CN102864447B - Compound passivating fluid for mechanical zinc coating - Google Patents
Compound passivating fluid for mechanical zinc coating Download PDFInfo
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- CN102864447B CN102864447B CN201210349474.8A CN201210349474A CN102864447B CN 102864447 B CN102864447 B CN 102864447B CN 201210349474 A CN201210349474 A CN 201210349474A CN 102864447 B CN102864447 B CN 102864447B
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Abstract
The invention belongs to the technical field of metal surface treatment and specifically relates to a compound passivating fluid for a mechanical zinc coating. The compound passivating fluid comprises a component A and a component B, wherein the component A is waterborne polyurethane, of which the weight percent is 8-18% in the compound passivating fluid; the component B is an inorganic passivator, of which the weight percent is 2.4-1.5% in the compound passivating fluid; and the balance is deionized water. The pH value of the compound passivating fluid is adjusted to 6-9 by using the sulfuric acid with the mass fraction of 98%. The compound passivating fluid has a better passivating function to a mechanical zinc coating workpiece; the environmental pollution caused by hexavalent chromium is avoided; a formed film is bright and transparent, is durable and excellent in flexibility, has a certain mechanical property, is excellent in water and chemical solvent resistance and is long in salt mist resisting time. The coating has the advantages of self-repairing function, high stability, low cost, simple preparation process and simple use method.
Description
Technical field
The invention belongs to field of metal surface treatment technology, specifically, relate to a kind of composite passivation solution for the treatment of mechanical galvanizing layer.
Background technology
Mechanical galvanizing layer is mainly used for preventing atomospheric corrosion, to protect steel part.But mechanical galvanizing layer, in damp-heat air, easily suffers corrosion to form " white rust " and gloomy thing, not only damages product appearance, and the position that is corroded also can be to horizontal and vertical continuous extension, and then corrosion iron and steel parts, generation iron rust.For improving the solidity to corrosion of mechanical galvanizing layer, the Passivation Treatment after must plating mechanical zinc-plating workpiece.
Existing passivation technology, generally adopts chromic salt and inorganic passivator to carry out passivation to mechanical galvanizing layer.But the liquid waste disposal after employing chromating is very difficult, and in waste liquid, contain poisonous sexavalent chrome, very large to human body and environmental hazard.Although existing inorganic passivator, not containing chromium, does not exist chromic pollution problem on market, its film-formation result is poor, poor stability, and passivation effect is bad.Although can add membrane-forming agent, promoting film forming, improving film-formation result, membrane-forming agent expensive, and preparation technology is loaded down with trivial details, is unfavorable for promoting the use of of inorganic passivator.
Summary of the invention
For solving the problems of the technologies described above, the present invention proposes a kind of composite passivation solution for mechanical galvanizing layer, its film-formation result is good, stability is high, and cost of manufacture is low, preparation technology is simple.
Technical scheme of the present invention is: for the composite passivation solution of mechanical galvanizing layer, comprise component A and B component, component A is aqueous polyurethane, and it accounts for 8-18% in described composite passivation solution; B component is inorganic passivator, and it accounts for 2.4-11.5% in described composite passivation solution; Surplus is deionized water; The sulfuric acid that the pH value of composite passivation solution is 98% by massfraction is adjusted to 6-9.
Described inorganic passivator comprises following component, its in above-mentioned composite passivation solution separately shared weight percentage be respectively: Sodium orthomolybdate 1.0-3.0%, titanium sulfate 0.1-1.5%, water glass 0.1-1.5%, cerous nitrate 1.0-3.0%, benzotriazole 0.1-1.0%, phytic acid 0.1-1.5%.
Described aqueous polyurethane is the mixture of cation-type water-thinned polyurethane, anion-type water-thinned polyurethane, non-ion aqueous polyurethane, cation-type water-thinned polyurethane and non-ion aqueous polyurethane or the mixture of anion-type water-thinned polyurethane and non-ion aqueous polyurethane.
The present invention is the main film forming substance as composite passivation solution by water-based organic polymer, add again inorganic passivator, passivator and organism are produced crosslinked, and form screen layer, activated zinc layer is active, increase electroconductibility, make passive film there is self-healing ability, effectively improved the resistance to corrosion of mechanical zinc-plating workpiece.
Its preparation method is: after aqueous polyurethane is mixed in water with inorganic passivator, the sulphur acid for adjusting pH value that is 98% with massfraction is between 6-9.
Passivation coated technique is as follows: first mechanical zinc-plating workpiece surface is cleaned up; hot-air seasoning; then by methods such as dip-coating, spraying, roller coating, passivating solution of the present invention is evenly coated on clean mechanical zinc-plating workpiece; after solution seasoning; generate the protective membrane that one deck has anti-" white rust " ability, dry and also can.
