CN102965656B - Low-temperature drying passivant and passivation method for hot-dip galvanized steel sheet - Google Patents
Low-temperature drying passivant and passivation method for hot-dip galvanized steel sheet Download PDFInfo
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- CN102965656B CN102965656B CN201210489741.1A CN201210489741A CN102965656B CN 102965656 B CN102965656 B CN 102965656B CN 201210489741 A CN201210489741 A CN 201210489741A CN 102965656 B CN102965656 B CN 102965656B
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Abstract
The invention relates to the technical field of surface treatment of hot-dip galvanized steel sheet materials and particularly discloses a low-temperature drying passivant for a hot-dip galvanized steel sheet. The low-temperature drying passivant contains water and comprises the following components by weight: 40-80 g/L of nano SiO2, 40-80 g/L of watercraft acrylic resin, 40-80 g/L of organic phosphonic acid, 5-15 g/L of ammonium fluorotitanate or titanyl sulfate and 10-20 g/L of ammonium metavanadate, wherein the pH value can be adjusted to 4-5 through diethylamine. The invention also discloses a passivation method which is mainly characterized in that the hot-dip galvanized steel sheet is coated with the passivant in a spray-coating or roll-coating way on the production line of the hot-dip galvanized steel sheet and the temperature for drying the sheet is only about 70 DEG C. The passivant and the passivation method have the advantages of simple formula, available materials, excellent passivation effect and low drying temperature, and is convenient to use, healthy and environment-friendly.
Description
Technical field
The invention belongs to the technical field of surface of steel plate, relate in particular to the passivator that a kind of hot-dip galvanizing sheet steel 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 one deck containing the passivation layer of 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 of European Union's issue has just clearly limited chromic use.In prior art, in order to reduce chromic harm, there is trivalent chromium passivator, but trivalent chromium is used as passivator, not only passivation effect is not so good as sexavalent chrome ideal, and it can change sexavalent chrome under certain condition, the same potential risk that has harm environment and human health.Therefore, with chrome-free tanning agent, replace and have chromium passivating 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.In addition, existing passivator bake out temperature is in use higher, and this not only increases energy consumption, increases the use cost of passivator, and has worsened the operating environment of passivating process, is unfavorable for the safety in production of passivation operation.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, baking and curing temperature is low, easy to use, passivation effect better, the passivator for hot-dip galvanizing sheet steel of health environment-friendly, also corresponding this passivator that provides carries out the method for passivation to hot-dip galvanizing sheet steel.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of oven drying at low temperature passivator for hot-dip galvanizing sheet steel, and described passivator comprises the component of water (preferably deionized water) and following concentration:
Nanometer SiO
240g/L～80g/L,
Water soluble acrylic resin 40g/L～80g/L,
Organic phospho acid 40g/L～80g/L,
Ammonium titanium fluoride and/or titanyl sulfate 5g/L～15g/L, and
Ammonium meta-vanadate 10g/L～20g/L.
The above-mentioned oven drying at low temperature passivator for hot-dip galvanizing sheet steel, in described passivator, also preferably containing being useful on the diethylamide that regulates passivator pH value, the pH value of described passivator is preferably 4～5.
The above-mentioned oven drying at low temperature 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 oven drying at low temperature passivator for hot-dip galvanizing sheet steel, described nanometer SiO
2median size be preferably 10nm～100nm.
The above-mentioned oven drying at low temperature passivator for hot-dip galvanizing sheet steel, described organic phospho acid preferably refers to one or more in the organic phosphine acids materials such as 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, Amino Trimethylene Phosphonic Acid, diethylenetriamine pentamethylene phosphonic acids, ethylenediamine tetramethylene phosphonic acid, polyamino polyether methylene phosphonic acids.
As a total technical conceive, the present invention also provides a kind of above-mentioned oven drying at low temperature 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 blade coating, spraying or roll coating model to make described passivator be coated to hot-dip galvanizing sheet steel, it dries plate temperature (PMT) is more than 70 ℃, and dries plate temperature more preferably less than 80 ℃.
