CN101358342A - Brilliant tin plate chromium-free passivation solution and passivation method - Google Patents
Brilliant tin plate chromium-free passivation solution and passivation method Download PDFInfo
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- CN101358342A CN101358342A CNA2008100487642A CN200810048764A CN101358342A CN 101358342 A CN101358342 A CN 101358342A CN A2008100487642 A CNA2008100487642 A CN A2008100487642A CN 200810048764 A CN200810048764 A CN 200810048764A CN 101358342 A CN101358342 A CN 101358342A
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- passivation
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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
- C23C22/40—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 molybdates, tungstates or vanadates
- C23C22/42—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 molybdates, tungstates or vanadates containing also phosphates
Abstract
The invention discloses bright tin plate non-chromium passivation solution, wherein, each liter of passivation solution contains 20g to 70g of trisodium phosphate, 0.1g to 5g of cobalt sulfate, 0.5g to 3g of sodium molybdate, 20g to 75g of phosphoric acid, the rest is water, and the ph value of the passivation solution is 3 to 5. The invention also discloses a tinplate passivation method; in the passivation with the non-chromium passivation solution of the invention, the working temperature of the passivation solution is 50 DEG C to 80 DEG C, the passivation time is 1s to 20s, and the passivation method is electro-chemical cathode passivation or chemical passivation. The tin plate non-chromium passivation solution of the invention does not contain hexavalent chrome, conducts chemical passivation or electro-chemical cathode passivation to the tinplate, and enables the tinplate to have the same high corrosion resistance and high oxidation resistance with a chromate passivation process. The welding performance, the adhesion performance to the coating and the like of the tinplate passivated through the non-chromium passivation process also meet the level of the tinplate passivated by chromate, which fundamentally solves the harm of the tinplate passivated by chromate with hexavalent chrome to the human body and the environment.
Description
Technical field
The present invention relates to a kind of tin plate passivating solution, particularly relate to a kind of brilliant tin plate chromium-free passivation solution, the invention still further relates to the method for this passivating solution of a kind of usefulness the tin plate passivation.
Background technology
Tin plate is after plating, soft heat, for corrosion resisting property, antioxidant property and the anti-sulphide staining performance that improves tin plate, to carry out Passivation Treatment to tin plate, passivation to tin plate in the at present domestic and international industrial production all is to adopt the chromic salt that contains 6 valency chromium to carry out passivation, because 6 valency chromium are a kind of highly toxic substances, it generally is packing timber as food-drink that human body and environment are all had the purposes of very big harm, particularly tin plate, so bigger to the harm of human body.In order to reduce the harm of 6 valency chromium to human body and environment, countries in the world all do not contain the tin plate chromium-free passivation novel process of 6 valency chromium in research.
The chromium-free deactivation Study on Technology can be divided into two big classes: mineral-type and organic class.The mineral-type passivation comprises that the molybdate passivation: employing molybdate/phosphoric acid salt such as Tang.P.T. replace chromate treating, and passivating solution mainly contains Sodium orthomolybdate, sulfuric acid and muriate.Tungstate passivation Sn-Zn alloy such as tungstate passivation: British Cowieson etc., and alloy salt fog resistance performance and the moisture-resistant studied after handling are hot.The phosphoric acid salt passivation: Tomofumi Shigekuni etc. carries out the tin plate passivation with P-Si, and contrasts with the tin plate model of phosphoric acid salt passivation, the tin plate of chromating, finds that the P-Si passivation has acid resistance, japanning property and anti-sulphur preferably.Zirconate passivation: AISI research titanium potassium oxalate(T.P.O.), zirconium sulfate have also been studied the fluorate of titanium, zirconium, and have been checked anti-sulphur, oxidation-resistance.Ten tame unit consolidations such as the tin product manufacturing joint study council of american steel research association carry out the exploitation of tin plate chromium-free passivation system, mainly study zirconium sulfate passivation system.PPG Industries and Valspar company assess chromium-free deactivation, and the organic coating that this passivation is follow-up is further optimized, and improve anti-sulphide discoloration performance.Rare earth metal salt passivation: N.Mora, E.Cano etc. are at 0.01mol/L Ce (NO
3)
36H
2Use cathode treatment method (i=1mA/cm in the O solution
2, t=30S) study the tin plate chromium-free passivation, and compare with chromating.Titanium salt and manganate passivation: Liu Fei handle tin coating with some mineral acids of interpolation and oxygenant in the titanium salt.Replace chromating liquid with the titanium salt passivating solution, tin coating is handled to obtain effect preferably, the coating luminance brightness is improved.Sampath is by to analyses such as the chemical property of manganese and chromium and structures, shows that both ionic radius and the ligancy of co-ordination state are very approaching, so propose to replace the theory that chromic salt is handled with permanganate.Organic class passivation comprises, phytate is handled: nontoxic salts such as employing phytate carry out passivation to tin plate, both can improve the solidity to corrosion of tin plate, prevent tin plate oxidation jaundice in depositing process, can prevent to adopt chromating to pollution that environment caused and the harm that human body is caused again, but up to the present can't reach the effect of chromating.Oleic acid is handled: Frenchman D.Fousse etc. has studied the effect of oleic acid in protecting metallic surface under laboratory condition, and its mechanism of action is analyzed.The collaborative passivation of organic-inorganic comprises that phytic acid and phosphoric acid salt and other materials are worked in coordination with passivation: the floating Tian Hengfu of Japan etc. has proposed a kind of method of tin plate chromium-free passivation.Its treatment solution is made up of phosphoric acid 0.5～10g/L, phytic acid or phytate 0.2～2g/L and sodium-chlor, calcium chloride, oxide compound etc.
