CN103805979B - A kind of electrolytic manganese chromium-free passivation liquid and electrolytic manganese passivating method - Google Patents
A kind of electrolytic manganese chromium-free passivation liquid and electrolytic manganese passivating method Download PDFInfo
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- CN103805979B CN103805979B CN201210439032.2A CN201210439032A CN103805979B CN 103805979 B CN103805979 B CN 103805979B CN 201210439032 A CN201210439032 A CN 201210439032A CN 103805979 B CN103805979 B CN 103805979B
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Abstract
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.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.Manganese metal after passivating solution process of the present invention better ensure original color and luster, there is well passivated effect prerequisite under, quality product meets national production standard.This passivator is nontoxic, simple to operate, with low cost, has stronger commercial introduction meaning.
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
The manganese that new electrolysis generates is oxidized variable color and affect outward appearance and the quality of product in atmosphere easily.In order to prevent the oxidation of electrolytic metal Mn sheet, in industry, conventional potassium bichromate carries out Passivation Treatment to it.The method is simple to operate, with low cost, and the manganese after process has good surface color and stronger solidity to corrosion.But the passive film that the waste liquid that chromating process produces and passivation are formed is all containing to being detrimental to health and the Cr (VI) of contaminate environment.Along with the enhancing of environmental consciousness, many countries have give stricted orders the use of restriction chromating technique all, 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 is that " a kind of for electrolytic metal Mn surface-treated passivator and preparation method thereof " discloses a kind of nontoxic passivator for electrolytic metal Mn sheet of novel non-chrome be prepared from raw materials such as silicate, solubility promoter, inhibiter, accelerator and water.Number of patent application is 200510086577.X, and denomination of invention is that " a kind of metal Mn passivating liquid and using method thereof " discloses a kind of manganese metal passivating solution be prepared from phosphoric acid, alkali and water.Number of patent application is 201010174132.8, and denomination of invention is that " for electrolytic metal Mn surface-treated chrome-free tanning agent and preparation method thereof " to disclose the inorganic salt of titaniferous (IV) element, solubility promoter, inhibiter, Potcrate and water be the chrome-free tanning agent of preparation of raw material.But in these passivator (liquid), it is unstable to there is passivator (liquid), or excessively dark because processing rear manganese metal surface color, or cannot commercial introduction be obtained because processing the reasons such as rear manganese metal corrosion resistance of surface difference.Up to now, yet there are no a kind of chrome-free tanning agent can 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, a kind of simple, efficient, with low cost, eco-friendly electrolytic manganese chromium-free passivation liquid is provided.
Another object of the present invention is to provide a kind of preparation method of above-mentioned electrolytic manganese chromium-free passivation liquid.
Another 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%, 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 arbitrary proportion mixing.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 arbitrary proportion mixing.Preferably, described main passivator is the mixture of 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 arbitrary proportion mixing.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 arbitrary proportion mixing.Preferably, described brightening agent is the mixture of zinc sulfate and nitrocalcite.
The method of the above-mentioned electrolytic manganese chromium-free passivation liquid of preparation of the present invention, is main passivator and solubility promoter are added to the water by weight, then adds inhibiter and brightening agent in solution, stir 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 freshly prepared electrolytic manganese negative plate being placed in 15 ~ 60 DEG C was taken out after 0.1 ~ 10 minute;
2) the electrolytic manganese negative plate clear water after step 1) passivation is fully rinsed, dry after namely obtain the manganese metal after passivation.
The advantage of electrolytic manganese chromium-free passivation liquid of the present invention is: the manganese metal after this passivating solution process better ensure original color and luster, there is well passivated effect prerequisite under, quality product meets national production standard.This passivator is nontoxic, simple to operate, with low cost, has stronger commercial introduction meaning.
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 after using electrolytic manganese chromium-free passivation liquid of the present invention passivation.
Embodiment
Embodiment 1
In 500 kg of water, add after 2 kilograms of main passivator and 0.5 kilogram of solubility promoter stir, then add 0.3 kilogram of inhibiter and 0.5 kilogram of brightening agent wherein, stir evenly both 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.
Brand-new manganese metal negative electrode is immersed and to be warming up in the passivating solution of 40 degree 10 seconds, fully washing after taking out, to dry, both finished product.Manganese metal surface after process have with potassium bichromate passivation after the similar brilliant metallic gloss (see figure 1) of product, erosion experiment result shows that CuSO is passed through on the manganese metal surface of the method process
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 the manganese metal after the method process surperficial have with potassium bichromate process after the close corrosion resisting property of manganese metal.Product foreign matter content detected result is: P0.0032%, S0.020%, C0.0064%.This result shows, the manganese metal after passivating solution process of the present invention meets national sector standard.
