CN115960479A - Nano-modified polymer self-repairing marine anticorrosive coating - Google Patents
Nano-modified polymer self-repairing marine anticorrosive coating Download PDFInfo
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Abstract
The invention discloses a nano-modified polymer self-repairing marine anticorrosive coating, and belongs to the technical field of marine anticorrosive materials. The coating is prepared from raw materials of epoxy resin, a curing agent, a solvent, zinc oxide, polymer nano-repair particles, talcum powder, n-butyl alcohol, a corrosion inhibitor and a bactericide. According to the invention, the polymer nanoparticles with self-repairing function are added into the traditional anticorrosive coating formula, so that the combination degree of the coating and the nanoparticles is enhanced; secondly, H can be lengthened 2 O、O 2 、Cl ‑ And the permeation path of corrosive media is equal, the permeation resistance of the coating is effectively enhanced, the physical impact resistance and the wear resistance of the coating are enhanced, and the corrosion prevention effect is obvious. Finally, when the coating is damaged, the polymer nano particles can promote the self-repairing of the coating and reduce the width of cracks. The coating of the invention is suitable forThe coating is used for various marine facilities with corrosion prevention requirements, such as marine building steel structures, ships and the like, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of marine anticorrosive materials, and particularly relates to a nano-modified polymer self-polishing marine anticorrosive coating.
Background
China has wide ocean area and long coastline, and can utilize a great number of ocean natural resources, especially wind energy. Among them, the wind energy resources are most abundant in the southeast coast of north to jiangsu province and south to hainan and the vicinity thereof. In order to develop and utilize wind energy resources more efficiently, offshore wind power generation is also increasingly emphasized and supported by the world.
However, in actual engineering implementation, the foundation structure of an offshore wind turbine is more complex than that of the ground, compared with the ground engineering, the offshore environment is more variable, the wind turbine is subject to long-term corrosion under the sea level and is also subject to the tests of offshore strong wind load and sea surface wave breaking impact, and higher requirements are provided for technical difficulty and construction cost. The steel pipe pile has high bearing capacity, high bending resistance and relatively simple pile sinking process, and is widely used in wind power engineering construction.
In the marine environment, particularly in the special area of spray splash, steel pipe piles are affected by more complex factors, such as: the corrosion of the steel pipe piles in the field can be relatively heavy due to the fact that the seawater surface is subjected to corrosion of oxygen and seawater at the same time, an environment of alternate wetting and drying formed by flowing seawater, stress action caused by spray impact and the like. Therefore, the research on the new technology and the new process for the long-acting corrosion prevention of the marine steel structure is a key point for breaking through the difficulties.
Organic coatings are one of the most common and effective means in metal protection. However, during transport and use, microscopic defects and macroscopic damage to the coating inevitably occur due to environmental and mechanical erosion, thereby impairing the protective properties of the coating. Therefore, the development of the self-repairing anticorrosive paint has great practical value.
However, the current marine coating research has single function, unstable corrosion resistance and no self-repairing capability at all. For example, CN103990588A discloses a long-acting protective heavy-duty anticorrosive coating for marine steel structures and a preparation method thereof, which mainly comprises a multi-carboxyl epoxy resin coating, a solvent-free epoxy coating, an acrylic epoxy finish or a polyurethane epoxy finish or an organosilicon epoxy finish or a fluorocarbon finish; CN202123747U invented an alloy resin composite anticorrosive coating for steel structure in marine environment, which comprises four layers including Zn coating, al coating, nano coating and polyurethane finish coating; CN200979035Y relates to a steel pipe with a marine anti-corrosion modified chlorinated rubber outer anti-corrosion coating; CN101987937A provides a super thick film anticorrosive coating of a splash zone marine steel structure, which consists of a primer, a finish coat and a finishing coat.
Therefore, how to develop a coating material with self-repairing function, which is suitable for the use in the high-salt and high-humidity environment of the ocean, is a technical problem to be solved urgently at present.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a polymer self-repairing marine anticorrosive coating with a self-repairing function and nano modification, which can realize long-acting stable corrosion prevention of parts such as marine ships, steel structures and the like and has a remarkable effect.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a nano-modified polymer self-repairing marine anticorrosive coating is prepared from the following raw materials in parts by weight: 30-40 parts of epoxy resin, 5-10 parts of curing agent, 20-25 parts of solvent, 5-8 parts of zinc oxide, 6-10 parts of polymer nano-repair particles, 1-3 parts of talcum powder, 1-3 parts of n-butanol, 1-3 parts of corrosion inhibitor and 1-3 parts of bactericide.
