CN103044991B - Titanium-silicon-containing chromium-free zinc-aluminum coating anti-corrosive paint - Google Patents

Abstract

The invention discloses titanium-silicon-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, Si and Ti. 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 titaniferous-silicon

Technical field

The present invention relates to a kind of metal anti-corrosive paint, particularly a kind of Non-chromium Zn-al Coating protective system of titaniferous-silicon.

Background technology

Non-chromium Zn-al Coating is the environmental requirement that VOC regulation and paint industry for meeting countries in the world specify, 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, a Di Kelong.Domestic called after zinc-chromium coating is a kind of novel protective system being main component with zinc powder, aluminium powder, chromic acid and deionized water.Its antiseptic principle is the zinc, the aluminium flake that adopt the hexavalent chromium in chromic salts to come in passivation coatings, improve the antiseptic power of zinc, aluminium flake self, through 300 DEG C of bakings, redox reaction forms amorphous nCr2O3mCrO3 composite salt, metallic surface is covered with zinc-aluminium sheet overlap, to make under the thickness film layer condition only having 6 ~ 8um, just under neutral salt spray 1000h condition, substantially red rust can not produced.It is also with or without hydrogen embrittlement simultaneously, the advantage that can be combined with the rete of multiple plating, coating.But containing the chromium ion be harmful to environment and human body in zinc-chromium coating, especially hexavalent chromium has carcinogenesis.Although the coating processes of zinc-chromium coating is a totally enclosed process, the not outer row of coating, chromic anhydride residual in coating can in use be discharged in environment lentamente, has certain potential hazard to human and environment.Therefore, relevant environment regulation puts into effect the content of the chromium in strict restriction Dyclo paint.In addition, this coating curing temperatures is up to 300 DEG C, and set time also reaches about 30 minutes, and energy consumption is large; Hardness is low, wears no resistance.Workpiece usually can be subject to scratch, scratch in transport, assembling, use procedure, affects outward appearance and the solidity to corrosion of product.

Aluminum Coating (chromium-free Dyclo) as the renewal product of Dacroment first by the general recognition and acceptance of automobile manufacture industry.The product that Non-chromium Zn-al Coating achieves industrialization at present cans be counted on one's fingers, and a kind of is the Geomet(Geomet released by MCI company of the U.S.) coating, a kind of Delta coating being German DELTA company and releasing, above two kinds of coatings generally use in developed country.

At present, all have the commercial application of Chrome-free Dacromet Technology both at home and abroad, but the more traditional Dacromet/steel of the solidity to corrosion of coating obviously reduces, and need arrange in pairs or groups with another layer of organic coating and use, considerably increase cost.The cost of Non-chromium Zn-al Coating is more much higher than zinc-chromium coating, and therefore its price is very high.The German spot price of Delta slurries is 40 Euros/kilogram, the Japanese spot price of Geomet Geomet slurries is 1750 yen/kilogram, estimates that they all should more than 250 yuans/kilogram in the sale price of China thus.Therefore, the focus that chromium-free Dyclo paint that a kind of cost is not less than traditional zinc-chromium coating higher than the corrosion resisting property of traditional Dyclo paint and existing zinc-aluminum paint, coating is the research of domestic and international anti-corrosion of metal is worked out.

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 titaniferous-silicon and preparation method thereof.

Concrete technical scheme of the present invention is as follows:

A Non-chromium Zn-al Coating protective system for titaniferous-silicon, is characterized in that: be made up of by 3:1 mass ratio A, B two-component, wherein: the prescription quality per-cent of component A is:

Zinc aluminium alloy 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%

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%

Deionized water surplus

Wherein, described zinc aluminium alloy powder is made up of Zn, Al, Ti, Si.

Wherein, the particle diameter of described nano silicon is 20 ~ 50nm.

Wherein, each composition mass percent of described zinc aluminium alloy powder is: Zn:60 ~ 70%, Ti:0.5% ~ 0.8%, Si:0.5% ~ 1.0%, and surplus is Al and inevitable impurity.

