CN109778159A - A kind of chromium-free zinc aluminum anticorrosive paint using phosphomolybdic acid as passivator - Google Patents
A kind of chromium-free zinc aluminum anticorrosive paint using phosphomolybdic acid as passivator Download PDFInfo
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- CN109778159A CN109778159A CN201910066116.8A CN201910066116A CN109778159A CN 109778159 A CN109778159 A CN 109778159A CN 201910066116 A CN201910066116 A CN 201910066116A CN 109778159 A CN109778159 A CN 109778159A
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- phosphomolybdic acid
- zinc
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- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910000611 Zinc aluminium Inorganic materials 0.000 title claims abstract description 42
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000003973 paint Substances 0.000 title claims abstract description 31
- 238000000576 coating method Methods 0.000 claims abstract description 192
- 239000011248 coating agent Substances 0.000 claims abstract description 191
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 60
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 32
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 28
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000004327 boric acid Substances 0.000 claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000077 silane Inorganic materials 0.000 claims abstract description 9
- -1 35-50% Substances 0.000 claims abstract description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 64
- 239000011701 zinc Substances 0.000 claims description 20
- 229910052725 zinc Inorganic materials 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 17
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 14
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 14
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 238000007711 solidification Methods 0.000 claims description 14
- 230000008023 solidification Effects 0.000 claims description 14
- 238000003618 dip coating Methods 0.000 claims description 13
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- 238000005507 spraying Methods 0.000 claims description 13
- 150000002191 fatty alcohols Chemical class 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 6
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000002562 thickening agent Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims 1
- 239000000853 adhesive Substances 0.000 abstract description 18
- 230000001070 adhesive effect Effects 0.000 abstract description 18
- 239000000843 powder Substances 0.000 abstract description 16
- 230000002421 anti-septic effect Effects 0.000 abstract description 15
- 239000004411 aluminium Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 29
- 150000003839 salts Chemical class 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 13
- 108010010803 Gelatin Proteins 0.000 description 12
- 229920000159 gelatin Polymers 0.000 description 12
- 239000008273 gelatin Substances 0.000 description 12
- 235000019322 gelatine Nutrition 0.000 description 12
- 235000011852 gelatine desserts Nutrition 0.000 description 12
- 230000001680 brushing effect Effects 0.000 description 11
- 230000008859 change Effects 0.000 description 11
- 238000005034 decoration Methods 0.000 description 11
- 230000008719 thickening Effects 0.000 description 11
- 101100111463 Arabidopsis thaliana BHLH74 gene Proteins 0.000 description 10
- 101100078869 Arabidopsis thaliana MUTE gene Proteins 0.000 description 10
- 230000007935 neutral effect Effects 0.000 description 10
- 239000003595 mist Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 238000002161 passivation Methods 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 7
- 239000011651 chromium Substances 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 5
- 235000018660 ammonium molybdate Nutrition 0.000 description 5
- 239000011609 ammonium molybdate Substances 0.000 description 5
- 229940010552 ammonium molybdate Drugs 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- DQIPXGFHRRCVHY-UHFFFAOYSA-N chromium zinc Chemical compound [Cr].[Zn] DQIPXGFHRRCVHY-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000005253 cladding Methods 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000008092 positive effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- GFISDBXSWQMOND-UHFFFAOYSA-N 2,5-dimethoxyoxolane Chemical compound COC1CCC(OC)O1 GFISDBXSWQMOND-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The aqueous chromium-free zinc aluminum anticorrosive paint that the invention discloses a kind of using phosphomolybdic acid as passivator, each component including following mass parts ratio: zinc powder 250-310, aluminium powder 10-30, phosphomolybdic acid 3-10, polyethylene glycol 110-150, silane coupling agent 70-140, ethylene glycol ether acetate 3-8, surfactant 1-18, defoaming agent 1-6, tetraisopropyl titanate 10-60, boric acid 10-18, deionized water 380-480.By polyethylene glycol, 35-50%, ethylene glycol ether acetate, surfactant and the defoaming agent of silane coupled agent prescription total amount, equal component A is made in stirring；B component is made in the deionized water of the weight ratio, phosphomolybdic acid, the 50-65% of silane coupled agent prescription total amount, tetraisopropyl titanate, boric acid stirring；Two component of A, B is mixed evenly by the weight ratio of 1:1~1.4 using preceding, is configured to finished product coating.Its thermal stability of product prepared by the present invention is improved, the coating after coating have meet fastening parts of automobiles requirement coating is thin, adhesive strength is high and the comprehensive performances such as antiseptic property is good require.
Description
Technical field
The invention belongs to anticorrosive paint technology fields, and in particular to a kind of chromium-free zinc aluminum using phosphomolybdic acid as passivator is anti-
Rotten coating.
Background technique
In existing metallic matrix corrosion-inhibiting coating, zinc-chromium coating (also known as Dacromet/steel) technology is contained pair due to coating
The harmful Cr VI of human body is not met " about the instruction for using certain harmful components in electronic and electrical equipment is limited in " (i.e.
RoHS standard).RoHS standard is the environmental protection mandatory standard formulated by European Union's legislation, for specification electronic and electrical equipment
Material and technological standards.The standard has been extended to many military use product fields and related to the people's livelihood at present.Countries in the world
The use for the measure limitation zinc-chromium coating technology being increasingly stringenter is begun to take.Substitute the Non-chromium Zn-al Coating skill of zinc-chromium coating
Art has become the new technology in metal coated anti-corrosion collar domain, and the update substitute technology as zinc-chromium coating has been obtained in numerous areas
To application.
