CN119119870B - A super hydrophobic thermal conductive insulating coating and preparation method thereof - Google Patents
A super hydrophobic thermal conductive insulating coating and preparation method thereof Download PDFInfo
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Abstract
本发明涉及一种超憎水性导热绝缘涂料及其制备方法，属于涂料技术领域。本发明公开的超憎水性导热绝缘涂料包括以下原料组分：含氟弹性体聚合物、有机酸、溶剂、硫化剂和改性石墨烯。本发明以改性石墨烯为填料，具备了高导热和绝缘特性，其表面被含氟弹性体聚合物包覆，形成两层低表面能物质，改性石墨烯表面的微纳粗糙结构形成超憎水效果。并且经过长时间表面包覆的含氟弹性体聚合物被磨掉后，里层的改性石墨烯仍具有超憎水效果提高了涂料的耐用性。另外通过引入疏水基团提高了氟化石墨烯的分散性及与含氟弹性体聚合物的相容性。The present invention relates to a super hydrophobic thermally conductive insulating coating and a preparation method thereof, and belongs to the technical field of coatings. The super hydrophobic thermally conductive insulating coating disclosed in the present invention comprises the following raw material components: a fluorine-containing elastomer polymer, an organic acid, a solvent, a vulcanizing agent and modified graphene. The present invention uses modified graphene as a filler, and has high thermal conductivity and insulation properties. Its surface is coated with a fluorine-containing elastomer polymer to form two layers of low surface energy substances, and the micro-nano rough structure on the surface of the modified graphene forms a super hydrophobic effect. And after the fluorine-containing elastomer polymer coated on the surface is worn off for a long time, the modified graphene in the inner layer still has a super hydrophobic effect, which improves the durability of the coating. In addition, the dispersibility of the fluorinated graphene and its compatibility with the fluorine-containing elastomer polymer are improved by introducing hydrophobic groups.
Description
Technical Field
The invention belongs to the technical field of coatings, and relates to an ultraphobic heat-conducting insulating coating and a preparation method thereof.
Background
Ultraphobic coatings refer to the application of one or more layers of ultraphobic materials to the surface of a research solid to achieve its corrosion protection, water repellency, ice protection, self-cleaning, etc. functions with a high water contact angle (> 150 °) and a low roll angle (< 10 °). Ultraphobic coatings have shown significant value in everyday life, industrial applications, and scientific research, and the low surface energy characteristics of the surface of the applied ultraphobic coatings can remain undisturbed for a long period of time, achieving good self-cleaning stain resistance. In nature, the lotus leaf surface not only has a layer of waxy substance serving as low surface energy, but also has a double-layer microstructure, namely, the lotus leaf surface consists of two parts of micrometer-scale cells and nanometer-scale waxy crystals on the cells. The formation of ultraphobic surfaces has been found to be due to two factors, one being low surface energy species and the other being surface micronano asperities.
The graphene has a lamellar crystal structure and has the characteristics of low interlayer shear strength and high in-plane strength, so that the graphene has excellent heat conduction performance, water resistance and chemical stability, research and development are carried out, the original sp 2 hybridized carbon atoms are converted into sp 3 hybridized forms by introducing fluorine atoms, fluorocarbon bonds (C-F) are formed with the fluorine atoms in a sigma bond mode, and meanwhile, a graphene honeycomb carbon skeleton structure is structurally reserved. With the increase of the number of introduced fluorine atoms, the conjugated structure of the graphene skeleton is continuously destroyed, and finally, the conductive graphene is converted into a fluorinated graphene insulating material with the resistance exceeding 1G omega. The surface energy is even lower than that of graphene, so that the graphene has defects in film forming property, dispersibility, non-covalent bonding strength and the like, and the application in various fields is limited.
Disclosure of Invention
The invention relates to an ultraphobic heat-conducting insulating coating and a preparation method thereof, belonging to the technical field of coatings. The ultraphobic heat-conducting insulating coating comprises the following raw material components of a fluorine-containing elastomer polymer, organic acid, a solvent, a vulcanizing agent and modified graphene. The modified graphene is used as a filler, has high heat conduction and insulation characteristics, and the surface of the modified graphene is coated by the fluorine-containing elastomer polymer to form two layers of low-surface-energy substances, and the micro-nano rough structure on the surface of the modified graphene forms an ultraphobic effect. And after the fluorine-containing elastomer polymer coated on the surface of the inner layer is worn away, the modified graphene of the inner layer still has the ultraphobic effect, so that the durability of the coating is improved. In addition, the dispersibility of the fluorinated graphene and the compatibility of the fluorinated graphene with the fluorine-containing elastomer polymer are improved by introducing hydrophobic groups.
