CN116285628A - Preparation method of pipeline steel-based underwater cooperative self-repairing super-hydrophobic coating - Google Patents
Preparation method of pipeline steel-based underwater cooperative self-repairing super-hydrophobic coating Download PDFInfo
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- 239000011248 coating agent Substances 0.000 title claims abstract description 72
- 238000000576 coating method Methods 0.000 title claims abstract description 72
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 47
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 43
- 239000010959 steel Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 36
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000004814 polyurethane Substances 0.000 claims abstract description 24
- 229920002635 polyurethane Polymers 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 16
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 12
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims description 47
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 26
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 230000002195 synergetic effect Effects 0.000 claims description 15
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- 238000005507 spraying Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- CLJTZNIHUYFUMR-UHFFFAOYSA-M sodium;hydrogen carbonate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].OC([O-])=O.OC(=O)CC(O)(C(O)=O)CC(O)=O CLJTZNIHUYFUMR-UHFFFAOYSA-M 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 7
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 7
- -1 hydroxypropyl Chemical group 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- 229920002545 silicone oil Polymers 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000011527 polyurethane coating Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 2
- KYIDJMYDIPHNJS-UHFFFAOYSA-N ethanol;octadecanoic acid Chemical compound CCO.CCCCCCCCCCCCCCCCCC(O)=O KYIDJMYDIPHNJS-UHFFFAOYSA-N 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 244000137852 Petrea volubilis Species 0.000 claims 1
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 12
- 239000001257 hydrogen Substances 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 4
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- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 description 6
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- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000003921 oil Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
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- 230000008439 repair process Effects 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
- B05D1/38—Successively applying liquids or other fluent materials, e.g. without intermediate treatment with intermediate treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/005—Repairing damaged coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/58—No clear coat specified
- B05D7/586—No clear coat specified each layer being cured, at least partially, separately
-
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/10—Metallic substrate based on Fe
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2503/00—Polyurethanes
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention discloses a preparation method of a pipeline steel-based underwater cooperative self-repairing super-hydrophobic coating. When the coating is cut or scratched, the damaged part is repaired by fast connection of hydrogen bonds on the polyurethane main chain in the atmosphere environment, and meanwhile, the modified particles on the upper layer are driven to recover the superhydrophobicity of the coating. In an underwater environment, the self-repairing of the polyurethane hydrogen bond needs a period of time, in which water reacts with the upper sodium bicarbonate and the citric acid layer to locally form bubbles at the damaged part, so that the coating is restored to a Cassie state for a period of time until the hydrogen bond is repaired and the scratch heals. The invention has the advantages of simple process, low production cost, high stability and the like, and has very wide application prospect.
Description
Technical Field
The invention relates to the technical field of metal material surface modification, in particular to a preparation method of a pipeline steel-based underwater cooperative self-repairing super-hydrophobic coating.
Background
In the field of offshore petroleum and petrochemical exploitation and transportation, pipeline steel is a common engineering metal material in the exploitation and transportation process. The hydrophilicity of the pipeline steel can lead to the reduction of transportation efficiency in the practical application process, directly influences production and transportation, and causes a plurality of problems such as energy waste, equipment damage, and increase of maintenance cost. The preparation of the super-hydrophobic surface on the pipeline steel matrix is a simpler method, so that the hydrophobicity of the water phase mixture on the pipeline wall is increased, the transportation efficiency is improved, the energy consumption in the transportation process is reduced, and the energy is saved.
The superhydrophobic surfaces prepared by various methods are poor in wear resistance at present, because the micro/nano-scale rough structures of the surfaces are extremely easy to damage. Chinese patent No. 108385139A discloses a pipeline steel-based decoupling wear-resistant super-hydrophobic oleophobic coating, a preparation method and application thereof, wherein the wear resistance of the coating is improved through the prepared CuO super-hydrophobic coating, but the coating does not have a self-repairing function. Researchers have suggested the introduction of multiple dynamic bonds in self-repairing elastomers to balance the above-described problems of preparing self-repairing composites with excellent overall properties. However, for most self-healing elastomers, their lower mechanical strength still does not meet the requirements of the structural material and also does not perform the self-healing function under water.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a preparation method of an underwater cooperative self-repairing super-hydrophobic coating of a pipeline steel base, which utilizes the self-repairing property of prepared polyurethane and the characteristic of self-generating bubbles generated by the reaction of sodium bicarbonate and citric acid when meeting water, and prepares the underwater cooperative self-repairing super-hydrophobic coating on the pipeline steel base by a spraying method.
