CN116694186A - Corrosion-resistant composite coating on surface of steel structure and preparation method and application thereof - Google Patents
Corrosion-resistant composite coating on surface of steel structure and preparation method and application thereof Download PDFInfo
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- CN116694186A CN116694186A CN202310728886.0A CN202310728886A CN116694186A CN 116694186 A CN116694186 A CN 116694186A CN 202310728886 A CN202310728886 A CN 202310728886A CN 116694186 A CN116694186 A CN 116694186A
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- 238000000576 coating method Methods 0.000 title claims abstract description 81
- 239000011248 coating agent Substances 0.000 title claims abstract description 77
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 68
- 239000010959 steel Substances 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 238000005260 corrosion Methods 0.000 title claims abstract description 57
- 230000007797 corrosion Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 110
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 64
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 64
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 57
- 239000003822 epoxy resin Substances 0.000 claims abstract description 32
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 32
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 15
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- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 27
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 27
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- 235000002949 phytic acid Nutrition 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 25
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- 238000002156 mixing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical group CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 claims description 10
- 238000005498 polishing Methods 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
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- 239000002994 raw material Substances 0.000 claims description 3
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- 239000000853 adhesive Substances 0.000 abstract description 3
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- 238000005536 corrosion prevention Methods 0.000 abstract description 3
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- 238000006243 chemical reaction Methods 0.000 description 14
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- -1 carbon nano tube modified fluorine Chemical class 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000013530 defoamer Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 2
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- BTBNYOKJERLLQI-UHFFFAOYSA-N 3-methylquinoline-8-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC2=CC(C)=CN=C21 BTBNYOKJERLLQI-UHFFFAOYSA-N 0.000 description 1
- QVLTVILSYOWFRM-UHFFFAOYSA-L CC1=C(C)C(C)([Rh](Cl)Cl)C(C)=C1C Chemical class CC1=C(C)C(C)([Rh](Cl)Cl)C(C)=C1C QVLTVILSYOWFRM-UHFFFAOYSA-L 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 238000010422 painting Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
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- 229910052725 zinc Inorganic materials 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
- 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
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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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)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the technical field of paint corrosion prevention, and discloses a corrosion-resistant composite coating on the surface of a steel structure, a preparation method and application thereof, wherein the corrosion-resistant composite coating comprises 40-50 parts of waterborne epoxy resin, 10-15 parts of curing agent, 4.5-7 parts of modified carbon nano tubes, 0.2-0.5 part of flatting agent, 0.05-0.2 part of defoaming agent and 15-20 parts of water; the preparation method comprises the following steps: treating the surface of the steel structure, preparing the modified carbon nano tube, preparing the anti-corrosion composite coating and preparing the salt spray-resistant anti-corrosion coating. According to the invention, the modified carbon nano tube is added into the waterborne epoxy resin, so that the corrosion resistance of the coating is enhanced, the good adhesive force and corrosion resistance of the epoxy resin to the metal substrate are utilized, after the waterborne epoxy resin is waterborne, the tolerance of the coating resin to moisture and air is obviously reduced, and after the modified carbon nano tube is added, the salt spray corrosion resistance of the coating is enhanced by utilizing the characteristic that the carbon nano tube can stably exist in a corrosion environment.
Description
Technical Field
The invention belongs to the technical field of paint corrosion prevention, and particularly relates to a corrosion prevention composite coating for a steel structure surface, a preparation method and application thereof.
Background
With the rapid development of economic construction in China, steel structure materials become one of the main materials for construction, and the waste caused by corrosion of metals such as steel is huge each year. The united kingdom is reported to lose several hundred million pounds per year due to metal corrosion; the loss of metal corrosion in the united states is about 4.2% of the total national production. To date, the application of corrosion protection coatings has been the most cost effective of many corrosion protection means (e.g., use of corrosion resistant metallic materials, electrochemical protection, addition of corrosion inhibitors, painting of corrosion protection coatings, etc.).
