CN116904089A - Steel surface anticorrosive paint and preparation method and application thereof - Google Patents
Steel surface anticorrosive paint and preparation method and application thereof Download PDFInfo
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- CN116904089A CN116904089A CN202311036323.1A CN202311036323A CN116904089A CN 116904089 A CN116904089 A CN 116904089A CN 202311036323 A CN202311036323 A CN 202311036323A CN 116904089 A CN116904089 A CN 116904089A
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- steel surface
- anticorrosive paint
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 103
- 239000010959 steel Substances 0.000 title claims abstract description 103
- 239000003973 paint Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 77
- 239000011248 coating agent Substances 0.000 claims abstract description 74
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 39
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims abstract description 28
- 229910000165 zinc phosphate Inorganic materials 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 239000003822 epoxy resin Substances 0.000 claims abstract description 21
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 21
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 239000000945 filler Substances 0.000 claims abstract description 10
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 229910001868 water Inorganic materials 0.000 claims description 51
- 239000000843 powder Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 27
- 238000000227 grinding Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001723 curing Methods 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000010445 mica Substances 0.000 claims description 8
- 229910052618 mica group Inorganic materials 0.000 claims description 8
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 8
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 238000003618 dip coating Methods 0.000 claims description 4
- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 claims description 3
- 244000137852 Petrea volubilis Species 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 230000003746 surface roughness Effects 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 39
- 230000007797 corrosion Effects 0.000 abstract description 31
- 239000000853 adhesive Substances 0.000 abstract description 7
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 239000002105 nanoparticle Substances 0.000 abstract description 7
- 238000005054 agglomeration Methods 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 6
- 239000011247 coating layer Substances 0.000 abstract description 6
- 238000005536 corrosion prevention Methods 0.000 abstract description 4
- 238000009210 therapy by ultrasound Methods 0.000 abstract description 3
- 239000007769 metal material Substances 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 239000007822 coupling agent Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 17
- 238000005299 abrasion Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 229910021485 fumed silica Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 229920006334 epoxy coating Polymers 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- -1 modified phenolic amide Chemical class 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004210 cathodic protection Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000003204 osmotic effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000011527 polyurethane coating Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 239000012528 membrane Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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Classifications
-
- 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
-
- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses an anticorrosive paint for a steel surface, a preparation method and application thereof, and relates to the technical field of surface corrosion prevention of metal materials. According to the invention, epoxy resin is used as a main body of the anticorrosive paint, nano particles are added to increase the adhesive force of the paint, so that the compactness, wear resistance and antifriction of the structure are improved, in order to solve the problem of easy agglomeration, a coupling agent is added to carry out surface modification on nano cellulose, and stable dispersed modified nano cellulose is obtained after ultrasonic treatment; then zinc phosphate is added to form a uniform coating layer, so that the hardness of the coating layer is improved, and the contact between the steel surface and corrosive medium is prevented; finally adding an anti-settling agent, a filler, a leveling agent and a dispersing agent to obtain the steel surface anti-corrosion coating with good corrosion resistance, high adhesiveness and good wear resistance. The invention also provides an application of the steel surface anticorrosive paint, wherein the 4, 4-diaminodiphenyl methane curing agent is added into the steel surface anticorrosive paint in a weight ratio of 1:1, and the steel surface is coated with the coating with the thickness of 0.1-1mm.
Description
Technical Field
The invention relates to the technical field of surface corrosion prevention of metal materials, in particular to an anticorrosive paint for a steel surface, a preparation method and application thereof.
Background
The anticorrosive paint for steel surface is one capable of protecting steel surface from corrosion, isolating oxygen and water from contact with air or environment and blocking oxidation reaction and electrochemical reaction to avoid corrosion. The surface anticorrosive paint is widely applied to the industries of automobiles, ships, bridges, buildings, oil gas and the like so as to improve the durability and the safety of steel materials. In the field of corrosion protection coating of steel surfaces, various coating types such as epoxy coating, polyurethane coating, silicone coating, acrylic coating and the like have been developed at present, wherein the epoxy coating is the most widely applied coating type, has the characteristics of excellent corrosion resistance, wear resistance, adhesive force and the like, and has become a main stream coating in the field of corrosion protection coating of steel surfaces; meanwhile, with the continuous emergence of novel materials and technologies, such as nanotechnology, functional coating and the like, the development prospect of the field of corrosion-resistant coating of the steel surface is also wider and wider.
