Preparation method of low-energy-consumption anti-icing / deicing super-hydrophobic coating

Abstract

The invention discloses a preparation method of a low-energy-consumption anti-icing / deicing super-hydrophobic coating, and belongs to the field of preparation of anti-icing coatings. The invention aims to solve the problems that the existing super-hydrophobic coating with the photo-thermal electric heating function adopts a fluorine-containing material as a raw material, and is poor in cycling stability and high in energy consumption. The method comprises the following steps: 1, preparing graphene slurry; 2, preparing an anti-icing / deicing super-hydrophobic coating solution; and 3, preparing the coating. The method is used for preparing the low-energy-consumption anti-icing / deicing super-hydrophobic coating.

Description

Technical Field

[0001] The invention belongs to the field of anti-icing coating preparation. Background Art

[0002] In recent years, the southern part of my country has been affected by winter cold waves, and ice has appeared on the surface of the power transmission lines of the power system, affecting the normal operation of power supply and equipment. At present, the methods of anti-icing / deicing of electrical equipment mainly include mechanical anti-icing and deicing methods, overcurrent methods, super-hydrophobic coating methods, photothermal methods, and super-hydrophobic coating methods combining photothermal and electrothermal. Mechanical anti-icing and deicing methods are harmful to equipment, reduce the life of the equipment, and have low deicing efficiency. Overcurrent deicing usually requires the use of electric heating elements to generate heat, which consumes a lot of electricity and is more complicated in circuit design. Photothermal coatings add light-absorbing substances to the coating to enable the coating to absorb sunlight, but their efficiency is largely limited by the weather. The electrothermal anti-icing coating can generate heat on the coating surface by powering on, so that the coating surface remains at a constant temperature to prevent ice formation, but powering on all day increases energy consumption to a certain extent. The super-hydrophobic coating with photothermal and electrothermal functions can use solar energy when there is sufficient light, and use electrothermal deicing when there is insufficient light, becoming one of the most promising methods in the field of anti-icing / deicing. Although super-hydrophobic coatings with photothermal and electrothermal functions can effectively slow down ice accumulation and reduce ice adhesion, they still use more fluorine-containing materials, have poor cycle stability and high energy consumption. Therefore, the research of a low-energy photothermal and electrothermal combined super-hydrophobic anti-icing / de-icing coating is an urgent problem to be solved. Summary of the invention

[0003] The present invention aims to solve the problems that the existing super-hydrophobic coatings with photothermal and electrothermal functions use fluorine-containing materials as raw materials and have poor cycle stability and high energy consumption, and further provide a method for preparing a low-energy anti-icing / de-icing super-hydrophobic coating.

[0004] A method for preparing a low-energy anti-icing / de-icing super-hydrophobic coating is carried out according to the following steps:

[0005] 1. Preparation of graphene slurry:

[0006] Adding graphene into deionized water, and then sequentially performing ultrasonic treatment and stirring and mixing to obtain graphene slurry;

[0007] 2. Preparation of anti-icing / de-icing super-hydrophobic coating solution:

[0008] Adding bisamino polydimethylsiloxane to the graphene slurry and stirring and mixing, then adding poly (3,4-ethylenedioxythiophene) and stirring and mixing, and then adding polymethylene polyphenyl polyisocyanate and heating and stirring and mixing to obtain an anti-icing / de-icing super hydrophobic coating solution;

[0009] 3. Coating preparation:

[0010] ① Spray the anti-icing / de-icing super-hydrophobic coating solution on the substrate and then dry it;

[0011] ② Repeat step 3① once, then attach the electrode, and repeat step 3① once again to obtain a low-energy anti-icing / de-icing super-hydrophobic coating.

[0012] The beneficial effects of the present invention are:

[0013] 1. The present invention uses poly (3,4-ethylenedioxythiophene) (PEDOT) as a conductive additive. Due to the good connectivity of the conjugated electron system in the molecule and the strong electron transport capacity in the molecular structure, under light-free conditions, when the input voltage is 20V, the temperature can rise from -15°C to 51°C in 20 minutes, with high thermal efficiency, which makes the energy consumption of the anti-icing coating lower.

