Linear reinforcement reinforced super-hydrophobic anti-icing and deicing coating and preparation method thereof

Abstract

The invention relates to a linear reinforcement reinforced super-hydrophobic anti-icing and deicing coating and a preparation method thereof, and belongs to the technical field of functional coating materials. In order to solve the problem of insufficient wear resistance of the existing super-hydrophobic anti-icing and deicing coating, the invention provides a linear reinforcement reinforced super-hydrophobic anti-icing and deicing coating which comprises the following components: nanoparticles, a micron-sized linear reinforcement, a modifier, a silicon source, ammonia water, a coupling agent A, E-51 epoxy resin, ethyl acetate, a coupling agent C and a curing agent. The nano particles are subjected to surface modification to form a three-dimensional covalent cross-linked network, so that the nano particles and the resin have more excellent bonding strength through double interlocking, and the wear resistance of the super-hydrophobic anti-icing and deicing coating is greatly improved. According to the invention, the micron-sized linear reinforcement is introduced as a framework, so that the area of a resin matrix in direct contact with a worn surface is reduced, the peeling of nano particles is favorably resisted, the microstructure required by a super-hydrophobic function is maintained, and the coating keeps excellent super-hydrophobic anti-icing and anti-deicing performance.

Description

Technical Field

[0001] This invention belongs to the field of functional coating materials technology, and in particular relates to a linearly reinforced superhydrophobic anti-icing coating and its preparation method. Background Technology

[0002] Icing is an unavoidable natural phenomenon in cold conditions, and the problem of preventing and removing ice from material surfaces is one of the key challenges faced by aerospace, transportation, and power systems. Superhydrophobic coatings, with their rough microstructure and low surface energy chemical composition, exhibit a contact angle with water greater than 150° and a roll-off angle less than 10°. This makes it difficult for water droplets to adhere to the coating surface, allowing them to easily roll and slide off. Superhydrophobic coatings can reduce droplet aggregation, delay freezing time, and reduce the adhesion strength of ice on solid surfaces, thus achieving passive anti-icing in low-temperature and frigid environments.

[0003] Patent application CN110734700A discloses a superhydrophobic coating composite material for de-icing, the material surface having a rough, uneven micro-nano structure; it is obtained by one-step polymerization of polydimethylsiloxane with cyclic crosslinked polyphosphonic acrylonitrile microspheres, followed by dip coating, brushing, or spraying onto the substrate surface. Patent CN120137488A discloses an MXene-based de-icing superhydrophobic coating, using MXene powder treated with fluorine-free long-chain silane as a superhydrophobic modified MXene photothermal material.

[0004] Existing superhydrophobic anti-icing coatings achieve their purpose by forming a "substrate + adhesive + hydrophobic particles" laminate structure with organic adhesives and inorganic particles. However, the interlocking and fixed bonding between the top-layer particles and the resin makes them highly susceptible to wear under external forces, leading to the loss of the top-layer superhydrophobic particles and thus weakening the coating's anti-icing ability. Therefore, developing a superhydrophobic anti-icing coating with excellent hydrophobic properties and good wear resistance is an urgent problem to be solved. Summary of the Invention

[0005] To address the problem of insufficient wear resistance in existing superhydrophobic anti-icing coatings, this invention provides a linearly reinforced superhydrophobic anti-icing coating and its preparation method.

[0006] The technical solution of the present invention:

[0007] A linearly reinforced superhydrophobic anti-icing coating contains the following components in parts by weight:

[0008] The composition includes 20-30 parts nanoparticles, 3-9 parts micron-sized linear reinforcement, 30-40 parts modifier, 10-20 parts silicon source, 40-50 parts ammonia, 5-15 parts coupling agent A, 16-50 parts E-51 epoxy resin, 30-75 parts ethyl acetate, 5-20 parts coupling agent C, and 15-25 parts curing agent.

[0009] Furthermore, the nanoparticles are silicon dioxide and / or alumina particles; the particle size of the nanoparticles is 20~60nm; the micron-scale linear reinforcement is one or a combination of several of α-cellulose, aramid fiber, carbon nanotubes or needle-shaped zinc oxide; the size of the micron-scale linear reinforcement is 10~50μm.