The paint has thousands of years history as simple, economical and effective anti-corrosion means, and the water-based anti-corrosion paint has the characteristics of relatively low toxicity, small smell, high construction and production safety and the like, and is more energy-saving and environment-friendly compared with a solvent-based paint system; the common water-based anticorrosive paint comprises a water-based acrylic paint, a water-based epoxy paint, a water-based inorganic zinc-rich paint, a water-based polyurethane paint and the like, wherein the water-based acrylic paint comprises the following components: the corrosion prevention mechanism mainly plays roles through two roles of physical isolation and chemical stabilization of a coating film. The coating can isolate the contact between the steel surface and the external environment, thereby reducing the chance of chemical reaction on the steel surface and preventing corrosion. The water-based acrylic coating utilizes the principle of crosslinking reaction between carboxyl and epoxy groups, and the coating is solidified on the surface of an object to form a layer of water-heat resistant, photoelectric and corrosion resistant protective film; the water-based epoxy paint plays a role in isolating the contact between the steel surface and the external environment through two effects of physical isolation and chemical reaction of a coating film, so that corrosion is prevented; the water-based inorganic zinc-rich coating plays a role in two roles of cathodic protection of zinc-rich particles and physical isolation of a coating film, and the zinc-rich particles can form a cathodic protection layer on the surface of the coating film and can effectively prevent corrosion of the surface of steel; the water-based polyurethane coating forms a coating after being solidified on the surface of a coated machine body, and the coating has the shielding effect of isolating the machine body from the environment so as not to be corroded, and preventing water, oxygen and the like from penetrating through the coating from the external environment to reach the steel interface, thereby playing a role in corrosion prevention.
CN105602401a discloses a water-based environment-friendly anion anticorrosive paint and a preparation method thereof, the formula of the invention comprises 20-40% of water-based epoxy resin emulsion, 10-20% of water-based polyurethane emulsion, 5-10% of water-based fluororesin emulsion, 10-15% of water-based nano anion slurry, 1-3% of water-based wetting dispersant, 0.1-1% of water-based defoamer, 1-3% of adhesion promoter, 5-10% of lead-free rust-proof pigment, 0.5-2.5% of antifouling agent, 5-10% of film forming auxiliary agent and 5-25% of deionized water. The paint product can be coated on the surfaces of base material components such as steel and the like to form effective anti-corrosion protection, has strong decoration, low energy consumption, negative ions release and long service life, can be widely used for materials in the fields of hardware steel structures, engineering machinery, locomotives, ships, road and bridge tunnels, sewage treatment, industrial terraces and the like, can form effective protection with strong sealing performance, corrosion resistance, abrasion scraping resistance, acid and alkali resistance and impact resistance on the base material, and can generate negative ions beneficial to the surrounding environment at the same time, and has remarkable effect.
CN112552779a discloses an environment-friendly low-surface-treatment aqueous epoxy thick slurry type acid-base resistant coating and a preparation method thereof, which can be used for corrosion resistant coatings in the fields of acid-base resistance, chemical medium resistance and the like of metal or steel materials in buildings under chemical environments. The coating consists of a component A and a component B according to the mass ratio of 4-8:1; wherein, the component A is composed of aqueous epoxy resin dispersoid, reactive diluent, pigment filler and auxiliary agent; the component B is a waterborne modified phenolic amide epoxy curing agent. Compared with the existing water-based paint, the environment-friendly low-surface-treatment water-based epoxy thick paste type acid-base resistant paint has low VOCs and high solid content, can be used for thick film coating of 200-300 mu m at one time, has good flexibility, strong cracking resistance, good adhesion to a base material, can be used for low-surface-treatment rust coating, has good adhesion to steel surfaces which are not easy to adhere to welding seams and the like, has good corrosion resistance, has excellent acid resistance, alkali resistance, oil resistance, solvent resistance and other chemical medium resistance, can be used under the condition of severe corrosive environment, prolongs the service life of equipment, and is particularly suitable for protecting steel and buildings in chemical environments.
The aqueous epoxy coatings prepared by the schemes reported in the above patent documents have poor dispersion stability against strong mechanical force; insufficient paint film hardness of the water-based paint can cause scratches on the surface; the aqueous solvent has high surface tension, and after the surface is corroded, shrinkage holes are easily formed in the coating film, so that the service life is shortened.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention provides an anticorrosive coating for steel surfaces, which has the characteristics of excellent corrosion resistance, adhesion, wear resistance, high hardness, etc.