[0014] 2. Methylene polyphenyl polyisocyanate (MDI) is used as a cross-linking agent. Its molecular structure is stable and it reacts with bisamino polydimethylsiloxane to form a polyurethane, giving the coating excellent cycle stability.

[0015] 3. The graphene flakes used in the present invention exhibit good inter-sheet contact, and the micro-nano structure can capture air. The bisamino polydimethylsiloxane reacts with the graphene to form a spherical structure on the flake structure, exhibiting high hydrophobicity, thereby increasing the water contact angle of the coating.

[0016] 4. The present invention adopts a photothermal and electrothermal collaborative anti-icing / de-icing method, and realizes rapid anti-icing / de-icing under extreme conditions through external energy input of light or electric field force. It does not use fluorine-containing materials and is green and environmentally friendly.

[0017] Attached Notes

[0018] Figure 1 A synthetic process diagram for preparing a low-energy anti-icing / de-icing super-hydrophobic coating according to the present invention;

[0019] Figure 2 This is a scanning electron microscope image of the low-energy anti-icing / de-icing super-hydrophobic coating prepared in Example 1;

[0020] Figure 3 This is a graph showing the electric heating surface temperature of the low-energy anti-icing / de-icing super-hydrophobic coating prepared in Example 1;

[0021] Figure 4 A temperature variation diagram of the cyclic anti-icing and de-icing of the low-energy anti-icing / de-icing super-hydrophobic coating prepared in Example 1;

[0022] Figure 5 The UV-Vis-NIR image of the low-energy anti-icing / de-icing super-hydrophobic coating prepared in Example 1;

[0023] Figure 6 This is a water contact angle diagram of the low-energy anti-icing / de-icing super-hydrophobic coating prepared in Example 1;

[0024] Figure 7 The electric heating surface temperature curve diagram of the low-energy anti-icing / de-icing super-hydrophobic coating prepared in Example 2 and Example 3, I is Example 2, and II is Example 3;

[0025] Figure 8 This is a temperature change diagram of the cyclic anti-icing and de-icing of the low-energy anti-icing / de-icing super-hydrophobic coating prepared in Example 4. DETAILED DESCRIPTION

[0026] Specific implementation method 1, combined with Figure 1 Specific description: This embodiment is a method for preparing a low-energy anti-icing / de-icing super-hydrophobic coating, which is carried out according to the following steps:

[0027] 1. Preparation of graphene slurry:

[0028] Adding graphene into deionized water, and then sequentially performing ultrasonic treatment and stirring and mixing to obtain graphene slurry;

[0029] 2. Preparation of anti-icing / de-icing super-hydrophobic coating solution:

[0030] Adding bisamino polydimethylsiloxane to the graphene slurry and stirring and mixing, then adding poly (3,4-ethylenedioxythiophene) and stirring and mixing, and then adding polymethylene polyphenyl polyisocyanate and heating and stirring and mixing to obtain an anti-icing / de-icing super hydrophobic coating solution;

[0031] 3. Coating preparation:

[0032] ① Spray the anti-icing / de-icing super-hydrophobic coating solution on the substrate and then dry it;

[0033] ② Repeat step 3① once, then attach the electrode, and repeat step 3① once again to obtain a low-energy anti-icing / de-icing super-hydrophobic coating.

[0034] Figure 1The synthesis process diagram of the low-energy anti-icing / de-icing super-hydrophobic coating prepared by the present invention; in the graphene water slurry, bisamino polydimethylsiloxane is added as a hydrophobic substance, poly 3,4-ethylenedioxythiophene (PEDOT) is used as a conductive additive, and polymethylene polyphenyl polyisocyanate (MDI) is used as a cross-linking agent to prepare an anti-icing / de-icing super-hydrophobic coating with photothermal and electrothermal functions. Poly 3,4-ethylenedioxythiophene (PEDOT) is used as a conductive additive, and the electronic energy band gap is small, and it is easy to form electron-hole pairs under light. Due to the good connectivity of the intramolecular conjugated electron system, the electron has a strong transport capacity in the molecular structure, and can quickly form a conductive band under the action of the external potential, which can increase the conductivity of the coating, so that it can be compounded with graphene to form a conductive network, thereby reducing the heating time of the coating surface, thereby reducing energy consumption. Polymethylene polyphenyl polyisocyanate (MDI) has multiple benzene rings and isocyanate groups in its molecular structure and its molecular structure is stable. It reacts with bisamino polydimethylsiloxane to form a polyurethane, which makes the coating have excellent cycle stability. Graphene is a new type of two-dimensional layered carbon material. The graphene flakes show good inter-sheet contact, and the micro-nano structure can capture air. The bisamino polydimethylsiloxane reacts with graphene to form a spherical structure on the sheet structure, showing high hydrophobicity, thereby increasing the water contact angle of the coating. The increase in surface roughness leads to an increase in specific surface area. Therefore, the coating maintains its excellent hydrophobicity and conductivity, which gives the coating stronger anti-icing / de-icing capabilities.

