CN109504238B - Single-component self-curing chromium-free zinc-aluminum anticorrosive paint and preparation and application thereof - Google Patents
Single-component self-curing chromium-free zinc-aluminum anticorrosive paint and preparation and application thereof Download PDFInfo
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- CN109504238B CN109504238B CN201811406872.2A CN201811406872A CN109504238B CN 109504238 B CN109504238 B CN 109504238B CN 201811406872 A CN201811406872 A CN 201811406872A CN 109504238 B CN109504238 B CN 109504238B
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- 229910000611 Zinc aluminium Inorganic materials 0.000 title claims abstract description 50
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000003973 paint Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003822 epoxy resin Substances 0.000 claims abstract description 55
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 55
- 238000000576 coating method Methods 0.000 claims abstract description 52
- 239000011248 coating agent Substances 0.000 claims abstract description 49
- 238000003756 stirring Methods 0.000 claims abstract description 46
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 13
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 13
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 10
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 10
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 10
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 7
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000003085 diluting agent Substances 0.000 claims abstract description 5
- 239000000080 wetting agent Substances 0.000 claims abstract description 5
- 239000007822 coupling agent Substances 0.000 claims abstract description 3
- 238000007865 diluting Methods 0.000 claims abstract description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 32
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 9
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000005536 corrosion prevention Methods 0.000 claims description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 9
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 9
- 238000010998 test method Methods 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- AIXMJTYHQHQJLU-UHFFFAOYSA-N chembl210858 Chemical compound O1C(CC(=O)OC)CC(C=2C=CC(O)=CC=2)=N1 AIXMJTYHQHQJLU-UHFFFAOYSA-N 0.000 description 7
- 239000012895 dilution Substances 0.000 description 7
- 238000010790 dilution Methods 0.000 description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000005028 tinplate Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 210000001015 abdomen Anatomy 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/103—Anti-corrosive paints containing metal dust containing Al
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—Aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0893—Zinc
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to the technical field of metal surface anticorrosion treatment, and discloses a single-component self-curing chromium-free zinc-aluminum anticorrosive paint, and preparation and application thereof. Diluting epoxy resin with a solvent, adding an aminosilane coupling agent, stirring at 60-90 ℃ for reaction, cooling, adding a silica sol and ammonium molybdate, and stirring and mixing at 45-70 ℃ to obtain a modified epoxy resin complex liquid; and uniformly dispersing zinc powder and aluminum powder in a metal powder wetting agent and a diluent, then adding the modified epoxy resin composite liquid, and uniformly stirring and mixing to obtain the single-component self-curing chromium-free zinc-aluminum anticorrosive paint. And coating the obtained anticorrosive paint on a metal substrate, and curing to obtain the chromium-free zinc-aluminum anticorrosive paint. The invention has the advantages of simple raw materials, easy operation of preparation process, no need of adding an epoxy resin curing agent, self-curing of the coating, convenient use, excellent mechanical property of the cured coating, inorganic corrosion resistance and organic corrosion resistance, and excellent corrosion resistance.
Description
Technical Field
The invention belongs to the technical field of metal surface anticorrosion treatment, and particularly relates to a single-component self-curing chromium-free zinc-aluminum anticorrosive paint, and preparation and application thereof.
Background
The dacromet technology is characterized in that flaky zinc powder, aluminum powder, chromic anhydride, a solvent and other additives are mixed and then uniformly coated on the surface of a workpiece, and then the mixture is cured at 300 ℃ to obtain a coating with anti-corrosion capability, and the coating is widely applied to the fields of automobiles, electric power, oil refining, machinery and the like. Compared with the traditional zinc electroplating layer by using an anticorrosion technology, the zinc electroplating layer overcomes the problems of no need of acid and alkali (plating solution), no hydrogen embrittlement, excellent heat resistance, better recoating capability and secondary and tertiary coating. More importantly, the corrosion resistance is greatly improved, the salt spray test time of the salt spray is greatly increased and is 7-10 times of that of the electrogalvanizing, and the price of the salt spray is equivalent to that of the electrogalvanizing. However, Cr6+Are highly toxic and carcinogenic, and their use is increasingly under strict control. At present, most of zinc-aluminum anticorrosive paint products are two-component, so that certain inconvenience is caused to construction. Therefore, the development of the single-component self-curing chromium-free zinc-aluminum anticorrosive paint and the coating has important significance.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a preparation method of a single-component self-curing chromium-free zinc-aluminum anticorrosive paint.