The technical scheme of the invention is as follows:
in a first aspect of the invention, a method for preparing a pipeline steel-based underwater cooperative self-repairing super-hydrophobic coating is provided, which comprises the following steps:
(1) Polishing a steel substrate to be smooth, ultrasonically cleaning, and drying for later use;
(2) Sequentially adding hexamethylene diisocyanate, hydroxypropyl silicone oil and a catalyst into an N, N-dimethylformamide solvent, heating the mixed solution to 60-80 ℃ for reaction for 6-8 hours, adding diluted 1, 4-butanediol into the solution, and heating the solution to 35-45 ℃ again for reaction for 6-9 hours to obtain polyurethane with self-repairing capability;
(3) Preparing a particle suspension, including unmodified micron silica suspension, modified nano titanium dioxide suspension and sodium bicarbonate-citric acid suspension;
(4) Coating self-repairing polyurethane on a steel substrate, and then sequentially spraying unmodified micron silicon dioxide suspension, sodium bicarbonate-citric acid suspension and modified nano titanium dioxide suspension to obtain the synergistic self-repairing super-hydrophobic coating.
The invention takes steel as a matrix, and the synergistic self-repairing super-hydrophobic coating is obtained through multi-step spraying, wherein self-repairing polyurethane is taken as a bonding layer in the coating, and nano titanium dioxide is taken as hydrophobic particles. When the coating is cut or scratched, in the atmosphere, the coating can repair damaged parts by fast connection of hydrogen bonds on a polyurethane main chain, and meanwhile, the modified particles on the upper layer are driven to restore the superhydrophobicity of the coating. In an underwater environment, the self-repairing of the polyurethane hydrogen bond needs a period of time, in which water reacts with the upper sodium bicarbonate and the citric acid layer to locally form bubbles at the damaged part, so that the coating is restored to a Cassie state for a period of time until the hydrogen bond is repaired and the scratch heals.
In some embodiments of the present invention, in step (1), the step (1) is performed by sequentially polishing with 240# water-abrasive paper, 400# water-abrasive paper and 1000# water-abrasive paper, and then performing ultrasonic cleaning in absolute ethanol for 15-20min.
The polished steel substrate can enable the coating to be better attached, and meanwhile, pollutants on the surface of the substrate can be removed through ultrasonic cleaning, so that the clean and smooth substrate surface can be obtained.
In some embodiments of the present invention, in step (2), 15-23 parts by weight of N, N-dimethylformamide solvent, 3-3.3 parts by weight of hexamethylene diisocyanate, 20-24 parts by weight of hydroxypropyl silicone oil, 1 part by weight of catalyst, and 0.75-0.9 part by weight of 1, 4-butanediol.
In some embodiments of the invention, in step (2), dibutyltin dilaurate is used as the catalyst.
In some embodiments of the invention, in step (3), 5-8 parts by weight of the microsilica particles are dispersed in 50-80 parts by weight of absolute ethanol, and then sonicated for 10-20 minutes to obtain an unmodified microsilica suspension.
In some embodiments of the present invention, in step (3), 0.8 to 1 part of stearic acid is dissolved in 80 to 120 parts of absolute ethanol solution, 5 to 8 parts of nano titanium dioxide particles are added thereto, magnetic stirring is performed for 1 to 2 hours, and then ultrasonic oscillation is performed for 20 to 40 minutes, so as to obtain a modified nano titanium dioxide suspension; further, the mass fraction of the stearic acid ethanol solution in the suspension was 1wt%.
In some embodiments of the invention, in step (3), the weight fractionGrinding 0.8-1.5 parts of sodium bicarbonate and 0.5-0.8 parts of citric acid with agate mortar for 8-10min, and 15-25 mg/mL -1 And (2) dispersing the mixture in an acetone solution to obtain a sodium bicarbonate-citric acid suspension, wherein the molar mass ratio of sodium bicarbonate to citric acid is 1:3.
since the layer is sensitive to moisture, it should be in an inert environment (N 2 ) And down-deposited to prevent condensation caused by evaporation of acetone as much as possible.