The above-mentioned oven drying at low temperature passivator for hot-dip galvanizing sheet steel, due to not phosphoric acid and phytic acid, and because the water-absorbent of organic phospho acid is low compared with phosphoric acid or phytic acid, therefore passivator of the present invention is easier to be dried, and in addition, the preferred pH value of the present invention conditioning agent diethylamide is also more volatile, the the optimizing and revising and improving formula by the present invention, passivator of the present invention is being promoted under the prerequisite of original passivation effect, and the drying temperature while making passivation significantly reduces, and energy consumption and cost be corresponding reducing all.
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, baking and curing temperature is lower.In preferred technical scheme, passivator of the present invention can be completely containing environmental and human health impacts being had to the heavy metal chromium of 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 oil removing is carried out with grease-removing agent in the hot-dip galvanizing sheet steel surface that is coated with oil guard of rolling off the production line, with tap water, rinse well, 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 16 groups of passivator of the present invention, and each organizes the formula (the preparation total amount of each embodiment is 1L) as shown in table 1 below of passivator.
Table 1: the system component list of each embodiment
| Embodiment numbering | Organic phospho acid g/L | Nanometer SiO 2g/L | Water soluble acrylic resin g/L | Ammonium titanium fluoride g/L | Titanyl sulfate g/L | Ammonium meta-vanadate g/L |
| 1 | 60 | 60 | 40 | 0 | 10 | 15 |
| 2 | 40 | 60 | 40 | 10 | 0 | 15 |
| 3 | 80 | 60 | 40 | 10 | 0 | 15 |
| 4 | 60 | 40 | 40 | 10 | 0 | 15 |
| 5 | 60 | 80 | 40 | 10 | 0 | 15 |
| 6 | 60 | 60 | 40 | 10 | 0 | 15 |
| 7 | 60 | 60 | 80 | 10 | 0 | 15 |
| 8 | 60 | 60 | 60 | 5 | 0 | 15 |
| 9 | 60 | 60 | 40 | 15 | 0 | 15 |
| 10 | 60 | 60 | 40 | 0 | 10 | 10 |
| 11 | 60 | 60 | 40 | 0 | 10 | 20 |
| 12 | 60 | 40 | 40 | 0 | 15 | 15 |
| 13 | 60 | 60 | 40 | 0 | 10 | 15 |
| 14 | 60 | 60 | 40 | 0 | 10 | 15 |
| 15 | 60 | 60 | 40 | 0 | 10 | 15 |
| 16 | 80 | 40 | 40 | 0 | 10 | 15 |
Note: in upper table 1, the organic phospho acid of selecting in embodiment 1～11 is 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, the organic phospho acid that embodiment 12 selects is Amino Trimethylene Phosphonic Acid, the organic phospho acid that embodiment 13 selects is diethylenetriamine pentamethylene phosphonic acids, the organic phospho acid that embodiment 14 selects is ethylenediamine tetramethylene phosphonic acid, and the organic phospho acid that embodiment 15 and embodiment 16 select is polyamino polyether methylene phosphonic acids.
What above embodiment was cited respectively organizes in passivator, all adopts diethylamide the pH value of each passivator to be adjusted in 4～5 scope, and respectively organizes passivator and be chrome-free tanning agent, and all, containing molybdate or rare earth compound, each organizes nanometer SiO in passivator
2median size all in the scope of 10nm～100nm.
Above-mentionedly until the passivation of the laboratory of passivation hot-dip galvanizing sheet steel, all adopt the 0# scraper of Britain RK company to carry out blade coating (approximately 4 μ m after wet film), in hot-air oven, dry, dry approximately 70 ℃ of plate temperature.Then the passivation steel plate galvanized of clip 150mm * 75mm size carries out the Performance Detection of the following as test piece respectively, specifically comprise and carry out neutral salt spray test, cold-workability test, X-scribe test, solvent resistance test, with the corroded area percentage ratio of 72 hours, evaluate its performance; Also carry out anti-blackening test, non-yellowing test, with its performance of colour-change degree evaluation simultaneously.At the heavy 0.5g/m of build 0.4 μ m～0.8 μ m(dry film
2～1.0g/m
2) situation under, the white erosion of neutral salt spray test 72 hours area is less than 3%.
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 with surface the corrosion resisting property that area is evaluated passive film.
