CN107267971B - A kind of passivator and preparation method thereof of without phosphorus Chrome-free - Google Patents
A kind of passivator and preparation method thereof of without phosphorus Chrome-free Download PDFInfo
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- CN107267971B CN107267971B CN201710376769.7A CN201710376769A CN107267971B CN 107267971 B CN107267971 B CN 107267971B CN 201710376769 A CN201710376769 A CN 201710376769A CN 107267971 B CN107267971 B CN 107267971B
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- nitrite
- silicate
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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
- C23C22/46—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 containing oxalates
Abstract
The invention discloses a kind of passivator of without phosphorus Chrome-free; it is made of nitrite, silicate and the complexing agent including tartaric acid; the present invention has the advantages that good passivation effect, passivation speed are fast, and the present invention is of great significance to environmental protection without containing extremely toxic substances such as hexavalent chromates.
Description
Technical field
The present invention relates to a kind of matal deactivator, especially a kind of passivator and preparation method thereof of without phosphorus Chrome-free.
Background technique
What the Passivation Treatment of electrolytic manganese metal generallyd use is Cr VI deactivation method, i.e., hexavalent chromate is used for electrolyzing gold
Belong to the surface passivation anti-corrosion of manganese, this method has many advantages, such as that corrosion resistance easy to operate, at low cost, passivating film is high, but sexavalence
Chromate is extremely toxic substance, has strong carcinogenesis, flushing waste water after the aerosol that generates in operating process, passivation and
Passivation waste liquid can all lead to serious environmental problem, therefore this method is gradually severely limited.With Public environmental attitude
Reinforce, hexavalent chromate passivating method will be cancelled, research environment friendly chromium-free deactivation processing technique, to replace sexavalence chromic acid
Salt passivating method, will be with important economic benefit, social benefit and environmental benefit.
Summary of the invention
The present invention provides a kind of passivator and preparation method thereof of without phosphorus Chrome-free, and passivation speed is fast, good passivation effect.
To achieve the above object, the technical solution of the present invention is as follows:
A kind of passivator of without phosphorus Chrome-free, is grouped as by the group of following weight: 1.25 ~ 5 parts of nitrite, silicic acid
0.5 ~ 2.5 part of salt, 0.06 ~ 4 part of tartaric acid, 0.06 ~ 4 part of sodium potassium tartrate tetrahydrate, 0 ~ 2 part of oxalic acid, 0 ~ 2 part of sodium oxalate.
The passivator of above-described without phosphorus Chrome-free, is preferably grouped as by the group of following weight: nitrite 2
~ 2.5 parts, 1 ~ 1.2 part of silicate, 1.8 ~ 2.5 parts of tartaric acid, 1.8 ~ 2.5 parts of sodium potassium tartrate tetrahydrate.It is furthermore preferred that including following heavy
The component of amount part proportion: 2.2 parts of nitrite, 1.1 parts of silicate, 1.9 parts of tartaric acid, 1.9 parts of sodium potassium tartrate tetrahydrate.
The present invention also provides the technical solutions of the passivator of another preferred without phosphorus Chrome-free, by following weight
Group be grouped as: 2.2 ~ 2.7 parts of nitrite, 0.5 ~ 0.6 part of silicate, 0.07 ~ 0.09 part of tartaric acid, sodium potassium tartrate tetrahydrate 0.07
~ 0.09 part, 0 ~ 1 part of oxalic acid, 0 ~ 1 part of sodium oxalate.It is furthermore preferred that being grouped as by the group of following weight: nitrite 2.5
Part, 0.55 part of silicate, 0.09 part of tartaric acid, 0.09 part of sodium potassium tartrate tetrahydrate, 0.5 part of oxalic acid, 0.5 part of sodium oxalate.
The nitrite is sodium nitrite or potassium nitrite, and the silicate is sodium metasilicate or potassium silicate.
The preparation method of the passivator of above-described without phosphorus Chrome-free, comprising the following steps:
(1) solid component nitrite, silicate, tartaric acid and sodium potassium tartrate tetrahydrate are weighed by weight, and weigh solid
The water that 200 ~ 300 times of raw material；
(2) nitrite is added to the water in advance, dissolves, adds silicate, dissolved, tartaric acid is then added, dissolved,
It is eventually adding sodium potassium tartrate tetrahydrate, the passivator of without phosphorus Chrome-free is obtained after dissolution.
The present invention also provides the passivator of above-described without phosphorus Chrome-free in the surface passivation anti-corrosion side of electrolytic manganese metal
The application in face.
The passivator of above-described without phosphorus Chrome-free, in the raw material for being included:
Sodium nitrite: main film forming matter is type oxide film corrosion inhibiter, can make manganese Metal surface oxidation, form one layer of densification
Corrosion resistant passivating film and prevent from corroding.
