CN107841731A - 一种橡胶快速化学镀铜的方法 - Google Patents
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Abstract
本发明涉及一种橡胶快速化学镀铜的方法,属于化学镀膜工艺技术领域。本发明包括步骤:对橡胶表面进行打磨,碱洗除油,粗化,酸洗,敏化,活化;配置化学镀液;其组成及浓度为:主盐五水硫酸铜20~30g/L;络合剂EDTA 20~40g/L,酒石酸钾钠5~15 g/L,选上述络合剂中的一种或多种;还原剂甲醛7~9ml/L;稳定剂甲醇5~8ml/L;碱性调节剂氢氧化钠;余量为水。化学镀铜;温度50~80℃,pH 12~14,施镀时间2~12分钟。水洗,并在40~90℃下烘干。本发明用于各类橡胶的镀铜,镀后镀层具有厚度均匀,结合力强的特点。
Description
技术领域
本发明涉及一种橡胶快速化学镀铜的方法,属于化学镀膜工艺技术领域。
背景技术
橡胶具有优异的耐磨性,很高的弹性、抗拉强度及伸长率,易清洗,更重要的是其环保无毒,但是橡胶不导电限制了其在很多领域的应用。近年来研究学者制备出导电橡胶,即在橡胶基体中加入导电填料制备的导电高分子材料。但是在加入导电填料的同时也使得其硬度增大,抗拉强度和抗撕裂强度等机械性能变差。鉴于橡胶的应用越来越广泛和导电橡胶的缺点,本发明提出一种橡胶表面快速化学镀铜的方法。橡胶表面化学镀铜不仅可以增加其导电导热性、可焊耐焊性、抗拉强度和抗撕裂强度等机械性能,又可以抗电磁干扰,同时铜的成本也相对低廉。橡胶表面镀铜处理后,不但具有较好的可焊耐焊性能、机械性能、电性能、耐老化以及耐蚀性能,而且还可以获得良好的化学稳定性和电磁屏蔽效能。镀铜橡胶由于其优良的可焊耐焊性能、机械性能、电学性能、耐老化性能、电磁屏蔽效能及耐蚀性能等优点,因而在功能型复合材料领域、耐腐蚀材料领域、电导材料领域、生物医学领域和信息材料领域等获得了巨大的应用空间。对于块、板、条、带、棒、管状橡胶成型件,都可以采用此方法。
发明内容
本发明提供了一种橡胶快速化学镀铜的方法,以用于解决以下问题:
(1)、橡胶表面镀铜困难且缓慢;
(2)、通过在橡胶基体中加入导电填料获得的导电橡胶硬度增大,抗拉强度和抗撕裂强度等机械性能变差;
(3)、化学镀铜时,橡胶与镀铜层结合力差,镀铜层起泡、不均匀且质量差,无金属光泽;
(4)、橡胶可焊耐焊性差;
(5)、电镀铜时,橡胶与镀层结合力差,镀铜层不均匀,且无金属光泽;
(6)、镀层会散发有害物质。
本发明的技术方案是:一种橡胶快速化学镀铜的方法,包括如下步骤:(1)打磨;(2)碱洗除油;(3)粗化;(4)酸洗;(5)敏化;(6)活化;(7)镀铜;(8)干燥。
所述方法的具体步骤如下:
(1)、打磨:用木砂纸打磨橡胶表面,去离子水洗;
(2)、碱洗除油:用10~30g/L的氢氧化钠溶液,在温度60~90℃下,浸泡橡胶5~15分钟,去离子水洗;
(3)、粗化:用高锰酸钾,浓度为98%的硫酸配置成水溶液,其中,高锰酸钾浓度为5~25g/L,硫酸浓度为30~50ml/L;在温度30~50℃下,浸泡橡胶5~15分钟,去离子水洗;
(4)、酸洗:用5~20g/L的草酸溶液,在温度20~40℃下,浸泡橡胶1~8分钟,去离子水洗;
(5)、敏化:用10~30g/L的氯化亚锡溶液,在温度25~45℃下,浸泡橡胶10~40分钟,去离子水洗;
(6)、活化:用0.3~1g/L的硝酸银溶液,在温度15~25℃下,浸泡橡胶5~20分钟,去离子水洗;