It emerges both at home and abroad there are many Non-chromium Zn-al Coating, is divided into aqueous and organic solvent type two by paint solvent type
Major class.Wherein aqueous chromium-free Aluminum Coating environmental-protecting performance is more preferable, and zinc-aluminium powder passivation difficulty is bigger, and technology complexity is higher.
There is harsher requirement in the preservative treatment application of automotive field fastener, basic demand is sought to aqueous chromium-free zinc aluminum
Coating technology.Fastener is due to needing lesser mechanical engagement tolerance, it is desirable that chromium-free zinc aluminum corrosion-inhibiting coating is thin with coating, adheres to
Intensity height and the stable particular/special requirement of antiseptic property.The passivation of sheet zinc-aluminium powder in Non-chromium Zn-al Coating and composition coating
Carrier phase structure is an important factor for meeting these particular/special requirements.
The passivator of substitution chromic anhydride or chromate in Non-chromium Zn-al Coating formula is applied to have molybdenum trioxide, phosphoric acid at present
Salt, dihydric phosphate, borate, molybdate, silicate, tungstates etc.；Or several aforementioned substances compounds, such as molybdate and tungsten
Hydrochlorate is compound to be used as passivator.Such as proprietary term are as follows: a kind of non-chrome water-based metal anti-corrosive paint and preparation method, application No. is
Molybdenum trioxide is used in the patent of CN201410534326.2；A kind of proprietary term are as follows: non-chrome water-based metal anti-corrosive paint of two-component
And preparation method, application No. is in the patent of CN201610033182.1 use sodium molybdate and ammonium molybdate combination be used as chromium-free zinc aluminum
Passivator in coating formula.
The passivation effect and coating thermal stability of above-mentioned technical proposal are all ideal not to the utmost.For aqueous chromium-free Aluminum Coating
Coating, there is water-soluble bad, dispersions to be not thorough for the passivator of metal oxide-type；There is zinc-aluminium powders for salt passivator
It is passivated the problems such as insufficient and unstable, is not met by the proposed coating thermostabilization of fastening parts of automobiles, coating is thin, adhesive strength
High and stable antiseptic property comprehensive performance requirement.
Summary of the invention
The aqueous chromium-free zinc aluminum anticorrosive paint that the object of the present invention is to provide a kind of using phosphomolybdic acid as passivator, heat are steady
Qualitative to be improved, coating after coating has that the coating for meeting fastening parts of automobiles requirement is thin, adhesive strength is high and anti-corrosive properties
Comprehensive performances can be waited to require well.
The present invention is achieved through the following technical solutions:
Composition quality portion rate
Zinc flake 250-310
Flake aluminum 10-30
Phosphomolybdic acid 3-10
Polyethylene glycol 110-150
Silane coupling agent 70-140
Ethylene glycol ether acetate 3-8
Surfactant 1-18
Defoaming agent 1-6
Tetraisopropyl titanate 10-60
Boric acid 10-18
Deionized water 380-480
Further: zinc flake, flake aluminum, piece diameter is no more than 20 μm, and thickness is no more than 0 .3 μm；
Further: phosphomolybdic acid is industrial phosphomolybdic acid；
Further: polyethylene glycol is room temperature liquid polyethylene glycol, and molecular weight is 200~400；
Further: silane coupling agent is Silane coupling agent KH550, KH560, KH570；
Further: ethylene glycol ether acetate is industrial CAC solvent；
Further: surfactant is polyethoxylated fatty alcohols EN90, EN20；Or nonylphenol polyoxyethylene ether NP-4, NP-
15；
It is further: defoaming agent W-052 or organosilicon 3270 or W-052 and 3270 intermixtures, ratio 1:1；
Further: tetraisopropyl titanate is industrial tetraisopropyl titanate；
Further: boric acid is industrial boric acid；
Further: deionized water used, conductivity are 0.1-30 us/cm.
Using phosphomolybdic acid as the preparation method of the chromium-free zinc aluminum anticorrosive paint of passivator, the specific steps of which are as follows:
(1) with the zinc flake and flake aluminum of the weight ratio, polyethylene glycol, silane coupled agent prescription total amount is added
35-50%, ethylene glycol ether acetate, surfactant and defoaming agent, dispersion is sufficiently stirred, and that uniform sheet zinc-aluminium is made is mixed
It closes slurry (component A)；
(2) by the deionized water of the weight ratio, phosphomolybdic acid, the 50-65% of silane coupled agent prescription total amount, four isopropyl of metatitanic acid
Paint solvent (B component) is made until being dispersed with stirring into uniform liquid in ester, boric acid mixed hydrolysis under agitation；
(3) zinc-aluminium is being mixed into slurry and two component of paint solvent A, B by the weight ratio mixing of the .4 of 1:1~1 using preceding
Uniformly, it is configured to finished product coating；Coating mode can brush, spray or dip coating manner carries out；Curing mode uses heat-agglomerating,
70 DEG C~100 DEG C dry 10~30 minutes, are warming up to 320 DEG C~350 DEG C with furnace and are sintered solidification, and 20~40 minutes.
It is prepared as described above the chromium-free zinc aluminum anticorrosive paint using phosphomolybdic acid as passivator of method preparation, technical conditions requirement
Its viscosity is 90-150 seconds (No. 2 cups of Cai Shi).Corresponding thickener improvement coating mobility can be added to obtain corresponding viscosity.
Thickener used is hydroxyethyl cellulose.