In order to achieve the aim, the invention provides an anti-corrosion coating for a steel surface, a preparation method and application thereof, wherein the anti-corrosion coating for the steel surface comprises the following components in parts by weight: 1-2 parts of modified nano-cellulose, 40-60 parts of epoxy resin, 2-4 parts of zinc phosphate powder, 1-3 parts of anti-settling agent, 15-25 parts of filler, 0.1-1 part of flatting agent and 2-4 parts of dispersing agent.
Specifically, the preparation method of the steel surface anticorrosive paint comprises the following steps of:
(1) Adding 2-3 parts of nanocellulose into 6-8 parts of water, performing ultrasonic dispersion for 5-10 minutes at 20-30w, adding 4-5 parts of methyltrimethoxysilane, stirring at room temperature and 400-600r/min for 1-2 hours to obtain modified nanocellulose gel, and finally concentrating at 85-95 ℃ for 1-3 hours to obtain modified nanocellulose;
(2) Adding 1-2 parts of diammonium hydrogen phosphate into 6-10 parts of water, stirring for 10-30 minutes, adding 2-3 parts of zinc oxide, stirring for 3-5 hours at 50-60 ℃, drying for 2-4 hours at 100-120 ℃, grinding to 40-80 mu m of granularity, and carrying out heat treatment on the obtained powder at 500-600 ℃ in an oxygen environment for 4-6 hours to obtain zinc phosphate powder;
(3) Adding 10-15 parts of water and 1-2 parts of modified nanocellulose into 40-60 parts of epoxy resin, stirring for 0.5-1 hour, ultrasonically dispersing for 1-2 hours at 70-80 ℃ under 20-30w, cooling to room temperature, adding 2-4 parts of zinc phosphate powder, 1-3 parts of anti-settling agent, 15-25 parts of filler, 0.1-1 part of flatting agent and 2-4 parts of dispersing agent, continuously stirring for 0.5-1 hour, grinding in a dispersing machine until the granularity is 40-80 mu m, and standing for 0.5-1 hour to obtain the steel surface anti-corrosion coating.
The anti-settling agent in the step (3) is fumed silica.
The filler in the step (3) is any one or mixture of aluminum tripolyphosphate, quartz powder and mica powder; preferably aluminum tripolyphosphate and mica powder are mixed in a weight ratio of 2-3:1.
The leveling agent in the step (3) is any one of SF-734KY, BYK-301, BYK-306, BYK-349, BYK-333 and QG-333.
The dispersing agent in the step (3) is any one of Sifast SF-734, SM-601, SM-603, EA-191H, BYK-3410, BYK-2055, BYK-190, BYK-191, BYK-193 and BYK-194.
The invention also provides application of the steel surface anticorrosive paint, and specifically the application method comprises the following steps:
m1, polishing steel with sand paper to make the surface roughness 40-80 mu M, washing with water and absolute ethyl alcohol in sequence, and finally drying at room temperature for 12-24 hours to finish pretreatment;
m2, adding a curing agent into the steel surface anticorrosive paint in a weight ratio of 1:1, dispersing for 5-10 minutes at 800-1000r/min, grinding to a granularity of 40-80 mu M, filtering, coating the pretreated steel surface by using a dip coating method, curing and drying at normal temperature for 10-12 hours, drying in a drying oven at 100-120 ℃ for 1-2 hours, and cooling to room temperature to obtain the steel surface anticorrosive paint with a coating thickness of 0.1-1mm.
The curing agent in the step M2 is 4, 4-diaminodiphenylmethane.
When oxygen and water exist on the surface of steel, the water becomes salt solution, iron ions are dissociated, the coating layer is equivalent to a semipermeable membrane with osmotic pressure, and under the action of osmotic pressure, the oxygen and the water rapidly pass through the coating layer, so that the iron ions are separated from the surface of steel to form a rust phenomenon; OH generated in the system when corrosion occurs - The ions hydrolyze some of the easily hydrolyzable groups, resulting in a substantial reduction in the hardness and abrasion resistance of the paint coating; therefore, zinc phosphate is added, and the steel is protected by utilizing the cathode protection principle of an electrochemical sacrificial anode; zinc phosphate is added to the application of paint, so that the coating forms a uniform coating layer, the hardness of the coating is improved, and the steel base material and corrosiveness are preventedThe contact of the medium inhibits the corrosion of the electrolyte solution to the steel positive electrode and the ion rearrangement of the surface structure in the corrosion process to a certain extent; the water resistance and weather resistance of the coating film can be improved, the adhesive force and hardness of the coating are enhanced, and the corrosion resistance of the steel structure can be enhanced in the steel structure corrosion-resistant coating.
