CN103232735A - Chrome-free zinc-aluminum coating anticorrosive paint comprising nickel-magnesium-manganese-silicon - Google Patents
Chrome-free zinc-aluminum coating anticorrosive paint comprising nickel-magnesium-manganese-silicon Download PDFInfo
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- CN103232735A CN103232735A CN201310000206XA CN201310000206A CN103232735A CN 103232735 A CN103232735 A CN 103232735A CN 201310000206X A CN201310000206X A CN 201310000206XA CN 201310000206 A CN201310000206 A CN 201310000206A CN 103232735 A CN103232735 A CN 103232735A
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Abstract
The invention discloses a chrome-free zinc-aluminum coating anticorrosive paint comprising nickel-magnesium-manganese-silicon. The paint is composed of a component A and a component B with a mass ratio of 3:1. The component A comprises the raw materials of zinc-aluminum alloy powder, nano-silica, lignin sodium sulfonate, benzotriazole, thio diethylene glycol, triphenylphosphine, and deionized water. The component B comprises zirconium tetrafluoride, gamma-aminopropyl triethoxysilane, inositol hexaphosphate, butyl cellulose acetate, ethanol, and deionized water. The zinc-aluminum alloy powder is composed of Zn, Al, Ni, Mg, Mn and Si. The product provided by the invention has the advantages of no toxicity, no harm, no pollution, low-temperature fast processing, simple operation, wide raw material source, low cost, clean production, and the like.
Description
Technical field
The present invention relates to a kind of metal anti-corrosive paint, particularly a kind of nickeliferous-the chromium-free zinc aluminum coating antiseptic coating of magnesium-manganese-silicon.
Background technology
The chromium-free zinc aluminum coating is the environmental requirement for the VOC rules that satisfy countries in the world and paint industry regulation, substitutes traditional Dacroment zinc-chromium coating technology and the surface treatment novel material developed.
Dacroment is DACROMET transliteration and abbreviation, is called for short Dacroment, reaches gram rust, Di Kelong.Domestic called after zinc-chromium coating, be a kind of be the novel protective system of main component with zinc powder, aluminium powder, chromic acid and deionized water.Its antiseptic principle is that the hexavalent chromium in the employing chromic salts takes zinc, the aluminium flake in the passivation coatings, improve the antiseptic power of zinc, aluminium flake self, through 300 ℃ of bakings, redox reaction forms amorphous nCr2O3mCrO3 composite salt, with the overlapping metallic surface that covers of zinc-aluminium sheet, so that only having under the thickness film layer condition of 6 ~ 8um, just can under neutral salt spray 1000h condition, not produce red rust substantially.It also has or not hydrogen embrittlement, the advantage that can be combined with the rete of multiple plating, coating simultaneously.Yet contain the chromium ion to environment and human body harmful in the zinc-chromium coating, especially hexavalent chromium has carcinogenesis.Though the coating processes of zinc-chromium coating is a totally enclosed process, coating does not efflux, and chromic anhydride residual in the coating can in use be discharged in the environment lentamente, and human and environment is had certain potential hazard.Therefore, the relevant environment rules are put into effect the content of the chromium in the strict restriction Dyclo paint.In addition, this coating curing temperature is up to 300 ℃, and also reach about 30 minutes set time, and energy consumption is big; Hardness is low, wears no resistance.Workpiece usually can be subjected to scratch, scratch in transportation, assembling, use, influence outward appearance and the solidity to corrosion of product.
Aluminum Coating (chromium-free Dyclo) as the renewal product of Dacroment at first by the general recognition and acceptance of automobile manufacture industry.The chromium-free zinc aluminum coating has realized that at present the product of industrialization is very few, and a kind of is the Geomet(Geomet of being released by U.S. MCI company) coating, a kind of is the Delta coating that German DELTA company releases, more than two kinds of coatings generally use in developed country.
At present, the commercial application of Chrome-free Dacromet Technology is all arranged, but the more traditional Dacroment coating of the solidity to corrosion of coating obviously reduces both at home and abroad, and need to use with the collocation of another layer organic coating, increased cost greatly.The cost of chromium-free zinc aluminum coating is more much higher than zinc-chromium coating, so its price is very high.The German spot price of Delta slurries is that 40 Euros/kilogram, the Japanese spot price of Geomet Geomet slurries are 1750 yen/kilogram, estimates that thus they all should be more than 250 yuans/kilogram in the sale price of China.Therefore, working out the chromium-free Dyclo paint that corrosion resisting property that a kind of cost is not higher than traditional Dyclo paint and existing zinc-aluminium coating, coating is not less than traditional zinc-chromium coating is the focus of domestic and international anti-corrosion of metal research.