[0035] The beneficial effects of this embodiment are:

[0036] 1. This embodiment uses poly (3,4-ethylenedioxythiophene) (PEDOT) as a conductive additive. Due to the good connectivity of the conjugated electron system within the molecule and the strong electron transport capacity within the molecular structure, under light-free conditions, when the input voltage is 20V, the temperature can rise from -15°C to 51°C in 20 minutes, with high thermal efficiency, which reduces the energy consumption of the anti-icing coating.

[0037] 2. Methylene polyphenyl polyisocyanate (MDI) is used as a cross-linking agent. Its molecular structure is stable and it reacts with bisamino polydimethylsiloxane to form a polyurethane, giving the coating excellent cycle stability.

[0038] 3. The graphene flakes used in this embodiment show good inter-sheet contact, the micro-nano structure can capture air, and the bisamino polydimethylsiloxane can react with graphene to form a spherical structure on the flake structure, showing high hydrophobicity, thereby increasing the water contact angle of the coating.

[0039] 4. This embodiment adopts a photothermal and electrothermal collaborative anti-icing / de-icing method, and realizes rapid anti-icing / de-icing under extreme conditions through external energy input of light or electric field force. It does not use fluorine-containing materials and is green and environmentally friendly.

[0040] Specific implementation method 2: This implementation method is different from specific implementation method 1 in that the volume ratio of the mass of graphene described in step 1 to deionized water is 1 g: (5-20) mL. Other aspects are the same as those of specific implementation method 1.

[0041] Specific embodiment 3: This embodiment is different from specific embodiment 1 or 2 in that the ultrasonic treatment and stirring and mixing described in step 1 are specifically carried out according to the following steps: ultrasonic treatment for 5 min to 20 min at a power of 200 W to 500 W, and then stirring and mixing for 3 min to 10 min at a stirring speed of 400 r / min to 600 r / min. The rest is the same as specific embodiment 1 or 2.

[0042] Specific embodiment 4: This embodiment is different from specific embodiments 1 to 3 in that the molecular weight of the bisamino polydimethylsiloxane described in step 2 is 2000 to 5000. Other aspects are the same as specific embodiments 1 to 3.

[0043] Specific embodiment 5: This embodiment differs from Specific embodiments 1 to 4 in that the mass ratio of graphene to bisamino polydimethylsiloxane in the graphene slurry described in step 2 is 1:(0.1-0.4). Other aspects are the same as Specific embodiments 1 to 4.

[0044] Specific embodiment 6: This embodiment is different from Specific embodiments 1 to 5 in that the mass ratio of graphene to poly (3,4-ethylenedioxythiophene) in the graphene slurry described in step 2 is 1:(0.2-0.4). Others are the same as Specific embodiments 1 to 5.

[0045] Specific embodiment 7: This embodiment is different from Specific embodiments 1 to 6 in that the mass ratio of graphene to polymethylene polyphenyl polyisocyanate in the graphene slurry described in step 2 is 1:(0.2-0.6). Others are the same as Specific embodiments 1 to 6.