According to the invention, the epoxy resin is used as a main body of the anticorrosive paint, the epoxy resin has good physical properties, alkali resistance, film forming property, adhesiveness and the like, and nano particles are added to increase the polarity of polymer chains, improve the adhesive force and the crosslinking density of the polymer chains, so that a cured film with compact and firm structure is obtained, and the flexibility, corrosion resistance, surface property and the like of a coating are improved; the cellulose has better wear resistance and friction resistance, can increase the wear resistance and scratch resistance of the coating, but the nano cellulose is easy to agglomerate, the epoxy resin has high viscosity, the nano cellulose is difficult to disperse uniformly, the nano cellulose is subjected to surface modification to solve the problem of easy agglomeration, and the modified nano cellulose which is stably dispersed is obtained after ultrasonic treatment; as a more compact polymer network is formed in the coating, the tighter the molecular chain is packed, the smaller the diffusion coefficient of the corrosion medium in the coating is, and compared with the epoxy resin monomer, the adhesion and the corrosion resistance are better.
In the step of modifying the nano cellulose, methyl trimethoxy silane is added to modify the nano cellulose, so that the density of the obtained modified nano cellulose aerogel is increased, and agglomeration is reduced; the hydroxyl groups of the nanocellulose and the methyltrimethoxysilane are subjected to substitution reaction, so that the porosity is reduced, and the modified aerogel has a more compact network structure.
The filler is added, so that the effects of filling, framework supporting and cost reduction are achieved, the thickness and mechanical strength of the coating are increased, and the wear resistance and durability are improved; the anti-settling agent prevents storage and application difficulties caused by settlement of zinc phosphate in the paint; the leveling agent is used for improving the fluidity and flatness of the paint and reducing the surface tension of the paint, so that the paint can be more lubricated, smoothed and even in the painting process. Leveling agents can reduce the surface tension of the coating so that the coating can spread more easily.
The invention has the beneficial effects that:
1. compared with the prior art, the invention adds zinc phosphate, and utilizes the principle of a cathode protection method of an electrochemical sacrificial anode to protect the steel as a cathode; zinc phosphate is added into the application of the paint, the coating forms a uniform coating layer, the hardness of the coating is improved, and the contact between the steel base material and the corrosive medium is prevented; the water resistance and weather resistance of the coating film can be improved, and the adhesive force and hardness of the coating are enhanced.
2. According to the invention, epoxy resin is used as a main body of the anticorrosive coating, and nano particles are added to increase the polarity of polymer chains, improve the adhesive force and increase the crosslinking density of the polymer chains, so that a solidified film with a compact and firm structure is obtained; the cellulose has better wear resistance and friction resistance, can increase the wear resistance and scratch resistance of the coating, and in order to solve the problem of easy agglomeration, the methyltrimethoxysilane is added to modify the surface of the nanocellulose, and the modified nanocellulose which is stably dispersed is obtained after ultrasonic treatment, so that the density is increased, the agglomeration is reduced, and the structure is more compact; as a more compact polymer network is formed in the coating, the tighter the molecular chain is packed, the smaller the diffusion coefficient of the corrosion medium in the coating is, and compared with the epoxy resin monomer, the adhesion and the corrosion resistance are better.
3. The invention also provides an application of the steel surface anticorrosive paint, wherein the 4, 4-diaminodiphenyl methane curing agent is added into the steel surface anticorrosive paint in a weight ratio of 1:1, and the steel surface after pretreatment is coated for 1-2 times by using a dip coating method, wherein the thickness of each coating is 0.1-1mm; the coating has excellent corrosion resistance, adhesiveness and wear resistance, and the properties of the coated steel surface are observed: the coating is smooth, has good adhesiveness, good compatibility, no bubbling and no falling of the coating.
Detailed Description
The parameters of the part of the chemistry used in the examples were derived as follows:
epoxy resin: the aqueous epoxy resin is a milky white liquid, has an industrial grade and a content of 99%, and is manufactured by mountain east Chang Yao New Material Co., ltd, and the model is CY-HR5.
Leveling agent: BKY-301 under the brand name Pick.
Dispersing agent: BKY-191, branded Pick.
Fumed silica: the active ingredient is 100wt.%, and is purchased from Santuo chemical industry Co., ltd. In Nanxiong, and the brand is Santuo, and the model is STA-200.
