High-binding-force ceramic coating special for etching pot and layered coating method of high-binding-force ceramic coating

Abstract

The invention discloses a high-binding-force ceramic coating special for an etching pot and a layered coating method of the high-binding-force ceramic coating, and particularly relates to the field of chemical engineering and material synthesis. The coating is composed of a bottom layer and a surface layer, the bottom layer forms a three-dimensional network through crosslinking of a modified silane compound, an organosilicon-polyimide block copolymer, nano polyurethane microspheres and superfine silicon carbide powder, and strong chemical bonding is formed by carboxyl at the tail end of the three-dimensional network and a metal base material. The surface layer comprises a nano boron nitride sheet layer and a three-dimensional heat-conducting network constructed by silicon nanowhiskers, and a ceramic base material, nano silver, pH response type modified hydroxyapatite and a SiO2 coating layer are embedded into the surface layer. The coating method comprises the steps of substrate etching, respective preparation of the bottom layer coating and the surface layer coating, layered spraying and gradient curing. According to the invention, high binding force and excellent thermal conductivity of the coating and the base material are realized, and the durability and reliability of the etching pot under the condition of rapid change of temperature difference are remarkably improved.

Description

Technical Field

[0001] This invention relates to the field of chemical engineering and materials synthesis technology, and to a ceramic coating for high-adhesion etching pans and its layered coating method. Background Technology

[0002] In daily home cooking, woks are one of the most frequently used kitchen utensils, enduring complex environments such as high-temperature heating, sudden temperature changes, frequent scraping, and contact with grease. Traditional non-stick pans often use a polytetrafluoroethylene coating, which, while providing some non-stick properties, is prone to releasing harmful substances at high temperatures, has poor wear resistance, is easy to peel off, and has a limited lifespan.

[0003] In recent years, etched cookware has gained popularity among consumers due to its ability to accommodate the use of metal spatulas in cooking. Ceramic-coated etched cookware has also become increasingly favored in the market due to its advantages such as high-temperature resistance, non-toxicity, and ease of cleaning. However, existing ceramic coatings generally suffer from insufficient adhesion, micro-cracking, and localized peeling under prolonged high-temperature cooking and alternating hot and cold-cold conditions. Especially under conditions such as high-temperature dry heating, scraping with a metal spatula, or prolonged stewing, stress delamination can easily occur between the coating and the metal substrate due to a mismatch in thermal expansion coefficients. This not only affects the lifespan but may also lead to substrate exposure, impacting cooking safety and food health. Currently, most ceramic-coated etched cookware on the market uses a three-layer composite coating structure, which is complex to apply. Furthermore, the bottom layer often lacks strong chemical bonding with the metal substrate, making it difficult to simultaneously achieve uniform heat conduction, wear resistance, and long-lasting non-stick properties. During continuous high-temperature use and frequent cleaning, the coating is prone to localized peeling or uneven heat conduction, affecting cooking performance and the durability of the cookware.

[0004] Therefore, developing ceramic-coated etched cookware that can adapt to the high-temperature cooking environment of home cooking, possesses excellent adhesion, wear resistance, uniform heat conduction, and health and safety has become an important direction for technological upgrading in the cookware industry. An ideal coating system should have good substrate adhesion, efficient thermal management capabilities, and stable surface properties, thereby improving the overall lifespan of the cookware, the cooking experience, and safety. Summary of the Invention

[0005] In order to overcome the above-mentioned defects of the prior art, the embodiments of the present invention provide a ceramic coating for etching pots with high adhesion and a layered coating method thereof, which solves the problems of easy peeling, uneven thermal conduction, interlayer separation and insufficient durability of etching pot coatings under high and low temperature alternating conditions.

[0006] To achieve the above objectives, the present invention provides the following technical solution: High-adhesion ceramic coating for etching pans, specifically comprising the following components: 1.0~5.0 parts by weight 0.05~0.3 parts by weight TEMPO, 0.5~1.5 parts by weight NaBr, 5.0~20.0 parts by weight NaClO containing 9-10 mmol of available chlorine, 5.0~20.0 parts by weight organosilicon-polyimide block copolymer, 2.0~10.0 parts by weight polyurethane nanospheres, 15.0~25.0 parts by weight 1M HCl, 15.0~25.0 parts by weight 1M 0.02~0.15 parts by weight of glacial acetic acid, 5.0~15.0 parts by weight of ultrafine silicon carbide powder, 0.2~1.0 parts by weight of 3.0~10.0 parts by weight of ascorbic acid solution, 0.5~3.0 parts by weight of TEOS, 0.5~3.0 parts by weight of modified hydroxyapatite, 5.0~12.0 parts by weight of nano boron nitride sheets, 3.0~10.0 parts by weight of silicon nano whiskers, 1.0~5.0 parts by weight of bio-based wetting agent, and 60.0~80.0 parts by weight of ceramic matrix.

[0007] Preferably, the ceramic coating consists of a topcoat and a basecoat.

[0008] Preferably, the base coat is modified. for The coating, which is then cross-linked with organosilicon-polyimide block copolymer, nano-polyurethane microspheres, and ultrafine silicon carbide powder to form a three-dimensional network structure, wherein the organosilicon-polyimide block copolymer has the following structural formula: - , It is benzoic acid dianhydride. It is a diaminodiphenyl ether, and the structural formula of the nano-polyurethane microspheres is as follows: , It is hexamethylene diisocyanate. It is a polycaprolactone polyol.

[0009] Preferably, the surface layer is a three-dimensional thermally conductive enhanced network system obtained by ultrasonically mixing boron nitride nanosheets, silicon nanocrystals, and a bio-based wetting agent. This three-dimensional thermally conductive enhanced network system is then embedded into a ceramic matrix. Formed in ascorbic acid solution, TEOS, and modified hydroxyapatite The coating forms a surface coating. The bio-based wetting agent is a hydrophilic ester with hydroxyl groups generated by the transesterification reaction of soybean oil and glycerol. The modified hydroxyapatite is obtained by replacing the strontium, magnesium, and zinc ions in hydroxyapatite with calcium ions. The ceramic matrix material is obtained by mixing silicon dioxide and aluminum oxide in a ratio of 1:1 to 4:1.

