CN102747352B - Passivator and passivation for hot galvanized sheet - Google Patents
Passivator and passivation for hot galvanized sheet Download PDFInfo
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- CN102747352B CN102747352B CN201210226010.8A CN201210226010A CN102747352B CN 102747352 B CN102747352 B CN 102747352B CN 201210226010 A CN201210226010 A CN 201210226010A CN 102747352 B CN102747352 B CN 102747352B
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Abstract
The invention discloses a passivator for hot galvanized sheet. The passivator comprises water and components with the following concentrations: 230g / L-90g / L of nano SiO, 30g / L-60g / L of water-soluble acrylic resin, 40g / L-80g / L of phytic acid and / or phosphoric acid, 3g / L-12g / L of titanium acetylacetonate, 10g / L-30g / L of vanadyl acetylacetonate and 50g / L-100g/ L of isopropanol. A hot galvanized sheet passivation method by using the passivator provided by the present invention is as below: passivator is coated on the hot galvanized sheet on a production line by means of spraying, blade coating or roll coating, with a drying plate at a temperature of 80-100 DEG C. The passivator provided by the invention has advantages of simple formula, easily available raw materials and convenient usage; besides, the passivator shows good passivation effect, and is healthy and environment-friendly.
Description
Technical field
The invention belongs to the technical field of surface of steel plate, relate in particular to passivator and passivating method that a kind of steel plate is used.
Background technology
Pot galvanize is the protective galvanic protection mode that cold-rolled steel sheet the most often adopts, but zinc coating is easily corroded in air (especially at wet air).In order to stop the corrosion of zinc coating, need to carry out Passivation Treatment, traditional passivation mode is to be coated on hot-dip galvanizing sheet steel surface with sexavalent chrome passivator, after dry, form the passivation layer of one deck containing sexavalence chromic salts, but sexavalent chrome is poisonous and carcinogenic, not only affect human health, and easily environment is worked the mischief, it will progressively be eliminated by market.The ROHS instruction that European Union issues has just clearly limited chromic use.In prior art, in order to reduce chromic harm, there is trivalent chromium passivator, but trivalent chromium uses as passivator, not only passivation effect is not so good as sexavalent chrome ideal, and it can change sexavalent chrome under certain condition into, the same potential risk that has harm environment and human health.Therefore, replace and have chromium passivating agent with chrome-free tanning agent, by the inexorable trend that is the art development.
In existing chrome-free tanning agent or take molybdate as main component, or take rare earth metal salt as main component, but the cost of these passivator is higher, passivation effect is also not satisfactory, can't meet the demand of cold rolling mill hot galvanizing line completely, up to now, the art does not also occur a kind of really satisfactory and have a chrome-free tanning agent of better market outlook.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provide a kind of fill a prescription simple, raw material is easy to get, easy to use, passivation effect better and the passivator for hot-dip galvanizing sheet steel of health environment-friendly, the also corresponding method that provides this passivator hot-dip galvanizing sheet steel to be carried out to passivation.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of passivator for hot-dip galvanizing sheet steel, and described passivator comprises the component of water and following concentration:
Nanometer SiO
230g/L～90g/L,
Water soluble acrylic resin 30g/L～60g/L,
Phytic acid and/or phosphatase 24 0g/L～80g/L,
Titanium acetylacetone 3g/L～12g/L,
Vanadium acetylacetonate 10g/L～30g/L, and
Virahol (solvability conditioning agent) 50g/L～100g/L.
The above-mentioned passivator for hot-dip galvanizing sheet steel, also preferably contains and is useful on the N that regulates passivator pH value in described passivator, N dimethylethanolamine, and the pH value of described passivator is preferably 4～5.
The above-mentioned passivator for hot-dip galvanizing sheet steel, described passivator is preferably chrome-free tanning agent.In described passivator, also can not contain expensive molybdate or rare earth compound.
The above-mentioned passivator for hot-dip galvanizing sheet steel, described nanometer SiO
2median size be preferably 10nm～100nm.
The above-mentioned passivator for hot-dip galvanizing sheet steel, described titanium acetylacetone generally refers to methyl ethyl diketone oxygen titanium or methyl ethyl diketone diisopropoxy titanium.
As a total technical conceive, the present invention also provides a kind of above-mentioned passivator hot-dip galvanizing sheet steel to be carried out to the method for passivation, the method mainly refers to and on the production line of described hot-dip galvanizing sheet steel, adopts spraying, blade coating or roll coating model to make described passivator be coated to hot-dip galvanizing sheet steel, and it dries plate temperature (PMT) is 80 ℃～100 ℃.