(7)、镀铜:将上述处理过的橡胶放入镀液中,加热镀铜液到50~80℃,镀铜2~12分钟,镀后用去离子水洗;所述镀铜液中含有主盐、络合剂、还原剂、稳定剂和碱性调节剂,其中,主盐为五水硫酸铜,其含量为五水硫酸铜20~30g/L;络合剂为络合剂EDTA、酒石酸钾钠中的一种或两种,其含量为络合剂EDTA 20~40g/L、酒石酸钾钠5~15g/L;还原剂为甲醛,其含量为7~9ml/L;稳定剂为甲醇,其含量为5~8ml/L;碱性调节剂为氢氧化钠,碱性调节剂调节镀铜液的pH为12~14;
(8)、干燥:放入烘箱在40~90℃下烘干。
本发明使用试剂有:五水硫酸铜、氢氧化钠、高锰酸钾、硫酸、草酸、氯化亚锡、硝酸银、乙二胺四乙酸、酒石酸钾钠、甲醇、甲醛,纯度为化学纯。
所使用的水是利用RO反渗透法制取的去离子水。
本发明的有益效果是:
1、用该方法镀铜,橡胶与镀铜层容易结合,且结合速度快,只需2~12分钟;
2、该方法处理的橡胶上的铜镀层厚度均匀,镀层与橡胶基体结合力强;
3、本工艺镀铜过程中的碱洗除油液、粗化液、酸洗液、敏化液可以反复多次使用,成本低,污染小;
4、用弯曲法测试,裂口处镀层无脱落;用拉伸法测试直至橡胶断裂,拉伸裂口处镀层无脱落;用硬物刮测,直至橡胶破损,镀层无脱落,证明镀层与基体间结合力良好;
5、用锡焊测试,可焊耐焊性良好;
6、抗拉强度和抗撕裂强度等机械性能良好;
7、该方法处理的橡胶镀层无毒,不会对人体产生伤害;
8、该方法制备的镀铜橡胶和导电橡胶相比,不仅成本低,而且硬度小,抗拉强度和断裂伸长率显著增加;
9、该方法制备的镀铜橡胶耐老化,导电性、导热性以及电磁屏蔽效能均良好;
10、该方法制备的镀铜橡胶可广泛应用于军事、生活、工业、工程、医疗、电子以及通信等方面。
具体实施方式
实施例1:一种橡胶快速化学镀铜的方法,橡胶为条状,长不限,宽2mm,高1mm,化学镀体系由橡胶和镀液构成,所述方法依序包括下列步骤:打磨-碱洗除油-粗化-酸洗-敏化-活化-镀铜-干燥;
所述方法的具体步骤如下:
(1)、打磨:用木砂纸打磨橡胶表面,去离子水洗;对橡胶表面进行打磨的木砂纸规格为:W40。
(2)、碱洗除油:用15g/L的氢氧化钠溶液,在温度60℃下,浸泡橡胶15分钟,去离子水洗;
(3)、粗化:用高锰酸钾,浓度为98%的硫酸配置成水溶液,其中,高锰酸钾浓度为10g/L,硫酸浓度为30ml/L;在温度30℃下,浸泡橡胶15分钟,去离子水洗;
(4)、酸洗:用8g/L的草酸溶液,在温度20℃下,浸泡橡胶5分钟,去离子水洗;
(5)、敏化:用10g/L的氯化亚锡溶液,在温度25℃下,浸泡橡胶30分钟,去离子水洗;
(6)、活化:用0.3g/L的硝酸银溶液,在温度15℃下,浸泡橡胶15分钟,去离子水洗;
(7)、镀铜:将上述处理过的橡胶放入镀液中,加热镀铜液到50℃,镀铜10分钟,镀后用去离子水洗;所述镀铜液采用如下配方配置成水溶液:20g/L 五水硫酸铜、20g/L EDTA、5g/L酒石酸钾钠、7ml/L甲醛、5ml/L甲醇,氢氧化钠调节镀铜液的pH为12;
(8)、干燥:放入烘箱在50℃下烘干。
实施例2:一种橡胶快速化学镀铜的方法,橡胶为条状,长不限,宽2mm,高1mm,化学镀体系由橡胶和镀液构成,所述方法依序包括下列步骤:打磨-碱洗除油-粗化-酸洗-敏化-活化-镀铜-干燥;
所述方法的具体步骤如下:
(1)、打磨:用木砂纸打磨橡胶表面,去离子水洗;对橡胶表面进行打磨的木砂纸规格为:W28。
(2)、碱洗除油:用20g/L的氢氧化钠溶液,在温度70℃下,浸泡橡胶10分钟,去离子水洗;
(3)、粗化:用高锰酸钾,浓度为98%的硫酸配置成水溶液,其中,高锰酸钾浓度为15g/L,硫酸浓度为40ml/L;在温度40℃下,浸泡橡胶10分钟,去离子水洗;
(4)、酸洗:用12g/L的草酸溶液,在温度30℃下,浸泡橡胶3分钟,去离子水洗;
