CN104060257A - Chromium-free passivator for zinc coating and preparation method of chromium-free passivator - Google Patents
Chromium-free passivator for zinc coating and preparation method of chromium-free passivator Download PDFInfo
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Abstract
The invention relates to the technical field of metal surface treatment and discloses a chromium-free passivator for a zinc coating and a preparation method of the chromium-free passivator. The chromium-free passivator comprises the following raw materials: 10-28g/L of sodium molybdate, 10-18g/L of sodium silicate, 48-55g/L of magnesium fluoride, 15-30g/L of citric acid, 10-25g/L of ethenyl-silanetrio triacetate, 8-13g/L of tungstate, 8-12g/L of acrylic resin, 5-15g/L of corrosion inhibitor, 5-10g/L of nitric acid and the balance of water. The chromium-free passivator is reasonable in formula, free of chromium, nontoxic, environment-friendly and efficient; the passivator is prepared by combining the advantages of molybdate and tungstate, so that the corrosion resistance of a passivation film is effectively improved, and the passivation film is compact in surface structure, free of obvious cracks, relatively good in adhesive force and capable of meeting the requirement for product performance; proved by a 93h salt spray test, the corrosion area of a metal part passivated by using the chromium-free passivator is only 3.2% which meets the standard requirement for less than 5%.
Description
Technical field
The present invention relates to field of metal surface treatment technology, refer more particularly to a kind of galvanized layer chromium-free passivant and preparation method thereof.
Background technology
On metallic element matrix, zinc-plated is in electroplating industry, to electroplate the most widely one of kind as protective coating.Because the Standard Electrode Potentials of zinc is more negative than iron, the coating on metallic element matrix conventionally need to carry out Passivation Treatment form fine and close passive film could be as protective coating.Tradition zinc coating mainly adopts chromatedsolution to carry out Passivation Treatment, and because the sexavalent chrome in chromatedsolution is a kind of toxic substance and has carcinogenesis, American-European countries has put into effect the chromic use of Series correlation legal restrictions.
The passivation of environment-friendly type mainly adopts trivalent chromium and chromium-free deactivation both direction.Chromium-free deactivation system has titanate, molybdates, tungstate, rare earth, silicate, current these Chrome-free system passive film asepsis environment-protectings, solidity to corrosion and outward appearance all improve a lot in recent years, met common handware and electroplated requirement, so non-chromium inactivating technique has wide practical use industrial.Chromium-free deactivation is with respect to above-mentioned two kinds of deactivating process for the treatment of, has the features such as asepsis environment-protecting, efficient, low consumption.Chromium-free deactivation comprises inorganic salts passivation, organism passivation and the compound passivation of organic-inorganic.Inorganic salts passivation comprises the inorganic salts passivation such as molybdate, tungstate, silicate and rare earth metal salt.Organism passivation comprises the organism passivation such as Weibull, phytic acid, oleic acid, organosilane.The compound passivation of organic-inorganic is the composite passivated methods such as composite passivated composite passivated, the silane coupling agent processing that comprises phytic acid and phosphoric acid salt etc. of Chrome-free, coating processing.The solidity to corrosion of early stage inorganic salts and organism chromium-free deactivation is not as sexavalent chrome passivation, and the passive film that inorganic salts passivation forms has self-reparing capability unlike sexavalent chrome passive film, and in the damaged situation of film, film cannot be repaired, and causes passive film solidity to corrosion to decline.Although organism passivation solidity to corrosion is better than inorganic salts passivation, there is defect in film, and solidity to corrosion is not as sexavalent chrome passivator.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of environment-protecting asepsis, galvanized layer chromium-free passivant of good corrosion resistance and preparation method thereof.
For solving the problems of the technologies described above, the present invention by the following technical solutions:
A kind of galvanized layer chromium-free passivant, it is characterized in that, comprise following raw material: containing Sodium orthomolybdate 10-28g/L, water glass 10-18g/L, magnesium fluoride 48-55g/L, citric acid 15-30g/L, vinyltriacetoxy silane 10-25g/L, tungstate 8-13g/L, acrylic resin 8-12g/L, inhibiter 5-15g/L, nitric acid 5-10g/L, surplus is water.