The invention also aims to provide the one-component self-curing chromium-free zinc-aluminum anticorrosive paint prepared by the method.
The invention also aims to provide the application of the single-component self-curing chromium-free zinc-aluminum anticorrosive paint in metal substrate corrosion prevention.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a single-component self-curing chromium-free zinc-aluminum anticorrosive paint comprises the following preparation steps:
(1) diluting 30-40 parts by mass of epoxy resin with 5-10 parts by mass of solvent, adding 0.5-1 part by mass of aminosilane coupling agent, stirring and reacting for 2-5 h at 60-90 ℃, cooling, adding 0.5-2 parts by mass of silica sol and 0.5-3 parts by mass of ammonium molybdate, stirring and mixing for 2-6 h at 45-70 ℃, and naturally cooling to obtain modified epoxy resin complex liquid;
(2) uniformly dispersing 20-35 parts by mass of zinc powder and 1-12 parts by mass of aluminum powder in 10-30 parts by mass of metal powder wetting agent and 1-10 parts by mass of diluent, adding 25-40 parts by mass of modified epoxy resin composite liquid, and uniformly stirring and mixing to obtain the single-component self-curing chromium-free zinc-aluminum anticorrosive coating.
Preferably, the epoxy resin in the step (1) refers to epoxy resin E-44 (with an epoxy value of 0.44); the solvent is n-butanol; the amino silane coupling agent is 3-aminopropyl triethoxysilane.
Preferably, the silica sol in step (1) is prepared by the following steps: adding tetraethoxysilane into absolute ethyl alcohol, then adding a mixed solution prepared from the absolute ethyl alcohol, deionized water and concentrated acid, uniformly stirring, and aging for 2 hours to 4 days to obtain the silicon dioxide sol. Further, the volume ratio of the ethyl orthosilicate to the absolute ethyl alcohol is (5-20) to (10-70); the volume ratio of the absolute ethyl alcohol to the deionized water to the concentrated acid in the mixed solution is (5-40): 1-15): 0.1-3; the concentrated acid is at least one of concentrated hydrochloric acid with the mass fraction of 35%, concentrated sulfuric acid with the mass fraction of 98% and concentrated nitric acid with the mass fraction of 65%.
Preferably, the zinc powder in the step (2) is flaky zinc powder with a flake diameter of 10-15 microns and a thickness of 0.1-0.2 microns.
Preferably, the aluminum powder in the step (2) is scaly aluminum powder with a flake diameter of 10-12 microns and a thickness of 0.1-0.2 microns.
Preferably, the metal powder wetting agent in the step (2) is at least one of ethyl acetate, butyl methacrylate and dioctyl phthalate.
Preferably, the diluent in the step (2) is at least one of 1, 2-propylene glycol methyl ether, isooctanol and n-butanol.
A single-component self-curing chromium-free zinc-aluminum anticorrosive paint is prepared by the method.
The single-component self-curing chromium-free zinc-aluminum anticorrosive paint is applied to corrosion prevention of metal substrates.
Preferably, the application process is as follows: coating the single-component self-curing chromium-free zinc-aluminum anticorrosive coating on a metal substrate, and baking at 180-250 ℃ for 30-60 min for curing to obtain the chromium-free zinc-aluminum anticorrosive coating.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention has simple raw materials, selects single organic resin, has easy operation of preparation process, can stably store the single-component coating liquid, does not need to add an epoxy resin curing agent, can self-cure the coating at high temperature and has convenient use.
