CN115369393B - Metal surface pretreatment film forming liquid and preparation method and application thereof - Google Patents
Metal surface pretreatment film forming liquid and preparation method and application thereof Download PDFInfo
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- CN115369393B CN115369393B CN202210962644.3A CN202210962644A CN115369393B CN 115369393 B CN115369393 B CN 115369393B CN 202210962644 A CN202210962644 A CN 202210962644A CN 115369393 B CN115369393 B CN 115369393B
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- film forming
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- forming material
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 51
- 239000002184 metal Substances 0.000 title claims abstract description 51
- 239000007788 liquid Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 12
- 239000008139 complexing agent Substances 0.000 claims abstract description 9
- 239000000419 plant extract Substances 0.000 claims abstract description 9
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 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 7
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 7
- 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 7
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 7
- 229920002258 tannic acid Polymers 0.000 claims abstract description 7
- 229940033123 tannic acid Drugs 0.000 claims abstract description 7
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 7
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 5
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 5
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- LRBQNJMCXXYXIU-QWKBTXIPSA-N gallotannic 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-QWKBTXIPSA-N 0.000 claims abstract 4
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 235000011054 acetic acid Nutrition 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 4
- -1 3-glycidyl propyl Chemical group 0.000 claims description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- 238000005238 degreasing Methods 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 238000006359 acetalization reaction Methods 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
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- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- LXAHHHIGZXPRKQ-UHFFFAOYSA-N 5-fluoro-2-methylpyridine Chemical compound CC1=CC=C(F)C=N1 LXAHHHIGZXPRKQ-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical compound [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 claims description 2
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims 1
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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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
- C23C22/40—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 molybdates, tungstates or vanadates
- C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides
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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)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention relates to a metal surface pretreatment film forming liquid and a preparation method and application thereof, belonging to the technical field of metal coating pretreatment. The mass fraction of the material comprises: 1-10% of basic film forming material, 0.5-2% of adhesion promoter, 0.3-3% of auxiliary film forming material, 0.2-2% of promoter, 0.1-0.5% of complexing agent and the balance of water; the base film-forming material comprises: 0.1-20% of plant extract, 0.1-10% of cross-linking agent and the balance of water; the plant extract is one or more of phytic acid, tannic acid and tannic acid; the cross-linking agent is one or more of polyvinyl alcohol, polyvinyl acetal Ding Quanzhi and polyethylene glycol; the adhesion promoter comprises: 0.1-10% of silane coupling agent, 0.05-10% of catalyst and the balance of water. The metal surface pretreatment film forming liquid can form a high-activity film layer with certain roughness and rich hydroxyl groups on the surface of a metal substrate.
Description
Technical Field
The invention belongs to the technical field of metal coating pretreatment, and particularly relates to a metal surface pretreatment film forming liquid, and a preparation method and application thereof.
Background
In the metal pretreatment industry, china still takes phosphating as the main material, but the traditional phosphating process has mature technology, but the pollution to the environment is increased increasingly, and the serious phosphorus-rich pollution is caused by the large-scale use of phosphating agent, so that the plant in the water body is overgrown, and meanwhile, the propagation of a large number of bacterial organisms is accompanied in the lake. Phosphorus-rich pollution is also a killer of water organisms, and a great amount of propagation can rob oxygen in lakes, so that the oxygen-dependent organisms in the lakes can be in competition, and the living organisms die. The phosphating medicament also contains a large amount of heavy metals and high-strength cancerogenic substances (such as chromium, nickel, cobalt, sodium nitrite and the like) which are strictly controlled by the nation, a large amount of phosphating slag byproducts are also accompanied in the using process of the phosphating bath solution, the phosphating slag treatment difficulty which is strictly controlled by the environmental protection department is high, the cost is high, and the upper limit requirements of partial regional governments on the total phosphating slag treatment amount are met.
The early 21 st century, german hangao introduced a novel environment-friendly treatment ceramic agent which mainly adopts fluorozirconic acid as a basic film forming substance, a layer of zirconium dioxide film is deposited on the surface of metal by reaction, and the agent composition has no phosphorus, chromium and nickel, so that the agent has the advantages of environment protection to a certain extent, and meanwhile, a plurality of problems exist: (1) The medicament contains a large amount of fluorochemical agents, which cause a large amount of fluorine pollution; (2) Fluoride sediment with 5-10% of the phosphorization sediment amount is still accompanied in the use process of the pottery technology, and the treatment difficulty is quite large; (3) The method has the advantages that the method has great limitation on processing boards, and has serious defects on pickling boards, cast iron, carbon gray boards and the like, so that quality failure is caused.