In some embodiments of the present invention, in step (4), the self-healing polyurethane is cured at a temperature of 60 to 80 ℃ for 1 to 2 hours after being coated on the steel substrate to obtain the self-healing polyurethane coating in a semi-cured state.
In some embodiments of the invention, in step (4), after spraying the unmodified microsilica suspension, curing and drying is performed at a temperature of 60-80 ℃ for 30-40 min.
In some embodiments of the present invention, in step (4), after spraying the modified nano-titania suspension, curing is performed at a temperature of 60-80 ℃ for 1-2 hours, thereby obtaining the synergistic self-repairing superhydrophobic coating.
And (3) dripping a water drop on the surface of the obtained cooperative self-repairing super-hydrophobic coating to measure the contact angle, wherein the contact angle is larger than 150 degrees, and the rolling angle is smaller than 10 degrees.
One or more of the technical schemes of the invention has the following beneficial effects:
(1) According to the preparation method of the underwater cooperative self-repairing super-hydrophobic coating, provided by the invention, the underwater cooperative self-repairing super-hydrophobic coating is prepared on a pipeline steel substrate by utilizing the self-repairing property of the prepared polyurethane and the characteristic of self-generating bubbles generated by the reaction of sodium bicarbonate and citric acid when meeting water through a spraying method, so that the underwater cooperative self-repairing super-hydrophobic coating has excellent wear resistance and self-repairing property, and the self-repairing of the super-hydrophobic coating can be realized under water.
(2) When the coating is cut or scratched, the damaged part can be repaired through the rapid connection of hydrogen bonds on a polyurethane main chain in the atmosphere environment, and the modified particles on the upper layer are driven to restore the superhydrophobicity of the coating. In an underwater environment, the self-repairing of the polyurethane hydrogen bond needs a period of time, in which water reacts with the upper sodium bicarbonate and the citric acid layer to locally form bubbles at the damaged part, so that the coating is restored to a Cassie state for a period of time until the hydrogen bond is repaired and the scratch heals.
(3) The preparation method of the underwater cooperative self-repairing super-hydrophobic coating has the advantages of simple equipment, low cost, higher success rate, no special requirement on the shape of a matrix sample, and good industrial application prospect.
Drawings
FIG. 1 is a SEM image of a synergistic self-repairing superhydrophobic coating of example 1 of the invention at 1000 times;
FIG. 2 is an EDS diagram of a synergistic self-repairing superhydrophobic coating of example 1 of the invention;
FIG. 3 is a graph showing the comparison of the self-repairing of the cooperative self-repairing super-hydrophobic coating in example 1 of the present invention;
fig. 4 is a graph of the contact angle of a water droplet on a synergistic self-healing superhydrophobic coating in example 1 of the invention.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Example 1
The coating No. 1 is prepared according to the following preparation method:
(1) Pretreatment of steel substrates: the steel coupon was polished smooth with sandpaper. The method comprises the following specific steps: and polishing the steel matrix sample by using 240# water-abrasive paper, 400# water-abrasive paper and 1000# water-abrasive paper, and putting the polished sample into absolute ethyl alcohol for ultrasonic cleaning for 20min so as to remove pollutants on the surface of the sample.
(2) Preparation of self-repairing polyurethane: 3.15g of hexamethylene diisocyanate and 24g of hydroxypropyl silicone oil (weight average molecular weight 2200) were added successively to 20ml of N, N-dimethylformamide solvent at room temperature, and 1 drop of dibutyltin dilaurate was added as a catalyst. Slowly warm to 60 ℃ in an oil bath and seal for 6h. After the prepolymerization reaction, the temperature was lowered to room temperature, 0.85g of 1, 4-butanediol was diluted with 10mL of N, N-dimethylformamide solvent, then the mixture was added dropwise to the solution cooled to room temperature, the temperature was raised to 40℃and the reaction was carried out for 6 hours, thereby obtaining polyurethane having self-repairing ability.
