A superhydrophobic anti-icing coating with photoelectric thermal coupling effect and its preparation method

Abstract

This invention provides a superhydrophobic anti-icing coating with photoelectric thermal coupling effect and its preparation method, relating to the field of functional coating materials and surface protection technology. The method involves dissolving polydimethylsiloxane in ethanol. This superhydrophobic anti-icing coating with photoelectric thermal coupling effect and its preparation method synergistically integrate a low surface energy hydrophobic matrix formed by polydimethylsiloxane, a micro-nano multi-level rough structure constructed from micron-sized zinc oxide and nano-sized silica, and a photoelectric thermal response network formed by modified carbon fibers. Combined with a spray curing process, a composite anti-icing coating is constructed on the substrate surface, achieving a unified superhydrophobic properties, photothermal / electrothermal heating capacity, and anti-icing and de-icing functions. This results in a coating that effectively delays the icing process, reduces ice adhesion strength, and possesses rapid active de-icing capability, thus improving the overall performance of the anti-icing coating.

Description

Technical Field

[0001] This invention relates to the field of functional coating materials and surface protection technology, specifically to a superhydrophobic anti-icing coating with photoelectric thermal coupling effect and its preparation method. Background Technology

[0002] In existing technologies, the common approaches to addressing icing issues on the surfaces of transmission line insulators and other easily icing equipment include structural optimization, mechanical de-icing, thermal de-icing, and surface functionalization for anti-icing. Among these, superhydrophobic anti-icing coatings reduce droplet adhesion, delay the icing process, and lower ice adhesion strength by constructing a low surface energy layer and micro / nano rough structures on the substrate surface. Meanwhile, photothermal de-icing, electrothermal de-icing, and low-ice-adhesion surfaces are also used to improve de-icing efficiency and surface anti-icing performance in low-temperature environments. These technologies, under certain conditions, can achieve icing suppression or post-icing removal, and have become an important research direction in the field of anti-icing coatings.

[0003] However, existing technologies still have significant shortcomings: single superhydrophobic surfaces are prone to frost accumulation, structural damage, and performance degradation under low temperature, high humidity, and repeated freeze-thaw conditions, making it difficult to maintain a stable anti-icing effect over a long period; single photothermal or electrothermal anti-icing solutions generally suffer from limited functionality, limited energy utilization efficiency, or strong dependence on external conditions, making it difficult to simultaneously meet the needs of ice suppression and rapid de-icing. Existing anti-icing coatings also generally suffer from insufficient adhesion to the substrate, poor wear resistance, and poor durability. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides a superhydrophobic anti-icing coating with photoelectric thermal coupling effect and its preparation method. The technical problem to be solved by this invention is: how to construct a composite coating that combines superhydrophobic structure, photothermal / electrothermal coupling heating capability, and interface reinforcement layer to solve the problems of existing anti-icing coatings that rely solely on passive hydrophobicity, have insufficient freezing delay and de-icing capability, and also have low adhesion to the substrate, poor wear resistance, and insufficient freeze-thaw cycle stability.

[0005] To achieve the above objectives, the present invention provides the following technical solution: a superhydrophobic anti-icing coating with photoelectric thermal coupling effect, comprising, by mass percentage: Polydimethylsiloxane 10%-20%; Micron-sized zinc oxide 12%-22%; Nano-silica 5%-12%; Carbon fiber 2%-8%; Epoxy resin 8%-18%; Aminosilane coupling agents 0.5%-4%; The remainder consists of dispersion and reaction media; The polydimethylsiloxane is used to form a low surface energy hydrophobic matrix, the micron-sized zinc oxide and the nano-sized silica are used to construct a micro-nano multi-level rough structure on the coating surface, the carbon fiber is used to form a conductive network in the coating and provide photothermal conversion effect and electrothermal conversion effect, and the epoxy resin and the aminosilane coupling agent are used to enhance the interfacial bonding strength between the coating and the substrate, so that the coating has the properties of delayed icing, reduced ice adhesion and rapid de-icing.

[0006] Preferably, the micron-sized zinc oxide and the nano-sized silica are co-distributed in a hydrophobic matrix formed by polydimethylsiloxane, so as to form a micro-nano multi-level rough surface on the coating surface that combines micron-level protrusions with nano-level refined structures.

[0007] Preferably, the carbon fibers are dispersed inside the coating and overlap each other to form a conductive path, so that the coating has photothermal heating capability under light irradiation and electrothermal heating capability under applied electricity.