The steel sample in the example is Q235 low-carbon steel with carbon content of 0.60% and standard of national standard
《GB/T 700-2006》。
Nanocellulose: the content is 99.5 wt%, the pH value in water is 7-8, the size after dispersion is 20nm wide and 2 μm long, the manufacturer is Wuhan Hua Xiangke Jietexilate Biotechnology Co., ltd, and the product number is EF234243.
Comparative example 1
The preparation method of the steel surface anticorrosive paint comprises the following steps:
adding 130g of water into 500g of epoxy resin, stirring for 1 hour, performing ultrasonic dispersion at 70 ℃ and 25w for 1 hour, cooling to room temperature, adding 15g of fumed silica, 150g of aluminum tripolyphosphate, 60g of 1000-mesh mica powder, 7g of BKY-301 and 24g of BYK-191, continuously stirring for 1 hour, grinding in a dispersing machine until the granularity is 60 mu m, and standing for 1 hour to obtain the steel surface anticorrosive paint.
Comparative example 2
The preparation method of the steel surface anticorrosive paint comprises the following steps:
(1) Adding 20g of nano cellulose into 70g of water, performing ultrasonic dispersion for 5 minutes at 25w, adding 40g of methyltrimethoxysilane, stirring at room temperature and 500r/min for 1 hour to obtain modified nano cellulose gel, and finally concentrating at 90 ℃ for 2 hours to obtain modified nano cellulose;
(2) Adding 130g of water and 16g of modified nanocellulose prepared in the step (1) into 500g of epoxy resin, stirring for 1 hour, ultrasonically dispersing for 1 hour at 70 ℃ and 25w, cooling to room temperature, adding 15g of fumed silica, 150g of aluminum tripolyphosphate, 60g of 1000-mesh mica powder, 7g of BKY-301 and 24g of BYK-191, continuously stirring for 1 hour, grinding in a dispersing machine to reach the granularity of 60 mu m, and standing for 1 hour to obtain the steel surface anticorrosive paint.
Example 1
The preparation method of the steel surface anticorrosive paint comprises the following steps:
(1) Adding 15g of diammonium hydrogen phosphate into 80g of water, stirring for 20 minutes, then adding 25g of zinc oxide, stirring for 3 hours at 55 ℃, drying for 4 hours at 100 ℃, grinding to 60 mu m, and carrying out heat treatment on the obtained powder for 5 hours at 600 ℃ in an oxygen environment to obtain zinc phosphate powder;
(2) Adding 130g of water into 500g of epoxy resin, stirring for 1 hour, ultrasonically dispersing for 1 hour at 70 ℃ under 25w, cooling to room temperature, adding 30g of zinc phosphate powder prepared in the step (1), 15g of fumed silica, 150g of aluminum tripolyphosphate, 60g of 1000-mesh mica powder, 7g of BKY-301 and 24g of BYK-191, continuously stirring for 1 hour, grinding in a dispersing machine until the granularity is 60 mu m, and standing for 1 hour to obtain the steel surface anticorrosive paint.
Example 2
The preparation method of the steel surface anticorrosive paint comprises the following steps:
(1) Adding 15g of diammonium hydrogen phosphate into 80g of water, stirring for 20 minutes, adding 25g of zinc oxide, stirring for 3 hours at 55 ℃, drying for 4 hours at 100 ℃, grinding to 60 mu m, and carrying out heat treatment on the obtained powder at 600 ℃ in an oxygen environment for 5 hours to obtain zinc phosphate powder;
(3) Adding 130g of water and 16g of nanocellulose into 500g of epoxy resin, stirring for 1 hour, ultrasonically dispersing for 1 hour at 70 ℃ and 25w, cooling to room temperature, adding 30g of zinc phosphate powder prepared in the step (1), 15g of fumed silica, 150g of aluminum tripolyphosphate, 60g of 1000-mesh mica powder, 7g of BKY-301 and 24g of BYK-191, continuously stirring for 1 hour, grinding in a dispersing machine until the granularity is 60 mu m, and standing for 1 hour to obtain the steel surface anticorrosive paint.
