CN1074950A - 镀锌件表面化学着黑剂 - Google Patents

镀锌件表面化学着黑剂 Download PDF

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CN1074950A
CN1074950A CN 92100656 CN92100656A CN1074950A CN 1074950 A CN1074950 A CN 1074950A CN 92100656 CN92100656 CN 92100656 CN 92100656 A CN92100656 A CN 92100656A CN 1074950 A CN1074950 A CN 1074950A
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CN1030778C (zh
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杨国梁
曹刚
郭伟强
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HANZHOU UNIV
Zhejiang University ZJU
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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
    • C23C—COATING 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
    • C23C22/00—Chemical 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
    • C23C22/05—Chemical 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
    • C23C22/06—Chemical 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
    • C23C22/24—Chemical 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 containing hexavalent chromium compounds
    • C23C22/26—Chemical 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 containing hexavalent chromium compounds containing also organic compounds
    • C23C22/27—Acids
    • 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
    • C23C—COATING 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
    • C23C22/00—Chemical 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
    • C23C22/05—Chemical 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
    • C23C22/06—Chemical 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
    • C23C22/24—Chemical 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 containing hexavalent chromium compounds
    • C23C22/33—Chemical 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 containing hexavalent chromium compounds containing also phosphates

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

本发明为一种用于镀锌制件表面化学着黑工艺 的着黑剂。该着黑剂采用Cu-Ag-Cr体系，并辅有 表面活性剂，有机酸或无机酸作为必要的添加成分。 该着黑剂着黑性能稳定，易于操作，抗干扰能力强，工 艺条件易掌握等特点、着黑膜黑度高，牢度好，膜厚、 均匀有光泽，抗蚀性优良。该体系用银量少，成本低， 配制方法易掌握，着黑剂可以再生使用。

Description

本发明涉及金属、非金属制品表面着色防蚀剂，是一种适用于锌制件或金属，非金属表面镀锌制件的化学着黑剂。
常用金属尤其是钢铁，由于大气中氧、水、二氧化碳等化学物质的侵蚀，会有不同程度的腐蚀现象，因此，提高金属防蚀能力，减少损耗，延长使用寿命，对增产节约有重要意义。目前国际上流行黑色精饰，汽车、自行车零件、电讯器材、家用电器、灯具及家具的外表面，经化学着黑处理形成色膜，既能防腐又能改进产品外观，明显地提高了产品的社会竞争能力。
目前化学着黑防蚀方法中“镀锌表面化学着黑”技术是比较理想的方法。对该项技术中所使用的着黑剂，不少国家均有研究。美、英、苏等国采用硫酸铜作为发黑体系（简称铜盐体系），这种体系只能得到黑灰色的钝化膜;日本Udylite和Dipsol公司开发的黑色钝化液均采用磷酸银作为发黑剂（简称银盐体系）。我国武汉材料保护研究所研制的与日本类型相同的ZB-82型镀锌层黑色钝化剂银用量高，原料依赖进口，此外，着黑钝化工艺繁琐，操作条件苛刻。如：不能将硝酸带入钝化液，出光零件必须严格水洗，迅速干燥，水洗和空停时间对钝化膜的质量会产生明显影响。着黑处理温度必须在20-30℃，否则明显影响着黑效果。台湾莱德化工有限公司的BD-200染黑剂对着黑时间要求苛刻，限在20秒以内，否则对着黑效果有严重影响，且抗蚀性能差。
为了稳定着黑工艺，提高着黑工艺中抗干扰能力，降低着黑剂成本，并使黑色钝化膜的性能达到或优于国内外同类产品，本发明提出一种独特的镀锌表面着黑剂。
本着黑剂采用铜-银-铬体系，它的组成为：每升着黑剂中含有（1）铜盐、银盐和铬化合物，其中Cu2+含量1-40克，Ag+含量0.001-8克，Cr（Ⅵ）含量2-80克;（2）表面活性剂1-60克，该表面活性剂必须是非离子表面活性剂，或两性离子表面活性剂，或阴离子表面活性剂，或上述各种表面活性剂的混合物;（3）醋酸和醋酸盐混合物5-120克，磷酸和磷酸盐混合物亦可代替醋酸和醋酸盐，用量为3-80克;（4）硫酸镁或硫酸钠5-25克。
将上述（1）、（2）、（3）、（4）类组分分别用水溶解、稀释，然后将铜盐、银盐、表面活性剂以及酸和盐混合物溶液混和、最后加入铬化合物溶液，并用水定容至1升，搅拌均匀。
本发明方案中所述的铜盐可采用硫酸铜、醋酸铜、氢氧化铜或氧化铜;所用银盐可用硝酸银、铬酸银、重铬酸银或硫酸银;所用铬化合物可采用铬酸、重铬酸、铬酸盐、重铬酸盐或三氧化铬。
本着黑剂适用于锌制件或镀锌制件的表面着黑工艺。镀锌制件可以是金属镀锌制件，亦可以是非金属镀锌制件。
本发明的铜-银-铬体系着黑剂在着黑工艺过程中抗干扰能力强，适用温度范围大，在40--5℃条件下着黑效果不受影响，着黑件浸泡时间为10分钟左右，NO- 3、水洗和空气中放置时间不影响黑膜质量，也易于掌握黑膜厚度。由于本发明的着黑剂用银量少，原料来源立足国内，因此成本较低。
本着黑剂应于密闭阴凉处保存，经多次使用着黑性能减退后，加入适量铬化合物、银盐、铜盐可恢复原着黑性能，经多次再生使用方作废弃。
为了详细说明本着黑剂的配方组分，特举以下实施例。
实施例一，原料采用硫酸铜、硝酸银、重铬酸钠，每升溶液中离子含量为：Cu2+5-10克，Ag+0.001-2克，Cr（Ⅵ）2-10克;采用OP乳化剂1-10克/升;醋酸和醋酸盐混合物5-20克/升;硫酸镁5-10克/升。上述各组分用蒸馏水溶解稀释备用，先将硫酸铜、硝酸银、OP乳化剂、醋酸和醋酸盐混合物、硫酸镁5种溶液混合稀释，搅拌均匀。再将重铬酸钠溶液并入，再用蒸馏水定容至1升，搅拌均匀。即可用于镀锌件的浸泡着黑。
实施例二，原料采用醋酸铜、铬酸银、三氧化铬、阴离子表面活性剂，醋酸和醋酸盐混合物、硫酸钠。每升着黑剂中上述物质含量为：Cu2+10-20克，Ag+5-8克，Cr（Ⅵ）70克，阴离子表面活性剂30-40克，醋酸和醋酸盐混合物80克，硫酸钠15克。
实施例三，每升着黑剂中各组分含量为：氢氧化铜（含Cu2+40克），硫酸银（含Ag+8克）、重铬酸（含Cr（Ⅵ）80克），非离子表面活性剂60克，磷酸和磷酸盐混合物60克，硫酸镁或硫酸钠11-25克，用水溶解稀释各组分并定容至1升。
实施例四，每升着黑剂中各组分含量为：氧化铜（含Cu2+1-40克），硫酸银（含Ag+0.001-8克），重铬酸盐（含Cr（Ⅵ）2-80克），两性离子表面活性剂1-60克，磷酸和磷酸盐混合物总量30-45克，硫酸镁5-25克，用水溶解并稀释各组分，用水定溶至1升。以上二、三、四例配制方法与实施例一相同。
实施例五，原料采用硫酸铜、硝酸银、三氧化铬、阴离子表面活性剂和非离子表面活性剂混合物、醋酸和醋酸盐混合物，硫酸镁。上述各组分含量分别为：硫酸铜含Cu2+5-30克/升，硝酸银含Ag+0.001-2克/升，三氧化铬含Cr（Ⅵ）5-40克/升，阴离子和非离子表面活性剂5-45克/升，醋酸和醋酸盐混合物：5-100克/升，硫酸镁1-15克/升。配制方法与实施例一相同。