Disclosure of Invention
In order to solve the technical problems, the invention provides a metal surface pretreatment film forming liquid and a preparation method and application thereof. The film forming liquid takes plant extracts as basic raw materials, biomass materials synthesized through catalysis and molecular structure regulation are taken as basic film forming materials, and compared with the traditional phosphating and zirconizing technology, the film forming liquid has no energy consumption, no byproducts and no sediment waste liquid discharge in the process, and can thoroughly solve the environmental pollution problem.
The first object of the present invention is to provide a metal surface pretreatment film-forming liquid comprising, in mass fraction: 1-10% of basic film forming material, 0.5-2% of adhesion promoter, 0.3-3% of auxiliary film forming material, 0.2-2% of promoter, 0.1-0.5% of complexing agent and the balance of water;
The basic film forming material comprises the following components in percentage by mass: 0.1-20% of plant extract, 0.1-10% of cross-linking agent and the balance of water; the plant extract is one or more of phytic acid, tannin and tannic acid; the cross-linking agent is one or more of polyvinyl alcohol PVA, polyvinyl Ding Quanzhi PVB and polyethylene glycol PEG;
the adhesion promoter comprises the following components in percentage by mass: 0.1-10% of silane coupling agent, 0.05-10% of catalyst and the balance of water.
In one embodiment of the present invention, the molecular weight of both the polyvinyl alcohol PVA and the polyvinyl butyral ester PVB is 1000-3000; the molecular weight of the polyethylene glycol PEG is 200-1000; the acetalization degree of the polyvinyl alcohol Ding Quanzhi is 68-88%.
In one embodiment of the present invention, the method of preparing a base film-forming material comprises the steps of: mixing plant extract, cross-linking agent and water, heating to 60-100deg.C, and reacting for 5-20 hr to obtain the final product. Under the high-temperature reaction, the space in the molecule is heated and deformed, and the molecule is rearranged and polymerized under the action of the affinity of hydroxyl groups, so that the base film-forming material with specific adsorption and layer-by-layer assembly capability is finally formed.
In one embodiment of the invention, the silane coupling agent is one or more of 3-glycidyl propyl trimethoxy coupling agent, aminopropyl trimethoxy silane coupling agent, gamma- (2, 3-glycidoxy) propyl trimethoxy silane, 3-aminopropyl triethoxysilane, gamma-aminoethylaminopropyl trimethoxy silane, 3- (trimethoxysilyl) propyl methacrylate.
In one embodiment of the invention, the catalyst is acetic acid and/or nitric acid.
In one embodiment of the present invention, the method for preparing the adhesion promoter comprises the steps of: and (3) reacting the silane coupling agent solution for 0.5-30 hours at the temperature of 5-90 ℃ under the action of a catalyst to obtain the adhesion promoter. The hydrolyzed Si-OH functional groups undergo polymerization reaction and crosslinking to form polymeric resin with the molecular weight of hundreds to thousands, and the polymeric resin has better deformability and toughness and has good promotion effect on improving the bare film corrosion resistance of a film layer and coating adhesion. The silane coupling agent monomer has smaller molecules, the mechanical property is insufficient after the silane coupling agent monomer is heated, and the adhesion promotion effect of the organic silicon resin synthesized under the condition of using the catalyst is greatly improved compared with the silane coupling agent monomer.
In one embodiment of the present invention, the auxiliary film-forming material is one or more of tungstate, metavanadate, zirconium fluoride, zirconium nitrate, zinc oxide, molybdate, vanadate, fluorotitanic acid, fluorozirconic acid, ammonium fluorozirconate, manganese nitrate, cerium nitrate, aluminum nitrate, magnesium nitrate and ammonium fluorotitanate, and the auxiliary film-forming material forms a film on the metal substrate in cooperation with the base film-forming material.
In one embodiment of the present invention, the accelerator is one or more of hydroxylamine sulfate, sodium chlorate, potassium permanganate, hydrogen peroxide and nitrate. The promoter increases the film formation rate of the base film forming material on the metal substrate.
