CN115029691A - Chromium-free passivator and preparation method thereof - Google Patents
Chromium-free passivator and preparation method thereof Download PDFInfo
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- CN115029691A CN115029691A CN202210738667.6A CN202210738667A CN115029691A CN 115029691 A CN115029691 A CN 115029691A CN 202210738667 A CN202210738667 A CN 202210738667A CN 115029691 A CN115029691 A CN 115029691A
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- 238000002360 preparation method Methods 0.000 title abstract description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 111
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 74
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 74
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 74
- 230000007797 corrosion Effects 0.000 claims abstract description 50
- 238000005260 corrosion Methods 0.000 claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 claims abstract description 45
- 239000002184 metal Substances 0.000 claims abstract description 45
- 239000003112 inhibitor Substances 0.000 claims abstract description 44
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 43
- 239000000440 bentonite Substances 0.000 claims abstract description 43
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 43
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 37
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 37
- 239000004471 Glycine Substances 0.000 claims abstract description 37
- 229960000583 acetic acid Drugs 0.000 claims abstract description 37
- 239000007864 aqueous solution Substances 0.000 claims abstract description 37
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 37
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 37
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 37
- 239000011592 zinc chloride Substances 0.000 claims abstract description 37
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 claims abstract description 36
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 36
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 36
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims abstract description 36
- 239000011259 mixed solution Substances 0.000 claims description 60
- 238000003756 stirring Methods 0.000 claims description 48
- 229940092782 bentonite Drugs 0.000 claims description 42
- 238000002156 mixing Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 8
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 claims description 8
- 108010064470 polyaspartate Proteins 0.000 claims description 8
- 229940080314 sodium bentonite Drugs 0.000 claims description 8
- 229910000280 sodium bentonite Inorganic materials 0.000 claims description 8
- 235000015393 sodium molybdate Nutrition 0.000 claims description 8
- 239000011684 sodium molybdate Substances 0.000 claims description 8
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 8
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 8
- 235000013808 oxidized starch Nutrition 0.000 claims description 7
- 239000001254 oxidized starch Substances 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 abstract description 6
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- 239000003973 paint Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 24
- 239000007921 spray Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002161 passivation Methods 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/46—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing oxalates
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- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention relates to a chromium-free passivator and a preparation method thereof, comprising 120 parts of acrylic resin aqueous solution 110-LT inorganic gel, 4-8 parts of LT inorganic gel, 5-10 parts of glacial acetic acid, 5-8 parts of zinc chloride, 4-5 parts of ethylene glycol phenyl ether, 10-12 parts of metal corrosion inhibitor, 7-11 parts of glycine, 5-10 parts of oxalic acid, 15-20 parts of organic bentonite, 5-10 parts of titanium acetylacetonate, 15-20 parts of ferric chloride, 2-5 parts of lanthanum chloride and 5-15 parts of pH regulator; the chromium-free passivator prepared by the invention has good acid resistance, can be used in an acidic environment, can be fully matched with paint to carry out good protection on a coated member, forms a compact passive film on the surface of the member, and improves the corrosion resistance and the wear resistance to a certain degree.
Description
Technical Field
The invention relates to the technical field of passivators, and particularly relates to a chromium-free passivator and a preparation method thereof.
Background
In a humid environment, a bare zinc coating is easy to corrode, the outer surface of the zinc coating needs to be passivated, and the traditional hexavalent chromate passivating agent has high toxicity and great harm. The existing chromium-free passivator on the market mainly comprises organic passivation, inorganic passivation and organic-inorganic composite passivation, a passivation film can be formed on the surface of a plated part after the plated part is treated, the film generally only has a simple protection effect, and the film has poor performances such as impact resistance, acid resistance and the like, and is easy to corrode or impact during use, so that the film is damaged and internal components cannot be protected.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention provides a chromium-free passivation agent and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
a chromium-free passivator comprises 120 parts of acrylic resin aqueous solution 110-one, 4-8 parts of LT inorganic gel, 5-10 parts of glacial acetic acid, 5-8 parts of zinc chloride, 4-5 parts of ethylene glycol phenyl ether, 10-12 parts of a metal corrosion inhibitor, 7-11 parts of glycine, 5-10 parts of oxalic acid, 15-20 parts of organic bentonite, 5-10 parts of titanium acetylacetonate, 15-20 parts of ferric chloride, 2-5 parts of lanthanum chloride and 5-15 parts of a pH regulator.