(5)、敏化:用20g/L的氯化亚锡溶液,在温度35℃下,浸泡橡胶20分钟,去离子水洗;
(6)、活化:用0.6g/L的硝酸银溶液,在温度20℃下,浸泡橡胶10分钟,去离子水洗;
(7)、镀铜:将上述处理过的橡胶放入镀液中,加热镀铜液到60℃,镀铜8分钟,镀后用去离子水洗;所述镀铜液采用如下配方配置成水溶液:25g/L 五水硫酸铜、30g/L EDTA、10 g/L酒石酸钾钠、8ml/L甲醛、6ml/L甲醇,氢氧化钠调节镀铜液的pH为13;
(8)、干燥:放入烘箱在60℃下烘干。
实施例3:一种橡胶快速化学镀铜的方法,橡胶为条状,长不限,宽2mm,高1mm,化学镀体系由橡胶和镀液构成,所述方法依序包括下列步骤:打磨-碱洗除油-粗化-酸洗-敏化-活化-镀铜-干燥;
所述方法的具体步骤如下:
(1)、打磨:用木砂纸打磨橡胶表面,去离子水洗;对橡胶表面进行打磨的木砂纸规格为:W20。
(2)、碱洗除油:用25g/L的氢氧化钠溶液,在温度80℃下,浸泡橡胶5分钟,去离子水洗;
(3)、粗化:用高锰酸钾,浓度为98%的硫酸配置成水溶液,其中,高锰酸钾浓度为20g/L,硫酸浓度为40ml/L;在温度50℃下,浸泡橡胶5分钟,去离子水洗;
(4)、酸洗:用16g/L的草酸溶液,在温度40℃下,浸泡橡胶2分钟,去离子水洗;
(5)、敏化:用30g/L的氯化亚锡溶液,在温度45℃下,浸泡橡胶10分钟,去离子水洗;
(6)、活化:用0.9g/L的硝酸银溶液,在温度25℃下,浸泡橡胶5分钟,去离子水洗;
(7)、镀铜:将上述处理过的橡胶放入镀液中,加热镀铜液到70℃,镀铜5分钟,镀后用去离子水洗;所述镀铜液采用如下配方配置成水溶液:30g/L 五水硫酸铜、40g/L EDTA、15 g/L酒石酸钾钠、9ml/L甲醛、7ml/L甲醇,氢氧化钠调节镀铜液的pH为14;
(8)、干燥:放入烘箱在70℃下烘干。
实施例4:一种橡胶快速化学镀铜的方法,橡胶为条状,长不限,宽2mm,高1mm,化学镀体系由橡胶和镀液构成,所述方法依序包括下列步骤:打磨-碱洗除油-粗化-酸洗-敏化-活化-镀铜-干燥;
所述方法的具体步骤如下:
(1)、打磨:用木砂纸打磨橡胶表面,去离子水洗;对橡胶表面进行打磨的木砂纸规格为:W40。
(2)、碱洗除油:用30g/L的氢氧化钠溶液,在温度90℃下,浸泡橡胶5分钟,去离子水洗;
(3)、粗化:用高锰酸钾,浓度为98%的硫酸配置成水溶液,其中,高锰酸钾浓度为5g/L,硫酸浓度为50ml/L;在温度50℃下,浸泡橡胶15分钟,去离子水洗;
(4)、酸洗:用5g/L的草酸溶液,在温度40℃下,浸泡橡胶1分钟,去离子水洗;
(5)、敏化:用30g/L的氯化亚锡溶液,在温度45℃下,浸泡橡胶40分钟,去离子水洗;
(6)、活化:用1g/L的硝酸银溶液,在温度25℃下,浸泡橡胶20分钟,去离子水洗;
(7)、镀铜:将上述处理过的橡胶放入镀液中,加热镀铜液到80℃,镀铜2分钟,镀后用去离子水洗;所述镀铜液采用如下配方配置成水溶液:30g/L 五水硫酸铜、40g/L EDTA、15 g/L酒石酸钾钠、9ml/L甲醛、8ml/L甲醇,氢氧化钠调节镀铜液的pH为14;
(8)、干燥:放入烘箱在40℃下烘干。
实施例5:一种橡胶快速化学镀铜的方法,橡胶为条状,长不限,宽2mm,高1mm,化学镀体系由橡胶和镀液构成,所述方法依序包括下列步骤:打磨-碱洗除油-粗化-酸洗-敏化-活化-镀铜-干燥;
所述方法的具体步骤如下:
(1)、打磨:用木砂纸打磨橡胶表面,去离子水洗;对橡胶表面进行打磨的木砂纸规格为:W40。
(2)、碱洗除油:用10g/L的氢氧化钠溶液,在温度90℃下,浸泡橡胶15分钟,去离子水洗;