Preferably, described galvanized layer chromium-free passivant, comprises following raw material: containing Sodium orthomolybdate 16-28g/L, and water glass 13-18g/L, magnesium fluoride 48-55g/L, citric acid 25-30g/L, vinyltriacetoxy silane 15-25g/L, tungstate 8-13g/L, acrylic resin 8-12g/L, inhibiter 5-10g/L, nitric acid 5-10g/L, surplus is water.
Preferably, described inhibiter be 1 hydroxyethylidine diphosphonate, nitrilo three methane phosphonic acids, ethylenediamine tetramethylene phosphonic acid salt wherein one or both.
Preferably, described tungstate is sodium wolframate, calcium wolframate wherein one or both.
A preparation method for galvanized layer chromium-free passivant, is characterized in that, comprises the following steps:
(1) Sodium orthomolybdate of calculated amount, water glass and tungstate are added in the water of half calculated amount, stir and make its dissolving;
(2) magnesium fluoride of calculated amount and inhibiter are added in the mixed solution of (1) gained, fully stir and make its dissolving; (3) citric acid of calculated amount, vinyltriacetoxy silane are added in the mixed solution of (2) gained, fully stir, add while stirring acrylic resin after being cooled to room temperature, with after the water constant volume of calculated amount, with nitric acid, adjust pH to 1.5-2.5.
The present invention fills a prescription rationally, and or not containing chromium, asepsis environment-protecting is not efficient, in conjunction with the advantage of molybdate and tungstate, jointly prepare passivator, effectively increased the antiseptic property of passive film, passive film surface tissue is fine and close, the obvious crackle of nothing, and sticking power is better, meets the requirement of product performance; 93 hours salt-fog test corroded areas of metallic element after passivation of the present invention only have 3.2%, and what conformance with standard required is less than 5%.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is further described in detail.
Embodiment mono-:
A kind of galvanized layer chromium-free passivant, comprise following raw material: containing Sodium orthomolybdate 28g/L, water glass 18g/L, magnesium fluoride 48g/L, citric acid 25g/L, vinyltriacetoxy silane 25g/L, tungstate 13g/L, acrylic resin 12g/L, 1 hydroxyethylidine diphosphonate 10g/L, nitric acid 10g/L, surplus is water.Its preparation method comprises the following steps:
(1) Sodium orthomolybdate of calculated amount, water glass and tungstate are added in the water of half calculated amount, stir and make its dissolving;
(2) magnesium fluoride of calculated amount and inhibiter are added in the mixed solution of (1) gained, fully stir and make its dissolving;
(3) citric acid of calculated amount, vinyltriacetoxy silane are added in the mixed solution of (2) gained, fully stir, add while stirring acrylic resin after being cooled to room temperature, with after the water constant volume of calculated amount, with nitric acid, adjust pH to 2.5.93 hours salt-fog test corroded areas of metallic element after passivation of the present invention only have 3.2%, and what conformance with standard required is less than 5%.
Embodiment bis-:
A galvanized layer chromium-free passivant, comprises following raw material: containing Sodium orthomolybdate 25g/L, and water glass 16g/L, magnesium fluoride 52g/L, citric acid 28g/L, vinyltriacetoxy silane 17g/L, tungstate 10g/L, acrylic resin 8g/L, nitrilo three methane phosphonic acid 5g/L, nitric acid 5g/L, surplus is water.Its preparation method comprises the following steps:
(1) Sodium orthomolybdate of calculated amount, water glass and tungstate are added in the water of half calculated amount, stir and make its dissolving;
(2) magnesium fluoride of calculated amount and nitrilo three methane phosphonic acids are added in the mixed solution of (1) gained, fully stir and make its dissolving;
(3) citric acid of calculated amount, vinyltriacetoxy silane are added in the mixed solution of (2) gained, fully stir, add while stirring acrylic resin after being cooled to room temperature, with after the water constant volume of calculated amount, with nitric acid, adjust pH to 1.5.93 hours salt-fog test corroded areas of metallic element after passivation of the present invention only have 3.2%, and what conformance with standard required is less than 5%.