The aim of the invention can be achieved by the following technical scheme:
The ultraphobic heat-conducting insulating coating comprises, by weight, 80-100 parts of fluorine-containing elastomer polymer, 2-5 parts of organic acid, 300-400 parts of solvent, 2-5 parts of vulcanizing agent and 20-40 parts of modified graphene.
Further, the preparation method of the modified graphene comprises the following steps:
(1) Ultrasonically mixing graphene oxide with distilled water, then adding ammonium fluotitanate and boric acid, stirring and mixing, transferring into a reaction kettle for heating, then cooling and washing with distilled water, and drying in a drying box to obtain the fluorinated graphene;
(2) Mixing the fluorinated graphene, 3- (trimethylsilyl) phenylboronic acid and distilled water, adding a palladium catalyst for heating, cooling, washing with distilled water, and drying to obtain the modified graphene.
Further, the ratio of graphene oxide to distilled water to ammonium fluotitanate to boric acid in the step (1) is 100-120 mg/100-120 mL/1-2 g/1 g, wherein the graphene oxide consists of nano graphene oxide and micro graphene oxide with the mass ratio of 1:1, and the stirring and mixing time is 6-9min.
Further, the heating temperature and the heating time in the step (1) are 160-180 ℃ and 5-6 hours respectively, the cooling refers to cooling to room temperature, and the drying temperature and the drying time are 80-100 ℃ and 1-2 hours respectively.
Further, in the step (2), the mass ratio of the fluorinated graphene to the 3- (trimethylsilyl) phenylboronic acid to the palladium catalyst is 5-8:2:0.1-0.2, the ratio of the fluorinated graphene to distilled water is 2g:30-40mL, the heating temperature and the heating time are respectively 80-120 ℃ and 30-60min, and the drying temperature and the drying time are respectively 80-100 ℃ and 30min.
Further, the preparation method of the palladium catalyst in the step (2) comprises the steps of mixing an aluminum nitrate solution and silicon dioxide to form a mixed solution, enabling the pH value of the mixed solution to be 6, calcining to obtain a solid, putting the solid into a sodium chloropalladate solution, drying and calcining to obtain the palladium catalyst, wherein the mass ratio of the aluminum nitrate solution to the silicon dioxide is 2:1.8, the mass ratio of the aluminum nitrate solution is 10-20%, the calcining temperature is 200-300 ℃, the mass ratio of the solid to the sodium chloropalladate solution is 1:0.15-0.18, and the mass ratio of the sodium chloropalladate solution is 20-35%.
Further, the fluorine-containing elastomer polymer consists of polytrifluoropropyl methyl siloxane and polyvinylidene fluoride-hexafluoropropylene copolymer with the mass ratio of 1:1, the organic acid is acetic acid, the solvent is acetone, and the vulcanizing agent consists of sodium thiocyanate and hydroquinone with the mass ratio of 1:1.
Further, the preparation method of the ultraphobic heat-conducting insulating coating comprises the steps of adding the modified graphene into a solvent, stirring and dispersing, and then adding other raw material components for stirring and mixing to obtain the ultraphobic heat-conducting insulating coating.
The invention has the beneficial effects that:
The modified graphene is used as a filler, has high heat conduction and insulation characteristics, and the surface of the modified graphene is coated by the fluorine-containing elastomer polymer to form two layers of low-surface-energy substances, and the micro-nano rough structure on the surface of the modified graphene forms an ultraphobic effect. And after the fluorine-containing elastomer polymer coated on the surface of the inner layer is worn away, the modified graphene of the inner layer still has the ultraphobic effect, so that the durability of the coating is improved. In addition, the hydrophobic group of 3- (trimethylsilyl) phenylboronic acid is introduced into the fluorinated graphene, so that the dispersibility and the compatibility with the fluorine-containing elastomer polymer are improved, and the superhydrophobicity is further improved;
the sodium thiocyanate and the hydroquinone are used as vulcanizing agents, the sodium thiocyanate can improve the speed and the efficiency of the vulcanization reaction, the hydroquinone can stabilize the vulcanization process and reduce the influence of side reactions and unstable factors, the vulcanization process is rapid and stable by combining the sodium thiocyanate and the hydroquinone, and the paint can be rapidly formed at a lower temperature by combining the sodium thiocyanate and the hydroquinone with organic acid, so that the complex condition that the paint needs to be dried at a high temperature is overcome.
