CN103060828B - Pickling passivation agent for copper and copper alloy as well as preparation method and application of pickling passivation agent - Google Patents

Pickling passivation agent for copper and copper alloy as well as preparation method and application of pickling passivation agent Download PDF

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Publication number
CN103060828B
CN103060828B CN201310042605.2A CN201310042605A CN103060828B CN 103060828 B CN103060828 B CN 103060828B CN 201310042605 A CN201310042605 A CN 201310042605A CN 103060828 B CN103060828 B CN 103060828B
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acid
copper
washing
passivating agent
passivation agent
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CN103060828A (en
Inventor
单素灵
王双田
曹季明
王晓琴
文措杰
李维
李海
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Beijing Bluestar Cleaning Co Ltd
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Beijing Bluestar Cleaning Co Ltd
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Abstract

The invention discloses a pickling passivation agent for copper and copper alloy as well as a preparation method and an application of the pickling passivation agent. The pickling passivation agent comprises the following components by weight percent: 5-15% of sulfuric acid, 1-5% of disodium hydrogen phosphate, 1-5% of sodium nitrate, 5-10% of an A-type passivation agent and the balance of water. According to the invention, after copper or copper alloy is soaked for 30 seconds of immersion, a discolored part, which is formed by high-temperature oxidization, on the surface of the copper or copper alloy can be completely removed, and then a quick and efficient washing effect can be achieved at normal temperature, and the copper or copper alloy does not rust again in a storage period of the process; and the pickling passivation agent is particularly applicable to washing and passivating copper alloy pipes for solar devices.

