CN115232537A - Photo-thermal response intelligent coating and preparation method thereof - Google Patents
Photo-thermal response intelligent coating and preparation method thereof Download PDFInfo
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- CN115232537A CN115232537A CN202210901915.4A CN202210901915A CN115232537A CN 115232537 A CN115232537 A CN 115232537A CN 202210901915 A CN202210901915 A CN 202210901915A CN 115232537 A CN115232537 A CN 115232537A
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- 238000000576 coating method Methods 0.000 title claims abstract description 69
- 239000011248 coating agent Substances 0.000 title claims abstract description 68
- 230000004044 response Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 30
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 21
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 claims abstract description 9
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 5
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- 229920000570 polyether Polymers 0.000 claims abstract description 5
- 239000000945 filler Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000006056 electrooxidation reaction Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 229920006334 epoxy coating Polymers 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 description 17
- 230000007797 corrosion Effects 0.000 description 17
- 239000000203 mixture Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 230000008439 repair process Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 229910000975 Carbon steel Inorganic materials 0.000 description 3
- 239000010962 carbon steel Substances 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 230000009545 invasion Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000000638 stimulation Effects 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a photo-thermal response intelligent coating and a preparation method thereof, wherein the photo-thermal response intelligent coating comprises silane coupling agent modified graphene oxide as a filler, film forming substances of neopentyl glycol diglycidyl ether and bisphenol A diglycidyl ether, and a curing agent of polyether amine D-230. The silane coupling agent modified graphene oxide can effectively improve the dispersion performance of graphene in an epoxy coating and avoid agglomeration. Graphene provides a physical shielding effect to prevent corrosive media from corroding metal substrates, and simultaneously, the damaged parts of the epoxy coating can be repaired through the photo-thermal conversion effect. The invention relates to a preparation process of an intelligent coating with photo-thermal response, which can realize self-repairing of a damaged part of the coating by near infrared light and has higher practicability and economic value.
Description
Technical Field
The invention belongs to the technical field of anticorrosive coatings, and particularly relates to an intelligent coating with photo-thermal response, and a preparation method and application thereof.
Background
Metal corrosion can result in significant economic losses and serious safety hazards. According to the related statistical data, the total corrosion cost in 2014 of China accounts for about 3.34% of the GDP in the same year. Corrosion of metals generally proceeds by two routes: (1) The metal is directly contacted with a corrosive medium to generate chemical corrosion caused by chemical reaction; (2) The metal material is in contact with the electrolyte solution, and electrode reaction occurs to cause electrochemical corrosion. In real life, the main route of metal corrosion is electrochemical corrosion. From the thermodynamic aspect, the Gibbs free energy is reduced in the metal corrosion process, and the process is a spontaneous process. In the case where metal corrosion cannot be avoided, the occurrence of corrosion can be delayed only by delaying it.
The main methods for protecting metals from corrosion include electrochemical protection, novel corrosion-resistant materials, corrosion inhibitor protection, coating protection and the like. The organic coating is a widely used anticorrosion method due to low cost and excellent anticorrosion effect, and accounts for about 2/3 of the total anticorrosion expenditure. The organic coating can inhibit electrode reaction in the corrosion process by isolating the metal material matrix from the corrosion medium, thereby effectively preventing the occurrence of corrosion electrochemistry. However, the organic coating causes micro-damage and micro-cracks during the service process due to inevitable external invasion. If the damaged part is not repaired timely and effectively, the corrosion medium can reach the metal matrix from the damaged part, so that the corrosion can occur.
The chemical inertness and the barrier property of the graphene are utilized to prolong the invasion path of a corrosive medium, so that a labyrinth effect is formed, which is the basic design concept of the graphene-based anticorrosive coating. However, graphene is easy to cause aggregation tendency due to high specific surface area and surface energy, and the key to enhancing the corrosion resistance is to improve the dispersibility of graphene in a coating and the compatibility with a coating.