Preferably, the metal corrosion inhibitor is prepared by mixing polyaspartic acid with one or more of sodium molybdate, sodium tungstate, oxidized starch and organic phosphorus.
Preferably, the pH regulator is one or a combination of nitric acid, hydrochloric acid, boric acid and hydrofluoric acid.
Preferably, the organic bentonite is prepared by taking sodium bentonite as a base in a wet method.
A preparation method of a chromium-free passivator comprises the following steps:
s1, firstly, mixing one third of the total amount of acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride, lanthanum chloride and one fourth of the total amount of LT inorganic gel, heating to 45-55 ℃, and stirring at 850-1050rpm for 60-70min to prepare mixed solution I;
s2, preheating one half of the remaining acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride and lanthanum chloride at the preheating temperature of 55-60 ℃ to obtain a mixed solution II;
s3, adding the mixed solution II into the mixed solution I, and stirring at the speed of 700-900rpm and the temperature of 45-55 ℃ for 65-85min to obtain a mixed solution III;
s4, mixing and stirring half of the remaining LT inorganic gel with half of the remaining acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride and lanthanum chloride, heating to 45-55 ℃, stirring at the speed of 800-900rpm for 30min to obtain a mixed solution IV;
s5, adding the mixed solution IV into the mixed solution III, and stirring at the speed of 650-750rpm at the temperature of 45-55 ℃ for 40min to prepare a mixed solution V;
s6, directly adding the residual acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride and lanthanum chloride into the mixed solution V, stirring at the speed of 850rpm at 750-55 ℃, and increasing the stirring speed of 250rpm every 30 min;
and S7, after the stirring is accelerated, standing and cooling to normal temperature.
Advantageous effects
The chromium-free passivator prepared by the invention is green and environment-friendly, has good acid resistance, can be used in an acidic environment, forms a compact passivation film on the surface of a component, can be fully matched with a coating to protect the component, and has the advantages that the corrosion resistance and the wear resistance of a metal component using the passivator are greatly improved through an impact resistance test, a bare film salt spray test and a salt spray test after coating.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A chromium-free passivator comprises 110 parts of acrylic resin aqueous solution, 4 parts of LT inorganic gel, 6 parts of glacial acetic acid, 6 parts of zinc chloride, 4 parts of ethylene glycol phenyl ether, 10 parts of metal corrosion inhibitor, 7 parts of glycine, 6 parts of oxalic acid, 15 parts of organic bentonite (the organic bentonite is prepared by taking sodium bentonite as a base by a wet method), 5 parts of titanium acetylacetonate, 15 parts of ferric chloride, 2 parts of lanthanum chloride and 5 parts of pH regulator nitric acid.
Furthermore, the metal corrosion inhibitor is prepared by mixing polyaspartic acid, sodium molybdate, sodium tungstate, oxidized starch and organic phosphorus.
The preparation method of the chromium-free passivator comprises the following steps:
s1, firstly, mixing one third of the total amount of acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride, lanthanum chloride and one fourth of the total amount of LT inorganic gel, heating to 45 ℃, and stirring at 850rpm for 70min to prepare mixed solution I;
s2, preheating one half of the residual acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride and lanthanum chloride at 55 ℃ to obtain a mixed solution II;
s3, adding the mixed solution II into the mixed solution I, and stirring at the speed of 700rpm and the temperature of 55 ℃ for 65min to obtain a mixed solution III;
s4, mixing and stirring half of the remaining LT inorganic gel with half of the remaining acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride and lanthanum chloride, heating to 55 ℃, stirring at 800rpm for 30min to obtain a mixed solution IV;
s5, adding the mixed solution IV into the mixed solution III, and stirring at the speed of 700rpm for 40min at 55 ℃ to prepare a mixed solution V;
s6, directly adding the residual acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride and lanthanum chloride into the mixed solution V, stirring at the speed of 750rpm at 55 ℃, simultaneously adding the residual pH regulator, and increasing the stirring speed of 200rpm every 30 min;
and S7, after the stirring is finished, standing and cooling to normal temperature.
Example 2
A chromium-free passivator comprises 115 parts of acrylic resin aqueous solution, 5 parts of LT inorganic gel, 7 parts of glacial acetic acid, 7 parts of zinc chloride, 5 parts of ethylene glycol phenyl ether, 11 parts of metal corrosion inhibitor, 8 parts of glycine, 7 parts of oxalic acid, 16 parts of organic bentonite, 7 parts of titanium acetylacetonate, 16 parts of ferric chloride, 3 parts of lanthanum chloride and 10 parts of pH regulator hydrochloric acid.