(3) Preparation of particle suspensions: after dispersing 6g of micron silica particles in 50mL of absolute ethanol, the mixture was sonicated for 20min to obtain an unmodified micron silica suspension. 0.8g of stearic acid is dissolved in 100mL of absolute ethanol solution, 6g of nano titanium dioxide particles are added into the solution, the solution is stirred for 2 hours by magnetic force, and ultrasonic oscillation is carried out for 30 minutes, so as to obtain modified nano titanium dioxide suspension. 1g of sodium bicarbonate and 0.76g of citric acid were ground with an agate mortar for 10min and 20mg mL -1 Is dispersed in an acetone solution to give a sodium bicarbonate-citric acid suspension.
(4) Preparing a synergistic self-repairing super-hydrophobic coating: the prepared self-repairing polyurethane was uniformly coated on a steel substrate with a coating rod and cured in an oven at 60 ℃ for 1 hour to obtain a self-repairing polyurethane coating in a semi-cured state. Using an air spray gun, spraying unmodified micron silicon dioxide suspension at a distance of 10-15cm under a pressure of 0.4MPa, and putting into an oven at 60 ℃ for 30min for curing and drying to obtain a firm micron layer. The mixed sodium bicarbonate-citric acid suspension is sprayed in the same way onto the micrometer layer, which, because of its sensitivity to moisture, should be in an inert environment (N 2 ) And down-deposited to prevent condensation caused by evaporation of acetone as much as possible. And finally spraying the modified nano titanium dioxide suspension, and placing the sprayed sample into a 60 ℃ oven for curing for 1h to obtain the super-hydrophobic coating with the synergistic self-repairing of the underwater hydrogen bond and the self-produced bubbles.
An SEM image 1000 times of the synergistic self-repairing super-hydrophobic coating prepared in the embodiment is shown in fig. 1, and the micro-nano structure exists on the surface of the prepared coating; the EDS diagram of the synergistic self-repairing super-hydrophobic coating prepared in the embodiment is shown in fig. 2, and the element composition of the prepared coating can be seen as C, O, si, na, ti element; the comparison of the self-repairing front and back of the cooperative self-repairing super-hydrophobic coating prepared in the embodiment is shown in fig. 3, and it can be seen from the graph that the self-repairing of the prepared coating can be completed after 5 minutes; the contact angle of the water drop on the cooperative self-repairing super-hydrophobic coating prepared in the embodiment is shown in fig. 4, and it can be seen from the graph that the contact angle of the prepared coating is larger than 150 degrees, and the super-hydrophobic effect is achieved.
Example 2
The coating No. 2 is prepared according to the following method:
(1) Pretreatment of steel substrates: the steel coupon was polished smooth with sandpaper. The method comprises the following specific steps: and polishing the steel matrix sample by using 240# water-abrasive paper, 400# water-abrasive paper and 1000# water-abrasive paper, and putting the polished sample into absolute ethyl alcohol for ultrasonic cleaning for 20min so as to remove pollutants on the surface of the sample.
(2) Preparation of self-repairing polyurethane: 3g of hexamethylene diisocyanate and 20g of hydroxypropyl silicone oil (weight average molecular weight 2200) were added in sequence to 15ml of N, N-dimethylformamide solvent at room temperature, and 1 drop of dibutyltin dilaurate was added as a catalyst. Slowly warm to 70 ℃ in an oil bath and seal for 7h. After the prepolymerization reaction, the temperature was lowered to room temperature, 0.7g of 1, 4-butanediol was diluted with 10mL of N, N-dimethylformamide solvent, then the mixture was added dropwise to the solution cooled to room temperature, the temperature was raised to 35℃and the reaction was carried out for 8 hours, thereby obtaining polyurethane having self-repairing ability.
(3) Preparation of particle suspensions: after dispersing 5g of micron silica particles in 60mL of absolute ethanol, the mixture was sonicated for 20min to obtain an unmodified micron silica suspension. 0.8g of stearic acid is dissolved in 80mL of absolute ethanol solution, 5g of nano titanium dioxide particles are added into the solution, the solution is stirred for 1h by magnetic force, and ultrasonic oscillation is carried out for 20min, so as to obtain modified nano titanium dioxide suspension. 0.8g of sodium bicarbonate and 0.5g of citric acid were ground with an agate mortar for 10min, and then dispersed in an acetone solution at a concentration of 20 mg.mL-1 to obtain a sodium bicarbonate-citric acid suspension.
