CN103044992A - Nickel-manganese-containing chromium-free zinc-aluminum coating anti-corrosive paint - Google Patents

Nickel-manganese-containing chromium-free zinc-aluminum coating anti-corrosive paint Download PDF

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CN103044992A
CN103044992A CN2013100002765A CN201310000276A CN103044992A CN 103044992 A CN103044992 A CN 103044992A CN 2013100002765 A CN2013100002765 A CN 2013100002765A CN 201310000276 A CN201310000276 A CN 201310000276A CN 103044992 A CN103044992 A CN 103044992A
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component
coating
chromium
deionized water
manganese
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CN103044992B (en
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张军
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Yangzhou Hong Ruixin Energy Products Science And Technology Development Co Ltd
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Abstract

The invention discloses nickel-manganese-containing chromium-free zinc-aluminum coating anti-corrosive paint which comprises an A component and a B component at a mass ratio of 3:1, wherein the A component comprises the following raw materials: allumen powder, nano-silica, sodium lignosulphonate, benzotriazole, sulpho-diethylene glycol, triphenylphosphine and deionized water; the B component comprises the following raw materials: zirconium tetrafluoride, gamma-aminopropyl triethoxy silane, inositol hexaphosphate, cellulose acetate-butyrate, ethanol and deionized water; and the allumen powder comprises Zn, Al, Ni and Mn. The paint has the characteristics of no toxicity, harmlessness, no pollution, low-temperature immediate processing, easiness in operation, extensive raw material sources, low price, cleaner production and the like.