Sodium metasilicate: auxiliary film forming matter is sedimentation type corrosion inhibiter, can form precipitate nucleation with manganese, nucleus is tightly packed most
Manganous silicate precipitation membrane is formed afterwards to be used cooperatively sodium nitrite and sodium metasilicate to prevent the corrosion of manganese Metal, can make up for it
Mutual deficiency enhances the corrosion resistance of manganese metal.
Tartaric acid and oxalic acid: complexing agent can effectively improve manganese piece surface state, so that the effective component in passivating solution
It can sufficiently be contacted with manganese piece, promote the progress of film formation reaction, while facilitate the uniform, fine and close of passivation film.
Sodium potassium tartrate tetrahydrate and sodium oxalate: complexant can control the rate of film forming and the stability of passivating solution.By tartaric acid
It is used cooperatively with sodium potassium tartrate tetrahydrate, is capable of forming buffer solution, have biggish buffer function for the entrance of cell liquid, thus
Stablize the pH value of passivating solution.
Above-mentioned raw materials are used cooperatively, and can form one layer of passivating film, the passivating film of formation in manganese metal product external surfaces rapidly
With certain thickness, and thickness is uniform, is able to maintain product and metachromatism does not occur in one month, corrosion resisting property is good.Therefore,
The present invention has the advantages that good passivation effect, passivation speed are fast, and the present invention does not contain the extremely toxic substances such as hexavalent chromate, to ring
Border protection is of great significance.
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described, but protection scope of the present invention be not limited to it is following
Embodiment.
Prepare embodiment 1
A kind of passivator of without phosphorus Chrome-free, is grouped as by the group of following weight: 1.25 parts of sodium nitrite, sodium metasilicate
0.5 part, 0.06 part of tartaric acid, 0.06 part of sodium potassium tartrate tetrahydrate.
Prepare embodiment 2
A kind of passivator of without phosphorus Chrome-free, is grouped as by the group of following weight: 5 parts of sodium nitrite, sodium metasilicate 2.5
Part, 4 parts of tartaric acid, 4 parts of sodium potassium tartrate tetrahydrate, 2 parts of oxalic acid, 2 parts of sodium oxalate.
Prepare embodiment 3
A kind of passivator of without phosphorus Chrome-free, is grouped as by the group of following weight: 2 parts of sodium nitrite, sodium metasilicate 1
Part, 1.8 parts of tartaric acid, 1.8 parts of sodium potassium tartrate tetrahydrate.
Prepare embodiment 4
A kind of passivator of without phosphorus Chrome-free, is grouped as by the group of following weight: 2.5 parts of potassium nitrite, potassium silicate
1.2 parts, 2.5 parts of tartaric acid, 2.5 parts of sodium potassium tartrate tetrahydrate.
Prepare embodiment 5
A kind of passivator of without phosphorus Chrome-free, is grouped as by the group of following weight: 2.2 parts of potassium nitrite, potassium silicate
1.1 parts, 1.9 parts of tartaric acid, 1.9 parts of sodium potassium tartrate tetrahydrate.
Prepare embodiment 6
A kind of passivator of without phosphorus Chrome-free, is grouped as by the group of following weight: 2.2 parts of potassium nitrite, potassium silicate
0.5 part, 0.07 part of tartaric acid, 0.07 part of sodium potassium tartrate tetrahydrate.
Prepare embodiment 7
A kind of passivator of without phosphorus Chrome-free, is grouped as by the group of following weight: 2.7 parts of sodium nitrite, potassium silicate
0.6 part, 0.09 part of tartaric acid, 0.09 part of sodium potassium tartrate tetrahydrate, 1 part of oxalic acid, 1 part of sodium oxalate.
Prepare embodiment 8
A kind of passivator of without phosphorus Chrome-free, is grouped as by the group of following weight: 2.5 parts of potassium nitrite, sodium metasilicate
0.55 part, 0.09 part of tartaric acid, 0.09 part of sodium potassium tartrate tetrahydrate, 0.5 part of oxalic acid, 0.5 part of sodium oxalate.
Above-mentioned preparation embodiment 1,3 ~ 6 is prepared using following preparation method:
(1) solid component nitrite, silicate, tartaric acid, sodium potassium tartrate tetrahydrate, oxalic acid and oxalic acid are weighed by weight
Sodium, and weigh 250 times of solid material of water；
(2) nitrite, silicate, tartaric acid, sodium potassium tartrate tetrahydrate, oxalic acid and sodium oxalate are successively added into water, to each
Component obtains the passivator of without phosphorus Chrome-free after successively dissolving.
Above-mentioned preparation embodiment 2,7,8 is prepared using following preparation method:
(1) solid component nitrite, silicate, tartaric acid and sodium potassium tartrate tetrahydrate are weighed by weight, and weigh solid
The water that 250 times of raw material；
(2) nitrite, silicate, tartaric acid and sodium potassium tartrate tetrahydrate are successively added into water, is successively dissolved to each component
The passivator of without phosphorus Chrome-free is obtained afterwards.