Though people have carried out a lot of researchs to Cr-Free Passivation in Tin-Plating Sheet technology, all can't wait tin plate with chromating because of its solidity to corrosion and antioxidant property, so up to the present, non-chromium inactivating technique never is applied to industrial production.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of brilliant tin plate chromium-free passivation solution, and this passivating solution does not contain 6 valency chromium, but can make the tin plate acquisition and use identical high anti-corrosion and the high antioxygenic property of chromating.
For solving the problems of the technologies described above, the invention provides a kind of brilliant tin plate chromium-free passivation solution, wherein, contain 20～70g tertiary sodium phosphate in every liter of passivating solution, 0.1～5g rose vitriol, 0.5～3g Sodium orthomolybdate, 20～75g phosphoric acid, all the other are water, wherein, phosphoric acid refers to the weight of pure phosphoric acid, can adopt commercially available industrial phosphoric acid preparation.
Above-mentioned tin plate chromium-free passivation solution, wherein, the pH value of passivating solution is 3～5.
Tin plate chromium-free passivation solution of the present invention can make through simply mixing.
The present invention also provides a kind of passivating method of brilliant tin plate, adopts above-mentioned passivating solution to carry out passivation, and the working temperature of passivating solution is 50～80 ℃; Passivation time is 1～20 second; The passivation mode is passivation of electrochemistry negative electrode or chemical passivation.
Brilliant tin plate chromium-free passivation solution of the present invention does not contain 6 valency chromium, under 50～80 ℃ of working temperatures tin plate is carried out chemical passivation or the passivation of electrochemistry negative electrode, tin plate has been obtained and identical high anti-corrosion and the high antioxygenic property of usefulness chromating technology.With the welding property of the tin plate of this non-chromium inactivating technique passivation, the adhesion property of coating has also been reached level with the tin plate of chromating.Fundamentally solved the harm that tin plate adopts the chromating that contains 6 valency chromium that human body and environment are brought.
Embodiment
Describe the present invention in detail below in conjunction with embodiment.
Embodiment 1
In every liter of chromium-free passivation liquid, contain the 20g tertiary sodium phosphate, the 2g rose vitriol, the 3g Sodium orthomolybdate, 40g phosphoric acid, all the other are water, the pH value of passivating solution is 4.5.
Above-mentioned chromium-free passivation liquid is carried out passivation to tin plate, adopt the passivation of electrochemistry negative electrode, passivation temperature is 70 ℃, and passivation time is 20 seconds.
With chromating liquid the tin plate of same model specification is carried out passivation, sodium dichromate 99 content is 10g/L in the passivating solution, and the passivation condition is identical with above-mentioned condition.
To carry out tests such as salt fog simultaneous test, laboratory atmospheric exposure test, coating adhesion test, the antioxidant property test of tin layer, anti-sulphide staining performance test and welding property with sample with the tin plate sample of present embodiment prescription and technology passivation with chromating.Test-results proves, has all reached the tin plate level of usefulness chromating with the tin plate of above-mentioned chromium-free deactivation prescription and technology passivation.