Summary of the invention
At problems of the prior art, the present invention aim to provide a kind of nickeliferous-the chromium-free zinc aluminum coating antiseptic coating of magnesium-manganese-silicon and preparation method thereof.
Concrete technical scheme of the present invention is as follows:
A kind of nickeliferous-the chromium-free zinc aluminum coating antiseptic coating of magnesium-manganese-silicon, it is characterized in that: be made up of by the 3:1 mass ratio the two components of A, B, wherein: the prescription quality per-cent of A component is:
Aluminium zinc powder 25 ~ 40%
Nano silicon 20 ~ 30%
Sodium lignosulfonate 12 ~ 18%
Benzotriazole 3 ~ 5%
Thio-diethylene glycol 0.2 ~ 0.5%
Triphenylphosphine 0.2 ~ 0.5%
The deionized water surplus
The prescription quality per-cent of B component is:
Zirconium tetrafluoride 20-30%
γ-An Bingjisanyiyangjiguiwan 15 ~ 20%
Myo-Inositol hexaphosphate 10 ~ 18%
Cellaburate 2 ~ 5%
Ethanol 5-9%
The deionized water surplus
Wherein, described aluminium zinc powder is made up of Zn, Al, Ni, Mg, Mn, Si.
Wherein, the particle diameter of described nano silicon is 20 ~ 50nm.
Wherein, each composition mass percent of described aluminium zinc powder is: Zn:60% ~ 70%, and Ni:0.5% ~ 0.8%, Mg:0.1% ~ 0.2%, Mn:0.1% ~ 0.2%, Si:0.5% ~ 1.0%, surplus is Al and unavoidable impurities.
Preferably, a kind of nickeliferous-the chromium-free zinc aluminum coating antiseptic coating of magnesium-manganese-silicon, it is characterized in that: be made up of by the 3:1 mass ratio the two components of A, B, wherein: the prescription quality per-cent of A component is:
Aluminium zinc powder 32%
Nano silicon 25%
Sodium lignosulfonate 15%
Benzotriazole 4%
Thio-diethylene glycol 0.35%
Triphenylphosphine 0.35%
The deionized water surplus
The prescription quality per-cent of B component is:
Zirconium tetrafluoride 25%
γ-An Bingjisanyiyangjiguiwan 18%
Myo-Inositol hexaphosphate 14%
Cellaburate 3.5%
Ethanol 7%
The deionized water surplus
Wherein, described aluminium zinc powder is made up of Zn, Al, Ni, Mg, Mn, Si.
Wherein, the particle diameter of described nano silicon is 20 ~ 50nm.
Wherein, each composition mass percent of described aluminium zinc powder is: Zn:60% ~ 70%, and Ni:0.5% ~ 0.8%, Mg:0.1% ~ 0.2%, Mn:0.1% ~ 0.2%, Si:0.5% ~ 1.0%, surplus is Al and unavoidable impurities.
The present invention also provides a kind of method for preparing the chromium-free zinc aluminum coating antiseptic coating of nickeliferous-magnesium-manganese-silicon, it is characterized in that:
(1) at first, press the prescription in the A component, take by weighing quantitative sodium lignosulfonate, benzotriazole, thio-diethylene glycol, triphenylphosphine and dissolve in the deionized water, under whipped state, slowly add nano silicon then, the aluminium zinc powder leaves standstill after stirring 2h;
(2) press prescription in the B component, take by weighing quantitative zirconium tetrafluoride, γ-An Bingjisanyiyangjiguiwan, myo-Inositol hexaphosphate and slowly join deionized water for stirring, slowly add cellaburate and ethanol after mixing while stirring, leave standstill after continuing to stir 2h;
(3) will leave standstill the above A component of 4h and B component and namely get described chromium-free zinc aluminum coating antiseptic coating by mass ratio 3:1 mixing.
Chromium-free zinc aluminum coating of the present invention and zinc-chromium coating are close applying production technique.After part was carried out pre-treatment, the chromium-free zinc aluminum coating was the same with zinc-chromium coating, the dipping of employing routine-centrifugal, spraying or dipping-drop liquid-centrifugal coating processes.Part behind the primary coating heats under 170 ℃ of conditions to be kept 15 minutes after fixing and obtains coating, carry out applying curing second time after then will part taking out cooling, and the regelate temperature is 170 ℃, time length 15-20 minute.Can obtain different coat-thicknesses by the processing parameter of adjusting coating procedure.