Embodiment 2
In 500 kg of water, add after 0.25 kilogram of main passivator and 0.15 kilogram of solubility promoter stir, then add 0.5 kilogram of inhibiter and 0.75 kilogram of brightening agent wherein, stir evenly both 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 to be immersed in the passivating solution of 60 degree 1 minute, fully washing after taking out, to dry, both obtain finished product.Manganese metal after process comparatively embodiment 1 surface color is slightly dark.Erosion experiment result shows that CuSO is passed through on the manganese metal surface of the method process
4the time of experiment is 6s, though lower slightly compared with the manganese metal surface corrosion resistance performance after potassium bichromate passivation, but still can meet industry preservation requirement.Product foreign matter content detected result is: P0.0028%, S0.017%, C0.0070%.This result shows, the manganese metal after passivating solution process of the present invention meets national sector standard.
Embodiment 3
In 500 kg of water, add after 2.5 kilograms of main passivator and 1.0 kilograms of solubility promoters stir, then add 3.5 kilograms of inhibiter and 5 kilograms of brightening agents wherein, stir evenly both 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.
Under manganese metal is immersed room temperature (about 15 degree) passivating solution in 30 seconds, fully washing after taking out, to dry, both finished product.Manganese metal surface color after process is darker.Erosion experiment result shows that CuSO is passed through on the manganese metal surface of the method process
4the time of experiment is 4s.Product foreign matter content detected result is: P0.0048%, S0.023%, C0.0054%.This result shows, the manganese metal after passivating solution process of the present invention meets national sector standard.
Embodiment 4
In 500 kg of water, add after 0.05 kilogram of main passivator and 0.05 kilogram of solubility promoter stir, then add 0.25 kilogram of inhibiter and 0.35 kilogram of brightening agent wherein, stir evenly both 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.
Under manganese metal is immersed room temperature (about 15 degree) passivating solution in 30 seconds, fully washing after taking out, to dry, both finished product.Manganese metal surface color after process is darker.Erosion experiment result shows that CuSO is passed through on the manganese metal surface of the method process
4the time of experiment is 4s.Product foreign matter content detected result is: P0.0034%, S0.027%, C0.0026%, and this result shows, the manganese metal after passivating solution process of the present invention meets national sector standard.
Embodiment 5
In 500 kg of water, add after 5 kilograms of main passivator and 2.5 kilograms of solubility promoters stir, then add 5 kilograms of inhibiter and 10 kilograms of brightening agents wherein, stir evenly both 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.
Brand-new manganese metal negative electrode is immersed and to be warming up in the passivating solution of 40 degree 10 seconds, fully washing after taking out, to dry, both finished product.Manganese metal surface after process have with potassium bichromate passivation after the similar brilliant metallic gloss of product, erosion experiment result shows that CuSO is passed through on the manganese metal surface of the method process
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 the manganese metal after the method process surperficial have with potassium bichromate process after the close corrosion resisting property of manganese metal.Product foreign matter content detected result is: P0.0031%, S0.0034%, C0.0021%.This result shows, the manganese metal after passivating solution process of the present invention meets national sector standard.
Claims (8)
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%, solubility promoter 0.01% ~ 0.5%, inhibiter 0.05% ~ 1%, brightening agent 0.07% ~ 2%, and surplus is water;
Wherein, described main passivator is one or more in phosphoric acid, disodium-hydrogen or SODIUM PHOSPHATE, MONOBASIC;
Described solubility promoter is one or more in citric acid, hydrochloric acid, nitric acid or acetic acid;
Described inhibiter is one or more in sodium tartrate, sodium tetraborate, Trisodium Citrate, sodium wolframate, Sodium orthomolybdate or S-WAT;
Described brightening agent is one or more in nitrocalcite, aluminum nitrate, zinc sulfate or stannous sulfate.
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, is characterized in that, described main passivator is phosphoric acid.
4. electrolytic manganese chromium-free passivation liquid according to claim 1, is characterized in that, described solubility promoter is the mixture of citric acid and acetic acid.
5. electrolytic manganese chromium-free passivation liquid according to claim 1, is characterized in that, described inhibiter is sodium tartrate.
6. electrolytic manganese chromium-free passivation liquid according to claim 1, is characterized in that, described brightening agent is the mixture of zinc sulfate and nitrocalcite.
7. prepare a method for electrolytic manganese chromium-free passivation liquid described in claim 1, described method comprises and main passivator and solubility promoter being added to the water by weight, then adds inhibiter and brightening agent in solution, the step of stirring.
8. an electrolytic manganese passivating method, said method comprising the steps of:
1) the chromium-free passivation liquid passivation according to claim 1 freshly prepared electrolytic manganese negative plate being placed in 15 ~ 60 DEG C was taken out after 0.1 ~ 10 minute;
2) by step 1) electrolytic manganese negative plate clear water after passivation fully rinses, dry after, obtain the manganese metal after passivation.
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| 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 |
| 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 |
| CN109457242B (en) * | 2018-12-19 | 2021-03-16 | 中南大学 | Chromium-free passivator and preparation method and application thereof |
| CN115323365B (en) * | 2021-05-10 | 2023-10-13 | 中南大学 | Chromium-free passivation method for electrolytic manganese |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1404550A1 (en) * | 1986-03-28 | 1988-06-23 | Буйский Химический Завод | Composition for phosphatizing metal surfaces |
| 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 |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1404550A1 (en) * | 1986-03-28 | 1988-06-23 | Буйский Химический Завод | Composition for phosphatizing metal surfaces |
| 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 |
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