The invention has the advantages that
1, corrosion-inhibiting coating thickness is in 6-10 μm of (coating amount 190-320mg/dm2) under conditions of, using phosphomolybdic acid as the painting of passivator
The neutral salt spray test that layer can meet 720~1500 hours reaches the requirement for anticorrosion of fastening parts of automobiles；Using phosphomolybdic acid as passivator
The compound coating that tetraisopropyl titanate is added, further improves antiseptic property, can meet greater than in 1200~2000 hours
The requirements at the higher level of property salt spray test；
2, corrosion-inhibiting coating thickness is in 6-10 μm of (coating amount 190-320mg/dm2) under conditions of, with tape method (Japanese gummed tape Pyatyi
Rating method JDIS K53114-4) coating adhesive strength reached 4-5 grades；
3, the chromium without any price, coating and coating process meet environmental requirement；
4, polyethoxylated fatty alcohols are more friendly to environment as surfactant；
5, it is compound to form molybdenum oxide, titanium oxide in hot setting sintering process for phosphomolybdic acid and tetraisopropyl titanate compound action
Ceramic phase plays ideal invigoration effect in coated substrate ceramic bonding phase.
6, the thermal stability of coating is improved, and tests, applies through 45 DEG C × 7 × 24 hours high temperature hot storage stabilities
Material does not generate gelatin phenomenon, and viscosity increases less than 20%, and the antiseptic property of coating does not change.
For the present invention using phosphomolybdic acid as passivator, addition tetraisopropyl titanate, boric acid, silane coupling agent are carrier, the technology
The non-chrome water-based metal anti-corrosive paint that scheme obtains, coating thermostabilization, coating is thin, adhesive strength is high and antiseptic property is stable
High comprehensive performance has obtained the approval of automobile major client.
In the present invention, phosphomolybdic acid is added in aqueous chromium-free zinc aluminum anticorrosive paint system as a kind of ideal passivator,
It so that corrosion resisting property, strength of coating and the adhesive force of coating is had significant improvement, the storage of coating can also be improved
Thermal stability.
The molecular structural formula of phosphomolybdic acid is H3[P(Mo3O10)4], molecular formula H3PO4·12MoO3；CAS No.:51429-
74-4.Phosphomolybdic acid is a kind of phosphoric acid with the sour general character and oxidation molybdenum complex.
Phosphomolybdic acid the positive effect of coating be in the water-based system of coating, can with molybdenum trioxide existing for complex status
It is dispersed among aqueous solution with admirably dissolving, complexing passivation is carried out to zinc powder and aluminium powder, to ensure that zinc-aluminium to a certain degree
The stability of powder.But the complexing passivation for relying only on phosphomolybdic acid is difficult to prevent the evolving hydrogen reaction of aluminum zinc powder completely, and phosphorus is being added in we
Silanization treatment is carried out to aluminum zinc powder surface before molybdic acid, phosphomolybdic acid be complexed to the incomplete aluminum zinc powder of cladding blunt
Change, plays the role of joint filling leak repairing, can also be complexed in silane film surface further progress, play the role of reinforcing.Sheet zinc
Double action of the aluminium powder body by silane cladding and phosphomolybdic acid complexing passivation, effective solution liberation of hydrogen of the aluminum zinc powder in coating
Problem, to ensure that the hot storage stability of coating.
The positive effect of phosphomolybdic acid in the coating is to improve the comprehensive performance of coating.Coating is by silane cladding and sufficiently
For the sheet zinc-aluminium powder of passivation in solidification sintering process, the coating ceramic carrier of formation mutually has good solid phase binding, improves
The compactness of coating.Phosphomolybdic acid, tetraisopropyl titanate, silane coupling agent, the boric acid added in this programme, it is solid in high temperature sintering
The coated body composition to form the oxide glass-ceramics phase such as molybdenum, titanium, boron, silicon, phosphorus is mutually provided during changing for coated carrier
Substance forms firm and fine and close coating structure with the sheet aluminum zinc powder body of passivation.Sexavalence molybdenum in phosphomolybdic acid passes through high temperature
Partial reduction forms fine and close film layer, to improve the corrosion resistance of coating at trivalent molybdenum.Tetraisopropyl titanate is in hot setting
Titanium oxide ceramics phase is formed in sintering process, is combined with the film forming that phosphomolybdic acid is formed, in coated substrate ceramic bonding carrier phase
In play ideal invigoration effect, improve the intensity and adhesive force of coating.
Specific embodiment
It, will the invention will be further described by specific embodiment in order to preferably verify effect of the invention.
Raw material selected by embodiment:
Selected zinc flake and flake aluminum is that Germany's love blocks (ECKART) Products；
Selected polyethylene glycol is Nanjing chemical reagent limited liability company product, molecular weight 200-400；
Selected Silane coupling agent KH550, KH560, KH570 are Nanjing Chen Gong organosilicon material Co., Ltd product；
Selected ethylene glycol ether acetate is that industrial CAC(molecular formula is C6H12O3) manufacturer be Jinan benefit Yang Huagong
Co., Ltd；
Selected surfactant polyethoxylated fatty alcohols be Sha Suo Chemical Co., Ltd., the U.S., Sha Suo group EN90 and
EN20；
Selected surfactant nonylphenol polyoxyethylene ether is the NP-4 and NP- of Nanjing chemical reagent limited liability company
15；
Selected defoaming agent is W-052 product and the Qingdao Penn spy Chemical Co., Ltd. of modest (Shanghai) Chemical Co., Ltd. of moral
3270 product；
Selected tetraisopropyl titanate, character are slight yellowish transparency liquid, and CAS No.:546-68-9 is the remote city in Wuhan
The product of development in science and technology Co., Ltd；
Selected tetraethyl titanate, character be it is colourless to pale yellowish oil thick liquid, CAS No.:3087-36-3 is
The product of Yixing City southern Jiangsu petrochemical additive Co., Ltd；
Selected phosphomolybdic acid is industrial phosphomolybdic acid, and character is orange crystals powder, and CAS No.:51429-74-4 is
The product of Shanghai prophyll Biotechnology Co., Ltd；
Selected ammonium molybdate be industrial ammonium molybdate, character be baby-blue (white) crystal powder, CAS No.:
51429-74-4, Taizhou City Southern Star tungsten products factory product；
Selected boric acid is industrial boric acid, and character is white powder crystallization, CAS No.:10043-35-3；
Selected is industrial deionized water, and conductivity is 0.1-30 us/cm；
Selected thickener is the hydroxyethyl cellulose of Shanghai Mai Ruier chemical technology Co., Ltd production.