[0046] Specific embodiment eight: This embodiment is different from specific embodiments one to seven in that: in step two, bisamino polydimethylsiloxane is added to the graphene slurry, stirred and mixed for 15min to 30min at a stirring speed of 400r / min to 600r / min, and then poly 3,4-ethylenedioxythiophene is added, stirred and mixed for 10min to 30min at a stirring speed of 400r / min to 600r / min, and then polymethylene polyphenyl polyisocyanate is added, and heated and stirred for 50min to 90min at a temperature of 35°C to 55°C and a stirring speed of 700r / min to 1000r / min to obtain an anti-icing / de-icing super hydrophobic coating solution. The rest is the same as specific embodiments one to seven.

[0047] Specific embodiment 9: This embodiment is different from specific embodiments 1 to 8 in that the spraying described in step 3① is carried out according to the following steps: spraying is carried out under the conditions of a spray gun pressure of 0.1MPa to 0.3MPa and a distance between the spray gun and the substrate of 20cm to 40cm. The rest is the same as specific embodiments 1 to 8.

[0048] Specific embodiment 10: This embodiment differs from Specific embodiments 1 to 9 in that the thickness of the low-energy anti-icing / de-icing super-hydrophobic coating described in step 3② is 1 mm to 2.5 mm. The rest is the same as Specific embodiments 1 to 9.

[0049] The following examples are used to verify the beneficial effects of the present invention:

[0050] Embodiment 1:

[0051] A method for preparing a low-energy anti-icing / de-icing super-hydrophobic coating is carried out according to the following steps:

[0052] 1. Preparation of graphene slurry:

[0053] Graphene was added to deionized water, and ultrasonicated for 5 min at a power of 400 W, and then stirred and mixed for 5 min at a stirring speed of 500 rpm / min to obtain a graphene slurry;

[0054] The mass of the graphene and the volume ratio of deionized water are 1 g:9 mL;

[0055] 2. Preparation of anti-icing / de-icing super-hydrophobic coating solution:

[0056] Add bisamino polydimethylsiloxane to the graphene slurry, stir and mix for 20 minutes at a stirring speed of 500 rpm / min, then add poly (3,4-ethylenedioxythiophene), stir and mix for 15 minutes at a stirring speed of 500 rpm / min, then add polymethylene polyphenyl polyisocyanate, heat and stir and mix for 60 minutes at a temperature of 45° C. and a stirring speed of 900 rpm / min to obtain an anti-icing / de-icing superhydrophobic coating solution;

[0057] The molecular weight of the bisamino polydimethylsiloxane is 4000; the mass ratio of graphene to bisamino polydimethylsiloxane in the graphene slurry is 1:0.2; the mass ratio of graphene to poly 3,4-ethylenedioxythiophene in the graphene slurry is 1:0.25; the mass ratio of graphene to polymethylene polyphenyl polyisocyanate in the graphene slurry is 1:0.4;

[0058] 3. Coating preparation:

[0059] ① Under the conditions of a spray gun pressure of 0.1 MPa and a distance of 20 cm between the spray gun and the substrate, the anti-icing / de-icing super-hydrophobic coating solution was sprayed on the substrate, and then dried for 1 h at a temperature of 60°C to obtain a primary spray coating;

[0060] ② Under the conditions of a spray gun pressure of 0.1 MPa and a distance of 20 cm between the spray gun and the substrate, the anti-icing / de-icing super-hydrophobic coating solution is sprayed on the primary spray layer, and then dried for 1 hour at a temperature of 60°C to obtain a secondary spray layer, and a copper electrode is attached to the secondary spray layer. Under the conditions of a spray gun pressure of 0.1 MPa and a distance of 20 cm between the spray gun and the substrate, the anti-icing / de-icing super-hydrophobic coating solution is sprayed on the secondary spray layer, and finally dried for 6 hours at a temperature of 60°C to obtain a low-energy anti-icing / de-icing super-hydrophobic coating;

[0061] The thickness of the low-energy anti-icing / de-icing super-hydrophobic coating is 1 mm.

[0062] Embodiment 2: This embodiment is different from Embodiment 1 in that the mass ratio of graphene to poly (3,4-ethylenedioxythiophene) in the graphene slurry described in step 2 is 1:0.4. Others are the same as Embodiment 1.

[0063] Embodiment 3: This embodiment is different from Embodiment 1 in that the mass ratio of graphene to poly (3,4-ethylenedioxythiophene) in the graphene slurry described in step 2 is 1:0.2. The rest is the same as Embodiment 1.