[0010] A layered coating method for a high-adhesion ceramic coating for etching pans includes the following steps: S1: Use HF on the surface of the etching pot substrate. The mixture of etching solution is used for chemical etching, followed immediately by thorough rinsing with deionized water and drying. S2: Dissolve KH-550 in THF, then add 1M HCl and 1M... The aqueous solution was then slowly heated to room temperature (25°C) and stirred at 500 rpm for 4–6 hours. After the reaction was complete, the mixture was extracted with dichloromethane, washed with saturated brine, dried over anhydrous magnesium sulfate, and finally evaporated by rotary evaporation to obtain the final product. ; S3: Transfer S2 Add acetone, then TEMPO and NaBr sequentially. Place the mixture in an ice-water bath at 0±2℃ and stir for 5 minutes. Add saturated sodium bicarbonate to NaClO to adjust the pH of the solution. Then, slowly add the pH-adjusted NaClO dropwise to the mixture and stir at 0-5℃ for 2 hours. Finally, extract with ethyl acetate, wash with 5% sodium thiosulfate solution and saturated brine, and rotary evaporate to obtain the final product. ; S4: The preparation obtained in S3 Dissolved in anhydrous toluene, a solution of deionized water and glacial acetic acid was mixed and then placed in anhydrous toluene and stirred vigorously at 1500 rpm. The product was then rotary evaporated, and the resulting product was immediately... Store in an airtight container; S5: The organosilicon-polyimide block copolymer and polyurethane nanospheres were dispersed in anhydrous ethanol and then ultrasonically dispersed, resulting in the product prepared in S4. Add it to the mixture and stir for 30 minutes at 25°C. Then add 8g of ultrafine silicon carbide powder to the mixture to obtain the bottom coating slurry. S6: The coating prepared in S5 is sprayed onto the surface of the etching pot substrate to form a coating with a thickness of 80 μm, and then cured at high temperature; S7: Add boron nitride nanosheets, silicon nanocrystals and bio-based wetting agent to anhydrous ethanol and stir at 8000 rpm for 20 min. Then, sonicate to obtain a three-dimensional thermally enhanced network system of sheets-whiskers. S8: Slowly add ceramic base material Then, 0.1M ascorbic acid solution was added dropwise and stirred at 45°C for 30 minutes. Next, TEOS and modified hydroxyapatite were added, and the pH of the system was adjusted to 9.0 and stirred to form... The coating layer was then formed by adding the three-dimensional thermally conductive network system of lamellae-whiskers prepared in S7 and the bio-based wetting agent to it and stirring at 300 rpm for 30 min. Then, glacial acetic acid was added dropwise to adjust the pH of the system and vacuum degassing was performed to obtain the surface coating. S9: Rinse the bottom coating with deionized water and dry it at 80°C for 10 min. Then, apply the surface coating prepared in S8 to the surface and control the thickness of the wet film to 50 μm. Finally, dry the coated substrate at high temperature to obtain the etching pot.

[0011] Preferably, HF in S1: Mix the KH-550 solution with an etchant at a volume ratio of 1:3 to 1:5 and chemically etch at 25 to 40°C for 5 to 15 minutes. In S2, KH-550 is dissolved in THF under an ice-water bath at 0±2°C.

[0012] Preferably, in step S3, saturated sodium bicarbonate is added to NaClO to adjust the pH of the solution to 8.5~9.5, and in step S4, the final product is rotary evaporated at 30±5℃ and then immediately sealed and stored in a refrigerator at -20℃.

[0013] Preferably, in step S5, the organosilicon-polyimide block copolymer and nano-polyurethane microspheres are ultrasonically dispersed at 50 kHz for 30 minutes, and then added sequentially. The base coat is obtained by ultrasonic mixing of ultrafine silicon carbide powder. In S6, the base coat is first cured at 80°C for 20 minutes, and then cured at 180°C for 2 hours.

[0014] Preferably, in step S7, the boron nitride nanosheets, silicon nanocrystals, and bio-based wetting agent are ultrasonically treated at an ultrasonic frequency of 50 kHz for 30 min. In step S8, glacial acetic acid is added to bring the pH of the system to 4.0-4.5 and the surface coating is obtained by vacuum degassing.

[0015] Preferably, in S9, the coating is first dried at 80°C for 20 minutes, then dried at 120°C for 30 minutes, and finally dried at 180°C for 1 hour to obtain the etching pot.

[0016] The technical effects and advantages of the high-adhesion ceramic coating for etching pans and its layered coating method of this invention are as follows: 1. This invention, KH-550 under acidic conditions, reacts with... A diazotization reaction occurs, transforming aminoKH-550... Converted to hydroxyl The process generates silane compounds with active hydroxyl groups, which are then further converted into carboxyl groups. The carboxyl groups generated in this step react with Fe and Al on the metal surface to form ionic bonds, causing the coating to adhere tightly to the metal surface.

[0017] 2. In this invention, an insufficient amount of dilute hydrochloric acid solution is added during the modification of KH-550 to convert the amino group in KH-550 into a hydroxyl group. The principle is as follows: Subsequently Extremely unstable generation And nitrogen, finally Hydrolysis Because the hydrogen ion content in hydrochloric acid is insufficient and the reaction preferentially reacts with amino groups to form hydroxyl groups without hydrolyzing siloxy groups, the molar amount of hydrogen ions needs to be strictly controlled to be lower than the molar amount of amino groups in KH-550 when amino groups are formed.

[0018] 3. This invention, in The added glacial acetic acid will - The group hydrolyzes to form a hydroxyl group, forming It contains Si-O groups, and Si-O groups can easily form Si-O-Si to form a three-dimensional network structure.

[0019] 4. In this invention, TEMPO is a catalytic system composed of 2,2,6,6-tetramethylpiperidine oxide, which converts alcohol hydroxyl groups... Selective oxidation to carboxyl groups This results in silane molecules having carboxyl groups at their ends, where the carboxylic acid reacts with metals to form metallic bonds.

[0020] 5. In this invention, organosilicon-polyimide provides high temperature resistance and flexibility, nano-polyurethane microspheres serve as fillers to enhance the toughness and impact resistance of the coating, and silicon carbide enhances wear resistance and thermal conductivity.

[0021] 6. In this invention, after spraying, the coating undergoes gradient curing from 80°C to 180°C to achieve cross-linking and curing, followed by application. The mixture chemically etches the coating surface to form a micro-nano-scale rough structure, increasing the surface area and providing a mechanical anchoring effect for subsequent surface coatings, thereby enhancing interlayer adhesion.

[0022] 7. In this invention, boron nitride has high thermal conductivity and insulation, silicon nanocrystals enhance the rigidity and crack resistance of the coating, and ultrasonication and high-speed stirring enable the two to form a three-dimensional interpenetrating network, thereby improving the overall thermal conductivity and mechanical strength.

[0023] 8. This invention, Ascorbic acid reduces the nanoparticles to silver nanoparticles, enhancing the conductivity or antibacterial properties of the coating. TEOS hydrolyzes to generate… The coating layer enhances the density and corrosion resistance of the coating. The addition of a three-dimensional thermal conductivity enhancement network system of lamellar-whiskers further improves the overall thermal conductivity. pH adjustment and vacuum degassing ensure that the coating is uniform and defect-free.

[0024] 9. In this invention, after the bottom layer is etched, cleaned and dried, a surface coating is applied, and then a gradient curing process is carried out from 80°C to 120°C and then to 180°C. The gradient temperature helps to reduce internal stress and promotes the chemical bonding and physical bonding between the two coating layers, forming a complete and highly adhesive composite coating system.