In recent years, environmental protection concepts advocate, and as the requirement of VOC content is more and more strict, water-based anticorrosive coatings gradually become the main stream. The water-based paint applied to corrosion protection at present mainly comprises water-based acrylic acid anticorrosive paint, water-based epoxy anticorrosive paint, water-based polyurethane anticorrosive paint and water-based inorganic zinc-rich paint. The acrylic resin can be modified according to the application conditions and the environmental requirements to prepare the water-based paint with excellent anti-corrosion performance. The use temperature of the water-based acrylic resin anticorrosive paint can be as low as 5 ℃, the water-based acrylic resin anticorrosive paint can be dried quickly within 1 hour, and the acrylic resin polymer contains groups with stronger hydrophilicity and is commonly used in a light anticorrosive or moderate anticorrosive environment. In the prior art, when the corrosion resistance of the coating is improved, a method for modifying both acrylic resin and carbon nanotubes is adopted, and reference is made to CN 114410171B, but the scheme is mainly aimed at electrochemical corrosion and does not relate to salt spray corrosion. Therefore, development of a salt spray resistant and corrosion resistant composite coating for the surface of a steel structure is urgently needed.
Disclosure of Invention
The invention discloses an anti-corrosion composite coating on the surface of a steel structure and a preparation method thereof, and solves the problems that the prior art mainly aims at electrochemical corrosion and salt spray corrosion is not involved when the anti-corrosion performance of the coating is improved.
An anticorrosive composite coating for a steel structure surface, comprising: 40-50 parts of water-based epoxy resin, 10-15 parts of curing agent, 4.5-7 parts of modified carbon nano tube, 0.2-0.5 part of leveling agent, 0.05-0.2 part of defoaming agent and 15-20 parts of water.
Preferably, the anticorrosive composite coating comprises: 43-46 parts of water-based epoxy resin, 12-14 parts of curing agent, 5-6 parts of modified carbon nano tube, 0.3-0.4 part of flatting agent, 0.1-0.15 part of defoaming agent and 16-18 parts of water.
Preferably, the anticorrosive composite coating comprises: 45 parts of aqueous epoxy resin, 13 parts of curing agent, 6 parts of modified carbon nano tube, 0.4 part of leveling agent, 0.4 part of defoaming agent and 17 parts of water.
Preferably, the preparation method of the anti-corrosion composite coating comprises the following steps:
s1, carrying out oil and rust removal treatment on the surface of a steel structure, and polishing and grinding to obtain a clean steel structure;
s2, carrying out acid modification on the carbon nano tube to obtain a modified carbon nano tube;
s3, adding the water-based epoxy resin, the modified carbon nanotubes prepared in the S2 and water according to the formula amount to obtain a base material A;
s4, adding the leveling agent and the defoaming agent into the base material A prepared in the step S3 according to the formula amount in a stirring state, adding the curing agent after stirring, and uniformly mixing to obtain the anti-corrosion composite coating.
Preferably, the preparation method of the anti-corrosion composite coating comprises the following steps:
(1) Treating the carbon nanotubes by using a mixed acid solution to obtain acidified carbon nanotubes;
(2) Adding the acidified carbon nanotube obtained in the step (1) into deionized water, performing ultrasonic dispersion, adding phytic acid, performing a phosphorylation reaction, filtering a solvent, and washing with deionized water to obtain the modified carbon nanotube modified by phytic acid.
Preferably, the mixed acid in the step (1) is a mixture of concentrated sulfuric acid and concentrated nitric acid, and the volume ratio is 3:1.
Preferably, the ratio of the mixed acid solution to the carbon nanotubes in (1) is 1g:150mL.
Preferably, the ratio of the phytic acid to the acidified carbon nanotubes in (2) is: 4:1.
Preferably, the curing agent is diethylaminopropylamine.