(4) Preparing a synergistic self-repairing super-hydrophobic coating: the prepared self-repairing polyurethane was uniformly coated on a steel substrate with a coating rod and cured in an oven at 60 ℃ for 1 hour to obtain a self-repairing polyurethane coating in a semi-cured state. Spraying unmodified micrometer silicon dioxide suspension at a distance of 10-15cm under 0.4MPa with air spray gun, and oven-drying at 60deg.C for 30min to obtain firm micrometer layer. The mixed sodium bicarbonate-citric acid suspension is sprayed in the same way onto the micrometer layer, which, because of its sensitivity to moisture, should be in an inert environment (N 2 ) And down-deposited to prevent condensation caused by evaporation of acetone as much as possible. And finally spraying the modified nano titanium dioxide suspension, and placing the sprayed sample into a 60 ℃ oven for curing for 1h to obtain the super-hydrophobic coating with the synergistic self-repairing of the underwater hydrogen bond and the self-produced bubbles.
Example 3
Coating No. 3 was prepared as follows:
(1) Pretreatment of steel substrates: the steel coupon was polished smooth with sandpaper. The method comprises the following specific steps: and polishing the steel matrix sample by using 240# water-abrasive paper, 400# water-abrasive paper and 1000# water-abrasive paper, and putting the polished sample into absolute ethyl alcohol for ultrasonic cleaning for 20min so as to remove pollutants on the surface of the sample.
(2) Preparation of self-repairing polyurethane: 3.3g of hexamethylene diisocyanate and 24g of hydroxypropyl silicone oil (weight average molecular weight 2200) were added in sequence to 23ml of N, N-dimethylformamide solvent at room temperature, and 1 drop of dibutyltin dilaurate was added as a catalyst. Slowly warm to 80 ℃ in an oil bath and seal for 8h. After the prepolymerization reaction, the temperature was lowered to room temperature, 0.9g of 1, 4-butanediol was diluted with 10mL of N, N-dimethylformamide solvent, then the mixture was added dropwise to the solution cooled to room temperature, the temperature was raised to 45℃and the reaction was carried out for 9 hours, thereby obtaining polyurethane having self-repairing ability.
(3) Preparation of particle suspensions: 880g of microsilica particles were dispersed in 60mL of absolute ethanol and sonicated for 20min to give an unmodified microsilica suspension. 1g of stearic acid is dissolved in 120mL of absolute ethanol solution, 8g of nano titanium dioxide particles are added into the solution, the solution is stirred for 2 hours by magnetic force, and ultrasonic vibration is carried out for 30 minutes, so as to obtain modified nano titanium dioxide suspension. 1.5g of sodium bicarbonate and 0.8g of citric acid were ground with an agate mortar for 10 minutes, and dispersed in an acetone solution at a concentration of 25 mg.mL-1 to obtain a sodium bicarbonate-citric acid suspension.
(4) Preparing a synergistic self-repairing super-hydrophobic coating: the prepared self-repairing polyurethane is uniformly coated on a steel substrate by a coating rod and is coated on the steel substrate by a coating rodCuring in an oven at 80 ℃ for 1h to obtain a self-repairing polyurethane coating in a semi-cured state. Using an air spray gun, spraying unmodified micron silicon dioxide suspension at a distance of 10-15cm under a pressure of 0.5MPa, and putting into an oven at 80 ℃ for 40min for curing and drying to obtain a firm micron layer. The mixed sodium bicarbonate-citric acid suspension is sprayed in the same way onto the micrometer layer, which, because of its sensitivity to moisture, should be in an inert environment (N 2 ) And down-deposited to prevent condensation caused by evaporation of acetone as much as possible. And finally spraying the modified nano titanium dioxide suspension, and placing the sprayed sample into an oven at 80 ℃ for curing for 1h to obtain the super-hydrophobic coating with the synergistic self-repairing of the underwater hydrogen bond and the self-produced bubbles.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The preparation method of the pipeline steel-based underwater cooperative self-repairing super-hydrophobic coating is characterized by comprising the following steps of:
(1) Polishing a steel substrate to be smooth, ultrasonically cleaning, and drying for later use;
(2) Sequentially adding hexamethylene diisocyanate, hydroxypropyl silicone oil and a catalyst into an N, N-dimethylformamide solvent, heating the mixed solution to 60-80 ℃ for reaction for 6-8 hours, adding diluted 1, 4-butanediol into the solution, and heating the solution to 35-45 ℃ again for reaction for 6-9 hours to obtain polyurethane with self-repairing capability;
(3) Preparing a particle suspension, including unmodified micron silica suspension, modified nano titanium dioxide suspension and sodium bicarbonate-citric acid suspension;
(4) Coating self-repairing polyurethane on a steel substrate, and then sequentially spraying unmodified micron silicon dioxide suspension, sodium bicarbonate-citric acid suspension and modified nano titanium dioxide suspension to obtain the synergistic self-repairing super-hydrophobic coating.