Embodiment 1
A kind of chromium-free zinc aluminum anticorrosive paint and preparation method thereof using phosphomolybdic acid as passivator, the specific steps are as follows:
(1) by 250 kilograms of zinc flake, 10 kilograms of flake aluminum, 110 kilograms of polyethylene glycol are added, silane coupling agent (KH550)
25 kilograms, 3 kilograms of ethylene glycol ether acetate, polyethoxylated fatty alcohols (EN20 is 0.2 kilogram, and EN90 is 0.8 kilogram) totally 1
Kilogram, 0.5 kilogram of defoaming agent (W-052), (3270) 0.5 kilograms of defoaming agent organosilicon are sufficiently stirred dispersion and sheet zinc are made
Aluminium mixes slurry, is directly prepared into component A；
(2) by 3 kilograms of phosphomolybdic acid, 45 kilograms of silane coupling agent (KH550), 10 kilograms of boric acid, is gone by 10 kilograms of tetraisopropyl titanate
B component is made until being dispersed with stirring into uniform liquid in 400 kilograms of ionized water mixed hydrolysis under agitation；
(3) two component of A, B is mixed evenly using preceding by the weight ratio of the .4 of 1:1~1, is configured to finished product coating；Make
The coating mode that used time is used can be carried out by brushing, spraying or dip coating manner；Curing mode use heat-agglomerating, 70 DEG C~
100 DEG C dry 10~30 minutes, then are sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes, i.e. completion coating decoration.
Through detecting, the present embodiment coating is after coating, and coating coated weight is in 220mg/dm2When left and right, resistance to neutral salt
The mist time can be more than 1600 hours, and coating hardness is greater than 5H, coating adhesion tape method (Japanese gummed tape Pyatyi rating method
JDIS K53114-4) coating adhesive strength reaches 4 grades or more.It is tested through 45 DEG C × 7 × 24 hours high high-temp stabilities, coating
Gelatin phenomenon is not generated, and antiseptic property does not change.
For different coating modes if it is desired, corresponding hydroxyethyl cellulose thickening can be added to obtain corresponding viscosity
Agent improves coating mobility.
Embodiment 2
A kind of chromium-free zinc aluminum anticorrosive paint and preparation method thereof using phosphomolybdic acid as passivator, the specific steps are as follows:
(1) by 310 kilograms of zinc flake, 30 kilograms of flake aluminum, addition polyethylene glycol: 150 kilograms, silane coupling agent
(KH560) 60 kilograms, 8 kilograms of ethylene glycol ether acetate, (NP-4 is 2 kilograms to nonylphenol polyoxyethylene ether, and NP-15 is 16 public
Jin) totally 18 kilograms, 3 kilograms of defoaming agent (W-052), (3270) 3 kilograms of defoaming agent organosilicon are sufficiently stirred dispersion and sheet are made
Zinc-aluminium mixes slurry, is directly prepared into component A；
(2) by 10 kilograms of phosphomolybdic acid, 80 kilograms of silane coupling agent (KH560), 60 kilograms of tetraisopropyl titanate, 18 kilograms of boric acid,
B component is made until being dispersed with stirring into uniform liquid in 480 kilograms of deionized water mixed hydrolysis under agitation；
(3) two component of A, B is mixed evenly using preceding by the weight ratio of the .4 of 1:1~1, is configured to finished product coating；
The coating mode used when use can be carried out by brushing, spraying or dip coating manner；Curing mode uses heat-agglomerating, at 70 DEG C
~100 DEG C dry 10~30 minutes, then are sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes, i.e. completion coating decoration.
Through detecting, the present embodiment coating is after coating, and coating coated weight is in 220mg/dm2When left and right, resistance to neutral salt
The mist time can be more than 2000 hours, and coating hardness is greater than 5H, coating adhesion tape method (Japanese gummed tape Pyatyi rating method
JDIS K53114-4) coating adhesive strength reaches 4 grades or more.It is tested through 45 DEG C × 7 × 24 hours high high-temp stabilities, coating
Gelatin phenomenon is not generated, and antiseptic property does not change.
For different coating modes if it is desired, corresponding hydroxyethyl cellulose thickening can be added to obtain corresponding viscosity
Agent improves coating mobility.