The invention further aims to provide an application of the anti-corrosion composite coating on the surface of the steel structure in preparing a salt spray-resistant anti-corrosion coating.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the modified carbon nano tube is added into the waterborne epoxy resin, so that the corrosion resistance of the coating is enhanced, the good adhesive force and corrosion resistance of the epoxy resin to the metal substrate are utilized, after the waterborne epoxy resin is waterborne, the tolerance of the resin to moisture and air is obviously reduced, and after the modified carbon nano tube is added, the salt spray corrosion resistance of the coating is enhanced by utilizing the characteristic that the carbon nano tube can stably exist in a corrosion environment.
2. The carbon nano tube is modified by using mixed solution of concentrated sulfuric acid and concentrated nitric acid to oxidize the carbon nano tube, introducing oxygen-containing functional groups such as carboxyl and the like, then adding phytic acid to carry out a phosphorylation reaction to generate phosphoric acid and phosphate groups, and chelating with metals in a steel structure, so that the adhesive force and compactness of the coating and the steel structure are improved, and the salt fog resistance of the coating is enhanced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the data in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that the technical terms used in the present invention are only for describing specific embodiments, and are not intended to limit the scope of the present invention, and various raw materials, reagents, instruments and equipment used in the following embodiments of the present invention may be purchased commercially or prepared by existing methods unless otherwise specifically described.
The types of reagents used in the examples and comparative examples of the present invention were:
leveling agent: BYK-333.
Defoaming agent: basoff FoamStar SI 2210 silicone defoamer.
Example 1
An anticorrosive composite coating for a steel structure surface, comprising: 40 parts of water-based epoxy resin, 10 parts of curing agent, 4.5 parts of modified carbon nano tube, 0.2 part of leveling agent, 0.05 part of defoaming agent and 15 parts of water.
The preparation method of the anti-corrosion composite coating on the surface of the steel structure specifically comprises the following steps:
s1, carrying out oil and rust removal treatment on the surface of the steel structure, and polishing and grinding to obtain the clean steel structure.
S2, carrying out acid modification on the carbon nano tube to obtain a modified carbon nano tube; the specific method comprises the following steps:
(1) Treating the carbon nanotubes by using a mixed acid solution to obtain acidified carbon nanotubes, wherein the reaction condition is 40 ℃ for 2 hours; wherein the mixed acid is a mixture of concentrated sulfuric acid and concentrated nitric acid, and the volume ratio is 3:1; the ratio of the mixed acid solution to the carbon nanotubes is 1g:150mL.
(2) Adding the acidified carbon nano tube obtained in the step (1) into deionized water, and adding phytic acid after ultrasonic dispersion, wherein the reaction conditions are as follows: reacting for 10 hours at 80 ℃, filtering the solvent, and washing with deionized water to obtain the modified carbon nano tube modified by the phytic acid; the mass ratio of the phytic acid to the acidified carbon nano tube is as follows: 4:1.
S3, adding the water-based epoxy resin, the modified carbon nanotubes prepared in the S2 and water according to the formula amount to obtain a base material A.
S4, adding the leveling agent and the defoaming agent into the base material A prepared in the step S3 according to the formula amount under the stirring state, adding the curing agent diethylaminopropylamine according to the formula amount after uniformly stirring, and uniformly mixing to obtain the anti-corrosion composite coating.
S5, spraying the prepared anticorrosive composite coating in the S4 on the surface of the clean steel structure prepared in the S1, and baking at 70 ℃ for 3 hours.
Example 2
An anticorrosive composite coating for a steel structure surface, comprising: 43 parts of water-based epoxy resin, 12 parts of curing agent, 5 parts of modified carbon nano tube, 0.3 part of leveling agent, 0.1 part of defoaming agent and 16 parts of water.
The preparation method of the anti-corrosion composite coating on the surface of the steel structure specifically comprises the following steps:
s1, carrying out oil and rust removal treatment on the surface of the steel structure, and polishing and grinding to obtain the clean steel structure.
