CN101886259A - Zinc coat environmental-friendly passivation solution and use method thereof - Google Patents
Zinc coat environmental-friendly passivation solution and use method thereof Download PDFInfo
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- CN101886259A CN101886259A CN 201010217659 CN201010217659A CN101886259A CN 101886259 A CN101886259 A CN 101886259A CN 201010217659 CN201010217659 CN 201010217659 CN 201010217659 A CN201010217659 A CN 201010217659A CN 101886259 A CN101886259 A CN 101886259A
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Abstract
The invention discloses a zinc coat environmental-friendly passivation solution and a use method thereof. The passivation solution is formed by dissolving a solute consisting of a plurality of materials into deionized water, wherein the solute in the solution comprises the following components: 80-120g/L of sodium molybdate, 20-30g/L of sodium tungstate, 2-7g/L of titanyl sulfate, 5-10g/L of phytic acid, 15-50g/L of acrylic acid and 20-40g/L of hydrogen peroxide, wherein the pH value of the solution is regulated to 1.5-2.5 by using dilute acid. It is found that the zinc coat environmental-friendly passivation solution contains no chromium ions and thoroughly solves the problem of environment pollution brought by chromating; through salt spray test examination, a zinc coating plate passivated by the passivation solution has corrosion resistance approximately consistent with that of the traditional passivation solution; meanwhile, the use method is simple and easy.
Description
Technical field
The invention belongs to the steel production field, be meant a kind of Zinc coat environmental-friendly passivation solution and using method thereof particularly.
Background technology
After galvanizing production gets off from production line, between storage, delivery period,, cause and get rusty (white rust) or variable color (ash) because the variation of outside air temperature and humidity etc. can produce dewfall on the zinc coating surface.In order to prevent galvanizing production generation corrosion, the manufacturing enterprise of galvanizing production just must carry out surface passivation to it and handle.Traditional Passivation Treatment is to adopt chromic salt as treatment agent, behind chromate treating, generates a kind of passive film on the zinc product surface, and this film has good isolation performance and self-healing properties, makes zinc coating have good solidity to corrosion.Though chromate passivation film has good provide protection to zinc coating, chromic water-soluble and hypertoxicity easily causes environmental pollution.Along with the raising of people's environment protection thought and the reinforcement of social enviroment protection consciousness, national governments strictness limit using and discharging of chromic salt, parliament of European Union and EU Council had once passed through the RoHS instruction in January, 2003, strictness has limited the use chromic salt and carried out the zinc coating passivation processing and limit all kinds of imports that contain the chromium product.
The domestic and international at present research to the chromium-free deactivation treatment process mainly contains inorganic salt passivation film forming and organism passivation film forming.Inorganic salt passivation film-forming process mainly adopts high-valency metal salt, as molybdate, tungstate, silicate etc. as passivating solution.Number for the patent of invention of US4385940 discloses a kind of " anti-corrosive treatment method of galvanized steel ", adopt the zine plate of molybdate passivating method passivation can anti-24 hours salt-fog tests as U. S. application, the white rust area be between 0～1%.Organism passivation film-forming process mainly is to adopt water soluble organic substance to add inorganic salt to constitute; as publication number is that the Chinese invention patent application of CN1268583A discloses a kind of " being used to protect the chromium-free passivation liquid and the coating method thereof of zinc coating ", adopts exactly that to add molybdate in the water soluble acrylate resin formulated." phytic acid is used for galvanized chromium-free deactivation liquid " literary composition in " corrosion and protection " 2002.23 (9), disclose the passivating solution that contains silicate 40g/L, sulfuric acid 3g/L, hydrogen peroxide 40g/L, nitric acid 5g/L, phytic acid 5g/L, pH value 2～3, its Corrosion Protection is better than various alkyl phosphonic acids.Publication number is for KR2006007565, name are called Korea S's patent of invention of " steel plate galvanized chromium-free deactivation solution ", and to disclose a kind of main component be polyethylene and add the chromium-free passivation liquid that 10～25% amine, silane, wax etc. are formed.U.S. Patent number is US, disclosed this inactivating treatment liquid of patent of invention that the 0908182A1 name is called " a kind of novel compound Zincing passivation treatment solution of organic/inorganic " comprises 0.01～40.00% phospho-molybdic acid polyamine, 1.00～30.00% silicofluoric acid, 0.01～20.00% organoalkoxysilane, 1.00～30.00% phosphoric acid, 0～40.00% filming emulsion, 0～5.00% lubricant, water and pH value conditioning agent, do not contain chromium, this sticking power and solidity to corrosion of handling film is all better.Though above-mentioned existing inorganic salt passivation film forming and organism passivation film forming passivating solution have had very big improvement aspect asepsis environment-protecting, but, the solidity to corrosion of solidity to corrosion, passivation speed and the traditional chromic acid salt passive film of the passive film after above-mentioned passivating solution is handled differs far away, is difficult to satisfy the requirement of modern zinc-plated production.Up to the present, still do not have a kind of solidity to corrosion of chromium-free passivation liquid to make people satisfied, be difficult to generally be accepted by people.
