CN116791072B - Metal surface treatment passivating agent and preparation method and application thereof - Google Patents
Metal surface treatment passivating agent and preparation method and application thereof Download PDFInfo
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- CN116791072B CN116791072B CN202311019284.4A CN202311019284A CN116791072B CN 116791072 B CN116791072 B CN 116791072B CN 202311019284 A CN202311019284 A CN 202311019284A CN 116791072 B CN116791072 B CN 116791072B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 34
- 239000002184 metal Substances 0.000 title claims abstract description 34
- 238000004381 surface treatment Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 43
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 30
- 239000010935 stainless steel Substances 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 239000011737 fluorine Substances 0.000 claims abstract description 22
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 22
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 22
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 22
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 19
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 18
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 18
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 18
- 229940033123 tannic acid Drugs 0.000 claims abstract description 18
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 18
- 229920002258 tannic acid Polymers 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000003112 inhibitor Substances 0.000 claims abstract description 5
- 238000002161 passivation Methods 0.000 claims description 33
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical group C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 10
- -1 fatty alcohol ether phosphates Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- 235000021317 phosphate Nutrition 0.000 claims description 5
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 5
- LBTSNEJGMVFUEW-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,8,8,8-dodecafluorooctoxy-dimethoxy-propylsilane Chemical compound FC(C(C(C(C(F)(F)CO[Si](OC)(OC)CCC)(F)F)(F)F)(F)F)CC(F)(F)F LBTSNEJGMVFUEW-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 159000000001 potassium salts Chemical class 0.000 claims description 4
- HJVAFZMYQQSPHF-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;boric acid Chemical class OB(O)O.OCCN(CCO)CCO HJVAFZMYQQSPHF-UHFFFAOYSA-N 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- URWIWRCHIPAGBL-UHFFFAOYSA-N OCC1OP(=O)OP(=O)O1 Chemical class OCC1OP(=O)OP(=O)O1 URWIWRCHIPAGBL-UHFFFAOYSA-N 0.000 claims description 2
- BJZIJOLEWHWTJO-UHFFFAOYSA-H dipotassium;hexafluorozirconium(2-) Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Zr+4] BJZIJOLEWHWTJO-UHFFFAOYSA-H 0.000 claims description 2
- RXCBCUJUGULOGC-UHFFFAOYSA-H dipotassium;tetrafluorotitanium;difluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[K+].[K+].[Ti+4] RXCBCUJUGULOGC-UHFFFAOYSA-H 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 18
- 230000007797 corrosion Effects 0.000 abstract description 17
- 230000000052 comparative effect Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002253 Tannate Polymers 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000007744 chromate conversion coating Methods 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 239000002966 varnish Substances 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
- C23C22/34—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 fluorides or complex fluorides
-
- 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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Abstract
The invention relates to a metal surface treatment passivating agent and a preparation method and application thereof, and belongs to the technical field of passivating agents. The metal surface treatment passivating agent comprises, by weight, 10-20 parts of fluorine-containing compounds, 2-5 parts of tannic acid, 2-5 parts of hydrogen peroxide, 5-10 parts of silica sol, 13-17 parts of antioxidants, 1-3 parts of silane coupling agents, 0.2-0.5 part of rust inhibitors and 300-400 parts of solvents. The metal surface treatment passivating agent disclosed by the invention is composed of fluorine-containing compounds, tannic acid, hydrogen peroxide, silica sol, antioxidants, silane coupling agents, rust removers, solvents and the like, can form compact multilayer crossed passivating films on the surfaces of stainless steel workpieces, and is high in film forming speed and efficiency, low in porosity of the obtained passivating films and capable of remarkably improving corrosion resistance of plated parts.
Description
Technical Field
The invention belongs to the technical field of passivating agents, and particularly relates to a metal surface treatment passivating agent, and a preparation method and application thereof.
Background
Stainless steel has good corrosion resistance and high-temperature oxidation resistance, but because of the high activity, surface dirt, rust, oxide film welding slag and the like are brought in the processing process, so that the corrosion resistance of stainless steel equipment and parts is affected, and therefore, the surface needs to be subjected to corrosion resistance treatment. The common method is a method of forming a complete, compact and uniform passivation layer on the surface of stainless steel and then spraying the passivation layer so as to improve the corrosion resistance of the metal surface, and is a common and effective additional protection measure.