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.
With the passivator of respectively organizing of above embodiment, treat passivation hot-dip galvanizing sheet steel and carry out after passivation, the test of the properties 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 | <3% | <3% | <3% | <5% | Slightly | Slightly |
| 2 | <3% | <3% | <3% | <5% | Slightly | Slightly |
| 3 | <3% | <3% | <3% | <5% | Slightly | Slightly |
| 4 | <3% | <3% | <3% | <5% | Slightly | Slightly |
| 5 | <3% | <3% | <3% | <5% | Slightly | Slightly |
| 6 | <3% | <3% | <3% | <5% | Slightly | Slightly |
| 7 | <3% | <3% | <3% | <5% | Slightly | Slightly |
| 8 | <3% | <3% | <3% | <5% | Slightly | Slightly |
| 9 | <3% | <3% | <3% | <5% | Slightly | Slightly |
| 10 | <3% | <3% | <3% | <5% | Slightly | Slightly |
| 11 | <3% | <3% | <3% | <5% | Slightly | Slightly |
| 12 | <3% | <3% | <3% | <5% | Slightly | Slightly |
| 13 | <3% | <3% | <3% | <5% | Slightly | Slightly |
| 14 | <3% | <3% | <3% | <5% | Slightly | Slightly |
| 15 | <3% | <3% | <3% | <5% | Slightly | Slightly |
| 16 | <3% | <3% | <3% | <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 (5)
1. for an oven drying at low temperature passivator for hot-dip galvanizing sheet steel, it is characterized in that, described passivator comprises the component of water and following concentration:
Nanometer SiO
240g/L～80g/L,
Water soluble acrylic resin 40g/L～80g/L,
Organic phospho acid 40g/L～80g/L,
Ammonium titanium fluoride and/or titanyl sulfate 5g/L～15g/L, and
Ammonium meta-vanadate 10g/L～20g/L;
Described organic phospho acid comprises at least one in Amino Trimethylene Phosphonic Acid, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, diethylenetriamine pentamethylene phosphonic acids, ethylenediamine tetramethylene phosphonic acid, polyamino polyether methylene phosphonic acids;
The oven dry plate temperature of described oven drying at low temperature passivator is more than 70 ℃, lower than 80 ℃.
2. the oven drying at low temperature passivator for hot-dip galvanizing sheet steel according to claim 1, is characterized in that, in described passivator, also containing being useful on the diethylamide that regulates passivator pH value, the pH value of described passivator is 4～5.
3. the oven drying at low temperature passivator for hot-dip galvanizing sheet steel according to claim 1 and 2, is characterized in that, described passivator is chrome-free tanning agent, and does not contain molybdate or rare earth compound in described passivator.
4. the oven drying at low temperature passivator for hot-dip galvanizing sheet steel according to claim 1 and 2, is characterized in that described nanometer SiO
2median size be 10nm～100nm.
5. one kind is carried out the method for passivation with the oven drying at low temperature passivator described in any one in claim 1～4 to hot-dip galvanizing sheet steel, the method mainly refers to and on the production line of described hot-dip galvanizing sheet steel, adopts blade coating, spraying or roll coating model to make described passivator be coated to hot-dip galvanizing sheet steel, and it dries plate temperature is more than 70 ℃; Described oven dry plate temperature is lower than 80 ℃.
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| CN116732507A (en) * | 2023-06-20 | 2023-09-12 | 保定奥琦圣新型金属材料制造有限公司 | Galvanized steel passivation solution and preparation method thereof |
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| CN101182640A (en) * | 2007-12-11 | 2008-05-21 | 中南大学 | Inactivating process of galvanized steel sheet and inactivating liquid thereof |
| CN102747352A (en) * | 2012-07-03 | 2012-10-24 | 中国人民解放军国防科学技术大学 | Passivator and passivation for hot galvanized sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101182640A (en) * | 2007-12-11 | 2008-05-21 | 中南大学 | Inactivating process of galvanized steel sheet and inactivating liquid thereof |
| CN102747352A (en) * | 2012-07-03 | 2012-10-24 | 中国人民解放军国防科学技术大学 | Passivator and passivation for hot galvanized sheet |
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