Summary of the invention
Purpose of the present invention will provide a kind of Zinc coat environmental-friendly passivation solution and using method thereof exactly, this passivating solution does not contain the material to environment and human body harmful, the salt spray corrosion resistance of its passive film and chromating are roughly suitable, and using method of the present invention is simple to operate.
For achieving the above object, the Zinc coat environmental-friendly passivation solution that the present invention is designed, the solute that it is made up of multiple material is dissolved in the solution that forms in the deionized water, the each component proportioning of solute is in the described solution: Sodium orthomolybdate 80～120g/L, sodium wolframate 20～30g/L, titanyl sulfate 2～7g/L, phytic acid 5～10g/L, acrylic acid 15～50g/L, hydrogen peroxide 20～40g/L, described solution adopt diluted acid to regulate its pH to 1.5～2.5.
Further, described solution adopts dilute phosphoric acid to regulate its pH to 1.5～2.5.
Use Zinc coat environmental-friendly passivation solution of the present invention to the method that galvanized sheet carries out passivation, may further comprise the steps:
At first treat the galvanized sheet surface of passivation and carry out purifying treatment;
Then described Zinc coat environmental-friendly passivation solution is warming up to 50～65 ℃;
With 50～65 ℃ passivating solution or the galvanized sheet after immersion or spray or the coating purification, passivation time is controlled at 0.5～4s again;
Get final product with the galvanized sheet oven dry after with passivation of 50～60 ℃ hot blast at last.
Each components selection principle and act on as follows in the Zinc coat environmental-friendly passivation solution of the present invention:
Sodium orthomolybdate: molybdenum element and chromium element all belong to the group vib element in chemical periodictable, chemical property is close, so the present invention carries out passivation with nontoxic molybdenum salt substitute chromium salt pair zinc coating surface, although the effect of passivation is not as chromic salts, but can overcome the problem of environmental pollution that causes because of chromic salts, can obviously improve the solidity to corrosion of zinc coating.
Sodium wolframate: tungsten and chromium in the chemical periodictable, molybdenum are of the same clan, and sodium wolframate is having similarity with Sodium orthomolybdate aspect metal inhibitor, and the tungstate passive film that generates at zinc surface also can improve the solidity to corrosion of zinc coating.The interaction of molybdate and tungstate particularly, the passive film that generates at zinc surface has better solidity to corrosion.
Titanyl sulfate: this high valence state titanium can improve the accuracy and the homogeneity of passivation layer as supplementary additive salt in passivating solution, the passivation film forming is had bigger help.
Phytic acid: phytic acid claims phytic acid again, is a kind of multiple tooth metal chelator, contains easily to form a plurality of chelate rings with 24 Sauerstoffatoms, 12 hydroxyls and 6 phosphates of metal cooperation.Formed complex compound all has extremely strong stability in the pH value scope widely, when with metal complex after, easily form the unit molecule protective membrane of one deck densification in the metallic surface, can stop oxygen to enter the metallic surface effectively, thereby coating is played a protective role.
Acrylic acid: be a kind of organic binder matter, can improve the compactness of molybdate passive film behind the adding passivating solution, thereby improve the salt spray resistance ability of passive film.
Hydrogen peroxide: hydrogen peroxide is as a kind of strong oxidizer, add passivating solution after, can guarantee the stable of high valence ion in the passivating solution.
The pH value is very big to the influence of Sodium orthomolybdate passive film solidity to corrosion, and the solidity to corrosion of Sodium orthomolybdate passive film was more excellent when pH was low.In addition, passivating solution temperature and passivation time are bigger to the growth process affects of passive film, and the temperature and time that the present invention sets can be suitable for using on the tinuous production.
Zinc coat environmental-friendly passivation solution of the present invention does not contain chromium ion, thoroughly solve chromating and handled the problem of environmental pollution that brings, check through salt-fog test, effect through the solidity to corrosion of the galvanized sheet of passivating solution Passivation Treatment of the present invention and traditional chromating liquid passivation is roughly suitable, and using method of the present invention is simple.
