，本发明的特点和优点将随着这些说明而变得更为清楚、明确。
在这里专用的词“示例性”意为“用作例子、实施例或说明性”。这里作为“示例性”所说明的任何实施例不必解释为优于或好于其它实施例。尽管在附图中示出了实施例的各种方面，但是除非特别指出，不必按比例绘制附图。
本发明的目的在于提供一种聚酰亚胺表面金属层制备方法，解决目前聚酰亚胺表面金属层不均匀，镀层结合强度不好，工艺不成熟的问题。
本发明聚酰亚胺表面金属层制备方法包括如下步骤：
对聚酰亚胺表面进行化学粗化处理，粗化后的材料进行表面活化、烘烤、活化、还原处理，再进行表面化学镀铜或者化学镀银。
其中，采用二次粗化法对聚酰亚胺表面进行粗化处理，包括预粗化和第二次粗化两个步骤。预粗化采用二甲苯作为处理液，处理时间为20～30℃，处理时间20～30min；第二次粗化采用以碱为主要成分的处理液对聚酰亚胺进行粗化处理，包括以下浓度的组分：碱120～1000g/L，KMnO4 82～100g/L，二氧化锰10～20g/L，粗化处理温度40～80℃，粗化时间5～60min；其中碱可以是NaOH、KOH中的一种或两种。
活化处理溶液为AgNO3 20～40g/L，活化处理温度20～60℃，活化处理时间为10～30min。活化处理也可以采用以下溶液：PdCl2 0.3～1.5g/L，盐酸2～10mL/L，活化处理温度20～40℃，活化处理时间为2～30min。
活化处理后再次进行活化处理，活化后进行烘烤，烘烤温度120～150℃，烘烤时间为10～30min。
活化、烘烤后进行还原处理，还原处理采用体积分数为30％过氧化氢溶液，处理时间为1～20min，还原也可采用10～30g/L次亚磷酸钠溶液，处理时间为1～20min。
粗化、活化、烘烤、活化、还原后的聚酰亚胺表面可以进行化学镀铜，也可以进行化学镀银，镀层厚度1～6微米。
化学镀铜层上进行电镀铜处理，之后可以进行电镀金或者化学镀金；或在化学镀银层上进行电镀银处理。电镀铜层的厚度为1～10微米，具体数值可根据需要确定。电镀层首先采用大电流冲击镀，利于镀层晶粒快速结晶，其后采用相对较高电流密度镀覆，利于实现镀层结晶和长大，提高镀层均匀性，最后采用小电流继续镀覆，有利于提高镀层致密性。
本发明提供的聚酰亚胺表面金属层制备方法，可操作性强，得到的镀层外观均匀，镀层结合力良好，可满足工作温度范围为-100℃～+100℃，表面电阻≤20mΩ。聚酰亚胺表面金属层制备方法可应用于需要轻量化、高导电等功能需求的产品。
实施例1
聚酰亚胺表面金属层制备方法包括如下步骤：
将聚酰亚胺在20℃条件下采用二甲苯进行预粗化30min，之后进行第二次粗化20min，粗化溶液为NaOH 800g/L，KMnO4 100g/L，二氧化锰12g/L。粗化后的工件采用40g/LAgNO3溶液在50℃条件下活化处理30min。活化后充分水洗，并用压缩空气吹干。将活化后的工件置于140℃烘箱中烘烤30min。烘烤处理过的工件再次采用40g/L AgNO3溶液在50℃条件下活化处理30min，之后置于体积分数为30％的过氧化氢溶液中还原处理20min。还原处理后的聚酰亚胺进行表面化学镀银，镀层厚度为1～2微米，之后进行电镀银处理，镀层厚度为3～4微米。
如图1所示为本实施例所制备的聚酰亚胺表面粗化后表面微观形貌，可看到粗化后聚酰亚胺表面刻蚀均匀，为后续步骤奠定了基础，如图2所示，镀层外观均匀，结晶细致。采用高低温环境试验，将工件置于100℃烘箱中，高温烘烤10分钟，然后迅速取出后置于-100℃低温箱中10分钟，冷热冲击后，聚酰亚胺材料表面镀银层无鼓包、开裂等现象，镀层结合力良好。采用微欧计对工件表面接触电阻进行测量，测得表面电阻平均值为4.3mΩ。
实施例2
聚酰亚胺表面金属层制备方法包括如下步骤：
