CN1024815C - Metal surface treating liquid - Google Patents
Metal surface treating liquid Download PDFInfo
- Publication number
- CN1024815C CN1024815C CN 92113031 CN92113031A CN1024815C CN 1024815 C CN1024815 C CN 1024815C CN 92113031 CN92113031 CN 92113031 CN 92113031 A CN92113031 A CN 92113031A CN 1024815 C CN1024815 C CN 1024815C
- Authority
- CN
- China
- Prior art keywords
- passive film
- treating liquid
- metal surface
- treatment solution
- activator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
- C23C22/24—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 hexavalent chromium compounds
- C23C22/30—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 hexavalent chromium compounds containing also trivalent chromium
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The present invention provides metal surface treating liquid 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, reducing agents and active agents. The present invention is characterized in that the treating liquid can generate a passive film on the passivated metal surface, the passive film uses SiO2-Cr<+3> as a skeleton, the inner interface of the passive film is formed from an indissoluble compound by the reaction of Cr<+6> and zinc layers, the passive film is tightly connected with a base body, the outer part of the passive film is arranged in a SiO2 micell mode, and the thickness of the passive film can be adjusted. The passive film has the advantages of compactness, stabilization, firm combination with the base body, and favorable corrosion resisting performance.
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.
Previous application for a patent for invention-metallic surface the treatment solution (application number CN92101318.3) that proposes of the applicant also is a kind of Passivation Treatment that is applicable to the hot-dip galvanizing sheet steel surface.This treatment solution is in passive film densification that the metallic surface generated, stable, and is strong with the bonding force of matrix, has certain solidity to corrosion.But its solidity to corrosion also is not too desirable; In addition, this treatment solution is strict to metal original surface state, and cost is improved.
The object of the present invention is to provide a kind of new metal surface treating liquid, with this treatment solution passivation steel plate galvanized, not only the bonding force of passive film and zinc layer is strong, passive film densification, stable, and have more excellent corrosion resisting property.
Based on above-mentioned purpose, the chemical ingredients of metal surface treating liquid of the present invention is at CrO
3, SiO
2, reductive agent, on the basis of emulsion stabilizer and dispersion agent, added a kind of activator again, so that further improve corrosion resisting property.Be that metal surface treating liquid of the present invention is by CrO
3, SiO
2, reductive agent, emulsion stabilizer, dispersion agent and activator form.The concrete composition proportion (g/l) of metal surface treating liquid is as follows:
CrO
38～60g/l, SiO
28～180g/l, activator 10～30g/l, emulsion stabilizer 0.01～0.1g/l, dispersion agent 0.01～0.1g/l, reductive agent 0.5～30g/l.
Wherein, activator be in ortho phosphorous acid or the phosphorous acid any; Emulsion stabilizer in refining deodorization lanolin anhydrous bp93, Modulan, ethoxylation (25 molecule) Wool wax alcohol or the acid of ethoxylation Wool wax alcohol alkyl any; Dispersion agent be in aliphatic alcohol polyethenoxy base silane or the aliphatic acid polyethenoxy base ether any; Reductive agent is methyl alcohol, ethanol, formaldehyde, H
2O
2In any.
Reductive agent in above-mentioned can be CrO
3Oxygenant restores 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 skeleton, internal interface is with Cr
+ 6Generate insoluble compound with zinc layer reaction and, outside allo with matrix 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
2O colloidal solution stability decreases.The Cr that restores
+ 3Benefit be to improve the chromium content of passive film, simultaneously owing to add Cr
+ 3Formed lCr.mSiO
2.nH
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 lCr.mSiO
2Structural instability, precipitated and separated descends the passivation of passivating solution greatly.
SiO
2Effect be to form silicon sol mSiO
2.nH
2O.MSiO
2.nH
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 lCr.mSiO
2.nH
2The O molecular grouping, solidity to corrosion descends; If SiO
2Too much, the surface quality of film is degenerated, it is loose coarse that the surface becomes, and solidity to corrosion descends.