Further, the epoxy resin is bisphenol A epoxy resin.
Further, the curing agent is one or more of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine and diethylaminopropylamine.
Further, the solvent is one of methanol, ethanol or xylene.
Further, the preparation method of the polymer nano-repairing particle comprises the following steps:
(1) Adding 15g of epoxy acrylate into 10-15mL of corn oil, adding 0.5-1g of polyvinyl alcohol, and dispersing at high speed for 1-2h to obtain polymer emulsion;
(2) Uniformly dispersing 3g of hexadecyl methyl ammonium bromide and 5mL of polymer emulsion in 50mL of potassium hydroxide solution, heating to 40 ℃, then dropwise adding 1.5mL of ethyl orthosilicate, stirring for 12h, then adding 1mL of hydrazine hydrate, and reacting for 12h at 70 ℃;
(3) And cooling to room temperature, dispersing the product in an ethanol solution of hydrochloric acid, ultrasonically stirring in an ice-water bath for 3-5h, and washing and drying the product to obtain the polymer nano repair particles.
Furthermore, the rotating speed of the high-speed dispersion in the step (1) is 600-800r/min.
Further, the concentration of the potassium hydroxide solution in the step (2) is 1mol/L.
Further, the ethanol solution of hydrochloric acid in the step (3) is: 50mL of hydrochloric acid having a mass concentration of 30% was dispersed in 100mL of an anhydrous ethanol solution.
Furthermore, the corrosion inhibitor is one or more of benzotriazole, methyl 1,2, 4-triazole-3-carboxylate or thiadiazole.
Further, the bactericide is an isothiazolinone derivative.
A preparation method of a nano-modified polymer self-repairing marine anticorrosive coating comprises the following steps:
(1) Firstly, preparing polymer nano repairing particles;
(2) Dispersing epoxy resin, zinc oxide, talcum powder, normal butanol, corrosion inhibitor and bactericide in a solvent according to the weight parts, then adding polymer nano-repair particles under strong stirring, continuously performing high-speed fraction for 1-2h, then adding curing agent,
stirring at high speed for 3-5h to obtain anticorrosive paint, and spraying or brushing the anticorrosive paint on the surface of metal to form an anticorrosive coating.
The raw materials used in the present invention are commercially available.
Advantageous effects
Firstly, polymer nano particles with a self-repairing function are added into a traditional anticorrosive coating formula, in the process of preparing mesoporous nano silicon dioxide, epoxy acrylate is used for wrapping the silicon dioxide, and the epoxy acrylate fully fills gaps on the surface and the inside of the nano silicon dioxide, so that the binding degree of the coating and the nano particles is enhanced to a great extent; secondly, the addition of polymeric nanoparticles, on the one hand, can prolong H 2 O、O 2 、Cl - And the nano particles coated by the polymer can be quickly filled and repaired for different base materials, so that the permeability resistance of the coating is effectively enhanced, the physical impact resistance and the wear resistance of the coating are enhanced, and the corrosion prevention effect is obvious. Finally, when the coating is damaged, the polymer nano particles can promote the self-repairing of the coating and reduce the width of cracks. The coating is suitable for various marine facilities with corrosion resistance requirements, such as marine building steel structures, ships and the like, and has a wide application prospect.
Drawings
FIG. 1 is a surface electron micrograph of a test piece coated with this coating example 3 and comparative examples 1 to 2 after the scratch repair test.
Detailed Description
The technical solution of the present invention is further described below with reference to specific embodiments, but is not limited thereto.
Example 1
A nano-modified polymer self-repairing marine anticorrosive coating is prepared from the following raw materials in parts by weight: 30 parts of epoxy resin, 5 parts of curing agent, 20 parts of solvent, 5 parts of zinc oxide, 6 parts of polymer nano-repair particles, 1 part of talcum powder, 1 part of n-butyl alcohol, 1 part of corrosion inhibitor and 1 part of bactericide.
The epoxy resin is bisphenol A type epoxy resin.
The curing agent is ethylenediamine.
The solvent is methanol.