[0008] Preferably, the epoxy resin and aminosilane coupling agent form an interface reinforcement layer on the substrate surface, and the polydimethylsiloxane, micron-sized zinc oxide, nano-sized silica and carbon fiber form a functional layer located outside the interface reinforcement layer to improve the adhesion, wear resistance and freeze-thaw cycle stability between the coating and the substrate.

[0009] A method for preparing a superhydrophobic anti-icing coating with photoelectric thermal coupling effect, comprising: S1. Polydimethylsiloxane is added to ethanol for mixing and dissolution, and impurities are removed by filtration to obtain a polydimethylsiloxane dispersion; S2. Surface modification of carbon fibers was performed using an aminosilane coupling agent to obtain modified carbon fibers; S3. Micron-sized zinc oxide, nano-sized silica and the modified carbon fiber are added to the polydimethylsiloxane dispersion for mixing and dispersion to obtain an optoelectronic, thermo-hydrophobic composite dispersion; S4. The photoelectric thermohydrophobic composite dispersion is blended with epoxy resin and aminosilane coupling agent and introduced into an alkaline reaction system to obtain an interface-enhanced composite coating system. S5. The interface-enhanced composite coating system is applied to the surface of the substrate to be protected from ice by spraying and then dried and cured, so that the epoxy resin forms an interface-enhancing layer on the surface of the substrate to be protected from ice, and at the same time, polydimethylsiloxane, micron-sized zinc oxide, nano-silica and carbon fiber form a photoelectric and thermal superhydrophobic functional layer located outside the interface-enhancing layer, thereby obtaining the superhydrophobic anti-icing coating with photoelectric and thermal coupling effect.

[0010] Preferably, the mixing and dissolving process includes: adding polydimethylsiloxane to ethanol and stirring for 20-60 minutes; after stirring, filtering with a filter with a pore size of 0.45-5 μm to remove undissolved particulate impurities and particulate impurities with a particle size greater than 5 μm to obtain a polydimethylsiloxane dispersion.

[0011] Preferably, the surface modification uses an aminosilane coupling agent, specifically: the carbon fiber is impregnated in an alcohol solution containing an aminosilane coupling agent for 30-120 minutes, and then dried to obtain modified carbon fiber.

[0012] Preferably, the pH value of the alkaline reaction system is 8-11. The photoelectric, thermo-hydrophobic composite dispersion is mixed with epoxy resin and aminosilane coupling agent and then added to the alkaline reaction system, and stirred continuously for 10 min-40 min to obtain an interface-enhanced composite coating system.

[0013] This invention provides a superhydrophobic anti-icing coating with photoelectric thermal coupling effect and its preparation method. It has the following beneficial effects: This superhydrophobic anti-icing coating with photoelectric-thermal coupling effect and its preparation method synergistically integrate a low surface energy hydrophobic matrix formed by polydimethylsiloxane, a micro-nano hierarchical rough structure constructed by micron-sized zinc oxide and nano-sized silica, and a photoelectric-thermal response network formed by modified carbon fibers. Combined with a spray curing process, a composite anti-icing coating is constructed on the substrate surface, achieving a unified superhydrophobic properties, photothermal / electrothermal heating capacity, and anti-icing and de-icing functions. This results in a coating that effectively delays the icing process, reduces ice adhesion strength, and possesses rapid active de-icing capability, thus improving the overall performance of the anti-icing coating.

[0014] An interface reinforcement layer is formed on the substrate surface using epoxy resin and aminosilane coupling agent, which enhances the interfacial bonding strength between the coating and the substrate, improves wear resistance, and improves freeze-thaw cycle stability. At the same time, conductive pathways are constructed using surface-modified carbon fibers, and a micro-nano composite rough surface is formed by micron-sized zinc oxide and nano-sized silica. This allows the coating to maintain good structural and functional stability under complex environments, improving the long-term service capability and actual anti-icing application effect of the coating. Attached Figure Description

[0015] Figure 1 This is a schematic diagram of the coating structure of the present invention; Figure 2 This is a schematic diagram illustrating the functional characteristics of the present invention; Figure 3 This is a flowchart of the preparation method of the present invention. Detailed Implementation

[0016] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0017] Example 1 like Figure 1-3 As shown, this embodiment of the invention provides a superhydrophobic anti-icing coating with photoelectric thermal coupling effect, comprising, by mass percentage: 10% polydimethylsiloxane.

[0018] 12% micron-sized zinc oxide.

[0019] 5% nano-silica. Micron-sized zinc oxide and nano-silica are co-distributed in a hydrophobic matrix formed by polydimethylsiloxane to form a micro-nano multi-level rough surface on the coating surface, combining micron-level protrusions and nano-level refined structures.