S2, carrying out acid modification on the carbon nano tube to obtain a modified carbon nano tube; the specific method comprises the following steps:
(1) Treating the carbon nanotubes by using a mixed acid solution to obtain acidified carbon nanotubes, wherein the reaction condition is 45 ℃ for 2-3 h; wherein the mixed acid is a mixture of concentrated sulfuric acid and concentrated nitric acid, and the volume ratio is 3:1; the ratio of the mixed acid solution to the carbon nanotubes is 1g:150mL.
(2) Adding the acidified carbon nano tube obtained in the step (1) into deionized water solvent, and adding phytic acid after ultrasonic dispersion, wherein the reaction conditions are as follows: reacting at 85 ℃ for 11 hours, filtering a solvent, and washing with deionized water to obtain a modified carbon nano tube modified by phytic acid; the mass ratio of the phytic acid to the acidified carbon nano tube is as follows: 4:1.
S3, adding the water-based epoxy resin, the modified carbon nanotubes prepared in the S2 and water according to the formula amount to obtain a base material A.
S4, adding the leveling agent and the defoaming agent into the base material A prepared in the step S3 according to the formula amount under the stirring state, adding the curing agent diethylaminopropylamine according to the formula amount after uniformly stirring, and uniformly mixing to obtain the anti-corrosion composite coating.
S5, spraying the prepared anticorrosive composite coating in the S4 on the surface of the clean steel structure prepared in the S1, and baking at 70 ℃ for 3 hours.
Example 3
An anticorrosive composite coating for a steel structure surface, comprising: 45 parts of aqueous epoxy resin, 13 parts of curing agent, 6 parts of modified carbon nano tube, 0.4 part of leveling agent, 0.15 part of defoaming agent and 17 parts of water.
The preparation method of the anti-corrosion composite coating on the surface of the steel structure specifically comprises the following steps:
s1, carrying out oil and rust removal treatment on the surface of the steel structure, and polishing and grinding to obtain the clean steel structure.
S2, carrying out acid modification on the carbon nano tube to obtain a modified carbon nano tube; the specific method comprises the following steps:
(1) Treating the carbon nanotubes by using a mixed acid solution to obtain acidified carbon nanotubes, wherein the reaction condition is 50 ℃ for 3 hours; wherein the mixed acid is a mixture of concentrated sulfuric acid and concentrated nitric acid, and the volume ratio is 3:1; the ratio of the mixed acid solution to the carbon nanotubes is 1g:150mL.
(2) Adding the acidified carbon nano tube obtained in the step (1) into deionized water, and adding phytic acid after ultrasonic dispersion, wherein the reaction conditions are as follows: reacting at 90 ℃ for 13 hours, filtering a solvent, and washing with deionized water to obtain the acid modified carbon nano tube modified by the phytic acid; the mass ratio of the phytic acid to the acidified carbon nano tube is as follows: 4:1.
S3, adding the water-based epoxy resin, the modified carbon nanotubes prepared in the S2 and water according to the formula amount to obtain a base material A.
S4, adding the leveling agent and the defoaming agent into the base material A prepared in the step S3 according to the formula amount under the stirring state, adding the curing agent diethylaminopropylamine according to the formula amount after uniformly stirring, and uniformly mixing to obtain the anti-corrosion composite coating.
S5, spraying the prepared anticorrosive composite coating in the S4 on the surface of the clean steel structure prepared in the S1, and baking at 70 ℃ for 3 hours.
Example 4
An anticorrosive composite coating for a steel structure surface, comprising: 46 parts of aqueous epoxy resin, 14 parts of curing agent, 6 parts of modified carbon nano tube, 0.4 part of leveling agent, 0.15 part of defoaming agent and 18 parts of water.
The preparation method of the anti-corrosion composite coating on the surface of the steel structure specifically comprises the following steps:
s1, carrying out oil and rust removal treatment on the surface of the steel structure, and polishing and grinding to obtain the clean steel structure.
