CN101429661B - Molybdate passivating liquid for continuous hot-dipping galvanizing steel plate - Google Patents
Molybdate passivating liquid for continuous hot-dipping galvanizing steel plate Download PDFInfo
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Abstract
The invention relates to a molybdate passivation liquid for a continuous hot dip galvanized steel sheet, and belongs to the technical field of metal surface treatment and corrosion prevention. The molybdate passivation liquid comprises the following components according to the proportion for 1L of water: 30 to 50g/L of molybdate, 3 to 10g/L of fluozirconate, 3 to 15g/L of HEOP, 5 to 25g/L of citric acid, 10 to 30g/L of oxydol, 10 to 30g/L of acidic silicasol, and 15 to 25g/L of phosphoric acid. The molybdate passivation liquid has the advantages that as the recipe does not contain chrome, the molybdate passivation liquid has no impact on human bodies and environment; the salt fog resistance of the galvanized steel sheet which has the galvanizing coating passivated by the molybdate passivation liquid is better than that of the steel sheet passivated by chromates.
Description
Technical field
The invention belongs to metal finishing and aseptic technic field, be specifically related to a kind of molybdate passivating liquid of continuous galvanizing by hot-dip galvanized steel sheet.
Background technology
Hot-dip galvanizing sheet steel is widely used in fields such as automobile, building and household electrical appliances.Theoretically, because zinc electropotential for ferrous materials is low, when therefore under the environment of humidity, corrosion taking place, can carry out electro-chemical protection to steel substrate as anode.Yet from the situation of reality, the zinc layer only under the condition of dry non-corrosiveness atmosphere, just can embody and provide the ideal protective effect to steel substrate.So under the storage and working conditions of reality, the zinc laminar surface can produce dewfall, cause and get rusty or variable color.In order to prevent this phenomenon, must carry out Passivation Treatment to zinc coating, to improve its corrosion resistance.
Traditional zinc coating is carried out deactivating process for the treatment of use the hexavalent chromate treatment process widely.This technology can make the zinc layer have superior corrosion resistance energy, self-repair function and art breading strong point with low cost, therefore is subjected to people's favor always.But because sexavalent chrome is carcinogenic, poisonous, European Union came into effect electronics from 2006, the electric type product does not have chromaking; Therefore the also strict discharging that has limited chromic salt of the Chinese government is developed and is a kind ofly had preferably that the zinc-plated non-chromium inactivating technique of erosion resistance just becomes the difficult problem that present urgent need solves.
At present, domestic and international research to chromium-free deactivation mainly divides both direction, i.e. inorganic salt passivation film-forming process and organism passivation film-forming process.The inorganic salt passivation technology mainly adopts high-valency metal salt (molybdate, tungstate, silicate or rare-earth salts etc.) mixed mutually with mineral acid.Molybdate passive film corrosion resistance nature in alkalescence and neutral environment is lower than chromating, and cost is too high; The tungstate passivation also slightly is worse than the molybdate passivation on performance; The corrosion resistance nature of silicate is relatively poor, and forms silicon oxide polymer, the following process of steel plate galvanized is handled caused difficulty; The film that the rare-earth salts passivation forms is very thin, and consuming time oversize, is not suitable for suitability for industrialized production.Such as: the A3 steel galvanizing layer molybdate passive film of researchs such as Hao Jianjun, peace Cheng Qiang was through behind 24 hours neutral salt spray tests in " investigation of materials journal " 20 volume fourth phases in 2006, and corroded area has reached 8.11%; Interim at " corrosion science and guard technology " 9 volumes 2, the silicate passivation of Han Keping research is 5～10% through 24 hours neutral salt spray test post-etching area percentages.
Organism passivation film-forming process mainly adopts and adds with water miscible organism or organic acid that organic metal inhibitor, sequestrant form.But the less stable of organism passivation technology cost height, plating bath, the adding and the service procedure complexity of plating bath; Passivation technology that has even needs upgrade and reforming equipment.Such as: all steel plate galvanized there is the certain protection effect in phytic acid passivation of " corrosion science and and guard technology " people's researchs such as 14 interim Zhang Hongsheng in 2002 and the Weibull passivation of studying people such as " electroplating and finish " central sill Qi Min, but does not far reach requirement of actual application.