[0020] 2% carbon fiber. The carbon fibers are dispersed inside the coating and overlap each other to form conductive paths, so that the coating has photothermal heating capability under light conditions and electrothermal heating capability under the action of external electricity.

[0021] Epoxy resin 8%.

[0022] 0.5% aminosilane coupling agent. Epoxy resin and aminosilane coupling agent form an interface reinforcement layer on the substrate surface. Polydimethylsiloxane, micron-sized zinc oxide, nano-sized silica, and carbon fibers form a functional layer located outside the interface reinforcement layer to improve the adhesion, abrasion resistance, and freeze-thaw cycle stability between the coating and the substrate.

[0023] The remainder consists of dispersion and reaction media.

[0024] Among them, polydimethylsiloxane is used to form a low surface energy hydrophobic matrix, micron-sized zinc oxide and nano-sized silica are used to construct a micro-nano multi-level rough structure on the coating surface, carbon fiber is used to form a conductive network in the coating and provide photothermal conversion effect and electrothermal conversion effect, and epoxy resin and aminosilane coupling agent are used to enhance the interfacial bonding strength between the coating and the substrate, so that the coating has both icing delay, ice adhesion reduction and rapid de-icing performance.

[0025] A method for preparing a superhydrophobic anti-icing coating with photoelectric thermal coupling effect, comprising: S1. Polydimethylsiloxane is added to ethanol for mixing and dissolution, and impurities are removed by filtration to obtain a polydimethylsiloxane dispersion. The mixing and dissolution includes: adding polydimethylsiloxane to ethanol and stirring for 20 minutes; after stirring, filtering with a 5 μm pore size filter to remove undissolved particulate impurities and particulate impurities with a particle size greater than 5 μm to obtain a polydimethylsiloxane dispersion.

[0026] S2. Surface modification of carbon fibers using an aminosilane coupling agent yields modified carbon fibers. The surface modification using an aminosilane coupling agent involves impregnating the carbon fibers in an alcohol solution containing the aminosilane coupling agent for 30 minutes, followed by drying to obtain the modified carbon fibers.

[0027] S3. Micron-sized zinc oxide, nano-sized silica and modified carbon fiber are added to polydimethylsiloxane dispersion for mixing and dispersion to obtain photoelectric, thermo-hydrophobic composite dispersion.

[0028] S4. The photoelectric, thermohydrophobic, and composite dispersion was blended with epoxy resin and aminosilane coupling agent, and then introduced into an alkaline reaction system to obtain an interface-enhanced composite coating system. The pH value of the alkaline reaction system was 11. After mixing the photoelectric, thermohydrophobic, and composite dispersion with epoxy resin and aminosilane coupling agent, the mixture was added to the alkaline reaction system and stirred continuously for 10 minutes to obtain the interface-enhanced composite coating system.

[0029] S5. Apply the interface-enhanced composite coating system to the surface of the substrate to be protected against ice by spraying and then dry and cure it. This allows the epoxy resin to form an interface-enhancing layer on the surface of the substrate to be protected against ice. At the same time, polydimethylsiloxane, micron-sized zinc oxide, nano-silica and carbon fiber form a photoelectric and thermal superhydrophobic functional layer located outside the interface-enhancing layer, thereby obtaining a superhydrophobic anti-icing coating with photoelectric and thermal coupling effect.

[0030] Even with polydimethylsiloxane, micron-sized zinc oxide, nano-sized silica, carbon fiber, epoxy resin, and aminosilane coupling agent all at their lower limits, and with relatively simplified stirring, filtering, impregnation, and blending conditions, a composite anti-icing coating with a hydrophobic matrix, micro / nano rough structure, conductive network, and interface reinforcement layer can still be formed. This indicates that the present invention can achieve basic superhydrophobic anti-icing and a certain degree of active de-icing function under relatively low material input and mild process conditions. It is suitable for scenarios with high requirements for cost control, construction efficiency, or large-area coverage, while having relatively moderate requirements for de-icing response speed and long-term durability.

[0031] Example 2 This invention provides a superhydrophobic anti-icing coating with photoelectric thermal coupling effect, comprising, by weight percentage: 15% polydimethylsiloxane.

[0032] 17% zinc oxide per micrometer.

[0033] 8.5% nano-silica. Micron-sized zinc oxide and nano-silica are co-distributed in a hydrophobic matrix formed by polydimethylsiloxane to form a micro-nano multi-level rough surface on the coating surface, combining micron-level protrusions with nano-level refined structures.