The effect of activator is an activated metal coating, improves the bonding force of passive film.Its mechanism is for after adding activator, its at first with lCr-mSiO
2-nH
2Cr among the O
+ 6Reaction becomes a macromolecular part, and when contacting with coating surface, the hydrogen bond on it can make the acidity at interface rise, and the speed of response of raising and zinc layer forms the bonding force that chromic acid one phosphate mixture has improved film and coating at the interface.The content of activator is less than 10.0g/l, and activation is not obvious; And content then causes macromolecular structural instability greater than 30.0g/l, and passive film is loose, and solidity to corrosion descends.Activator has also reduced the requirement of passivating solution to the metal original surface.
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 lCr.mSiO
2.nH
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
Adopt treatment 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 treatment 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 treatment solution gained of the present invention not only form compact and stable, strong with the bonding force of zinc layer, and have more excellent corrosion resisting property; Simultaneously, since low to the requirement of metal original surface, can reduce cost; In addition,, accelerated speed of response, improved production efficiency, had tangible economic benefit owing to add activator.
Embodiment
According to composition proportion of the present invention, prepared 5 batches of metal surface treating liquids, its concrete composition proportion is as described in Table 1.With the treatment 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.
This proportioning of composition (g/L) of table 1 embodiment metal surface treating liquid
Lot number CrO
3SiO
2Dispersion agent reductive agent emulsion stabilizer activator
The anhydrous sheep ortho phosphorous acid of 1 10.0 10.0 Fatty Alcohol(C12-C14 and C12-C18) polyoxy second methyl alcohol 15 deodorizations
0.021 mao of fat of thiazolinyl silane 0.029 23
2 11.2 11.3 Fatty Alcohol(C12-C14 and C12-C18) polyoxy second formaldehyde ethoxylation lanolin ortho phosphorous acids
The 0.019 20 pure alkyl acid 0.022 20 of thiazolinyl silane
3 12.4 18.8 Fatty Alcohol(C12-C14 and C12-C18) polyoxy second formaldehyde ethoxylation lanolin ortho phosphorous acids
The 0.025 10 pure alkyl acid 0.019 15 of thiazolinyl silane
4 50.2 75 lipid acid polyoxy second H
2O
2Ethoxylation lanolin phosphorous acid
Alkene ether 0.124 12 alcohol 0.117 20
5 24.4 37.4 lipid acid polyoxy second ethanol acetylated lanolin phosphorous acid
Alkene ether 0.035 16 fat 0.040 25
The Cr that contains of table 2 embodiment gained passive film measures and solidity to corrosion
Anti-/erosion property that lot number contains the Cr amount
mg/M
2hrs
1 17.2 290
2 29.8 336
3 36.5 368
4 40.4 396
5 35.7 360
Claims (5)
1, a kind of metal surface treating liquid is characterized in that its composition proportion (g/1) is: CrO
38～60g/1, SiO
28～180g/1, activator 10～30g/1, emulsion stabilizer 0.01～0.1g/1, dispersion agent 0.01～0.1g/1, reductive agent 0.5～30g/1.
2, treatment solution according to claim 1, it is characterized in that activator be in ortho phosphorous acid or the phosphorous acid any.
3, treatment 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.
4, treatment 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.
5, treatment 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 92113031 CN1024815C (en) | 1992-11-18 | 1992-11-18 | Metal surface treating liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92113031 CN1024815C (en) | 1992-11-18 | 1992-11-18 | Metal surface treating liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1074716A CN1074716A (en) | 1993-07-28 |
| CN1024815C true CN1024815C (en) | 1994-06-01 |
Family
ID=4946214
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92113031 Expired - Fee Related CN1024815C (en) | 1992-11-18 | 1992-11-18 | Metal surface treating liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1024815C (en) |
Families Citing this family (3)
| 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 |
| 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 |
| CN107699881A (en) * | 2017-09-30 | 2018-02-16 | 武汉钢铁有限公司 | Steel plate with organic coating pre-treatment pretreating agent and preparation method and its usage |
-
1992
- 1992-11-18 CN CN 92113031 patent/CN1024815C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1074716A (en) | 1993-07-28 |
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| C14 | Grant of patent or utility model | ||
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| CF01 | Termination of patent right due to non-payment of annual fee |