Embodiment 2
In every liter of chromium-free passivation liquid, contain the 40g tertiary sodium phosphate, the 5g rose vitriol, the 1g Sodium orthomolybdate, 20g phosphoric acid, all the other are water, the pH value of passivating solution is 5.
Above-mentioned chromium-free passivation liquid is carried out passivation to tin plate, adopt the passivation of electrochemistry negative electrode, passivation temperature is 80 ℃, and passivation time is 1 second.
With chromating liquid the tin plate of same model specification is carried out passivation, sodium dichromate 99 content is 10g/L in the passivating solution, and the passivation condition is identical with above-mentioned condition.
To carry out tests such as salt fog simultaneous test, laboratory atmospheric exposure test, coating adhesion test, the antioxidant property test of tin layer, anti-sulphide staining performance test and welding property with sample with the tin plate sample of present embodiment prescription and technology passivation with chromating.Test-results proves, has all reached the tin plate level of usefulness chromating with the tin plate of above-mentioned chromium-free deactivation prescription and technology passivation.
Embodiment 3
In every liter of chromium-free passivation liquid, contain the 50g tertiary sodium phosphate, the 1g rose vitriol, the 2g Sodium orthomolybdate, 60g phosphoric acid, all the other are water, the pH value of passivating solution is 3.5.
Above-mentioned chromium-free passivation liquid is carried out passivation to tin plate, adopt the passivation of electrochemistry negative electrode, passivation temperature is 60 ℃, and passivation time is 8 seconds.
With chromating liquid the tin plate of same model specification is carried out passivation, sodium dichromate 99 content is 10g/L in the passivating solution, and the passivation condition is identical with above-mentioned condition.
To carry out tests such as salt fog simultaneous test, laboratory atmospheric exposure test, coating adhesion test, the antioxidant property test of tin layer, anti-sulphide staining performance test and welding property with sample with the tin plate sample of present embodiment prescription and technology passivation with chromating.Test-results proves, has all reached the tin plate level of usefulness chromating with the tin plate of above-mentioned chromium-free deactivation prescription and technology passivation.
Embodiment 4
In every liter of chromium-free passivation liquid, contain the 70g tertiary sodium phosphate, the 0.1g rose vitriol, the 0.5g Sodium orthomolybdate, 75g phosphoric acid, all the other are water, the pH value of passivating solution is 3.
Above-mentioned chromium-free passivation liquid is carried out passivation to tin plate, adopt the passivation of electrochemistry negative electrode, passivation temperature is 50 ℃, and passivation time is 15 seconds.
With chromating liquid the tin plate of same model specification is carried out passivation, sodium dichromate 99 content is 10g/L in the passivating solution, and the passivation condition is identical with above-mentioned condition.
To carry out tests such as salt fog simultaneous test, laboratory atmospheric exposure test, coating adhesion test, the antioxidant property test of tin layer, anti-sulphide staining performance test and welding property with sample with the tin plate sample of present embodiment prescription and technology passivation with chromating.Test-results proves, has all reached the tin plate level of usefulness chromating with the tin plate of above-mentioned chromium-free deactivation prescription and technology passivation.
Claims (5)
1, a kind of brilliant tin plate chromium-free passivation solution is characterized in that, contains 20～70g tertiary sodium phosphate in every liter of passivating solution, 0.1～5g rose vitriol, and 0.5～3g Sodium orthomolybdate, 20～75g phosphoric acid, all the other are water.
2, tin plate chromium-free passivation solution as claimed in claim 1 is characterized in that, the pH value of described passivating solution is 3～5.
3, a kind of passivating method of brilliant tin plate is characterized in that, adopts the described passivating solution of claim 1 to carry out passivation, and the working temperature of passivating solution is 50～80 ℃.
4, passivating method as claimed in claim 3 is characterized in that, passivation time is 1～20 second.