[0034] 5% carbon fiber. The carbon fibers are dispersed inside the coating and interlock to form conductive pathways, so that the coating has photothermal heating capability under light irradiation and electrothermal heating capability under applied electricity.

[0035] Epoxy resin 13%.

[0036] Aminosilane coupling agent 2.25%. Epoxy resin and aminosilane coupling agent form an interface reinforcement layer on the substrate surface. Polydimethylsiloxane, micron-sized zinc oxide, nano-sized silica and carbon fibers form a functional layer located outside the interface reinforcement layer to improve the adhesion, abrasion resistance and freeze-thaw cycle stability between the coating and the substrate.

[0037] The remainder consists of dispersion and reaction media.

[0038] Among them, polydimethylsiloxane is used to form a low surface energy hydrophobic matrix, micron-sized zinc oxide and nano-sized silica are used to construct a micro-nano multi-level rough structure on the coating surface, carbon fiber is used to form a conductive network in the coating and provide photothermal conversion effect and electrothermal conversion effect, and epoxy resin and aminosilane coupling agent are used to enhance the interfacial bonding strength between the coating and the substrate, so that the coating has both icing delay, ice adhesion reduction and rapid de-icing performance.

[0039] A method for preparing a superhydrophobic anti-icing coating with photoelectric thermal coupling effect, comprising: S1. Polydimethylsiloxane is added to ethanol for mixing and dissolution, and impurities are removed by filtration to obtain a polydimethylsiloxane dispersion. The mixing and dissolution includes: adding polydimethylsiloxane to ethanol and stirring for 40 minutes. After stirring, the mixture is filtered through a 2.73 μm filter to remove undissolved particulate impurities and particulate impurities with a particle size greater than 5 μm to obtain a polydimethylsiloxane dispersion.

[0040] S2. Surface modification of carbon fibers using an aminosilane coupling agent yields modified carbon fibers. The surface modification using an aminosilane coupling agent involves impregnating the carbon fibers in an alcohol solution containing the aminosilane coupling agent for 75 minutes, followed by drying to obtain the modified carbon fibers.

[0041] S3. Micron-sized zinc oxide, nano-sized silica and modified carbon fiber are added to polydimethylsiloxane dispersion for mixing and dispersion to obtain photoelectric, thermo-hydrophobic composite dispersion.

[0042] S4. The photoelectric, thermohydrophobic, and composite dispersion was blended with epoxy resin and aminosilane coupling agent, and then introduced into an alkaline reaction system to obtain an interface-enhanced composite coating system. The pH value of the alkaline reaction system was 9.5. After mixing the photoelectric, thermohydrophobic, and composite dispersion with epoxy resin and aminosilane coupling agent, the mixture was added to the alkaline reaction system and stirred continuously for 25 minutes to obtain the interface-enhanced composite coating system.

[0043] S5. Apply the interface-enhanced composite coating system to the surface of the substrate to be protected against ice by spraying and then dry and cure it. This allows the epoxy resin to form an interface-enhancing layer on the surface of the substrate to be protected against ice. At the same time, polydimethylsiloxane, micron-sized zinc oxide, nano-silica and carbon fiber form a photoelectric and thermal superhydrophobic functional layer located outside the interface-enhancing layer, thereby obtaining a superhydrophobic anti-icing coating with photoelectric and thermal coupling effect.

[0044] When the content of each component and the process parameters are taken to the middle value, there is a good matching relationship between the construction of the hydrophobic matrix, the formation of the surface micro-nano rough structure, the establishment of the carbon fiber conductive path and the generation of the interface reinforcement layer. This indicates that the present invention can achieve a relatively balanced comprehensive effect between anti-icing performance, de-icing capability, adhesion stability and process operability. Therefore, it is more suitable as a representative implementation of the present invention. It is applicable to conventional outdoor anti-icing scenarios that require both the ability to delay icing and reduce ice adhesion, as well as a certain photothermal / electrothermal active de-icing capability, while also taking into account the stability of the coating and universal construction.

[0045] Example 3 This invention provides a superhydrophobic anti-icing coating with photoelectric thermal coupling effect, comprising, by weight percentage: 20% polydimethylsiloxane.

[0046] 22% zinc oxide per micrometer.

[0047] 12% nano-silica. Micron-sized zinc oxide and nano-silica are co-distributed in a hydrophobic matrix formed by polydimethylsiloxane to form a micro-nano multi-level rough surface on the coating surface, combining micron-level protrusions and nano-level refined structures.

[0048] 8% carbon fiber. The carbon fibers are dispersed inside the coating and interlock to form conductive pathways, so that the coating has photothermal heating capability under light irradiation and electrothermal heating capability under applied electricity.