2. The method for preparing the pipeline steel-based underwater cooperative self-repairing super-hydrophobic coating according to claim 1, wherein in the step (1), the water-abrasive sand paper of No. 240, no. 400 and No. 1000 is adopted for polishing in sequence, and then ultrasonic cleaning is carried out in absolute ethyl alcohol for 15-20min.
3. The method for preparing the pipeline steel-based underwater cooperative self-repairing super-hydrophobic coating according to claim 1, wherein in the step (2), 15-23 parts by weight of N, N-dimethylformamide solvent, 3-3.3 parts by weight of hexamethylene diisocyanate, 20-24 parts by weight of hydroxypropyl silicone oil, 1 part by weight of catalyst and 0.75-0.9 part by weight of 1, 4-butanediol are used.
4. The method for preparing the pipeline steel-based underwater cooperative self-repairing super-hydrophobic coating according to claim 1, wherein in the step (2), dibutyltin dilaurate is adopted as a catalyst.
5. The method for preparing the pipeline steel-based underwater cooperative self-repairing super-hydrophobic coating according to claim 1, wherein in the step (3), 5-8 parts of micron silica particles are dispersed in 50-80 parts of absolute ethyl alcohol according to weight fraction, and then ultrasonic treatment is carried out for 10-20min to obtain unmodified micron silica suspension.
6. The method for preparing the pipeline steel-based underwater cooperative self-repairing super-hydrophobic coating according to claim 1, wherein in the step (3), 0.8-1 part of stearic acid is dissolved in 80-120 parts of absolute ethanol solution according to weight fraction, 5-8 parts of nano titanium dioxide particles are added into the solution, magnetic stirring is carried out for 1-2 hours, and then ultrasonic oscillation is carried out for 20-40 minutes, so as to obtain modified nano titanium dioxide suspension; further, the mass fraction of the stearic acid ethanol solution in the suspension was 1wt%.
7. The method for preparing the pipeline steel-based underwater cooperative self-repairing super-hydrophobic coating according to claim 1, which is characterized in that,in the step (3), 0.8 to 1.5 parts of sodium bicarbonate and 0.5 to 0.8 parts of citric acid are ground for 8 to 10 minutes by using an agate mortar according to weight percentage, and then 15 to 25 mg.mL -1 And (2) dispersing the mixture in an acetone solution to obtain a sodium bicarbonate-citric acid suspension, wherein the molar mass ratio of sodium bicarbonate to citric acid is 1:3.
8. the method for preparing the pipeline steel-based underwater cooperative self-repairing super-hydrophobic coating according to claim 1, wherein in the step (4), the self-repairing polyurethane is subjected to curing treatment at 60-80 ℃ for 1-2 hours after being coated on a steel substrate, so as to obtain the self-repairing polyurethane coating in a semi-cured state.
9. The method for preparing the pipeline steel-based underwater cooperative self-repairing super-hydrophobic coating according to claim 1, wherein in the step (4), after the unmodified micron silica suspension is sprayed, curing and drying are carried out at the temperature of 60-80 ℃ for 30-40 min.
10. The method for preparing the pipeline steel-based underwater cooperative self-repairing super-hydrophobic coating according to claim 1, wherein in the step (4), after the modified nano titanium dioxide suspension is sprayed, the coating is cured for 1-2 hours at the temperature of 60-80 ℃ to obtain the cooperative self-repairing super-hydrophobic coating.
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