[0025] 10. This invention, in the base coat... The TEOS in the surface coating hydrolyzes to generate siloxane, which then undergoes a condensation reaction at high temperature to form a Si-O-Si network, thus connecting the surface layer with the underlying chemical layer.

[0026] 11. The bio-based wetting agent used in this invention is a modified soybean oil derivative, which enhances interlayer wetting and bonding. The modified soybean oil derivative is formed by introducing hydrophilic hydroxyl groups into the molecular chain of soybean oil and glycerol through transesterification. During the preparation of the coating, the hydroxyl groups significantly reduce the surface tension of the coating, allowing it to spread well on the surface of the underlying coating. At the same time, the adsorption and compatibility between the surface coating and the underlying coating are enhanced through hydrogen bonding, providing a basis for the subsequent formation of tight chemical bonds.

[0027] 12. This invention constructs a highly efficient three-dimensional thermally conductive network structure using boron nitride sheets. Boron nitride has a graphene-like layered structure with high in-plane thermal conductivity and excellent electrical insulation. Dispersed boron nitride sheets are oriented and overlapped in the coating through ultrasonication and high-speed stirring, forming a through-through three-dimensional thermally conductive pathway. This network can quickly conduct and uniformly disperse locally accumulated heat along the in-plane direction, significantly reducing the thermal stress generated by the temperature gradient in the coating and avoiding cracking or peeling of the coating due to local overheating.

[0028] 13. The invention uses modified hydroxyapatite as pH-responsive nanoparticles. Through co-precipitation, hydrothermal treatment, and ion exchange, strontium, magnesium, and zinc ions in hydroxyapatite are replaced with calcium ions, thereby regulating the crystal structure and surface chemical activity of hydroxyapatite. When the pH changes, the modified hydroxyapatite releases alkaline ions to buffer the pH change.

[0029] 14. In this invention, ascorbic acid reduces silver ions into silver nanoparticles. The high surface area and surface activity of silver can destroy the cell membrane of microorganisms, interfere with their metabolism, and thus inhibit the growth of bacteria on the coating.

[0030] 15. This invention utilizes silicon carbide nanocrystals, which have high hardness and chemical stability. The nanocrystals have a high aspect ratio, which plays a role in structural reinforcement in the coating. By deflecting cracks and pulling out whiskers, the fracture energy is consumed, significantly improving the impact resistance, crack resistance, and wear resistance of the coating.

[0031] 16. This invention uses a ceramic matrix as the main corrosion-resistant and stable framework, which is a composite of silicon dioxide and alumina. Silica provides chemical inertness and acid resistance, while alumina imparts high hardness and high-temperature resistance. The combination of the two forms a dense ceramic phase structure that effectively isolates the penetration of the medium. Attached Figure Description

[0032] Figure 1 This is a flowchart of the high-adhesion etching pot ceramic coating and its layered coating method proposed in this invention. Detailed Implementation

[0033] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0034] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0035] Example 1 This embodiment provides a high-adhesion ceramic coating for etching pans and its layered coating method, the specific implementation steps of which include: Experimental materials: 2g, TEMPO 0.14g, NaBr 0.9g, 5g NaClO containing 9-10mmol of available chlorine, 40mL acetone, 10g organosilicon-polyimide block copolymer (- - -, It is benzoic acid dianhydride. (Diaminodiphenyl ether), 5g nano polyurethane microspheres (- -, It is hexamethylene diisocyanate. (Polycaprolactone polyol), 15 mL 1M HCl, 15 mL 1M Dichloromethane, saturated saline solution, anhydrous magnesium sulfate, acetone, anhydrous toluene, 0.47g deionized water, 0.05g glacial acetic acid, 8g ultrafine silicon carbide powder. 0.5g 3.0g ascorbic acid solution, 0.5g TEOS, 0.5g modified hydroxyapatite, 5.0g nano boron nitride sheets, 3.0g silicon nano whiskers, 2.0g bio-based wetting agent, 60.0g ceramic matrix.

[0036] Experimental objective: A ceramic coating with high adhesion for etching pans was prepared and its application was investigated.

[0037] Experimental steps: S1: Use HF on the surface of the etching pot substrate. The etching solution, mixed in a volume ratio of 1:3 to 1:5, was chemically etched at 25 to 40°C for 5 to 15 minutes, followed by immediate and thorough rinsing with deionized water and drying. S2: Dissolve KH-550 in THF in an ice-water bath at 0±2℃, then add 1M HCl and 1M THF. The aqueous solution was then slowly heated to room temperature (25°C) and stirred at 500 rpm for 4–6 hours. After the reaction was complete, the mixture was extracted with dichloromethane, washed with saturated brine, dried over anhydrous magnesium sulfate, and finally evaporated by rotary evaporation to obtain the final product. ; S3: Transfer S2 Add acetone, then TEMPO and NaBr sequentially. Place the mixture in an ice-water bath at 0±2℃ and stir for 5 minutes. Adjust the pH of the NaClO solution to 8.5-9.5 by adding saturated sodium bicarbonate. Then, slowly add the pH-adjusted NaClO dropwise to the mixture and stir at 0-5℃ for 2 hours. Finally, extract with ethyl acetate, wash with 5% sodium thiosulfate solution and saturated brine, and rotary evaporate to obtain the final product. ; S4: The preparation obtained in S3 Dissolved in anhydrous toluene, a solution of deionized water and glacial acetic acid was mixed and then placed in anhydrous toluene and stirred vigorously at 1500 rpm. The product was then subjected to rotary evaporation at 30°C, and the resulting product was immediately... Store in a sealed container in a refrigerator at -20°C. S5: The organosilicon-polyimide block copolymer and polyurethane nanospheres were dispersed in anhydrous ethanol and then ultrasonically dispersed at 50 kHz for 30 minutes. The mixture prepared in S4 was then... Add it to the mixture and stir for 30 minutes at 25°C. Then add 8g of ultrafine silicon carbide powder to the mixture and sonicate it at 50kHz for 1 hour to form the bottom coating slurry. S6: Spray the coating prepared in S5 onto the surface of the etching pot substrate to form a coating with a thickness of 80μm, then place it in an environment of 80℃ for 20 minutes to cure, and then place it in an environment of 180℃ for 2 hours to cure. S7: Add boron nitride nanosheets, silicon nanowhiskers and bio-based wetting agent to anhydrous ethanol and stir at 8000 rpm for 20 min, then sonicate at 50 kHz for 30 min to obtain a three-dimensional thermally conductive network system of sheets-whiskers. S8: Slowly add ceramic base material Then, 0.1M ascorbic acid solution was added dropwise and stirred at 45°C for 30 minutes. Next, TEOS and modified hydroxyapatite were added, and the pH of the system was adjusted to 9.0 and stirred to form... The coating layer was then prepared by adding the three-dimensional thermally conductive network system of lamellae-whiskers and the bio-based wetting agent obtained in S7 to the coating layer and stirring at 300 rpm for 30 min. Then, glacial acetic acid was added dropwise to adjust the pH of the system to 4.0-4.5 and the coating layer was degassed under vacuum to obtain the surface coating. S9: Rinse the bottom coating with deionized water and dry it at 80°C for 10 min. Then, apply the surface coating prepared in S8 to the surface and control the thickness of the wet film to 50 μm. Finally, place the coated substrate at 80°C for 20 min, raise the temperature to 120°C for 30 min, raise the temperature to 180°C and continue drying for 1 h to obtain the etching pot.