Compared with prior art, the invention has the advantages that: passivator of the present invention is not only filled a prescription simply, raw material is easy to get, easy to use, and passivation effect is better.In preferred technical scheme, passivator of the present invention can be completely containing the heavy metal chromium that environmental and human health impacts is had to larger harm, passivator of the present invention also can be completely containing higher molybdate or the rare earth compound of cost, there is of fine quality, inexpensive, environmental protection, healthy feature, have a extensive future.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but following embodiment is only embodiment more preferably, protection domain not thereby limiting the invention.
embodiment:
First will be not through any Passivation Treatment but the hot-dip galvanizing sheet steel surface grease-removing agent that is coated with oil guard that rolls off the production line carries out oil removing, rinse well with tap water, then with distilled water or rinsed with deionized water, after hot blast drying, treat passivation.
Based on technical scheme of the present invention, the present embodiment is described 13 groups of passivator of the present invention (the desirable 1L of passivator total amount), and the formula of respectively organizing passivator is as shown in table 1 below.
Table 1: the system component list of each embodiment
| Embodiment numbering | Phytic acid g/L | Phosphoric acid g/L | Nanometer SiO 2g/L | Water soluble acrylic resin g/L | Titanium acetylacetone g/L | Vanadium acetylacetonate g/L | Virahol g/L |
| 1 | 60 | 0 | 50 | 40 | 10 | 20 | 50 |
| 2 | 40 | 0 | 50 | 40 | 10 | 20 | 50 |
| 3 | 80 | 0 | 50 | 40 | 10 | 20 | 50 |
| 4 | 60 | 0 | 30 | 40 | 10 | 20 | 50 |
| 5 | 60 | 0 | 90 | 40 | 10 | 20 | 50 |
| 6 | 60 | 0 | 50 | 30 | 10 | 20 | 50 |
| 7 | 60 | 0 | 50 | 60 | 10 | 20 | 50 |
| 8 | 60 | 0 | 50 | 40 | 3 | 20 | 50 |
| 9 | 60 | 0 | 50 | 40 | 12 | 20 | 60 |
| 10 | 60 | 0 | 50 | 40 | 10 | 10 | 50 |
| 11 | 60 | 0 | 50 | 40 | 10 | 30 | 80 |
| 12 | 30 | 30 | 50 | 40 | 10 | 20 | 50 |
| 13 | 0 | 60 | 50 | 40 | 10 | 20 | 50 |
In the cited each group of passivator of above embodiment, all adopt N, N-dimethylethanolamine is adjusted to the pH value of each passivator in 4～5 scope, and respectively organizes passivator and be chrome-free tanning agent, all, not containing molybdate or rare earth compound, respectively organize nanometer SiO in passivator
2median size all in the scope of 10nm～100nm.
Above-mentioned all adopt the 0# scraper of RK company of Britain to carry out blade coating until the passivation of the laboratory of passivation hot-dip galvanizing sheet steel (after wet film, approximately 4 μ m), are dried in hot-air oven, dry approximately 90 ℃ of plate temperature.Then the passivation steel plate galvanized of distinguishing clip 150mm × 75mm size carries out the Performance Detection of the following as test piece, specifically comprise and carry out neutral salt spray test, cold-workability test, X-scribe test, solvent resistance test, evaluate its performance with the corroded area percentage ratio of 72 hours; Also carry out anti-blackening test, non-yellowing test, with its performance of colour-change degree evaluation simultaneously.At build 0.4 ~ 0.8 μ m(0.5 ~ 1.0g/m
2) situation under, the white erosion of neutral salt spray test 72 hours area is less than 1%.
1. neutral salt spray test: the hot-dip galvanizing sheet steel test piece after passivation is carried out to neutral salt spray test according to GB/T10125-1997, lose in vain the corrosion resisting property of area evaluation passive film with surface.
2. cold-workability test: the hot-dip galvanizing sheet steel test piece after passivation is carried out to cup punching, then carry out neutral salt spray test, to detect the cold-forming property of passive film.
3. X-scribe test: the hot-dip galvanizing sheet steel test piece after passivation is carried out to diagonal angle line with blade, scratch passive film, then carry out neutral salt spray test, to detect the corrosion resisting property under X-line post-passivation membrane damage condition.
4. solvent resistance test: by absorbent cotton libation at an ancient wedding ceremony ethanol 10 observation surface variations afterwards of wiping repeatedly for the hot-dip galvanizing sheet steel test piece after passivation, then carry out neutral salt spray test to detect the resistance to solvent nature of passive film.
5. anti-blackening test: the hot-dip galvanizing sheet steel test piece after passivation is placed in climatic chamber, under 70 ℃ × 80% relative humidity condition, carry out resistance to black change test, the test piece that detects passive film anti-blackening energy is hung on the automatic rotary rack in humidity cabinet, and automatic rotary rack rotated and reverse by identical interval time.
6. non-yellowing test: the hot-dip galvanizing sheet steel test piece after passivation is placed at 220 ℃ and toasts 30min, contrast the colour-change of its bake plate, test is carried out in baking oven.
Treat passivation hot-dip galvanizing sheet steel with the each group of passivator of above embodiment and carry out after passivation, the properties test of its passivation effect is as shown in table 2 below.
