CN103805979A - Chromium-free passivation solution for electrolytic manganese and passivation method of electrolytic manganese - Google Patents
Chromium-free passivation solution for electrolytic manganese and passivation method of electrolytic manganese Download PDFInfo
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- CN103805979A CN103805979A CN201210439032.2A CN201210439032A CN103805979A CN 103805979 A CN103805979 A CN 103805979A CN 201210439032 A CN201210439032 A CN 201210439032A CN 103805979 A CN103805979 A CN 103805979A
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Abstract
The invention relates to the technical field of anti-oxidation of metal manganese, and particularly the invention relates to a chromium-free passivation solution for electrolytic manganese and a passivation method of electrolytic manganese. The chromium-free passivation solution for electrolytic manganese provided by the invention comprises, by weight, 0.01%-1% of a main passivation agent, 0.01%-0.5% of a cosolvent, 0.05-1% of an inhibitor, 0.07%-2% of a brightening agent and the balance of water. The metal manganese treated by the passivation solution provided by the invention, in the premise of maintaining the original color and good passivation effect, has product quality in line with national standards of production. The passivation agent has no toxicity or harm, simple operation, low cost, and strong industrial promotion significance.
Description
Technical field
The present invention relates to manganese metal oxidation proof technical field, particularly, the present invention relates to a kind of electrolytic manganese chromium-free passivation liquid and electrolytic manganese passivating method.
Background technology
Easily oxidized variable color and affect outward appearance and the quality of product in air of the manganese that new electrolysis generates.In order to prevent the oxidation of electrolytic metal Mn sheet, in industry, conventional potassium bichromate is carried out Passivation Treatment to it.The method is simple to operate, with low cost, and manganese after treatment has good surface color and stronger solidity to corrosion.But the passive film that the waste liquid that chromating process produces and passivation form all contains being detrimental to health and the Cr (VI) of contaminate environment.Along with the enhancing of environmental consciousness, many countries have all give stricted orders the use of restriction chromating technique, and scientific worker also can substitute the novel metal manganese passivator of chromating at active development.Number of patent application is 200610018760.0, and denomination of invention discloses a kind of nontoxic passivator for electrolytic metal Mn sheet of novel non-chrome being prepared from raw materials such as silicate, solubility promoter, inhibiter, accelerator and water for " a kind of for electrolytic metal Mn surface-treated passivator and preparation method thereof ".Number of patent application is 200510086577.X, and denomination of invention discloses a kind of manganese metal passivating solution being prepared from phosphoric acid, alkali and water for " a kind of metal Mn passivating liquid and using method thereof ".Number of patent application is 201010174132.8, and denomination of invention discloses for " for electrolytic metal Mn surface-treated chrome-free tanning agent and preparation method thereof " chrome-free tanning agent that inorganic salt, solubility promoter, inhibiter, Potcrate and the water of titaniferous (IV) element are preparation of raw material.But in these passivator (liquid), or exist passivator (liquid) unstable, and or excessively dark because processing rear manganese metal surface color, or poor etc. former thereby cannot obtain industry and promote because processing rear manganese metal corrosion resistance of surface.Up to now, yet there are no a kind of chrome-free tanning agent effectively substitute chromium hydrochlorate for the industrial report of manganese metal.
Summary of the invention
The object of the invention is to, unresolved the problems referred to above, provide a kind of simple, efficient, with low cost, eco-friendly electrolytic manganese chromium-free passivation liquid.
Another object of the present invention is to provide a kind of preparation method of above-mentioned electrolytic manganese chromium-free passivation liquid.
A further object of the present invention is to provide a kind of electrolytic manganese passivating method.
Electrolytic manganese chromium-free passivation liquid of the present invention, formula is by weight percentage: main passivator 0.01% ~ 1%, solubility promoter 0.01% ~ 0.5%, inhibiter 0.05% ~ 1%, brightening agent 0.07% ~ 2%, surplus is water.
According to electrolytic manganese chromium-free passivation liquid of the present invention, preferably, formula is by weight percentage: main passivator 0.05% ~ 0.5%, and solubility promoter 0.03% ~ 0.2%, inhibiter 0.1% ~ 0.7%, brightening agent 0.15% ~ 1%, surplus is water.
According to electrolytic manganese chromium-free passivation liquid of the present invention, wherein, described main passivator is one or more in phosphoric acid, disodium-hydrogen or SODIUM PHOSPHATE, MONOBASIC, and each component can be mixed by arbitrary proportion.Preferably, described main passivator is phosphoric acid.
According to electrolytic manganese chromium-free passivation liquid of the present invention, wherein, described solubility promoter is one or more in citric acid, hydrochloric acid, nitric acid or acetic acid, and each component can be mixed by arbitrary proportion.Preferably, the mixture that described main passivator is citric acid and acetic acid.