Beneficial effect of the present invention is:
1, the present invention is better to the passivation of mechanical zinc-plating workpiece, by macromolecule polyurethane and inorganic inhibitor, jointly combine with metallic matrix, can form fine and close screen layer, thereby strengthen the corrosion stability of film, can reach the requirement of mechanical zinc-plating workpiece corrosion resistance nature;
2, avoid the pollution of sexavalent chrome to environment;
3, there is film forming clear transparent, wear-resisting, flexibility good, has certain mechanical property, and water-fast, chemical solvent resistance can be good, and salt-fog resistant time is long, and rete has self-repair function, after scuffing or water soaking are dry, can carry out self-regeneration, make rete keep complete and continuity;
4, stability of the present invention is high, and stability of solution is up to 6 months;
5, with low cost, preparation technology is simple, and using method is simple.
Embodiment
Below in conjunction with embodiment, illustrate the present invention.
Get uniform steel plate, be divided into 6, on its surface, form mechanical galvanizing layer, respectively called after plate A, plate B, plate C, plate D, plate E and plate F.
Embodiment 1
1, raw material and the content of preparing composite passivation solution:
Cation-type water-thinned polyurethane 8g, Sodium orthomolybdate 3g, titanium sulfate 0.1g, water glass 1.5g, cerous nitrate 2.5g, benzotriazole 0.1g, phytic acid 1.5g, deionized water 83.3g.
2, preparation method is: after above-mentioned raw materials is mixed, the sulfuric acid that functional quality mark is 98% is adjusted the pH value to 8 of the aqueous solution.
Get plate A, carry out following test:
(1) content of 6-valence Cr ions detects
According to mensuration the 5th part of GB/T 9758.5-1988 < < paint and varnish " solubility " metal content: in the pigment part of liquid colored paint or Powdered colored paint, the mensuration diphenylcarbazone spectrophotometry > > of content of 6-valence Cr ions carries out the detection of solubility content of 6-valence Cr ions.
(2) neutral salt spray corrosion test (NSS)
Adopt FQY025 type salt fog cabinet, according to GB/T 10125-1997 < < artificial atmosphere corrosion test-salt-fog test > >.Carry out artificial atmosphere salt air corrosion, with specimen surface, produce the area evaluation anticorrosion effect of white rust.
(3) resistance to solvent (80% ethanol and butanone) detects test
According to HG/T 3792-2005 < < cross-linking type fluorine resin coating > >, carry out resistance to solvent (80% ethanol and butanone) and detect test, wiping number of times is greater than 15 times, observes the variation of filming.
(4) saline soak test
With 5wt%NaCl aqueous solution submergence sample under temperature (25 ± 2) ° C, record the time that corrosion appears in sample.
(5) film resistance to elevated temperatures test
According to the stable on heating mensuration of GB/T 1735-2009 < < paint and varnish > >, carry out thermotolerance test, sample is placed under baking oven (200 ± 2) ° C and dries 30min, check that rete has or not the phenomenons such as variable color, aliquation, elephant skin, bubbling, cracking.
(6) resistance to boiling water test
According to GB/T 1733-1993 < < paint film water tolerance assay method > >, carry out resistance to boiling water test, sample is boiled to 1h in 100 ° of C water, the visual observation whether variable color of filming.
Test-results sees the following form 1.
Embodiment 2
Outside lower difference, other are with embodiment 1.
1, raw material and the content of preparing composite passivation solution:
Anion-type water-thinned polyurethane 10g, Sodium orthomolybdate 2.5g, titanium sulfate 1.5g, water glass 0.1g, cerous nitrate 3g, benzotriazole 1g, phytic acid 0.1g, deionized water 81.8g.
2, preparation method is: after above-mentioned raw materials is mixed, the sulfuric acid that functional quality mark is 98% is adjusted the pH value to 7 of the aqueous solution.
Get plate B, carry out (1) described in above-described embodiment 1-(6) test, test-results sees the following form 1.
Embodiment 3
Outside lower difference, other are with embodiment 1.
1, raw material and the content of preparing composite passivation solution:
Cation-type water-thinned polyurethane 12g, Sodium orthomolybdate 2g, titanium sulfate 1g, water glass 1g, cerous nitrate 2g, benzotriazole 0.6g, phytic acid 1.2g, deionized water 80.2g.
2, preparation method is: after above-mentioned raw materials is mixed, the sulfuric acid that functional quality mark is 98% is adjusted the pH value to 6 of the aqueous solution.
Get plate C, carry out (1) described in above-described embodiment 1-(6) test, test-results sees the following form 1.Embodiment 4
Outside lower difference, other are with embodiment 1.
1, raw material and the content of preparing composite passivation solution:
Non-ion aqueous polyurethane 14g, Sodium orthomolybdate 2g, titanium sulfate 0.8g, water glass 0.8g, cerous nitrate 2g, benzotriazole 0.4g, phytic acid 1g, deionized water 79g.