S2, carrying out acid modification on the carbon nano tube to obtain a modified carbon nano tube; the specific method comprises the following steps:
(1) Treating the carbon nanotubes by using a mixed acid solution to obtain acidified carbon nanotubes, wherein the reaction condition is 60 ℃ for 3 hours; wherein the mixed acid is a mixture of concentrated sulfuric acid and concentrated nitric acid, and the volume ratio is 3:1; the ratio of the mixed acid solution to the carbon nanotubes is 1g:150mL.
(2) Adding the acidified carbon nano tube obtained in the step (1) into deionized water, and adding phytic acid after ultrasonic dispersion, wherein the reaction conditions are as follows: reacting at 95 ℃ for 14 hours, filtering a solvent, and washing with deionized water to obtain the acid modified carbon nano tube modified by the phytic acid; the mass ratio of the phytic acid to the acidified carbon nano tube is as follows: 4:1.
S3, adding the water-based epoxy resin, the modified carbon nanotubes prepared in the S2 and water according to the formula amount to obtain a base material A.
S4, adding the leveling agent and the defoaming agent into the base material A prepared in the step S3 according to the formula amount under the stirring state, adding the curing agent diethylaminopropylamine according to the formula amount after uniformly stirring, and uniformly mixing to obtain the anti-corrosion composite coating.
S5, spraying the prepared anticorrosive composite coating in the S4 on the surface of the clean steel structure prepared in the S1, and baking at 80 ℃ for 4 hours.
Example 5
An anticorrosive composite coating for a steel structure surface, comprising: 50 parts of water-based epoxy resin, 15 parts of curing agent, 7 parts of modified carbon nano tube, 0.5 part of leveling agent, 0.2 part of defoaming agent and 20 parts of water.
The preparation method of the anti-corrosion composite coating on the surface of the steel structure specifically comprises the following steps:
s1, carrying out oil and rust removal treatment on the surface of the steel structure, and polishing and grinding to obtain the clean steel structure.
S2, carrying out acid modification on the carbon nano tube to obtain a modified carbon nano tube; the specific method comprises the following steps:
(1) Treating the carbon nanotubes by using a mixed acid solution to obtain acidified carbon nanotubes, wherein the reaction condition is 60 ℃ for 3 hours; wherein the mixed acid is a mixture of concentrated sulfuric acid and concentrated nitric acid, and the volume ratio is 3:1; the ratio of the mixed acid solution to the carbon nanotubes is 1g:150mL.
(2) Adding the acidified carbon nano tube obtained in the step (1) into deionized water, and adding phytic acid after ultrasonic dispersion, wherein the reaction conditions are as follows: reacting for 15 hours at 100 ℃, filtering the solvent, and washing with deionized water to obtain the acid modified carbon nano tube modified by the phytic acid; the mass ratio of the phytic acid to the acidified carbon nano tube is as follows: 4:1.
S3, adding the water-based epoxy resin, the modified carbon nanotubes prepared in the S2 and water according to the formula amount to obtain a base material A.
S4, adding the leveling agent and the defoaming agent into the base material A prepared in the step S3 according to the formula amount under the stirring state, adding the curing agent diethylaminopropylamine according to the formula amount after uniformly stirring, and uniformly mixing to obtain the anti-corrosion composite coating.
S5, spraying the prepared anticorrosive composite coating in the S4 on the surface of the clean steel structure prepared in the S1, and baking at 80 ℃ for 4 hours.
Comparative example 1
An anticorrosive composite coating for a steel structure surface, comprising: 45 parts of aqueous epoxy resin, 13 parts of curing agent, 6 parts of modified carbon nano tube, 0.4 part of leveling agent, 0.15 part of defoaming agent and 17 parts of water.
The preparation method of the anti-corrosion composite coating on the surface of the steel structure specifically comprises the following steps:
s1, carrying out oil and rust removal treatment on the surface of the steel structure, and polishing and grinding to obtain the clean steel structure.