The traditional passivating agent for passivating the surface of the stainless steel consists of chromate, alkaline auxiliary agent, antioxidant, stabilizer, complexing agent and the like, and after the chromate passivation treatment is adopted, a protective conversion film consisting of chromium compounds, namely a chromate conversion film, is generated on the surface of the stainless steel, and the chromate passivation film has good corrosion resistance and self-repairing performance. The chromium in the chromate conversion coating mainly exists in the form of trivalent chromium and hexavalent chromium, wherein the trivalent chromium plays a role of a framework in the passivation coating, and the oxide of the hexavalent chromium is filled in the passivation coating to play a role of self-repairing. However, chromium is a heavy metal, has strong oxidizing property, has high toxicity, is a cancerogenic substance and seriously damages the environment and human health, so that chromium-free passivation is taken as the main research and development direction at present.
Disclosure of Invention
In order to solve the technical problems, the invention provides a metal surface treatment passivating agent, and a preparation method and application thereof.
The invention provides a metal surface treatment passivating agent which comprises, by weight, 10-20 parts of fluorine-containing compounds, 2-5 parts of tannic acid, 2-5 parts of hydrogen peroxide, 5-10 parts of silica sol, 13-17 parts of antioxidants, 1-3 parts of silane coupling agents, 0.2-0.5 part of rust inhibitors and 300-400 parts of solvents.
In one embodiment of the invention, the fluorine-containing compound is selected from potassium fluorozirconate and/or potassium fluorotitanate. The fluorine in the fluorine-containing compound can accelerate the formation of the passivation film, can improve the thickness uniformity of the passivation film, and can improve the color depth and the glossiness of the passivation film.
In one embodiment of the invention, the hydrogen peroxide is beneficial to the formation of the passivation film, and when the addition amount of the hydrogen peroxide is small, OH is generated - The concentration of ions is small, which is unfavorable for film forming reaction, hydrogen peroxide is simultaneously used as an oxidant, but when the addition amount is too large, the hydrogen peroxide directly reacts with metal ions to form precipitate, and the uniformity of film forming is affected.
In one embodiment of the invention, the fluorine-containing compound and hydrogen peroxide undergo a coordination reaction to form titanium dioxide or zirconium dioxide colloid particles which are adsorbed and deposited on the surface of the plating layer to form a passivation film, so that the entry of corrosive media such as air moisture can be prevented, and good corrosion resistance can be obtained. Tannic acid is added to enhance the stability of the passivation solution because the passivating agent of the fluorine-containing compound is not easy to stabilize, but when the tannic acid is excessive, free fluorine ions are accumulated to damage the adhesive force of the passivation film.
In one embodiment of the present invention, the tannic acid is a polybasic acid containing both hydroxyl and carboxyl groups, which has a relatively large molecular weight and is mixed with Fe under certain conditions 3+ Chelation takes place to produce a kind ofThe black brown iron tannate chelate with a reticular structure and stable performance is tightly adsorbed on the surface of a stainless steel workpiece, and plays a role in rust prevention.
In one embodiment of the invention, the silica sol belongs to a colloidal solution, is odorless and nontoxic, is a dispersion liquid of nano-scale silica particles in water or a solvent, has quite large specific surface area, is colorless and transparent, does not affect the natural color of a covered, has low viscosity, can permeate in water permeable places, and has good dispersibility and permeability when mixed with other substances. The addition of the silica sol can solve the problem that the passivation film has poor flexibility after the passivation agent is formed into a film. However, the single fluorine-containing compound exists in the passivation film after film formation in the form of particles on the surface of the plating layer, and a plurality of micropores exist to influence corrosion resistance, so that silica sol is added to fill in gaps of the passivation film, the compactness of the passivation film is enhanced, further infiltration of a corrosion medium is blocked, and further the corrosion resistance of a stainless steel workpiece is better improved. When the silica sol is added less, the effect of promoting film formation and filling a film layer is weaker, and when the silica sol is added more, the welding performance of the stainless steel workpiece is affected due to the organic component of the silane coupling agent.