2, preparation method is: after above-mentioned raw materials is mixed, the sulfuric acid that functional quality mark is 98% is adjusted the pH value to 9 of the aqueous solution.
Get plate D, carry out (1) described in above-described embodiment 1-(6) test, test-results sees the following form 1.
Embodiment 5
Outside lower difference, other are with embodiment 1.
1, raw material and the content of preparing composite passivation solution:
Cation-type water-thinned polyurethane 3g, non-ion aqueous polyurethane 13g, Sodium orthomolybdate 1g, titanium sulfate 1g, water glass 1g, cerous nitrate 1g, benzotriazole 0.4g, phytic acid 1g, deionized water 78.6g.
2, preparation method is: after above-mentioned raw materials is mixed, the sulfuric acid that functional quality mark is 98% is adjusted the pH value to 7.5 of the aqueous solution.
Get plate E, carry out (1) described in above-described embodiment 1-(6) test, test-results sees the following form 1.
Embodiment 6
Outside lower difference, other are with embodiment 1.
1, raw material and the content of preparing composite passivation solution:
Anion-type water-thinned polyurethane 13g, non-ion aqueous polyurethane 5g, Sodium orthomolybdate 1.5g, titanium sulfate 1g, water glass 1g, cerous nitrate 1.5g, benzotriazole 0.6g, phytic acid 1.2g, deionized water 75.2g.
2, preparation method is: after above-mentioned raw materials is mixed, the sulfuric acid that functional quality mark is 98% is adjusted the pH value to 8.2 of the aqueous solution.
Get plate F, carry out (1) described in above-described embodiment 1-(6) test, test-results sees the following form 1.
Table 1: embodiment 1-6 corrosion test assay
By upper table, can be learnt: the composite passivation solution that embodiment 1-6 makes, its erosion resistance in hygrothermal environment is better, and chemical solvent resistance is good, good film-forming property, salt-fog resistant time is long.
Claims (1)
1. for a composite passivation solution for mechanical galvanizing layer, it is characterized in that, comprise component A and B component,
Described component A is aqueous polyurethane, and it accounts for 8～12% in described composite passivation solution;
Described B component is inorganic passivator, and it accounts for 5.4～11.5% in described composite passivation solution;
Surplus is deionized water;
The pH value of described composite passivation solution is 6～9;
Described aqueous polyurethane is selected from a kind of in following material: cation-type water-thinned polyurethane, non-ion aqueous polyurethane, non-ion aqueous polyurethane and cation-type water-thinned polyurethane mixture, non-ion aqueous polyurethane and anion-type water-thinned polyurethane mixture;
Described inorganic passivator comprises following component, its in described composite passivation solution separately shared weight percentage be respectively: Sodium orthomolybdate 1.0-3.0%, titanium sulfate 0.1-1.5%, water glass 0.1-1.5%, cerous nitrate 1.0-3.0%, benzotriazole 0.1-1.0%, phytic acid 0.1-1.5%.
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| CN201210349474.8A CN102864447B (en) | 2012-09-19 | 2012-09-19 | Compound passivating fluid for mechanical zinc coating |
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| CN201210349474.8A CN102864447B (en) | 2012-09-19 | 2012-09-19 | Compound passivating fluid for mechanical zinc coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105951080B (en) * | 2016-06-27 | 2018-11-20 | 力同铝业（广东）有限公司 | Aluminum alloy surface composite passivant and preparation method thereof |
| WO2019006622A1 (en) * | 2017-07-03 | 2019-01-10 | 深圳市宏昌发科技有限公司 | Passivator, metal workpiece and passivation process therefor |
| CN109957093B (en) * | 2019-03-26 | 2021-12-14 | 武汉迪赛环保新材料股份有限公司 | Ultrahigh-crosslinking-degree waterborne polyurethane, galvanized sheet surface treatment liquid and preparation method thereof |
| CN111575690A (en) * | 2020-06-24 | 2020-08-25 | 攀钢集团攀枝花钢铁研究院有限公司 | Hot-dip galvanized aluminum-magnesium steel plate surface chromium-free passivation solution and preparation method of hot-dip galvanized aluminum-magnesium chromium-free passivation plate |
| CN114605854A (en) * | 2022-03-11 | 2022-06-10 | 旭贞新能源科技(上海)有限公司 | Anticorrosive coating with super hydrophobic performance and ultralow surface energy |
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| CN101886260A (en) * | 2010-07-08 | 2010-11-17 | 南通飞拓生物科技有限公司 | Composite film chromium-free passivant |
| CN102586768A (en) * | 2011-01-10 | 2012-07-18 | 中国石油化工股份有限公司 | Zinc layer surface passivating treatment liquid |
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| US20100297454A1 (en) * | 2007-12-07 | 2010-11-25 | Dipsol Chemicals Co., Ltd. | Surface-Treating Aqueous Solution and Treatment Methods for Forming Corrosion-Resistant Coating Film Over Zinc or Zinc Alloy Deposit |
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