Embodiment
Come zinc layer of the present invention is elaborated with environment-friendly type passivation liquid and using method thereof below in conjunction with specific embodiment:
Embodiment 1:
Get Sodium orthomolybdate 90g, sodium wolframate 30g, titanyl sulfate 3g, acrylic acid 15g, hydrogen peroxide 40g, phytic acid 10g are dissolved in deionized water and are mixed with 1L solution, are adjusted to pH=2 with phosphoric acid.
When utilizing above-mentioned Zinc coat environmental-friendly passivation solution that galvanized sheet is carried out passivation,
It is stand-by that electrochemical deoiling, tap water flushing, rinsed with deionized water, hot blast drying are carried out with degreasing fluid in the galvanized sheet surface that at first will treat passivation;
Passivating solution is warming up to 65 ℃ then;
Immerse passivating solution, passivation 0.5～1s with the galvanized sheet after the purifying treatment again;
The galvanized sheet that to cross through Passivation Treatment promptly forms passive film with 50～55 ℃ hot blast baking 10min at last.
Neutral salt spray corrosion test (NSS): the galvanized sheet sample after above-mentioned Zinc coat environmental-friendly passivation solution Passivation Treatment is put into salt fog cabinet, with reference to the IS03768 standard, the employing weight percentage is 5% NaCl solution, in pH=6.5～7.2, temperature is spraying continuously under 2 ℃ of conditions of 35 soil, the area that occurs " white rust " when viewing test finishes, the percentage ratio of surface measurements " white rust " area is to estimate the solidity to corrosion of passive film.
Galvanized sheet in the present embodiment after the Passivation Treatment is through the neutral salt spray corrosion test of 72h, and specimen surface " white rust " area illustrates that less than 5% the solidity to corrosion of passive film is good.
Embodiment 2:
Get Sodium orthomolybdate 100g, sodium wolframate 30g, titanyl sulfate 3g, acrylic acid 20g, hydrogen peroxide 20g, phytic acid 5g are dissolved in deionized water and are mixed with 1L solution, are adjusted to pH=1.5 with phosphoric acid.
When utilizing above-mentioned Zinc coat environmental-friendly passivation solution that galvanized sheet is carried out passivation,
It is stand-by that electrochemical deoiling, tap water flushing, rinsed with deionized water, hot blast drying are carried out with degreasing fluid in the galvanized sheet surface that at first will treat passivation;
Passivating solution is warming up to 60 ℃ then;
Again with the galvanized sheet surface of passivating solution spray after purifying treatment, passivation 1～2s;
The galvanized sheet that to cross through Passivation Treatment promptly forms passive film with 55～60 ℃ hot blast baking 10min at last.
Galvanized sheet after the Passivation Treatment in the present embodiment is carried out neutral salt spray corrosion test (NSS) by the mode of embodiment 1 record, and through the neutral salt spray corrosion test of 72h, specimen surface " white rust " area illustrates that less than 2% the solidity to corrosion of passive film is good.
Embodiment 3:
Get Sodium orthomolybdate 100g, sodium wolframate 20g, titanyl sulfate 5g, acrylic acid 20g, hydrogen peroxide 20g, phytic acid 10g are dissolved in deionized water and are mixed with 1L solution, are adjusted to pH=2.5 with phosphoric acid.
When utilizing above-mentioned Zinc coat environmental-friendly passivation solution that galvanized sheet is carried out passivation,
It is stand-by that electrochemical deoiling, tap water flushing, rinsed with deionized water, hot blast drying are carried out with degreasing fluid in the galvanized sheet surface that at first will treat passivation;
Passivating solution is warming up to 50 ℃ then;
Again passivating solution is coated in the galvanized sheet surface after the purifying treatment, passivation 2～3s;
The galvanized sheet that to cross through Passivation Treatment promptly forms passive film with 60～65 ℃ hot blast baking 5min at last.
Galvanized sheet after the Passivation Treatment in the present embodiment is carried out neutral salt spray corrosion test (NSS) by the mode of embodiment 1 record, and through the neutral salt spray corrosion test of 78h, specimen surface " white rust " area illustrates that less than 6% the solidity to corrosion of passive film is good.
Embodiment 4:
Get Sodium orthomolybdate 80g, sodium wolframate 26g, titanyl sulfate 7g, acrylic acid 50g, hydrogen peroxide 30g, phytic acid 8g are dissolved in deionized water and are mixed with 1L solution, are adjusted to pH=2.0 with phosphoric acid.