[0064] Embodiment 4: This embodiment is different from Embodiment 1 in that the mass ratio of graphene to polymethylene polyphenyl polyisocyanate in the graphene slurry described in step 2 is 1:0.3. The rest is the same as Embodiment 1.

[0065] Figure 2 This is a scanning electron microscope image of the low-energy anti-icing / de-icing super-hydrophobic coating prepared in Example 1; the graphene flakes used in the example show a good micro-nano structure, and the reaction of bisamino polydimethylsiloxane and graphene can form a spherical structure on the sheet structure, thereby increasing the water contact angle of the coating and making the coating show higher hydrophobicity.

[0066] Figure 3 This is the electric heating surface temperature curve of the low-energy anti-icing / de-icing super-hydrophobic coating prepared in Example 1; it can be seen from the figure that the surface temperature of the low-energy anti-icing / de-icing super-hydrophobic coating increases with the increase of electric energy. Under the voltage input of 20V, the surface temperature of the coating can rise from -15°C to 51°C in 20 minutes. Therefore, it can be concluded that since poly 3,4-ethylenedioxythiophene (PEDOT) is used as a conductive additive, the electron transport capacity in the molecular structure is strong, thereby making the energy consumption of the anti-icing coating lower.

[0067] Place the coating sample on a semiconductor cooler, which is placed in a transparent acrylic semi-enclosed box, and monitor the surface temperature of the coating sample; when the surface temperature reaches -10°C, power on the coating sample and start timing. When the temperature no longer rises, turn off the power and record the time and temperature, and repeat the above operation; Figure 4 The cyclic anti-icing and de-icing temperature change diagram of the low-energy anti-icing / de-icing super-hydrophobic coating prepared in Example 1; it can be seen from the figure that the temperature change of the low-energy anti-icing / de-icing super-hydrophobic coating is the same in 8 cycles, and the final temperature after heating and cooling is almost the same. Therefore, it can be concluded that the low-energy anti-icing / de-icing super-hydrophobic coating has excellent electrothermal performance and stability.

[0068] Figure 5 This is a UV-Vis-NIR image of the low-energy anti-icing / de-icing super-hydrophobic coating prepared in Example 1; as can be seen from the figure, the transmittance of the low-energy anti-icing / de-icing super-hydrophobic coating to light at 500nm~2600nm is less than 5%, indicating that the coating has a good ability to absorb light, so that the coating can utilize solar energy more efficiently.

[0069] Figure 6 This is a water contact angle diagram of the low-energy anti-icing / de-icing super-hydrophobic coating prepared in Example 1; as can be seen from the figure, the water contact angle of the low-energy anti-icing / de-icing super-hydrophobic coating is 150°, therefore, it can be concluded that the low-energy anti-icing / de-icing super-hydrophobic coating has super-hydrophobic properties and can achieve effective passive anti-icing.

[0070] Figure 7 The electric heating surface temperature curve of the low-energy anti-icing / de-icing super-hydrophobic coating prepared in Example 2 and Example 3, I is Example 2, and II is Example 3; It can be seen from the figure that the surface temperature of the low-energy anti-icing / de-icing super-hydrophobic coating increases with the increase of the mass of poly 3,4-ethylenedioxythiophene. In Example 2, under a voltage input of 10V, the surface temperature of the coating can rise from -15°C to 41°C in 20min. In Example 3, under a voltage input of 10V, the surface temperature of the coating can rise from -15°C to 30°C in 20min. Therefore, it can be concluded that since poly 3,4-ethylenedioxythiophene (PEDOT) is used as a conductive additive, the surface temperature of the coating after power-on can be increased, thereby making the energy consumption of the anti-icing coating lower.

[0071] Place the coating sample on a semiconductor cooler, which is placed in a transparent acrylic semi-enclosed box, and monitor the surface temperature of the coating sample; when the surface temperature reaches -10°C, power on the coating sample and start timing. When the temperature no longer rises, turn off the power and record the time and temperature, and repeat the above operation; Figure 8 The cyclic anti-icing and de-icing temperature change diagram of the low-energy anti-icing / de-icing super-hydrophobic coating prepared in Example 4; it can be seen from the figure that the temperature change of the low-energy anti-icing / de-icing super-hydrophobic coating in 8 cycles is almost the same. Therefore, it can be concluded that the low-energy anti-icing / de-icing super-hydrophobic coating has excellent electrothermal performance and stability.