In one embodiment of the invention, the complexing agent is one or more of sodium fluoride, potassium fluoride, tartaric acid, citric acid, disodium EDTA, malic acid, oxalic acid, and acetic acid. The complexing agent improves the compactness and rubbing resistance of the film forming material on the assembled film layer of the metal substrate.
The second purpose of the invention is to provide an application of the film forming liquid for pretreatment of the metal surface in treatment of metal base materials, wherein the metal base materials are subjected to degreasing treatment, soaked in the film forming liquid for 0.5-30min after being washed by water, taken out, washed by water and dried, and the metal base materials with pretreated surfaces are obtained.
In one embodiment of the invention, the metal substrate is one or more of a cold rolled steel sheet, a galvanized sheet, a hot rolled sheet, a pickled sheet, and cast iron.
In one embodiment of the present invention, a metal substrate with a colorless, yellow, purple, and blue film layer on the surface is obtained according to the material and carbon content of the metal substrate.
In one embodiment of the invention, as the number of workpieces to be processed increases, the concentration of H + in the bath gradually decreases due to the hydrogen etching reaction, i.e., the pH of the solution increases, and the use process should maintain the pH of the solution between 2.5 and 5.5.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The adhesion promoter is added into the film forming liquid for metal surface pretreatment, and the film is formed under an acidic condition, so that the compactness of a film layer and the content of active functional groups of the surface layer are improved.
(2) The metal surface pretreatment film-forming solution uses biomass materials as basic film-forming materials, replaces the traditional phosphating technology and the ceramic technology, and adopts pure chemical preparations. Is environment-friendly, does not contain sensitive substances such as phosphate, chromium ions, nickel ions and the like, and meets the environmental protection requirement.
(3) The film forming liquid for pretreatment of the metal surface can improve the corrosion resistance of the bare film of the metal substrate and enhance the corrosion resistance among the working procedures of the metal substrate.
(4) The metal surface pretreatment film forming liquid can form a high-activity film layer with certain roughness and rich hydroxyl groups on the surface of a metal substrate. The high roughness can improve the biting force of the film layer and the subsequent paint, and the active groups on the surface can react with epoxy groups and polyurethane groups in the paint, so that the film layer has more excellent adhesive capability after being coated with the paint, powder or electrophoretic paint under the dual effects.
(5) After the cold-rolled steel sheet treated by the film forming liquid for the pretreatment of the metal surface is coated with the electrophoretic paint, the hundred-cell experiment can reach zero level (no paint film falls off). The impact force experiment can reach 80N/cm 2, and no crack exists. The plastic spraying rear scratching fork can resist 700h of salt fog, the electrophoresis rear scratching fork can resist 1000h of salt fog, and the single-side wide extension is lower than 2mm.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which:
FIG. 1 is a schematic diagram of a cold-rolled sheet treated with a film-forming liquid according to example 1 of the present invention.
FIG. 2 is a physical view of a galvanized sheet after the film forming liquid treatment in example 2 of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
In the present invention, unless otherwise specified, the rice bran extract is phytic acid and tannic acid, and the mass ratio of phytic acid to tannic acid is 1:1.
Example 1
A metal surface pretreatment film forming liquid and a preparation method and application thereof specifically comprise the following steps:
(1) Base film-forming material: 12 parts by mass of rice bran extract, 3 parts by mass of PVB (molecular weight 2000, acetalization degree 68%) and 85 parts by mass of water; sequentially adding the rice bran extract, PVB and water into a reaction kettle, stirring vigorously, and heating while stirring after the materials are dissolved and dispersed uniformly, and keeping the temperature for 20 hours when the temperature is 85 ℃ to obtain the basic film-forming material.
(2) Adhesion promoters: 3 parts by mass of gamma-aminoethylaminopropyl trimethoxysilane, 1 part by mass of 3-glycidyl propyl trimethoxy coupling agent, 0.15 part by mass of catalyst acetic acid and 95.85 parts by mass of water; adding water, catalyst acetic acid, gamma-aminoethylaminopropyl trimethoxysilane and 3-glycidyl propyl trimethoxy coupling agent into a reaction kettle in sequence, slowly stirring, heating to 70 ℃ while stirring after the components are dissolved and dispersed uniformly, and keeping the temperature for 6 hours to obtain the adhesion promoter.