[0049] Epoxy resin 18%.

[0050] 4% aminosilane coupling agent. Epoxy resin and aminosilane coupling agent form an interface reinforcement layer on the substrate surface. Polydimethylsiloxane, micron-sized zinc oxide, nano-sized silica and carbon fibers form a functional layer located outside the interface reinforcement layer to improve the adhesion, abrasion resistance and freeze-thaw cycle stability between the coating and the substrate.

[0051] The remainder consists of dispersion and reaction media.

[0052] Among them, polydimethylsiloxane is used to form a low surface energy hydrophobic matrix, micron-sized zinc oxide and nano-sized silica are used to construct a micro-nano multi-level rough structure on the coating surface, carbon fiber is used to form a conductive network in the coating and provide photothermal conversion effect and electrothermal conversion effect, and epoxy resin and aminosilane coupling agent are used to enhance the interfacial bonding strength between the coating and the substrate, so that the coating has both icing delay, ice adhesion reduction and rapid de-icing performance.

[0053] A method for preparing a superhydrophobic anti-icing coating with photoelectric thermal coupling effect, comprising: S1. Polydimethylsiloxane is added to ethanol for mixing and dissolution, and impurities are removed by filtration to obtain a polydimethylsiloxane dispersion. The mixing and dissolution includes: adding polydimethylsiloxane to ethanol and stirring for 60 minutes. After stirring, the mixture is filtered through a 0.45 μm filter to remove undissolved particulate impurities and particulate impurities with a particle size greater than 5 μm to obtain a polydimethylsiloxane dispersion.

[0054] S2. Surface modification of carbon fibers using an aminosilane coupling agent yields modified carbon fibers. The surface modification using an aminosilane coupling agent involves impregnating the carbon fibers in an alcohol solution containing the aminosilane coupling agent for 120 minutes, followed by drying to obtain the modified carbon fibers.

[0055] S3. Micron-sized zinc oxide, nano-sized silica and modified carbon fiber are added to polydimethylsiloxane dispersion for mixing and dispersion to obtain photoelectric, thermo-hydrophobic composite dispersion.

[0056] S4. The photoelectric, thermohydrophobic, and composite dispersion was blended with epoxy resin and aminosilane coupling agent, and then introduced into an alkaline reaction system to obtain an interface-enhanced composite coating system. The pH value of the alkaline reaction system was 8. After mixing the photoelectric, thermohydrophobic, and composite dispersion with epoxy resin and aminosilane coupling agent, the mixture was added to the alkaline reaction system and stirred continuously for 40 minutes to obtain the interface-enhanced composite coating system.

[0057] S5. Apply the interface-enhanced composite coating system to the surface of the substrate to be protected against ice by spraying and then dry and cure it. This allows the epoxy resin to form an interface-enhancing layer on the surface of the substrate to be protected against ice. At the same time, polydimethylsiloxane, micron-sized zinc oxide, nano-silica and carbon fiber form a photoelectric and thermal superhydrophobic functional layer located outside the interface-enhancing layer, thereby obtaining a superhydrophobic anti-icing coating with photoelectric and thermal coupling effect.

[0058] When the upper limit of the range of polydimethylsiloxane, micron-sized zinc oxide, nano-sized silica, carbon fiber, epoxy resin, and aminosilane coupling agent is taken, and a longer stirring time, finer filtration conditions, and more thorough carbon fiber surface modification treatment are adopted, it shows that the present invention can further enhance the synergistic construction of hydrophobic phase, rough structure phase, conductive phase, and interface bonding phase. It has the technical potential to expand towards higher photothermal / electrothermal response capability, stronger interface bonding capability, and higher structural stability. It is suitable for complex service environments with low temperature and severe cold, frequent icing, high requirements for de-icing efficiency, or higher requirements for wear resistance, adhesion, and freeze-thaw cycle stability.

[0059] Example 4 This embodiment illustrates the differences in hydrophobicity, heating performance, anti-icing performance, and durability of the opto-thermal coupling superhydrophobic anti-icing coatings prepared under different parameter combinations.

[0060] 1. Experimental Objective Based on the technical approach of constructing a low surface energy substrate with PDMS, forming a multi-level rough structure with micron-sized zinc oxide and nano-sized silica, imparting photothermal and electrothermal effects with carbon fibers, and enhancing interfacial adhesion with epoxy resin and aminosilane coupling agent, this embodiment uses three different parameter combinations for horizontal comparison to examine the impact of changes in the proportion of each functional group on the overall performance of the final coating.