(3)、粗化:用高锰酸钾,浓度为98%的硫酸配置成水溶液,其中,高锰酸钾浓度为25g/L,硫酸浓度为50ml/L;在温度30℃下,浸泡橡胶5分钟,去离子水洗;
(4)、酸洗:用20g/L的草酸溶液,在温度40℃下,浸泡橡胶8分钟,去离子水洗;
(5)、敏化:用30g/L的氯化亚锡溶液,在温度25℃下,浸泡橡胶40分钟,去离子水洗;
(6)、活化:用1g/L的硝酸银溶液,在温度15℃下,浸泡橡胶18分钟,去离子水洗;
(7)、镀铜:将上述处理过的橡胶放入镀液中,加热镀铜液到50℃,镀铜12分钟,镀后用去离子水洗;所述镀铜液采用如下配方配置成水溶液:20~30g/L 五水硫酸铜、40g/LEDTA、15 g/L酒石酸钾钠、8ml/L甲醛、8ml/L甲醇,氢氧化钠调节镀铜液的pH为12;
(8)、干燥:放入烘箱在90℃下烘干。
实施例6:一种橡胶快速化学镀铜的方法,本实施例与实施例1相同,其中:
所述镀铜液采用如下配方配置成水溶液:20g/L 五水硫酸铜、20g/L EDTA、7ml/L甲醛、5ml/L甲醇,氢氧化钠调节镀铜液的pH为12。
实施例7:一种橡胶快速化学镀铜的方法,本实施例与实施例1相同,其中:
所述镀铜液采用如下配方配置成水溶液:20g/L 五水硫酸铜、5g/L酒石酸钾钠、8ml/L甲醇、7ml/L甲醛,氢氧化钠调节镀铜液的pH为12。
实施例8:一种橡胶快速化学镀铜的方法,本实施例与实施例1相同,其中:所述镀铜液采用如下配方配置成水溶液:30g/L 五水硫酸铜、40g/L EDTA、15g/L酒石酸钾钠、8ml/L甲醇、7ml/L甲醛,氢氧化钠调节镀铜液的pH为12。
上面对本发明的具体实施方式作了详细说明,但是本发明并不限于上述实施方式,在本领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下作出各种变化。
Claims (2)
1.一种橡胶快速化学镀铜的方法,其特征在于:包括如下步骤:(1)打磨;(2)碱洗除油;(3)粗化;(4)酸洗;(5)敏化;(6)活化;(7)镀铜;(8)干燥。
2.根据权利要求1所述的橡胶快速化学镀铜的方法,其特征在于:所述方法的具体步骤如下:
(1)、打磨:用木砂纸打磨橡胶表面,去离子水洗;
(2)、碱洗除油:用10~30g/L的氢氧化钠溶液,在温度60~90℃下,浸泡橡胶5~15分钟,去离子水洗;
(3)、粗化:用高锰酸钾,浓度为98%的硫酸配置成水溶液,其中,高锰酸钾浓度为5~25g/L,硫酸浓度为30~50ml/L;在温度30~50℃下,浸泡橡胶5~15分钟,去离子水洗;
(4)、酸洗:用5~20g/L的草酸溶液,在温度20~40℃下,浸泡橡胶1~8分钟,去离子水洗;
(5)、敏化:用10~30g/L的氯化亚锡溶液,在温度25~45℃下,浸泡橡胶10~40分钟,去离子水洗;
(6)、活化:用0.3~1g/L的硝酸银溶液,在温度15~25℃下,浸泡橡胶5~20分钟,去离子水洗;
(7)、镀铜:将上述处理过的橡胶放入镀液中,加热镀铜液到50~80℃,镀铜2~12分钟,镀后用去离子水洗;所述镀铜液中含有主盐、络合剂、还原剂、稳定剂和碱性调节剂,其中,主盐为五水硫酸铜,其含量为五水硫酸铜20~30g/L;络合剂为络合剂EDTA、酒石酸钾钠中的一种或两种,其含量为络合剂EDTA 20~40g/L、酒石酸钾钠5~15g/L;还原剂为甲醛,其含量为7~9ml/L;稳定剂为甲醇,其含量为5~8ml/L;碱性调节剂为氢氧化钠,碱性调节剂调节镀铜液的pH为12~14;
(8)、干燥:放入烘箱在40~90℃下烘干。
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