Embodiment 3
A kind of chromium-free zinc aluminum anticorrosive paint and preparation method thereof using phosphomolybdic acid as passivator, the specific steps are as follows:
(1) by 290 kilograms of zinc flake, 25 kilograms of flake aluminum, addition polyethylene glycol: 130 kilograms, silane coupling agent
(KH570) 50 kilograms, 4 kilograms of ethylene glycol ether acetate, (EN20 is 2 kilograms to polyethoxylated fatty alcohols, and EN90 is 10 public
Jin) totally 12 kilograms, 2 kilograms of defoaming agent (W-052), (3270) 1 kilograms of defoaming agent organosilicon are sufficiently stirred dispersion and sheet are made
Zinc-aluminium mixes slurry, is directly prepared into component A；
(2) by 8 kilograms of phosphomolybdic acid, 70 kilograms of silane coupling agent (KH570), 15 kilograms of boric acid, is gone by 55 kilograms of tetraisopropyl titanate
B component is made until being dispersed with stirring into uniform liquid in 450 kilograms of ionized water mixed hydrolysis under agitation；
(3) two component of A, B is mixed evenly using preceding by the weight ratio of the .4 of 1:1~1, is configured to finished product coating；
The coating mode used when use can be carried out by brushing, spraying or dip coating manner；Curing mode uses heat-agglomerating, at 70 DEG C
~100 DEG C dry 10~30 minutes, then are sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes, i.e. completion coating decoration.
Through detecting, the present embodiment coating is after coating, and coating coated weight is in 220 mg/dm2When left and right, resistance to neutral salt
The mist time can be more than 2000 hours, and coating hardness is greater than 5H, coating adhesion tape method (Japanese gummed tape Pyatyi rating method
JDIS K53114-4) coating adhesive strength reaches 4 grades or more.It is tested through 45 DEG C × 7 × 24 hours high high-temp stabilities, coating
Gelatin phenomenon is not generated, and antiseptic property does not change.
For different coating modes if it is desired, corresponding hydroxyethyl cellulose thickening can be added to obtain corresponding viscosity
Agent improves coating mobility.
Embodiment 4
A kind of chromium-free zinc aluminum anticorrosive paint and preparation method thereof using phosphomolybdic acid as passivator, the specific steps are as follows:
(1) by 280 kilograms of zinc flake, 15 kilograms of flake aluminum, addition polyethylene glycol: 140 kilograms, silane coupling agent
(KH560) 50 kilograms, 4 kilograms of ethylene glycol ether acetate, (EN20 is 2 kilograms to polyethoxylated fatty alcohols, and EN90 is 10 public
Jin) totally 12 kilograms, 2 kilograms of defoaming agent (W-052), (3270) 1 kilograms of defoaming agent organosilicon are sufficiently stirred dispersion and sheet are made
Zinc-aluminium mixes slurry, is directly prepared into component A；
(2) by 4 kilograms of phosphomolybdic acid, 60 kilograms of silane coupling agent (KH560), 13 kilograms of boric acid, is gone by 30 kilograms of tetraisopropyl titanate
B component is made until being dispersed with stirring into uniform liquid in 430 kilograms of ionized water mixed hydrolysis under agitation；
(3) two component of A, B is mixed evenly using preceding by the weight ratio of the .4 of 1:1~1, is configured to finished product coating；Make
The coating mode that used time is used can be carried out by brushing, spraying or dip coating manner；Curing mode use heat-agglomerating, 70 DEG C~
100 DEG C dry 10~30 minutes, then are sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes, i.e. completion coating decoration.
Through detecting, the present embodiment coating is after coating, and coating coated weight is in 220 mg/dm2When left and right, resistance to neutral salt
The mist time can be more than 1800 hours, and coating hardness is greater than 5H, coating adhesion tape method (Japanese gummed tape Pyatyi rating method
JDIS K53114-4) coating adhesive strength reaches 4 grades or more.It is tested through 45 DEG C × 7 × 24 hours high high-temp stabilities, coating
Gelatin phenomenon is not generated, and antiseptic property does not change.
For different coating modes if it is desired, corresponding hydroxyethyl cellulose thickening can be added to obtain corresponding viscosity
Agent improves coating mobility.
Embodiment 5
A kind of chromium-free zinc aluminum anticorrosive paint and preparation method thereof using phosphomolybdic acid as passivator, the specific steps are as follows:
(1) by 280 kilograms of zinc flake, 25 kilograms of flake aluminum, addition polyethylene glycol: 130 kilograms, silane coupling agent
(KH560) 40 kilograms, 4 kilograms of ethylene glycol ether acetate, (EN20 is 2 kilograms to polyethoxylated fatty alcohols, and EN90 is 10 public
Jin) totally 12 kilograms, 2 kilograms of defoaming agent (W-052), (3270) 2 kilograms of defoaming agent organosilicon are sufficiently stirred dispersion and sheet are made
Zinc-aluminium mixes slurry, is directly prepared into component A；
(2) by 8 kilograms of phosphomolybdic acid, 70 kilograms of silane coupling agent (KH560), 13 kilograms of boric acid, is gone by 35 kilograms of tetraisopropyl titanate
B component is made until being dispersed with stirring into uniform liquid in 400 kilograms of ionized water mixed hydrolysis under agitation；
(3) two component of A, B is mixed evenly using preceding by the weight ratio of the .4 of 1:1~1, is configured to finished product coating；Make
The coating mode that used time is used can be carried out by brushing, spraying or dip coating manner；Curing mode use heat-agglomerating, 70 DEG C~
100 DEG C dry 10~30 minutes, then are sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes, i.e. completion coating decoration.
Through detecting, the present embodiment coating is after coating, and coating coated weight is in 220 mg/dm2When left and right, resistance to neutral salt
The mist time can be more than 1900 hours, and coating hardness is greater than 5H, coating adhesion tape method (Japanese gummed tape Pyatyi rating method
JDIS K53114-4) coating adhesive strength reaches 4 grades or more.It is tested through 45 DEG C × 7 × 24 hours high high-temp stabilities, coating
Gelatin phenomenon is not generated, and antiseptic property does not change.
For different coating modes if it is desired, corresponding hydroxyethyl cellulose thickening can be added to obtain corresponding viscosity
Agent improves coating mobility.
