CN1021705C - Passivating liquid for surface of galvanized steel plate - Google Patents
Passivating liquid for surface of galvanized steel plate Download PDFInfo
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- CN1021705C CN1021705C CN 92101318 CN92101318A CN1021705C CN 1021705 C CN1021705 C CN 1021705C CN 92101318 CN92101318 CN 92101318 CN 92101318 A CN92101318 A CN 92101318A CN 1021705 C CN1021705 C CN 1021705C
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- Prior art keywords
- passive film
- treating liquid
- sio2
- passivating solution
- steel plate
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Abstract
The present invention relates to treating liquid for metal surfaces, which is especially suitable for the surface passivation of a galvanized steel sheet. The treating liquid is prepared from CrO3, SiO2, emulsion stabilizers, dispersing agents and reducing agents. The treating liquid is characterized in that the treating liquid can generate a passive film on the surface of passivated metal, the passive film uses SiO2-Cr<+3> as a skeleton, the inner interface is tightly connected with a base body in a form of an indissoluble compound generated by the reaction of Cr<+6> and a zinc layer, the outer part is arranged in a form of SiO2 rubber lumps, and the thickness of the passive film can be adjusted. The passive film has the advantages of compact and stable structure, firm combination of the passive film and the base body, and favorable performance of corrosion resistance.
Description
The invention belongs to the surface treatment liquid of metallic substance, the surface passivation that is specially adapted to hot-dip galvanizing sheet steel is handled.
At present, galvanized steel sheet surface is handled the chromating method that extensively adopts.The treatment solution that this method adopted (passivating solution) is a kind of chromic acid solution that contains the silicon sol inorganic fluoride, contains partial reduction Cr in the solution
+ 3Ion.It is a method of utilizing roller coat, and above-mentioned treatment solution is coated in surface of steel plate, then under non-washed situation, directly use hot blast drying, make galvanized steel sheet surface generate one deck and contain the adjustable passive film of Cr amount, improve the solidity to corrosion of steel plate galvanized, 61-585 is described as Japanese Patent Publication.
The principle of above-mentioned passivating method is based on and adds inorganic fluorion in the treatment solution, utilizes the activation of fluorion to make the surperficial zinc layer and the Cr of steel plate galvanized
+ 6Reaction generates fine and close chromic salt product.Its shortcoming is owing to when adding inorganic fluorion in the treatment solution, introduced additional soluble cation (as Na
+ 1Ion), cause the solidity to corrosion of passive film to descend; Simultaneously, fluorion is very big to the corrodibility of equipment, causes maintenance cost to rise.
The object of the present invention is to provide a kind of new hot-dip galvanizing sheet steel surface passivation liquid, with this passivating solution passivation hot-dip galvanizing sheet steel, not only the bonding force of passive film and zinc layer is strong, and passive film is stable, has good corrosion resisting property.
Based on above-mentioned purpose, hot-dip galvanizing sheet steel surface passivation liquid of the present invention is by CrO
3, SiO
2, reductive agent, emulsion stabilizer, dispersion agent form.Wherein, reductive agent can be CrO
3Restore portion C r
+ 3; SiO
2With H
2O is in conjunction with forming silicon sol mSiO
2-nH
2O(m, n are coefficient).
The outstanding feature of the present invention on technical scheme, the film forming principle that at first is passive film is with existing theoretical different.It is considered herein that, and through experimental verification, the formation of passive film not merely is Cr
+ 6Ionic oxygenizement, but Cr
+ 6The combined action of ion and silicon sol.After adding silicon sol in the chromic acid solution, under constantly stirring, silicon sol has particular performances as colloid, and if any bigger specific surface area and wetting ability preferably, it makes chromium be dispersed in SiO with ionic species
2Micelle between, forming a kind of monomeric form is lCr-mSiO
2-nH
2The molecular grouping of O (L.m.n) is a coefficient.Wherein Cr comprises Cr
+ 6And Cr
+ 3When contacting with steel plate galvanized, the Cr on each molecular grouping
+ 6With the zinc generation insoluble compound that reacts, thereby combine closely, and be connected with SiO with galvanized sheet
2And Cr
+ 3The other end outside, connect other molecular grouping with colloidal form.All repeating said process at whole galvanizing surface, so just on whole plate face, generate one deck with SiO
2-Cr
+ 3For the internal interface of skeleton with Cr
+ 6Generate the insoluble compound form with zinc layer reaction and matrix is allo, the outside is SiO
2The passive film that the micelle form is compact arranged, thickness is adjustable.The Cr of the some amount that is scattered here and there in this layer passive film
+ 3And Cr
+ 6, behind hot blast drying, just form the good passive film of solidity to corrosion of one deck densification.