Description

A kind of Copper and its alloy passivating agent for acid-washing, preparation method and application thereof
Technical field
The present invention relates to a kind of Copper and its alloy passivating agent for acid-washing and preparation method thereof, belong to cleaning metal surface field, be specifically related to the surface cleaning of Copper and its alloy material.
Background technology
Copper and its alloy goods widely use in fields such as heavy industry, light industry, household appliances and instrument appliance products.But Copper and its alloy is easy oxidation discoloration in an atmosphere, goods particularly can be made in the presence of a harsh environment to get rusty, form verdigris, change the color and luster that copper is original.This not only affects the visual appearance of product but also has damaged some performances of itself.For this reason, many facing operation persons, through long-time effort, develop many special treatment processs, namely prevent product itself to be oxidized, and give again product appearance attractive in appearance.In many treatment processs, chemical pickling method because of its cost minimum, efficiency higher and application comparatively extensive.
Traditional chemical pickling method has: sulfonitric type; The processing methodes such as sulfuric acid-chromic acid type and " three acid " type.But these processing methodes all be unable to do without the very strong chromic anhydride of toxicity and oxynitride, thus pollute.
Decontamination, protection of the environment is the basic demand of human survival.Our several generations scientific worker through unremitting effort, progressively there being the copper piece acid washing passivation technology of higher hazardness to be converted into low concentration, the acid washing passivation technology of less contamination operation of putting into production.But, although tobacco and pollution of chromium have been in lower numerical value, but still fail to reach the processing requirement of free of contamination Copper and its alloy bright dipped finish and chromium-free deactivation.
Summary of the invention
The present invention seeks to avoid prior art not enough, provide one at normal temperatures, remove Copper and its alloy surface oxidation or color change portion and do not return the quick passivating agent for acid-washing of Copper and its alloy of rust at operation memory period.
One aspect of the present invention relates to a kind of passivating agent for acid-washing, and it comprises the component of following weight proportion:
Sulfuric acid 5 ~ 15%, Sodium phosphate dibasic 1 ~ 5%, SODIUMNITRATE 1 ~ 5%, A type passivator 5 ~ 10%, suitable quantity of water, described A type passivator is the complex composition of benzotriazole and ferric sulfate, and wherein benzotriazole and ferric sulfate mass ratio are 1:5-15.
In a preferred embodiment of the present invention, wherein sulfuric acid massfraction is 6% ~ 12%.
In a preferred embodiment of the present invention, wherein said passivating agent for acid-washing does not comprise concentrated nitric acid, hydrochloric acid and/or the compound containing chromium, and preferably, described passivating agent for acid-washing does not comprise other component outside listed component.
In a preferred embodiment of the present invention, it is characterized in that A type passivator is benzotriazole, ferric sulfate forms so that mass ratio 1:8-12 is composite.
The present invention also relates to above-mentioned passivating agent for acid-washing preparation method on the other hand, comprises the steps: that a. takes raw material according to got raw material ratio; B. first in water, slowly add sulfuric acid, then add Sodium phosphate dibasic and SODIUMNITRATE, stirring and dissolving in the water of sulfuric acid heat release thus.C. add A type passivator, after being uniformly mixed, namely obtain Rapid Cleaning passivator.
Another object of the present invention is to provide a kind of method of Copper and its alloy acid wash passivation, namely at normal temperatures, Copper and its alloy material is soaked 30S, takes out rinsing.
Sulfuric acid of the present invention is the technical grade that working substance content is not less than 98%, sulfuric acid belongs to a kind of strong acid, at normal temperatures, can rapid etching Copper and its alloy oxide on surface, but with Copper substrate does not react, therefore adopt the sulfuric acid of appropriate amount can remove Copper and its alloy surface fast and ensure that Copper substrate exempts from corrosion in the good situation of cleaning performance.
Adopt Sodium phosphate dibasic and SODIUMNITRATE in the present invention, object plays the surface cleaning promoter action to Copper and its alloy.
In the present invention, Copper and its alloy passivating agent for acid-washing composition is by benzotriazole and ferric sulfate compound, the corrosion inhibition of benzotriazole to copper is unquestionable, after composite upper ferric sulfate, passivation effect is strengthened, and its reason may be ferric sulfate facilitates benzotriazole film forming passivation as a kind of weak oxidant.
Passivating agent for acid-washing of the present invention at least possesses in following advantage one or all:
1. the present invention does not easily produce the acid of acid mist containing concentrated nitric acid, hydrochloric acid etc., and passivation composition is not containing sexavalent chrome, and operation hazardness is extremely low.
2. present invention process is simple, Copper and its alloy surface discolouration part can be removed clean.
3. the present invention reaches cleaning effect in the soak time of 30S, and ensures not occur returning rust at inter process to copper surface passivation.
embodiment:
Embodiment one:
Clean-out system proportioning: sulfuric acid 7%, Sodium phosphate dibasic 2%, SODIUMNITRATE 4%, A type passivator 5%, all the other are water, and A type passivator is benzotriazole, ferric sulfate mass ratio 1:10 is composite forms;
Liquid pool: stainless steel reservoir;
Concrete operations: at room temperature, are manually placed in Rapid Cleaning passivator 30s by red copper pipe fitting (hollow elongated tubular, length 2m, empty footpath 6mm, wall thickness 1.5mm), take out, take out after clear water rinsing;
Cleaning performance: red copper pipe fitting surface presentation minute surface light tone, to be placed in Yanjiao factory workshop 48 hours without variable color.
Embodiment two:
Clean-out system proportioning: sulfuric acid 10%, Sodium phosphate dibasic 4%, SODIUMNITRATE 2%, A type passivator 9%, all the other are water, and A type passivator is benzotriazole, ferric sulfate mass ratio 1:10 is composite forms;
Soda liquor container: stainless steel reservoir;
Concrete practical operation is done: at room temperature, manually brass pipe fitting is placed in Rapid Cleaning passivator 30s, takes out.Take out after clear water rinsing;
Cleaning performance: brass pipe fitting surface presentation minute surface light tone, to be placed in Yanjiao factory workshop 48 hours without variable color.
The above, be only the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, and any change of expecting without creative work or replacement, all should be encompassed within protection scope of the present invention.Therefore, the protection domain that protection scope of the present invention should limit with claims is as the criterion.