Aiming at the problems, the invention designs a preparation process of an intelligent coating with photo-thermal response, which can improve the dispersion performance of graphene in an epoxy coating, repair the damaged part through near infrared light when the coating is locally damaged, and prolong the service life of the coating.
Disclosure of Invention
In order to solve the technical problems that graphene is aggregated due to poor dispersibility in an organic coating and an existing anticorrosive coating is difficult to repair, the invention designs a preparation process of an intelligent coating with photo-thermal response. The preparation method is simple and safe to operate and low in preparation cost, and the electrochemical corrosion resistance of the coating can be effectively improved and the service life of the coating can be prolonged by repairing the coating part as a novel intelligent response coating.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a photo-thermal response intelligent coating is characterized in that graphene oxide modified by a silane coupling agent is used as a filler and added into bisphenol A diglycidyl ether and neopentyl glycol diglycidyl ether, then curing agent polyether amine D-230 is added, and the modified graphene doped self-repairing coating with a self-repairing function is obtained through curing, namely the photo-thermal response intelligent coating can repair damaged parts of the coating under the stimulation of near infrared light.
The specific method for modifying the graphene oxide by the silane coupling agent comprises the following steps: and dispersing graphene oxide in an organic solvent, performing ultrasonic treatment dispersion at room temperature for 30-60min, adding a silane coupling agent into the dispersed mixture, stirring for 10-12h in an oil bath kettle at 50-70 ℃, and finally washing, filtering and vacuum drying the obtained product to obtain the silane coupling agent modified graphene oxide.
Further, the silane coupling agent used in the present invention is a silane coupling agent having an epoxy group at one end, and the mass ratio of the silane coupling agent to graphene oxide is 10 to 15:1.
further, the proportions of the bisphenol A diglycidyl ether, the neopentyl glycol diglycidyl ether and the curing agent polyether amine D-230 of the organic coating are as follows (mass ratio): bisphenol a diglycidyl ether: neopentyl glycol diglycidyl ether: curing agent polyetheramine D-230=1:1:0.8 to 1.
Further, the addition amount of the filler silane coupling agent modified graphene oxide is 0.5 to 1.0 wt.% of the photothermal response intelligent coating. The coating is prepared by blade coating, and the curing temperature is 50 to 70 ℃. The thickness of the self-repairing coating of the modified graphene is 60-100 mu m.
Drawings
In order to more clearly illustrate the technical scheme of the preparation method of the modified graphene-based smart response coating, the drawings needed to be used in the embodiments are briefly introduced below;
FIG. 1 is a confocal drawing at the coating scribing in example 2;
FIG. 2 is a confocal image of the scribe coating after near-infrared repair in example 2;
FIG. 3 is a scanning electrochemical microscope image of the coating at the scribe line in example 2;
FIG. 4 is a scanning electrochemical microscope image of the coating of example 2 after near-infrared repair at the coating scribe.
Detailed description of the preferred embodiment
The invention will be further illustrated by the following specific examples, without limiting the scope of the invention thereto.
Example 1
The specific method for modifying graphene oxide by using the silane coupling agent comprises the following steps: dispersing 10 g of graphene oxide into isopropanol, performing ultrasonic treatment for 30min at room temperature, dispersing, adding 15 g of silane coupling agent into the dispersed mixture, stirring in an oil bath kettle at 50 ℃ for 10h, and finally washing, filtering and vacuum drying the obtained product to obtain the silane coupling agent modified graphene oxide.
Preparing an intelligent response coating of modified graphene: weighing 2 g of the mixture according to a mass ratio of 1:1 bisphenol a diglycidyl ether: neopentyl glycol diglycidyl ether was then put into a glass bottle and mixed well. 0.2 g of silane coupling agent modified graphene oxide is weighed and added into a glass bottle to be uniformly stirred, and then 0.8 g of curing agent polyetheramine D-230 is weighed and added into the glass bottle to be uniformly stirred. And coating the mixture on the surface of carbon steel by a scraper, and curing for 24 hours in a thermostat at 50 ℃ to obtain the intelligent response coating of the modified graphene.