(2) Compared with the traditional Dacromet coating and some water-based chromium-free Dacromet coatings, the coating curing temperature is low, and the energy consumption is saved.
(3) According to the invention, the silica sol and the aminosilane modified epoxy resin are selected, so that the epoxy resin is toughened and enhanced, the coating adhesion is provided, and the cured coating has excellent mechanical properties.
(4) The modified epoxy resin prepared by the invention forms an organic-inorganic composite network after being cured, and the coating has the characteristics of inorganic corrosion resistance and organic corrosion resistance and excellent corrosion resistance.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The single-component self-curing chromium-free zinc-aluminum anticorrosive paint and the coating are prepared by the following method:
(1) adding 10 unit volume of ethyl orthosilicate into 40 unit volume of absolute ethyl alcohol, slowly adding a mixed solution prepared from 20 unit volume of absolute ethyl alcohol, 2 unit volume of deionized water and 0.8 unit volume of concentrated nitric acid (65% mass fraction), uniformly stirring, and aging for 2 hours to prepare silicon dioxide sol;
(2) adding 7 parts by mass of n-butyl alcohol into 30 parts by mass of epoxy resin E-44 (the epoxy value is 0.44) for dilution, adding 0.6 part by mass of 3-aminopropyltriethoxysilane, stirring and reacting for 2 hours at 80 ℃, cooling for standby application, then adding 1 part by mass of silica sol and 2 parts by mass of ammonium molybdate into the amino modified epoxy resin, stirring and mixing for 2 hours at 55 ℃, and naturally cooling to obtain a modified epoxy resin complex liquid;
(3) dispersing 33 parts by mass of flaky zinc powder (with the sheet diameter of 10-15 micrometers and the thickness of 0.1-0.2 micrometer) and 7 parts by mass of flaky aluminum powder (with the sheet diameter of 10-12 micrometers and the thickness of 0.1-0.2 micrometer) in 20 parts by mass of ethyl acetate and 7 parts by mass of 1, 2-propylene glycol methyl ether, uniformly stirring, adding 33 parts by mass of prepared modified epoxy resin composite liquid into the metal powder dispersion liquid, and uniformly mixing the modified epoxy resin composite liquid and the metal powder dispersion liquid by stirring to obtain the single-component self-curing chromium-free zinc-aluminum anticorrosive paint containing the modified epoxy resin;
(4) the prepared single-component self-curing chromium-free zinc-aluminum anticorrosive coating is coated on a tinplate (12cm multiplied by 5cm multiplied by 0.28cm), and is baked at 200 ℃ for 40min for curing to obtain the chromium-free zinc-aluminum anticorrosive coating. The tinplate is polished by 500# abrasive paper, washed clean by clear water and dried to remove surface grease.
In order to determine the hardness of the prepared chromium-free zinc-aluminum anticorrosive coating, the method of ASTM D3363-05 is adopted for determination. The procedure for the determination was as follows: the tinplate coated with the coating to be tested is placed horizontally, the wooden pencil is polished smoothly, and from the hardest pencil, the pencil is fixed by using a coating pencil hardness tester, so that the pencil and the test coating form a 45-degree angle and point to the direction opposite to that of an experimenter. The tester is pushed away from the experimenter by fingertips on the side surface of the tester. The test hardness was gradually decreased until a pencil lead was found that neither pierced nor scratched the coating surface within a distance of 3 mm.
In order to determine the adhesion of the prepared chromium-free zinc-aluminum anticorrosive coating, the adhesion is determined by using the method of ASTM D3359-08 (ISO 2409-2007). The test procedure was as follows: and cutting 11 mutually parallel cutting marks with the interval of 1mm on the coating by using a paint film scriber, and then vertically cutting the cutting marks with the same number and the same interval as the cutting marks on the coating to form the grids. After cutting, the chips are lightly brushed away along the directions of the two diagonal lines of the square by using a soft brush. A3M scotch tape was glued to the grid parallel to the score line, rubbed flat with the finger abdomen, and allowed to vent air bubbles. Grasping one end of the adhesive tape, tearing within 0.5-1.0s at an angle close to 60 degrees, and detecting the state of the cutting part.