Example 3
The preparation method of the steel surface anticorrosive paint comprises the following steps:
(1) Adding 20g of nano cellulose into 70g of water, performing ultrasonic dispersion for 5 minutes at 25w, adding 40g of methyltrimethoxysilane, stirring at room temperature and 500r/min for 1 hour to obtain modified nano cellulose gel, and finally concentrating at 90 ℃ for 2 hours to obtain modified nano cellulose;
(2) Adding 15g of diammonium hydrogen phosphate into 80g of water, stirring for 20 minutes, then adding 25g of zinc oxide, stirring for 3 hours at 55 ℃, drying for 4 hours at 100 ℃, grinding to 60 mu m of granularity, and carrying out heat treatment on the obtained powder at 600 ℃ in an oxygen environment for 5 hours to obtain zinc phosphate powder;
(3) Adding 130g of water and 16g of modified nanocellulose prepared in the step (1) into 500g of epoxy resin, stirring for 1 hour, ultrasonically dispersing for 1 hour at 70 ℃ and 25w, cooling to room temperature, adding 30g of zinc phosphate powder prepared in the step (2), 15g of fumed silica, 150g of aluminum tripolyphosphate, 60g of 1000-mesh mica powder, 7g of BKY-301 and 24g of BYK-191, continuously stirring for 1 hour, grinding in a dispersing machine until the granularity is 60 mu m, and standing for 1 hour to obtain the steel surface anti-corrosion coating.
Example 4
The steel surface anticorrosive paint obtained by the preparation methods in comparative examples 1-2 and examples 1-3 is coated according to the application method of the steel surface anticorrosive paint, and the application method of the steel surface anticorrosive paint is as follows:
m1, polishing steel with sand paper to make the surface roughness 40 mu M, washing with water and ethanol in sequence, and finally drying at room temperature for 12 hours to finish pretreatment;
m2, adding 4, 4-diaminodiphenyl methane into the steel surface anticorrosive paint in a weight ratio of 1:1, dispersing for 10 minutes at 800r/min, grinding to reach a granularity of 40 mu M, filtering, coating the pretreated steel surface by using a dip coating method, curing and drying at normal temperature for 10 hours, drying in a 120 ℃ oven for 1 hour, and cooling to the room temperature to obtain the steel surface anticorrosive coating, wherein the thickness of the coating is 0.5mm.
Test example 1
Neutral salt spray resistance test
15 steel samples with the size of 150mm and 100mm and 1mm are prepared, the steel samples are coated with the steel surface anticorrosive paint obtained by the preparation methods in comparative examples 1-2 and examples 1-3 according to the application method of example 4, five groups of steel samples in comparative examples 1-2 and examples 1-3 are obtained, 3 steel samples are added in each group, and the test data are averaged. According to national standard GB/T1771-2007 determination of neutral salt spray resistance of paint and varnish, neutral salt spray resistance is tested in 3.5wt.% NaCl aqueous solution, and the test results are shown in Table 1.
Placing a steel sample into a salt fog box, wherein the coating of the steel sample faces upwards and the vertical included angle is 20 ℃; the temperature of the salt fog box is 35 ℃, and the salt fog pressure is 1kg/cm 2 The air source is 5kg/cm 2 Periodically and continuously spraying atomized 3.5wt.% NaCl aqueous solution, and uniformly settling the fine mist on the surface of the sample under the action of dead weight; during spraying, the steel samples were periodically observed without heating the salt spray tank and observing the change in the substrate of the coated samples, and the time at which corrosion started to occur was recorded. In the neutral salt spray resistance test, the longer the first corrosion phenomenon is, the better the corrosion resistance of the coating is.
TABLE 1 neutral salt spray resistance test results
As can be seen from the comparison of the test example 1, the anticorrosive paint of the comparison example 1 has the lowest anticorrosive effect without adding nano particles and zinc phosphate; the anticorrosive coatings of comparative example 2 and example 1 only have one of nano particles and zinc phosphate added, so that the anticorrosive effect is improved; the anticorrosive paint in the embodiment 2 is added with nanocellulose and zinc phosphate, but the problems of low nanocellulose density and easy agglomeration are not solved, so that uneven distribution is caused, and the improvement of corrosion resistance is limited; compared with the anticorrosive paint in the example 3, the anticorrosive paint in the example 2 has the advantages of better adhesion, denser coating and best corrosion resistance because the nanocellulose is modified.
Test example 2
Hardness test
15 steel samples with the size of 150mm and 100mm and 1mm are prepared, the steel samples are coated with the steel surface anticorrosive paint obtained by the preparation methods in comparative examples 1-2 and examples 1-3 according to the application method of example 4, five groups of steel samples in comparative examples 1-2 and examples 1-3 are obtained, 3 steel samples are added in each group, and the test data are averaged. The hardness of the coating was measured according to national standard GB/T6739-2006 paint film hardness measured by the paint and varnish and pencil method, and the test results are shown in Table 2.