Interim in " Chinese corrosion and protection journal " nineteen ninety-five the 4th, Chen Xujun has proposed a kind of new thinking, be that inorganic salts and organic compound combine, also promptly rely on the functional group in the organic molecule, the molecular gene when interionic synergy of group and metallate and film form and the effect of metallic cation form the long-chain chelate structure and improve solidity to corrosion.Chinese invention patent application number 200810046857.4 discloses a kind of chromium-free passivation liquid that is used for galvanized steel sheet surface, adopting components such as molybdate, tungstate and organic compound vinylformic acid in the prescription, is 3～8% through 72 hours neutral salt spray test post-etching area percentages.The passivating solution of this patent application scheme is after cost improves more than 10 times, and the corrosion resistance nature of passive film still can not be satisfactory.
In sum, though the chromium-free deactivation of numerous researchs to zinc coating arranged, also proposed various schemes and solution both at home and abroad, it is with respect to chromating, and its weak point: solidity to corrosion differs far away.Therefore, up to the present, still do not have a kind of corrosion resistance nature can be with the chromating liquid phase match in excellence or beauty even even more ideal chromium-free passivation liquid.
Summary of the invention
The object of the present invention is to provide a kind of can avoiding that human body and environment structure are endangered the molybdate passivating liquid that has again than the solidity to corrosion ideal continuous galvanizing by hot-dip galvanized steel sheet of chromating liquid.
Task of the present invention is finished like this, a kind of molybdate passivating liquid of continuous galvanizing by hot-dip galvanized steel sheet, it is characterized in that its component and the proportioning content in every premium on currency is: molybdate 30～50g/L, fluozirconate 3～10g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 3～15g/L, citric acid 5～25g/L, hydrogen peroxide 10～30g/L, acidic silicasol 10～30g/L, phosphatase 11 5～25g/L, described molybdate be Sodium orthomolybdate or potassium molybdate or both by the mixture that any proportioning mixes, described fluozirconate is sodium fluozirconate or potassium fluozirconate or mixture that both mix by any proportioning.
The advantage of the technical scheme that the present invention recommended: prescription of the present invention is not owing to contain chromium, therefore human body and environment are not had influence, zinc coating is carried out the salt spray corrosion resistance of the steel plate galvanized after the Passivation Treatment than chromating plate good (the neutral salt spray test corroded area was no more than 5% in 168 hours) with prescription of the present invention.
Embodiment
Embodiment 1:
In every premium on currency, the shared weight part of following raw materials is: Sodium orthomolybdate 30g/L, potassium fluozirconate 3g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 3g/L, citric acid 5g/L, hydrogen peroxide 10g/L, acidic silicasol 10g/L, phosphatase 11 5g/L.
Embodiment 2:
Sodium orthomolybdate 35g/L, potassium fluozirconate 7g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 12g/L, citric acid 25g/L, hydrogen peroxide 15g/L, acidic silicasol 20g/L, phosphoric acid 21g/L.
Embodiment 3:
Sodium orthomolybdate 40g/L, potassium fluozirconate 9g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 15g/L, citric acid 20g/L, hydrogen peroxide 20g/L, acidic silicasol 30g/L, phosphoric acid 23g/L.
Embodiment 4:
Sodium orthomolybdate 45g/L, potassium fluozirconate 10g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 6g/L, citric acid 15g/L, hydrogen peroxide 25g/L, acidic silicasol 25g/L, phosphoric acid 25g/L.
Embodiment 5:
Sodium orthomolybdate 50g/L, potassium fluozirconate 5g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 3g/L, citric acid 10g/L, hydrogen peroxide 30g/L, acidic silicasol 15g/L, phosphatase 11 9g/L.
Embodiment 6:
Sodium orthomolybdate 45g/L, sodium fluozirconate 6g/L, potassium fluozirconate 3g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 12g/L, citric acid 5g/L, hydrogen peroxide 25g/L, acidic silicasol 15g/L, phosphatase 11 7g/L.
Embodiment 7:
Potassium molybdate 40g/L, potassium fluozirconate 10g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 9g/L, citric acid 25g/L, hydrogen peroxide 20g/L, acidic silicasol 25g/L, phosphatase 11 9g/L.