In order to evaluate the corrosion resistance of the prepared chromium-free zinc-aluminum anticorrosive coating, rapid test of ammonium nitrate resistance is selected. The test procedure was as follows: heating 20% ammonium nitrate solution by mass fraction to 70 +/-5 ℃ in water bath. The tinplate pieces coated with the test coatings were immersed in the ammonium nitrate solution and suspended for fixation. The operation avoids the contact between the sample and between the sample and the wall of the beaker. During the test, the temperature of the ammonium nitrate solution was controlled to 70 + -1 deg.C.
In order to determine the salt spray time of the prepared chromium-free zinc-aluminum anticorrosive coating, GB6458-86 metal covering layer-neutral salt spray test (NSS test) is adopted for determination. The test procedure was as follows: the sample plates are exposed in a salt spray test box with the temperature of 35 +/-2 ℃, the surface to be tested faces upwards, the exposure angle of each sample plate in the box and the vertical included angle form 20 +/-5 degrees (the sample plates are not contacted with each other and are not contacted with the box body), atomized sodium chloride solution is sprayed in during the experiment, the sample plates are inspected for 1 time within 48 hours, the sample plates are inspected for 1 time within 2 times within 72 hours until the sample plates have corrosion traces, and the time is recorded.
Example 2
The single-component self-curing chromium-free zinc-aluminum anticorrosive paint and the coating are prepared by the following method:
(1) adding 10 unit volume of ethyl orthosilicate into 40 unit volume of absolute ethyl alcohol, slowly adding a mixed solution prepared from 20 unit volume of absolute ethyl alcohol, 2 unit volume of deionized water and 0.8 unit volume of concentrated nitric acid (65% mass fraction), uniformly stirring, and aging for 2 hours to prepare silicon dioxide sol;
(2) adding 7 parts by mass of n-butyl alcohol into 30 parts by mass of epoxy resin E-44 (the epoxy value is 0.44) for dilution, adding 0.6 part by mass of 3-aminopropyltriethoxysilane, stirring and reacting for 2 hours at 80 ℃, cooling for standby application, then adding 1 part by mass of silica sol and 2 parts by mass of ammonium molybdate into the amino modified epoxy resin, stirring and mixing for 2 hours at 55 ℃, and naturally cooling to obtain a modified epoxy resin complex liquid;
(3) dispersing 30 parts by mass of flaky zinc powder (with the sheet diameter of 10-15 micrometers and the thickness of 0.1-0.2 micrometer) and 10 parts by mass of flaky aluminum powder (with the sheet diameter of 10-12 micrometers and the thickness of 0.1-0.2 micrometer) in 15 parts by mass of ethyl acetate, 5 parts by mass of butyl methacrylate and 10 parts by mass of 1, 2-propylene glycol methyl ether, uniformly stirring, adding 30 parts by mass of prepared modified epoxy resin composite liquid into the metal powder dispersion liquid, and uniformly stirring to mix the two to obtain the single-component self-curing chromium-free zinc-aluminum anticorrosive paint containing the modified epoxy resin;
(4) the preparation method and test method of the anticorrosive coating of this example were the same as those of example 1.
