ZIF-8-derived ZnO-C composite material modified epoxy resin coating and preparation method thereof
By modifying the epoxy resin coating with ZnO@C composite material derived from ZIF-8 and combining it with silane coupling agent modification, the problems of high brittleness and noise of epoxy resin coating were solved, and the drag reduction and noise reduction effect of hydropower station metal structure was achieved.
Patent Information
- Application Number
- CN202511636965.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-10
- Publication Date
- 2026-01-23
AI Technical Summary
Epoxy resin coatings are prone to vibration and noise on key metal structures in hydropower stations, and are brittle and prone to microcracks, making it difficult to achieve a balance between hardness and toughness.
An epoxy resin coating was modified using ZnO@C composite material derived from ZIF-8. The modified coating was formed by combining ZnO@C composite material with epoxy resin matrix components through modification with silane coupling agent.
It achieves drag reduction and noise reduction effects of epoxy resin coating, improves the balance between hardness and toughness of coating, and is suitable for the protection of key metal structures of water turbines.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of epoxy resin coating technology, specifically relating to a ZIF-8 derived ZnO@C composite material modified epoxy resin coating and its preparation method. Background Technology
[0002] To address the vibration and noise issues generated during the operation of key metal structures in hydropower stations, functional modification of epoxy resin coatings is a feasible research direction for achieving drag reduction and noise reduction.
[0003] Due to its unique molecular structure (containing epoxy groups and hydroxyl groups), epoxy resin coatings possess the following core advantages: high adhesion, mainly due to the hydrogen bonds that can be formed between the polar groups and the metal matrix; and excellent chemical inertness, with the cured coating resistant to corrosion from acids, alkalis, and organic solvents. However, the main drawbacks of epoxy resin coatings are high brittleness, susceptibility to microcracks, and noise generation during flow.
[0004] Metal-organic framework (MOF)-derived composites inherit the advantages of MOFs, combining the high porosity and tunable pore structure of MOFs with the excellent physicochemical properties of ZnO and porous carbon materials. ZnO@C composites can be prepared directly using zinc-based MOFs as precursor templates via pyrolysis under an inert atmosphere. Because ZnO@C composites retain many advantages of MOFs, they hold promise as an excellent nanofiller for modifying epoxy resin coatings.
[0005] Based on this, the present invention proposes a method for modifying epoxy resin coatings. The core of this method is to use ZnO@C composite material modified with silane coupling agent to modify epoxy resin coatings, which can achieve a balance between hardness and toughness, while also reducing drag and noise. Summary of the Invention
[0006] The purpose of this invention is to provide a ZIF-8 derived ZnO@C composite material modified epoxy resin coating and its preparation method, thereby achieving the functionalization of epoxy resin coating for drag reduction and noise reduction.
[0007] The modified epoxy resin coating obtained by this invention can be used for the protection of flow-through components such as key metal structures of water turbines.
[0008] This invention is achieved through the following technical solution: A method for preparing a ZIF-8 derived ZnO@C composite material modified epoxy resin coating includes the following steps: (1) The precursor ZIF-8 was prepared by reacting zinc salt with 2-methylimidazole in an organic solvent by magnetic stirring; (2) The precursor ZIF-8 obtained in step (1) is carbonized in an inert atmosphere to obtain ZnO@C composite material, which has a porous carbon skeleton and uniformly dispersed nano ZnO. (3) The ZnO@C composite material obtained in step (2) is reacted with a silane coupling agent to obtain the modified ZnO@C composite material; (4) The modified ZnO@C composite material obtained in step (3) is dispersed in the curing agent component, and after adding the epoxy resin matrix component, it is coated on the surface of the metal sample plate and cured to obtain the modified epoxy resin coating.
[0009] In a preferred embodiment, the zinc salt in step (1) is one or more of zinc acetate dihydrate and zinc nitrate hexahydrate; the organic solvent is one or more of methanol and N,N-dimethylamide.
[0010] As a preferred embodiment, in step (1), the ratio of zinc salt (preferably zinc acetate dihydrate), 2-methylimidazole, and organic solvent (preferably methanol) is 22g:65.6g:600mL.
[0011] As a preferred embodiment, in step (1), a white turbid liquid is obtained by magnetic stirring at room temperature (10-30℃) for at least 30 minutes, then allowed to stand for 12 hours, and then centrifuged, washed and dried to obtain the precursor ZIF-8.