Preferably, a kind of Non-chromium Zn-al Coating protective system of titaniferous-silicon, is characterized in that: be made up of by 3:1 mass ratio A, B two-component, wherein: the prescription quality per-cent of component A is:

Zinc aluminium alloy powder 32%

Nano silicon 25%

Sodium lignosulfonate 15%

Benzotriazole 4%

Thio-diethylene glycol 0.35%

Triphenylphosphine 0.35%

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%

Deionized water surplus

Wherein, described zinc aluminium alloy powder is made up of Zn, Al, Ti, Si.

Wherein, the particle diameter of described nano silicon is 20 ~ 50nm.

Wherein, each composition mass percent of described zinc aluminium alloy powder is: Zn:60 ~ 70%, Ti:0.5% ~ 0.8%, Si:0.5% ~ 1.0%, and surplus is Al and inevitable impurity.

Present invention also offers a kind of method preparing the Non-chromium Zn-al Coating protective system of titaniferous-silicon, it is characterized in that:

(1) first, by the formula in component A, take quantitative sodium lignosulfonate, benzotriazole, thio-diethylene glycol, triphenylphosphine dissolve in deionized water, under whipped state, then slowly add nano silicon, zinc aluminium alloy powder leaves standstill after stirring 2h;

(2) by the formula in B component, take quantitative zirconium tetrafluoride, γ-aminopropyl triethoxysilane, myo-Inositol hexaphosphate slowly join deionized water for stirring, slowly add cellaburate and ethanol while stirring after mixing, leave standstill after Keep agitation 2h;

(3) by the component A of standing more than 4h and B component in mass ratio 3:1 mix and obtain described Non-chromium Zn-al Coating protective system.

Non-chromium Zn-al Coating of the present invention and zinc-chromium coating are close applying in production technique.After carrying out pre-treatment to part, Non-chromium Zn-al Coating is the same with zinc-chromium coating, adopts the coating processes of conventional soaking-centrifugation, spraying or dipping-drop liquid-centrifugal.Part after primary coating heats maintenance 15 minutes after fixing and obtains coating under 170 DEG C of conditions, and carry out second time after then part being taken out cooling and apply solidification, regelate temperature is 170 DEG C, time length 15-20 minute.Different coat-thicknesses can be obtained by the processing parameter adjusting coating procedure.

Beneficial effect of the present invention: adopt coating of the present invention to make antiseptic engineering component and there is many excellent properties, solidity to corrosion as low, excellent in: coating curing temperatures, excellent shock resistance, strong with basal body binding force, also have good bonding force with other various additional coatings simultaneously, compensate for the deficiency that in prior art, its rigidity is lower simultaneously, coating wear resistance is good, and high heat/corrosion resistance is fabulous, extreme environment long service life.Product of the present invention has nontoxic, harmless, pollution-free, low temperature fast processing, the feature such as simple to operate, 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 is only 120 yuans/kilogram, thus greatly reduce the processing coating cost of Non-chromium Zn-al Coating, for China's large-scale application Non-chromium Zn-al Coating creates condition.

Embodiment

Provide some preferred embodiments of formulation for coating material proportioning of the present invention below, but the content of each moiety of the present invention is not limited to the numerical value provided, for a person skilled in the art, reasonably can summarize and reasoning in formula numerical range completely.

Embodiment 1:

A Non-chromium Zn-al Coating protective system for titaniferous-silicon, is made up of by 3:1 mass ratio A, B two-component, wherein: the prescription quality per-cent of component A is:

Zinc aluminium alloy powder 32%

Nano silicon 25%

Sodium lignosulfonate 15%

Benzotriazole 4%

Thio-diethylene glycol 0.35%

Triphenylphosphine 0.35%

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%

Deionized water surplus

Wherein, described zinc aluminium alloy powder is made up of Zn, Al, Ti, Si.

Wherein, the particle diameter of described nano silicon is 20 ~ 50nm.