Embodiment 6
One kind is using phosphomolybdic acid as passivator, the chromium-free zinc aluminum anticorrosive paint and preparation method thereof without tetraisopropyl titanate, tool
Steps are as follows for body:
(1) by 260 kilograms of zinc flake, 15 kilograms of flake aluminum, addition polyethylene glycol: 130 kilograms, silane coupling agent
(KH560) 50 kilograms, 4 kilograms of ethylene glycol ether acetate, (NP-4 is 2 kilograms to nonylphenol polyoxyethylene ether, and NP-15 is 10 public
Jin) totally 12 kilograms, 2 kilograms of defoaming agent (W-052), (3270) 2 kilograms of defoaming agent organosilicon are sufficiently stirred dispersion and sheet are made
Zinc-aluminium mixes slurry, is directly prepared into component A；
(2) by 8 kilograms of phosphomolybdic acid, 70 kilograms of silane coupling agent (KH560), 12 kilograms of boric acid, 420 kilograms of deionized water are being stirred
Under the conditions of mixed hydrolysis B component is made until be dispersed with stirring into uniform liquid；
(3) two component of A, B is mixed evenly using preceding by the weight ratio of the .4 of 1:1~1, is configured to finished product coating；
The coating mode used when use can be carried out by brushing, spraying or dip coating manner；Curing mode uses heat-agglomerating, at 70 DEG C
~100 DEG C dry 10~30 minutes, then are sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes, i.e. completion coating decoration.
Through detecting, the coating of the present embodiment is after coating, and coating coated weight is in 220 mg/dm2When left and right, resistance to neutrality
The salt fog time can reach 1200 hours, and coating hardness is greater than 4H, coating adhesion tape method (Japanese gummed tape Pyatyi rating method
JDIS K53114-4) coating adhesive strength reaches 4 grades.It is tested through 45 DEG C × 7 × 24 hours high high-temp stabilities, coating part
Gelatin phenomenon is generated, antiseptic property does not change.
For different coating modes if it is desired, corresponding hydroxyethyl cellulose thickening can be added to obtain corresponding viscosity
Agent improves coating mobility.
Embodiment 7
A kind of chromium-free zinc aluminum anticorrosive paint and preparation method thereof using ammonium molybdate as passivator, the specific steps are as follows:
(1) by 26 kilograms of zinc flake, 1.2 kilograms of flake aluminum, addition polyethylene glycol: 12 kilograms, silane coupling agent (KH560)
4 kilograms, 0.4 kilogram of ethylene glycol ether acetate, polyethoxylated fatty alcohols (EN20 is 0.1 kilogram, and EN90 is 0.6 kilogram) are altogether
0.7 kilogram, 0.3 kilogram of defoaming agent (W-052), (3270) 0.3 kilograms of defoaming agent organosilicon are sufficiently stirred dispersion and sheet are made
Zinc-aluminium mixes slurry, is directly prepared into component A；
(2) by 0.5 kilogram of ammonium molybdate, 8.5 kilograms of silane coupling agent (KH560), 1.2 kilograms of boric acid, 40 kilograms of deionized water exists
B component is made until being dispersed with stirring into uniform liquid in mixed hydrolysis under stirring condition；
(3) two component of A, B is mixed evenly using preceding by the weight ratio of the .4 of 1:1~1, is configured to finished product coating；Make
The coating mode that used time is used can be carried out by brushing, spraying or dip coating manner；Curing mode use heat-agglomerating, 70 DEG C~
100 DEG C dry 10~30 minutes, then are sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes, i.e. completion coating decoration.
Through detecting, the coating of the present embodiment is after coating, and coating coated weight is in 220 mg/dm2When left and right, resistance to neutrality
The salt fog time can reach 1080 hours, and coating hardness is greater than 4H, coating adhesion tape method (Japanese gummed tape Pyatyi rating method
JDIS K53114-4) coating adhesive strength reaches 4 grades.It is tested through 45 DEG C × 7 × 24 hours high high-temp stabilities, coating generates
Gelatin phenomenon.
For different coating modes if it is desired, corresponding hydroxyethyl cellulose thickening can be added to obtain corresponding viscosity
Agent improves coating mobility.
Embodiment 8
A kind of chromium-free zinc aluminum anticorrosive paint and preparation method thereof using phosphomolybdic acid as passivator, the specific steps are as follows:
(1) by 270 kilograms of zinc flake, 20 kilograms of flake aluminum, addition polyethylene glycol: 130 kilograms, silane coupling agent
(KH550) 50 kilograms, 5 kilograms of ethylene glycol ether acetate, (NP-4 is 2 kilograms to nonylphenol polyoxyethylene ether, and NP-15 is 10 public
Jin) totally 12 kilograms, 1.5 kilograms of defoaming agent (W-052), (3270) 1.5 kilograms of defoaming agent organosilicon are sufficiently stirred dispersion and are made
Sheet zinc-aluminium mixes slurry, is directly prepared into component A；
(2) by 10 kilograms of phosphomolybdic acid, 70 kilograms of silane coupling agent (KH550), 50 kilograms of tetraisopropyl titanate, 15 kilograms of boric acid,
B component is made until being dispersed with stirring into uniform liquid in 420 kilograms of deionized water mixed hydrolysis under agitation；
(3) two component of A, B is mixed evenly using preceding by the weight ratio of the .4 of 1:1~1, is configured to finished product coating；Make
The coating mode that used time is used can be carried out by brushing, spraying or dip coating manner；Curing mode use heat-agglomerating, 70 DEG C~
100 DEG C dry 10~30 minutes, then are sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes, i.e. completion coating decoration.