According to electrolytic manganese chromium-free passivation liquid of the present invention, wherein, described inhibiter is one or more in sodium tartrate, sodium tetraborate, Trisodium Citrate, sodium wolframate, Sodium orthomolybdate or S-WAT, and each component can be mixed by arbitrary proportion.Preferably, described inhibiter is sodium tartrate.
According to electrolytic manganese chromium-free passivation liquid of the present invention, wherein, described brightening agent is one or more in nitrocalcite, aluminum nitrate, zinc sulfate or stannous sulfate, and each component can be mixed by arbitrary proportion.Preferably, described brightening agent is the mixture of zinc sulfate and nitrocalcite.
The method of chromium-free passivation liquid for the above-mentioned electrolytic manganese of preparation of the present invention, is that main passivator and solubility promoter are added to the water by weight, then adds inhibiter and brightening agent in solution, stirs and obtain electrolytic manganese chromium-free passivation liquid of the present invention.
Electrolytic manganese passivating method of the present invention, comprises the following steps:
1) the above-mentioned electrolytic manganese chromium-free passivation liquid passivation that the electrolytic manganese negative plate newly making is placed in to 15 ~ 60 ℃ was taken out after 0.1 ~ 10 minute;
2) after fully being rinsed, dried with clear water, the electrolytic manganese negative plate after step 1) passivation obtains the manganese metal after passivation.
Electrolytic manganese of the present invention is by the advantage of chromium-free passivation liquid: this passivating solution manganese metal after treatment is better guaranteeing original color and luster, having under the prerequisite of well passivated effect, and quality product meets national production standard.This passivator is nontoxic, simple to operate, with low cost, has stronger industrial dissemination.
Accompanying drawing explanation
Fig. 1 is the manganese after passivation; Wherein, left figure is the manganese after the passivation of commerical test gained potassium bichromate, and right figure is the manganese using after the passivation of electrolytic manganese of the present invention chromium-free passivation liquid.
Embodiment
Embodiment 1
In 500 kg of water, after adding 2 kilograms of main passivator and 0.5 kilogram of solubility promoter to stir, then add wherein 0.3 kilogram of inhibiter and 0.5 kilogram of brightening agent, stir evenly and both obtain passivating solution.
Above-mentioned main passivator is phosphoric acid; Solubility promoter is citric acid; Inhibiter be sodium tartrate with sodium tetraborate in proportion 1:1 mix; Brightening agent be nitrocalcite with nitrocalcite in proportion 1:1 mix.
New system manganese metal negative electrode is immersed and is warming up in the passivating solution of 40 degree 10 seconds, fully washing after taking out, dry, both finished product.Manganese metal after treatment surface have with potassium bichromate passivation after the similar brilliant metallic gloss of product (see figure 1), erosion experiment result shows that the manganese metal surface of the method processing passes through CuSO
4the time of experiment is 10s, passes through CuSO with the manganese metal surface after potassium bichromate passivation
4the time of experiment is that 8s is close, illustrates that the method manganese metal after treatment surface has the corrosion resisting property close with potassium bichromate manganese metal after treatment.Product foreign matter content detected result is: P 0.0032%, S 0.020%, C 0.0064%.This result shows, passivating solution of the present invention manganese metal after treatment meets national sector standard.
Embodiment 2
In 500 kg of water, after adding 0.25 kilogram of main passivator and 0.15 kilogram of solubility promoter to stir, then add wherein 0.5 kilogram of inhibiter and 0.75 kilogram of brightening agent, stir evenly and both obtain passivating solution.
Above-mentioned main passivator be disodium-hydrogen with SODIUM PHOSPHATE, MONOBASIC in proportion 1:1 mix; Solubility promoter is hydrochloric acid; Inhibiter is Trisodium Citrate; Brightening agent is zinc sulfate.
Manganese metal is immersed in the passivating solutions of 60 degree 1 minute, fully washing after taking out, dries, both finished product.Manganese metal after treatment is slightly dark compared with embodiment 1 surface color.Erosion experiment result shows that the manganese metal surface of the method processing passes through CuSO
4the time of experiment is 6s, though lower slightly compared with the manganese metal surface corrosion resistance performance after potassium bichromate passivation, preserve requirement but still can meet industry.Product foreign matter content detected result is: P 0.0028%, S 0.017%, C 0.0070%.This result shows, passivating solution of the present invention manganese metal after treatment meets national sector standard.
Embodiment 3
In 500 kg of water, after adding 2.5 kilograms of main passivator and 1.0 kilograms of solubility promoters to stir, then add wherein 3.5 kilograms of inhibiter and 5 kilograms of brightening agents, stir evenly and both obtain passivating solution.