And (3) damaged coating repairing process: manually cutting a cut on the surface of the cured coating, and then irradiating the cut part for 60s by using near infrared light with the wavelength of 808 nanometers to realize the repair of the damaged part.
Example 2
The specific method for modifying the graphene oxide by the silane coupling agent comprises the following steps: dispersing 10 g of graphene oxide into isopropanol, performing ultrasonic treatment for 30min at room temperature, dispersing, adding 10 g of silane coupling agent into the dispersed mixture, stirring in an oil bath kettle at 70 ℃ for 12h, and finally washing, filtering and vacuum drying the obtained product to obtain the silane coupling agent modified graphene oxide.
Preparing an intelligent response coating of modified graphene: weighing 2 g of the mixture according to a mass ratio of 1:1 bisphenol a diglycidyl ether: neopentyl glycol diglycidyl ether was then put into a glass bottle and mixed well. 0.1 g of silane coupling agent modified graphene oxide is weighed and added into a glass bottle to be uniformly stirred, and then 1 g of curing agent polyether amine D-230 is weighed and added into the glass bottle to be uniformly stirred. And coating the mixture on the surface of carbon steel by a scraper, and curing for 24 hours in a thermostat at 50 ℃ to obtain the intelligent response coating of the modified graphene.
And (3) damaged coating repairing process: manually notching the cured coating surface, and then irradiating the notched part for 60 seconds by using near infrared light with the wavelength of 808 nanometers to realize the repair of the damaged part.
Example 3
The specific method for modifying the graphene oxide by the silane coupling agent comprises the following steps: dispersing 10 g of graphene oxide into isopropanol at room temperature for 30min, adding 20 g of silane coupling agent into the dispersed mixture, stirring in an oil bath kettle at 70 ℃ for 12h, and finally washing, filtering and vacuum-drying the obtained product to obtain the silane coupling agent modified graphene oxide.
Preparing an intelligent response coating of modified graphene: weighing 2 g of the mixture according to the mass ratio of 1:1 bisphenol a diglycidyl ether: neopentyl glycol diglycidyl ether was then put into a glass bottle and mixed well. 0.3 g of silane coupling agent modified graphene oxide is weighed and added into a glass bottle to be uniformly stirred, and then 1 g of curing agent polyetheramine D-230 is weighed and added into the glass bottle to be uniformly stirred. And (3) coating the mixture on the surface of the carbon steel by a scraper, and curing for 24 hours in a 70 ℃ thermostat to obtain the intelligent response coating of the modified graphene.
And (3) repairing the damaged coating: manually cutting a cut on the surface of the cured coating, and then irradiating the cut part for 60s by using near infrared light with the wavelength of 808 nanometers to realize the repair of the damaged part.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
It is to be understood that the present invention is not limited to what has been described above, and that various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (10)
1. A preparation method of an intelligent coating with photo-thermal response is characterized in that graphene oxide modified by a silane coupling agent is used as a filler and added into bisphenol A diglycidyl ether and neopentyl glycol diglycidyl ether, then curing agent polyether amine D-230 is added, and the modified graphene doped self-repairing coating with the self-repairing function, namely the intelligent coating with photo-thermal response, is obtained through curing.
2. The method for preparing the photothermal response intelligent coating according to claim 1, wherein the silane coupling agent modified graphene oxide is prepared by the following specific method: and dispersing graphene oxide in an organic solvent, performing ultrasonic treatment at room temperature for 30-60min, adding a silane coupling agent, stirring in an oil bath kettle at 50-70 ℃ for 10-12 h, and finally washing, filtering and vacuum drying the obtained product to obtain the silane coupling agent modified graphene oxide.
3. The method for preparing the photothermal response smart coating according to claim 1 or 2, wherein the silane coupling agent is a silane coupling agent having an epoxy group at one end, and the mass ratio of the silane coupling agent to the graphene oxide is 10 to 15:1.