Example 3
The single-component self-curing chromium-free zinc-aluminum anticorrosive paint and the coating are prepared by the following method:
(1) adding 10 unit volume of ethyl orthosilicate into 40 unit volume of absolute ethyl alcohol, slowly adding a mixed solution prepared from 20 unit volume of absolute ethyl alcohol, 2 unit volume of deionized water and 0.8 unit volume of concentrated nitric acid (65% mass fraction), uniformly stirring, and aging for 2 hours to prepare silicon dioxide sol;
(2) adding 7 parts by mass of n-butyl alcohol into 30 parts by mass of epoxy resin E-44 (the epoxy value is 0.44) for dilution, adding 0.6 part by mass of 3-aminopropyltriethoxysilane, stirring and reacting for 2 hours at 80 ℃, cooling for standby application, then adding 1 part by mass of silica sol and 2 parts by mass of ammonium molybdate into the amino modified epoxy resin, stirring and mixing for 2 hours at 55 ℃, and naturally cooling to obtain a modified epoxy resin complex liquid;
(3) dispersing 30 parts by mass of flaky zinc powder (with the sheet diameter of 10-15 micrometers and the thickness of 0.1-0.2 micrometer) and 10 parts by mass of flaky aluminum powder (with the sheet diameter of 10-12 micrometers and the thickness of 0.1-0.2 micrometer) in 15 parts by mass of ethyl acetate, 5 parts by mass of dioctyl phthalate, 5 parts by mass of 1, 2-propylene glycol methyl ether and 5 parts by mass of n-butyl alcohol, uniformly stirring, adding 30 parts by mass of prepared modified epoxy resin composite liquid into the metal powder dispersion liquid, and uniformly stirring to mix the two to obtain the single-component self-curing chromium-free zinc-aluminum anticorrosive paint containing the modified epoxy resin;
(4) the preparation method and test method of the anticorrosive coating of this example were the same as those of example 1.
Example 4
The single-component self-curing chromium-free zinc-aluminum anticorrosive paint and the coating are prepared by the following method:
(1) adding 10 unit volume of ethyl orthosilicate into 40 unit volume of absolute ethyl alcohol, slowly adding a mixed solution prepared from 20 unit volume of absolute ethyl alcohol, 2 unit volume of deionized water and 0.8 unit volume of concentrated nitric acid (65% mass fraction), uniformly stirring, and aging for 2 hours to prepare silicon dioxide sol;
(2) adding 7 parts by mass of n-butyl alcohol into 30 parts by mass of epoxy resin E-44 (the epoxy value is 0.44) for dilution, adding 0.6 part by mass of 3-aminopropyltriethoxysilane, stirring and reacting for 2 hours at 80 ℃, cooling for standby application, then adding 1 part by mass of silica sol and 2 parts by mass of ammonium molybdate into the amino modified epoxy resin, stirring and mixing for 2 hours at 55 ℃, and naturally cooling to obtain a modified epoxy resin complex liquid;
(3) dispersing 28 parts by mass of flaky zinc powder (with the sheet diameter of 10-15 micrometers and the thickness of 0.1-0.2 micrometer) and 12 parts by mass of flaky aluminum powder (with the sheet diameter of 10-12 micrometers and the thickness of 0.1-0.2 micrometer) in 25 parts by mass of ethyl acetate and 10 parts by mass of 1, 2-propylene glycol methyl ether, uniformly stirring, adding the prepared 25 parts by mass of modified epoxy resin composite liquid into the metal powder dispersion liquid, and uniformly mixing the two through stirring to obtain the single-component self-curing chromium-free zinc-aluminum anticorrosive paint containing the modified epoxy resin;
(4) the preparation method and test method of the anticorrosive coating of this example were the same as those of example 1.