In one embodiment of the invention, the antioxidant is mercaptobenzothiazole and/or methylbenzotriazole. The antioxidant forms covalent bonds and coordination bonds with copper atoms of the stainless steel, and the covalent bonds and the coordination bonds are mutually alternated into chain polymers, and a multi-layer passivation film is formed on the surface of the stainless steel, so that the surface of the stainless steel does not have oxidation-reduction reaction and hydrogen, and the stainless steel has an anti-corrosion effect.
In one embodiment of the present invention, the silane coupling agent is selected from one or more of dodecafluoroheptyl propyl trimethoxysilane, vinyltriethoxysilane, and 3- (2, 3-glycidoxy) propyl trimethoxysilane. The single silica sol is easy to agglomerate due to smaller nano particle size, so that the silane coupling agent is used for modification to reduce agglomeration caused by mutual adsorption between the surface energy nano particles, and meanwhile, the compatibility of the silica sol and the passivating agent is enhanced, and film formation is promoted.
In one embodiment of the present invention, the rust remover is selected from one or more of phosphate esters, triethanolamine borate esters, potassium salts of fatty alcohol ether phosphates, and potassium salts of hydroxyethylidene diphosphonate. The antioxidant and the rust remover can be complexed to generate slow-release complexing, and the slow-release complexing generated by using a film adsorption principle can be automatically adsorbed on the passivation film of the stainless steel, so that the passivation film becomes more compact and more uniform, and the stainless steel substrate can be better isolated from external corrosive substances, thereby effectively and greatly improving the corrosion resistance of the stainless steel.
In one embodiment of the present invention, the solvent is a mixed solvent of ethanol, isopropanol and water.
In one embodiment of the invention, the volume ratio of ethanol, isopropanol and water is 10:1-3:20-30. The isopropanol and the ethanol are matched, so that the rust transforming agent reacts with the inner layer rust, and the anode reaction in the corrosion process is inhibited, thereby effectively delaying the corrosion process.
The second purpose of the invention is to provide a preparation method of the metal surface treatment passivating agent, which comprises the steps of dissolving fluorine-containing compounds, silica sol, silane coupling agents and rust inhibitors in a solvent according to a proportion, uniformly stirring and standing for 20-30 min, and then adding tannic acid, hydrogen peroxide and antioxidants, and uniformly stirring to obtain the metal surface treatment passivating agent.
The third object of the invention is to provide an application of the metal surface treatment passivating agent in stainless steel treatment, wherein a stainless steel workpiece is immersed into the passivating agent for passivation, and the stainless steel workpiece is taken out after passivation, washed with water and dried.
In one embodiment of the invention, the temperature of the passivation is 40 ℃ to 50 ℃; the passivation time is 30s-60s.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The metal surface treatment passivating agent disclosed by the invention is composed of fluorine-containing compounds, tannic acid, hydrogen peroxide, silica sol, antioxidants, silane coupling agents, rust removers, solvents and the like, can form compact multilayer crossed passivating films on the surfaces of stainless steel workpieces, and is high in film forming speed and efficiency, low in porosity of the obtained passivating films and capable of remarkably improving corrosion resistance of plated parts.
(2) The metal surface treatment passivating agent disclosed by the invention is used for passivating a stainless steel workpiece, is easy to form a film, has a good binding force between the formed passivating film and stainless steel, can obviously improve the corrosion resistance of the stainless steel, and is environment-friendly.
Detailed Description
The present invention will be further described with reference to specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the present invention and practice it.
Example 1
The invention relates to a metal surface treatment passivating agent and a preparation method thereof, which concretely comprise the following steps:
ethanol, isopropanol and water are mixed according to the volume ratio of 10:2: and (3) preparing a solvent with the weight of 350 parts, adding 15 parts of fluorine-containing compound potassium fluorozirconate, 8 parts of silica sol, 2 parts of silane coupling agent dodecafluoroheptyl propyl trimethoxy silane and 0.4 part of rust remover phosphate into the solvent, uniformly stirring and standing for 25min, then adding 3 parts of tannic acid, 4 parts of hydrogen peroxide and 15 parts of antioxidant mercaptobenzothiazole, and uniformly stirring to obtain the metal surface treatment passivating agent.