Embodiment 8:
Sodium orthomolybdate 25g/L, potassium molybdate 10g/L, sodium fluozirconate 2g/L, potassium fluozirconate 5g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 6g/L, citric acid 20g/L, hydrogen peroxide 15g/L, acidic silicasol 10g/L, phosphoric acid 23g/L.
Embodiment 9:
Sodium orthomolybdate 50g/L, potassium fluozirconate 10g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 15g/L, citric acid 25g/L, hydrogen peroxide 30g/L, acidic silicasol 30g/L, phosphoric acid 25g/L.
Do not reach content all with description among the foregoing description 2-9 to embodiment 1.
The chemical degreasing oil removing is adopted on the continuous hot-dipping galvanizing steel plate surface, in being 0.6% salpeter solution, mass percent concentration activates 10～15s then, again with behind the deionized water rinsing, put into of the present invention by passivation 30s in the resulting passivating solution of arbitrary embodiment of the foregoing description 1-9, adopt experiment rub bar roller coat to remove unnecessary passivating solution, 75 ℃ of air cooking 30s.Inspecting standard adopts GB/T 10125-1997 artificial atmosphere corrosion test salt-fog test standard, and the area that occurs white rust after experiments of measuring finishes is estimated the corrosion resistance nature of passive film.
Application examples 1:
Follow these steps to:
1. degreasing: earlier to the continuous hot-dipping galvanizing steel plate surface with Henkel grease-removing agent degreasing degreasing, make again through continuous hot-dipping galvanizing steel plate behind the degreasing degreasing and in mass percent concentration is 0.6% salpeter solution, activate 10～15s, use deionized water rinsing again;
2. Passivation Treatment: join and get passivating solution, get Sodium orthomolybdate 30g/L, potassium fluozirconate 3g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 3g/L, citric acid 5g/L, hydrogen peroxide 10g/L, acidic silicasol 10g/L, phosphatase 11 5g/L, the continuous hot-dipping galvanizing steel plate Passivation Treatment time in passivating solution is 30s, and passivation finishes the back with 75 ℃ of baking 30s;
3. neutral salt spray test: with reference to GB GB/T 10125-1997, through the 168h neutral salt spray test, the specimen surface white rust illustrates that less than 5% the passive film solidity to corrosion is good.
Application examples 2:
Follow these steps to:
1. degreasing: earlier to the continuous hot-dipping galvanizing steel plate surface with Henkel grease-removing agent degreasing degreasing, make again through continuous hot-dipping galvanizing steel plate behind the degreasing degreasing and in mass percent concentration is 0.6% salpeter solution, activate 10～15s, use deionized water rinsing again;
2. Passivation Treatment: join and get passivating solution, get Sodium orthomolybdate 35g/L, potassium fluozirconate 7g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 12g/L, citric acid 25g/L, hydrogen peroxide 15g/L, acidic silicasol 20g/L, phosphoric acid 21g/L, the continuous hot-dipping galvanizing steel plate Passivation Treatment time in passivating solution is 30s, and passivation finishes the back with 75 ℃ of baking 30s;
3. neutral salt spray test: with reference to GB GB/T 10125-1997, through the 168h neutral salt spray test, the specimen surface white rust illustrates that less than 5% the passive film solidity to corrosion is good.
Application examples 3:
Follow these steps to:
1. degreasing: earlier to the continuous hot-dipping galvanizing steel plate surface with Henkel grease-removing agent degreasing degreasing, make again through continuous hot-dipping galvanizing steel plate behind the degreasing degreasing and in mass percent concentration is 0.6% salpeter solution, activate 10～15s, use deionized water rinsing again;
2. Passivation Treatment: join and get passivating solution, get Sodium orthomolybdate 40g/L, potassium fluozirconate 9g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 15g/L, citric acid 20g/L, hydrogen peroxide 20g/L, acidic silicasol 30g/L, phosphoric acid 23g/L, the continuous hot-dipping galvanizing steel plate Passivation Treatment time in passivating solution is 30s, and passivation finishes the back with 75 ℃ of baking 30s;
3. neutral salt spray test: with reference to GB GB/T 10125-1997, through the 168h neutral salt spray test, the specimen surface white rust illustrates that less than 4% the passive film solidity to corrosion is good.