Example 5
The single-component self-curing chromium-free zinc-aluminum anticorrosive paint and the coating are prepared by the following method:
(1) adding 10 unit volume of ethyl orthosilicate into 40 unit volume of absolute ethyl alcohol, slowly adding a mixed solution prepared from 20 unit volume of absolute ethyl alcohol, 2 unit volume of deionized water and 0.8 unit volume of concentrated nitric acid (65% mass fraction), uniformly stirring, and aging for 2 hours to prepare silicon dioxide sol;
(2) adding 7 parts by mass of n-butyl alcohol into 30 parts by mass of epoxy resin E-44 (the epoxy value is 0.44) for dilution, adding 0.6 part by mass of 3-aminopropyltriethoxysilane, stirring and reacting for 2 hours at 80 ℃, cooling for standby application, then adding 2 parts by mass of silica sol and 2 parts by mass of ammonium molybdate into the amino modified epoxy resin, stirring and mixing for 4 hours at 65 ℃, and naturally cooling to obtain a modified epoxy resin complex liquid;
(3) dispersing 33 parts by mass of flaky zinc powder (with the sheet diameter of 10-15 micrometers and the thickness of 0.1-0.2 micrometer) and 7 parts by mass of flaky aluminum powder (with the sheet diameter of 10-12 micrometers and the thickness of 0.1-0.2 micrometer) in 20 parts by mass of ethyl acetate and 10 parts by mass of 1, 2-propylene glycol methyl ether, uniformly stirring, adding 30 parts by mass of prepared modified epoxy resin composite liquid into the metal powder dispersion liquid, and uniformly mixing the two through stirring to obtain the single-component self-curing chromium-free zinc-aluminum anticorrosive paint containing the modified epoxy resin;
(4) the preparation method and test method of the anticorrosive coating of this example were the same as those of example 1.
Example 6
The single-component self-curing chromium-free zinc-aluminum anticorrosive paint and the coating are prepared by the following method:
(1) adding 10 unit volume of ethyl orthosilicate into 40 unit volume of absolute ethyl alcohol, slowly adding a mixed solution prepared from 20 unit volume of absolute ethyl alcohol, 2 unit volume of deionized water and 0.8 unit volume of concentrated nitric acid (65% mass fraction), uniformly stirring, and aging for 2 hours to prepare silicon dioxide sol;
(2) adding 7 parts by mass of n-butyl alcohol into 30 parts by mass of epoxy resin E-44 (the epoxy value is 0.44) for dilution, adding 0.6 part by mass of 3-aminopropyltriethoxysilane, stirring and reacting for 2 hours at 80 ℃, cooling for standby application, then adding 2 parts by mass of silica sol and 1 part by mass of ammonium molybdate into the amino modified epoxy resin, stirring and mixing for 2 hours at 65 ℃, and naturally cooling to obtain a modified epoxy resin complex liquid;
(3) dispersing 30 parts by mass of flaky zinc powder (with the sheet diameter of 10-15 micrometers and the thickness of 0.1-0.2 micrometer) and 10 parts by mass of flaky aluminum powder (with the sheet diameter of 10-12 micrometers and the thickness of 0.1-0.2 micrometer) in 10 parts by mass of ethyl acetate, 10 parts by mass of butyl methacrylate and 10 parts by mass of 1, 2-propylene glycol methyl ether, uniformly stirring, adding 30 parts by mass of prepared modified epoxy resin composite liquid into the metal powder dispersion liquid, and uniformly stirring to mix the two to obtain the single-component self-curing chromium-free zinc-aluminum anticorrosive paint containing the modified epoxy resin;
(4) the preparation method and test method of the anticorrosive coating of this example were the same as those of example 1.