S2, carrying out acid modification on the carbon nano tube to obtain a modified carbon nano tube; the specific method comprises the following steps:
adding phytic acid into deionized water solvent after ultrasonic dispersion, wherein the reaction conditions are as follows: reacting at 90 ℃ for 13 hours, filtering a solvent, and washing with deionized water to obtain the acid modified carbon nano tube modified by the phytic acid; the mass ratio of the phytic acid to the acidified carbon nano tube is as follows: 4:1.
S3, adding the water-based epoxy resin, the modified carbon nanotubes prepared in the S2 and water according to the formula amount to obtain a base material A.
S4, adding the leveling agent and the defoaming agent into the base material A prepared in the step S3 according to the formula amount under the stirring state, adding the curing agent diethylaminopropylamine according to the formula amount after uniformly stirring, and uniformly mixing to obtain the anti-corrosion composite coating.
S5, spraying the prepared anticorrosive composite coating in the S4 on the surface of the clean steel structure prepared in the S1, and baking at 70 ℃ for 3 hours.
Comparative example 2
An anticorrosive composite coating for a steel structure surface, comprising: 45 parts of aqueous epoxy resin, 13 parts of curing agent, 6 parts of modified carbon nano tube, 0.4 part of leveling agent, 0.15 part of defoaming agent and 17 parts of water.
The preparation method of the anti-corrosion composite coating on the surface of the steel structure specifically comprises the following steps:
s1, carrying out oil and rust removal treatment on the surface of the steel structure, and polishing and grinding to obtain the clean steel structure.
S2, carrying out acid modification on the carbon nano tube to obtain a modified carbon nano tube; the specific method comprises the following steps:
treating the carbon nanotubes by using a mixed acid solution to obtain modified carbon nanotubes, wherein the reaction condition is 50 ℃ for 3 hours; wherein the mixed acid is a mixture of concentrated sulfuric acid and concentrated nitric acid, and the volume ratio is 3:1; the ratio of the mixed acid solution to the carbon nanotubes is 1g:150mL.
S3, adding the water-based epoxy resin, the modified carbon nanotubes prepared in the S2 and water according to the formula amount to obtain a base material A.
S4, adding the leveling agent and the defoaming agent into the base material A prepared in the step S3 according to the formula amount under the stirring state, adding the curing agent diethylaminopropylamine according to the formula amount after uniformly stirring, and uniformly mixing to obtain the anti-corrosion composite coating.
S5, spraying the prepared anticorrosive composite coating in the S4 on the surface of the clean steel structure prepared in the S1, and baking at 70 ℃ for 3 hours.
Comparative example 3
An anticorrosive composite coating for a steel structure surface, comprising: 45 parts of aqueous epoxy resin, 13 parts of curing agent, 0.4 part of leveling agent, 0.15 part of defoaming agent and 17 parts of water.
The preparation method of the anti-corrosion composite coating on the surface of the steel structure specifically comprises the following steps:
s1, carrying out oil and rust removal treatment on the surface of the steel structure, and polishing and grinding to obtain the clean steel structure.
S2, adding water-based epoxy resin and water according to the formula amount to obtain a base material A.
S3, adding the leveling agent and the defoaming agent into the base material A prepared in the step S2 according to the formula amount under the stirring state, adding the curing agent diethylaminopropylamine according to the formula amount after uniformly stirring, and uniformly mixing to obtain the anti-corrosion composite coating.
S4, spraying the prepared anticorrosive composite coating in the S3 on the surface of the clean steel structure prepared in the S1, and baking at 70 ℃ for 3 hours.
Comparative example 4
The water-based paint is characterized by comprising the following raw materials in parts by weight:
40 parts of carbon nano tube modified fluorine-containing polyacrylate emulsion, 0.2 part of defoamer, 0.2 part of flatting agent, 2 parts of film forming auxiliary agent and 15 parts of deionized water.