1. Instrument for measuring and controlling the intensity of light
The test instrument consists of a metal block with wheels at two sides, and the wheels should not scratch the surface of a paint film in the measurement process; a cylindrical hole clamp inclined at an angle of 45 degrees for holding the pencil is arranged in the middle of the metal block, so that the pencil can be fixed on an instrument and always kept at the same position; a level gauge is arranged at the top of the instrument and is used for ensuring the level of the instrument when the test is carried out; the instrument is designed so that it is in a horizontal position with a pencil port applying a load of 7.35N to the paint film surface.
2. Operating procedure
(1) The test was carried out at 23℃and a relative humidity of 50%.
(2) The special mechanical pencil sharpener cuts 5mm of wood at one end of each pencil, so that the pencil core is in an original, unbreakable and smooth cylindrical state.
(3) Holding the pencil vertically, moving the pencil back and forth on the abrasive paper at 90 degrees with the plane of the abrasive paper, grinding the end of the pencil core flat, and continuously moving the pencil until a flat and smooth circular cross section is obtained, wherein the edge is free of scraps and gaps, and the step is repeated before the pencil is used each time.
(4) Placing the coated steel sample on a horizontal and stable surface, inserting a pencil into a test instrument and fixing the pencil by using a clamp, so that the instrument is kept horizontal, and placing a port of the pencil on the surface of a paint film;
(5) Immediately after the port of the pencil contacts the paint film, pushing the pencil in a direction away from an operator at a slow and uniform speed, and pushing a long enough distance to perform visual judgment;
(6) Wiping the paint film surface by using a cotton swab dipped with a small amount of water, and wiping all fragments of pencil leads on the paint film surface; observing the surface of the paint film under artificial sunlight by using normal corrected vision, and checking whether any one of plastic deformation and cohesive failure occurs or simultaneously, wherein the plastic deformation is detected: permanent indentation of the paint film surface, but no cohesive failure; cohesive failure: the paint film surface exhibited visible scratches or scratches and chipping of the paint film.
If no defect occurs, repeating the test by replacing the pencil with higher hardness in the area where the test is not performed until the defect of at least 3mm occurs; if the defect occurs, the hardness of the pencil is reduced, and the test is repeated until the defect does not occur any more; the pencil hardness of a paint film is expressed as the hardness of the hardest pencil that does not cause defects to the paint film. The pencil hardness is divided into 9B, 8B, 7B, 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, 9H and 9B in sequence, and the hardness is the smallest and the hardness is the highest.
TABLE 2 hardness test results
| Examples | Comparative example 1 | Comparative example 2 | Example 1 | Example 2 | Example 3 |
| Hardness of | 4H | 4H | 5H | 5H | 5H |
As is evident from test example 2, the anticorrosive coatings of examples 1 to 3, to which zinc phosphate was added, have higher hardness than comparative examples 1 to 2, and are advantageous in terms of resistance to physical damage and better durability.
Test example 3
Abrasion resistance test
15 steel samples with the size of 100mm and 1mm are prepared, the steel surface anticorrosive paint obtained by the preparation methods in comparative examples 1-2 and examples 1-3 is respectively coated on the steel samples according to the application method of example 4, five groups of steel samples in comparative examples 1-2 and examples 1-3 are obtained, 3 steel samples are added in each group, and test data are averaged. The abrasion resistance of the coating was measured according to national standard GB/T1768-2006 "measurement of paint and varnish, abrasion resistance, rotary rubber grinding wheel method", and the abrasion resistance test results are shown in Table 3.
A paint film abrasion resistance instrument is adopted for testing, before the testing is carried out, the abrasion resistance instrument is connected with a dust collector, a working turntable is cleaned, and a 500g weight and a grinding wheel are added to a pressurizing arm; firstly, weighing the weight of the steel sample before the test by using an analytical balance to the accuracy of 0.1mg; fixing an iron sheet on a rotary table, lightly putting down a pressurizing arm to ensure that a grinding wheel on the pressurizing arm is in full contact with the iron sheet, and putting down a dust suction nozzle to be 1.5mm away from the steel surface; starting a power supply of the abrasion instrument and the dust collector, setting the rotating speed of the rotary table to be 60r/min, setting the running revolution to be 500r, setting the running time to be 1 hour, and starting the instrument; after the operation is finished, the working turntable automatically stops, the pressurizing materials such as the pressurizing materials and the dust suction nozzle are lifted, the abrasive dust remained on the iron sheet is removed by using the non-fluffing paper, and the steel sample is weighed again to the accuracy of 0.1mg; the difference between the two weighing results is the quality loss of the coating and can be used as the result of the wear resistance of the coating; the smaller the mass loss, the better the abrasion resistance of the coating.