[0038] Experimental results: See Table 1 for details.

[0039] Table 1: Test Results of Example 1

[0040] Example 2 This embodiment provides a high-adhesion ceramic coating for etching pans and its layered coating method, the specific implementation steps of which include: Experimental materials: 2g, TEMPO 0.14g, NaBr 0.9g, 5g NaClO containing 9-10mmol of available chlorine, 40mL acetone, 10g organosilicon-polyimide block copolymer (- - -, It is benzoic acid dianhydride. (Diaminodiphenyl ether), 5g nano polyurethane microspheres (- -, It is hexamethylene diisocyanate. (Polycaprolactone polyol), 15 mL 1M HCl, 15 mL 1M Dichloromethane, saturated saline solution, anhydrous magnesium sulfate, acetone, anhydrous toluene, 0.47g deionized water, 0.05g glacial acetic acid, 8g ultrafine silicon carbide powder. 0.5g 3.0g ascorbic acid solution, 0.5g TEOS, 0.1g modified hydroxyapatite, 5.0g nano boron nitride sheets, 3.0g silicon nano whiskers, 2.0g bio-based wetting agent, 60.0g ceramic matrix.

[0041] Experimental objective: To investigate the effects of reducing the content of functional fillers and simplifying their preparation process on coating performance.

[0042] Experimental steps: S1: Use HF on the surface of the etching pot substrate. The etching solution, mixed in a volume ratio of 1:3 to 1:5, was chemically etched at 25 to 40°C for 5 to 15 minutes, followed by immediate and thorough rinsing with deionized water and drying. S2: Dissolve KH-550 in THF in an ice-water bath at 0±2℃, then add 1M HCl and 1M THF. The aqueous solution was then slowly heated to room temperature (25°C) and stirred at 500 rpm for 4–6 hours. After the reaction was complete, the mixture was extracted with dichloromethane, washed with saturated brine, dried over anhydrous magnesium sulfate, and finally evaporated by rotary evaporation to obtain the final product. ; S3: Transfer S2 Add acetone, then TEMPO and NaBr sequentially. Place the mixture in an ice-water bath at 0±2℃ and stir for 5 minutes. Adjust the pH of the NaClO solution to 8.5-9.5 by adding saturated sodium bicarbonate. Then, slowly add the pH-adjusted NaClO dropwise to the mixture and stir at 0-5℃ for 2 hours. Finally, extract with ethyl acetate, wash with 5% sodium thiosulfate solution and saturated brine, and rotary evaporate to obtain the final product. ; S4: The preparation obtained in S3 Dissolved in anhydrous toluene, a solution of deionized water and glacial acetic acid was mixed and then placed in anhydrous toluene and stirred vigorously at 1500 rpm. The product was then subjected to rotary evaporation at 30°C, and the resulting product was immediately... Store in a sealed container in a refrigerator at -20°C. S5: The organosilicon-polyimide block copolymer and polyurethane nanospheres were dispersed in anhydrous ethanol and then ultrasonically dispersed at 50 kHz for 30 minutes. The mixture prepared in S4 was then... Add it to the mixture and stir for 30 minutes at 25°C. Then add 8g of ultrafine silicon carbide powder to the mixture and sonicate it at 50kHz for 1 hour to form the bottom coating slurry. S6: Spray the coating prepared in S5 onto the surface of the etching pot substrate to form a coating with a thickness of 80μm, then place it in an environment of 80℃ for 20 minutes to cure, and then place it in an environment of 180℃ for 2 hours to cure. S7: Add boron nitride nanosheets, silicon nanowhiskers and bio-based wetting agent to anhydrous ethanol and stir at 8000 rpm for 20 min, then sonicate at 50 kHz for 30 min to obtain a three-dimensional thermally conductive network system of sheets-whiskers. S8: Slowly add ceramic base material Then, 0.1M ascorbic acid solution was added dropwise and stirred at 45℃ for 30 min. TEOS and modified hydroxyapatite were then added and mixed. Finally, the lamellar-whisker three-dimensional thermally conductive enhanced network system and bio-based wetting agent prepared in S7 were added and stirred at 300 rpm for 30 min. Then, glacial acetic acid was added dropwise to adjust the pH of the system to 4.0-4.5 and vacuum degassing was performed to obtain the surface coating. S9: Rinse the bottom coating with deionized water and dry it at 80°C for 10 min. Then, apply the surface coating prepared in S8 to the surface and control the thickness of the wet film to 50 μm. Finally, place the coated substrate at 80°C for 20 min, raise the temperature to 120°C for 30 min, raise the temperature to 180°C and continue drying for 1 h to obtain the etching pot.

[0043] Experimental results: See Table 2 for details.

[0044] Table 2: Test Results of Example 2

[0045] The significant reduction in modified hydroxyapatite content and the simplification of its preparation method have led to a substantial decrease in the number of active sites in the coating that have pH-responsive and ion-releasing functions. In the simplified method, the strontium, magnesium, and zinc ions in the material are only attached to the surface and fail to penetrate into the crystal lattice through ion exchange to form stable structural defects. Therefore, the dissolution controllability is poor and the ion release efficiency is low. This weakens the coating's ability to neutralize local acidity and induce the formation of a dense protective film, resulting in a significant deficiency in its ability to dynamically repair micro-defects and a decrease in coating durability.

[0046] Example 3 This embodiment provides a high-adhesion ceramic coating for etching pans and its layered coating method, the specific implementation steps of which include: Experimental materials: 2g, TEMPO 0.14g, NaBr 0.9g, 5g NaClO containing 9-10mmol of available chlorine, 40mL acetone, 10g organosilicon-polyimide block copolymer (- - -, It is benzoic acid dianhydride. (Diaminodiphenyl ether), 5g nano polyurethane microspheres (- -, It is hexamethylene diisocyanate. (Polycaprolactone polyol), 15 mL 1M HCl, 15 mL 1M Dichloromethane, saturated saline solution, anhydrous magnesium sulfate, acetone, anhydrous toluene, 0.47g deionized water, 0.05g glacial acetic acid, 8g ultrafine silicon carbide powder. 0.5g 3.0g ascorbic acid solution, 0.5g TEOS, 0.5g modified hydroxyapatite, 2.0g nano boron nitride sheets, 1.0g silicon nano whiskers, 2.0g bio-based wetting agent, 60.0g ceramic matrix.

[0047] Experimental objective: To investigate the effects of reducing the content of high thermal conductivity fillers on the overall thermal conductivity uniformity, thermal stress dissipation ability, and stability of the coating under alternating high and low temperature conditions.

