CN1076225A - 黑色磷化液 - Google Patents

黑色磷化液 Download PDF

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Publication number
CN1076225A
CN1076225A CN 92107316 CN92107316A CN1076225A CN 1076225 A CN1076225 A CN 1076225A CN 92107316 CN92107316 CN 92107316 CN 92107316 A CN92107316 A CN 92107316A CN 1076225 A CN1076225 A CN 1076225A
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Prior art keywords
liquid
phosphatization
phosphating solution
black phosphating
giving
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CN 92107316
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王学渊
赵玉萤
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Individual
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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
    • C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/50—Treatment of iron or alloys based thereon
    • 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
    • C23C22/78—Pretreatment of the material to be coated

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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

本发明属于金属表面化学处理用的磷化液，它由 预处理黑化液和磷化液二部分组成。预处理黑化液 成分及浓度为：Na2S2O3·5H2O25—35g/l；HCl (d1.16-1.18)17—22ml/l；余水。磷化液为Zn2+17 —20g/l；NO3 -12—16g/l；P2O515—19g/l；Fe2+≤ 1g/l；余水。若预处理黑化液添加Bi3+＜0.5g/l，磷 化液添加Mn2+≤5g/l，作为促进剂则效果更佳。
本发明的黑色磷化液不含稀有重金属，成本较 低，使用方便，磷化膜为深黑色，耐锈蚀及装饰性能良 好。

Description

本发明属于金属表面化学处理用的磷化液。
金属表面黑色磷化处理是提高金属抗锈蚀性能和装饰性能的有效方法。我国国防工业出版社编写的《电镀手册》（一九八八年修订本）介绍的黑色磷化溶液配方复杂，磷化膜为灰黑色，抗锈蚀性能较差。英国专利说明书1214544介绍的黑色磷化技术，工件先经过含Bi、Sb、Te等氧化物的酸性溶液予浸处理，再进行专用含镍锌盐溶液磷化，上述磷化技术工艺复杂，磷化溶液含稀有重金属、价格昂贵，结晶粗糙，黑色偏低，装饰效果较差。
本发明的目的是提供一种不含稀有重金属，成本较低，使用方便，磷化膜质量好，黑色度深，耐锈蚀，装饰性能好的黑色磷化液。
本发明的黑色磷化液由予处理黑化液和磷化液二部份组成，予处理黑化液成份及浓度为：
Na2S2O3·5H2O 25-35g/L
HCl（d1.16-1.18）    17-22ml/L
上述予处理黑化液利用化学氧化-还原着色原理将FeS微粒沉积于工件基体上，在工件表面形成黑色薄膜。
本发明的予处理黑化液制备方法：先将Na2S2O3溶解于水，再加入HCl，搅拌后，液体呈浅黄色，取样测定酸度8-12点，正常使用酸度5-10点（移植游离酸度测定法）。
上述予处理黑化液还可用HNO3替代HCl，其组成为：Na2S2O3·5H2O 20-30g/L;HNO3（d1.40）15-20ml/L;余水。配液中若添加Bi3+＜0.5g/L，可进一步提高黑化程度。
本发明的予处理黑化液，也可先将Na2S2O3溶于水配成饱和溶液，使用时加入适量HCl或HNO3再加水混和配用。
室温下，经热处理淬火-回火的工件在本发明的予处理黑化液中浸渍时间为2-3分钟，未经热处理的工件浸渍时间为5-6分钟。浸渍后工件表面FeS微粒薄膜呈深黑色。
工件经黑化予浸处理水洗后，再进行85-98℃浸渍磷化10-15分钟，磷化规范可采用以磷酸二氢锌，或磷酸二氢锰为主要成份的防锈磷化。
本发明的第二个组成部份，磷化液的成份及浓度为：
Zn2+17-20g/L
NO- 312-16g/L
P2O515-19g/L
Fe2+≤1g/L
上述磷化液的游离酸度为5.5-8点，总酸度为45-62点。溶液内另可添加Mn2+≤5g/L作为促进剂。
本发明的黑色磷化液不含稀有重金属，成本较低，使用简便。经本发明的黑色磷化液磷化的工件，磷化膜色泽深、无偏色、浮色，脱色及色差等缺陷、固色效果好、防腐装饰性能都优于一般磷化液。
本发明的实施例一：
1、予处理黑化配方为：Na2S2O3·5H2O25g/L;HCld1.16 20mL/L;余水配置液。酸度5-10点。
2、磷化液配方为：ZnO33g/L;H3PO4d1.68 20ml/L;HNO3d1.40 20ml/L，余水。游离酸度7点，总酸度54点。
20＃钢墙板螺钉经渗碳淬火处理。先经去油、去锈清洁处理，再在以上予处理黑化液中浸渍2分钟（室温），经水洗后浸渍于90-96℃磷化液中15分钟，膜深黑，再经水洗，甩干浸防锈油（105-110℃）膜黑亮。
上述磷化后的墙板螺钉按GB6807-86标准进行点蚀试验，钉R处膜变（红）色时间最短4.5分钟，比一般磷化耐蚀0.5-1分钟以上。
磷化膜上油干燥后，按GB6458-86标准进行盐雾试验（5%NaCl）48小时未出现锈蚀斑。
实施例2：
予处理黑化液配方为：Na2S2O3·5H2O 32g/L，HCl d1.16 20ml/L余水配液，酸度6-10点，工件为08F钢元钉，室温浸渍5分钟，膜黑，水洗磷化等同实施例1，磷化膜深黑。按GB6807-86标准点蚀试验，膜变色时间不少于5.0分钟。

Claims (5)

1、一种黑色磷化液，其特征在于由予处理黑化液和磷化液二部份组成，其成份及浓度为：
1)、予处理黑化液：
Na2S2O3·5H2O 25-35g/L
HCL(d1.16-1.18)  17-22ml/L
其余为水
2)、磷化液：
Zn2+17-20g/L
NO- 312-16g/L
P2O515-19g/L
Fe2+≤1g/L
其余为水。
2、按权利要求1所述黑色磷化液，其特征在于予处理黑化液酸度为5-10点（移植磷化液游离酸度测定法），室温浸渍。
3、按权利要求1所述的黑色磷化液，其特征在于磷化液游离酸度为5.5-8点，总酸度45-62点，磷化温度85℃-98℃。
4、按权利要求1所述黑色磷化液，其特征在于予处理黑化液配方中的HCl可用HNO3（d1.40）代替。
5、按权利要求1所述的黑色磷化液，其特征在于予处理黑化液可添加Bi3+＜0.5g/L，磷化液可添加Mn2+≤5g/L，作为促进剂。
CN 92107316 1992-03-11 1992-03-11 黑色磷化液 Pending CN1076225A (zh)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101200799B (zh) * 2006-12-15 2012-05-23 西安工业大学 钢铁表面中低温高耐蚀黑色磷化液
CN102817022A (zh) * 2012-07-28 2012-12-12 蚌埠市福沃特车轮制造科技有限公司 一种含有硫代硫酸钠的常温磷化液
CN104328427A (zh) * 2014-11-05 2015-02-04 衡阳市金化科技有限公司 一种钢铁发黑剂

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101200799B (zh) * 2006-12-15 2012-05-23 西安工业大学 钢铁表面中低温高耐蚀黑色磷化液
CN102817022A (zh) * 2012-07-28 2012-12-12 蚌埠市福沃特车轮制造科技有限公司 一种含有硫代硫酸钠的常温磷化液
CN104328427A (zh) * 2014-11-05 2015-02-04 衡阳市金化科技有限公司 一种钢铁发黑剂

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