Beneficial effect of the present invention: adopt coating of the present invention to make antiseptic engineering component and have many excellent properties, as: the solidity to corrosion that the coating curing temperature is low, excellent, good shock resistance, strong with basal body binding force, with other various additional coatings bonding force is preferably arranged also simultaneously, remedied the lower deficiency of self hardness in the prior art simultaneously, coating wear resistance is good, and high heat/corrosion resistance is fabulous, long service life under the extreme environment.That product of the present invention has is nontoxic, harmless, pollution-free, low temperature fast processing, simple to operate, characteristics such as raw material sources are extensive, price is low, cleaner production, the home market price of chromium-free zinc aluminum coating slurries of the present invention only is 120 yuans/kilogram, thereby the processing that greatly reduces the chromium-free zinc aluminum coating applies cost, for China's large-scale application chromium-free zinc aluminum coating has been created condition.
Embodiment
Provide some preferred embodiments of formulation for coating material proportioning of the present invention below, but the numerical value that the content of each moiety of the present invention is not limited to provide, for a person skilled in the art, can in the prescription numerical range, reasonably summarize and reasoning fully.
Embodiment 1:
A kind of nickeliferous-the chromium-free zinc aluminum coating antiseptic coating of magnesium-manganese-silicon, formed by the 3:1 mass ratio by the two components of A, B, wherein: the prescription quality per-cent of A component is:
Aluminium zinc powder 32%
Nano silicon 25%
Sodium lignosulfonate 15%
Benzotriazole 4%
Thio-diethylene glycol 0.35%
Triphenylphosphine 0.35%
The deionized water surplus
The prescription quality per-cent of B component is:
Zirconium tetrafluoride 25%
γ-An Bingjisanyiyangjiguiwan 18%
Myo-Inositol hexaphosphate 14%
Cellaburate 3.5%
Ethanol 7%
The deionized water surplus
Wherein, described aluminium zinc powder is made up of Zn, Al, Ni, Mg, Mn, Si.
Wherein, the particle diameter of described nano silicon is 20 ~ 50nm.
Prepare above-mentioned nickeliferous-method of the chromium-free zinc aluminum coating antiseptic coating of magnesium-manganese-silicon:
(1) at first, press the prescription in the A component, take by weighing quantitative sodium lignosulfonate, benzotriazole, thio-diethylene glycol, triphenylphosphine and dissolve in the deionized water, under whipped state, slowly add nano silicon then, the aluminium zinc powder leaves standstill after stirring 2h;
(2) press prescription in the B component, take by weighing quantitative zirconium tetrafluoride, γ-An Bingjisanyiyangjiguiwan, myo-Inositol hexaphosphate and slowly join deionized water for stirring, slowly add cellaburate and ethanol after mixing while stirring, leave standstill after continuing to stir 2h;
(3) will leave standstill the above A component of 4h and B component and namely get described chromium-free zinc aluminum coating antiseptic coating by mass ratio 3:1 mixing.
Embodiment 2:
A kind of nickeliferous-the chromium-free zinc aluminum coating antiseptic coating of magnesium-manganese-silicon, formed by the 3:1 mass ratio by the two components of A, B, wherein: the prescription quality per-cent of A component is:
Aluminium zinc powder 25%
Nano silicon 30%
Sodium lignosulfonate 12%
Benzotriazole 5%
Thio-diethylene glycol 0.2%
Triphenylphosphine 0.5%
The deionized water surplus
The prescription quality per-cent of B component is:
Zirconium tetrafluoride 20%
γ-An Bingjisanyiyangjiguiwan 20%
Myo-Inositol hexaphosphate 10%
Cellaburate 5%
Ethanol 5%
The deionized water surplus
Wherein, described aluminium zinc powder is made up of Zn, Al, Ni, Mg, Mn, Si.
Wherein, the particle diameter of described nano silicon is 20 ~ 50nm.
The preparation method is with embodiment 1.
Embodiment 3:
A kind of nickeliferous-the chromium-free zinc aluminum coating antiseptic coating of magnesium-manganese-silicon, formed by the 3:1 mass ratio by the two components of A, B, wherein: the prescription quality per-cent of A component is:
Aluminium zinc powder 40%
Nano silicon 20%
Sodium lignosulfonate 18%
Benzotriazole 3%
Thio-diethylene glycol 0.5%
Triphenylphosphine 0.2%
The deionized water surplus
The prescription quality per-cent of B component is:
Zirconium tetrafluoride 30%
γ-An Bingjisanyiyangjiguiwan 15%
Myo-Inositol hexaphosphate 18%
Cellaburate 2%
Ethanol 9%
The deionized water surplus
Wherein, described aluminium zinc powder is made up of Zn, Al, Ni, Mg, Mn, Si.