[0048] Experimental steps: S1: Use HF on the surface of the etching pot substrate. The etching solution, mixed in a volume ratio of 1:3 to 1:5, was chemically etched at 25 to 40°C for 5 to 15 minutes, followed by immediate and thorough rinsing with deionized water and drying. S2: Dissolve KH-550 in THF in an ice-water bath at 0±2℃, then add 1M HCl and 1M THF. The aqueous solution was then slowly heated to room temperature (25°C) and stirred at 500 rpm for 4–6 hours. After the reaction was complete, the mixture was extracted with dichloromethane, washed with saturated brine, dried over anhydrous magnesium sulfate, and finally evaporated by rotary evaporation to obtain the final product. ; S3: Transfer S2 Add acetone, then TEMPO and NaBr sequentially. Place the mixture in an ice-water bath at 0±2℃ and stir for 5 minutes. Adjust the pH of the NaClO solution to 8.5-9.5 by adding saturated sodium bicarbonate. Then, slowly add the pH-adjusted NaClO dropwise to the mixture and stir at 0-5℃ for 2 hours. Finally, extract with ethyl acetate, wash with 5% sodium thiosulfate solution and saturated brine, and rotary evaporate to obtain the final product. ; S4: The preparation obtained in S3 Dissolved in anhydrous toluene, a solution of deionized water and glacial acetic acid was mixed and then placed in anhydrous toluene and stirred vigorously at 1500 rpm. The product was then subjected to rotary evaporation at 30°C, and the resulting product was immediately... Store in a sealed container in a refrigerator at -20°C. S5: The organosilicon-polyimide block copolymer and polyurethane nanospheres were dispersed in anhydrous ethanol and then ultrasonically dispersed at 50 kHz for 30 minutes. The mixture prepared in S4 was then... Add it to the mixture and stir for 30 minutes at 25°C. Then add 8g of ultrafine silicon carbide powder to the mixture and sonicate it at 50kHz for 1 hour to form the bottom coating slurry. S6: Spray the coating prepared in S5 onto the surface of the etching pot substrate to form a coating with a thickness of 80μm, then place it in an environment of 80℃ for 20 minutes to cure, and then place it in an environment of 180℃ for 2 hours to cure. S7: Add boron nitride nanosheets, silicon nanocrystals and bio-based wetting agent to anhydrous ethanol and stir at 4000 rpm for 20 min, then sonicate at 30 kHz for 15 min to obtain a three-dimensional thermally conductive network system of sheets-whiskers. S8: Slowly add ceramic base material Then, 0.1M ascorbic acid solution was added dropwise and stirred at 45°C for 30 minutes. Next, TEOS and modified hydroxyapatite were added, and the pH of the system was adjusted to 9.0 and stirred to form... The coating layer was then prepared by adding the three-dimensional thermally conductive network system of lamellae-whiskers and the bio-based wetting agent obtained in S7 to the coating layer and stirring at 300 rpm for 30 min. Then, glacial acetic acid was added dropwise to adjust the pH of the system to 4.0-4.5 and the coating layer was degassed under vacuum to obtain the surface coating. S9: Rinse the bottom coating with deionized water and dry it at 80°C for 10 min. Then, apply the surface coating prepared in S8 to the surface and control the thickness of the wet film to 50 μm. Finally, place the coated substrate at 80°C for 20 min, raise the temperature to 120°C for 30 min, raise the temperature to 180°C and continue drying for 1 h to obtain the etching pot.

[0049] Experimental results: See Table 3 for details.

[0050] Table 3: Test Results of Example 3

[0051] The reduced amount of boron nitride sheets and silicon nanocrystals, coupled with insufficient dispersion energy, prevents the formation of a complete and interconnected three-dimensional interpenetrating thermal network within the coating. This results in localized agglomeration and uneven dispersion of the filler, creating "discontinuities" in the heat flow channels. Consequently, the coating experiences increased localized thermal resistance, hindering rapid and uniform heat dissipation. During drastic temperature changes, the stress generated by differences in thermal expansion coefficients within the coating cannot be effectively released, leading to the initiation and propagation of microcracks and reducing the coating's thermal shock resistance and long-term thermal stability.

[0052] Example 4 This embodiment provides a high-adhesion ceramic coating for etching pans and its layered coating method, the specific implementation steps of which include: Experimental materials: 2g, TEMPO 0.14g, NaBr 0.9g, 5g NaClO containing 9-10mmol of available chlorine, 40mL acetone, 10g organosilicon-polyimide block copolymer (- - -, It is benzoic acid dianhydride. (Diaminodiphenyl ether), 5g nano polyurethane microspheres (- -, It is hexamethylene diisocyanate. (Polycaprolactone polyol), 15 mL 1M HCl, 15 mL 1M Dichloromethane, saturated saline solution, anhydrous magnesium sulfate, acetone, anhydrous toluene, 0.47g deionized water, 0.05g glacial acetic acid, 8g ultrafine silicon carbide powder. 0.5g 3.0g ascorbic acid solution, 0.5g TEOS, 0.5g modified hydroxyapatite, 5.0g nano boron nitride sheets, 3.0g silicon nano whiskers, 2.0g bio-based wetting agent, 60.0g ceramic matrix.

[0053] Experimental objective: To investigate the effects of non-gradient curing processes on the crosslinking density of the undercoat, its bonding strength with the substrate, and the interlayer stress matching.