Above-mentioned main passivator is phosphoric acid; Solubility promoter is nitric acid and acetic acid 2:1 mixing in proportion; Inhibiter is sodium wolframate and Sodium orthomolybdate 1:1 mixing in proportion; Brightening agent is stannous sulfate.
Manganese metal is immersed under room temperature in the passivating solution of (approximately 15 degree) 30 seconds, fully washing after taking out, dries, both finished product.Manganese metal surface color after treatment is darker.Erosion experiment result shows that the manganese metal surface of the method processing passes through CuSO
4the time of experiment is 4s.Product foreign matter content detected result is: P 0.0048%, S 0.023%, C 0.0054%.This result shows, passivating solution of the present invention manganese metal after treatment meets national sector standard.
Embodiment 4
In 500 kg of water, after adding 0.05 kilogram of main passivator and 0.05 kilogram of solubility promoter to stir, then add wherein 0.25 kilogram of inhibiter and 0.35 kilogram of brightening agent, stir evenly and both obtain passivating solution.
Above-mentioned main passivator is phosphoric acid; Solubility promoter is citric acid and acetic acid 2:1 mixing in proportion; Inhibiter is sodium tartrate; Brightening agent be zinc sulfate with nitrocalcite in proportion 2:1 mix.
Manganese metal is immersed under room temperature in the passivating solution of (approximately 15 degree) 30 seconds, fully washing after taking out, dries, both finished product.Manganese metal surface color after treatment is darker.Erosion experiment result shows that the manganese metal surface of the method processing passes through CuSO
4the time of experiment is 4s.Product foreign matter content detected result is: P 0.0034%, and S 0.027%, C 0.0026%, this result shows, passivating solution of the present invention manganese metal after treatment meets national sector standard.
Embodiment 5
In 500 kg of water, after adding 5 kilograms of main passivator and 2.5 kilograms of solubility promoters to stir, then add wherein 5 kilograms of inhibiter and 10 kilograms of brightening agents, stir evenly and both obtain passivating solution.
Above-mentioned main passivator be disodium-hydrogen with SODIUM PHOSPHATE, MONOBASIC in proportion 2:1 mix; Solubility promoter is nitric acid and acetic acid 1:1 mixing in proportion; Inhibiter is sodium tartrate; Brightening agent is nitrocalcite.
New system manganese metal negative electrode is immersed and is warming up in the passivating solution of 40 degree 10 seconds, fully washing after taking out, dry, both finished product.Manganese metal after treatment surface have with potassium bichromate passivation after the similar brilliant metallic gloss of product, erosion experiment result shows that the manganese metal surface of the method processing passes through CuSO
4the time of experiment is 8s, passes through CuSO with the manganese metal surface after potassium bichromate passivation
4the time of experiment is that 8s is close, illustrates that the method manganese metal after treatment surface has the corrosion resisting property close with potassium bichromate manganese metal after treatment.Product foreign matter content detected result is: P 0.0031%, S 0.0034%, C 0.0021%.This result shows, passivating solution of the present invention manganese metal after treatment meets national sector standard.
Claims (12)
1. an electrolytic manganese chromium-free passivation liquid, is characterized in that, described chromium-free deactivation liquid formula is by weight percentage, main passivator 0.01% ~ 1%, and solubility promoter 0.01% ~ 0.5%, inhibiter 0.05% ~ 1%, brightening agent 0.07% ~ 2%, surplus is water.
2. electrolytic manganese chromium-free passivation liquid according to claim 1, is characterized in that, described chromium-free deactivation liquid formula is by weight percentage, main passivator 0.05% ~ 0.5%, solubility promoter 0.03% ~ 0.2%, inhibiter 0.1% ~ 0.7%, brightening agent 0.15% ~ 1%, surplus is water.
3. electrolytic manganese chromium-free passivation liquid according to claim 1 and 2, is characterized in that, described main passivator is one or more in phosphoric acid, disodium-hydrogen or SODIUM PHOSPHATE, MONOBASIC.
4. electrolytic manganese chromium-free passivation liquid according to claim 3, is characterized in that, described main passivator is phosphoric acid.
5. electrolytic manganese chromium-free passivation liquid according to claim 1 and 2, is characterized in that, described solubility promoter is one or more in citric acid, hydrochloric acid, nitric acid or acetic acid.
6. electrolytic manganese chromium-free passivation liquid according to claim 5, is characterized in that, described solubility promoter is the mixture of citric acid and acetic acid.
7. electrolytic manganese chromium-free passivation liquid according to claim 1 and 2, is characterized in that, described inhibiter is one or more in sodium tartrate, sodium tetraborate, Trisodium Citrate, sodium wolframate, Sodium orthomolybdate or S-WAT.