5, passivating method as claimed in claim 3 is characterized in that, the passivation mode is passivation of electrochemistry negative electrode or chemical passivation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNA2008100487642A CN101358342A (en) | 2008-08-12 | 2008-08-12 | Brilliant tin plate chromium-free passivation solution and passivation method |
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| CNA2008100487642A CN101358342A (en) | 2008-08-12 | 2008-08-12 | Brilliant tin plate chromium-free passivation solution and passivation method |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906629A (en) * | 2010-08-09 | 2010-12-08 | 哈尔滨工业大学 | Blue write chromate-free passivation liquid of electrogalvanized layer and method for passivating electrogalvanized layer by adopting same |
| CN104233251A (en) * | 2014-09-16 | 2014-12-24 | 朱忠良 | Non-chromium passivation technology for zinc coating |
| CN104451636A (en) * | 2014-11-14 | 2015-03-25 | 无锡伊佩克科技有限公司 | Chromium-free passivation solution for tin-plated steel plate and preparation method of chromium-free passivation solution |
| CN104451646A (en) * | 2014-12-11 | 2015-03-25 | 天长市飞龙金属制品有限公司 | Tin coating passivator |
| CN105021516A (en) * | 2014-04-15 | 2015-11-04 | 上海梅山钢铁股份有限公司 | Testing liquid and testing adhesion film for detecting tin plating plate corrosion resistance, and detection method thereof |
| CN105483674A (en) * | 2015-12-17 | 2016-04-13 | 山东建筑大学 | Treatment method for brown surface of office furniture |
| CN107326350A (en) * | 2017-06-19 | 2017-11-07 | 苏州莱特复合材料有限公司 | A kind of preparation method of household electrical appliance metal powder parts passivator |
| CN107488844A (en) * | 2016-06-11 | 2017-12-19 | 上海梅山钢铁股份有限公司 | A kind of fluoride-free chromium-free passivating solution and its application method for tin plate |
| WO2019006612A1 (en) * | 2017-07-03 | 2019-01-10 | 深圳市宏昌发科技有限公司 | Passivator, passivation process for metal-plated part and metal workpiece |
| CN110691864A (en) * | 2017-05-27 | 2020-01-14 | 深圳市恒兆智科技有限公司 | Film passivating agent, metal piece and passivating treatment method thereof |
| CN112024339A (en) * | 2020-09-04 | 2020-12-04 | 江苏佰大幕墙科技有限公司 | Processing technology of aluminum veneer |
-
2008
- 2008-08-12 CN CNA2008100487642A patent/CN101358342A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906629A (en) * | 2010-08-09 | 2010-12-08 | 哈尔滨工业大学 | Blue write chromate-free passivation liquid of electrogalvanized layer and method for passivating electrogalvanized layer by adopting same |
| CN105021516B (en) * | 2014-04-15 | 2018-11-23 | 上海梅山钢铁股份有限公司 | A kind of test fluid and test pad pasting and its detection method of detection tin-plated board corrosion-resistance |
| CN105021516A (en) * | 2014-04-15 | 2015-11-04 | 上海梅山钢铁股份有限公司 | Testing liquid and testing adhesion film for detecting tin plating plate corrosion resistance, and detection method thereof |
| CN104233251A (en) * | 2014-09-16 | 2014-12-24 | 朱忠良 | Non-chromium passivation technology for zinc coating |
| CN104451636A (en) * | 2014-11-14 | 2015-03-25 | 无锡伊佩克科技有限公司 | Chromium-free passivation solution for tin-plated steel plate and preparation method of chromium-free passivation solution |
| CN104451646A (en) * | 2014-12-11 | 2015-03-25 | 天长市飞龙金属制品有限公司 | Tin coating passivator |
| CN105483674B (en) * | 2015-12-17 | 2018-05-11 | 山东建筑大学 | A kind of office furniture brown surface processing method |
| CN105483674A (en) * | 2015-12-17 | 2016-04-13 | 山东建筑大学 | Treatment method for brown surface of office furniture |
| CN107488844A (en) * | 2016-06-11 | 2017-12-19 | 上海梅山钢铁股份有限公司 | A kind of fluoride-free chromium-free passivating solution and its application method for tin plate |
| CN107488844B (en) * | 2016-06-11 | 2020-01-21 | 上海梅山钢铁股份有限公司 | Fluoride-free chromium-free passivation solution for tin-plated steel plate and use method thereof |
| CN110691864A (en) * | 2017-05-27 | 2020-01-14 | 深圳市恒兆智科技有限公司 | Film passivating agent, metal piece and passivating treatment method thereof |
| CN107326350A (en) * | 2017-06-19 | 2017-11-07 | 苏州莱特复合材料有限公司 | A kind of preparation method of household electrical appliance metal powder parts passivator |
| WO2019006612A1 (en) * | 2017-07-03 | 2019-01-10 | 深圳市宏昌发科技有限公司 | Passivator, passivation process for metal-plated part and metal workpiece |
| CN112024339A (en) * | 2020-09-04 | 2020-12-04 | 江苏佰大幕墙科技有限公司 | Processing technology of aluminum veneer |
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