The metal corrosion inhibitor is prepared by mixing polyaspartic acid, sodium molybdate and sodium tungstate.
The organic bentonite is prepared by taking sodium bentonite as a base by a wet method.
The preparation method of the chromium-free passivator comprises the following steps:
s1, firstly, mixing one third of the total amount of acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride, lanthanum chloride and one fourth of the total amount of LT inorganic gel, heating to 55 ℃, and stirring at 1050rpm for 70min to prepare mixed solution I;
s2, preheating one half of the residual acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride and lanthanum chloride at 60 ℃ to obtain a mixed solution II;
s3, adding the mixed solution II into the mixed solution I, and stirring at the speed of 900rpm and the temperature of 45 ℃ for 65min to obtain a mixed solution III;
s4, mixing and stirring half of the residual LT inorganic gel and half of the residual acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride and lanthanum chloride, heating to 45 ℃, stirring at 900rpm for 30min to obtain a mixed solution IV;
s5, adding the mixed solution IV into the mixed solution III, and stirring at the speed of 750rpm for 40min at the temperature of 45 ℃ to obtain mixed solution V;
s6, directly adding the residual acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride and lanthanum chloride into the mixed solution V, stirring at the speed of 750rpm at 45 ℃, simultaneously adding the residual pH regulator, and increasing the stirring speed of 200rpm every 30 min;
and S7, after the stirring is accelerated, standing and cooling to normal temperature.
Example 3
A chromium-free passivator comprises 115 parts of acrylic resin aqueous solution, 6.5 parts of LT inorganic gel, 7 parts of glacial acetic acid, 7 parts of zinc chloride, 4.5 parts of ethylene glycol phenyl ether, 11 parts of metal corrosion inhibitor, 9 parts of glycine, 7 parts of oxalic acid, 17 parts of organic bentonite (prepared by taking sodium bentonite as a base by a wet method), 7 parts of titanium acetylacetonate, 7 parts of ferric chloride, 4 parts of lanthanum chloride and 10 parts of hydrofluoric acid serving as a pH regulator.
The metal corrosion inhibitor is prepared by mixing polyaspartic acid, sodium molybdate, sodium tungstate and oxidized starch.
The preparation method of the chromium-free passivator comprises the following steps:
s1, firstly, mixing one third of the total amount of acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride, lanthanum chloride and one fourth of the total amount of LT inorganic gel, heating to 52 ℃, and stirring at 930rpm for 67min to prepare mixed solution I;
s2, preheating one half of the remaining acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride and lanthanum chloride at the preheating temperature of 60 ℃ to obtain a mixed solution II;
s3, adding the mixed solution II into the mixed solution I, and continuously stirring at the speed of 830rpm under the environment of 50 ℃ for 75min to obtain a mixed solution III;
s4, mixing and stirring half of the residual LT inorganic gel and half of the residual acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride and lanthanum chloride, heating to 50 ℃, stirring at 880rpm for 30min to obtain a mixed solution IV;
s5, adding the mixed solution IV into the mixed solution III, and stirring at the speed of 730rpm for 40min at the temperature of 50 ℃ to obtain a mixed solution V;
s6, directly adding the residual acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride and lanthanum chloride into the mixed solution V, stirring at the speed of 830rpm in the environment of 50 ℃, simultaneously adding the residual pH regulator, and increasing the stirring speed of 200rpm every 30 min;
and S7, after the stirring is finished, standing and cooling to normal temperature.
Example 4
A chromium-free passivator comprises 120 parts of acrylic resin aqueous solution, 8 parts of LT inorganic gel, 10 parts of glacial acetic acid, 8 parts of zinc chloride, 5 parts of ethylene glycol phenyl ether, 12 parts of metal corrosion inhibitor, 11 parts of glycine, 10 parts of oxalic acid, 20 parts of organic bentonite, 10 parts of titanium acetylacetonate, 20 parts of ferric chloride, 5 parts of lanthanum chloride and 15 parts of mixed acid pH regulator.
The metal corrosion inhibitor is prepared by mixing polyaspartic acid, sodium molybdate, sodium tungstate, oxidized starch and organic phosphorus.
The organic bentonite is prepared by a wet method based on sodium bentonite.