Application examples 4:
Follow these steps to:
1. degreasing: earlier to the continuous hot-dipping galvanizing steel plate surface with Henkel grease-removing agent degreasing degreasing, make again through continuous hot-dipping galvanizing steel plate behind the degreasing degreasing and in mass percent concentration is 0.6% salpeter solution, activate 10～15s, use deionized water rinsing again;
2. Passivation Treatment: join and get passivating solution, get Sodium orthomolybdate 45g/L, potassium fluozirconate 10g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 6g/L, citric acid 15g/L, hydrogen peroxide 25g/L, acidic silicasol 25g/L, phosphoric acid 25g/L, the continuous hot-dipping galvanizing steel plate Passivation Treatment time in passivating solution is 30s, and passivation finishes the back with 75 ℃ of baking 30s;
3. neutral salt spray test: with reference to GB GB/T 10125-1997, through the 168h neutral salt spray test, the specimen surface white rust illustrates that less than 4% the passive film solidity to corrosion is good.
Application examples 5:
Follow these steps to:
1. degreasing: earlier to the continuous hot-dipping galvanizing steel plate surface with Henkel grease-removing agent degreasing degreasing, make again through continuous hot-dipping galvanizing steel plate behind the degreasing degreasing and in mass percent concentration is 0.6% salpeter solution, activate 10～15s, use deionized water rinsing again;
2. Passivation Treatment: join and get passivating solution, get Sodium orthomolybdate 50g/L, potassium fluozirconate 5g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 3g/L, citric acid 10g/L, hydrogen peroxide 30g/L, acidic silicasol 15g/L, phosphatase 11 9g/L, the continuous hot-dipping galvanizing steel plate Passivation Treatment time in passivating solution is 30s, and passivation finishes the back with 75 ℃ of baking 30s;
3. neutral salt spray test: with reference to GB GB/T 10125-1997, through the 168h neutral salt spray test, the specimen surface white rust illustrates that less than 4% the passive film solidity to corrosion is good.
Application examples 6:
Follow these steps to:
1. degreasing: earlier to the continuous hot-dipping galvanizing steel plate surface with Henkel grease-removing agent degreasing degreasing, make again through continuous hot-dipping galvanizing steel plate behind the degreasing degreasing and in mass percent concentration is 0.6% salpeter solution, activate 10～15s, use deionized water rinsing again;
2. Passivation Treatment: join and get passivating solution, get Sodium orthomolybdate 45g/L, sodium fluozirconate 6g/L, potassium fluozirconate 3g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 12g/L, citric acid 5g/L, hydrogen peroxide 25g/L, acidic silicasol 15g/L, phosphatase 11 7g/L, the Passivation Treatment time of continuous hot-dipping galvanizing steel plate in passivating solution is 30s, and passivation finishes the back with 75 ℃ of baking 30s;
3. neutral salt spray test: with reference to GB GB/T 10125-1997, through the 168h neutral salt spray test, the specimen surface white rust illustrates that less than 5% the passive film solidity to corrosion is good.
Application examples 7:
Follow these steps to:
1. degreasing: earlier to the continuous hot-dipping galvanizing steel plate surface with Henkel grease-removing agent degreasing degreasing, make again through continuous hot-dipping galvanizing steel plate behind the degreasing degreasing and in mass percent concentration is 0.6% salpeter solution, activate 10～15s, use deionized water rinsing again;
2. Passivation Treatment: join and get passivating solution, get potassium molybdate 40g/L, potassium fluozirconate 10g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 9g/L, citric acid 25g/L, hydrogen peroxide 20g/L, acidic silicasol 25g/L, phosphatase 11 9g/L, the continuous hot-dipping galvanizing steel plate Passivation Treatment time in passivating solution is 30s, and passivation finishes the back with 75 ℃ of baking 30s;
3. neutral salt spray test: with reference to GB GB/T 10125-1997, through the 168h neutral salt spray test, the specimen surface white rust illustrates that less than 5% the passive film solidity to corrosion is good.