[0010] Furthermore, the modifier is one of heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltriethoxysilane, or perfluorodecyltriethoxysilane; the silicon source is one of tetraethyl orthosilicate, methyl orthosilicate, or methyltrimethoxysilane; and the coupling agent A is one of KH-560, KH-561, or A-187.

[0011] Furthermore, the coupling agent C is one of KH-792, KH-602, or A1120; the curing agent is one of alicyclic amine 3388 epoxy resin curing agent or alicyclic amine 3396 epoxy resin curing agent.

[0012] A method for preparing a superhydrophobic anti-icing coating reinforced by the linear reinforcement described above, comprising the following steps:

[0013] Step 1: Disperse nanoparticles and micron-sized linear reinforcements in anhydrous ethanol, then add modifier, silicon source, ammonia, and coupling agent A, stir evenly and sonicate, then place in a water bath and stir for a certain time to obtain solution A;

[0014] Step 2: Dissolve E-51 epoxy resin in ethyl acetate and stir until homogeneous to obtain solution B;

[0015] Step 3: Dissolve coupling agent C in anhydrous ethanol, sonicate, add modifier, and stir for a certain time under water bath heating to obtain solution C;

[0016] Step 4: Mix the obtained solution A with the obtained solution B, stir for a certain time under water bath heating, then cool to room temperature and add the obtained solution C and curing agent, stir and sonicate to obtain composite coating;

[0017] Step 5: Spray the composite coating obtained in Step 4 onto the substrate, and after drying, a superhydrophobic anti-icing coating is obtained.

[0018] Furthermore, the ultrasonic treatment time in step one is 10-20 minutes, the water bath heating temperature is 55-60°C, and the stirring time under the water bath heating condition is 3-4 hours.

[0019] Furthermore, the ultrasonic treatment time in step three is 8-15 minutes, the water bath heating temperature is 55-60°C, and the stirring time under the water bath heating condition is 1-2.5 hours.

[0020] Furthermore, in step four, the water bath heating temperature is 55~60℃, the overtime under the water bath heating condition is 1~1.5h, the stirring time after adding C solution and curing agent is 10~15min, and the ultrasonic treatment time is 5~10min.

[0021] Furthermore, the drying process described in step five involves drying at 70-85°C for 3.5-4 hours.

[0022] The beneficial effects of this invention are:

[0023] This invention modifies the surface of nanoparticles by coupling agent A, introducing epoxy groups on their surface. The epoxy groups of the resin react synchronously with the amino group of the curing agent to form a three-dimensional covalent cross-linked network that spans the inorganic and organic phases. The nanoparticles and resin have a better bonding strength through the dual interlocking of physical and chemical bonds, which greatly improves the wear resistance of the superhydrophobic anti-icing coating.

[0024] This invention introduces micron-scale linear reinforcements as a framework, which can effectively transfer and disperse stress, preventing crack formation. Furthermore, the high-hardness linear reinforcements exhibit excellent wear resistance, forming "protrusions" or support structures on the coating surface. This reduces the area of ​​the resin matrix directly contacting the wear surface, helping to resist the shedding of nanoparticles during friction, thereby maintaining the microstructure required for superhydrophobic functionality and ensuring the coating retains excellent superhydrophobic and de-icing properties. Attached Figure Description

[0025] Figure 1 The figures show the contact angle changes of the superhydrophobic anti-icing coatings prepared in Examples 1-4 under different polishing cycles. a represents Example 1, b represents Example 2, c represents Example 3, and d represents Example 4. Detailed Implementation

[0026] The technical solution of the present invention will be further described below with reference to embodiments, but it is not limited thereto. Any modifications or equivalent substitutions to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention should be covered within the protection scope of the present invention. In the following embodiments, the process equipment or apparatus not specifically specified are all conventional equipment or apparatus in the art. Unless otherwise specified, the raw materials used in the embodiments of the present invention are all commercially available; unless otherwise specified, the technical means used in the embodiments of the present invention are all conventional means well known to those skilled in the art.