The preparation method of the polymer nano repairing particle comprises the following steps:
(1) Adding 15g of epoxy acrylate into 10mL of corn oil, adding 0.5g of polyvinyl alcohol, and dispersing at a high speed for 1h to obtain a polymer emulsion;
(2) Uniformly dispersing 3g of hexadecyl methyl ammonium bromide and 5mL of polymer emulsion in 50mL of potassium hydroxide solution, heating to 40 ℃, then dropwise adding 1.5mL of ethyl orthosilicate, stirring for 12h, then adding 1mL of hydrazine hydrate, and reacting for 12h at 70 ℃;
(3) And cooling to room temperature, dispersing the product in an ethanol solution of hydrochloric acid, ultrasonically stirring for 3 hours in an ice water bath, and washing and drying the product to obtain the polymer nano repairing particles.
The rotating speed of the high-speed dispersion in the step (1) is 600r/min.
The concentration of the potassium hydroxide solution in the step (2) is 1mol/L.
The ethanol solution of hydrochloric acid in the step (3) is as follows: 50mL of hydrochloric acid having a mass concentration of 30% was dispersed in 100mL of an anhydrous ethanol solution.
The corrosion inhibitor is benzotriazole.
The bactericide is an isothiazolinone derivative.
A preparation method of a nano-modified polymer self-repairing marine anticorrosive coating comprises the following steps:
(1) Firstly, preparing polymer nano repair particles;
(2) Dispersing epoxy resin, zinc oxide, talcum powder, n-butanol, corrosion inhibitor and bactericide in a solvent according to parts by weight, adding polymer nano-repair particles under strong stirring, continuously performing high-speed fractional 1h, then adding curing agent,
stirring at high speed for 3h to obtain the anticorrosive coating, and spraying or brushing the anticorrosive coating on the surface of the metal to form the anticorrosive coating.
Example 2
A nano-modified polymer self-repairing marine anticorrosive coating is prepared from the following raw materials in parts by weight: 35 parts of epoxy resin, 7 parts of curing agent, 22 parts of solvent, 6 parts of zinc oxide, 8 parts of polymer nano-repair particles, 2 parts of talcum powder, 2 parts of n-butyl alcohol, 2 parts of corrosion inhibitor and 2 parts of bactericide.
The epoxy resin is bisphenol A type epoxy resin.
The curing agent is hexamethylene diamine.
The solvent is ethanol.
The preparation method of the polymer nano repairing particle comprises the following steps:
(1) Adding 15g of epoxy acrylate into 15mL of corn oil, adding 1g of polyvinyl alcohol, and dispersing at a high speed for 2 hours to obtain a polymer emulsion;
(2) Uniformly dispersing 3g of hexadecyl methyl ammonium bromide and 5mL of polymer emulsion in 50mL of potassium hydroxide solution, heating to 40 ℃, then dropwise adding 1.5mL of tetraethoxysilane, stirring for 12 hours, then adding 1mL of hydrazine hydrate, and reacting for 12 hours at 70 ℃;
(3) And cooling to room temperature, dispersing the product in an ethanol solution of hydrochloric acid, ultrasonically stirring in an ice water bath for 4 hours, and washing and drying the product to obtain the polymer nano repairing particles.
The rotating speed of the high-speed dispersion in the step (1) is 700r/min.
The concentration of the potassium hydroxide solution in the step (2) is 1mol/L.
The ethanol solution of hydrochloric acid in the step (3) is as follows: 50mL of hydrochloric acid having a mass concentration of 30% was dispersed in 100mL of an anhydrous ethanol solution.
The corrosion inhibitor is 1,2, 4-triazole-3-methyl carboxylate.
The bactericide is an isothiazolinone derivative.
A preparation method of a nano-modified polymer self-repairing marine anticorrosive coating comprises the following steps:
(1) Firstly, preparing polymer nano repair particles;
(2) Dispersing epoxy resin, zinc oxide, talcum powder, n-butanol, corrosion inhibitor and bactericide in a solvent according to parts by weight, adding polymer nano-repair particles under strong stirring, continuously performing high-speed fractional 1h, then adding curing agent,
stirring at high speed for 3h to obtain the anticorrosive coating, and spraying or brushing the anticorrosive coating on the surface of the metal to form the anticorrosive coating.
Example 3
A nano-modified polymer self-repairing marine anticorrosive coating is prepared from the following raw materials in parts by weight: 40 parts of epoxy resin, 10 parts of curing agent, 25 parts of solvent, 8 parts of zinc oxide, 10 parts of polymer nano-repair particles, 3 parts of talcum powder, 3 parts of n-butyl alcohol, 3 parts of corrosion inhibitor and 3 parts of bactericide.
The epoxy resin is bisphenol A type epoxy resin.
The curing agent is diethylenetriamine.
The solvent is xylene.