将聚酰亚胺在30℃条件下采用二甲苯进行预粗化20min，之后进行第二次粗化10min，粗化温度40℃，粗化溶液为KOH 120g/L，KMnO4 85g/L，二氧化锰15g/L。粗化后的工件采用含有0.3g/L PdCl2和2mL/L盐酸的活化溶液在25℃条件下活化处理5min。活化后充分水洗，并用压缩空气吹干。将活化后的工件置于120℃烘箱中烘烤15min。烘烤处理过的工件再次采用含有0.3g/LPdCl2和2mL/L盐酸的活化溶液在25℃条件下活化处理5min，之后置于15g/L次亚磷酸钠溶液中还原处理2min。还原处理后的聚酰亚胺进行表面化学镀铜，镀层厚度约为2微米。化学镀铜溶液含有以下组分：硫酸铜6g/L；甲醛12mL/L；氢氧化钾2g/L；酒石酸钾钠28g/L；稳定剂0.2mg/L。化学镀铜时采用的溶液温度为33℃。在化学镀铜的基础上进行电镀铜，镀铜层厚度约7微米。电镀铜溶液包括硫酸铜200g/L、硫酸30mL/L、盐酸80mg/L、光亮剂3mL/L、填平剂7mL/L，溶液使用温度18℃，首先在3A/dm2电流密度下冲击1min左右，然后在1.5A/dm2电流密度条件下镀覆3微米，然后在1A/dm2下镀铜4微米。之后进行电镀金，镀金层厚度0.5微米。
如图3所示，镀层外观均匀，结晶细致。采用高低温环境试验，将工件置于100℃烘箱中，高温烘烤10分钟，然后迅速取出后置于-100℃低温箱中10分钟，冷热冲击后，聚酰亚胺材料表面镀铜层无鼓包、开裂等现象，镀层结合力良好。采用微欧计对工件表面接触电阻进行测量，测得表面电阻平均值为2.8mΩ。
实施例3
聚酰亚胺表面金属层制备方法包括如下步骤：
将聚酰亚胺在40℃条件下化学粗化处理10min，粗化溶液为KOH 120g/L，KMnO485g/L。粗化后的工件采用含有0.3g/L PdCl2和2mL/L盐酸的活化溶液在25℃条件下活化处理5min。活化后充分水洗，并用压缩空气吹干。将活化后的工件置于120℃烘箱中烘烤15min。烘烤处理过的工件置于15g/L次亚磷酸钠溶液中还原处理2min。还原处理后的聚酰亚胺进行表面化学镀铜，镀层厚度约为5微米。
如图4所示，镀层外观均匀，结晶细致。采用高低温环境试验，将工件置于100℃烘箱中，高温烘烤10分钟，然后迅速取出后置于-100℃低温箱中10分钟，冷热冲击后，聚酰亚胺材料表面镀铜层无鼓包、开裂等现象，镀层结合力良好。采用微欧计对工件表面接触电阻进行测量，测得表面电阻平均值为4.9mΩ。
对比例1
“CN 103540915 A一种聚酰亚胺表面化学镀铜的方法”专利中聚酰亚胺表面粗化方法为在70℃条件下，40～60g/L NaOH溶液中浸渍5～15min，之后进行活化、烘烤、还原，实现聚酰亚胺表面镀铜，对铜镀层的结合强度没有进行研究和分析。与该对比例相比，本专利采用含KOH(或NaOH)和高锰酸钾的溶液，刻蚀均匀，利于镀层的均匀附着，且粗化效果好，镀层可耐受-100℃～+100℃冷热冲击，说明本发明中的化学粗化液有效提升了粗化效果。
对比例2
聚酰亚胺表面金属层制备方法包括如下步骤：
将聚酰亚胺在40℃条件下化学粗化处理10min，粗化溶液为KOH 120g/L。粗化后的工件采用含有0.3g/L PdCl2和2mL/L盐酸的活化溶液在25℃条件下活化处理5min。活化后充分水洗，并用压缩空气吹干。将活化后的工件置于120℃烘箱中烘烤15min。烘烤处理过的工件置于15g/L次亚磷酸钠溶液中还原处理2min。还原处理后的聚酰亚胺进行表面化学镀铜，镀层厚度约为2微米，在镀铜层基础上镀镍4微米。
镀层外观均匀，结晶细致。采用高低温环境试验，将工件置于100℃烘箱中，高温烘烤10分钟，然后迅速取出后置于-100℃低温箱中10分钟，冷热冲击后，如图5所示，聚酰亚胺材料表面镀镍层出现鼓包、开裂，说明相对于实施例1-3，镀层与基材之间的结合强度较差，本发明中提供的二次粗化法及化学粗化液配方有效提升了粗化效果。
以上具体实施方式描述了本发明的基本原理和主要特征。本行业的技术人员应该了解，本发明不受上述实施例的限制，任何不经过创造性劳动想到的变化或变换，都应涵盖在本发明的保护范围内。在不脱离本发明范围的前提下，本发明还会有各种变化和改进，这些变化和改进都将落入要求保护的范围内
以上结合具体实施方式和范例性实例对本发明进行了详细说明，不过这些说明并不能理解为对本发明的限制。本领域技术人员理解，在不偏离本发明精神和范围的情况下，可以对本发明技术方案及其实施方式进行多种等价替换、修饰或改进，这些均落入本发明的范围内。本发明的保护范围以所附权利要求为准。
