CN113151811A - 一种非钯活化镀镍液、镀镍方法 - Google Patents
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 238000007747 plating Methods 0.000 title claims abstract description 134
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 90
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052802 copper Inorganic materials 0.000 claims abstract description 36
- 239000010949 copper Substances 0.000 claims abstract description 36
- -1 palladium activated nickel Chemical class 0.000 claims abstract description 31
- 230000004913 activation Effects 0.000 claims abstract description 17
- 229920003023 plastic Polymers 0.000 claims abstract description 15
- 150000002815 nickel Chemical class 0.000 claims abstract description 10
- 239000000919 ceramic Substances 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 6
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001509 sodium citrate Substances 0.000 claims abstract description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 6
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims abstract description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 21
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 206010070834 Sensitisation Diseases 0.000 claims description 6
- 230000008313 sensitization Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical group [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 229940074404 sodium succinate Drugs 0.000 claims description 3
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical group [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 12
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000001994 activation Methods 0.000 description 14
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012190 activator Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000003814 drug Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 229940053662 nickel sulfate Drugs 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 2
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2073—Multistep pretreatment
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
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Abstract
本发明公开了一种非钯活化镀镍液、镀镍方法。每1L所述非钯活化镀镍液包含如下质量组分:镍盐15~70g;焦磷酸钾5~100g;柠檬酸钠5~50g;EDTA 5~50g;促进剂2~8g;二甲基胺硼烷2~8g;稳定剂3~15mg;表面活性剂2~5mg。将待镀件放入到本发明所述的非钯活化镀镍液中,调节pH为9~11即可进行镀镍。所述的活性镀镍液能够直接在铜表面镀一层活性镍而不需要经过钯活化,显著节约了成本;对塑料或陶瓷表面,活化镀镍液能够和专利CN 111763930A公开的活化剂反应,从而在待镀件表面预镀一层活性镍,进一步进行化学镀镍,在摒除了钯活化的同时解决了铜表面不能直接化学镀镍的问题。
Description
技术领域
本发明属于表面处理技术领域,具体涉及一种非钯活化镀镍液、镀镍方法。
背景技术
一直以来,工业生产上,塑料表面镀镍普遍采用锡敏化、钯活化的“二步法”或胶体钯活化的“一步法”使经过除油、粗化的塑料件表面预镀一层镍,再根据需要的厚度继续化学镀镍,以达到工艺要求。而在铜表面镀镍同样需要钯活化处理才能化学镀镍。
随着工业化的发展,钯的使用量大幅增加,而钯的价格昂贵,一路走高,并且在工业生产上,虽然钯活化工艺已经很普通,但是在实际操作中,存在一定的缺陷,主要体现在两方面:一是铜基工件水洗不充分就会把钯带入化学镍药水中,使后者催化分解而无法使用;二是在线路镀工艺上,例如LDS天线镀铜后活化镀镍,水洗时间过长就会造成镀件缺镀,水洗时间不够没线路的地方溢镀,累计带入镍药水中的钯会催化镍剧烈反应,药水报废。专利CN 111763930A公开了一种非钯活化镀铜工艺及其敏化剂、活化剂,所述的敏化剂和活化剂配合使用能够替代现有的钯活化,从而有效的降低了镀铜的成本,但是,对于塑料材质来说,该专利所述的活化剂仅仅对镀铜有效果,所述的活化剂不能催化镍离子的还原反应,因此,使用该专利所述的活化剂不能直接采用化学镀镍的方式镀镍。
发明内容
为了降低现有铜表面镀镍的成本、解决塑料(或陶瓷)表面无法直接化学镀镍的问题,本发明的目的在于提供一种非钯活化镀镍液、镀镍方法。
本发明的目的通过以下技术方案得到:
一种非钯活化镀镍液,每1L所述非钯活化镀镍液包含如下质量组分:镍盐15~70g;焦磷酸钾5~100g;柠檬酸钠5~50g;EDTA 5~50g;促进剂2~8g;二甲基胺硼烷2~8g;稳定剂3~15mg;表面活性剂2~5mg;溶剂为水。
优选的,所述每1L非钯活化镀镍液包含如下质量组分:镍盐25~70g;焦磷酸钾35~100g;柠檬酸钠20~50g;EDTA 15~50g;促进剂2.5~8g;二甲基胺硼烷2.5~8g;稳定剂5~15mg;表面活性剂2~5mg;溶剂为水。
优选的,所述稳定剂为硫脲和碘化钾。
优选的,每1L非钯活化镀镍液包含:所述硫脲2~10mg、所述碘化钾1~5mg。
优选的,所述表面活性剂为异构十三醇聚氧乙烯醚磷酸酯。
优选的,所述促进剂为丁二酸钠。
优选的,所述镍盐为硫酸镍和/或醋酸镍;更优选的,所述硫酸镍的来源为六水硫酸镍。
一种镀镍方法,包括如下步骤:
将待镀件放入到本发明所述的非钯活化镀镍液中,调节pH为9~11进行镀镍;所述待镀件为塑料、陶瓷、和具有铜表面的器件中的一种;当所述待镀件为塑料或陶瓷时,在放入所述非钯活化镀镍液之前需要进行敏化、活化处理,所述敏化、活化处理的具体方法参见专利CN 111763930 A记载的内容。
优选的,所述镀镍的温度为40~60℃。
优选的,所述镀镍的时间为2~10min。
优选的,所述具有铜表面的器件为LDS天线镀铜件或五金铜件。
与现有技术相比,本发明具有以下的有益效果和进步:
对于塑料或陶瓷待镀件而言,本发明所述的活化镀镍液能够和专利CN111763930A公开的活化剂反应,从而在待镀件表面预镀一层活性镍,进一步进行化学镀镍,以实现工艺要求,解决现有镀镍工艺中,经专利CN 111763930A中的活化剂处理后的待镀件表面不能直接化学镀镍的问题。
对于具有铜表面的待镀件而言,应用本发明所述的活性镀镍液能够直接在铜表面镀一层活性镍,再进行传统的化学镀镍,以实现工艺要求。解决了现有技术中钯活化镀镍造成的成本较高的问题,大大节约了成本。
附图说明
图1为实施例1所述的ABS塑料上镀镍之前的实物照片图。
图2为实施例1所述的ABS塑料上镀镍后的实物照片图。
图3为对比例1所述的ABS塑料上镀镍后的实物照片图。
图4为实施例2所述的LDS天线镀铜未镀镍之前的实物照片图。
图5对比例3所述的LDS天线镀铜后镀镍的实物照片图。
图6实施例2所述的LDS天线镀铜后镀镍的实物照片图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
实施例所述硫酸镍的来源为六水硫酸镍。
实施例1
ABS塑料上镀镍
一种非钯活化镀镍液,所述每1L非钯活化镀镍液包含如下质量组分:硫酸镍25g;焦磷酸钾35g;柠檬酸钠20g;EDTA 15g;丁二酸钠2.5g;二甲基胺硼烷2.5g;硫脲2mg;碘化钾3mg;异构十三醇聚氧乙烯醚磷酸酯2mg;溶剂为去离子水。
镀镍方法具体为:ABS塑料经过除油-粗化-敏化-活化处理后,再放入所述非钯活化镀镍液中,采用硫酸溶液和氨水调节体系的pH为11,在60℃下静置2min,即在ABS塑料表面镀了一层致密平整的镍。后续可根据需要进行化学镀镍。