Through detecting, the present embodiment coating is after coating, and coating coated weight is in 220 mg/dm2When left and right, resistance to neutral salt
The mist time can be more than 2000 hours, and coating hardness is greater than 5H, coating adhesion tape method (Japanese gummed tape Pyatyi rating method
JDIS K53114-4) coating adhesive strength reaches 4 grades or more.It is tested through 45 DEG C × 7 × 24 hours high high-temp stabilities, coating
Gelatin phenomenon is not generated, and antiseptic property does not change.
For different coating modes if it is desired, corresponding hydroxyethyl cellulose thickening can be added to obtain corresponding viscosity
Agent improves coating mobility.
Embodiment 9
A kind of chromium-free zinc aluminum anticorrosive paint and preparation method thereof using phosphomolybdic acid as passivator, the specific steps are as follows:
(1) by 260 kilograms of zinc flake, 20 kilograms of flake aluminum, polyethylene glycol: 120 kg, silane coupling agent is added
(KH560) 50 kilograms, 4 kilograms of ethylene glycol ether acetate, (EN20 is 2 kilograms to polyethoxylated fatty alcohols, and EN90 is 10 public
Jin) totally 12 kilograms, (3270) 4 kilograms of defoaming agent organosilicon, dispersion is sufficiently stirred, sheet zinc-aluminium mixing slurry is made, directly made
At component A；
(2) by 10 kilograms of phosphomolybdic acid, 70 kilograms of silane coupling agent (KH560), 55 kilograms of tetraisopropyl titanate, 15 kilograms of boric acid,
B component is made until being dispersed with stirring into uniform liquid in 420 kilograms of deionized water mixed hydrolysis under agitation；
(3) two component of A, B is mixed evenly using preceding by the weight ratio of the .4 of 1:1~1, is configured to finished product coating；Make
The coating mode that used time is used can be carried out by brushing, spraying or dip coating manner；Curing mode use heat-agglomerating, 70 DEG C~
100 DEG C dry 10~30 minutes, then are sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes, i.e. completion coating decoration.
Through detecting, the present embodiment coating is after coating, and coating coated weight is in 220 mg/dm2When left and right, resistance to neutral salt
The mist time can be more than 2000 hours, and coating hardness is greater than 5H, coating adhesion tape method (Japanese gummed tape Pyatyi rating method
JDIS K53114-4) coating adhesive strength reaches 4 grades or more.It is tested through 45 DEG C × 7 × 24 hours high high-temp stabilities, coating
Gelatin phenomenon is not generated, and antiseptic property does not change.
For different coating modes if it is desired, corresponding hydroxyethyl cellulose thickening can be added to obtain corresponding viscosity
Agent improves coating mobility.
Embodiment 10
A kind of chromium-free zinc aluminum anticorrosive paint and preparation method thereof using phosphomolybdic acid as passivator, the specific steps are as follows:
(1) by 300 kilograms of zinc flake, 25 kilograms of flake aluminum, addition polyethylene glycol: 140 kilograms, silane coupling agent
(KH570) 50 kilograms, 6 kilograms of ethylene glycol ether acetate, (EN20 is 2 kilograms to polyethoxylated fatty alcohols, and EN90 is 10 public
Jin) totally 12 kilograms, (3270) 4 kilograms of defoaming agent organosilicon, dispersion is sufficiently stirred, sheet zinc-aluminium mixing slurry is made, directly made
At component A；
(2) by 10 kilograms of phosphomolybdic acid, 70 kilograms of silane coupling agent (KH570), 25 kilograms of tetraisopropyl titanate, 15 kilograms of boric acid,
B component is made until being dispersed with stirring into uniform liquid in 420 kilograms of deionized water mixed hydrolysis under agitation；
(3) two component of A, B is mixed evenly using preceding by the weight ratio of the .4 of 1:1~1, is configured to finished product coating；Make
The coating mode that used time is used can be carried out by brushing, spraying or dip coating manner；Curing mode use heat-agglomerating, 70 DEG C~
100 DEG C dry 10~30 minutes, then are sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes, i.e. completion coating decoration.
Through detecting, the present embodiment coating is after coating, and coating coated weight is in 220 mg/dm2When left and right, resistance to neutral salt
The mist time can be more than 2000 hours, and coating hardness is greater than 5H, coating adhesion tape method (Japanese gummed tape Pyatyi rating method
JDIS K53114-4) coating adhesive strength reaches 4 grades or more, it is tested through 45 DEG C × 7 × 24 hours high high-temp stabilities, coating
Gelatin phenomenon is not generated, and antiseptic property does not change.
For different coating modes if it is desired, corresponding hydroxyethyl cellulose thickening can be added to obtain corresponding viscosity
Agent improves coating mobility.
Embodiment 11
A kind of chromium-free zinc aluminum anticorrosive paint and preparation method thereof using phosphomolybdic acid as passivator, the specific steps are as follows:
(1) by 280 kilograms of zinc flake, 20 kilograms of flake aluminum, addition polyethylene glycol: 130 kilograms, silane coupling agent
(KH560) 50 kilograms, 4 kilograms of ethylene glycol ether acetate, (EN20 is 2 kilograms to polyethoxylated fatty alcohols, and EN90 is 10 public
Jin) totally 12 kilograms, 2 kilograms of defoaming agent (W-052), (3270) 2 kilograms of defoaming agent organosilicon are sufficiently stirred dispersion and sheet are made
Zinc-aluminium mixes slurry, is directly prepared into component A；
(2) by 8 kilograms of phosphomolybdic acid, 70 kilograms of silane coupling agent (KH560), 50 kilograms of tetraethyl titanate, 15 kilograms of boric acid,
B component is made until being dispersed with stirring into uniform liquid in mixed hydrolysis under stirring condition in 420 kilograms of deionized waters；
(3) two component of A, B is mixed evenly using preceding by the weight ratio of the .4 of 1:1~1, is configured to finished product coating；Make
The coating mode that used time is used can be carried out by brushing, spraying or dip coating manner；Curing mode use heat-agglomerating, 70 DEG C~
100 DEG C dry 10~30 minutes, then are sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes, i.e. completion coating decoration.