Prepare the method for the Non-chromium Zn-al Coating protective system of above-mentioned titaniferous-silicon:

(1) first, by the formula in component A, take quantitative sodium lignosulfonate, benzotriazole, thio-diethylene glycol, triphenylphosphine dissolve in deionized water, under whipped state, then slowly add nano silicon, zinc aluminium alloy powder leaves standstill after stirring 2h;

(2) by the formula in B component, take quantitative zirconium tetrafluoride, γ-aminopropyl triethoxysilane, myo-Inositol hexaphosphate slowly join deionized water for stirring, slowly add cellaburate and ethanol while stirring after mixing, leave standstill after Keep agitation 2h;

(3) by the component A of standing more than 4h and B component in mass ratio 3:1 mix and obtain described Non-chromium Zn-al Coating protective system.

Embodiment 2:

A Non-chromium Zn-al Coating protective system for titaniferous-silicon, is made up of by 3:1 mass ratio A, B two-component, wherein: the prescription quality per-cent of component A is:

Zinc aluminium alloy powder 25%

Nano silicon 30%

Sodium lignosulfonate 12%

Benzotriazole 5%

Thio-diethylene glycol 0.2%

Triphenylphosphine 0.5%

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%

Deionized water surplus

Wherein, described zinc aluminium alloy powder is made up of Zn, Al, Ti, Si.

Wherein, the particle diameter of described nano silicon is 20 ~ 50nm.

Preparation method is with embodiment 1.

Embodiment 3:

A Non-chromium Zn-al Coating protective system for titaniferous-silicon, is made up of by 3:1 mass ratio A, B two-component, wherein: the prescription quality per-cent of component A is:

Zinc aluminium alloy powder 40%

Nano silicon 20%

Sodium lignosulfonate 18%

Benzotriazole 3%

Thio-diethylene glycol 0.5%

Triphenylphosphine 0.2%

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%

Deionized water surplus

Wherein, described zinc aluminium alloy powder is made up of Zn, Al, Ti, Si.

Wherein, the particle diameter of described nano silicon is 20 ~ 50nm.

Preparation method is with embodiment 1.

Embodiment 4:

A Non-chromium Zn-al Coating protective system for titaniferous-silicon, is made up of by 3:1 mass ratio A, B two-component, wherein: the prescription quality per-cent of component A is:

Zinc aluminium alloy powder 26%

Nano silicon 29%

Sodium lignosulfonate 13%

Benzotriazole 4.5%

Thio-diethylene glycol 0.25%

Triphenylphosphine 0.45%

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%

Deionized water surplus

Wherein, described zinc aluminium alloy powder is made up of Zn, Al, Ti, Si.

Wherein, the particle diameter of described nano silicon is 20 ~ 50nm.

Preparation method is with embodiment 1.

Embodiment 5:

A Non-chromium Zn-al Coating protective system for titaniferous-silicon, is made up of by 3:1 mass ratio A, B two-component, wherein: the prescription quality per-cent of component A is:

Zinc aluminium alloy powder 38%

Nano silicon 22%

Sodium lignosulfonate 17%

Benzotriazole 3.5%

Thio-diethylene glycol 0.45%

Triphenylphosphine 0.25%

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%

Deionized water surplus

Wherein, described zinc aluminium alloy powder is made up of Zn, Al, Ti, Si.

Wherein, the particle diameter of described nano silicon is 20 ~ 50nm.

Preparation method is with embodiment 1.

Zinc aluminium alloy powder described in above embodiment 1 ~ 5 is by Zn, Al, Ti and Si forms, below, associative list 1 provides some preferred embodiments of each moiety mass percent of zinc aluminium alloy powder of the present invention, but the content of each moiety of zinc aluminium alloy powder of the present invention is not limited to listed numerical value in this table, and it should be noted that, although give the mass percent numerical value of Related Component in table 1, but these are described as essential features, be all as preferred condition, all to provide technical intelligence of the present invention in more detail, and described as prerequisite of the present invention.

The each moiety mass percentage content (%) of table 1 zinc aluminium alloy powder

The performance test of the coating of the Non-chromium Zn-al Coating protective system of the titaniferous-silicon of above-mentioned 5 kinds of embodiments is as follows:

(1) erosion resistance of coating

Adopt resistance to ammonium nitrate and salt-fog test two kinds of method tests.