[0027] Example 1

[0028] This embodiment provides a linearly reinforced superhydrophobic anti-icing coating containing the following components in parts by weight:

[0029] The composition includes 2.5g of silica nanoparticles, 0.5g of micron-sized linear reinforcing α-cellulose, 3.3g of modifier tridecafluorooctyltriethoxysilane, 1.4g of silicon-derived methyltrimethoxysilane, 4.5g of ammonia, 1g of coupling agent A KH-560, 3g of E-51 epoxy resin, 5g of ethyl acetate, 1g of coupling agent C KH-792, and 2g of alicyclic amine 3388 epoxy resin curing agent. The particle size of the silica nanoparticles is 20~60nm; the size of the micron-sized linear reinforcing α-cellulose is 10~50μm.

[0030] This embodiment provides a method for preparing a linearly reinforced superhydrophobic anti-icing coating, comprising the following steps:

[0031] Step 1: Disperse 2.5g of nanoparticles and 0.5g of micron-sized linear reinforcement in 50mL of anhydrous ethanol, then add 2.5g of modifier, 1.4g of silicon source, 4.5g of ammonia water and 1g of coupling agent A, stir evenly and sonicate for 15min, then place in a 60℃ water bath and stir for 4h to obtain solution A;

[0032] Step 2: Dissolve 3g of E-51 epoxy resin in 5g of ethyl acetate and stir until homogeneous to obtain solution B;

[0033] Step 3: Dissolve 1g of coupling agent C in 12mL of anhydrous ethanol, sonicate for 12min, add 0.8g of modifier, and stir for 1.5h under a 60℃ water bath heating condition to obtain solution C;

[0034] Step 4: Mix the obtained solution A with the obtained solution B, stir for 1.5 h under a water bath heating condition of 60℃, then cool to room temperature and add the obtained solution C and 2g of curing agent, stir for 12 min and ultrasonically treat for 10 min to obtain the composite coating;

[0035] Step 5: Spray the composite coating obtained in Step 4 onto the substrate after sanding, and dry it in an oven at 80°C for 4 hours to obtain a superhydrophobic anti-icing coating.

[0036] Example 2

[0037] This embodiment provides a linearly reinforced superhydrophobic anti-icing coating containing the following components in parts by weight:

[0038] The composition includes 2.5g of alumina nanoparticles, 0.5g of micron-sized linearly reinforced needle-shaped zinc oxide, 3.3g of modifier heptadecafluorodecyltrimethoxysilane, 1.4g of silicon-derived methyltrimethoxysilane, 4.5g of ammonia, 1g of coupling agent A KH-561, 3g of E-51 epoxy resin, 5g of ethyl acetate, 1g of coupling agent C KH-792, and 2g of alicyclic amine 3388 epoxy resin curing agent. The alumina nanoparticles have a particle size of 20-60nm; the micron-sized linearly reinforced needle-shaped zinc oxide has a size of 10-50μm.

[0039] This embodiment provides a method for preparing a linearly reinforced superhydrophobic anti-icing coating, comprising the following steps:

[0040] Step 1: Disperse 2.5g of nanoparticles and 0.5g of micron-sized linear reinforcement in 50mL of anhydrous ethanol, then add 2.5g of modifier, 1.4g of silicon source, 4.5g of ammonia water and 1g of coupling agent A, stir evenly and sonicate for 15min, then place in a 60℃ water bath and stir for 4h to obtain solution A;

[0041] Step 2: Dissolve 3g of E-51 epoxy resin in 5g of ethyl acetate and stir until homogeneous to obtain solution B;

[0042] Step 3: Dissolve 1g of coupling agent C in 12mL of anhydrous ethanol, sonicate for 12min, add 0.8g of modifier, and stir for 1.5h under a 60℃ water bath heating condition to obtain solution C;

[0043] Step 4: Mix the obtained solution A with the obtained solution B, stir for 1.5 h under a water bath heating condition of 60℃, then cool to room temperature and add the obtained solution C and 2g of curing agent, stir for 12 min and ultrasonically treat for 10 min to obtain the composite coating;

[0044] Step 5: Spray the composite coating obtained in Step 4 onto the substrate after sanding, and dry it in an oven at 80°C for 4 hours to obtain a superhydrophobic anti-icing coating.