Example 2
The invention relates to a metal surface treatment passivating agent and a preparation method thereof, which concretely comprise the following steps:
ethanol, isopropanol and water are mixed according to the volume ratio of 10:1: and (3) preparing a solvent with the weight of 300 parts, adding 10 parts of fluorine-containing compound potassium fluorozirconate, 5 parts of silica sol, 1 part of silane coupling agent dodecafluoroheptyl propyl trimethoxy silane and 0.2 part of rust remover phosphate into the solvent, uniformly stirring and standing for 20min, then adding 2 parts of tannic acid, 2 parts of hydrogen peroxide and 13 parts of antioxidant mercaptobenzothiazole, and uniformly stirring to obtain the metal surface treatment passivating agent.
Example 3
The invention relates to a metal surface treatment passivating agent and a preparation method thereof, which concretely comprise the following steps:
ethanol, isopropanol and water are mixed according to the volume ratio of 10:3:30 parts of a solvent is prepared into 400 parts, 20 parts of fluorine-containing compound potassium fluorozirconate, 10 parts of silica sol, 3 parts of silane coupling agent 3- (2, 3-glycidoxy) propyl trimethoxy silane and 0.5 part of rust remover phosphate are added into the solvent, uniformly stirred and stood for 30min, and then 5 parts of tannic acid, 5 parts of hydrogen peroxide and 17 parts of antioxidant mercaptobenzothiazole are added into the solvent, and uniformly stirred to obtain the metal surface treatment passivating agent.
Example 4
The invention relates to a metal surface treatment passivating agent and a preparation method thereof, which concretely comprise the following steps:
ethanol, isopropanol and water are mixed according to the volume ratio of 10:2: and (3) preparing 350 parts of a solvent, adding 15 parts of fluorine-containing compound potassium fluotitanate, 8 parts of silica sol, 2 parts of silane coupling agent vinyl triethoxysilane and 0.4 part of rust remover triethanolamine borate into the solvent, uniformly stirring and standing for 25min, then adding 3 parts of tannic acid, 4 parts of hydrogen peroxide and 15 parts of antioxidant methylbenzotriazole, and uniformly stirring to obtain the metal surface treatment passivating agent.
Example 5
The invention relates to a metal surface treatment passivating agent and a preparation method thereof, which concretely comprise the following steps:
ethanol, isopropanol and water are mixed according to the volume ratio of 10:2:25 parts of a solvent is prepared into 350 parts, 15 parts of fluorine-containing compound potassium fluotitanate, 8 parts of silica sol, 2 parts of silane coupling agent 3- (2, 3-glycidoxy) propyl trimethoxy silane and 0.4 part of rust remover fatty alcohol ether phosphate potassium salt are added into the solvent, uniformly stirred and stood for 25 minutes, and then 3 parts of tannic acid, 4 parts of hydrogen peroxide and 15 parts of antioxidant methylbenzotriazole are added into the solvent, and uniformly stirred to obtain the metal surface treatment passivating agent.
Example 6
The invention relates to a metal surface treatment passivating agent and a preparation method thereof, which concretely comprise the following steps:
ethanol, isopropanol and water are mixed according to the volume ratio of 10:2:25 parts of a solvent is prepared into 350 parts, 15 parts of fluorine-containing compound potassium fluotitanate, 8 parts of silica sol, 2 parts of silane coupling agent 3- (2, 3-glycidoxy) propyl trimethoxy silane and 0.4 part of rust remover potassium hydroxyethylidene bisphosphonate are added into the solvent, uniformly stirred and stood for 25 minutes, and then 3 parts of tannic acid, 4 parts of hydrogen peroxide and 15 parts of antioxidant methylbenzotriazole are added into the solvent, and uniformly stirred to obtain the metal surface treatment passivating agent.
Comparative example 1
Substantially the same as in example 1, except that isopropyl alcohol was not added.
Comparative example 2
Substantially the same as in example 1, except that no silica sol was added.
Comparative example 3
Substantially the same as in example 1, except that the silane coupling agent was not added.
Comparative example 4
Substantially the same as in example 1, except that no rust remover was added.
Comparative example 5
Substantially the same as in example 1, except that tannic acid was not added.