(3) Pretreatment of film forming liquid on metal surface: 8 parts of basic film forming material, 1 part of adhesion promoter, 0.3 part of auxiliary film forming material magnesium nitrate, 0.3 part of promoter sodium chlorate, 0.2 part of complexing agent citric acid and 90.2 parts of water; and (3) uniformly mixing the materials, and regulating the pH value of the solution to 4.5 to obtain the metal surface pretreatment film-forming solution.
(4) Application of film forming liquid for pretreatment of metal surface:
S1, placing a cold-rolled steel plate sample in the prepared degreasing fluid, soaking for 8min, and washing with water to form a uniform water film;
s2, immersing the cold-rolled steel plate sample cleaned in the step S1 in a film forming liquid for 4min;
And S3, taking out the cold-rolled steel sheet sample processed in the step S2, washing with pure water, and drying or naturally drying to obtain the cold-rolled steel sheet with the pretreated surface.
Example 2
A metal surface pretreatment film forming liquid and a preparation method and application thereof specifically comprise the following steps:
(1) Base film-forming material: 10 parts by mass of rice bran extract, 17880.5 parts by mass of PVA and 89.5 parts by mass of water; sequentially adding the rice bran extract, PVA1788 and water into a reaction kettle, stirring vigorously, heating while stirring after the materials are dissolved and dispersed uniformly, and keeping the temperature for 20 hours at 65 ℃ to obtain the basic film-forming material.
(2) Adhesion promoters: 3 parts by mass of gamma- (2, 3-glycidoxy) propyl trimethoxy silane, 0.5 part by mass of gamma-aminoethyl aminopropyl trimethoxy silane, 0.05 part by mass of catalyst nitric acid and 96.45 parts by mass of water; adding water, catalyst nitric acid, gamma- (2, 3-glycidoxy) propyl trimethoxy silane and gamma-aminoethyl aminopropyl trimethoxy silane into a reaction kettle in sequence, slowly stirring, heating to 90 ℃ while stirring after the materials are uniformly dissolved and dispersed, and keeping the temperature for 6 hours to obtain the adhesion promoter.
(3) Pretreatment of film forming liquid on metal surface: 1 part by weight of basic film forming material, 0.5 part by weight of adhesion promoter, 2 parts by weight of auxiliary film forming material zirconium nitrate, 0.2 part by weight of promoter hydroxylamine sulfate, 0.1 part by weight of complexing agent EDTA disodium and 96.2 parts by weight of water; and (3) uniformly mixing the materials, and regulating the pH value of the solution to 5 to obtain the metal surface pretreatment film-forming solution.
(4) Application of film forming liquid for pretreatment of metal surface:
s1, placing a galvanized sheet sample in the prepared degreasing fluid, dipping for 8min, and washing with water to form a uniform water film;
s2, immersing the galvanized sheet sample cleaned and cleaned in the step S1 in a film forming liquid for 4min;
And S3, taking out the galvanized sheet sample treated in the step S2, washing with pure water, and drying or naturally drying to obtain the galvanized sheet with the pretreated surface.
Example 3
A metal surface pretreatment film-forming liquid and a preparation method thereof specifically comprise the following steps:
(1) Base film-forming material: 10 parts by mass of rice bran extract, 5 parts by mass of PVB (molecular weight 2000, alcoholysis degree 88%) and 85 parts by mass of water; sequentially adding the rice bran extract, PVB and water into a reaction kettle, stirring vigorously, and heating while stirring after the materials are dissolved and dispersed uniformly, and keeping the temperature for 10 hours when the temperature is 85 ℃ to obtain the basic film-forming material.
(2) Adhesion promoters: 3 parts by mass of 3-aminopropyl triethoxysilane, 1 part by mass of gamma-aminoethyl aminopropyl trimethoxysilane, 0.1 part by mass of catalyst acetic acid and 95.9 parts by mass of water; adding water, catalyst acetic acid, 3-aminopropyl triethoxysilane and gamma-aminoethyl aminopropyl trimethoxysilane into a reaction kettle in sequence, slowly stirring, heating to 70 ℃ while stirring after the materials are dissolved and dispersed uniformly, and keeping the temperature for 3 hours to obtain the adhesion promoter.