上述除油-粗化-敏化-活化处理的具体方法参见专利CN 111763930 A记载的内容。
实施例2
LDS天线镀铜后镀镍
所述的非钯活化镀镍液同实施例1。
镀镍方法具体为:LDS天线经过除油-触发铜-厚铜处理后,再放入所述的非钯活化镀镍液中,采用硫酸溶液和氨水调节体系的pH为9,在50℃下静置5min,即在铜线路表面镀了一层致密平整的镍。后续可根据需要进行化学镀镍。
实施例3
五金铜件上镀镍
所述的非钯活化镀镍液同实施例1。
镀镍方法具体为:将五金铜件除油后放入所述的非钯活化镀镍液中,采用硫酸溶液和氨水调节体系的pH为9,在50℃下静置5min,即在五金铜件表面镀了一层致密平整的镍。后续可根据需要进行化学镀镍。
实施例4
PPS塑料上镀镍
所述的非钯活化镀镍液同实施例1。
镀镍方法,具体为:PPS塑料经过除油-粗化-敏化-活化处理后,再放入所述的非钯活化镀镍液中,采用硫酸溶液和氨水提节体系的pH为9,在50℃下静置3min,即在PPS塑料表面镀了一层致密平整的镍。后续可根据需要进行化学镀镍。
上述除油-粗化-敏化-活化处理的具体方法参见专利CN 111763930 A记载的内容。
对比例1
ABS塑料上镀镍
所述镀镍液的组成中硫脲为11mg,碘化钾为6mg,其他操作同实施例1。
镀镍方法同实施例1,结果显示ABS塑料表面缺镀。
对比例2
ABS塑料上镀镍
所述镀镍液的组成中硫脲为1mg,碘化钾为0.5mg,其他操作同实施例1。
镀镍方法同实施例1,结果显示ABS塑料表面上镀速度快,镀层表面粗糙。其原因为所述镀镍液容易起渣沉淀,药水活性强,稳定性差。
对比例3
LDS天线镀铜后镀镍
所述镀镍液的组成同实施例2。
镀镍方法中的pH为8,其他操作同实施例2,结果显示LDS天线镀铜后的表面缺镀,其实物照片图见图5,图中箭头A标出的地方即为缺镀的部位。
对比例4
LDS天线镀铜后镀镍
所述镀镍液的组成同实施例2。
镀镍方法中的pH为12,其他操作同实施例2,结果显示LDS天线镀铜后的表面上镀速度快,镀层表面粗糙。其原因是镀镍液容易起渣沉淀,药水活性强,稳定性差。
对比例5
五金铜件上镀镍
所述镀镍液的组成同实施例3。
镀铜方法中的pH为8,其他操作同实施例3,结果显示五金铜件表面缺镀。
对比例6
五金铜件上镀镍
所述镀镍液的组成同实施例3。
镀铜方法中的pH为12,其他操作同实施例3,结果显示五金铜件表面上镀速度快,镀层表面粗糙。其原因是镀镍液容易起渣沉淀,药水活性强,稳定性差。
对比图1~3看以得出,采用本发明所述的非钯活化镀镍液能够在塑料上镀覆一层活性镍,镀层均匀平整,没有缺镀的情况,而采用不在本发明所述配比的镀镍液时,则待镀件的周边缺镀,镀不上镍(见图3);对比图4~6看以得出:采用本发明所述的非钯活化镀镍液能够在铜表面上镀覆一层活性镍,镀层均匀平整,没有缺镀的情况,而采用不在本发明所述配比的镀镍液时,则待镀件上有的部位镀不上镍,见图5中箭头A所指示的部位。
以上所述本发明的具体实施方式,并不构成对本发明保护范围的限定。任何根据本发明的技术构思所做出的各种其他相应的改变与变形,均应包含在本发明权利要求的保护范围内。
Claims (10)
1.一种非钯活化镀镍液,其特征在于,每1L所述非钯活化镀镍液包含如下质量组分:镍盐15~70g;焦磷酸钾5~100g;柠檬酸钠5~50g;EDTA 5~50g;促进剂2~8g;二甲基胺硼烷2~8g;稳定剂3~15mg;表面活性剂2~5mg;溶剂为水。
2.根据权利要求1所述一种非钯活化镀镍液,其特征在于,每1L所述非钯活化镀镍液包含如下质量组分:镍盐25~70g;焦磷酸钾35~100g;柠檬酸钠20~50g;EDTA 15~50g;促进剂2.5~8g;二甲基胺硼烷2.5~8g;稳定剂5~15mg;表面活性剂2~5mg;溶剂为水。
3.根据权利要求1或2所述一种非钯活化镀镍液,其特征在于,所述稳定剂为硫脲和碘化钾。
4.根据权利要求3所述一种非钯活化镀镍液,其特征在于,每1L所述非钯活化镀镍液中,所述硫脲为2~10mg,所述碘化钾为1~5mg。
5.根据权利要求1或2所述一种非钯活化镀镍液,其特征在于,所述表面活性剂为异构十三醇聚氧乙烯醚磷酸酯;所述促进剂为丁二酸钠。
6.根据权利要求1或2所述一种非钯活化镀镍液,其特征在于,所述镍盐为硫酸镍和/或醋酸镍。
7.一种利用权利要求1~6任一项所述非钯活化镀镍液镀镍的方法,其特征在于,包括如下步骤:
将待镀件放入到所述非钯活化镀镍液中,调节体系pH为9~11进行镀镍;所述待镀件为塑料、陶瓷、和具有铜表面的器件中的一种;当所述待镀件为塑料或陶瓷时,在放入所述非钯活化镀镍液之前需要进行敏化、活化处理。
8.根据权利要求7所述的镀镍方法,其特征在于,所述镀镍的温度为40~60℃。
9.根据权利要求7所述的镀镍方法,其特征在于,所述镀镍的时间为2~10min。
10.根据权利要求7所述的镀镍方法,其特征在于,所述具有铜表面的器件为LDS天线镀铜件或五金铜件。
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