8. electrolytic manganese chromium-free passivation liquid according to claim 7, is characterized in that, described inhibiter is sodium tartrate.
9. electrolytic manganese chromium-free passivation liquid according to claim 1 and 2, is characterized in that, described brightening agent is one or more in nitrocalcite, aluminum nitrate, zinc sulfate or stannous sulfate.
10. electrolytic manganese chromium-free passivation liquid according to claim 9, is characterized in that, described brightening agent is the mixture of zinc sulfate and nitrocalcite.
Prepare the method for electrolytic manganese chromium-free passivation liquid described in claim 1 for 11. 1 kinds, described method comprises main passivator and solubility promoter is added to the water by weight, then in solution, adds inhibiter and brightening agent, the step of stirring.
12. 1 kinds of electrolytic manganese passivating methods, said method comprising the steps of:
1) the chromium-free passivation liquid passivation claimed in claim 1 that the electrolytic manganese negative plate newly making is placed in to 15 ~ 60 ℃ was taken out after 0.1 ~ 10 minute;
2) after the electrolytic manganese negative plate after step 1) passivation is fully rinsed, dried with clear water, obtain the manganese metal after passivation.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104060259A (en) * | 2014-06-30 | 2014-09-24 | 句容市博远电子有限公司 | Environment-friendly phosphating solution and preparation method thereof |
| CN107177842A (en) * | 2017-05-25 | 2017-09-19 | 中信大锰矿业有限责任公司 | A kind of metal surface passivant of without phosphorus Chrome-free and preparation method thereof |
| CN109112554A (en) * | 2018-10-31 | 2019-01-01 | 三达奥克化学股份有限公司 | Aluminum alloy pattern plate cement slurry efficient cleaner for building and preparation method thereof |
| CN109457242A (en) * | 2018-12-19 | 2019-03-12 | 中南大学 | Chrome-free tanning agent and its preparation method and application |
| CN115323365A (en) * | 2021-05-10 | 2022-11-11 | 中南大学 | Chromium-free passivation method for electrolytic manganese |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1752286A (en) * | 2005-10-10 | 2006-03-29 | 北京科技大学 | Metal Mn passivating liquid and use method thereof |
| CN101285186A (en) * | 2008-05-30 | 2008-10-15 | 重庆大学 | Passivation solution for surface treatment of electrolytic manganese metal, and preparing and using method thereof |
| CN100425730C (en) * | 2006-09-21 | 2008-10-15 | 北京科技大学 | Manganese metal oxidation proof passivation liquid and use method thereof |
| CN101824615A (en) * | 2010-05-11 | 2010-09-08 | 贵州省铜仁市武陵锰业新材料有限公司 | Chrome-free tanning agent for electrolytic metal manganese surface treatment and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1404550A1 (en) * | 1986-03-28 | 1988-06-23 | Буйский Химический Завод | Composition for phosphatizing metal surfaces |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1752286A (en) * | 2005-10-10 | 2006-03-29 | 北京科技大学 | Metal Mn passivating liquid and use method thereof |
| CN100425730C (en) * | 2006-09-21 | 2008-10-15 | 北京科技大学 | Manganese metal oxidation proof passivation liquid and use method thereof |
| CN101285186A (en) * | 2008-05-30 | 2008-10-15 | 重庆大学 | Passivation solution for surface treatment of electrolytic manganese metal, and preparing and using method thereof |
| CN101824615A (en) * | 2010-05-11 | 2010-09-08 | 贵州省铜仁市武陵锰业新材料有限公司 | Chrome-free tanning agent for electrolytic metal manganese surface treatment and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104060259A (en) * | 2014-06-30 | 2014-09-24 | 句容市博远电子有限公司 | Environment-friendly phosphating solution and preparation method thereof |
| CN107177842A (en) * | 2017-05-25 | 2017-09-19 | 中信大锰矿业有限责任公司 | A kind of metal surface passivant of without phosphorus Chrome-free and preparation method thereof |
| CN107177842B (en) * | 2017-05-25 | 2020-01-21 | 中信大锰矿业有限责任公司 | Phosphorus-free and chromium-free metal surface passivator and preparation method thereof |
| CN109112554A (en) * | 2018-10-31 | 2019-01-01 | 三达奥克化学股份有限公司 | Aluminum alloy pattern plate cement slurry efficient cleaner for building and preparation method thereof |
| CN109457242A (en) * | 2018-12-19 | 2019-03-12 | 中南大学 | Chrome-free tanning agent and its preparation method and application |
| CN115323365A (en) * | 2021-05-10 | 2022-11-11 | 中南大学 | Chromium-free passivation method for electrolytic manganese |
| CN115323365B (en) * | 2021-05-10 | 2023-10-13 | 中南大学 | Chromium-free passivation method for electrolytic manganese |
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