CN108588700A - 一种镀铜件无铬钝化液及其钝化处理方法 - Google Patents

一种镀铜件无铬钝化液及其钝化处理方法 Download PDF

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CN108588700A
CN108588700A CN201810834867.5A CN201810834867A CN108588700A CN 108588700 A CN108588700 A CN 108588700A CN 201810834867 A CN201810834867 A CN 201810834867A CN 108588700 A CN108588700 A CN 108588700A
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copper piece
plating copper
chromium
benzotriazole
treatment
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文庆杰
王力强
王利华
杜楠
廖志祥
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Chengdu Aircraft Industrial Group Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/52Treatment of copper or alloys based thereon
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    • C23COATING 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
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82After-treatment
    • C23C22/83Chemical after-treatment

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Abstract

本发明公开了一种镀铜件无铬钝化液及其钝化处理方法,针对六价铬钝化污染严重,现有无铬钝化工艺存在耐体积比1:1硝酸点滴时间较短,钝化液成本较高等不足。本发明中钝化液的组成为:硫酸140‑180ml/L,二水合草酸7‑10g/L,85%磷酸100‑130ml/L,缓蚀剂2‑10g/L,聚乙二醇2‑5g/L,30%过氧化氢7‑10ml/L;封闭液的组成为:缓蚀剂2‑10g/L,无水乙醇4‑10ml/L,十二水磷酸钠2‑6g/L,丙三醇2‑4ml/L,2‑疏基苯并噻唑0.01‑0.1g/L,表面活性剂。表面活性剂可为脂肪醇聚氧乙烯醚0.3‑1g/L或烷基酚聚氧乙烯醚0.5‑3ml/L。缓蚀剂可为苯并三氮唑、N‑甲基苯并三氮唑、N‑乙基苯并三氮唑、N‑丙基苯并三氮唑中的一种。该钝化工艺简单,易于操作,可控性好,适用范围广,且经过该钝化方法处理的试样耐体积比1:1硝酸腐蚀性能优异,符合航空标准HB‑5064。

Description

一种镀铜件无铬钝化液及其钝化处理方法
技术领域
本发明属于金属材料表面技术领域,具体涉及一种镀铜件无铬钝化液及其钝化处理方法。
背景技术
在潮湿的环境中,镀铜件表面易变色、锈蚀,特别是具有严格尺寸要求的零件和机构元件,问题尤为严重。目前,为防止镀铜件表面因氧化造成变色和性能下降,航空制造业普遍采用铬酐及铬酸盐的钝化工艺。其钝化工艺的质量按HB5064进行检测,即用体积比1:1硝酸进行点滴试验,观察气泡形成所需时间。使用铬酐及铬酸盐的钝化处理,虽然镀铜层的耐蚀性得到较大提高,但因钝化工艺含有剧毒的六价铬,严重危害操作人员健康并会产生大的环境污染。而普通的BTA钝化工艺并不耐强氧化性酸的腐蚀,难符合航空制造的要求。
因此,如何消除钝化后废水中的六价铬离子,以及寻找同样耐蚀性能优异的钝化液是镀铜件钝化处理技术需要解决的。
发明内容
本发明的目的是针对上述技术现状,提供一种硝酸的镀铜件无铬钝化液及其钝化处理方法,经该钝化处理液钝化后,用体积比1:1硝酸点滴,耐蚀时间大于8s,符合HB5064标准。并且该钝化液中不含铬酐等重金属、利于环保,钝化工艺操作简单、使用方便,具有良好的市场应用前景。
本发明采用的技术方案为:
一种镀铜件无铬钝化液,配方为:硫酸140-180ml/L,二水合草酸7-10g/L,85%磷酸100-130ml/L,缓蚀剂2-10g/L,聚乙二醇 2-5g/L,30%过氧化氢7-10ml/L。
一种耐硝酸的镀铜件无铬钝化液的钝化处理方法,步骤如下:
1)将洁净的镀铜件置于钝化液中,控制温度为25-35℃,钝化时间10-40s,钝化后镀铜件用去离子水漂洗处理;
2)将过镀铜件置于封闭液中,控制封闭液的温度25-35℃,封闭时间2-10min,封闭后用去离子水漂洗处理;
3)烘干。
所述步骤2)中封闭液配方为:缓蚀剂2-10g/L,无水乙醇4-10ml/L,十二水磷酸钠2-6g/L,丙三醇2-4ml/L,2-疏基苯并噻唑0.01-0.1g/L,表面活性剂。
所述表面活性剂为脂肪醇聚氧乙烯醚0.3-1g/L或烷基酚聚氧乙烯醚0.5-3ml/L。
本申请的无铬钝化液和封闭液中,所述缓蚀剂为苯并三氮唑、N-甲基苯并三氮唑、N-乙基苯并三氮唑、N-丙基苯并三氮唑中的一种或其混合物。
与现有技术相比,本发明提供的对镀铜件的无铬钝化处理方法通过两步处理在镀铜层表面形成多层膜结构,从而实现对镀铜层表面的钝化效果。本产品具有如下优点:
(1)钝化产品耐1:1硝酸点滴时间大于8s;
(2)不含有污染环境及影响人体健康的物质,是一种环保型的钝化处理液,避 免了传统含铬钝化中产生大量六价铬而污染环境及影响人身体健康等问题;
(3)使用方便,操作简单。
因此,本发明提供的一种镀铜件无铬钝化液及其钝化处理方法,其钝化效果符合HB5064要求,且具有操作简单、处理迅速、效果显著、环保健康等优点,能够作为替代铜六价铬钝化剂的新型钝化产品。
具体实施方式
实施例1
一种镀铜件无铬钝化液及,钝化液配方为:98%硫酸150ml/L、85%磷酸110ml/L、缓蚀剂4g/L、聚乙二醇 3.5g/L、30%过氧化氢8ml/L,溶剂为水;封闭液配方为:缓蚀剂4g/L、无水乙醇6ml/L、十二水磷酸钠5g/L、丙三醇4ml/L、脂肪醇聚氧乙烯醚0.9g/L、2-疏基苯并噻唑0.05g/L;
使用上述钝化处理液及封闭液对钝化样品表面进行钝化处理的具体步骤为:
1)将洁净镀铜件样品放入钝化液中,保持温度为30℃,钝化时间为30s,钝化处理后镀铜件用去离子漂洗;
2)将经过步骤1)处理后的镀铜件静置于封闭液中,保持温度为30℃,封闭时间为5min,清水漂洗后样品烘干即可。
按HB5064进行1:1硝酸点滴试验,镀铜件耐蚀时间为9s。
实施例2
一种镀铜件无铬钝化液,钝化液配方为:98%硫酸180ml/L、85%磷酸130ml/L、缓蚀剂5g/L、聚乙二醇 2g/L、30%过氧化氢10ml/L,溶剂为水;封闭液配方为:缓蚀剂3g/L、无水乙醇10ml/L、十二水磷酸钠3g/L、丙三醇3ml/L、脂肪醇聚氧乙烯醚0.3g/L、2-疏基苯并噻唑0.07g/L;
使用上述钝化处理液及封闭液对钝化样品表面进行钝化处理的具体步骤为:
1)将洁净镀铜件样品放入钝化液中,保持温度为30℃,钝化时间为20s,钝化处理后镀铜件用去离子漂洗;
2)将经过步骤1)处理后的镀铜件静置于封闭液中,保持温度为25℃,封闭时间为6min,清水漂洗后样品烘干即可。
按HB5064进行1:1硝酸点滴试验,镀铜件耐蚀时间为9s。
实施例3
一种镀铜件无铬钝化液,钝化液配方为:98%硫酸160ml/L、85%磷酸100ml/L、缓蚀剂3g/L、聚乙二醇 2g/L、30%过氧化氢10ml/L,溶剂为水;封闭液配方为:缓蚀剂4g/L、无水乙醇10ml/L、十二水磷酸钠3g/L、丙三醇3ml/L、辛基酚聚氧乙烯醚1ml/L、2-疏基苯并噻唑0.05g/L;
使用上述钝化处理液及封闭液对钝化样品表面进行钝化处理的具体步骤为:
1)将洁净镀铜件样品放入钝化液中,保持温度为30℃,钝化时间为30s,钝化处理后镀铜件用去离子漂洗;
2)将经过步骤1)处理后的镀铜件静置于封闭液中,保持温度为30℃,封闭时间为5min,清水漂洗后样品烘干即可。
按HB5064进行体积比1:1硝酸点滴试验,镀铜件耐蚀时间为10s。