[0012] As a preferred embodiment, in step (1), the centrifugal washing and drying are performed by centrifuging at least 3 times each with deionized water and anhydrous ethanol at 3000 rpm, and then vacuum drying at 80°C for at least 12 hours to obtain the precursor ZIF-8 powder.
[0013] As a preferred embodiment, in step (2), the inert atmosphere is nitrogen or argon, the heating rate of the carbonization treatment is 2-5℃ / min, the carbonization temperature is 700-900℃, and the holding time is at least 2h.
[0014] As a preferred embodiment, the silane coupling agent in step (3) is KH570. The modification specifically involves: mixing anhydrous ethanol and deionized water at a volume ratio of 9:1, adding acetic acid to adjust the pH to 4-5 to obtain a mixed solution, adding KH570, magnetically stirring for at least 30 minutes, then adding the ZnO@C composite material, mixing thoroughly, centrifuging, washing, and drying to obtain the modified ZnO@C composite material. The ratio of the mixed solution, KH570, and ZnO@C composite material is 1000 mL: 20 mL: 100 g.
[0015] In a preferred embodiment, the matrix component in step (4) is E51 epoxy resin and reactive diluent AGE, and the curing agent component is polyetheramine D230, accelerator DMP-30, and defoamer. The mass ratio of the matrix component, the curing agent component, and the modified ZnO@C composite material is preferably 100:31.3:(1~5), and more preferably 100:31.3:(2~3).
[0016] Compared with the prior art, the beneficial effects of the present invention are: (1) In the synthesis of ZIF-8, the present invention uses room temperature magnetic stirring to avoid the energy consumption caused by traditional MOF solvothermal synthesis, and the synthesis process is more simplified.
[0017] (2) The present invention is simple to operate, and the synthesized modified ZnO@C composite material realizes the functional modification of epoxy resin coating to reduce drag and noise. Detailed Implementation
[0018] The present invention will now be described in further detail with reference to specific embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, but are not limited thereto. The raw materials used in the embodiments can all be commercially available or prepared by conventional methods.
[0019] Example 1: (1) First, weigh 22g of zinc acetate dihydrate and add it to 300ml of methanol. Then, stir magnetically to dissolve it completely to obtain solution A. Next, weigh 65.6g of 2-methylimidazole and add it to 300ml of methanol. Stir magnetically to dissolve it completely to obtain solution B. Add solution B to solution A and continue to stir magnetically for 30 minutes to obtain white mixed solution C. Stop stirring and let it stand for 12 hours.
[0020] (2) Collect the mixture C, centrifuge at 3000 rpm, collect the white solid product, wash it three times each with deionized water and anhydrous ethanol at 3000 rpm, and vacuum dry at 80℃ for 12h to obtain a white block solid. Grind it in a mortar for 10 min and collect the white powder, which is the precursor ZIF-8.
[0021] (3) Weigh 200g of precursor ZIF-8 and place it in a ceramic boat, then place it in a box furnace. Under argon conditions, change the gas three times and raise the temperature to 700℃ at a rate of 2℃ / min. Hold the temperature for 1h. After the temperature drops to room temperature, collect the black powder, which is the ZnO@C composite material.
[0022] Mix 900 ml of anhydrous ethanol and 100 ml of deionized water and stir magnetically. Add acetic acid to adjust the pH to 4-5, then add 20 ml of KH570 and stir magnetically for 30 min. Weigh 100 g of ZnO@C composite material and add it to the above solution. First, ultrasonically disperse for 20 min, then stir magnetically for 2 h. Collect the product by centrifugation at 3000 rpm, wash three times with anhydrous ethanol at 3000 rpm, and vacuum dry at 80℃ for 12 h to obtain a black product, which is the modified ZnO@C composite material.
[0023] Weigh out 95 parts of E51 epoxy resin and 5 parts of reactive diluent AGE according to the mass composition, and stir thoroughly to obtain the matrix component; weigh out 30 parts of polyetheramine D230, 1 part of modified ZnO@C composite material, 1 part of accelerator DMP-30, and 0.3 parts of defoamer, sonicate for 20 minutes, and then stir thoroughly with PTFE for 1 hour to obtain the curing agent component.
[0024] The surface of the metal sample plate was sandblasted with white fused alumina, and then the surface was cleaned with ethanol to remove oil and ensure that the surface cleanliness of the sample plate reached Sa2.5.
[0025] The matrix component and curing agent component are thoroughly mixed and then evenly coated onto the surface of the treated metal sample plate by spraying.