本发明说明书中未作详细描述的内容属本领域技术人员的公知技术。

Claims (12)

1.一种聚酰亚胺表面金属层制备方法，其特征在于，包括以下步骤：
(1)采用二次粗化法对聚酰亚胺表面进行粗化处理，所述粗化处理包括预粗化和第二次粗化两个步骤：
预粗化采用二甲苯作为处理液，处理温度为20～30℃，处理时间20～30min；第二次粗化采用的处理液包括以下浓度的组分：
碱 120～1000g/L；
高锰酸钾 82～100g/L；
二氧化锰 10～20g/L；
所述第二次粗化处理的温度为40～80℃，粗化时间为5～60min；
(2)对粗化处理后的聚酰亚胺进行活化和烘烤处理；
(3)对步骤(2)所得产物再次进行活化处理，所述活化处理过程与步骤(2)中的活化处理过程相同；
(4)对步骤(3)所得产物进行还原处理；
(5)在步骤(4)所得产物表面进行化学镀铜或者化学镀银；
(6)在步骤(5)所得产物的铜层表面进行电镀铜，或在银层表面进行电镀银处理。
(7)在步骤(6)所得产物的铜层或银层表面进行电镀金或者化学镀金。
2.根据权利要求1所述的一种聚酰亚胺表面金属层制备方法，其特征在于，所述步骤(1)中，第二次粗化采用的处理液中的碱为NaOH或KOH中的一种或一种以上组合。
3.根据权利要求1所述的一种聚酰亚胺表面金属层制备方法，其特征在于，所述步骤(2)中，采用浓度为20～40g/L的AgNO3溶液对粗化处理后的聚酰亚胺进行活化处理，活化处理温度为20～60℃，活化处理时间为10～30min。
4.根据权利要求1所述的一种聚酰亚胺表面金属层制备方法，其特征在于，所述步骤(2)中，采用活化处理溶液对粗化处理后的聚酰亚胺进行活化处理，所述活化处理溶液包括如下组分：
PdCl2 0.3～1.5g/L；
盐酸 2～10mL/L；
活化处理温度为20～40℃，活化处理时间为2～30min。
5.根据权利要求1所述的一种聚酰亚胺表面金属层制备方法，其特征在于，所述步骤(2)中，烘烤处理的温度为120～150℃，烘烤时间为10～30min。
6.根据权利要求1所述的一种聚酰亚胺表面金属层制备方法，其特征在于，所述步骤(4)中，采用浓度为10～30g/L的次亚磷酸钠溶液或体积分数为30％的过氧化氢溶液对步骤(3)所得产物进行还原处理，处理时间为1～20min。
7.根据权利要求1所述的一种聚酰亚胺表面金属层制备方法，其特征在于，所述步骤(5)中，化学镀铜镀层或者化学镀银镀层的厚度为1～6微米。
8.根据权利要求1所述的一种聚酰亚胺表面金属层制备方法，其特征在于，所述步骤(5)中，化学镀铜溶液含有以下组分：
Figure FDA0003329777120000021
化学镀铜时采用的溶液温度为30～40℃。
9.根据权利要求1所述的一种聚酰亚胺表面金属层制备方法，其特征在于，所述步骤(6)中，电镀铜层或者电镀银层的厚度为1～10微米。
10.根据权利要求1所述的一种聚酰亚胺表面金属层制备方法，其特征在于，所述步骤(6)中，电镀铜溶液含有以下组分：
Figure FDA0003329777120000022
Figure FDA0003329777120000031
电镀采用的电镀铜溶液温度为18～30℃，阴极电流密度为0.5～3A/dm2。
11.根据权利要求1所述的一种聚酰亚胺表面金属层制备方法，其特征在于，所述步骤(6)中，记电镀铜层的预设厚度为d0，在步骤(5)所得产物的铜层表面进行电镀铜的具体步骤如下：
(61)在阴极电流密度为2～3A/dm2的条件下对步骤化学镀铜层表面冲击50～70s；
(62)在阴极电流密度为1～1.5A/dm2的条件下镀覆铜镀层，直至电镀铜层的厚度d1符合：
Figure FDA0003329777120000032
(63)在阴极电流密度为0.5～1A/dm2的条件下镀覆铜镀层，直至电镀铜层的厚度达到预设厚度d0。
12.根据权利要求1所述的一种聚酰亚胺表面金属层制备方法，其特征在于，所述步骤(7)中，电镀金或者化学镀金层的厚度为0.2～3微米。
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