The preparation method of the polymer nano repair particle comprises the following steps:
(1) Adding 15g of epoxy acrylate into 15mL of corn oil, adding 1g of polyvinyl alcohol, and dispersing at a high speed for 2 hours to obtain a polymer emulsion;
(2) Uniformly dispersing 3g of hexadecyl methyl ammonium bromide and 5mL of polymer emulsion in 50mL of potassium hydroxide solution, heating to 40 ℃, then dropwise adding 1.5mL of ethyl orthosilicate, stirring for 12h, then adding 1mL of hydrazine hydrate, and reacting for 12h at 70 ℃;
(3) And cooling to room temperature, dispersing the product in an ethanol solution of hydrochloric acid, ultrasonically stirring for 5 hours in an ice water bath, and washing and drying the product to obtain the polymer nano repairing particles.
The rotating speed of the high-speed dispersion in the step (1) is 800r/min.
The concentration of the potassium hydroxide solution in the step (2) is 1mol/L.
The ethanol solution of hydrochloric acid in the step (3) is as follows: 50mL of hydrochloric acid having a mass concentration of 30% was dispersed in 100mL of an anhydrous ethanol solution.
The corrosion inhibitor is thiadiazole.
The bactericide is an isothiazolinone derivative.
A preparation method of a nano-modified polymer self-repairing marine anticorrosive coating comprises the following steps:
(1) Firstly, preparing polymer nano repair particles;
(2) Dispersing epoxy resin, zinc oxide, talcum powder, n-butyl alcohol, corrosion inhibitor and bactericide in a solvent according to parts by weight, then adding polymer nano repair particles under strong stirring, continuously performing high-speed fraction for 2 hours, then adding curing agent,
stirring at high speed for 5h to obtain the anticorrosive coating, and spraying or brushing the anticorrosive coating on the surface of the metal to form the anticorrosive coating.
Comparative example 1
A nano-modified self-repairing marine anticorrosive coating is prepared from the following raw materials in parts by weight: 40 parts of epoxy resin, 10 parts of curing agent, 25 parts of solvent, 8 parts of zinc oxide, 10 parts of nano-repair particles, 3 parts of talcum powder, 3 parts of n-butyl alcohol, 3 parts of corrosion inhibitor and 3 parts of bactericide.
The epoxy resin is bisphenol A type epoxy resin.
The curing agent is diethylenetriamine.
The solvent is xylene.
The preparation method of the nano repairing particles comprises the following steps:
(1) Uniformly dispersing 3g of hexadecyl methyl ammonium bromide in 50mL of potassium hydroxide solution, heating to 40 ℃, then dropwise adding 1.5mL of tetraethoxysilane, stirring for 12 hours, then adding 1mL of hydrazine hydrate, and reacting for 12 hours at 70 ℃;
(2) And cooling to room temperature, dispersing the product in an ethanol solution of hydrochloric acid, ultrasonically stirring for 5 hours in an ice water bath, and washing and drying the product to obtain the nano repairing particles.
The concentration of the potassium hydroxide solution in the step (2) is 1mol/L.
The ethanol solution of hydrochloric acid in the step (3) is as follows: 50mL of hydrochloric acid having a mass concentration of 30% was dispersed in 100mL of an anhydrous ethanol solution.
The corrosion inhibitor is thiadiazole.
The bactericide is an isothiazolinone derivative.
A preparation method of a nano-modified self-repairing marine anticorrosive coating comprises the following steps:
(1) Firstly, preparing nano repairing particles;
(2) Dispersing epoxy resin, zinc oxide, talcum powder, n-butyl alcohol, corrosion inhibitor and bactericide in a solvent according to parts by weight, then adding the nano repairing particles under strong stirring, continuing to perform high-speed fractional treatment for 2 hours, then adding the curing agent, stirring at high speed for 5 hours to obtain an anticorrosive coating, and spraying or brushing the anticorrosive coating on the surface of metal to form the anticorrosive coating.
The comparative example is the same as example 3 except that no polymer emulsion is used for coating in the preparation process of the nano-repair particles.
Comparative example 2
A nano-modified polymer self-repairing marine anticorrosive coating is prepared from the following raw materials in parts by weight: 40 parts of epoxy resin, 10 parts of curing agent, 25 parts of solvent, 8 parts of zinc oxide, 10 parts of nano silicon dioxide, 3 parts of talcum powder, 3 parts of n-butyl alcohol, 3 parts of corrosion inhibitor and 3 parts of bactericide.