When utilizing above-mentioned Zinc coat environmental-friendly passivation solution that galvanized sheet is carried out passivation,
It is stand-by that electrochemical deoiling, tap water flushing, rinsed with deionized water, hot blast drying are carried out with degreasing fluid in the galvanized sheet surface that at first will treat passivation;
Passivating solution is warming up to 65 ℃ then;
Again passivating solution is sprayed at the galvanized sheet surface for the treatment of passivation, passivation 2～3s;
The galvanized sheet that to cross through Passivation Treatment promptly forms passive film with 50～55 ℃ hot blast baking 8min at last.
Galvanized sheet after the Passivation Treatment in the present embodiment is carried out neutral salt spray corrosion test (NSS) by the mode of embodiment 1 record, and through the neutral salt spray corrosion test of 78h, specimen surface " white rust " illustrates that less than 4% the solidity to corrosion of passive film is good.
Embodiment 5
Get Sodium orthomolybdate 120g, sodium wolframate 25g, titanyl sulfate 4g, acrylic acid 40g, hydrogen peroxide 25g, phytic acid 10g are dissolved in deionized water and are mixed with 1L solution, are adjusted to pH=2.5 with phosphoric acid.
When utilizing above-mentioned Zinc coat environmental-friendly passivation solution that galvanized sheet is carried out passivation,
It is stand-by that electrochemical deoiling, tap water flushing, rinsed with deionized water, hot blast drying are carried out with degreasing fluid in the galvanized sheet surface that at first will treat passivation;
Passivating solution is warming up to 55 ℃ then;
Again the galvanized sheet after the purifying treatment is immersed passivating solution, passivation 3～4s;
The galvanized sheet that to cross through Passivation Treatment promptly forms passive film with 55～60 ℃ hot blast baking 6min at last.
Galvanized sheet after the Passivation Treatment in the present embodiment is carried out neutral salt spray corrosion test (NSS) by the mode of embodiment 1 record, and through the neutral salt spray corrosion test of 78h, specimen surface " white rust " area illustrates that less than 2% the solidity to corrosion of passive film is good.
Embodiment 6
Get Sodium orthomolybdate 110g, sodium wolframate 30g, titanyl sulfate 5g, acrylic acid 45g, hydrogen peroxide 20g, phytic acid 5g are dissolved in deionized water and are mixed with 1L solution, are adjusted to pH=2.0 with phosphoric acid.
When utilizing above-mentioned Zinc coat environmental-friendly passivation solution that galvanized sheet is carried out passivation,
It is stand-by that electrochemical deoiling, tap water flushing, rinsed with deionized water, hot blast drying are carried out with degreasing fluid in the galvanized sheet surface that at first will treat passivation;
Passivating solution is warming up to 60 ℃ then;
Again passivating solution is sprayed at the galvanized sheet surface for the treatment of passivation, passivation 1～2s;
The galvanized sheet that to cross through Passivation Treatment promptly forms passive film with 50～60 ℃ hot blast baking 5min at last.
Galvanized sheet after the Passivation Treatment in the present embodiment is carried out neutral salt spray corrosion test (NSS) by the mode of embodiment 1 record, and through the neutral salt spray corrosion test of 78h, specimen surface " white rust " area illustrates that less than 5% the solidity to corrosion of passive film is good.
Claims (3)
1. Zinc coat environmental-friendly passivation solution, the solute that it is made up of multiple material is dissolved in the solution that forms in the deionized water, the each component proportioning of solute is in the described solution: Sodium orthomolybdate 80～120g/L, sodium wolframate 20～30g/L, titanyl sulfate 2～7g/L, phytic acid 5～10g/L, acrylic acid 15～50g/L, hydrogen peroxide 20～40g/L, described solution adopt diluted acid to regulate its pH to 1.5～2.5.
2. Zinc coat environmental-friendly passivation solution according to claim 1 is characterized in that: described diluted acid is a dilute phosphoric acid.
3. one kind is used the described Zinc coat environmental-friendly passivation solution of claim 1 to the method that galvanized sheet carries out passivation, may further comprise the steps:
At first treat the galvanized sheet surface of passivation and carry out purifying treatment;
Then described Zinc coat environmental-friendly passivation solution is warming up to 50～65 ℃
With 50～65 ℃ passivating solution or the galvanized sheet after immersion or spray or the coating purification, passivation time is controlled at 0.5～4s again;
Get final product with the galvanized sheet oven dry after with passivation of 50～60 ℃ hot blast at last.