CrO
3Effect one be and mSiO
2NH
2O unites the formation passive film, and the 2nd, resolve into reductive trivalent chromium Cr
+ 3, and can not introduce other additional yin, yang ion.Therefore, if CrO
3Very little, be lower than 8.0g/l, then can not form and have certain thickness complete passive film; And CrO
3Too much, greater than 60.0g/l, the passivating solution cost is risen, and make mSiO
2NH
2Of colloidal solution stability decreases.The Cr that restores
+ 3Benefit be to improve the chromium content of passive film, simultaneously owing to add Cr
+ 3Formed lCrmSiO
2NH
2The O macromolecular mass, its outside surface produces hydrophobic nature, improves the work-ing life of passive film under humid atmosphere; But Cr
+ 3In the time of too much, can make lCrmSiO
2NH
2The O structural instability, precipitated and separated descends the passivation of passivating solution greatly.
SiO
2Effect be to form silicon sol mSiO
2NH
2O.MSiO
2NH
2It is big that the characteristic of O is that it can adsorb Cr ionic quantitative range, SiO
2Content be advisable with 8.0～180g/l.If content is very few, can not form good lCrmSiO
2NH
2The O molecular grouping, patience descends; If SiO
2Too much, the surface quality of film is degenerated, surface porosity is coarse, and solidity to corrosion descends.
The effect of dispersion agent and emulsion stabilizer is as follows: the one, and wetting metallic surface makes zinc and Cr
+ 6Direct reaction; The 2nd, improve lCrmSiO
2NH
2The stability of O molecular grouping promptly improves the stability of passive film compactness and passivating solution, but when both content all＜during 0.01g/l, effect is not remarkable, if their content is during all greater than 0.1g/l, then frothing is serious, the passive film surface is imperfect.
The effect of reductive agent is from CrO
3In restore Cr
+ 3
In sum, the proportioning components (g/l) of hot-dip galvanizing sheet steel surface passivation liquid of the present invention is: CrO
38～60g/l, SiO
28～180g/l, emulsion stabilizer 0.01～0.1g/l, dispersion agent 0.01～0.1g/l, reductive agent 0.5～30g/l.
Emulsion stabilizer can be in deodorization lanolin anhydrous bp93, Modulan, ethoxylation (25 molecule) Wool wax alcohol or the acid of ethoxylation Wool wax alcohol alkyl any.
Dispersion agent can be in aliphatic alcohol polyethenoxy base silane and the aliphatic acid polyethenoxy base ether any.
Reductive agent can be methyl alcohol, ethanol, formaldehyde, H
2O
2Any.
Adopt passivating solution of the present invention that metal sheet (as steel plate galvanized) is carried out Passivation Treatment, only need or be immersed in the metallic surface with the direct roller coat of passivating solution, hot blast drying gets final product then, can obtain the chromate passivation film of surperficial different chrome contents.
Compared with prior art, adopt the passive film of passivating solution gained of the present invention not only form compact and stable, strong with the bonding force of zinc layer, and also the solidity to corrosion of film is good.
Embodiment
According to composition proportion of the present invention, prepared 5 batches of hot-dip galvanizing sheet steel surface passivation liquid, its concrete proportioning components is as described in Table 1.With the passivating solution of preparation respectively roller coat on steel plate galvanized, and use hot blast drying, that measures passive film then contains that Cr measures and its result of solidity to corrosion (hrs) lists table 2 in.