The epoxy resin is bisphenol A type epoxy resin.
The curing agent is diethylenetriamine.
The solvent is xylene.
The corrosion inhibitor is thiadiazole.
The bactericide is an isothiazolinone derivative.
A preparation method of a nano-modified polymer self-repairing marine anticorrosive coating comprises the following steps:
(1) Dispersing epoxy resin, zinc oxide, talcum powder, n-butyl alcohol, a corrosion inhibitor and a bactericide in a solvent according to parts by weight, adding nano silicon dioxide under strong stirring, continuing to perform high-speed fractional treatment for 2 hours, then adding a curing agent, stirring at high speed for 5 hours to obtain an anticorrosive coating, and spraying or brushing the anticorrosive coating on the surface of metal to form the anticorrosive coating.
This comparative example was conducted in the same manner as example 3 except that the polymeric nano-sized repair particles in example 3 were replaced with conventional commercially available nano-silica.
Performance testing
The pencil hardness test is carried out on the coating according to GB/T6739-2006 paint film hardness determined by a color paint and varnish pencil method, the coating adhesion test is carried out according to GB/T5210-2006 paint and varnish pull-open method adhesion test, and the flexibility test is carried out according to GB/1731-1993 paint film flexibility test method. The impact resistance of the coatings was tested in accordance with GB/T1732-1993 "determination of paint film impact resistance", the water resistance of the coatings was tested in accordance with method A of GB/T1733-1933 "determination of paint film Water resistance", the 10% HCl and 10% NaOH resistance of the coatings was tested in accordance with GB/T9274-1988 "determination of the liquid Medium resistance of paints and varnishes", and the neutral salt spray resistance of the coatings was tested in accordance with GB/T1771-2007 "determination of the neutral salt spray resistance of paints and varnishes".
The coatings of examples 1-3 and comparative examples 1-2 were applied to different positions of the same sample, and 20ml of bacterial suspension was applied at a concentration of 10 5 The suspension of cfu. ML of E.coli was dropped on the surface of the sterilized coated sample (the dry coating film was baked beforehand to remove the interference of VOC), and the initial plate colony count was A 0 (ii) a Covering with polyethylene film, culturing in a constant temperature and humidity incubator at 37 deg.C and relative humidity of 90% for 24 hr, counting plate colonies, and recording as A 1 。
Several performance tests are shown in Table 1
TABLE 1 Performance test results
The self-repairing effect of the coatings is further verified, mechanical scratches with the width of about 30 micrometers are scribed on each coating by using an art knife, after 7d, the self-repairing effect of the paint film is observed by using a scanning electron microscope, the effect is shown in fig. 1, the scratches of the coatings in the embodiment 3 are narrowed, the good self-repairing effect is shown, the comparative example 1 has obvious scratches and pores, the comparative example 2 is poor in repairing effect, and the scratches are obvious.
It should be noted that the above-mentioned embodiments are only some of the preferred modes for implementing the invention, and not all of them. Obviously, all other embodiments obtained by persons of ordinary skill in the art based on the above-mentioned embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Claims (9)
1. The nano-modified polymer self-repairing marine anticorrosive coating is characterized by comprising the following raw materials in parts by weight: 30-40 parts of epoxy resin, 5-10 parts of curing agent, 20-25 parts of solvent, 5-8 parts of zinc oxide, 6-10 parts of polymer nano-repair particles, 1-3 parts of talcum powder, 1-3 parts of n-butanol, 1-3 parts of corrosion inhibitor and 1-3 parts of bactericide.
2. The nano-modified polymer self-healing marine anticorrosive coating according to claim 1, wherein the epoxy resin is bisphenol a epoxy resin.
3. The nano-modified polymer self-repairing marine anticorrosive coating according to claim 1, wherein the curing agent is one or more of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine and diethylaminopropylamine.
4. The nano-modified polymeric self-healing marine anticorrosive coating according to claim 1, wherein the solvent is one of methanol, ethanol, or xylene.
5. The nano-modified polymer self-repairing marine anticorrosive coating as claimed in claim 1, wherein the preparation method of the polymer nano-repairing particles comprises:
(1) Adding 15g of epoxy acrylate into 10-15mL of corn oil, adding 0.5-1g of polyvinyl alcohol, and dispersing at high speed for 1-2h to obtain polymer emulsion;
(2) Uniformly dispersing 3g of hexadecyl methyl ammonium bromide and 5mL of polymer emulsion in 50mL of potassium hydroxide solution, heating to 40 ℃, then dropwise adding 1.5mL of ethyl orthosilicate, stirring for 12h, then adding 1mL of hydrazine hydrate, and reacting for 12h at 70 ℃;
(3) And cooling to room temperature, dispersing the product in an ethanol solution of hydrochloric acid, ultrasonically stirring in an ice-water bath for 3-5h, and washing and drying the product to obtain the polymer nano repair particles.