(3) Pretreatment of film forming liquid on metal surface: 10 parts of basic film forming material, 2 parts of adhesion promoter, 1 part of auxiliary film forming material aluminum nitrate, 1 part of promoter sodium nitrate, 0.5 part of complexing agent oxalic acid and 85.5 parts of water; and mixing the materials uniformly to obtain the metal surface pretreatment film forming liquid.
Example 4
A metal surface pretreatment film-forming liquid and a preparation method thereof specifically comprise the following steps:
(1) Base film-forming material: 20 parts by weight of rice bran extract, 17881 parts by weight of PVA and 79 parts by weight of water; sequentially adding the rice bran extract, PVA1788 and water into a reaction kettle, stirring vigorously, heating while stirring after the materials are dissolved and dispersed uniformly, and keeping the temperature at 75 ℃ for 12 hours to obtain the basic film-forming material.
(2) Adhesion promoters: 3 parts by mass of gamma- (2, 3-glycidoxy) propyl trimethoxysilane, 1 part by mass of 3- (trimethoxysilyl) propyl methacrylate, 0.2 part by mass of catalyst nitric acid and 95.8 parts by mass of water; adding water, catalyst nitric acid, gamma- (2, 3-glycidoxy) propyl trimethoxy silane and methacrylic acid-3- (trimethoxysilyl) propyl ester into a reaction kettle in sequence, slowly stirring, heating to 60 ℃ while stirring after the components are uniformly dissolved and dispersed, and keeping the temperature constant for 5 hours to obtain the adhesion promoter.
(3) Pretreatment of film forming liquid on metal surface: 5 parts of basic film forming material, 1 part of adhesion promoter, 3 parts of auxiliary film forming material manganese nitrate, 2 parts of promoter sodium chlorate, 0.3 part of complexing tartaric acid and 88.7 parts of water; and mixing the materials uniformly to obtain the metal surface pretreatment film forming liquid.
Test example 1
The performance and appearance of the cold rolled sheet sample and the galvanized sheet sample treated with the film forming liquid prepared in examples 1-2 were observed as follows:
as shown in fig. 1, a uniform blue biomass conversion film layer can be formed on the surface of the cold-rolled sheet material; as shown in fig. 2, a uniform yellowish conversion coating layer can be formed on the surface of the galvanized sheet material.
Test example 2
The film adhesion experiments of the cold-rolled sheet sample and the galvanized sheet sample prepared in the examples 1-2 after the film forming liquid treatment are carried out, and the test items and the results are as follows:
(1) And (3) plastic spraying hundred grid test: and (3) carrying out electrostatic plastic spraying coating on the plate sample treated by the film forming liquid, and testing the paint film by using a hundred grid plotter to obtain the adhesive force grade which can reach zero level.
(2) And (3) performing hammering test on the plastic powder heavy hammer: and (3) carrying out impact resistance test on the plate sample treated by the film forming liquid with a force of 80N/cm 2, wherein a paint film has no crack trace.
(3) Neutral salt spray experiment: and (3) after the plate sample treated by the film forming liquid is subjected to electrostatic plastic spraying and coating, the scribing fork is broken, the plate sample is placed in a neutral salt spray test box for 700 hours, and the scribing edge is mechanically stripped by a craft knife, wherein the single-side wide extension is smaller than 1mm.
(4) And (3) testing the neutral salt spray of the electrophoretic paint coating: and (3) carrying out the electro-coating on the plate sample treated by the film forming liquid by using an electro-coating method, marking and breaking, placing the plate sample in a neutral salt spray test box for 1000 hours, and mechanically stripping the marked edge by using an art designer knife, wherein the single-side wide extension is smaller than 2mm.
Test example 3
Copper sulfate drip experiments were performed on cold-rolled sheet samples and galvanized sheet samples treated with the film forming liquid prepared in examples 1-2: preparing a copper sulfate solution according to national standards: 13mL/L, 0.1mol/L HCl, 41g/LCuSO 4·5H2 O, 35g/LNaCl.
The copper sulfate titration resistant time of the plate sample treated by the film forming liquid is respectively as follows: and the copper sulfate drop test is far superior to other similar products in 100s and 150 s.