Neutral salt spray test is undertaken by GB/T1771 " the resistance to 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) DEG C, continuous spraying, records specimen surface corrosion condition simultaneously.

The operation steps of resistance to ammonium nitrate test is as follows: in beaker, prepare the ammonium nitrate solution of 20%, beaker is put into water bath with thermostatic control and be heated to (70 ± 1) DEG C.(with thermometer measure and control bath temperature), all or part of dipping of the model that will test wherein, hangs fixing, and records the time that red rust appears in model.

(2) shock-resistance of coating

GB/T l732-1993 " the shock-resistant assay method of paint film " is adopted to judge the shock-resistance of coating.Step is as follows: lain in upward on anvil by japanning test plate (panel) paint film, and the test plate (panel) part edge that is hit is not less than 15mm, and the border of each shock point must not be less than 15mm.Weight borrows control device to be fixed on a certain height (this height is specified by product standard or decides through consultation) of slide cartridge, and pressing control knob, namely weight freely falls within drift.Mention weight, take out test plate (panel), record weight falls within the height on test plate (panel).Same test plate (panel) carries out 3 Secondary Shocks tests.Observe with 4 times of magnifying glasses, judge that paint film has flawless, wrinkle and the phenomenon such as to peel off.

(3) coating humidity resistance

GB/T1740-1979 " paint film wet-heat resisting assay method " is adopted to judge the humidity resistance of coating.

Performance test data:

Certain marine oil company drilling well vital part drill conductor (material 35CrMo), namely the former protective treatment adopting routine, only produce significant corrosion after the several months.Adopt coating of the present invention on phosphatize phosphate coat basis, apply formation 30 μm of thick coatings, show that its main performance index reached is in seawater splash band environment through accelerated corrosion analog reslt:

	The Neutral Salt Spray Corrosion life-span	300 DEG C of humidity resistance life-spans	Coating shock-resistance	The ammonium nitrate fast erosion life-span
					Embodiment 1	Be greater than 1400 hours	Be greater than 240 hours	50N	Be greater than 9 hours
Embodiment 2	Be greater than 1200 hours	Be greater than 200 hours	50N	Be greater than 8 hours
					Embodiment 3	Be greater than 1200 hours	Be greater than 200 hours	50N	Be greater than 8 hours
Embodiment 4	Be greater than 1200 hours	Be greater than 200 hours	50N	Be greater than 8 hours
					Embodiment 5	Be greater than 1200 hours	Be greater than 200 hours	50N	Be greater than 8 hours

Claims (2)

1. a Non-chromium Zn-al Coating protective system for titaniferous-silicon, is characterized in that: be made up of by 3:1 mass ratio A, B two-component, wherein: the prescription quality per-cent of component A is:

The prescription quality per-cent of B component is:

The particle diameter of described nano silicon is 20 ~ 50nm;

Described zinc aluminium alloy powder is made up of Zn, Al, Ti, Si, and the mass percent of each component is: Zn:60 ~ 70%, Ti:0.5% ~ 0.8%, Si:0.5% ~ 1.0%, and surplus is Al.

2. the Non-chromium Zn-al Coating protective system of a kind of titaniferous-silicon according to claim 1, it is characterized in that, preparation method is:

(1) first, by the formula in component A, take quantitative sodium lignosulfonate, benzotriazole, thio-diethylene glycol, triphenylphosphine dissolve in deionized water, under whipped state, then slowly add nano silicon, zinc aluminium alloy powder leaves standstill after stirring 2h;

(2) by the formula in B component, take quantitative zirconium tetrafluoride, γ-aminopropyl triethoxysilane, myo-Inositol hexaphosphate slowly join deionized water for stirring, slowly add cellaburate and ethanol while stirring after mixing, leave standstill after Keep agitation 2h;

(3) by the component A of standing more than 4h and B component in mass ratio 3:1 mix and obtain described Non-chromium Zn-al Coating protective system.