Embodiment tri-:
A kind of galvanized layer chromium-free passivant, comprise following raw material: containing Sodium orthomolybdate 23g/L, water glass 15g/L, magnesium fluoride 55g/L, citric acid 30g/L, vinyltriacetoxy silane 20g/L, tungstate 11g/L, acrylic resin 11g/L, ethylenediamine tetramethylene phosphonic acid salt 7g/L, nitric acid 7g/L, surplus is water.Its preparation method comprises the following steps:
(1) Sodium orthomolybdate of calculated amount, water glass and tungstate are added in the water of half calculated amount, stir and make its dissolving;
(2) magnesium fluoride of calculated amount and ethylenediamine tetramethylene phosphonic acid salt are added in the mixed solution of (1) gained, fully stir and make its dissolving;
(3) citric acid of calculated amount, vinyltriacetoxy silane are added in the mixed solution of (2) gained, fully stir, add while stirring acrylic resin after being cooled to room temperature, with after the water constant volume of calculated amount, with nitric acid, adjust pH to 1.8.93 hours salt-fog test corroded areas of metallic element after passivation of the present invention only have 3.2%, and what conformance with standard required is less than 5%.
Embodiment tetra-:
A kind of galvanized layer chromium-free passivant, comprise following raw material: containing Sodium orthomolybdate 20g/L, water glass 13g/L, magnesium fluoride 51g/L, citric acid 26g/L, vinyltriacetoxy silane 22g/L, tungstate 9g/L, acrylic resin 9g/L, 1 hydroxyethylidine diphosphonate 5g/L, nitrilo three methane phosphonic acid 9g/L, nitric acid 6g/L, surplus is water.Its preparation method comprises the following steps:
(1) Sodium orthomolybdate of calculated amount, water glass and tungstate are added in the water of half calculated amount, stir and make its dissolving;
(2) magnesium fluoride of calculated amount, 1 hydroxyethylidine diphosphonate, nitrilo three methane phosphonic acid inhibiter are added in the mixed solution of (1) gained, fully stir and make its dissolving;
(3) citric acid of calculated amount, vinyltriacetoxy silane are added in the mixed solution of (2) gained, fully stir, add while stirring acrylic resin after being cooled to room temperature, with after the water constant volume of calculated amount, with nitric acid, adjust pH to 2.0.93 hours salt-fog test corroded areas of metallic element after passivation of the present invention only have 3.2%, and what conformance with standard required is less than 5%.
Embodiment five:
A galvanized layer chromium-free passivant, comprises following raw material: containing Sodium orthomolybdate 16g/L, and water glass 17g/L, magnesium fluoride 54g/L, citric acid 26g/L, vinyltriacetoxy silane 16g/L, tungstate 12g/L, acrylic resin 8g/L, inhibiter 8g/L, nitric acid 8g/L, surplus is water.Its preparation method comprises the following steps:
(1) Sodium orthomolybdate of calculated amount, water glass and tungstate are added in the water of half calculated amount, stir and make its dissolving;
(2) magnesium fluoride of calculated amount, nitrilo three methane phosphonic acid ethylenediamine tetramethylene phosphonic acid salt are added in the mixed solution of (1) gained, fully stir and make its dissolving;
(3) citric acid of calculated amount, vinyltriacetoxy silane are added in the mixed solution of (2) gained, fully stir, add while stirring acrylic resin after being cooled to room temperature, with after the water constant volume of calculated amount, with nitric acid, adjust pH to 2.2.93 hours salt-fog test corroded areas of metallic element after passivation of the present invention only have 3.2%, and what conformance with standard required is less than 5%.
It should be noted last that, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement technical scheme of the present invention, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (5)
1. a galvanized layer chromium-free passivant, it is characterized in that, comprise following raw material: containing Sodium orthomolybdate 10-28g/L, water glass 10-18g/L, magnesium fluoride 48-55g/L, citric acid 15-30g/L, vinyltriacetoxy silane 10-25g/L, tungstate 8-13g/L, acrylic resin 8-12g/L, inhibiter 5-15g/L, nitric acid 5-10g/L, surplus is water.
2. galvanized layer chromium-free passivant according to claim 1, it is characterized in that, comprise following raw material: containing Sodium orthomolybdate 16-28g/L, water glass 13-18g/L, magnesium fluoride 48-55g/L, citric acid 25-30g/L, vinyltriacetoxy silane 15-25g/L, tungstate 8-13g/L, acrylic resin 8-12g/L, inhibiter 5-10g/L, nitric acid 5-10g/L, surplus is water.