[0026] Example 2: (1) First, weigh 22g of zinc acetate dihydrate and add it to 300ml of methanol. Then, stir magnetically to dissolve it completely to obtain solution A. Next, weigh 65.6g of 2-methylimidazole and add it to 300ml of methanol. Stir magnetically to dissolve it completely to obtain solution B. Add solution B to solution A and continue to stir magnetically for 30 minutes to obtain white mixed solution C. Stop stirring and let it stand for 12 hours.
[0027] (2) Collect the mixture C, centrifuge at 3000 rpm, collect the white solid product, wash it three times each with deionized water and anhydrous ethanol at 3000 rpm, and vacuum dry at 80℃ for 12h to obtain a white block solid. Grind it in a mortar for 10 min and collect the white powder, which is the precursor ZIF-8.
[0028] (3) Weigh 200g of precursor ZIF-8 and place it in a ceramic boat, then place it in a box furnace. Under argon conditions, change the gas three times and raise the temperature to 700℃ at a rate of 2℃ / min. Hold the temperature for 1h. After the temperature drops to room temperature, collect the black powder, which is the ZnO@C composite material.
[0029] Mix 900 ml of anhydrous ethanol and 100 ml of deionized water and stir magnetically. Add acetic acid to adjust the pH to 4-5, then add 20 ml of KH570 and stir magnetically for 30 min. Weigh 100 g of ZnO@C composite material and add it to the above solution. First, ultrasonically disperse for 20 min, then stir magnetically for 2 h. Collect the product by centrifugation at 3000 rpm, wash three times with anhydrous ethanol at 3000 rpm, and vacuum dry at 80℃ for 12 h to obtain a black product, which is the modified ZnO@C composite material.
[0030] Weigh out 95 parts of E51 epoxy resin and 5 parts of reactive diluent AGE according to the mass composition, and stir thoroughly to obtain the matrix component; weigh out 30 parts of polyetheramine D230, 2 parts of modified ZnO@C composite material, 1 part of accelerator DMP-30, and 0.3 parts of defoamer, sonicate for 20 minutes, and then stir thoroughly with PTFE for 1 hour to obtain the curing agent component.
[0031] The surface of the metal sample plate was sandblasted with white fused alumina, and then the surface was cleaned with ethanol to remove oil and ensure that the surface cleanliness of the sample plate reached Sa2.5.
[0032] The matrix component and curing agent component are thoroughly mixed and then evenly coated onto the surface of the treated metal sample plate by spraying.
[0033] Example 3: (1) First, weigh 22g of zinc acetate dihydrate and add it to 300ml of methanol. Then, stir magnetically to dissolve it completely to obtain solution A. Next, weigh 65.6g of 2-methylimidazole and add it to 300ml of methanol. Stir magnetically to dissolve it completely to obtain solution B. Add solution B to solution A and continue to stir magnetically for 30 minutes to obtain white mixed solution C. Stop stirring and let it stand for 12 hours.
[0034] (2) Collect the mixture C, centrifuge at 3000 rpm, collect the white solid product, wash it three times each with deionized water and anhydrous ethanol at 3000 rpm, and vacuum dry at 80℃ for 12h to obtain a white block solid. Grind it in a mortar for 10 min and collect the white powder, which is the precursor ZIF-8.
[0035] (3) Weigh 200g of precursor ZIF-8 and place it in a ceramic boat, then place it in a box furnace. Under argon conditions, change the gas three times and raise the temperature to 700℃ at a rate of 2℃ / min. Hold the temperature for 1h. After the temperature drops to room temperature, collect the black powder, which is the ZnO@C composite material.
[0036] Mix 900 ml of anhydrous ethanol and 100 ml of deionized water and stir magnetically. Add acetic acid to adjust the pH to 4-5, then add 20 ml of KH570 and stir magnetically for 30 min. Weigh 100 g of ZnO@C composite material and add it to the above solution. First, ultrasonically disperse for 20 min, then stir magnetically for 2 h. Collect the product by centrifugation at 3000 rpm, wash three times with anhydrous ethanol at 3000 rpm, and vacuum dry at 80℃ for 12 h to obtain a black product, which is the modified ZnO@C composite material.
[0037] Weigh out 95 parts of E51 epoxy resin and 5 parts of reactive diluent AGE according to the mass composition, and stir thoroughly to obtain the matrix component; weigh out 30 parts of polyetheramine D230, 3 parts of modified ZnO@C composite material, 1 part of accelerator DMP-30, and 0.3 parts of defoamer, sonicate for 20 minutes, and then stir thoroughly with PTFE for 1 hour to obtain the curing agent component.