Table 3 abrasion resistance test results
| Examples | Comparative example 1 | Comparative example 2 | Example 1 | Example 2 | Example 3 |
| Quality loss | -5.8mg | -4.5mg | -3.2mg | -3.9mg | -1.8mg |
As can be seen from the comparison of test example 3, the anticorrosive paint of comparative example 1 has no nano particles and zinc phosphate added, and the mass loss before and after abrasion is the greatest; only one of nano particles and zinc phosphate is added into the anticorrosive paint of comparative example 2 and example 2, and the anticorrosive paint of example 2 is added with unmodified easily-agglomerated nano cellulose and zinc phosphate, so that the mass loss before and after abrasion is large, and the nano cellulose and the zinc phosphate both affect the abrasion resistance of the coating; compared with the anticorrosive paint in the example 2, the anticorrosive paint in the example 3 has the advantages of better adhesive force, more compact and uniform coating, minimum mass loss before and after abrasion and best abrasion resistance after the nanocellulose is modified.
Claims (10)
1. An anticorrosive paint for steel surfaces is characterized by comprising the following components: modified nanocellulose, epoxy resin, zinc phosphate powder, an anti-settling agent, a filler, a leveling agent and a dispersing agent.
2. The steel surface anticorrosive paint according to claim 1, comprising the following components in parts by weight: 1-2 parts of modified nano-cellulose, 40-60 parts of epoxy resin, 2-4 parts of zinc phosphate powder, 1-3 parts of anti-settling agent, 15-25 parts of filler, 0.1-1 part of flatting agent and 2-4 parts of dispersing agent.
3. The steel surface anticorrosive paint according to claim 1 or 2, characterized in that the modified nanocellulose is prepared from the following components: nanocellulose, methyltrimethoxysilane and water.
4. The steel surface anticorrosive paint according to claim 1 or 2, wherein the zinc phosphate powder is prepared from the following components: diammonium phosphate, zinc oxide and water.
5. The steel surface anticorrosive paint according to claim 1 or 2, wherein the filler is any one or a mixture of aluminum tripolyphosphate, quartz powder and mica powder.
6. The steel surface anticorrosive paint according to claim 1 or 2, wherein the leveling agent is any one of SF-734KY, BYK-301, BYK-306, BYK-349, BYK-333, QG-333.
7. The steel surface anticorrosive paint according to claim 1 or 2, wherein the dispersant is any one of SiFast SF-734, SM-601, SM-603, EA-191H, BYK-3410, BYK-2055, BYK-190, BYK-191, BYK-193, BYK-194.
8. A method of preparing an anticorrosive coating for steel surfaces as claimed in any one of claims 1 to 7 comprising the steps of:
(1) Adding nano cellulose into water, performing ultrasonic dispersion, adding methyltrimethoxysilane, stirring at room temperature to obtain modified nano cellulose gel, and concentrating at 85-95 ℃ to obtain modified nano cellulose;
(2) Adding diammonium hydrogen phosphate into water, stirring, adding zinc oxide, stirring, drying, grinding, and performing heat treatment on the obtained powder in an oxygen environment at 500-600 ℃ to obtain zinc phosphate powder;
(3) Adding water and modified nano cellulose into epoxy resin, stirring, performing ultrasonic dispersion, adding zinc phosphate powder, an anti-settling agent, a filler, a leveling agent and a dispersing agent, grinding in a dispersing machine, and standing to obtain the steel surface anticorrosive paint.
9. Use of the steel surface anticorrosive paint according to any one of claims 1-7, characterized by the following method of application:
m1, polishing steel with sand paper to make the surface roughness 40-80 mu M, washing with water and ethanol in sequence, and finally drying at room temperature for 12-24 hours to finish pretreatment;
m2, adding a curing agent into the steel surface anticorrosive paint according to any one of claims 1-7 in a weight ratio of 1:1, dispersing for 5-10 minutes at 800-1000r/min, grinding to a granularity of 40-80 mu M, filtering, coating the pretreated steel surface by using a dip coating method, curing and drying at normal temperature for 10-12 hours, drying in a drying oven at 100-120 ℃ for 1-2 hours, and cooling to room temperature to obtain the steel surface anticorrosive coating with the thickness of 0.1-1mm.
10. The use of the steel surface anticorrosive coating according to claim 9, wherein the curing agent is 4, 4-diaminodiphenylmethane.
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