The preparation method of the chromium-free passivator comprises the following steps:
s1, firstly, mixing one third of the total amount of acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride, lanthanum chloride and one fourth of the total amount of LT inorganic gel, heating to 52 ℃, and stirring at the speed of 1000rpm for 67min to prepare mixed solution I;
s2, preheating one half of the remaining acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride and lanthanum chloride at the preheating temperature of 52 ℃ to obtain a mixed solution II;
s3, adding the mixed solution II into the mixed solution I, and stirring at the speed of 850rpm and the temperature of 52 ℃ for 85min to obtain a mixed solution III;
s4, mixing and stirring half of the residual LT inorganic gel and half of the residual acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride and lanthanum chloride, heating to 52 ℃, stirring at 850rpm for 30min to obtain a mixed solution IV;
s5, adding the mixed solution IV into the mixed solution III, and stirring at the speed of 750rpm for 40min at the temperature of 52 ℃ to obtain mixed solution V;
s6, directly adding the residual acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride and lanthanum chloride into the mixed solution V, stirring at the speed of 850rpm in the environment of 52 ℃, simultaneously adding the residual pH regulator, and increasing the stirring speed of 200rpm every 30 min;
and S7, after the stirring is accelerated, standing and cooling to normal temperature.
Comparative example 1
A chromium-free passivator comprises 110 parts of acrylic resin aqueous solution, 4 parts of LT inorganic gel, 5 parts of glacial acetic acid, 5 parts of zinc chloride, 4 parts of ethylene glycol phenyl ether, 7 parts of glycine, 5 parts of oxalic acid, 15 parts of organic bentonite, 5 parts of titanium acetylacetonate, 15 parts of ferric chloride, 2 parts of lanthanum chloride and 10 parts of nitric acid and hydrochloric acid pH regulator.
The organic bentonite is prepared by a wet method based on sodium bentonite.
The preparation method of the chromium-free passivator comprises the following steps:
sequentially mixing the following components in parts by weight: acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride, lanthanum chloride and LT inorganic gel are uniformly mixed, heated to 55 ℃, stirred for 60min at the speed of 930rpm, and kept stand and cooled to normal temperature.
Comparative example 2
A chromium-free passivator comprises 120 parts of acrylic resin aqueous solution, 8 parts of LT inorganic gel, 10 parts of glacial acetic acid, 8 parts of zinc chloride, 5 parts of ethylene glycol phenyl ether, 12 parts of metal corrosion inhibitor, 11 parts of glycine, 10 parts of oxalic acid, 20 parts of ferric chloride, 5 parts of lanthanum chloride and 15 parts of pH regulator (mixed acid).
The metal corrosion inhibitor is prepared by mixing polyaspartic acid with sodium molybdate, sodium tungstate, oxidized starch and organic phosphorus.
The preparation method of the chromium-free passivator comprises the following steps:
sequentially mixing the following components in parts by weight: acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride, lanthanum chloride and LT inorganic gel are uniformly mixed, heated to 52 ℃, stirred for 60min at the speed of 850rpm, and kept stand and cooled to normal temperature.
Comparative example 3
A chromium-free passivator comprises 115 parts of acrylic resin aqueous solution, 8 parts of glacial acetic acid, 7 parts of zinc chloride, 4.5 parts of ethylene glycol phenyl ether, 11 parts of metal corrosion inhibitor, 10 parts of glycine, 8 parts of oxalic acid, 18 parts of organic bentonite, 8 parts of titanium acetylacetonate and 10 parts of pH regulator (nitric acid, hydrochloric acid and boric acid).
The metal corrosion inhibitor is prepared by mixing polyaspartic acid, sodium molybdate, sodium tungstate and oxidized starch.
The organic bentonite is prepared by taking sodium bentonite as a base by a wet method.
The preparation method of the chromium-free passivator comprises the following steps:
sequentially mixing the following components in parts by weight: acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride, lanthanum chloride and LT inorganic gel are uniformly mixed, heated to 45 ℃, stirred for 30min at the speed of 800rpm, and kept stand and cooled to normal temperature.
Performance test
The performance tests of examples 1-4 and comparative examples 1-3 were carried out, and the test pieces obtained after painting the passivator in each example and comparative example were selected, the surface area of the paint was 1 square meter, and the results were as follows:
acid test: blending sulfuric acid until the pH value is 4 +/-0.5, then spraying the sulfuric acid on a test piece at the ambient temperature of 25 +/-0.5 ℃, wherein the specification of a spray head is 3 minutes, and observing the time of corrosion points on the surface of the test piece.