Through detecting, the present embodiment coating is after coating, and coating coated weight is in 220 mg/dm2When left and right, resistance to neutral salt
The mist time can be more than 1800 hours, and coating hardness is greater than 4H, coating adhesion tape method (Japanese gummed tape Pyatyi rating method
JDIS K53114-4) coating adhesive strength reaches 4 grades or more.It is tested through 45 DEG C × 7 × 24 hours high high-temp stabilities, coating
Generate gelatin phenomenon.
For different coating modes if it is desired, corresponding hydroxyethyl cellulose thickening can be added to obtain corresponding viscosity
Agent improves coating mobility.
Claims (10)
1. a kind of chromium-free zinc aluminum anticorrosive paint using phosphomolybdic acid as passivator, it is characterised in that the material quality number of each component
Are as follows:
Composition quality portion rate
Zinc flake 250-310
Flake aluminum 10-30
Phosphomolybdic acid 3-10
Polyethylene glycol 110-150
Silane coupling agent 70-140
Ethylene glycol ether acetate 3-8
Surfactant 1-18
Defoaming agent 1-6
Tetraisopropyl titanate 10-60
Boric acid 10-18
Deionized water 380-480.
2. anticorrosive paint according to claim 1, it is characterised in that: the piece diameter of the zinc flake and flake aluminum is not
Greater than 20 μm, thickness is not more than 0.3 μm.
3. phosphomolybdic acid according to claim 1 is industrial phosphomolybdic acid；Phosphomolybdic acid be a kind of phosphoric acid with the sour general character and
Aoxidize molybdenum complex, molecular structural formula H3[P(Mo3O10)4], molecular formula H3PO4·12MoO3。
4. anticorrosive paint according to claim 1, it is characterised in that: the polyethylene glycol is room temperature liquid polyethylene glycol,
Its molecular weight is 200~400；Ethylene glycol ether acetate is industrial CAC solvent；Tetraisopropyl titanate is industrial metatitanic acid four
Isopropyl ester；Boric acid is industrial boric acid.
5. anticorrosive paint according to claim 1, it is characterised in that: the silane coupling agent is silane coupling agent
KH550, KH560, KH570；The surfactant is polyethoxylated fatty alcohols or nonylphenol polyoxyethylene ether；It is described to disappear
Infusion is W-052 or organosilicon 3270 or the intermixture of 1:1 in mass ratio of W-052 and 3270.
6. anticorrosive paint according to claim 1, it is characterised in that: the deionized water, conductivity 0.1-30
us/cm。
7. using phosphomolybdic acid as the preparation method of the chromium-free zinc aluminum anticorrosive paint of passivator, which comprises the steps of:
(1) with the zinc flake and flake aluminum of the mass ratio, polyethylene glycol, silane coupled agent prescription total amount is added
35-50%, ethylene glycol ether acetate, surfactant and defoaming agent are made sheet zinc-aluminium mixing slurry, are directly prepared into A group
Point；
(2) first by the phosphomolybdic acid of the weight ratio, 50-65%, tetraisopropyl titanate, the boric acid of silane coupled agent prescription total amount
B component is made until being dispersed with stirring into uniform liquid in mixed hydrolysis under agitation；
(3) using it is preceding by two component of A, B by 1:(1~1.4) mass ratio be mixed and stirred for uniformly, as finished product coating.
8. preparation method as claimed in claim 7, it is characterised in that: further include step (4), mixed in step (3)
Corresponding thickener is added in finished product.
9. preparation method as claimed in claim 8, it is characterised in that: the thickener is hydroxyethyl cellulose.
10. the preparation method as described in claim 7~9 is any, it is characterised in that: carry out coating, coating mode after mixing
Can brush, spray or dip coating manner carry out；Curing mode uses heat-agglomerating, dries 10~30 minutes at 70 DEG C~100 DEG C, then
It is sintered solidification at 320 DEG C~350 DEG C, 20~40 minutes.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111117311A (en) * | 2020-02-27 | 2020-05-08 | 沈阳市航达科技有限责任公司 | Water-based zinc-aluminum coating containing borate and/or aluminate |
| CN113445035A (en) * | 2021-07-07 | 2021-09-28 | 上海库曜新材料有限公司 | Passivation method of zinc powder |
| CN113831766A (en) * | 2021-09-18 | 2021-12-24 | 吉林莱德化学科技有限公司 | Water-based zinc-aluminum coating, primer coating, preparation method of primer coating and composite coating |
| CN114592186A (en) * | 2022-04-27 | 2022-06-07 | 上海库曜新材料有限公司 | Chromium-free passivation method of zinc powder |
| CN116445078A (en) * | 2023-03-27 | 2023-07-18 | 上海德修化工有限公司 | Chromium-free anti-corrosion coating for automobile fasteners and preparation method thereof |
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| CN114592186B (en) * | 2022-04-27 | 2024-03-12 | 上海库曜新材料有限公司 | Chromium-free passivation method for zinc powder |
| CN116445078A (en) * | 2023-03-27 | 2023-07-18 | 上海德修化工有限公司 | Chromium-free anti-corrosion coating for automobile fasteners and preparation method thereof |
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