Table 2: the performance test results after hot-dip galvanizing sheet steel passivation
| Embodiment numbering | Neutral salt spray test | Cold-workability | X-line | Solvent resistance | Resistance to xanthochromia | Resistance to black change |
| 1 | <1% | <1% | <1% | <5% | Slightly | Slightly |
| 2 | <3% | <5% | <5% | <5% | Slightly | Obviously |
| 3 | <1% | <1% | <1% | <5% | Slightly | Slightly |
| 4 | <1% | <1% | <1% | <5% | Slightly | Slightly |
| 5 | <1% | <1% | <1% | <5% | Slightly | Slightly |
| 6 | <1% | <1% | <1% | <5% | Slightly | Slightly |
| 7 | <1% | <1% | <1% | <5% | Obviously | Slightly |
| 8 | <5% | <5% | <5% | <5% | Slightly | Obviously |
| 9 | <1% | <1% | <1% | <5% | Slightly | Slightly |
| 10 | <1% | <1% | <1% | <5% | Slightly | Slightly |
| 11 | <1% | <1% | <1% | <5% | Slightly | Slightly |
| 12 | <1% | <1% | <1% | <5% | Slightly | Slightly |
| 13 | <1% | <1% | <1% | <5% | Slightly | Slightly |
Note: the every percentage ratio in upper table 2 represents the corroded area percentage ratio after 72 hours neutral salt spray tests.
Claims (4)
1. for a passivator for hot-dip galvanizing sheet steel, it is characterized in that, described passivator comprises the component of water and following concentration:
Nanometer SiO
230g/L～90g/L,
Water soluble acrylic resin 30g/L～60g/L,
Phytic acid and/or phosphatase 24 0g/L～80g/L,
Titanium acetylacetone 3g/L～12g/L,
Vanadium acetylacetonate 10g/L～30g/L, and
Virahol 50g/L～100g/L;
In described passivator, also contain and be useful on the N that regulates passivator pH value, N dimethylethanolamine, the pH value of described passivator is 4～5;
Described passivator is chrome-free tanning agent, and does not contain molybdate or rare earth compound in described passivator.
2. the passivator for hot-dip galvanizing sheet steel according to claim 1, is characterized in that, described nanometer SiO
2median size be 10nm～100nm.
3. the passivator for hot-dip galvanizing sheet steel according to claim 1, is characterized in that, described titanium acetylacetone refers to methyl ethyl diketone oxygen titanium or methyl ethyl diketone diisopropoxy titanium.
4. one kind is carried out the method for passivation to hot-dip galvanizing sheet steel with the passivator described in any one in claim 1～3, the method mainly refers to and on the production line of described hot-dip galvanizing sheet steel, adopts spraying, blade coating or roll coating model to make described passivator be coated to hot-dip galvanizing sheet steel, and it dries plate temperature is 80 ℃～100 ℃.
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| CN102965656B (en) * | 2012-11-27 | 2014-10-29 | 中国人民解放军国防科学技术大学 | Low-temperature drying passivant and passivation method for hot-dip galvanized steel sheet |
| CN103205742A (en) * | 2013-04-09 | 2013-07-17 | 海宁市科泰克金属表面技术有限公司 | Chromate-free passivator for zinc coating |
| CN105839098B (en) * | 2016-05-31 | 2018-09-07 | 湖南省鎏源新能源有限责任公司 | Hot-dip galvanizing sheet steel chrome-free tanning agent and preparation method thereof |
| CN105839095B (en) * | 2016-05-31 | 2018-07-03 | 无锡伊佩克科技有限公司 | A kind of hot-dip galvanizing sheet steel chrome-free tanning agent and preparation method thereof |
| CN107012454A (en) * | 2017-04-10 | 2017-08-04 | 武汉迪赛鸿印科技有限公司 | A kind of bolt surface antirust fastening agent |
| CN109280868A (en) * | 2017-07-20 | 2019-01-29 | 安徽宏源铁塔有限公司 | A kind of galvanized method of electric power tower steel |
| CN107557780A (en) * | 2017-09-11 | 2018-01-09 | 苏州盈腾五金制品有限公司 | A kind of surface full non-chromium inactivating technique of zinc-plated handware |
| CN108866526A (en) * | 2018-08-06 | 2018-11-23 | 广州和力表面处理技术有限公司 | A kind of cover packaging material pre-treatment chromium-free environment-friendly passivator and preparation method thereof |
| CN115726016B (en) * | 2022-12-05 | 2023-08-11 | 仙桃市伟方新材料科技有限公司 | Nickel-free fluoride-free medium-temperature sealing agent containing rare earth component and preparation method thereof |
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| CN1386901A (en) * | 2001-05-01 | 2002-12-25 | 日本巴卡莱近估股份有限公司 | Metal surface treating agent and method, and surface treatment of metal material |
| CN102373453B (en) * | 2010-08-05 | 2014-05-07 | 攀钢集团钢铁钒钛股份有限公司 | Chromium-free passivation solution and hot-dip galvanized metal material |
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