[0054] Experimental steps: S1: Use HF on the surface of the etching pot substrate. The etching solution, mixed in a volume ratio of 1:3 to 1:5, was chemically etched at 25 to 40°C for 5 to 15 minutes, followed by immediate and thorough rinsing with deionized water and drying. S2: Dissolve KH-550 in THF in an ice-water bath at 0±2℃, then add 1M HCl and 1M THF. The aqueous solution was then slowly heated to room temperature (25°C) and stirred at 500 rpm for 4–6 hours. After the reaction was complete, the mixture was extracted with dichloromethane, washed with saturated brine, dried over anhydrous magnesium sulfate, and finally evaporated by rotary evaporation to obtain the final product. ; S3: Transfer S2 Add acetone, then TEMPO and NaBr sequentially. Place the mixture in an ice-water bath at 0±2℃ and stir for 5 minutes. Adjust the pH of the NaClO solution to 8.5-9.5 by adding saturated sodium bicarbonate. Then, slowly add the pH-adjusted NaClO dropwise to the mixture and stir at 0-5℃ for 2 hours. Finally, extract with ethyl acetate, wash with 5% sodium thiosulfate solution and saturated brine, and rotary evaporate to obtain the final product. ; S4: The preparation obtained in S3 Dissolved in anhydrous toluene, a solution of deionized water and glacial acetic acid was mixed and then placed in anhydrous toluene and stirred vigorously at 1500 rpm. The product was then subjected to rotary evaporation at 30°C, and the resulting product was immediately... Store in a sealed container in a refrigerator at -20°C. S5: The organosilicon-polyimide block copolymer and polyurethane nanospheres were dispersed in anhydrous ethanol and then ultrasonically dispersed at 50 kHz for 30 minutes. The mixture prepared in S4 was then... Add it to the mixture and stir for 30 minutes at 25°C. Then add 8g of ultrafine silicon carbide powder to the mixture and sonicate it at 50kHz for 1 hour to form the bottom coating slurry. S6: Spray the coating prepared in S5 onto the surface of the etching pot substrate to form a coating with a thickness of 80 μm, and then place it at 180°C for 2.5 hours to cure. S7: Add boron nitride nanosheets, silicon nanowhiskers and bio-based wetting agent to anhydrous ethanol and stir at 8000 rpm for 20 min, then sonicate at 50 kHz for 30 min to obtain a three-dimensional thermally conductive network system of sheets-whiskers. S8: Slowly add ceramic base material Then, 0.1M ascorbic acid solution was added dropwise and stirred at 45°C for 30 minutes. Next, TEOS and modified hydroxyapatite were added, and the pH of the system was adjusted to 9.0 and stirred to form... The coating layer was then prepared by adding the three-dimensional thermally conductive network system of lamellae-whiskers and the bio-based wetting agent obtained in S7 to the coating layer and stirring at 300 rpm for 30 min. Then, glacial acetic acid was added dropwise to adjust the pH of the system to 4.0-4.5 and the coating layer was degassed under vacuum to obtain the surface coating. S9: Rinse the bottom coating with deionized water and dry it at 80°C for 10 min. Then, apply the surface coating prepared in S8 to the surface and control the thickness of the wet film to 50 μm. Finally, place the coated substrate at 80°C for 20 min, raise the temperature to 120°C for 30 min, raise the temperature to 180°C and continue drying for 1 h to obtain the etching pot.

[0055] Experimental results: See Table 4 for details.

[0056] Table 4: Test Results of Example 4

[0057] By omitting the 80℃ gradient pre-curing step and directly subjecting the coating to high-temperature curing, the solvent rapidly evaporates, and the crosslinking reaction rate between the silicone-polyimide copolymer and the silane coupling agent becomes excessively fast and uneven. This results in significant shrinkage stress and porosity defects within the coating, weakening its cohesive strength. Furthermore, the overly vigorous reaction may affect the formation of stable chemical bonds (Me-O-Si) between the silane hydrolysis products and the hydroxyl groups on the metal surface, leading to insufficient interfacial chemical bonding. Defects and residual stress in the underlying layer itself affect the reliability of its bonding with the surface coating, making it prone to interlayer delamination under thermal stress.

[0058] Example 5 This embodiment provides a high-adhesion ceramic coating for etching pans and its layered coating method, the specific implementation steps of which include: Experimental materials: 2g, TEMPO 0.14g, NaBr 0.9g, 5g NaClO containing 9-10mmol of available chlorine, 40mL acetone, 10g organosilicon-polyimide block copolymer (- - -, It is benzoic acid dianhydride. (diaminodiphenyl ether), 2g nano polyurethane microspheres (- -, It is hexamethylene diisocyanate. (Polycaprolactone polyol), 15 mL 1M HCl, 15 mL 1M Dichloromethane, saturated saline solution, anhydrous magnesium sulfate, acetone, anhydrous toluene, 0.47g deionized water, 0.05g glacial acetic acid, 4g ultrafine silicon carbide powder. 0.5g 3.0g ascorbic acid solution, 0.5g TEOS, 0.5g modified hydroxyapatite, 5.0g boron nitride nanosheets, 3.0g silicon nanocrystals, 1.0g bio-based wetting agent, 60.0g ceramic matrix ( = 4:1).

[0059] Experimental objective: To investigate the negative impacts of comprehensively reducing the content of key bonding, toughening, and wear-resistant components and adjusting the proportion of the binder on the overall performance of the coating.

[0060] Experimental steps: S1: Use HF on the surface of the etching pot substrate. The etching solution, mixed in a volume ratio of 1:3 to 1:5, was chemically etched at 25 to 40°C for 5 to 15 minutes, followed by immediate and thorough rinsing with deionized water and drying. S2: Dissolve KH-550 in THF in an ice-water bath at 0±2℃, then add 1M HCl and 1M THF. The aqueous solution was then slowly heated to room temperature (25°C) and stirred at 500 rpm for 4–6 hours. After the reaction was complete, the mixture was extracted with dichloromethane, washed with saturated brine, dried over anhydrous magnesium sulfate, and finally evaporated by rotary evaporation to obtain the final product. ; S3: Transfer S2 Add acetone, then TEMPO and NaBr sequentially. Place the mixture in an ice-water bath at 0±2℃ and stir for 5 minutes. Adjust the pH of the NaClO solution to 8.5-9.5 by adding saturated sodium bicarbonate. Then, slowly add the pH-adjusted NaClO dropwise to the mixture and stir at 0-5℃ for 2 hours. Finally, extract with ethyl acetate, wash with 5% sodium thiosulfate solution and saturated brine, and rotary evaporate to obtain the final product. ; S4: The preparation obtained in S3 Dissolved in anhydrous toluene, a solution of deionized water and glacial acetic acid was mixed and then placed in anhydrous toluene and stirred vigorously at 1500 rpm. The product was then subjected to rotary evaporation at 30°C, and the resulting product was immediately... Store in a sealed container in a refrigerator at -20°C. S5: The organosilicon-polyimide block copolymer and polyurethane nanospheres were dispersed in anhydrous ethanol and then ultrasonically dispersed at 50 kHz for 30 minutes. The mixture prepared in S4 was then... Add the mixture and stir for 30 minutes at 25°C. Then add 4g of ultrafine silicon carbide powder to the mixture and sonicate it at 50kHz for 1 hour to form the bottom coating slurry. S6: Spray the coating prepared in S5 onto the surface of the etching pot substrate to form a coating with a thickness of 80μm, then place it in an environment of 80℃ for 20 minutes to cure, and then place it in an environment of 180℃ for 2 hours to cure. S7: Add boron nitride nanosheets, silicon nanowhiskers and bio-based wetting agent to anhydrous ethanol and stir at 8000 rpm for 20 min, then sonicate at 50 kHz for 30 min to obtain a three-dimensional thermally conductive network system of sheets-whiskers. S8: Slowly add ceramic base material Then, 0.1M ascorbic acid solution was added dropwise and stirred at 45°C for 30 minutes. Next, TEOS and modified hydroxyapatite were added, and the pH of the system was adjusted to 9.0 and stirred to form... The coating layer was then prepared by adding the three-dimensional thermally conductive network system of lamellae-whiskers and the bio-based wetting agent obtained in S7 to the coating layer and stirring at 300 rpm for 30 min. Then, glacial acetic acid was added dropwise to adjust the pH of the system to 4.0-4.5 and the coating layer was degassed under vacuum to obtain the surface coating. S9: Rinse the bottom coating with deionized water and dry it at 80°C for 10 min. Then, apply the surface coating prepared in S8 to the surface and control the thickness of the wet film to 50 μm. Finally, place the coated substrate at 80°C for 20 min, raise the temperature to 120°C for 30 min, raise the temperature to 180°C and continue drying for 1 h to obtain the etching pot.