Detailed Description
In order to further describe the technical means and effects adopted by the present invention for achieving the intended purpose, the following detailed description will refer to the specific embodiments, structures, features and effects according to the present invention in conjunction with examples.
The ultraphobic heat-conducting insulating coating comprises, by weight, 80 parts of fluorine-containing elastomer polymer, 2 parts of organic acid, 300 parts of solvent, 2 parts of vulcanizing agent and 20 parts of modified graphene.
The preparation method of the modified graphene comprises the following steps:
(1) Ultrasonically mixing graphene oxide with distilled water, then adding ammonium fluotitanate and boric acid, stirring and mixing, transferring into a reaction kettle for heating, then cooling and washing with distilled water, and drying in a drying box to obtain the fluorinated graphene;
(2) Mixing the fluorinated graphene, 3- (trimethylsilyl) phenylboronic acid and distilled water, adding a palladium catalyst for heating, cooling, washing with distilled water, and drying to obtain the modified graphene.
In the step (1), the ratio of graphene oxide to distilled water to ammonium fluotitanate to boric acid is 100mg to 100mL to 1g, wherein the graphene oxide consists of nano graphene oxide and micro graphene oxide with the mass ratio of 1 to 1, and the stirring and mixing time is 6min.
The heating temperature and the heating time in the step (1) are 160 ℃ and 5 hours respectively, the cooling is that the cooling is carried out to room temperature, and the drying temperature and the drying time are 80 ℃ and 1 hour respectively.
In the step (2), the mass ratio of the fluorinated graphene to the 3- (trimethylsilyl) phenylboronic acid to the palladium catalyst is 5:2:0.1, the ratio of the fluorinated graphene to distilled water is 2g:30mL, the heating temperature and the heating time are respectively 80 ℃ and 30min, and the drying temperature and the drying time are respectively 80 ℃ and 30min.
The preparation method of the palladium catalyst in the step (2) comprises the steps of mixing an aluminum nitrate solution and silicon dioxide to form a mixed solution, enabling the pH value of the mixed solution to be 6, calcining to obtain a solid, putting the solid into a sodium chloropalladate solution, drying and calcining to obtain the palladium catalyst, wherein the mass ratio of the aluminum nitrate solution to the silicon dioxide is 2:1.8, the mass ratio of the aluminum nitrate solution is 10%, the calcining temperature is 200 ℃, the mass ratio of the solid to the sodium chloropalladate solution is 1:0.15, and the mass ratio of the sodium chloropalladate solution is 20%.
The fluorine-containing elastomer polymer consists of polytrifluoropropyl methyl siloxane and polyvinylidene fluoride-hexafluoropropylene copolymer with the mass ratio of 1:1, the organic acid is acetic acid, the solvent is acetone, and the vulcanizing agent consists of sodium tripolythiocyanate and hydroquinone with the mass ratio of 1:1.
The preparation method of the ultraphobic heat-conducting insulating coating comprises the steps of adding modified graphene into a solvent, stirring and dispersing, and then adding other raw material components for stirring and mixing to obtain the ultraphobic heat-conducting insulating coating.
The silicon dioxide is purchased from Jikang/631-86-9, the polytrifluoropropyl methyl siloxane is purchased from Shi Nei/63148-56-1, the polyvinylidene fluoride-hexafluoropropylene copolymer is purchased from Rana white/9011-17-0, and the cyanuric acid monosodium salt is purchased from Jiahui Xingjingjingzheng/41450-97-9.
The ultraphobic heat-conducting insulating coating comprises, by weight, 90 parts of a fluorine-containing elastomer polymer, 3.5 parts of an organic acid, 350 parts of a solvent, 3.5 parts of a vulcanizing agent and 30 parts of modified graphene.
The preparation method of the modified graphene comprises the following steps:
(1) Ultrasonically mixing graphene oxide with distilled water, then adding ammonium fluotitanate and boric acid, stirring and mixing, transferring into a reaction kettle for heating, then cooling and washing with distilled water, and drying in a drying box to obtain the fluorinated graphene;
(2) Mixing the fluorinated graphene, 3- (trimethylsilyl) phenylboronic acid and distilled water, adding a palladium catalyst for heating, cooling, washing with distilled water, and drying to obtain the modified graphene.
