CN105350005A - Compound acid washing liquid containing passivation agent, and preparation method thereof - Google Patents

Compound acid washing liquid containing passivation agent, and preparation method thereof Download PDF

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Publication number
CN105350005A
CN105350005A CN201410411056.6A CN201410411056A CN105350005A CN 105350005 A CN105350005 A CN 105350005A CN 201410411056 A CN201410411056 A CN 201410411056A CN 105350005 A CN105350005 A CN 105350005A
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China
Prior art keywords
water
copper
acid
passivator
bucket
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CN201410411056.6A
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Chinese (zh)
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CN105350005B (en
Inventor
李艳荣
朱立忠
李忠建
陆建国
朱伟
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Research Institute of Nanjing Chemical Industry Group Co Ltd
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Abstract

The present invention belongs to the field of pure copper or copper alloy cleaning, and relates to an acid washing liquid obtained by adding other substances to a sulfuric acid solution to compound and having a passivation effect. According to the present invention, contaminated pure copper or copper alloy is washed, such that the pure copper or copper alloy restores the metal luster, is not damaged, and form a layer of a dense passivation film on the surface of the pure copper or copper alloy so as to maintain brightness and beautiful look and so as not to produce darkening after being stored for a long time; and the acid mist is less so as to easily achieve environmental protection and operator body health, the acid washing amount is high, and the acid treatment cost is low.