[0045] Example 3

[0046] This embodiment provides a linearly reinforced superhydrophobic anti-icing coating containing the following components in parts by weight:

[0047] The mixture comprises 2.5 g of silica and alumina nanoparticles, 0.5 g of micron-sized linearly reinforced carbon nanotubes, 3.3 g of modifier tridecafluorooctyltriethoxysilane, 1.4 g of tetraethyl orthosilicate, 4.5 g of ammonia, 1 g of coupling agent AKH-560, 3 g of E-51 epoxy resin, 5 g of ethyl acetate, 1 g of coupling agent C KH-792, and 2 g of cycloaliphatic amine 3388 epoxy resin curing agent. The particle size of the silica and alumina nanoparticles is 20–60 nm; the size of the micron-sized linearly reinforced carbon nanotubes is 10–50 μm.

[0048] This embodiment provides a method for preparing a linearly reinforced superhydrophobic anti-icing coating, comprising the following steps:

[0049] Step 1: Disperse 2.5g of nanoparticles and 0.5g of micron-sized linear reinforcement in 50mL of anhydrous ethanol, then add 2.5g of modifier, 1.4g of silicon source, 4.5g of ammonia water and 1g of coupling agent A, stir evenly and sonicate for 15min, then place in a 60℃ water bath and stir for 4h to obtain solution A;

[0050] Step 2: Dissolve 3g of E-51 epoxy resin in 5g of ethyl acetate and stir until homogeneous to obtain solution B;

[0051] Step 3: Dissolve 1g of coupling agent C in 12mL of anhydrous ethanol, sonicate for 12min, add 0.8g of modifier, and stir for 1.5h under a 60℃ water bath heating condition to obtain solution C;

[0052] Step 4: Mix the obtained solution A with the obtained solution B, stir for 1.5 h under a water bath heating condition of 60℃, then cool to room temperature and add the obtained solution C and 2g of curing agent, stir for 12 min and ultrasonically treat for 10 min to obtain the composite coating;

[0053] Step 5: Spray the composite coating obtained in Step 4 onto the substrate after sanding, and dry it in an oven at 80°C for 4 hours to obtain a superhydrophobic anti-icing coating.

[0054] Example 4

[0055] This embodiment provides a linearly reinforced superhydrophobic anti-icing coating containing the following components in parts by weight:

[0056] The mixture comprises 2.5 g of silica and alumina nanoparticles (mixed in equal mass ratio), 0.5 g of micron-sized linearly reinforced aramid fibers, 3.3 g of modifier heptadecafluorodecyltrimethoxysilane, 1.4 g of silicon-based methyltrimethoxysilane, 4.5 g of ammonia, 1 g of coupling agent A KH-560, 3 g of E-51 epoxy resin, 5 g of ethyl acetate, 1 g of coupling agent C KH-602, and 2 g of alicyclic amine 3388 epoxy resin curing agent. The particle size of the silica and alumina nanoparticles is 20–60 nm; the size of the micron-sized linearly reinforced aramid fibers is 10–50 μm.

[0057] This embodiment provides a method for preparing a linearly reinforced superhydrophobic anti-icing coating, comprising the following steps:

[0058] Step 1: Disperse 2.5g of nanoparticles and 0.5g of micron-sized linear reinforcement in 50mL of anhydrous ethanol, then add 2.5g of modifier, 1.4g of silicon source, 4.5g of ammonia water and 1g of coupling agent A, stir evenly and sonicate for 15min, then place in a 60℃ water bath and stir for 4h to obtain solution A;

[0059] Step 2: Dissolve 3g of E-51 epoxy resin in 5g of ethyl acetate and stir until homogeneous to obtain solution B;

[0060] Step 3: Dissolve 1g of coupling agent C in 12mL of anhydrous ethanol, sonicate for 12min, add 0.8g of modifier, and stir for 1.5h under a 60℃ water bath heating condition to obtain solution C;

[0061] Step 4: Mix the obtained solution A with the obtained solution B, stir for 1.5 h under a water bath heating condition of 60℃, then cool to room temperature and add the obtained solution C and 2g of curing agent, stir for 12 min and ultrasonically treat for 10 min to obtain the composite coating;

[0062] Step 5: Spray the composite coating obtained in Step 4 onto the substrate after sanding, and dry it in an oven at 80°C for 4 hours to obtain a superhydrophobic anti-icing coating.