Claims (3)

1、一种用于镀锌制件表面化学着黑的着黑剂，其特征在于，该着黑剂以铜盐、银盐、铬化合物为主要成分，每升着黑剂中含Cu2+1-40克，Ag+0.001-8克，Cr(VI)2-80克。
2、根据权利要求1所述镀锌制件表面着黑剂，其特征在于，每升着黑剂中含有（1）表面活性剂1-60克，该表面活性剂必须是非离子表面活性剂，或两性离子表面活性剂，或阴离子表面活性剂，或上述各种表面活性剂的混合物;（2）醋酸和醋酸盐混合物5-120克，或磷酸和磷酸盐混合物3-80克;（3）硫酸镁或硫酸钠5-25克。
1、根据权利要求1或2所述镀锌制件表面着色剂，其特征在于它的配制方法是：先将各组分用水溶解、然后将铜盐、银盐、表面活性剂、醋酸和醋酸盐混合物或磷酸和磷酸盐混合物，硫酸镁或硫酸钠溶液混合，稀释，最后加入铬化合物溶液，并用水定容至1升，搅拌均匀。
CN 92100656 1992-01-28 1992-01-28 镀锌件表面化学着黑剂 Expired - Fee Related CN1030778C (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111101122A (zh) * 2020-02-19 2020-05-05 广州三孚新材料科技股份有限公司 一种电镀锌黑色钝化液及其制备方法
CN115386868A (zh) * 2022-09-22 2022-11-25 贵州航天精工制造有限公司 一种镀锌黑色钝化溶液及其制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111101122A (zh) * 2020-02-19 2020-05-05 广州三孚新材料科技股份有限公司 一种电镀锌黑色钝化液及其制备方法
CN115386868A (zh) * 2022-09-22 2022-11-25 贵州航天精工制造有限公司 一种镀锌黑色钝化溶液及其制备方法

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