[0061] Experimental results: See Table 5 for details.

[0062] Table 5: Test Results of Example 5

[0063] The reduced amount of silane precursors directly leads to an insufficient quantity of active silanol-SiOH that can be used for bonding with the substrate and constructing a three-dimensional network, resulting in a decrease in both interfacial chemical bond density and bulk crosslinking density. The reduction in the amount of nano-polyurethane microspheres and silicon carbide weakens the toughening and wear-resistant framework of the coating, making it more prone to crack initiation and propagation under mechanical stress. Insufficient bio-based wetting agents reduce the wettability of the coating to the substrate and fillers, potentially introducing more microscopic defects. While a lower proportion of base material may result in lower costs, its corrosion resistance and high-temperature stability are typically inferior to those of an appropriately proportioned base material. In composite systems, the synergistic negative effects of these factors lead to significant performance defects in the coating under combined mechanical, chemical, and thermal loads, resulting in a substantial reduction in durability.

[0064] Comparative Example 1 This embodiment provides a traditional ceramic coating specifically for etching pans and its layered coating method, the specific implementation steps of which include: Experimental materials: 10.0 parts by weight of ethyl silicate, 5.0 parts by weight of methyltrimethoxysilane, 30.0 parts by weight of silica sol, 10.0 parts by weight of alumina powder, 5.0 parts by weight of silicon carbide powder, 1.0 part by weight of silane coupling agent, 40.0 parts by weight of ethanol, 5.0 parts by weight of deionized water, and 0.5 parts by weight of hydrochloric acid (1M).

[0065] Experimental objective: The performance differences in adhesion, thermal conductivity, wear resistance, and impact resistance between traditional single-layer ceramic coatings and the double-layer structure coating of this invention are compared.

[0066] Experimental steps: S1: The surface of the etching pot substrate is sanded with sandpaper to a roughness of Ra≈3.2μm, then cleaned with ethanol and dried; S2: Mix ethyl silicate, methyltrimethoxysilane, ethanol, deionized water and hydrochloric acid, and stir at room temperature for 2 hours to hydrolyze and form silica sol; S3: Add silica sol, alumina powder, and silicon carbide powder to the silica sol above, and stir at 2000 rpm for 30 minutes. S4: Add silane coupling agent KH-560 and continue stirring for 20 minutes to obtain traditional ceramic coating; S5: Spray the coating onto the surface of the etching pot substrate, controlling the wet film thickness to be approximately 100μm; S6: Place the sprayed substrate in an 80℃ oven for pre-curing for 30 minutes, then raise the temperature to 180℃ for curing for 2 hours to obtain a traditional etching pan coating.

[0067] Experimental results: See Table 6 for details.

[0068] Table 6: Test Results of Comparative Example 1

[0069] Comparative Example 1 uses a traditional single-layer ceramic coating system, based on silica sol, with small amounts of alumina and silicon carbide added as fillers. No functional design or layered construction of the bottom and top layers was performed. The coating structure is simple, lacking chemical bonding enhancement mechanisms, a three-dimensional thermally conductive network, and pH-responsive functional materials. Its bonding strength, thermal conductivity, wear resistance, and impact resistance are significantly lower than those of the embodiments of this invention. It is particularly prone to cracking and peeling in alternating high and low temperature environments, exhibiting poor durability.

[0070] Example 1 employs optimized component design and meticulous process control to achieve a balanced and optimal performance across all aspects, with a bonding strength of 45.2 MPa and a thermal conductivity of 15.8 W / m·K, demonstrating outstanding comprehensive protective capabilities.

[0071] The example exhibits good basic bonding and thermal conductivity, but due to insufficient content of the key functional filler modified hydroxyapatite and simplified preparation, its weight loss reaches 5.8%. Its impact resistance is significantly inferior to that of Example 1.

[0072] Example 3 employs a strategy of reducing the amount of high thermal conductivity filler and lowering dispersion energy, resulting in a significant decrease in thermal conductivity to 10.5 W / m·K. At the same time, the bonding strength and impact resistance are also reduced, demonstrating the crucial role of a well-developed three-dimensional thermally conductive network in the coating's resistance to thermal shock and overall mechanical stability.

[0073] Example 4 employed an aggressive curing process that neglected the importance of gradient temperature rise, resulting in a sharp drop in bond strength to 32.0 MPa and reduced wear resistance and impact resistance. This highlights the criticality of optimizing the curing process for obtaining a high-bonding substrate.

[0074] Example 5 employs a low-cost approach that comprehensively reduces key components, resulting in a bond strength of 26.5 MPa and a wear resistance weight loss of 7.5 MPa across all core properties. The overall decline demonstrates the necessity of the specific formulation range of this invention; any reduction would destroy the synergistic effect of the system.

[0075] Comparative Example 1 uses a traditional coating system, and its performance is far inferior to that of the embodiments of the present invention, highlighting the functional limitations of traditional technology in dealing with complex working conditions of alternating high and low temperatures.

[0076] refer to Figure 1 This invention provides a high-adhesion ceramic coating for etching pans and its layered coating method. This technical solution utilizes a dual-layer coating system with clearly defined functions for the bottom and top layers, coupled with a refined gradient coating and curing process to handle extreme working conditions. The bottom layer employs a three-dimensional network formed by cross-linking modified silane compounds with organosilicon-polyimide copolymers, nano-polyurethane microspheres, and ultrafine silicon carbide. The carboxyl groups at the ends of this network form strong chemical bonds with the metal substrate, laying the foundation for excellent adhesion and toughness. The top layer constructs a three-dimensional interpenetrating thermally conductive network composed of nano-boron nitride sheets and silicon nanocrystals, and embeds nano-silver, pH-responsive modified hydroxyapatite, and... The ceramic matrix of the coating layer simultaneously imparts excellent thermal conductivity and wear resistance to the coating. The entire process includes substrate etching and activation, separate preparation and layered spraying of the bottom and top slurries, as well as a strict gradient temperature curing process, which effectively promotes interlayer chemical bonding and reduces internal stress.

[0077] The above description is merely a specific embodiment of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in this application should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of protection of the claims.