4. the method for preparing a photothermal responsive smart coating of claim 2, wherein the organic solvent is one or more of isopropyl alcohol, ethanol, tetrahydrofuran and toluene.
5. The method for preparing a photothermal responsive smart coating of claim 1, wherein the mass ratio of bisphenol a diglycidyl ether, neopentyl glycol diglycidyl ether, and curing agent polyetheramine D-230 is 1:1:0.8 to 1.
6. The method for preparing the photothermal response smart coating according to claim 1, wherein the silane coupling agent modified graphene oxide is added in an amount of 0.5 to 1.0 wt.% based on the photothermal response smart coating.
7. The method for preparing the photothermal response smart coating according to claim 1, wherein the curing temperature is 50 to 70 ℃.
8. The method for preparing the photothermal response smart coating according to claim 1, wherein the thickness of the photothermal response smart coating is 60 to 100 μm.
9. A photothermal responsive smart coating prepared by the method of any one of claims 1-8.
10. Use of the photothermal responsive smart coating of claim 9 for electrochemical corrosion protection.
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| CN202210901915.4A CN115232537A (en) | 2022-07-28 | 2022-07-28 | Photo-thermal response intelligent coating and preparation method thereof |
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| CN202210901915.4A CN115232537A (en) | 2022-07-28 | 2022-07-28 | Photo-thermal response intelligent coating and preparation method thereof |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105505128A (en) * | 2016-02-23 | 2016-04-20 | 南京工业大学 | Near-infrared light response type self-repair coating and preparation method thereof |
| CN106497341A (en) * | 2016-10-27 | 2017-03-15 | 北京科技大学 | Compound coatings of a kind of thermal response shape memory and preparation method thereof |
| CN111826074A (en) * | 2020-07-09 | 2020-10-27 | 北京科技大学 | Titanium nitride photo-thermal response based dual self-repairing coating and preparation method thereof |
| CN112920689A (en) * | 2021-03-11 | 2021-06-08 | 荆楚理工学院 | Heavy-duty anticorrosive paint with self-healing function and preparation and use methods thereof |
| CN113527983A (en) * | 2021-07-30 | 2021-10-22 | 中山大学 | Preparation method of decoration-free recyclable photo-thermal driving self-repairing epoxy anticorrosive coating material |
| CN113861800A (en) * | 2021-10-08 | 2021-12-31 | 中山大学 | Sunlight-driven self-repairing coating, coating and preparation method thereof |
| CN114517047A (en) * | 2022-03-03 | 2022-05-20 | 江南大学 | Preparation method of water-based epoxy-modified graphene oxide nano composite coating |
-
2022
- 2022-07-28 CN CN202210901915.4A patent/CN115232537A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105505128A (en) * | 2016-02-23 | 2016-04-20 | 南京工业大学 | Near-infrared light response type self-repair coating and preparation method thereof |
| CN106497341A (en) * | 2016-10-27 | 2017-03-15 | 北京科技大学 | Compound coatings of a kind of thermal response shape memory and preparation method thereof |
| CN111826074A (en) * | 2020-07-09 | 2020-10-27 | 北京科技大学 | Titanium nitride photo-thermal response based dual self-repairing coating and preparation method thereof |
| CN112920689A (en) * | 2021-03-11 | 2021-06-08 | 荆楚理工学院 | Heavy-duty anticorrosive paint with self-healing function and preparation and use methods thereof |
| CN113527983A (en) * | 2021-07-30 | 2021-10-22 | 中山大学 | Preparation method of decoration-free recyclable photo-thermal driving self-repairing epoxy anticorrosive coating material |
| CN113861800A (en) * | 2021-10-08 | 2021-12-31 | 中山大学 | Sunlight-driven self-repairing coating, coating and preparation method thereof |
| CN114517047A (en) * | 2022-03-03 | 2022-05-20 | 江南大学 | Preparation method of water-based epoxy-modified graphene oxide nano composite coating |
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