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 (4)
1. The metal surface pretreatment film forming liquid is characterized by comprising the following components in percentage by mass: 1-10% of basic film forming material, 0.5-2% of adhesion promoter, 0.3-3% of auxiliary film forming material, 0.2-2% of promoter, 0.1-0.5% of complexing agent and the balance of water; the auxiliary film forming material is one or more of tungstate, metavanadate, zirconium fluoride, zirconium nitrate, zinc oxide, molybdate, vanadate, fluotitanic acid, fluozirconic acid, ammonium fluozirconate, manganese nitrate, cerium nitrate, aluminum nitrate, magnesium nitrate and ammonium fluotitanate; the promoter is one or more of hydroxylamine sulfate, sodium chlorate, potassium permanganate, hydrogen peroxide and nitrate; the complexing agent is one or more of sodium fluoride, potassium fluoride, tartaric acid, citric acid, EDTA disodium, malic acid, oxalic acid and acetic acid;
the basic film forming material comprises the following components in percentage by mass: 0.1-20% of plant extract, 0.1-10% of cross-linking agent and the balance of water; the plant extract is one or more of phytic acid, tannic acid and tannic acid; the cross-linking agent is one or more of polyvinyl alcohol, polyvinyl acetal Ding Quanzhi and polyethylene glycol; the preparation method of the basic film-forming material comprises the following steps: uniformly mixing the plant extract, the cross-linking agent and water, and heating to 60-100 ℃ to react for 5-20h to obtain the basic film-forming material;
The adhesion promoter comprises the following components in percentage by mass: 0.1-10% of silane coupling agent, 0.05-10% of catalyst and the balance of water; the preparation method of the adhesion promoter comprises the following steps: reacting the silane coupling agent solution for 0.5-30 hours at the temperature of 5-90 ℃ under the action of a catalyst to obtain the adhesion promoter; the catalyst is acetic acid and/or nitric acid.
2. The metal surface pretreatment film-forming liquid according to claim 1, wherein the polyvinyl alcohol and polyvinyl alcohol Ding Quanzhi have molecular weights of 1000 to 3000; the molecular weight of the polyethylene glycol is 200-1000; the acetalization degree of the polyvinyl alcohol Ding Quanzhi is 68-88%.
3. The metal surface pretreatment film-forming liquid according to claim 1, wherein the silane coupling agent is one or more of 3-glycidyl propyl trimethoxy coupling agent, aminopropyl trimethoxy silane coupling agent, γ - (2, 3-glycidoxy) propyl trimethoxy silane, 3-aminopropyl triethoxy silane, γ -aminoethylaminopropyl trimethoxy silane, and 3- (trimethoxysilyl) propyl methacrylate.
4. Use of a metal surface pretreatment film forming liquid according to any one of claims 1 to 3 in the treatment of a metal substrate, characterized in that: degreasing the metal substrate, washing with water, soaking in the film forming liquid for 0.5-30min, taking out, washing with water, and drying to obtain the surface pretreated metal substrate.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017000315A1 (en) * | 2015-07-02 | 2017-01-05 | 许昌学院 | Titanium-zirconium coloured chromium-free passivation solution for surface treatment of aluminium alloy, method for treating aluminium alloy surface using same, and use thereof |
| CN106906462A (en) * | 2017-02-15 | 2017-06-30 | 武汉大学 | A kind of metal surface pretreating reagent and preparation method thereof, application |
| CN111534815A (en) * | 2020-05-22 | 2020-08-14 | 山东大学 | Pretreatment liquid capable of forming washable natural color conversion film on metal surface and preparation method thereof |
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| US7867570B2 (en) * | 2006-10-26 | 2011-01-11 | Basf Coatings Gmbh | Method of producing a coating having metal coordinating and film-forming materials |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017000315A1 (en) * | 2015-07-02 | 2017-01-05 | 许昌学院 | Titanium-zirconium coloured chromium-free passivation solution for surface treatment of aluminium alloy, method for treating aluminium alloy surface using same, and use thereof |
| CN106906462A (en) * | 2017-02-15 | 2017-06-30 | 武汉大学 | A kind of metal surface pretreating reagent and preparation method thereof, application |
| CN111534815A (en) * | 2020-05-22 | 2020-08-14 | 山东大学 | Pretreatment liquid capable of forming washable natural color conversion film on metal surface and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 黄文润.硅烷偶联剂及硅树脂.四川科学技术出版社,第96页. * |
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