And (3) impact resistance test: selecting a regular tetrahedron as an impact piece, wherein the side length of the regular tetrahedron is 6CM, the total mass of the impact piece is adjusted to 10kg, the impact piece is hung at a position 1m above a test piece, the upper surface of the test piece is in a horizontal state, the impact piece falls in a free-falling state during testing, the tail end of a crack is used as an end point to connect a peripheral line, and the ratio of the cracked area of a film surface to the total area is measured.
Bare film salt spray test: in a salt spray box, salt water containing (5 Shi 0.5)% of sodium chloride and having a pH value of 7 +/-0.5 is sprayed on a test piece, the specification of a spray head is 6 minutes, and the time of white corrosion points on the surface of the test piece is observed.
Salt spray test after coating: firstly, cutting a grid in the middle of a test piece, wherein the grid meshes are square meshes of 2CM, then placing the test piece in a salt spray box, spraying saline water containing (5 m 0.5)% of sodium chloride and having a pH value of 7 +/-0.5 on the test piece, wherein the specification of a spray head is 6 minutes, and observing the corrosion state of the surface after a certain time until the surface is foamed or the edges at two sides of a cutting fork are foamed and depainted for more than 4 mm.
The test results are referred to the following table:
the comparison shows that the invention has the following effects:
the time for the test piece (examples 1-4) treated by the passivator obtained by the preparation method to generate rust under the acidic condition is 45-48h, and compared with a comparative example, the test piece can have a better rust prevention effect under the acidic environment; the crack area in the impact resistance test is about 15 percent, the impact resistance is better than that of a comparative example, and the coating has excellent corrosion resistance in a salt spray test and a salt spray test after coating.
Claims (5)
1. A chromium-free passivator, which is characterized in that: comprises 120 parts of acrylic resin aqueous solution 110-one, 4-8 parts of LT inorganic gel, 5-10 parts of glacial acetic acid, 5-8 parts of zinc chloride, 4-5 parts of ethylene glycol phenyl ether, 10-12 parts of metal corrosion inhibitor, 7-11 parts of glycine, 5-10 parts of oxalic acid, 15-20 parts of organic bentonite, 5-10 parts of titanium acetylacetonate, 15-20 parts of ferric chloride, 2-5 parts of lanthanum chloride and 5-15 parts of pH regulator.
2. The chromium-free passivating agent according to claim 1, wherein: the metal corrosion inhibitor is prepared by mixing polyaspartic acid and one or more of sodium molybdate, sodium tungstate, oxidized starch and organic phosphorus.
3. The chromium-free passivating agent according to claim 1, wherein: the pH regulator is one or a combination of nitric acid, hydrochloric acid, boric acid and hydrofluoric acid.
4. The chromium-free passivating agent according to claim 1, wherein: the organic bentonite is prepared by a wet method based on sodium bentonite.
5. The method for preparing the chromium-free passivating agent according to claim 1, comprising the steps of:
s1, firstly, mixing one third of the total amount of acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride, lanthanum chloride and one fourth of the total amount of LT inorganic gel, heating to 45-55 ℃, and stirring at 850-1050rpm for 60-70min to prepare mixed solution I;
s2, preheating one half of the remaining acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride and lanthanum chloride at 55-60 ℃ to obtain a mixed solution II;
s3, adding the mixed solution II into the mixed solution I, and continuously stirring at 45-55 ℃ at the speed of 700-900rpm for 65-85min to prepare a mixed solution III;
s4, mixing and stirring half of the residual LT inorganic gel with half of the residual acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride and lanthanum chloride, heating to 45-55 ℃, stirring at the speed of 800-900rpm for 30min to prepare a mixed solution IV;
s5, adding the mixed solution IV into the mixed solution III, and stirring at the speed of 650-750rpm at the temperature of 45-55 ℃ for 40min to prepare a mixed solution V;
s6, directly adding the residual acrylic resin aqueous solution, glacial acetic acid, zinc chloride, ethylene glycol phenyl ether, metal corrosion inhibitor, glycine, oxalic acid, organic bentonite, titanium acetylacetonate, ferric chloride and lanthanum chloride into the mixed solution V, stirring at the speed of 850rpm at 750-55 ℃, and increasing the stirring speed of 250rpm every 30 min;
and S7, after the stirring is accelerated, standing and cooling to normal temperature.
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