The proportioning components (g/l) of table 1 embodiment hot-dip galvanizing sheet steel surface passivation liquid
Lot number CrO
3SiO
2Emulsion stabilizer reductive agent dispersion agent
Deodorization anhydrous fatty alcohol polyoxy second
Lanolin methyl alcohol thiazolinyl silane
1 10.0 10.0 0.029 15 0.021
Ethoxylation sheep formaldehyde Fatty Alcohol(C12-C14 and C12-C18) polyoxy second
Hair lipidol alkyl acid thiazolinyl silane
2 11.2 11.3 0.022 20 0.019
Ethoxylation sheep formaldehyde Fatty Alcohol(C12-C14 and C12-C18) polyoxy second
Hair lipidol alkyl acid thiazolinyl silane
3 12.4 18.8 0.019 10 0.025
Ethoxylation sheep H
2O
2Lipid acid polyoxy second
Hair lipidol alkene ether
4 50.2 75.0 0.117 12 0.1
Modulan alcohol fatty acid polyoxy second
Alkene ether
5 24.4 37.4 0.040 16 0.035
The Cr that contains of table 2 embodiment gained passive film measures and solidity to corrosion
Lot number contains Cr amount solidity to corrosion
mg/M
2hrs
1 16.7 284
2 29.0 312
3 35.1 360
4 40.0 384
5 37.0 360
Annotate: (1) contains the Cr amount and detects by standard GB 9791-88;
(2) solidity to corrosion detects by standard GB 6458-86.
Claims (4)
1, a kind of hot-dip galvanizing sheet steel surface passivation liquid is characterized in that its composition proportion (g/l) is: CrO
38～60g/l, SiO
28～180g/l, emulsion stabilizer 0.01～0.1g/l, dispersion agent 0.01～0.1g/l, reductive agent 0.5～30g/l.
2, passivating solution according to claim 1, it is characterized in that emulsion stabilizer be in deodorization lanolin anhydrous bp93, Modulan, ethoxylation Wool wax alcohol or the acid of ethoxylation Wool wax alcohol alkyl any.
3, passivating solution according to claim 1, it is characterized in that dispersion agent be in aliphatic alcohol polyethenoxy base silane or the aliphatic acid polyethenoxy base ether any.
4, passivating solution according to claim 1 is characterized in that reductive agent is methyl alcohol, ethanol, formaldehyde, H
2O
2In any.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92101318 CN1021705C (en) | 1992-03-07 | 1992-03-07 | Passivating liquid for surface of galvanized steel plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92101318 CN1021705C (en) | 1992-03-07 | 1992-03-07 | Passivating liquid for surface of galvanized steel plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1063129A CN1063129A (en) | 1992-07-29 |
| CN1021705C true CN1021705C (en) | 1993-07-28 |
Family
ID=4939068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92101318 Expired - Fee Related CN1021705C (en) | 1992-03-07 | 1992-03-07 | Passivating liquid for surface of galvanized steel plate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1021705C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341913C (en) * | 2006-04-27 | 2007-10-10 | 南京红宝丽股份有限公司 | Rigid polyurethane foam prepared by using rape seed oil |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100213852B1 (en) * | 1995-11-13 | 1999-08-02 | 구마모토 마사히로 | Steel plate with good fire burning properties and the method of same |
| CN1089122C (en) * | 1999-09-03 | 2002-08-14 | 杨继玉 | Inner surface treating process for refrigerator steel tube |
| JP3952198B2 (en) * | 2002-08-01 | 2007-08-01 | 日本ペイント株式会社 | Metal surface treatment method and galvanized steel sheet |
| CN101519775B (en) * | 2008-02-28 | 2011-01-19 | 宝山钢铁股份有限公司 | Environmental-friendly chrome-free phosphating electrogalvanized sealed steel sheet and manufacturing method thereof |
| CN103805981B (en) * | 2012-11-13 | 2017-05-31 | 比亚迪股份有限公司 | A kind of nickel passivating solution and preparation method thereof and the method for nickel surface passivation |
| CN103834938A (en) * | 2014-03-05 | 2014-06-04 | 东北大学 | Steel mill continuous annealing galvanized sheet chromium-free compound passivator and preparation method thereof |
| CN106399990B (en) * | 2016-08-16 | 2019-09-20 | 深圳市诚达科技股份有限公司 | A kind of anti-coking nano material and preparation method thereof based on stainless steel surface |
| CN109055939A (en) * | 2018-09-17 | 2018-12-21 | 佛山市禅城区诺高环保科技有限公司 | A kind of preparation method of deburring liquid |
-
1992
- 1992-03-07 CN CN 92101318 patent/CN1021705C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100341913C (en) * | 2006-04-27 | 2007-10-10 | 南京红宝丽股份有限公司 | Rigid polyurethane foam prepared by using rape seed oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1063129A (en) | 1992-07-29 |
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