[0061] 2. Experimental subjects and sample grouping Experimental subject: Porcelain insulator glaze test pieces from the same batch were selected as the experimental substrate, with test piece dimensions of 50mm×50mm×4mm.

[0062] Before coating, each sample was rinsed with deionized water, cleaned with anhydrous ethanol, and dried at 60°C in sequence to minimize the influence of differences in substrate surface condition on the test results.

[0063] Sample grouping: Based on the preparation of 100g of spray liquid per group, three groups of samples were set up: Group A, Group B, and Group C.

[0064] Group A contains 10g of polydimethylsiloxane, 12g of micronized zinc oxide, 5g of nano-silica, 2g of carbon fiber, 8g of epoxy resin, and 0.5g of aminosilane coupling agent.

[0065] Group B contains 15g of polydimethylsiloxane, 17g of micronized zinc oxide, 8.5g of nano-silica, 5g of carbon fiber, 13g of epoxy resin, and 2.25g of aminosilane coupling agent.

[0066] Group C contains 20g of polydimethylsiloxane, 22g of micronized zinc oxide, 12g of nano-silica, 8g of carbon fiber, 18g of epoxy resin, and 4g of aminosilane coupling agent.

[0067] Group A corresponds to lower parameter combinations, Group B corresponds to intermediate parameter combinations, and Group C corresponds to higher parameter combinations.

[0068] 3. Preparation of polydimethylsiloxane dispersion The polydimethylsiloxane required for groups A, B and C were added to ethanol and dispersed by stirring at room temperature.

[0069] Group A was stirred for 20 minutes and then filtered through a 5 μm filter membrane; Group B was stirred for 40 minutes and then filtered through a 2.73 μm filter membrane; and Group C was stirred for 60 minutes and then filtered through a 0.45 μm filter membrane, resulting in three polydimethylsiloxane dispersions.

[0070] Stirring and dispersion are mainly used to improve the dispersion state of polydimethylsiloxane in the ethanol system and to remove undispersed impurities as much as possible, so that the low surface energy layer formed later is more uniform.

[0071] 4. Carbon fiber modification treatment The three groups of carbon fibers were immersed in an aminosilane coupling agent solution for surface modification to improve the interfacial bonding ability between the carbon fibers and the organic system.

[0072] Group A was impregnated for 30 minutes, Group B for 75 minutes, and Group C for 120 minutes. After removal, they were dried at 70°C for 40 minutes to obtain modified carbon fibers.

[0073] Surface modification enhances the dispersion of carbon fibers in the coating and facilitates the formation of more continuous internal thermal and electrical conduction pathways after film formation, thereby enabling the coating to possess both photothermal and electrothermal response capabilities.

[0074] 5. Preparation of composite spraying liquid First, add the micron-sized zinc oxide, nano-sized silica and modified carbon fiber of each group to the corresponding polydimethylsiloxane dispersion, mechanically stir at 800 r / min for 20 min, and then ultrasonically disperse for 15 min to obtain a mixture with relatively uniform particle dispersion.

[0075] Subsequently, epoxy resin and aminosilane coupling agent of appropriate mass were added to each group of mixtures, and the pH value of the system was adjusted.

[0076] Group A was adjusted to pH 11 and stirred for 10 minutes; Group B was adjusted to pH 9.5 and stirred for 25 minutes; Group C was adjusted to pH 8 and stirred for 40 minutes, resulting in three groups of spray solutions.

[0077] Among them, micron-sized zinc oxide and nano-sized silica are mainly used to construct a multi-level rough surface structure and also have a certain resistance to ultraviolet aging. Epoxy resin and aminosilane coupling agent are used to enhance the interfacial bonding between the coating and the insulator substrate, so that the formed hydrophobic layer is not easy to fall off during subsequent freeze-thaw or de-icing processes.

[0078] 6. Spraying and curing to form a film Three sets of coating liquids were sprayed onto the surface of the insulator glaze test piece using an air spray gun. The spraying pressure was 0.30 MPa, and the distance between the spray gun and the substrate was about 18 cm. Each sample was sprayed twice, with a 5-minute interval between the two sprays.

[0079] After spraying, the coating was first allowed to stand at room temperature for 15 minutes, then dried at 80℃ for 1 hour, and finally cured at 120℃ for 2 hours to obtain three groups of coating samples: Group A, Group B, and Group C. The thickness of the obtained coatings was controlled between 78μm and 86μm.

[0080] After spraying, it can be observed that Group A has good atomization, but the surface particle undulation is weak; Group C has high viscosity of spray liquid and slight local accumulation; Group B has good spray uniformity and the micro-rough structure formed on the surface is relatively continuous.