Wherein, the particle diameter of described nano silicon is 20 ~ 50nm.
The preparation method is with embodiment 1.
Embodiment 4:
A kind of nickeliferous-the chromium-free zinc aluminum coating antiseptic coating of magnesium-manganese-silicon, formed by the 3:1 mass ratio by the two components of A, B, wherein: the prescription quality per-cent of A component is:
Aluminium zinc powder 26%
Nano silicon 29%
Sodium lignosulfonate 13%
Benzotriazole 4.5%
Thio-diethylene glycol 0.25%
Triphenylphosphine 0.45%
The deionized water surplus
The prescription quality per-cent of B component is:
Zirconium tetrafluoride 22%
γ-An Bingjisanyiyangjiguiwan 18.5%
Myo-Inositol hexaphosphate 12%
Cellaburate 4.5%
Ethanol 6%
The deionized water surplus
Wherein, described aluminium zinc powder is made up of Zn, Al, Ni, Mg, Mn, Si.
Wherein, the particle diameter of described nano silicon is 20 ~ 50nm.
The preparation method is with embodiment 1.
Embodiment 5:
A kind of nickeliferous-the chromium-free zinc aluminum coating antiseptic coating of magnesium-manganese-silicon, formed by the 3:1 mass ratio by the two components of A, B, wherein: the prescription quality per-cent of A component is:
Aluminium zinc powder 38%
Nano silicon 22%
Sodium lignosulfonate 17%
Benzotriazole 3.5%
Thio-diethylene glycol 0.45%
Triphenylphosphine 0.25%
The deionized water surplus
The prescription quality per-cent of B component is:
Zirconium tetrafluoride 28%
γ-An Bingjisanyiyangjiguiwan 16%
Myo-Inositol hexaphosphate 17%
Cellaburate 2.5%
Ethanol 8%
The deionized water surplus
Wherein, described aluminium zinc powder is made up of Zn, Al, Ni, Mg, Mn, Si.
Wherein, the particle diameter of described nano silicon is 20 ~ 50nm.
The preparation method is with embodiment 1.
Aluminium zinc powder described in the above embodiment 1 ~ 5 is by Zn, Al, Ni, Mg and Mn form, below, associative list 1 provides some preferred embodiments of each moiety mass percent of aluminium zinc powder of the present invention, but the content of each moiety of aluminium zinc powder of the present invention is not limited to listed numerical value in this table, and of particular note, although provided the mass percent numerical value of relevant composition in the table 1, but these are described as essential features, all be as preferred condition, all be in order to provide technical intelligence of the present invention in more detail, and described as prerequisite of the present invention.
Each moiety mass percentage content (%) of table 1 aluminium zinc powder
The performance test of the coating of the chromium-free zinc aluminum coating antiseptic coating of nickeliferous-magnesium-manganese-silicon of above-mentioned 5 kinds of embodiment is as follows:
(1) erosion resistance of coating
Adopt two kinds of method tests of anti-ammonium nitrate and salt-fog test.
Neutral salt spray test is undertaken by GB/T1771 " the anti-neutral salt spray performance measurement of paint and varnish ", test conditions is: sodium-chlor (50 ± 10) g/L, pH:6.5 ~ 7.2, salt fog the temperature inside the box: (35 ± 2) ℃, specimen surface corrosion situation is recorded in spraying continuously simultaneously.
The operation steps of anti-ammonium nitrate test is as follows: the ammonium nitrate solution of preparation 20% in beaker, and beaker is put into water bath with thermostatic control be heated to (70 ± 1) ℃.(with thermometer measure and control bath temperature), all or part of dipping of the model that will test wherein hang fixingly, and the time of red rust appears in the record model.
(2) shock-resistance of coating
Adopt GB/T l732-1993 " the shock-resistant assay method of paint film " to judge the shock-resistance of coating.Step is as follows: the test plate (panel) paint film of will painting lies on the anvil up, and the test plate (panel) part edge that is hit is not less than 15mm, and the edge of each shock point is at a distance of being less than 15mm.The a certain height (this height is stipulated by product standard or decided through consultation) that weight borrows control device to be fixed on slide cartridge is pressed control knob, and weight is freely to fall within on the drift.Mention weight, take out test plate (panel), the record weight falls within the height on the test plate (panel).Same test plate (panel) carries out shock test 3 times.Observe with 4 times of magnifying glasses, judge that paint film has flawless, wrinkle and phenomenon such as peels off.
(3) coating humidity resistance
Adopt GB/T1740-1979 " paint film moisture-proof heat determination method " to judge the humidity resistance of coating.