Compliance test result embodiment
The passivator of dissolved without phosphorus Chrome-free is put into deactivation slot, will first be transferred from the metal manganese product in electrolytic cell slightly
Add and drain, place into deactivation slot and be passivated, passivation time 5s observes passivation effect after the completion of passivation.Gold after passivation
Belong to manganese product the case where sealing indoor preservation one month, observing metal manganese product after saving one month.
Within 6h of the passivator of dissolved without phosphorus Chrome-free from using, the metal manganese product effect of acquisition is shown in Table 1:
1 manganese metal product appearance testing result of table
Metal manganese product indices testing result after passivation is shown in Table 2:
Metal manganese product indices testing result after the passivation of table 2
Claims (5)
1. a kind of application of passivator of without phosphorus Chrome-free in terms of the surface passivation anti-corrosion of electrolytic manganese metal, it is characterised in that:
The passivator of the without phosphorus Chrome-free is grouped as by the group of following weight: 1.25 ~ 5 parts of nitrite, silicate 0.5
~ 2.5 parts, 0.06 ~ 4 part of tartaric acid, 0.06 ~ 4 part of sodium potassium tartrate tetrahydrate, 0 ~ 2 part of oxalic acid, 0 ~ 2 part of sodium oxalate；
The nitrite is sodium nitrite or potassium nitrite, and the silicate is sodium metasilicate or potassium silicate；
The preparation method of the passivator of the without phosphorus Chrome-free, comprising the following steps:
(1) solid component nitrite, silicate, tartaric acid, sodium potassium tartrate tetrahydrate, oxalic acid and sodium oxalate are weighed by weight, and
Weigh 200 ~ 300 times of solid material of water；
(2) nitrite, silicate, tartaric acid, sodium potassium tartrate tetrahydrate, oxalic acid and sodium oxalate are successively added into water, to each component
The passivator of without phosphorus Chrome-free is obtained after successively dissolving.
2. application according to claim 1, it is characterised in that:
It is grouped as by the group of following weight: 2 ~ 2.5 parts of nitrite, 1 ~ 1.2 part of silicate, 1.8 ~ 2.5 parts of tartaric acid,
1.8 ~ 2.5 parts of sodium potassium tartrate tetrahydrate.
3. application according to claim 1, it is characterised in that:
It is grouped as by the group of following weight: 2.2 ~ 2.7 parts of nitrite, 0.5 ~ 0.6 part of silicate, tartaric acid 0.07 ~
0.09 part, 0.07 ~ 0.09 part of sodium potassium tartrate tetrahydrate, 0 ~ 1 part of oxalic acid, 0 ~ 1 part of sodium oxalate.
4. application according to claim 2, it is characterised in that:
It is grouped as by the group of following weight: 2.2 parts of nitrite, 1.1 parts of silicate, 1.9 parts of tartaric acid, potassium tartrate
1.9 parts of sodium.
5. application according to claim 3, it is characterised in that:
It is grouped as by the group of following weight: 2.5 parts of nitrite, 0.55 part of silicate, 0.09 part of tartaric acid, tartaric acid
0.09 part of potassium sodium, 0.5 part of oxalic acid, 0.5 part of sodium oxalate.
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| CN201710376769.7A CN107267971B (en) | 2017-05-25 | 2017-05-25 | A kind of passivator and preparation method thereof of without phosphorus Chrome-free |
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| CN201710376769.7A CN107267971B (en) | 2017-05-25 | 2017-05-25 | A kind of passivator and preparation method thereof of without phosphorus Chrome-free |
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| TWI221861B (en) * | 1998-04-22 | 2004-10-11 | Toyo Boseki | Agent for treating metallic surface, surface-treated metal material and coated metal material |
| ATE482303T1 (en) * | 2005-10-25 | 2010-10-15 | Atotech Deutschland Gmbh | COMPOSITION AND METHOD FOR IMPROVING ADHESION OF POLYMERIC MATERIALS ON COPPER OR COPPER ALLOY SURFACES |
| JP2011074490A (en) * | 2009-09-07 | 2011-04-14 | Ofutekku Kk | Surface treatment method of magnesium and magnesium alloy for imparting brightness/decorating property, high corrosion resistance and functionality |
| CN102061465B (en) * | 2010-12-31 | 2012-02-22 | 大连工业大学 | Chrome-free sealing agent |
| CN105401139A (en) * | 2015-10-29 | 2016-03-16 | 王璐 | Improved alloy surface treating agent |
| CN105566960A (en) * | 2015-12-31 | 2016-05-11 | 安徽红桥金属制造有限公司 | Aqueous galvanizing sealing agent and preparation method thereof |
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Address after: 532200 Shilin Road, Chongzuo City, Guangxi Zhuang Autonomous Region Patentee after: Nanfang Manganese Industry Group Co.,Ltd. Address before: 532200 Shilin Road, Chongzuo City, Guangxi Zhuang Autonomous Region Patentee before: CITIC DAMENG MINING INDUSTRIES Ltd. |
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