Description

A kind of composite pickle solution containing passivator and preparation method thereof
Technical field
The invention belongs to Copper and its alloy cleaning technique field, relate to a kind of pickle solution passivator that copper and various copper-bearing alloy are cleaned.
Background technology
Traditional copper and alloy acid wash passivation thereof adopt high nitric acid acidwashing, middle chromium passivating technique, in acid wash passivation process, temperature rise is very fast, also larger to the etching extent of part, especially those local precision work is easily made, rest part has the machined surface of the part of severe oxidation skin or carbon to occur excessive erosion phenomenon, cause batch waste product, produce a large amount of NOx in acid cleaning process simultaneously, seriously contaminate environment and infringement workman healthy, in addition, because chromic anhydride content is higher in passivating solution, cause production cost also high, and affect the surface luster of part after passivation, the contaminated wastewater environment of discharging.
Present pickle solution tend to add in acid different materials playing stable acid solution, promote cleaning, slowly-releasing copper and copper-bearing alloy, increase glossiness effect.
Report about the mordant additive of this type of Copper and its alloy is less.
Document " application of Copper and its alloy acid wash passivation novel process " describes pre-pickling, pickling, passivation technology to the cleaning of Copper and its alloy.Although it is better to introduce effect in literary composition, containing HNO in pickle solution 3, use procedure can send a large amount of tobacco, contaminate environment, contains Cr simultaneously, all bring harm to operator or to environment in passivator.
Through electrochemical deoiling, salt acid rinse, chemical bright dipping several flow process, Copper and its alloy is cleaned in document " novel Copper and its alloy bright dipped finish technique ", although avoid disadvantage described in above-mentioned document, but technical process is complicated, and use hydrochloric acid, acid mist is comparatively large, to operator and environment unfavorable; Chemical bright dipping formula relates to multiple acids in addition, also more complicated.
Summary of the invention
The object of the invention is proposition a kind of for pickle solution cleaning Copper and its alloy and preparation method thereof.
Technical solution of the present invention is: containing the composite pickle solution of passivator, by sulfuric acid be main component, Mixed Surfactant System, water forms, its content is respectively: H 2sO 4(ρ: 1.84 × 10 3g/L) 12 ~ 500mL/L, Mixed Surfactant System are 0.7 ~ 19.0g/L, water is surplus.
Described Mixed Surfactant System is made up of urotropine, thionamic acid, thionamic acid sodium, glycerine, alkanes tensio-active agent.
Described Mixed Surfactant System comprises urotropine 0.3 ~ 10.0g/L, thionamic acid 0.15 ~ 3.0g/L, thionamic acid sodium 0.1 ~ 2.0g/L, glycerine 0.1 ~ 2.0g/L and one or more mixtures of alkanes tensio-active agent 0.05 ~ 2.0g/L composition.A kind of typical composition comprises urotropine 1.0g/L, thionamic acid 0.2g/L, thionamic acid sodium 0.2g/L, glycerine 0.2g/L, one or more mixing compositions of alkanes tensio-active agent 0.05g/L.
The present invention is containing the preparation method of Mixed Surfactant System pickle solution: get 5 ~ 30L water and be placed in bucket, get 98% vitriol oil 12 ~ 500mL/L and slowly add along bucket wall, and constantly stir; Be join in bucket after 0.7 ~ 19.0g/L passivator dissolves in water by content, stir, be diluted with water to desired concn.
Usually, the optimal technical scheme of preparation method of the present invention is: in bucket, add 2.0L water, is slowly added by 98% vitriol oil 1.5L, and constantly stir along bucket wall; Added after water dissolution in bucket by 47.0g passivator, stir, slowly add water 4.0L.
Soaked by the pickle solution that the copper corroded or copper alloy are placed in above-mentioned preparation, depending on copper or copper alloy surface situation and soak 1 ~ 15 minute, pull out to surface-brightening, clear water washes down.
The present invention is applicable to the acid wash passivation of various copper or copper alloy, the Copper and its alloy of original blackout obfuscation can be made within the shorter time (1 ~ 15 minute) to wash to obtain surface-brightening, in metal true qualities, and surfaces externally and internally is equally bright attractive in appearance, and copper or copper alloy itself without any damage, and the passive film of one deck densification is formed at copper or copper alloy surface, long-term storage still can keep light attractive in appearance, not rubescent, not dimmed in atmosphere.Another feature of the present invention there is not acid mist, is conducive to environmental protection and operator are healthy, and pickling amount is large, and acid treatment cost is low, and can effectively shorten pickling frequency, reduces acid consumption.
Copper after process of the present invention or copper alloy surface light attractive in appearance, uniform color.And form passivation thin layer because of copper or copper alloy surface, therefore not easily rust corrosion again.Cost of the present invention is not high, and treatment effect is obviously better than conventional treatment process.
Embodiment
Below by way of specific embodiment, the inventive method is described in detail.
Embodiment 1: sample preparation
Pickle solution containing passivator used in embodiment, adopts and prepares with the following method: get 30.0L water and be placed in bucket, get 98% vitriol oil 0.5L and slowly add along bucket wall, and constantly stir below; Be join in bucket after 28.0g passivator (comprising urotropine 12.0g, thionamic acid 6.0g, thionamic acid sodium 4.0g, glycerine 4.0g, one or more mixing compositions of alkanes tensio-active agent 2.0g) dissolves in water by content, stir, be diluted with water to 40.0L.Preparation completes, stand-by.
Embodiment 2: sample preparation
Pickle solution containing passivator used in embodiment, adopts and prepares with the following method: get 15.0L water and be placed in bucket, get 98% vitriol oil 20.0L and slowly add along bucket wall, and constantly stir below; Be join in bucket after 760.0g passivator (comprising urotropine 400.0g, thionamic acid 120.0g, thionamic acid sodium 80.0g/L, glycerine 80.0g, one or more mixing compositions of alkanes tensio-active agent 80.0g) dissolves in water by content, stir, be diluted with water to 40.0L.Preparation completes, stand-by.
Embodiment 3: sample preparation
Pickle solution containing passivator used in embodiment, adopts and prepares with the following method: get 20.0L water and be placed in bucket, get 98% vitriol oil 12.0L and slowly add along bucket wall, and constantly stir below; Be join in bucket after 470.0g passivator (comprising urotropine 210.0g, thionamic acid 100.0g, thionamic acid sodium 60.0g/L, glycerine 50.0g, one or more mixing compositions of alkanes tensio-active agent 50.0g) dissolves in water by content, stir, be diluted with water to 40.0L.Preparation completes, stand-by.
Embodiment 4: application
Get certain company H85 type copper alloy carry out acid wash passivation and measure effect.
1, the mensuration of sour appearance after laundering
The H85 type copper alloy of the surface dulling through long storage time is placed in this product soak, after soaking 2min, depending on pulling out after copper alloy surface light, clean residual acid with clear water, then in 50 ° of C3.5% (wt) NaCl alkali lye, clean one time to neutralize residual acid, then clean alkali lye with clear water, last 2 ~ the 3min that soaks in about 80 ° of C hot water takes out, visual copper alloy surface light is attractive in appearance, uniform color, in faint yellow.
2, the mensuration of passivation ability
The copper alloy of pickling is placed in the 3.5%NaCl aqueous solution, and take out after at room temperature soaking 20h and check, copper alloy surface light is without obvious rubescent blackout.
Embodiment 5: application
The T2 copper material getting certain company carries out acid wash passivation and measures effect.
1, the mensuration of sour appearance after laundering
The above-mentioned copper material of surface dulling is placed in this product soak, after soaking 2min, depending on pulling out after copper material material surface-brightening, clean residual acid with clear water, then in 50 ° of C3.5% (wt) NaCl alkali lye, clean one time to neutralize residual acid, then clean alkali lye with clear water, last 2 ~ the 3min that soaks in about 80 ° of C hot water takes out, visual copper material surface-brightening is attractive in appearance, and uniform color, in red-purple.
2, the mensuration of passivation ability
The copper material of pickling is placed in the 3.5%NaCl aqueous solution, and take out after at room temperature soaking 20h and check, copper material surface-brightening is without obvious variable color.
Embodiment 6: application
Get the unknown model copper alloy of certain company carry out acid wash passivation and measure effect.
1, the mensuration of sour appearance after laundering
The copper alloy of the surface dulling through long storage time is placed in this product soak, after soaking 20min, depending on pulling out after copper alloy surface light, clean residual acid with clear water, then in 50 ° of C3.5% (wt) NaCl alkali lye, clean one time to neutralize residual acid, then clean alkali lye with clear water, last 2 ~ the 3min that soaks in about 80 ° of C hot water takes out, visual copper alloy surface light is attractive in appearance, uniform color, in faint yellow.
2, the mensuration of passivation ability
The copper alloy of pickling is placed in the 3.5%NaCl aqueous solution, and take out after at room temperature soaking 20h and check, copper alloy surface light is without obvious variable color.