3. galvanized layer chromium-free passivant according to claim 1, is characterized in that, described inhibiter be 1 hydroxyethylidine diphosphonate, nitrilo three methane phosphonic acids, ethylenediamine tetramethylene phosphonic acid salt wherein one or both.
4. galvanized layer chromium-free passivant according to claim 1, is characterized in that, described tungstate is sodium wolframate, calcium wolframate wherein one or both.
5. a preparation method for the galvanized layer chromium-free passivant described in one of claim 1 to 4, is characterized in that, comprises the following steps:
(1) Sodium orthomolybdate of calculated amount, water glass and tungstate are added in the water of half calculated amount, stir and make its dissolving;
(2) magnesium fluoride of calculated amount and inhibiter are added in the mixed solution of (1) gained, fully stir and make its dissolving;
(3) citric acid of calculated amount, vinyltriacetoxy silane are added in the mixed solution of (2) gained, fully stir, add while stirring acrylic resin after being cooled to room temperature, with after the water constant volume of calculated amount, with nitric acid, adjust pH to 1.5-2.5.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104988488A (en) * | 2015-07-11 | 2015-10-21 | 合肥正浩机械科技有限公司 | Dispersed and esterified metal surface treatment agent and preparation method thereof |
| 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 |
| 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 |
| CN106637173A (en) * | 2017-01-13 | 2017-05-10 | 昆明理工大学 | Hot galvanized environment-friendly passivation solution and preparation method thereof |
| CN108004536A (en) * | 2017-11-22 | 2018-05-08 | 无锡伊佩克科技有限公司 | A kind of chrome-free tanning agent and preparation method thereof |
| CN108004533A (en) * | 2017-12-31 | 2018-05-08 | 天长市飞龙金属制品有限公司 | A kind of galvanized sheet passivating solution |
| CN108690981A (en) * | 2018-06-29 | 2018-10-23 | 宜兴大平杆塔制造有限公司 | With no sodium chromate passivator and preparation method thereof after a kind of metal product is zinc-plated |
| WO2019006623A1 (en) * | 2017-07-03 | 2019-01-10 | 深圳市盈恒科技有限公司 | Chromium-free passivator, aluminum product and surface passivation process therefor |
| WO2019006625A1 (en) * | 2017-07-03 | 2019-01-10 | 深圳市盈恒科技有限公司 | Chromium-free passivator, aluminum workpiece and surface passivation process therefor |
| CN113583745A (en) * | 2021-07-09 | 2021-11-02 | 煤炭科学技术研究院有限公司 | Compatible concentrated solution for hydraulic support and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104988488A (en) * | 2015-07-11 | 2015-10-21 | 合肥正浩机械科技有限公司 | Dispersed and esterified metal surface treatment agent and preparation method thereof |
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| 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 |
| 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 |
| CN106637173A (en) * | 2017-01-13 | 2017-05-10 | 昆明理工大学 | Hot galvanized environment-friendly passivation solution and preparation method thereof |
| WO2019006623A1 (en) * | 2017-07-03 | 2019-01-10 | 深圳市盈恒科技有限公司 | Chromium-free passivator, aluminum product and surface passivation process therefor |
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| CN108004536A (en) * | 2017-11-22 | 2018-05-08 | 无锡伊佩克科技有限公司 | A kind of chrome-free tanning agent and preparation method thereof |
| CN108004533A (en) * | 2017-12-31 | 2018-05-08 | 天长市飞龙金属制品有限公司 | A kind of galvanized sheet passivating solution |
| CN108690981A (en) * | 2018-06-29 | 2018-10-23 | 宜兴大平杆塔制造有限公司 | With no sodium chromate passivator and preparation method thereof after a kind of metal product is zinc-plated |
| CN113583745A (en) * | 2021-07-09 | 2021-11-02 | 煤炭科学技术研究院有限公司 | Compatible concentrated solution for hydraulic support and preparation method thereof |
| CN113583745B (en) * | 2021-07-09 | 2022-08-26 | 煤炭科学技术研究院有限公司 | Compatible concentrated solution for hydraulic support and preparation method thereof |
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