Claims (9)

1. a passivating agent for acid-washing, it comprises the component of following weight proportion:
Sulfuric acid 5 ~ 15%, Sodium phosphate dibasic 1 ~ 5%, SODIUMNITRATE 1 ~ 5%, A type passivator 5 ~ 10%, suitable quantity of water, described A type passivator is the complex composition of benzotriazole and ferric sulfate, and wherein benzotriazole and ferric sulfate mass ratio are 1:5-15.
2. passivating agent for acid-washing according to claim 1, wherein sulfuric acid massfraction is 6% ~ 12%.
3. passivating agent for acid-washing according to claim 1 and 2, wherein said passivating agent for acid-washing does not comprise concentrated nitric acid, hydrochloric acid and/or the compound containing chromium.
4. passivating agent for acid-washing according to claim 1 and 2, described passivating agent for acid-washing does not comprise other component outside listed component.
5., according to passivating agent for acid-washing according to claim 3, it is characterized in that A type passivator is benzotriazole, ferric sulfate forms so that mass ratio 1:8-12 is composite.
6. the preparation method of the arbitrary described passivating agent for acid-washing of claim 1 ~ 5, comprises the steps:
A. raw material is taken according to got raw material ratio;
B. first in water, slowly add sulfuric acid, then add Sodium phosphate dibasic and SODIUMNITRATE, stirring and dissolving in the water of sulfuric acid heat release thus;
C. add A type passivator, after being uniformly mixed, namely obtain Rapid Cleaning passivator.
7. the passivating agent for acid-washing as described in as arbitrary in claim 1 ~ 5 is in the application of Cleaning and Passivation copper or Cu alloy material.
8. application according to claim 7, is characterized in that: at normal temperatures copper to be cleaned or Cu alloy material are soaked 20-40s in described passivating agent for acid-washing, takes out rinsing.
9. application according to claim 7, is characterized in that copper or Cu alloy material are sun power device copper alloy materials heat exchanger tube.
CN201310042605.2A 2013-02-04 2013-02-04 Pickling passivation agent for copper and copper alloy as well as preparation method and application of pickling passivation agent Active CN103060828B (en)

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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105350005B (en) * 2014-08-20 2018-04-03 中国石油化工股份有限公司 A kind of compounding pickle containing passivator and preparation method thereof
CN104962935A (en) * 2015-06-13 2015-10-07 周彩球 Copper alloy acid pickling passivant
CN105040010A (en) * 2015-07-03 2015-11-11 合肥卡诺汽车空调有限公司 Air conditioner system pipeline member pickling passivation technology
WO2017219254A1 (en) * 2016-06-21 2017-12-28 深圳市恒兆智科技有限公司 Passivator, copper part and passivation treatment method therefor
CN107299358A (en) * 2017-06-28 2017-10-27 富威科技(吴江)有限公司 A kind of cleaning of the hard state copper foil of short route
CN109880161A (en) * 2019-02-26 2019-06-14 张坤 A kind of Compositional type copper resistant agent and its preparation and verification method
CN112064006B (en) * 2020-09-23 2023-04-14 东莞长盈精密技术有限公司 Passivation method of copper part

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1865505A (en) * 2006-06-14 2006-11-22 内蒙古第一机械制造(集团)有限公司 Acidwash solution for copper and copper alloy
CN101353793A (en) * 2007-07-26 2009-01-28 江苏海迅实业集团股份有限公司 Copper alloy antirust agent

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1865505A (en) * 2006-06-14 2006-11-22 内蒙古第一机械制造(集团)有限公司 Acidwash solution for copper and copper alloy
CN101353793A (en) * 2007-07-26 2009-01-28 江苏海迅实业集团股份有限公司 Copper alloy antirust agent

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Address after: 101318 Beijing city B District Shunyi District Tianzhu Airport Industrial Zone Anxiang Street No. 5

Applicant after: BEIJING BLUESTAR CLEANING CO., LTD.

Address before: 101318 Beijing city B District Shunyi District Tianzhu Airport Industrial Zone of Peace Road No. 5

Applicant before: Beijing Bluestar Technology Co., Ltd.

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Free format text: CORRECT: APPLICANT; FROM: BEIJING BLUESTAR TECHNOLOGY CO., LTD. TO: BEIJING BLUESTAR WASHING CO., LTD.

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