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Cited By (11)
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| CN102943257A (en) * | 2012-10-31 | 2013-02-27 | 戴亚洲 | Manufacturing method of rare earth nanometer composite alloy coating steel band and steel wire |
| CN103276386A (en) * | 2013-05-06 | 2013-09-04 | 大庆宝丰科技有限公司 | Chromium-free environment-friendly passivator for brass cartridge case of cartridge and preparation method |
| CN104233251A (en) * | 2014-09-16 | 2014-12-24 | 朱忠良 | Non-chromium passivation technology for zinc coating |
| CN104404492A (en) * | 2014-12-24 | 2015-03-11 | 湖南金裕化工有限公司 | Chromium-free passivation solution as well as preparation and using methods thereof |
| CN104775110A (en) * | 2015-04-17 | 2015-07-15 | 沈阳师范大学 | Additive for restoring passivation performance of molybdate treating fluid applicable to galvanizing coat surface |
| CN104913957A (en) * | 2015-05-04 | 2015-09-16 | 中国石油化工股份有限公司 | Preparation method for TEM in-situ observation material matrix/passivation film interface structure sample |
| CN105386025A (en) * | 2015-11-25 | 2016-03-09 | 河北工业大学 | Hot dip galvanizing coating chromate-free passivation agent and preparation method thereof |
| CN106399995A (en) * | 2016-11-30 | 2017-02-15 | 淄博传能新材料科技有限公司 | Non-chrome hot galvanizing passivation solution and preparing method thereof |
| CN106835100A (en) * | 2016-12-30 | 2017-06-13 | 张庆 | A kind of polyaniline epoxy resin corrosion resistance composite passivation film |
| CN107090576A (en) * | 2017-05-22 | 2017-08-25 | 厦门建霖健康家居股份有限公司 | A kind of kirsite chromium-free passivation liquid |
| WO2017219371A1 (en) * | 2016-06-24 | 2017-12-28 | 深圳市恒兆智科技有限公司 | Passivator, zinc plated workpiece and passivation treatment method therefor |
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| CN102943257B (en) * | 2012-10-31 | 2014-10-22 | 戴亚洲 | Manufacturing method of rare earth nanometer composite alloy coating steel band and steel wire |
| CN102943257A (en) * | 2012-10-31 | 2013-02-27 | 戴亚洲 | Manufacturing method of rare earth nanometer composite alloy coating steel band and steel wire |
| CN103276386A (en) * | 2013-05-06 | 2013-09-04 | 大庆宝丰科技有限公司 | Chromium-free environment-friendly passivator for brass cartridge case of cartridge and preparation method |
| CN103276386B (en) * | 2013-05-06 | 2015-11-11 | 大庆宝丰科技有限公司 | Brass artillery shell chromium-free environment-friendly type passivator and preparation method |
| CN104233251A (en) * | 2014-09-16 | 2014-12-24 | 朱忠良 | Non-chromium passivation technology for zinc coating |
| CN104404492B (en) * | 2014-12-24 | 2017-07-11 | 湖南金裕化工有限公司 | Chromium-free passivation liquid, preparation method and its application method |
| CN104404492A (en) * | 2014-12-24 | 2015-03-11 | 湖南金裕化工有限公司 | Chromium-free passivation solution as well as preparation and using methods thereof |
| CN104775110A (en) * | 2015-04-17 | 2015-07-15 | 沈阳师范大学 | Additive for restoring passivation performance of molybdate treating fluid applicable to galvanizing coat surface |
| CN104913957A (en) * | 2015-05-04 | 2015-09-16 | 中国石油化工股份有限公司 | Preparation method for TEM in-situ observation material matrix/passivation film interface structure sample |
| CN105386025A (en) * | 2015-11-25 | 2016-03-09 | 河北工业大学 | Hot dip galvanizing coating chromate-free passivation agent and preparation method thereof |
| CN105386025B (en) * | 2015-11-25 | 2018-06-15 | 河北工业大学 | A kind of hot galvanized layer chrome-free tanning agent and its preparation method |
| WO2017219371A1 (en) * | 2016-06-24 | 2017-12-28 | 深圳市恒兆智科技有限公司 | Passivator, zinc plated workpiece and passivation treatment method therefor |
| CN106399995A (en) * | 2016-11-30 | 2017-02-15 | 淄博传能新材料科技有限公司 | Non-chrome hot galvanizing passivation solution and preparing method thereof |
| CN106835100A (en) * | 2016-12-30 | 2017-06-13 | 张庆 | A kind of polyaniline epoxy resin corrosion resistance composite passivation film |
| CN107090576A (en) * | 2017-05-22 | 2017-08-25 | 厦门建霖健康家居股份有限公司 | A kind of kirsite chromium-free passivation liquid |
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Application publication date: 20101117 |