In the step (1), the ratio of graphene oxide to distilled water to ammonium fluotitanate to boric acid is 110mg to 110mL to 1.5g to 1g, wherein the graphene oxide consists of nano graphene oxide and micro graphene oxide with the mass ratio of 1 to 1, and the stirring and mixing time is 7min.
The heating temperature and the heating time in the step (1) are respectively 170 ℃ and 5.5 hours, the cooling is to cool to room temperature, and the drying temperature and the drying time are respectively 90 ℃ and 1.5 hours.
In the step (2), the mass ratio of the fluorinated graphene to the 3- (trimethylsilyl) phenylboronic acid to the palladium catalyst is 7:2:0.15, the ratio of the fluorinated graphene to distilled water is 2g:35mL, the heating temperature and the heating time are respectively 100 ℃ and 45min, and the drying temperature and the drying time are respectively 90 ℃ and 30min.
The preparation method of the palladium catalyst in the step (2) comprises the steps of mixing an aluminum nitrate solution and silicon dioxide to form a mixed solution, enabling the pH of the mixed solution to be 6, calcining to obtain a solid, putting the solid into a sodium chloropalladate solution, drying and calcining to obtain the palladium catalyst, wherein the mass ratio of the aluminum nitrate solution to the silicon dioxide is 2:1.8, the mass ratio of the aluminum nitrate solution is 15%, the calcining temperature is 250 ℃, the mass ratio of the solid to the sodium chloropalladate solution is 1:0.16, and the mass ratio of the sodium chloropalladate solution is 28%.
The fluorine-containing elastomer polymer consists of polytrifluoropropyl methyl siloxane and polyvinylidene fluoride-hexafluoropropylene copolymer with the mass ratio of 1:1, the organic acid is acetic acid, the solvent is acetone, and the vulcanizing agent consists of sodium tripolythiocyanate and hydroquinone with the mass ratio of 1:1.
The preparation method of the ultraphobic heat-conducting insulating coating comprises the steps of adding modified graphene into a solvent, stirring and dispersing, and then adding other raw material components for stirring and mixing to obtain the ultraphobic heat-conducting insulating coating.
The silicon dioxide is purchased from Jikang/631-86-9, the polytrifluoropropyl methyl siloxane is purchased from Shi Nei/63148-56-1, the polyvinylidene fluoride-hexafluoropropylene copolymer is purchased from Rana white/9011-17-0, and the cyanuric acid monosodium salt is purchased from Jiahui Xingjingjingzheng/41450-97-9.
The ultraphobic heat-conducting insulating coating comprises, by weight, 100 parts of a fluorine-containing elastomer polymer, 5 parts of an organic acid, 400 parts of a solvent, 5 parts of a vulcanizing agent and 40 parts of modified graphene.
The preparation method of the modified graphene comprises the following steps:
(1) Ultrasonically mixing graphene oxide with distilled water, then adding ammonium fluotitanate and boric acid, stirring and mixing, transferring into a reaction kettle for heating, then cooling and washing with distilled water, and drying in a drying box to obtain the fluorinated graphene;
(2) Mixing the fluorinated graphene, 3- (trimethylsilyl) phenylboronic acid and distilled water, adding a palladium catalyst for heating, cooling, washing with distilled water, and drying to obtain the modified graphene.
In the step (1), the ratio of graphene oxide to distilled water to ammonium fluotitanate to boric acid is 120mg to 120mL to 2g to 1g, wherein the graphene oxide consists of nano graphene oxide and micro graphene oxide with the mass ratio of 1 to 1, and the stirring and mixing time is 9min.
The heating temperature and the heating time in the step (1) are 180 ℃ and 6 hours respectively, the cooling is that the cooling is carried out to room temperature, and the drying temperature and the drying time are 100 ℃ and 2 hours respectively.
In the step (2), the mass ratio of the fluorinated graphene to the 3- (trimethylsilyl) phenylboronic acid to the palladium catalyst is 8:2:0.2, the ratio of the fluorinated graphene to distilled water is 2g:40mL, the heating temperature and the heating time are 120 ℃ and 60min respectively, and the drying temperature and the drying time are 100 ℃ and 30min respectively.