[0063] The wear resistance of the superhydrophobic anti-icing coatings prepared in Examples 1-4 was tested, and the results are as follows: Figure 1 As shown, without sanding, the contact angle of the coating can reach over 158°, with a maximum of about 167°, exhibiting excellent hydrophobic properties and thus achieving the purpose of anti-icing. After sanding 200 times, the contact angle can still reach over 150°, allowing the coating to maintain its superhydrophobic anti-icing properties.

[0064] In summary, it can be seen that the superhydrophobic anti-icing coating prepared by this method has excellent superhydrophobic and wear-resistant properties, which can meet the requirements of long-term anti-icing in practical applications.

Claims

1. A superhydrophobic anti-icing coating reinforced with linear reinforcement, characterized in that, Components containing the following parts by weight: The composition includes 20-30 parts nanoparticles, 3-9 parts micron-sized linear reinforcement, 30-40 parts modifier, 10-20 parts silicon source, 40-50 parts ammonia, 5-15 parts coupling agent A, 16-50 parts E-51 epoxy resin, 30-75 parts ethyl acetate, 5-20 parts coupling agent C, and 15-25 parts curing agent.

2. The superhydrophobic anti-icing coating reinforced with a linear reinforcement as described in claim 1, characterized in that, The nanoparticles are silicon dioxide and / or alumina particles; the particle size of the nanoparticles is 20~60nm; the micron-scale linear reinforcement is one or a combination of several of α-cellulose, aramid fiber, carbon nanotubes or needle-shaped zinc oxide; the size of the micron-scale linear reinforcement is 10~50μm.

3. The superhydrophobic anti-icing coating reinforced with a linear reinforcement as described in claim 1 or 2, characterized in that, The modifier is one of heptadecafluorodecyltrimethoxysilane, tridecafluorooctyltriethoxysilane, or perfluorodecyltriethoxysilane; the silicon source is one of tetraethyl orthosilicate, methyl orthosilicate, or methyltrioxysilane; and the coupling agent A is one of KH-560, KH-561, or A-187.

4. The superhydrophobic anti-icing coating reinforced with a linear reinforcement as described in claim 3, characterized in that, The coupling agent C is one of KH-792, KH-602 or A1120; the curing agent is one of alicyclic amine 3388 epoxy resin curing agent or alicyclic amine 3396 epoxy resin curing agent.

5. A method for preparing a superhydrophobic anti-icing coating reinforced with linear reinforcement as described in any one of claims 1-4, characterized in that, The steps are as follows: Step 1: Disperse nanoparticles and micron-sized linear reinforcements in anhydrous ethanol, then add modifier, silicon source, ammonia, and coupling agent A, stir evenly and sonicate, then place in a water bath and stir for a certain time to obtain solution A; Step 2: Dissolve E-51 epoxy resin in ethyl acetate and stir until homogeneous to obtain solution B; Step 3: Dissolve coupling agent C in anhydrous ethanol, sonicate, add modifier, and stir for a certain time under water bath heating to obtain solution C; Step 4: Mix the obtained solution A with the obtained solution B, stir for a certain time under water bath heating, then cool to room temperature and add the obtained solution C and curing agent, stir and sonicate to obtain composite coating; Step 5: Spray the composite coating obtained in Step 4 onto the substrate, and after drying, a superhydrophobic anti-icing coating is obtained.

6. The method for preparing the superhydrophobic anti-icing coating reinforced by the linear reinforcement according to claim 5, characterized in that, The ultrasonic treatment time in step one is 10-20 minutes, the water bath heating temperature is 55-60°C, and the stirring time under the water bath heating condition is 3-4 hours.

7. The method for preparing the superhydrophobic anti-icing coating reinforced by the linear reinforcement according to claim 5 or 6, characterized in that, The ultrasonic treatment time in step three is 8-15 minutes, the water bath heating temperature is 55-60°C, and the stirring time under the water bath heating condition is 1-2.5 hours.

8. The method for preparing the superhydrophobic anti-icing coating reinforced by the linear reinforcement according to claim 7, characterized in that, The water bath heating temperature in step four is 55~60℃, the overtime under the water bath heating condition is 1~1.5h, the stirring time after adding C solution and curing agent is 10~15min, and the ultrasonic treatment time is 5~10min.

9. The method for preparing the superhydrophobic anti-icing coating reinforced by the linear reinforcement according to claim 7, characterized in that, The drying process described in step five involves drying at 70-85℃ for 3.5-4 hours.

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