Claims (6)

1.一种镀铜件无铬钝化液,其特征在于,配方为:硫酸140-180ml/L,二水合草酸7-10g/L,85%磷酸100-130ml/L,缓蚀剂2-10g/L,聚乙二醇 2-5g/L,30%过氧化氢7-10ml/L。
2.一种耐硝酸的镀铜件无铬钝化液的钝化处理方法,其特征在于,步骤如下:
1)将洁净的镀铜件置于钝化液中,控制温度为25-35℃,钝化时间10-40s,钝化后镀铜件用去离子水漂洗处理;
2)将过镀铜件置于封闭液中,控制封闭液的温度25-35℃,封闭时间2-10min,封闭后用去离子水漂洗处理;
3)烘干。
3.根据权利要求2所述的一种镀铜件无铬钝化液的钝化处理方法,其特征在于,所述步骤2)中封闭液配方为:缓蚀剂2-10g/L,无水乙醇4-10ml/L,十二水磷酸钠2-6g/L,丙三醇2-4ml/L,2-疏基苯并噻唑0.01-0.1g/L,表面活性剂。
4.根据权利要求3所述的一种镀铜件无铬钝化液的钝化处理方法,其特征在于,所述表面活性剂为脂肪醇聚氧乙烯醚0.3-1g/L或烷基酚聚氧乙烯醚0.5-3ml/L。
5.根据权利要求1所述的一种镀铜件无铬钝化液的钝化处理方法,其特征在于,所述缓蚀剂为苯并三氮唑、N-甲基苯并三氮唑、N-乙基苯并三氮唑、N-丙基苯并三氮唑中的一种或其混合物。
6.根据权利要求4所述的一种镀铜件无铬钝化液的钝化处理方法,其特征在于,所述缓蚀剂为苯并三氮唑、N-甲基苯并三氮唑、N-乙基苯并三氮唑、N-丙基苯并三氮唑中的一种或其混合物。
CN201810834867.5A 2018-07-26 2018-07-26 一种镀铜件无铬钝化液及其钝化处理方法 Pending CN108588700A (zh)

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