Example 7
The single-component self-curing chromium-free zinc-aluminum anticorrosive paint and the coating are prepared by the following method:
(1) adding 10 unit volume of ethyl orthosilicate into 40 unit volume of absolute ethyl alcohol, slowly adding a mixed solution prepared from 20 unit volume of absolute ethyl alcohol, 2 unit volume of deionized water and 0.8 unit volume of concentrated nitric acid (65% mass fraction), uniformly stirring, and aging for 2 hours to prepare silicon dioxide sol;
(2) adding 7 parts by mass of n-butyl alcohol into 30 parts by mass of epoxy resin E-44 (the epoxy value is 0.44) for dilution, adding 0.9 part by mass of 3-aminopropyltriethoxysilane, stirring and reacting for 3 hours at 80 ℃, cooling for standby application, then adding 2 parts by mass of silica sol and 2 parts by mass of ammonium molybdate into the amino modified epoxy resin, stirring and mixing for 4 hours at 65 ℃, and naturally cooling to obtain a modified epoxy resin complex liquid;
(3) dispersing 30 parts by mass of flaky zinc powder (with the sheet diameter of 10-15 micrometers and the thickness of 0.1-0.2 micrometer) and 10 parts by mass of flaky aluminum powder (with the sheet diameter of 10-12 micrometers and the thickness of 0.1-0.2 micrometer) in 10 parts by mass of ethyl acetate and 10 parts by mass of 1, 2-propylene glycol methyl ether, uniformly stirring, adding 40 parts by mass of prepared modified epoxy resin composite liquid into the metal powder dispersion liquid, and uniformly mixing the modified epoxy resin composite liquid and the metal powder dispersion liquid by stirring to obtain the single-component self-curing chromium-free zinc-aluminum anticorrosive paint containing the modified epoxy resin;
(4) the preparation method and test method of the anticorrosive coating of this example were the same as those of example 1.
The main performance indicators achievable with the coatings tested in the above examples are shown in table 1:
TABLE 1
Examples | Hardness of | Adhesion force | Rapid test for ammonium nitrate resistance | Neutral salt spray test |
1 | 4H | ISO 1 | >3.5h | >1000h |
2 | 3H | ISO 1 | >3.5h | >1200h |
3 | 3H | ISO 1 | >3.5h | >1200h |
4 | 3H | ISO 1 | >3.5h | >1000h |
5 | 4H | ISO 1 | >3.5h | >1200h |
6 | 4H | ISO 1 | >3.5h | >1400h |
7 | 4H | ISO 1 | >3.5h | >1400h |
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a single-component self-curing chromium-free zinc-aluminum anticorrosive paint is characterized by comprising the following preparation steps:
(1) diluting 30-40 parts by mass of epoxy resin with 5-10 parts by mass of solvent, adding 0.5-1 part by mass of aminosilane coupling agent, stirring and reacting for 2-5 h at 60-90 ℃, cooling, adding 0.5-2 parts by mass of silica sol and 0.5-3 parts by mass of ammonium molybdate, stirring and mixing for 2-6 h at 45-70 ℃, and naturally cooling to obtain modified epoxy resin complex liquid;
(2) uniformly dispersing 20-35 parts by mass of zinc powder and 1-12 parts by mass of aluminum powder in 10-30 parts by mass of metal powder wetting agent and 1-10 parts by mass of diluent, adding 25-40 parts by mass of modified epoxy resin composite liquid, and uniformly stirring and mixing to obtain the single-component self-curing chromium-free zinc-aluminum anticorrosive coating.
2. The preparation method of the one-component self-curing chromium-free zinc-aluminum anticorrosive paint according to claim 1, characterized in that: the epoxy resin in the step (1) is epoxy resin E-44; the solvent is n-butanol; the amino silane coupling agent is 3-aminopropyl triethoxysilane.
3. The preparation method of the one-component self-curing chromium-free zinc-aluminum anticorrosive paint according to claim 1, wherein the silica sol in the step (1) is prepared by the following steps: adding tetraethoxysilane into absolute ethyl alcohol, then adding a mixed solution prepared from the absolute ethyl alcohol, deionized water and concentrated acid, uniformly stirring, and aging for 2 hours to 4 days to obtain the silicon dioxide sol.
4. The preparation method of the one-component self-curing chromium-free zinc-aluminum anticorrosive paint according to claim 3, characterized in that: the volume ratio of the ethyl orthosilicate to the absolute ethyl alcohol is (5-20) to (10-70); the volume ratio of the absolute ethyl alcohol to the deionized water to the concentrated acid in the mixed solution is (5-40): 1-15): 0.1-3; the concentrated acid is at least one of concentrated hydrochloric acid with the mass fraction of 35%, concentrated sulfuric acid with the mass fraction of 98% and concentrated nitric acid with the mass fraction of 65%.