Performance test data:
Certain marine oil company drilling well vital part drill conductor (material 35CrMo), the former protective treatment of adopting routine only namely produces significant corrosion after the several months.Adopt coating of the present invention to apply on the phosphatize phosphate coat basis and form 30 μ m thick coatings, show that through the accelerated corrosion analog reslt its main performance index that reaches is in seawater splash(spray)zone environment:
| ? | The neutral salt spray corrosion life | 300 ℃ of humidity resistance life-spans | The coating shock-resistance | The quick corrosion life of ammonium nitrate |
| Embodiment 1 | Greater than 1400 hours | Greater than 240 hours | 50N | Greater than 9 hours |
| Embodiment 2 | Greater than 1200 hours | Greater than 200 hours | 50N | Greater than 8 hours |
| Embodiment 3 | Greater than 1200 hours | Greater than 200 hours | 50N | Greater than 8 hours |
| Embodiment 4 | Greater than 1200 hours | Greater than 200 hours | 50N | Greater than 8 hours |
| Embodiment 5 | Greater than 1200 hours | Greater than 200 hours | 50N | Greater than 8 hours |
Claims (2)
1. the chromium-free zinc aluminum coating antiseptic coating of nickeliferous-magnesium-manganese is characterized in that: be made up of by the 3:1 mass ratio the two components of A, B, wherein: the prescription quality per-cent of A component is:
Aluminium zinc powder 32%
Nano silicon 25%
Sodium lignosulfonate 15%
Benzotriazole 4%
Thio-diethylene glycol 0.35%
Triphenylphosphine 0.35%
The deionized water surplus
The prescription quality per-cent of B component is:
Zirconium tetrafluoride 25%
γ-An Bingjisanyiyangjiguiwan 18%
Myo-Inositol hexaphosphate 14%
Cellaburate 3.5%
Ethanol 7%
The deionized water surplus
The particle diameter of described nano silicon is 20 ~ 50nm;
Described aluminium zinc powder is made up of Zn, Al, Ni, Mg, Mn, Si, and the mass percent of each component is: Zn:60% ~ 70%, Ni:0.5% ~ 0.8%, Mg:0.1% ~ 0.2%, Mn:0.1% ~ 0.2%, Si:0.5% ~ 1.0%, surplus is Al and unavoidable impurities.
According to claim 1 a kind of nickeliferous-the chromium-free zinc aluminum coating antiseptic coating of magnesium-manganese-silicon, it is characterized in that the preparation method is:
(1) at first, press the prescription in the A component, take by weighing quantitative sodium lignosulfonate, benzotriazole, thio-diethylene glycol, triphenylphosphine and dissolve in the deionized water, under whipped state, slowly add nano silicon then, the aluminium zinc powder leaves standstill after stirring 2h;
(2) press prescription in the B component, take by weighing quantitative zirconium tetrafluoride, γ-An Bingjisanyiyangjiguiwan, myo-Inositol hexaphosphate and slowly join deionized water for stirring, slowly add cellaburate and ethanol after mixing while stirring, leave standstill after continuing to stir 2h;
(3) will leave standstill the above A component of 4h and B component and namely get described chromium-free zinc aluminum coating antiseptic coating by mass ratio 3:1 mixing.
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| CN201310000206.XA CN103232735B (en) | 2013-01-03 | 2013-01-03 | Chrome-free zinc-aluminum coating anticorrosive paint comprising nickel-magnesium-manganese-silicon |
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| CN201310000206.XA CN103232735B (en) | 2013-01-03 | 2013-01-03 | Chrome-free zinc-aluminum coating anticorrosive paint comprising nickel-magnesium-manganese-silicon |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112387983A (en) * | 2020-11-30 | 2021-02-23 | 浙江华朔科技股份有限公司 | Preparation method of aluminum alloy surface damping corrosion-resistant composite structure layer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09268265A (en) * | 1996-03-29 | 1997-10-14 | Nippon Light Metal Co Ltd | Coating composition for preventing corrosion of metal |
| CN101925457A (en) * | 2008-01-24 | 2010-12-22 | 油研工业股份有限公司 | Member with corrosion-resistant coating film, process for production of the same, and coating composition for production thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09268265A (en) * | 1996-03-29 | 1997-10-14 | Nippon Light Metal Co Ltd | Coating composition for preventing corrosion of metal |
| CN101925457A (en) * | 2008-01-24 | 2010-12-22 | 油研工业股份有限公司 | Member with corrosion-resistant coating film, process for production of the same, and coating composition for production thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112387983A (en) * | 2020-11-30 | 2021-02-23 | 浙江华朔科技股份有限公司 | Preparation method of aluminum alloy surface damping corrosion-resistant composite structure layer |
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