Description

A kind of Non-chromium Zn-al Coating protective system of nickel-manganese-contained
Technical field
The present invention relates to the Non-chromium Zn-al Coating protective system of a kind of metal anti-corrosive paint, particularly a kind of nickel-manganese-contained.
Background technology
Non-chromium Zn-al 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 technique 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 is a kind of novel protective system take zinc powder, aluminium powder, chromic acid and deionized water as main component.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, substantially not produce red rust.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.Although 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 large; Hardness is low, wears no resistance.Workpiece usually can be subject to scratch, scratch in transportation, assembling, use procedure, affect 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.Non-chromium Zn-al 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 Dacromet/steel 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, greatly increased cost.The cost of Non-chromium Zn-al 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
For problems of the prior art, the present invention aims to provide Non-chromium Zn-al Coating protective system of a kind of nickel-manganese-contained and preparation method thereof.
Concrete technical scheme of the present invention is as follows:
A kind of Non-chromium Zn-al Coating protective system of nickel-manganese-contained is characterized in that: be comprised 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-aminopropyl triethoxysilane 15 ~ 20%
Myo-Inositol hexaphosphate 10 ~ 18%
Cellaburate 2 ~ 5%
Ethanol 5-9%
The deionized water surplus
Wherein, described aluminium zinc powder is comprised of Zn, Al, Ni, Mn.
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%, Mn:0.1 ~ 0.2%, surplus is Al.
Preferably, a kind of Non-chromium Zn-al Coating protective system of nickel-manganese-contained is characterized in that: be comprised 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-aminopropyl triethoxysilane 18%
Myo-Inositol hexaphosphate 14%
Cellaburate 3.5%
Ethanol 7%
The deionized water surplus
Wherein, described aluminium zinc powder is comprised of Zn, Al, Ni, M n.
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%, Mn:0.1 ~ 0.2%, surplus is Al.
The present invention also provides a kind of method for preparing the Non-chromium Zn-al Coating protective system of nickel-manganese-contained, 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, then under whipped state, slowly add nano silicon, the aluminium zinc powder leaves standstill after stirring 2h;
(2) press prescription in the B component, take by weighing quantitative zirconium tetrafluoride, γ-aminopropyl triethoxysilane, myo-Inositol hexaphosphate and slowly join deionized water for stirring, slowly add while stirring cellaburate and ethanol after mixing, leave standstill after continuing to stir 2h;
(3) will leave standstill the above A component of 4h and B component in mass ratio 3:1 mix and namely get described Non-chromium Zn-al Coating protective system.
Non-chromium Zn-al Coating of the present invention and zinc-chromium coating are close applying production technique.After part was carried out pre-treatment, Non-chromium Zn-al 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 preferably bonding force is arranged also simultaneously, remedied simultaneously the lower deficiency of self hardness in the prior art, coating wear resistance is good, and high heat/corrosion resistance is fabulous, the extreme environment long service life.That product of the present invention has is nontoxic, harmless, pollution-free, low temperature fast processing, simple to operate, the characteristics such as raw material sources are extensive, price is low, cleaner production, the home market price of Non-chromium Zn-al Coating slurries of the present invention only is 120 yuans/kilogram, thereby the processing that greatly reduces Non-chromium Zn-al Coating applies cost, for China's large-scale application Non-chromium Zn-al Coating has been created condition.
Further by the aluminium zinc powder is made micron-sized powder, the more traditional zinc chrome Dacromet/steel of solidity to corrosion, wear resistance, shock resistance and the existing Aluminum Coating of coating are greatly improved, are applicable to the corrodibility severe environment such as rainy, the hot and humid degree of atmosphere, many salt fogs and high wind stream.Practical application proves, when the particle diameter of powder during at the 20-50 micron, it is best that Aluminum Coating property indices of the present invention reaches.
Embodiment
The below provides some preferred embodiments of formulation for coating material proportioning of the present invention, 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 Non-chromium Zn-al Coating protective system of nickel-manganese-contained is comprised of by the 3:1 mass ratio the two components of A, B, and 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-aminopropyl triethoxysilane 18%
Myo-Inositol hexaphosphate 14%
Cellaburate 3.5%
Ethanol 7%
The deionized water surplus
Wherein, described aluminium zinc powder is comprised of Zn, Al, Ni, Mn.
Wherein, the particle diameter of described nano silicon is 20 ~ 50nm.
The method for preparing the Non-chromium Zn-al Coating protective system of above-mentioned nickel-manganese-contained:
(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, then under whipped state, slowly add nano silicon, the aluminium zinc powder leaves standstill after stirring 2h;
(2) press prescription in the B component, take by weighing quantitative zirconium tetrafluoride, γ-aminopropyl triethoxysilane, myo-Inositol hexaphosphate and slowly join deionized water for stirring, slowly add while stirring cellaburate and ethanol after mixing, leave standstill after continuing to stir 2h;
(3) will leave standstill the above A component of 4h and B component in mass ratio 3:1 mix and namely get described Non-chromium Zn-al Coating protective system.
Embodiment 2:
A kind of Non-chromium Zn-al Coating protective system of nickel-manganese-contained is comprised of by the 3:1 mass ratio the two components of A, B, and 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-aminopropyl triethoxysilane 20%
Myo-Inositol hexaphosphate 10%
Cellaburate 5%
Ethanol 5%
The deionized water surplus
Wherein, described aluminium zinc powder is comprised of Zn, Al, Ni, Mn.
Wherein, the particle diameter of described nano silicon is 20 ~ 50nm.
The preparation method is with embodiment 1.
Embodiment 3:
A kind of Non-chromium Zn-al Coating protective system of nickel-manganese-contained is comprised of by the 3:1 mass ratio the two components of A, B, and 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-aminopropyl triethoxysilane 15%
Myo-Inositol hexaphosphate 18%
Cellaburate 2%
Ethanol 9%
The deionized water surplus
Wherein, described aluminium zinc powder is comprised of Zn, Al, Ni, Mn.
Wherein, the particle diameter of described nano silicon is 20 ~ 50nm.
The preparation method is with embodiment 1.
Embodiment 4:
A kind of Non-chromium Zn-al Coating protective system of nickel-manganese-contained is comprised of by the 3:1 mass ratio the two components of A, B, and 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-aminopropyl triethoxysilane 18.5%
Myo-Inositol hexaphosphate 12%
Cellaburate 4.5%
Ethanol 6%
The deionized water surplus
Wherein, described aluminium zinc powder is comprised of Zn, Al, Ni, Mn.
Wherein, the particle diameter of described nano silicon is 20 ~ 50nm.
The preparation method is with embodiment 1.
Embodiment 5:
A kind of Non-chromium Zn-al Coating protective system of nickel-manganese-contained is comprised of by the 3:1 mass ratio the two components of A, B, and 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-aminopropyl triethoxysilane 16%
Myo-Inositol hexaphosphate 17%
Cellaburate 2.5%
Ethanol 8%
The deionized water surplus
Wherein, described aluminium zinc powder is comprised of Zn, Al, Ni, Mn.
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 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 Related Component in the table 1, but these are described as essential features, all be as preferred condition, all be in order to provide in more detail technical intelligence of the present invention, and described as prerequisite of the present invention.
Each moiety mass percentage content (%) of table 1 aluminium zinc powder
Figure 2013100002765100002DEST_PATH_IMAGE002
The performance test of the coating of the Non-chromium Zn-al Coating protective system of the nickel-manganese-contained 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) ℃, the specimen surface corrosion condition is recorded in spraying simultaneously continuously.
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 namely freely falls 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 the phenomenon such as peels off.
(3) coating humidity resistance
Adopt GB/T1740-1979 " paint film wet-heat resisting assay 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 band 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 Non-chromium Zn-al Coating protective system of a nickel-manganese-contained is characterized in that: be comprised 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-aminopropyl triethoxysilane 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 comprised of Zn, Al, Ni, Mn, and the mass percent of each component is: Zn:60% ~ 70%, and Ni:0.5% ~ 0.8%, Mn:0.1% ~ 0.2%, surplus is Al and inevitable impurity.
2. the Non-chromium Zn-al Coating protective system of a kind of nickel-manganese-contained according to claim 1 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, then under whipped state, slowly add nano silicon, the aluminium zinc powder leaves standstill after stirring 2h;
(2) press prescription in the B component, take by weighing quantitative zirconium tetrafluoride, γ-aminopropyl triethoxysilane, myo-Inositol hexaphosphate and slowly join deionized water for stirring, slowly add while stirring cellaburate and ethanol after mixing, leave standstill after continuing to stir 2h;
(3) will leave standstill the above A component of 4h and B component in mass ratio 3:1 mix and namely get described Non-chromium Zn-al Coating protective system.
CN201310000276.5A 2013-01-03 2013-01-03 Nickel-manganese-containing chromium-free zinc-aluminum coating anti-corrosive paint Active CN103044992B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102199372A (en) * 2011-04-12 2011-09-28 合肥云荣机电科技有限公司 Graphene-La2Ti2O7/zinc-aluminum-zirconium corrosion resisting coating for polycrystalline silicon ingot casting furnace
CN102391762A (en) * 2011-09-23 2012-03-28 北京国泰瑞华硅藻应用科技有限公司 Epoxy abrasion-resisting anticorrosive paint

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102199372A (en) * 2011-04-12 2011-09-28 合肥云荣机电科技有限公司 Graphene-La2Ti2O7/zinc-aluminum-zirconium corrosion resisting coating for polycrystalline silicon ingot casting furnace
CN102391762A (en) * 2011-09-23 2012-03-28 北京国泰瑞华硅藻应用科技有限公司 Epoxy abrasion-resisting anticorrosive paint

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