Claims (4)

1., containing a composite pickle solution for passivator, it is characterized in that being made up of sulfuric acid, Mixed Surfactant System, water, its mass content is respectively:
H 2sO 4(ρ: 1.84 × 10 3g/L) 12 ~ 500mL/L, Mixed Surfactant System be 0.7 ~ 19.0g/L, water is surplus.
2. pickle solution according to claim 1, is characterized in that described passivator is made up of urotropine 0.3 ~ 10.0g/L, thionamic acid 0.15 ~ 3.0g/L, thionamic acid sodium 0.1 ~ 2.0g/L, glycerine 0.1 ~ 2.0g/L and one or more mixtures of alkanes tensio-active agent 0.05 ~ 2.0g/L.
3., containing the composite pickle solution preparation method of passivator, it is characterized in that: get 5 ~ 30L water and be placed in bucket, get 98% vitriol oil 12 ~ 500mL/L and slowly add along bucket wall, and constantly stir; Be join in bucket after 0.7 ~ 19.0g/L passivator dissolves in water by content, stir, be diluted with water to desired concn.
4. preparation method according to claim 3, is characterized in that in bucket, add 2.0L water, is slowly added by 98% vitriol oil 1.0L, and constantly stir along bucket wall; Added after water dissolution in bucket by 47.0g passivator, stir, slowly add water 4.0L, and preparation completes.
CN201410411056.6A 2014-08-20 2014-08-20 A kind of compounding pickle containing passivator and preparation method thereof Active CN105350005B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112981383A (en) * 2021-02-10 2021-06-18 重庆大学 Surface treatment liquid and surface treatment method of copper radiating fin
CN113088982A (en) * 2021-04-01 2021-07-09 江西中晟金属有限公司 Production method of glossy copper rod
CN113215579A (en) * 2021-03-11 2021-08-06 中国科学院近代物理研究所 Surface treatment method of radio frequency four-stage field acceleration cavity
CN113235100A (en) * 2021-03-11 2021-08-10 中国科学院近代物理研究所 Surface treatment method before oxygen-free copper brazing

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN86103745A (en) * 1986-05-26 1987-12-02 国营锦山机械厂 The pickling solution of copper and copper alloy
JPH09291372A (en) * 1996-02-26 1997-11-11 Shikoku Chem Corp Surface treating agent of copper and copper alloy
CN103060828A (en) * 2013-02-04 2013-04-24 北京蓝星科技有限公司 Pickling passivation agent for copper and copper alloy as well as preparation method and application of pickling passivation agent
CN103484872A (en) * 2012-06-15 2014-01-01 中国石油化工股份有限公司 Pickling solution containing compounded passivating agent, and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN86103745A (en) * 1986-05-26 1987-12-02 国营锦山机械厂 The pickling solution of copper and copper alloy
JPH09291372A (en) * 1996-02-26 1997-11-11 Shikoku Chem Corp Surface treating agent of copper and copper alloy
CN103484872A (en) * 2012-06-15 2014-01-01 中国石油化工股份有限公司 Pickling solution containing compounded passivating agent, and preparation method thereof
CN103060828A (en) * 2013-02-04 2013-04-24 北京蓝星科技有限公司 Pickling passivation agent for copper and copper alloy as well as preparation method and application of pickling passivation agent

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112981383A (en) * 2021-02-10 2021-06-18 重庆大学 Surface treatment liquid and surface treatment method of copper radiating fin
CN113215579A (en) * 2021-03-11 2021-08-06 中国科学院近代物理研究所 Surface treatment method of radio frequency four-stage field acceleration cavity
CN113235100A (en) * 2021-03-11 2021-08-10 中国科学院近代物理研究所 Surface treatment method before oxygen-free copper brazing
CN113088982A (en) * 2021-04-01 2021-07-09 江西中晟金属有限公司 Production method of glossy copper rod

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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699

Patentee after: China Petroleum & Chemical Corp.

Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd.

Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699

Patentee before: China Petroleum & Chemical Corp.

Patentee before: Nanhua Group Research Institute