Application examples 8:
Follow these steps to:
1. degreasing: earlier to the continuous hot-dipping galvanizing steel plate surface with Henkel grease-removing agent degreasing degreasing, make again through continuous hot-dipping galvanizing steel plate behind the degreasing degreasing and in mass percent concentration is 0.6% salpeter solution, activate 10～15s, use deionized water rinsing again;
2. Passivation Treatment: join and get passivating solution, get Sodium orthomolybdate 25g/L, potassium molybdate 10g/L, sodium fluozirconate 2g/L, potassium fluozirconate 5g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 6g/L, citric acid 20g/L, hydrogen peroxide 15g/L, acidic silicasol 10g/L, phosphoric acid 23g/L, the continuous hot-dipping galvanizing steel plate Passivation Treatment time in passivating solution is 30s, and passivation finishes the back with 75 ℃ of baking 30s;
3. neutral salt spray test: with reference to GB GB/T 10125-1997, through the 168h neutral salt spray test, the specimen surface white rust illustrates that less than 4% the passive film solidity to corrosion is good.
Application examples 9:
Follow these steps to:
1. degreasing: earlier to the continuous hot-dipping galvanizing steel plate surface with Henkel grease-removing agent degreasing degreasing, make again through continuous hot-dipping galvanizing steel plate behind the degreasing degreasing and in mass percent concentration is 0.6% salpeter solution, activate 10～15s, use deionized water rinsing again;
2. Passivation Treatment: join and get passivating solution, get Sodium orthomolybdate 50g/L, potassium fluozirconate 10g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 15g/L, citric acid 25g/L, hydrogen peroxide 30g/L, acidic silicasol 30g/L, phosphoric acid 25g/L, the continuous hot-dipping galvanizing steel plate Passivation Treatment time in passivating solution is 30s, and passivation finishes the back with 75 ℃ of baking 30s;
3. neutral salt spray test: with reference to GB GB/T 10125-1997, through the 168h neutral salt spray test, the specimen surface white rust illustrates that less than 4% the passive film solidity to corrosion is good.
Claims (1)
1. the molybdate passivating liquid of a continuous galvanizing by hot-dip galvanized steel sheet, it is characterized in that its component and the proportioning content in every premium on currency is: molybdate 30～50g/L, fluozirconate 3～10g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 3～15g/L, citric acid 5～25g/L, hydrogen peroxide 10～30g/L, acidic silicasol 10～30g/L, phosphatase 11 5～25g/L, described molybdate be Sodium orthomolybdate or potassium molybdate or both by the mixture that any proportioning mixes, described fluozirconate is sodium fluozirconate or potassium fluozirconate or mixture that both mix by any proportioning.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109112512A (en) * | 2018-07-27 | 2019-01-01 | 常州工程职业技术学院 | A kind of Treatment of Metal Surface aqueous passivating solution and preparation method thereof |
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| CN102965654B (en) * | 2012-12-16 | 2014-11-19 | 况金权 | High-salt-fog-resistance aluminum product passivator and preparation method thereof |
| CN103205740B (en) * | 2013-04-16 | 2015-04-29 | 石佳正 | Zinc-plating chromium-free blue-white passivating agent |
| CN103255403B (en) * | 2013-05-16 | 2015-07-01 | 山东建筑大学 | Non-chrome black passivator |
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| CN105862020A (en) * | 2016-05-31 | 2016-08-17 | 无锡伊佩克科技有限公司 | Steel surface fluoroferrite conversion plating solution and preparation method thereof |
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| CN107523820A (en) * | 2017-07-04 | 2017-12-29 | 安徽腾龙泵阀制造有限公司 | A kind of inorganic acid passivating solution for electro-galvanized layer |
| CN109267055B (en) * | 2018-11-20 | 2020-11-10 | 重庆广仁铁塔制造有限公司 | Environment-friendly chromium-free passivator and preparation method thereof |
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| CN101161861A (en) * | 2007-11-22 | 2008-04-16 | 东北大学 | Non-chromium deactivation liquid for processing aluminium alloy and method of use thereof |
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| CN109112512A (en) * | 2018-07-27 | 2019-01-01 | 常州工程职业技术学院 | A kind of Treatment of Metal Surface aqueous passivating solution and preparation method thereof |
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