[0038] The surface of the metal sample plate was sandblasted with white fused alumina, and then the surface was cleaned with ethanol to remove oil and ensure that the surface cleanliness of the sample plate reached Sa2.5.
[0039] The matrix component and curing agent component are thoroughly mixed and then sprayed evenly onto the surface of the treated metal sample plate.
[0040] Example 4: (1) First, weigh 22g of zinc acetate dihydrate and add it to 300ml of methanol. Then, stir magnetically to dissolve it completely to obtain solution A. Next, weigh 65.6g of 2-methylimidazole and add it to 300ml of methanol. Stir magnetically to dissolve it completely to obtain solution B. Add solution B to solution A and continue to stir magnetically for 30 minutes to obtain white mixed solution C. Stop stirring and let it stand for 12 hours.
[0041] (2) Collect the mixture C, centrifuge at 3000 rpm, collect the white solid product, wash it three times each with deionized water and anhydrous ethanol at 3000 rpm, and vacuum dry at 80℃ for 12h to obtain a white block solid. Grind it in a mortar for 10 min and collect the white powder, which is the precursor ZIF-8.
[0042] (3) Weigh 200g of precursor ZIF-8 and place it in a ceramic boat, then place it in a box furnace. Under argon conditions, change the gas three times and raise the temperature to 700℃ at a rate of 2℃ / min. Hold the temperature for 1h. After the temperature drops to room temperature, collect the black powder, which is the ZnO@C composite material.
[0043] Mix 900 ml of anhydrous ethanol and 100 ml of deionized water and stir magnetically. Add acetic acid to adjust the pH to 4-5, then add 20 ml of KH570 and stir magnetically for 30 min. Weigh 100 g of ZnO@C composite material and add it to the above solution. First, ultrasonically disperse for 20 min, then stir magnetically for 2 h. Collect the product by centrifugation at 3000 rpm, wash three times with anhydrous ethanol at 3000 rpm, and vacuum dry at 80℃ for 12 h to obtain a black product, which is the modified ZnO@C composite material.
[0044] Weigh out 95 parts of E51 epoxy resin and 5 parts of reactive diluent AGE according to the mass composition, and stir thoroughly to obtain the matrix component; weigh out 30 parts of polyetheramine D230, 4 parts of modified ZnO@C composite material, 1 part of accelerator DMP-30, and 0.3 parts of defoamer, sonicate for 20 minutes, and then stir thoroughly with PTFE for 1 hour to obtain the curing agent component.
[0045] The surface of the metal sample plate was sandblasted with white fused alumina, and then the surface was cleaned with ethanol to remove oil and ensure that the surface cleanliness of the sample plate reached Sa2.5.
[0046] The matrix component and curing agent component are thoroughly mixed and then evenly coated onto the surface of the treated metal sample plate by spraying.
[0047] Example 5: (1) First, weigh 22g of zinc acetate dihydrate and add it to 300ml of methanol. Then, stir magnetically to dissolve it completely to obtain solution A. Next, weigh 65.6g of 2-methylimidazole and add it to 300ml of methanol. Stir magnetically to dissolve it completely to obtain solution B. Add solution B to solution A and continue to stir magnetically for 30 minutes to obtain white mixed solution C. Stop stirring and let it stand for 12 hours.
[0048] (2) Collect the mixture C, centrifuge at 3000 rpm, collect the white solid product, wash it three times each with deionized water and anhydrous ethanol at 3000 rpm, and vacuum dry at 80℃ for 12h to obtain a white block solid. Grind it in a mortar for 10 min and collect the white powder, which is the precursor ZIF-8.
[0049] (3) Weigh 200g of precursor ZIF-8 and place it in a ceramic boat, then place it in a box furnace. Under argon conditions, change the gas three times and raise the temperature to 700℃ at a rate of 2℃ / min. Hold the temperature for 1h. After the temperature drops to room temperature, collect the black powder, which is the ZnO@C composite material.
[0050] Mix 900 ml of anhydrous ethanol and 100 ml of deionized water and stir magnetically. Add acetic acid to adjust the pH to 4-5, then add 20 ml of KH570 and stir magnetically for 30 min. Weigh 100 g of ZnO@C composite material and add it to the above solution. First, ultrasonically disperse for 20 min, then stir magnetically for 2 h. Collect the product by centrifugation at 3000 rpm, wash three times with anhydrous ethanol at 3000 rpm, and vacuum dry at 80℃ for 12 h to obtain a black product, which is the modified ZnO@C composite material.