A method of preparing a coating composition comprising the steps of: (1) pretreating the carbon nanotubes: adding 1g of carbon nano tube and 150l of sodium hydroxide into a three-mouth bottle, heating to 100+/-3 ℃ under stirring at 500rpm, carrying out constant-temperature reflux treatment for 2 hours, naturally cooling to room temperature, adding distilled water, filtering and washing for many times to neutrality, and then adjusting to the required pH concentration by using NaOH to obtain the hydroxylated carbon nano tube sodium hydroxide solution.
(2) 20ml of 3-methyl-8-quinoline sulfonic acid, a proper amount of hydroxylated carbon nano tube sodium hydroxide solution with pH of 8-9, 0.1mg of dichloro pentamethyl cyclopentadienyl rhodium dimer, isopropanol and water deionized water are added into a three-neck flask, the volume ratio of the isopropanol to the water deionized water is 3:1, and the mixture is stirred for 10min at the temperature of 20 ℃; then adding an inert metal anode and an inert metal cathode into the three-mouth bottle, carrying out electrochemical synthesis at 45 ℃ under the direct current of 10mA for 10h, and removing part of solvent by using a rotary evaporator after the reaction is finished to obtain the modified carbon tube dispersion liquid.
(3) Adding 0.5g of sorbitan monooleate nonionic surfactant and 0.5g of sodium dodecyl benzene sulfonate anionic surfactant into 30g of deionized water solution, heating to 35 ℃, stirring for 10min, and cooling to room temperature.
(4) To the solution obtained in the step (3), 0.025g of ammonium persulfate, 7g of methyl methacrylate, 5g of butyl acrylate, 0.3g of ethyl methacrylate, 1.5g of hydroxypropyl acrylate and 1.4g of dodecafluoroheptyl methacrylate were added in this order, and the mixture was sufficiently stirred to obtain a solution A.
(5) Into a four-necked flask, 0.5g of sorbitan monooleate nonionic surfactant and 0.5g of sodium dodecyl benzene sulfonate anionic surfactant are added into 30g of deionized water solution, the temperature is raised to 35 ℃, stirring is carried out for 10min, after cooling to room temperature, shielding gas is introduced, 0.025g of ammonium persulfate, 3.5g of methyl methacrylate, 2.5g of butyl acrylate, 0.15g of ethyl methacrylate, 0.75g of hydroxypropyl acrylate, 0.7g of dodecafluoroheptyl methacrylate and 10ml of 2wt.% modified carbon tube dispersion are added, and after sufficient stirring, the temperature is raised to 75 ℃ to obtain solution B.
(6) And (3) dropwise adding the solution A obtained in the step (4) into the solution B obtained in the step (5), controlling the dropwise adding time to be within 2 hours, controlling the temperature to 75 ℃, keeping the temperature for 2 hours after dropwise adding is stopped, cooling to 30 ℃, and regulating the pH to be neutral to obtain the carbon nano tube modified fluorine-containing polyacrylate emulsion.
(7) Adding the carbon nanotube-containing acrylate copolymer emulsion, the organosilicon defoamer, the leveling agent, the film-forming auxiliary agent and the deionized water into a reaction kettle, and stirring for 10min at the rotation speed of 600r/min to disperse and defoam the carbon nanotube-containing acrylate copolymer emulsion to obtain the coating composition. When the coating composition is used, the Bayer curing agent XP2655 is emulsified by deionized water, then the Bayer curing agent emulsion is added into the coating composition, stirred for 10min at the rotating speed of 600r/min, then sprayed on the surface of a substrate to be treated, and dried and cured at room temperature to obtain the coating.
Salt spray resistance test: and (3) placing the coating in an SST-100 salt spray test box for salt spray resistance test, and observing the surface phenomenon of the coating. The specific test results are shown in table 1.