The preparation method of the palladium catalyst in the step (2) comprises the steps of mixing an aluminum nitrate solution and silicon dioxide to form a mixed solution, enabling the pH value of the mixed solution to be 6, calcining to obtain a solid, putting the solid into a sodium chloropalladate solution, drying and calcining to obtain the palladium catalyst, wherein the mass ratio of the aluminum nitrate solution to the silicon dioxide is 2:1.8, the mass ratio of the aluminum nitrate solution is 20%, the calcining temperature is 300 ℃, the mass ratio of the solid to the sodium chloropalladate solution is 1:0.18, and the mass ratio of the sodium chloropalladate solution is 35%.
The fluorine-containing elastomer polymer consists of polytrifluoropropyl methyl siloxane and polyvinylidene fluoride-hexafluoropropylene copolymer with the mass ratio of 1:1, the organic acid is acetic acid, the solvent is acetone, and the vulcanizing agent consists of sodium tripolythiocyanate and hydroquinone with the mass ratio of 1:1.
The preparation method of the ultraphobic heat-conducting insulating coating comprises the steps of adding modified graphene into a solvent, stirring and dispersing, and then adding other raw material components for stirring and mixing to obtain the ultraphobic heat-conducting insulating coating.
The silicon dioxide is purchased from Jikang/631-86-9, the polytrifluoropropyl methyl siloxane is purchased from Shi Nei/63148-56-1, the polyvinylidene fluoride-hexafluoropropylene copolymer is purchased from Rana white/9011-17-0, and the cyanuric acid monosodium salt is purchased from Jiahui Xingjingjingzheng/41450-97-9.
Comparative example 1
Based on example 2, an ultraphobic thermally conductive insulating coating comprises, by weight, 90 parts of a fluoroelastomer polymer, 3.5 parts of an organic acid, 350 parts of a solvent, 3.5 parts of a vulcanizing agent, and 30 parts of graphene.
The fluorine-containing elastomer polymer consists of polytrifluoropropyl methyl siloxane and polyvinylidene fluoride-hexafluoropropylene copolymer with the mass ratio of 1:1, the organic acid is acetic acid, the solvent is acetone, and the vulcanizing agent consists of sodium tripolythiocyanate and hydroquinone with the mass ratio of 1:1.
The preparation method of the ultraphobic heat-conducting insulating coating comprises the steps of adding modified graphene into a solvent, stirring and dispersing, and then adding other raw material components for stirring and mixing to obtain the ultraphobic heat-conducting insulating coating.
The poly (trifluoropropyl methyl siloxane) is purchased from Shi Neng/63148-56-1, the poly (vinylidene fluoride-hexafluoropropylene) copolymer is purchased from Rana white/9011-17-0, and the sodium salt of cyanuric acid is purchased from Jiahui Xingcheng/41450-97-9.
Comparative example 2
Based on example 2, an ultraphobic thermally conductive insulating coating comprises, by weight, 90 parts of a fluoroelastomer polymer, 3.5 parts of an organic acid, 350 parts of a solvent, 3.5 parts of a vulcanizing agent, and 30 parts of fluorinated graphene.
The preparation method of the fluorinated graphene comprises the following steps:
(1) And ultrasonically mixing graphene oxide with distilled water, then adding ammonium fluotitanate and boric acid, stirring and mixing, transferring into a reaction kettle for heating, then cooling, washing with distilled water, and drying in a drying oven to obtain the fluorinated graphene.
In the step (1), the ratio of graphene oxide to distilled water to ammonium fluotitanate to boric acid is 110mg to 110mL to 1.5g to 1g, wherein the graphene oxide consists of nano graphene oxide and micro graphene oxide with the mass ratio of 1 to 1, and the stirring and mixing time is 7min.
The heating temperature and the heating time in the step (1) are respectively 170 ℃ and 5.5 hours, the cooling is to cool to room temperature, and the drying temperature and the drying time are respectively 90 ℃ and 1.5 hours.
The fluorine-containing elastomer polymer consists of polytrifluoropropyl methyl siloxane and polyvinylidene fluoride-hexafluoropropylene copolymer with the mass ratio of 1:1, the organic acid is acetic acid, the solvent is acetone, and the vulcanizing agent consists of sodium tripolythiocyanate and hydroquinone with the mass ratio of 1:1.