5. The preparation method of the one-component self-curing chromium-free zinc-aluminum anticorrosive paint according to claim 1, characterized in that: the zinc powder in the step (2) is flaky zinc powder with the flake diameter of 10-15 microns and the thickness of 0.1-0.2 microns.
6. The preparation method of the one-component self-curing chromium-free zinc-aluminum anticorrosive paint according to claim 1, characterized in that: the aluminum powder in the step (2) is scaly aluminum powder with the flake diameter of 10-12 microns and the thickness of 0.1-0.2 microns.
7. The preparation method of the one-component self-curing chromium-free zinc-aluminum anticorrosive paint according to claim 1, characterized in that: in the step (2), the metal powder wetting agent is at least one of ethyl acetate, butyl methacrylate and dioctyl phthalate; the diluent is at least one of 1, 2-propylene glycol methyl ether, isooctanol and n-butanol.
8. A single-component self-curing chromium-free zinc-aluminum anticorrosive paint is characterized in that: prepared by the method of any one of claims 1 to 7.
9. The use of the one-component self-curing chromium-free zinc-aluminum anticorrosive coating of claim 8 in the corrosion prevention of metal substrates.
10. The application of the one-component self-curing chromium-free zinc-aluminum anticorrosive coating in metal substrate corrosion prevention according to claim 9 is characterized in that the application process comprises the following steps: coating the single-component self-curing chromium-free zinc-aluminum anticorrosive coating on a metal substrate, and baking at 180-250 ℃ for 30-60 min for curing to obtain the chromium-free zinc-aluminum anticorrosive coating.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101899254A (en) * | 2010-07-13 | 2010-12-01 | 襄樊普士利工程器材有限公司 | Chromium-free zinc aluminum anticorrosive paint and preparation method |
CN104558520A (en) * | 2014-10-25 | 2015-04-29 | 重庆市金渝管道设备有限公司 | Synthesis method of silica sol modified epoxy resin |
CN106147564A (en) * | 2015-04-05 | 2016-11-23 | 泉州市合创涂料科技有限公司 | A kind of preparation method of Chrome-free anticorrosive paint |
JP2018048332A (en) * | 2012-07-11 | 2018-03-29 | 大日本塗料株式会社 | Rust preventive coating material, rust preventive coating film, and rust preventive laminated coating film |
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KR101560929B1 (en) * | 2013-12-20 | 2015-10-15 | 주식회사 포스코 | Surface treatment composition for Zn coated steel sheet with excellent corrosion resistance, and surface treated Zn coated steel sheet using the same |
EP3207100A4 (en) * | 2014-10-16 | 2018-11-21 | Queen's University At Kingston | Anti-smudge and anti-graffiti compositions |
CN107964351B (en) * | 2017-09-28 | 2019-12-31 | 永星化工(上海)有限公司 | Water-based composite zinc-aluminum anticorrosive paint |
-
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101899254A (en) * | 2010-07-13 | 2010-12-01 | 襄樊普士利工程器材有限公司 | Chromium-free zinc aluminum anticorrosive paint and preparation method |
JP2018048332A (en) * | 2012-07-11 | 2018-03-29 | 大日本塗料株式会社 | Rust preventive coating material, rust preventive coating film, and rust preventive laminated coating film |
CN104558520A (en) * | 2014-10-25 | 2015-04-29 | 重庆市金渝管道设备有限公司 | Synthesis method of silica sol modified epoxy resin |
CN106147564A (en) * | 2015-04-05 | 2016-11-23 | 泉州市合创涂料科技有限公司 | A kind of preparation method of Chrome-free anticorrosive paint |
Non-Patent Citations (1)
Title |
---|
"硅溶胶改性环氧树脂E-44的合成及其涂料制备";张金昌等;《新型建筑材料》;20110331;第8-10和40页 * |
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