6. The nano-modified polymer self-repairing marine anticorrosive coating as claimed in claim 5, wherein the rotation speed of the high-speed dispersion in the step (1) is 600-800r/min.
7. The nano-modified polymer self-repairing marine anticorrosive coating of claim 5, wherein the ethanol solution of hydrochloric acid in step (3) is: 50mL of hydrochloric acid having a mass concentration of 30% was dispersed in 100mL of an anhydrous ethanol solution.
8. The nano-modified polymer self-repairing marine anticorrosive coating of claim 1, wherein the corrosion inhibitor is one or more of benzotriazole, methyl 1,2, 4-triazole-3-carboxylate or thiadiazole.
9. The nano-modified polymer self-repairing marine anticorrosive coating according to claim 1, wherein the bactericide is an isothiazolinone derivative.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575463A (en) * | 2009-06-04 | 2009-11-11 | 天津大学 | Composite electrophoresis particle of silicon dioxide and polymer core-shell structure and preparation method thereof |
| CN102390147A (en) * | 2011-09-06 | 2012-03-28 | 华南理工大学 | Automobile anticorrosive coating with self-recovery function and application thereof |
| CN102964956A (en) * | 2012-12-20 | 2013-03-13 | 上海滋普环保科技有限公司 | Environment-friendly antimicrobial odorless latex paint |
| US20130145957A1 (en) * | 2011-12-12 | 2013-06-13 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Corrosion inhibiting pigments and methods for preparing the same |
| CN105255324A (en) * | 2015-11-25 | 2016-01-20 | 蓬莱蔚阳新材料有限公司 | Hydrophobic and oleophobic coating with super-long durable corrosion resistance and low surface energy and preparation process of hydrophobic and oleophobic coating |
| CN107522868A (en) * | 2017-10-16 | 2017-12-29 | 湖北工业大学 | The preparation method of epoxy nano silica/block polymer complex emulsions |
| JP2020533424A (en) * | 2018-08-16 | 2020-11-19 | 中国科学院▲寧▼波材料技▲術▼▲与▼工程研究所Ｎｉｎｇｂｏ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｍａｔｅｒｉａｌｓ Ｔｅｃｈｎｏｌｏｇｙ ＆ Ｅｎｇｉｎｅｅｒｉｎｇ，Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ | Graphene nano-container-based paints, self-healing coating layers and their manufacturing methods and applications |
-
2023
- 2023-02-09 CN CN202310086983.4A patent/CN115960479A/en not_active Withdrawn
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575463A (en) * | 2009-06-04 | 2009-11-11 | 天津大学 | Composite electrophoresis particle of silicon dioxide and polymer core-shell structure and preparation method thereof |
| CN102390147A (en) * | 2011-09-06 | 2012-03-28 | 华南理工大学 | Automobile anticorrosive coating with self-recovery function and application thereof |
| US20130145957A1 (en) * | 2011-12-12 | 2013-06-13 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Corrosion inhibiting pigments and methods for preparing the same |
| CN102964956A (en) * | 2012-12-20 | 2013-03-13 | 上海滋普环保科技有限公司 | Environment-friendly antimicrobial odorless latex paint |
| CN105255324A (en) * | 2015-11-25 | 2016-01-20 | 蓬莱蔚阳新材料有限公司 | Hydrophobic and oleophobic coating with super-long durable corrosion resistance and low surface energy and preparation process of hydrophobic and oleophobic coating |
| CN107522868A (en) * | 2017-10-16 | 2017-12-29 | 湖北工业大学 | The preparation method of epoxy nano silica/block polymer complex emulsions |
| JP2020533424A (en) * | 2018-08-16 | 2020-11-19 | 中国科学院▲寧▼波材料技▲術▼▲与▼工程研究所Ｎｉｎｇｂｏ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｍａｔｅｒｉａｌｓ Ｔｅｃｈｎｏｌｏｇｙ ＆ Ｅｎｇｉｎｅｅｒｉｎｇ，Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅｓ | Graphene nano-container-based paints, self-healing coating layers and their manufacturing methods and applications |
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