Claims

1. A method for preparing a low-energy anti-icing / de-icing super-hydrophobic coating, characterized in that It is carried out in the following steps:

1. Preparation of graphene slurry: Adding graphene into deionized water, and then sequentially performing ultrasonic treatment and stirring and mixing to obtain graphene slurry; 2. Preparation of anti-icing / de-icing super-hydrophobic coating solution: Adding bisamino polydimethylsiloxane to the graphene slurry and stirring and mixing, then adding poly (3,4-ethylenedioxythiophene) and stirring and mixing, and then adding polymethylene polyphenyl polyisocyanate and heating and stirring and mixing to obtain an anti-icing / de-icing super hydrophobic coating solution; 3. Coating preparation: ① Spray the anti-icing / de-icing super-hydrophobic coating solution on the substrate and then dry it; ② Repeat step 3① once, then attach the electrode, and repeat step 3① once again to obtain a low-energy anti-icing / de-icing super-hydrophobic coating.

2. The method for preparing a low-energy anti-icing / de-icing super-hydrophobic coating according to claim 1, characterized in that The volume ratio of the mass of graphene described in step 1 to deionized water is 1 g: (5-20) mL.

3. The method for preparing a low-energy anti-icing / de-icing super-hydrophobic coating according to claim 1, characterized in that The ultrasonic treatment and stirring and mixing described in step 1 are specifically carried out according to the following steps: ultrasonic treatment for 5min to 20min at a power of 200W to 500W, and then stirring and mixing for 3min to 10min at a stirring speed of 400r / min to 600r / min.

4. The method for preparing a low-energy anti-icing / de-icing super-hydrophobic coating according to claim 1, characterized in that The molecular weight of the bisamino polydimethylsiloxane described in step 2 is 2000-5000.

5. The method for preparing a low-energy anti-icing / de-icing super-hydrophobic coating according to claim 1, characterized in that The mass ratio of graphene to bisamino polydimethylsiloxane in the graphene slurry described in step 2 is 1:(0.1-0.4).

6. The method for preparing a low-energy anti-icing / de-icing super-hydrophobic coating according to claim 1, characterized in that The mass ratio of graphene to poly (3,4-ethylenedioxythiophene) in the graphene slurry described in step 2 is 1:(0.2-0.4).

7. The method for preparing a low-energy anti-icing / de-icing super-hydrophobic coating according to claim 1, characterized in that The mass ratio of graphene to polymethylene polyphenyl polyisocyanate in the graphene slurry described in step 2 is 1:(0.2-0.6).

8. The method for preparing a low-energy anti-icing / de-icing super-hydrophobic coating according to claim 1, characterized in that In step 2, bisamino polydimethylsiloxane is added to the graphene slurry, stirred and mixed for 15 min to 30 min at a stirring speed of 400 r / min to 600 r / min, and then poly (3,4-ethylenedioxythiophene) is added, stirred and mixed for 10 min to 30 min at a stirring speed of 400 r / min to 600 r / min, and then polymethylene polyphenyl polyisocyanate is added, and heated and stirred for 50 min to 90 min at a temperature of 35° C. to 55° C. and a stirring speed of 700 r / min to 1000 r / min to obtain an anti-icing / de-icing super hydrophobic coating solution.

9. The method for preparing a low-energy anti-icing / de-icing super-hydrophobic coating according to claim 1, characterized in that The spraying described in step 3① is carried out according to the following steps: spraying is carried out under the conditions of a spray gun pressure of 0.1MPa to 0.3MPa and a distance between the spray gun and the substrate of 20cm to 40cm.

10. The method for preparing a low-energy anti-icing / de-icing super-hydrophobic coating according to claim 1, characterized in that The thickness of the low-energy anti-icing / de-icing super-hydrophobic coating described in step 3② is 1 mm to 2.5 mm.

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