[0081] 7. Performance Testing Methods Hydrophobicity test: The static water contact angle and sliding angle of the sample surface were measured using a contact angle meter. The test droplet volume was 5 μL, and each group of samples was tested in parallel 5 times, and the average value was taken.

[0082] Test results: The static water contact angle of group A samples was 153.4° and the sliding angle was 8.6°; the static water contact angle of group B samples was 161.2° and the sliding angle was 4.3°; and the static water contact angle of group C samples was 158.1° and the sliding angle was 5.9°.

[0083] The results show that all three groups of samples have reached the level of superhydrophobicity, but group B performed better.

[0084] Analysis suggests that Group A has relatively low contents of micron-sized zinc oxide, nano-sized silica, and carbon fiber, resulting in limited surface roughness. Although Group C has further enhanced roughness, the local surface uniformity has decreased due to the high total filler content. Group B, on the other hand, has achieved a more suitable match between low surface energy components and multi-level roughness, thus resulting in a larger contact angle and a smaller sliding angle.

[0085] Photothermal heating performance test: Xenon lamps were used to simulate sunlight irradiation, with the light intensity set at 800W / m². 2 The sample was continuously irradiated for 300 seconds, and the temperature change of the sample surface was recorded. The photothermal response capability was characterized by the temperature difference before and after irradiation.

[0086] Electrothermal heating performance test: A 12V DC voltage was applied to both ends of the sample and energized for 180s. The temperature rise of the sample surface was recorded to evaluate the electrothermal response capability of carbon fiber after forming a conductive circuit inside the coating.

[0087] Test results: at 800W / m 2 After 300 seconds of illumination, the surface temperature of samples A was 16.3℃, group B was 25.1℃, and group C was 32.6℃. After 180 seconds of application of a 12V voltage, the surface temperature of samples A was 11.9℃, group B was 21.7℃, and group C was 30.4℃.

[0088] Test results show that as the carbon fiber content increases, the photothermal and electrothermal responses of the samples gradually increase, indicating that the introduction of carbon fiber does indeed improve the energy conversion capability of the coating. Among them, group C heated up the fastest, indicating that group C is more conducive to active de-icing under external light or power conditions. Although the heating level of group B is slightly lower than that of group C, it still has a significant active heating capability.

[0089] Freezing delay and ice adhesion strength tests: The sample was placed on a self-built cold stage, with the stage temperature controlled at -10℃. 50 μL of deionized water was dropped onto the sample surface. Timing began when the droplet contacted the sample surface and stopped when the droplet completely changed from transparent to opaque and a distinct solidified peak appeared at the top. This recorded time was taken as the freezing delay time. After freezing, the maximum force during ice desorption was tested using a push-shear method and converted into ice adhesion strength.

[0090] Test results: At -10℃, the freezing delay time of sample A was 436s and the ice adhesion strength was 84kPa; the freezing delay time of sample B was 689s and the ice adhesion strength was 46kPa; and the freezing delay time of sample C was 601s and the ice adhesion strength was 55kPa.

[0091] This shows that Group B was the most effective in delaying icing and reducing ice adhesion. The reason is: On the one hand, the surface of group B has a better superhydrophobic state, and the actual contact area between the droplet and the solid surface is smaller. On the other hand, the amount of epoxy resin and aminosilane coupling agent added in group B can achieve good interface enhancement, so that the surface micro-nano structure maintains high integrity during the freezing and de-icing process, thus the overall anti-icing performance is better.

[0092] Durability testing: The three groups of samples were subjected to 30 high and low temperature cycles, each cycle consisting of two phases: holding at -20℃ for 30 minutes and holding at 25℃ for 30 minutes. After the cycles were completed, the static water contact angle and ice adhesion strength were tested again to evaluate the performance retention of the coating under alternating hot and cold conditions.

[0093] Test results: After 30 high and low temperature cycles, the static water contact angle of the group A sample decreased to 145.6° and the ice adhesion strength increased to 109 kPa. The static water contact angle of the group B sample remained at 154.8° and the ice adhesion strength was 62 kPa. The static water contact angle of the group C sample was 149.6° and the ice adhesion strength was 78 kPa.

[0094] Meanwhile, the adhesion performance was compared using the cross-cut adhesion test. Group A had an adhesion rating of 1, Group B 0, and Group C 1. The results showed that the Group B samples still exhibited good surface stability and low ice adhesion strength after being subjected to alternating high and low temperatures, indicating that a moderate amount of epoxy resin and coupling agent is more beneficial in balancing hydrophobic layer stability and interfacial bonding strength.