The preparation method of the ultraphobic heat-conducting insulating coating comprises the steps of adding modified graphene into a solvent, stirring and dispersing, and then adding other raw material components for stirring and mixing to obtain the ultraphobic heat-conducting insulating coating.
The poly (trifluoropropyl methyl siloxane) is purchased from Shi Neng/63148-56-1, the poly (vinylidene fluoride-hexafluoropropylene) copolymer is purchased from Rana white/9011-17-0, and the sodium salt of cyanuric acid is purchased from Jiahui Xingcheng/41450-97-9.
Comparative example 3
On the basis of example 2, the monosodium salt of cyanuric acid in the vulcanizing agent was removed and replaced with hydroquinone of equal mass, the other conditions being identical to those of example 2.
Comparative example 4
On the basis of example 2, hydroquinone in the vulcanizing agent was removed, and replaced with an equal mass of monosodium thiocyanate salt, with the other conditions being identical to those of example 2.
1. Performance testing
Thermal conductivity test and insulation test the coatings prepared in example 2 and comparative examples 1-2 were coated with coatings of the same thickness on both sides of 1030 type aluminum foil plate of the same specification, and as a test sample, the test sample was measured for thermal conductivity by DZDR-S thermal conductivity meter, and the test sample was subjected to volume resistivity test by 7122 ac/dc withstand voltage insulation tester, and volume resistivity of the test sample was measured by using instrument volume resistivity module, and the volume resistivity of the coating was calculated by the specific formula: wherein P v is volume resistivity, R v is volume resistivity, s is electrode effective area, and h is sample thickness;
Measurement of hydrophobicity the coatings prepared in example 2 and comparative examples 1-2 were used as test samples, respectively, coated with the same thickness of the coating on an aluminum foil plate of the same specification, and the Contact Angle (CA) and the rolling angle (SA) were measured with a contact angle measuring instrument, the contact angle of the coating being an average of contact angles of 3 different points measured with 4. Mu.L of water drops on the surface of the test sample, and the rolling angle being an average of rolling angles of 3 different points measured with 10. Mu.L of water drops on the surface of the test sample;
Surface drying time test the coatings prepared in example 2 and comparative examples 3 to 4 were used as test pieces, which were coated on aluminum foil plates at normal temperature with the same thickness, and the surface drying time was obtained by using a cotton ball blowing method.
The results of the above tests are shown in Table 1.
Table 1 test results
Note that the critical resistivity of the insulating material (10 7. Omega. M)
As can be seen from table 1, example 2 is 0.76 different from comparative example 1 by 0.04, whereas in comparative example 2, the volume resistance of example 2 is larger than the critical resistivity of the insulating material, whereas comparative example 1 is much smaller than 10 7 Ω·m, comparative example 2 is equal to 10 7 Ω·m, the contact angle of example 2 is maximum and greater than 150 °, and the rolling angle is minimum and smaller than 10 °. Therefore, example 2 has good thermal conductivity and insulation while having ultraphobic effect, comparative example 1 uses graphene as a filler, which has excellent electrical conductivity and does not achieve ultraphobic effect, comparative example 2 uses fluorinated graphene as a filler, which has smaller volume resistivity than example 2, insulation effect is inferior to example 2, dispersibility and compatibility with fluoroelastomer polymer are inferior due to the fact that comparative example 2 does not use 3- (trimethylsilyl) phenylboronic acid to further modify fluorinated graphene, and thus the ultraphobic effect is inferior to example 2, and the addition of a single vulcanizing agent in comparative examples 3-4 affects film forming speed, and when both monosodium thiocyanate and hydroquinone act together, film forming process is rapid and stable.
The present invention is not limited in any way by the above-described preferred embodiments, but is not limited to the above-described preferred embodiments, and any person skilled in the art will appreciate that the present invention can be embodied in the form of a program for carrying out the method of the present invention, while the above disclosure is directed to equivalent embodiments capable of being modified or altered in some ways, it is apparent that any modifications, equivalent variations and alterations made to the above embodiments according to the technical principles of the present invention fall within the scope of the present invention.
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| CN118146697A (en) * | 2024-03-19 | 2024-06-07 | 烯旺新材料科技股份有限公司 | A method for preparing graphene-modified anticorrosive coating |
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| CN118146697A (en) * | 2024-03-19 | 2024-06-07 | 烯旺新材料科技股份有限公司 | A method for preparing graphene-modified anticorrosive coating |
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