[0078] In conclusion, the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A ceramic coating for high-adhesion etching pans, characterized in that, Specifically, it includes the following components: 1.0~5.0 parts by weight 0.05~0.3 parts by weight TEMPO, 0.5~1.5 parts by weight NaBr, 5.0~20.0 parts by weight NaClO containing 9-10 mmol of available chlorine, 5.0~20.0 parts by weight organosilicon-polyimide block copolymer, 2.0~10.0 parts by weight polyurethane nanospheres, 15.0~25.0 parts by weight 1M HCl, 15.0~25.0 parts by weight 1M 0.02~0.15 parts by weight of glacial acetic acid, 5.0~15.0 parts by weight of ultrafine silicon carbide powder, 0.2~1.0 parts by weight of 3.0~10.0 parts by weight of ascorbic acid solution, 0.5~3.0 parts by weight of TEOS, 0.5~3.0 parts by weight of modified hydroxyapatite, 5.0~12.0 parts by weight of nano boron nitride sheets, 3.0~10.0 parts by weight of silicon nano whiskers, 1.0~5.0 parts by weight of bio-based wetting agent, and 60.0~80.0 parts by weight of ceramic matrix.

2. The high-adhesion etching pot-specific ceramic coating as described in claim 1, characterized in that, The ceramic coating consists of a topcoat and a basecoat.

3. The high-adhesion etching pot-specific ceramic coating as described in claim 2, characterized in that, The base coat is modified. for The coating, which is then cross-linked with organosilicon-polyimide block copolymer, nano-polyurethane microspheres, and ultrafine silicon carbide powder to form a three-dimensional network structure, wherein the organosilicon-polyimide block copolymer has the following structural formula: - , It is benzoic acid dianhydride. It is a diaminodiphenyl ether, and the structural formula of the nano-polyurethane microspheres is as follows: , It is hexamethylene diisocyanate. It is a polycaprolactone polyol.

4. The high-adhesion etching pot-specific ceramic coating as described in claim 2, characterized in that, The surface layer is composed of boron nitride nanosheets, silicon nanocrystals, and a bio-based wetting agent, which are then ultrasonically mixed and embedded in a ceramic matrix. Formed in ascorbic acid solution, TEOS, and modified hydroxyapatite The surface coating of the three-dimensional thermally enhanced network system is obtained by coating. The bio-based wetting agent is a hydrophilic ester with hydroxyl groups generated by the transesterification reaction of soybean oil and glycerol. The modified hydroxyapatite is obtained by replacing the strontium, magnesium and zinc ions in hydroxyapatite with calcium ions. The ceramic matrix material is obtained by mixing silicon dioxide and aluminum oxide in a ratio of 1:1 to 4:

1.

5. A layered coating method for a high-adhesion etching pot-specific ceramic coating, characterized in that, Includes the following steps: S1: Use HF on the surface of the etching pot substrate. The mixture of etching solution is used for chemical etching, followed immediately by thorough rinsing with deionized water and drying. S2: Dissolve KH-550 in THF, then add 1M HCl and 1M... The aqueous solution was then slowly heated to room temperature (25°C) and stirred at 500 rpm for 4–6 hours. After the reaction was complete, the mixture was extracted with dichloromethane, washed with saturated brine, dried over anhydrous magnesium sulfate, and finally evaporated by rotary evaporation to obtain the final product. ; S3: Transfer S2 Add acetone, then TEMPO and NaBr sequentially. Place the mixture in an ice-water bath at 0±2℃ and stir for 5 minutes. Add saturated sodium bicarbonate to NaClO to adjust the pH of the solution. Then, slowly add the pH-adjusted NaClO dropwise to the mixture and stir at 0-5℃ for 2 hours. Finally, extract with ethyl acetate, wash with 5% sodium thiosulfate solution and saturated brine, and rotary evaporate to obtain the final product. ; S4: The preparation obtained in S3 Dissolved in anhydrous toluene, a solution of deionized water and glacial acetic acid was mixed and then placed in anhydrous toluene and stirred vigorously at 1500 rpm. The product was then rotary evaporated, and the resulting product was immediately... Store in an airtight container; S5: The organosilicon-polyimide block copolymer and polyurethane nanospheres were dispersed in anhydrous ethanol and then ultrasonically dispersed, resulting in the product prepared in S4. Add it to the mixture and stir for 30 minutes at 25°C. Then add 8g of ultrafine silicon carbide powder to the mixture to obtain the bottom coating slurry. S6: The coating prepared in S5 is sprayed onto the surface of the etching pot substrate to form a coating with a thickness of 80 μm, and then cured at high temperature; S7: Add boron nitride nanosheets, silicon nanocrystals and bio-based wetting agent to anhydrous ethanol and stir at 8000 rpm for 20 min. Then, sonicate to obtain a three-dimensional thermally enhanced network system of sheets-whiskers. S8: Slowly add ceramic base material Then, 0.1M ascorbic acid solution was added dropwise and stirred at 45°C for 30 minutes. Next, TEOS and modified hydroxyapatite were added, and the pH of the system was adjusted to 9.0 and stirred to form... The coating layer was then formed by adding the three-dimensional thermally conductive network system of lamellae-whiskers prepared in S7 and the bio-based wetting agent to it and stirring at 300 rpm for 30 min. Then, glacial acetic acid was added dropwise to adjust the pH of the system and vacuum degassing was performed to obtain the surface coating. S9: Rinse the bottom coating with deionized water and dry it at 80°C for 10 min. Then, apply the surface coating prepared in S8 to the surface and control the thickness of the wet film to 50 μm. Finally, dry the coated substrate at high temperature to obtain the etching pot.

6. The layered coating method for the high-adhesion etching pot ceramic coating as described in claim 5, characterized in that, HF in S1: Mix the KH-550 solution with an etchant at a volume ratio of 1:3 to 1:5 and chemically etch at 25 to 40°C for 5 to 15 minutes. In S2, KH-550 is dissolved in THF under an ice-water bath at 0±2°C.

7. The layered coating method for the high-adhesion etching pot ceramic coating as described in claim 5, characterized in that, In step S3, saturated sodium bicarbonate is added to NaClO to adjust the pH of the solution to 8.5-9.

5. In step S4, the final product is rotary evaporated at 30±5℃ and then immediately sealed and stored in a refrigerator at -20℃.

8. The layered coating method for the high-adhesion etching pot ceramic coating as described in claim 5, characterized in that, In S5, the organosilicon-polyimide block copolymer and nano-polyurethane microspheres were dispersed by ultrasonication at 50 kHz for 30 minutes, and then added sequentially. The base coat is obtained by ultrasonic mixing of ultrafine silicon carbide powder. In S6, the base coat is first cured at 80°C for 20 minutes, and then cured at 180°C for 2 hours.

9. The layered coating method for the high-adhesion etching pot ceramic coating as described in claim 5, characterized in that, In S7, the boron nitride nanosheets, silicon nanocrystals, and bio-based wetting agent are ultrasonically treated at a frequency of 50 kHz for 30 min. In S8, glacial acetic acid is added to bring the pH of the system to 4.0-4.5 and vacuum degassing is performed to obtain the surface coating.

10. The layered coating method for the high-adhesion etching pan-specific ceramic coating as described in claim 5, characterized in that, In S9, the coating is first dried at 80°C for 20 minutes, then at 120°C for 30 minutes, and finally at 180°C for 1 hour to obtain the etching pot.

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