Table 1 results of Performance tests (120 h) for the different examples and comparative examples
As can be seen from Table 1, the anti-corrosion composite coatings prepared in examples 1 to 5 of the invention have better salt spray resistance, and comparative example 1 does not oxidize the carbon nanotubes with mixed acid, and the coating film is pulverized after the test, which shows that the mixed acid oxidation promotes the dispersion of the carbon nanotubes; comparative example 2, in which the carbon nanotubes were not subjected to phytic acid modification, the coating film was cracked and pulverized after the test, shows that the phytic acid modification makes the carbon nanotubes uniformly dispersed and not easy to agglomerate, and plays an important role; comparative example 3, in which no carbon nanotubes were added, the coating film peeled off, demonstrating that the carbon nanotubes enhanced the salt spray resistance of the coating; comparative example 4 uses a modified acrylic resin and modified carbon nanotubes, and the salt spray resistance is inferior to examples 1 to 5, probably because the acrylic resin itself has weaker adhesion to the steel structure than the epoxy resin.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The anti-corrosion composite coating for the surface of the steel structure is characterized by comprising the following raw materials: 40-50 parts of water-based epoxy resin, 10-15 parts of curing agent, 4.5-7 parts of modified carbon nano tube, 0.2-0.5 part of leveling agent, 0.05-0.2 part of defoaming agent and 15-20 parts of water.
2. An anticorrosive composite coating for a steel structure surface, comprising: 43-46 parts of water-based epoxy resin, 12-14 parts of curing agent, 5-6 parts of modified carbon nano tube, 0.3-0.4 part of flatting agent, 0.1-0.15 part of defoaming agent and 16-18 parts of water.
3. An anticorrosive composite coating for a steel structure surface, comprising: 45 parts of aqueous epoxy resin, 13 parts of curing agent, 6 parts of modified carbon nano tube, 0.4 part of leveling agent, 0.15 part of defoaming agent and 17 parts of water.
4. The method for preparing the anti-corrosion composite coating on the surface of the steel structure according to claim 1, which is characterized by comprising the following steps:
s1, carrying out oil and rust removal treatment on the surface of a steel structure, and polishing and grinding to obtain a clean steel structure;
s2, carrying out acid modification on the carbon nano tube to obtain a modified carbon nano tube;
s3, adding the water-based epoxy resin, the modified carbon nanotubes prepared in the S2 and water according to the formula amount to obtain a base material A;
s4, adding the leveling agent and the defoaming agent into the base material A prepared in the step S3 according to the formula amount in a stirring state, adding the curing agent after stirring, and uniformly mixing to obtain the anti-corrosion composite coating.
5. The method for preparing the corrosion-resistant composite coating on the surface of the steel structure according to claim 4, wherein the method for preparing the acid-modified carbon nano tube comprises the following steps:
(1) Treating the carbon nanotubes by using a mixed acid solution to obtain acidified carbon nanotubes;
(2) Adding the acidified carbon nanotube obtained in the step (1) into deionized water, adding phytic acid after ultrasonic dispersion, filtering a solvent, and washing with deionized water to obtain the modified carbon nanotube modified by phytic acid.
6. The method for preparing an anticorrosive composite coating for a steel structure surface according to claim 5, wherein the mixed acid in (1) is a mixture of concentrated sulfuric acid and concentrated nitric acid, and the volume ratio is 3:1.
7. The method for producing an anticorrosive composite coating for a steel structure surface according to claim 6, wherein the ratio of the mixed acid solution to the carbon nanotubes in (1) is 1g:150mL.
8. The method for preparing an anticorrosive composite coating for a steel structure surface according to claim 7, wherein the mass ratio of the phytic acid to the acidified carbon nanotubes in (2) is: 4:1.
9. The corrosion resistant composite coating for a steel structure surface according to claim 1, wherein said curing agent is diethylaminopropylamine.
10. Use of an anticorrosive composite coating according to claim 1 for the preparation of a salt spray resistant anticorrosive coating for a steel structure surface.
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