Comparative example 6
Substantially the same as in example 1, except that hydrogen peroxide was not added.
Comparative example 7
Substantially the same as in example 1, except that no antioxidant was added.
Test example 1
Based on the passivating agents prepared in examples 1-6 and comparative examples 1-7, the stainless steel workpiece is immersed in the passivating agent and passivated for 45s at 45 ℃, and the stainless steel workpiece is taken out after passivation, washed with water and dried in the air.
And (3) performing performance test on the processed workpiece:
(1) Salt spray test after coating: in a salt fog box at 35 ℃, compressed air is preheated to about 45 ℃ and is regulated to a sufficient pressure, salt water containing 5+/-1% sodium chloride and having a pH value of 6.5-7.2 is sprayed by a spraying device, salt fog is allowed to sink onto a workpiece to be detected (the middle of the workpiece is scratched by a blade for one cross), and the surface corrosion state is observed for a certain time until the surface is foamed or the edges of the two edges of the scratched fork are foamed and stripped to be more than 3mm.
(2) And (3) performing baking varnish treatment on the passivated workpiece, and then performing binding force test on the sample according to GB/T9286-1998, namely, marking vertical and horizontal lines on the coating film of the test piece at intervals of 1mm, and judging whether the brittleness of the coating film and the adhesion performance to the material are good or not according to the size of crack expansion at the breaking position. The combined grade was rated from 0 to 5, with 5B being the best, 0B being the worst, and the test results are shown in Table 1.
TABLE 1
As can be seen from table 1, the workpiece passivated by the example has excellent salt spray test effect, binding force and appearance effect under the same passivation time, passivation temperature and other conditions. The effect of the workpiece passivated by the comparative example is relatively poor, because the components of fluorine-containing compound, tannic acid, hydrogen peroxide, silica sol, antioxidant, silane coupling agent, rust remover, solvent and the like adopted in the embodiment cooperate with each other, a compact multilayer crossed passivation film can be formed on the surface of the stainless steel workpiece, and the corrosion resistance of the plated workpiece is remarkably improved.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (7)
1. The metal surface treatment passivating agent is characterized by comprising, by weight, 10-20 parts of fluorine-containing compounds, 2-5 parts of tannic acid, 2-5 parts of hydrogen peroxide, 5-10 parts of silica sol, 13-17 parts of antioxidants, 1-3 parts of silane coupling agents, 0.2-0.5 part of rust inhibitors and 300-400 parts of solvents; the fluorine-containing compound is selected from potassium fluorozirconate and/or potassium fluorotitanate; the antioxidant is mercaptobenzothiazole and/or methylbenzotriazole; the solvent is a mixed solvent of ethanol, isopropanol and water.
2. The metal surface treatment passivating agent according to claim 1, wherein said silane coupling agent is selected from one or more of dodecafluoroheptyl propyl trimethoxysilane, vinyl triethoxysilane, and 3- (2, 3-glycidoxy) propyl trimethoxysilane.
3. The metal surface treatment passivating agent according to claim 1, wherein said rust remover is selected from one or more of phosphate esters, triethanolamine borate esters, potassium salts of fatty alcohol ether phosphates, and potassium salts of hydroxyethylidene diphosphonate.
4. The metal surface treatment passivating agent according to claim 1, characterized in that the volume ratio of ethanol, isopropanol and water is 10:1-3:20-30.
5. The method for preparing the metal surface treatment passivating agent as defined in any one of claims 1-4, which is characterized in that fluorine-containing compounds, silica sol, silane coupling agents and rust inhibitors are dissolved in a solvent according to a proportion, stirred uniformly and stood for 20-30 min, and then tannic acid, hydrogen peroxide and antioxidants are added and stirred uniformly to obtain the metal surface treatment passivating agent.
6. Use of the metal surface treatment passivating agent according to any one of claims 1-4 in stainless steel treatment, characterized in that a stainless steel workpiece is immersed in the passivating agent for passivation, and the stainless steel workpiece is taken out after passivation, washed with water and dried in the air.
7. Use of a metal surface treatment passivating agent according to claim 6 in stainless steel treatment, characterized in that the passivating temperature is 40-50 ℃; the passivation time is 30s-60s.
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