[0095] This comparative experiment shows that the lower parameter combination in group A can form a functional coating with certain superhydrophobicity and anti-icing ability, but it is still insufficient in terms of active heating capability and post-cycle stability. The higher parameter combination in group C is most effective in terms of photothermal and electrothermal response, and is more suitable for application scenarios with high requirements for rapid ice melting and active de-icing. The intermediate parameter combination in group B achieves a good balance between surface hydrophobicity, ice formation delay time, ice adhesion strength, interface adhesion performance and cycle stability, and has the best overall performance. It can be used as the preferred parameter combination embodiment of the present invention.

[0096] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A superhydrophobic anti-icing coating having a photovoltaic-thermal coupling effect, characterized in that, By weight percentage, including: Polydimethylsiloxane 10%-20%; Micron-sized zinc oxide 12%-22%; Nano-silica 5%-12%; Carbon fiber 2%-8%; Epoxy resin 8%-18%; Aminosilane coupling agents 0.5%-4%; The remainder consists of dispersion and reaction media.

2. The superhydrophobic anti-icing coating with photoelectric-thermal coupling effect according to claim 1, characterized in that: The micron-sized zinc oxide and the nano-sized silica are co-distributed in a hydrophobic matrix formed by polydimethylsiloxane, so as to form a micro-nano multi-level rough surface on the coating surface that combines micron-level protrusions and nano-level refined structures.

3. The superhydrophobic anti-icing coating with photoelectric thermal coupling effect according to claim 1, characterized in that: The carbon fibers are dispersed inside the coating and overlap each other to form conductive pathways.

4. The superhydrophobic anti-icing coating with photoelectric thermal coupling effect according to claim 1, characterized in that: The epoxy resin and aminosilane coupling agent form an interface reinforcement layer on the substrate surface, and the polydimethylsiloxane, micron-sized zinc oxide, nano-sized silica and carbon fiber form a functional layer located outside the interface reinforcement layer.

5. A method for preparing a superhydrophobic anti-icing coating with photoelectric thermal coupling effect, used to prepare a superhydrophobic anti-icing coating with photoelectric thermal coupling effect as described in any one of claims 1-4, characterized in that, include: S1. Polydimethylsiloxane is added to ethanol for mixing and dissolution, and impurities are removed by filtration to obtain a polydimethylsiloxane dispersion; S2. Surface modification of carbon fibers was performed using an aminosilane coupling agent to obtain modified carbon fibers; S3. Micron-sized zinc oxide, nano-sized silica and the modified carbon fiber are added to the polydimethylsiloxane dispersion for mixing and dispersion to obtain an optoelectronic, thermo-hydrophobic composite dispersion; S4. The photoelectric thermohydrophobic composite dispersion is blended with epoxy resin and aminosilane coupling agent and introduced into an alkaline reaction system to obtain an interface-enhanced composite coating system. S5. The interface-enhanced composite coating system is applied to the surface of the substrate to be protected from ice by spraying and then dried and cured, so that the epoxy resin forms an interface-enhancing layer on the surface of the substrate to be protected from ice, and at the same time, polydimethylsiloxane, micron-sized zinc oxide, nano-silica and carbon fiber form a photoelectric and thermal superhydrophobic functional layer located outside the interface-enhancing layer, thereby obtaining the superhydrophobic anti-icing coating with photoelectric and thermal coupling effect.

6. The method for preparing a superhydrophobic anti-icing coating with photoelectric thermal coupling effect according to claim 5, characterized in that: The mixing and dissolution process includes: adding polydimethylsiloxane to ethanol and stirring for 20-60 minutes; after stirring, filtering with a filter with a pore size of 0.45-5 μm to remove undissolved particulate impurities and particulate impurities with a particle size greater than 5 μm to obtain a polydimethylsiloxane dispersion.

7. The method for preparing a superhydrophobic anti-icing coating with photoelectric thermal coupling effect according to claim 5, characterized in that: The surface modification uses an aminosilane coupling agent, specifically: carbon fibers are impregnated in an alcohol solution containing an aminosilane coupling agent for 30-120 minutes, followed by drying to obtain modified carbon fibers.

8. The method for preparing a superhydrophobic anti-icing coating with photoelectric thermal coupling effect according to claim 5, characterized in that: The pH value of the alkaline reaction system is 8-11. The photoelectric, thermo-hydrophobic composite dispersion is mixed with epoxy resin and aminosilane coupling agent and then added to the alkaline reaction system. The mixture is stirred continuously for 10 min-40 min to obtain an interface-enhanced composite coating system.

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