[0051] Weigh out 95 parts of E51 epoxy resin and 5 parts of reactive diluent AGE according to the mass composition, and stir thoroughly to obtain the matrix component; weigh out 30 parts of polyetheramine D230, 5 parts of modified ZnO@C composite material, 1 part of accelerator DMP-30, and 0.3 parts of defoamer, sonicate for 20 minutes, and then stir thoroughly with PTFE for 1 hour to obtain the curing agent component.
[0052] The surface of the metal sample plate was sandblasted with white fused alumina, and then the surface was cleaned with ethanol to remove oil and ensure that the surface cleanliness of the sample plate reached Sa2.5.
[0053] The matrix component and curing agent component are thoroughly mixed and then evenly coated onto the surface of the treated metal sample plate by spraying.
[0054] Comparative Example 1: The only difference from Example 1 is that the modified ZnO@C composite material was not added.
[0055] Comparative Example 2: The only difference from Example 1 is the addition of 1 part of unmodified ZnO@C composite material.
[0056] Comparative Example 3: The only difference from Example 1 is the addition of 1 part of ZnO@C composite material modified only with KH570 (KH570 and ZnO@C composite material were added simultaneously in a ratio of 20 mL: 100 g, and no modification steps such as pH adjustment with acetic acid were performed).
[0057] Test Example: The coatings prepared in Examples 1-5 and Comparative Examples 1-3 were sprayed onto the models, and model experiments were conducted to evaluate the drag reduction and noise reduction performance of the coatings. The results obtained when the water flow rate was 7 m / s are shown in the table below: It should be noted that the embodiments listed above are merely preferred embodiments of the present invention, but are not limited thereto, and various arrangements and variations are possible.
Claims
1. A method for preparing a ZIF-8 derived ZnO@C composite material modified epoxy resin coating, characterized in that, Includes the following steps: (1) The precursor ZIF-8 was prepared by reacting zinc salt with 2-methylimidazole in an organic solvent by magnetic stirring; (2) The precursor ZIF-8 obtained in step (1) is carbonized in an inert atmosphere to obtain ZnO@C composite material; (3) The ZnO@C composite material obtained in step (2) is reacted with a silane coupling agent to obtain the modified ZnO@C composite material; (4) The modified ZnO@C composite material obtained in step (3) is dispersed in the curing agent component, and after adding the epoxy resin matrix component, it is coated on the surface of the metal sample plate and cured to obtain the modified epoxy resin coating.
2. The method according to claim 1, characterized in that, The zinc salt mentioned in step (1) is one or more of zinc acetate dihydrate and zinc nitrate hexahydrate.
3. The method according to claim 1, characterized in that, The organic solvent mentioned in step (1) is one or more of methanol and N,N-dimethylamide.
4. The method according to claim 1, characterized in that, The magnetic stirring reaction temperature in step (1) is 10-30℃, and the stirring time is at least 30min.
5. The method according to claim 1, characterized in that, The inert atmosphere mentioned in step (2) is nitrogen or argon.
6. The method according to claim 1, characterized in that, In step (2), the heating rate of the carbonization process is 2-5℃ / min, the carbonization temperature is 700-900℃, and the holding time is at least 2h.
7. The method according to claim 1, characterized in that, In step (3), the silane coupling agent used is KH570.
8. The method according to claim 7, characterized in that, The specific steps in step (3) are as follows: anhydrous ethanol and deionized water are mixed and stirred at a volume ratio of 9:1, acetic acid is added to adjust the pH to 4-5 to obtain a mixed solution, KH570 is added, magnetic stirring is performed for at least 30 minutes, ZnO@C composite material is added, and after mixing evenly, the mixture is centrifuged, washed, and dried to obtain the modified ZnO@C composite material; the ratio of the amount of the mixed solution, KH570 and ZnO@C composite material is 1000mL:20mL:100g.
9. The method according to claim 1, characterized in that, The matrix components in step (4) are E51 epoxy resin and reactive diluent AGE, and the curing agent components are polyetheramine D230, accelerator DMP-30 and defoamer.
10. A ZnO@C composite material modified epoxy resin coating, characterized in that, It is prepared by the preparation method described in any one of claims 1 to 9.