Preparation Method and Application of a Polydimethylsiloxane Superhydrophobic Anti-icing and De-icing Material

Abstract

The invention discloses a preparation method and application of a polydimethylsiloxane superhydrophobic anti-icing and de-icing material, belonging to the technical field of anti-icing and de-icing coating materials for polydimethylsiloxane coatings and fields such as ships, airplanes, high-speed rails, and ocean engineering. It includes: preparing PDMS / CNTs porous foam using polydimethylsiloxane and carbon nanotubes; spraying and modifying the PDMS / CNTs porous foam with a CNTs / SiO2 superhydrophobic composite coating solution, and obtaining a polydimethylsiloxane superhydrophobic anti-icing and de-icing material after curing. The polydimethylsiloxane superhydrophobic anti-icing and de-icing material prepared by the invention can perform photothermal de-icing and defrosting, and it has excellent photothermal stability, excellent superhydrophobicity, good corrosion resistance, and good wear resistance. The polydimethylsiloxane superhydrophobic anti-icing and de-icing material prepared by the invention has a good ice melting effect and defrosting ability.

Description

Technical Field

[0001] The present invention belongs to the technical field of anti-icing and de-icing coating materials for polydimethylsiloxane coatings and fields such as ships, airplanes, high-speed rails, and ocean engineering. More specifically, the present invention relates to a preparation method and application of a polydimethylsiloxane superhydrophobic anti-icing and de-icing material. Background Art

[0002] Ice formation is a common natural phenomenon, but icing and ice accretion on the surface of equipment can cause a large amount of economic and energy losses, and even threaten people's lives and property safety. Therefore, it is of great and urgent significance to study reliable, efficient, and economical anti-icing and de-icing technologies.

[0003] Traditional de-icing solutions include mechanical de-icing, pulsed de-icing, and chemical de-icing. However, these de-icing methods are more restricted in practical applications due to low efficiency, high cost, and environmental pollution. In recent years, photothermal superhydrophobic materials with superhydrophobicity and photothermal conversion ability have been regarded as a new generation of anti-icing and de-icing technologies because they have the two major advantages of passive de-icing and active de-icing. Summary of the Invention

[0004] An object of the present invention is to solve at least the above problems and / or defects and provide at least the advantages described hereinafter.

[0005] In view of the fact that the surface of the superhydrophobic material is easily damaged, thereby significantly reducing its superhydrophobicity and destroying its photothermal performance, a porous foam prepared from PDMS and CNTs is used as a skeleton surface to spray and modify a CNTs / SiO2 composite coating solution. It is expected that the material can have good photothermal performance, photothermal stability, superhydrophobicity, corrosion resistance, and excellent de-icing and defrosting performance.

[0006] To achieve these objects and other advantages according to the present invention, a preparation method of a polydimethylsiloxane superhydrophobic anti-icing and de-icing material is provided, which is characterized by including:

[0007] Preparing PDMS / CNTs porous foam using polydimethylsiloxane and carbon nanotubes; spraying and modifying the PDMS / CNTs porous foam with a CNTs / SiO2 superhydrophobic composite coating solution, and obtaining a polydimethylsiloxane superhydrophobic anti-icing and de-icing material after curing.

[0008] Preferably, it includes the following steps:

[0009] Step 1: Mix polydimethylsiloxane, a curing agent, and carbon nanotubes evenly, and then place them in a vacuum drying oven to evacuate to remove air bubbles;

[0010] Step 2: Weigh a certain amount of sodium chloride and mix it evenly with the mixture obtained in Step 1 in a certain proportion. Put it into a mold and compact it, and then place it in a drying oven for curing. After taking out the mold, place the cured sample in a solvent and perform ultrasonic treatment in an ultrasonic machine. After all the sodium chloride particles are precipitated, cut it into pieces to obtain PDMS / CNTs porous foam.

[0011] Step 3: Respectively take a certain amount of nano-SiO2 and carbon nanotubes, then respectively add a certain amount of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, respectively add a certain amount of absolute ethanol, add hydrochloric acid to adjust the pH value, and then respectively perform magnetic stirring and ultrasonic treatment. Then, dry and grind the obtained mixtures respectively to obtain modified SiO2 nanoparticles and modified carbon nanotubes.

[0012] Step 4: Add the modified SiO2 nanoparticles, modified carbon nanotubes, binder, and curing agent obtained in Step 3 to a solvent in a certain proportion, and then perform magnetic stirring to obtain the CNTs / SiO2 superhydrophobic composite coating solution.

[0013] Step 5: Spray the CNTs / SiO2 superhydrophobic composite coating solution obtained in Step 4 onto the surface of the PDMS / CNTs porous foam obtained in Step 2, and then dry and cure the sample to obtain the polydimethylsiloxane superhydrophobic anti-icing and de-icing material.

[0014] Preferably, in Step 1, the ratio of polydimethylsiloxane, curing agent, and CNTs is 50:5:1; the polydimethylsiloxane is the A component of Dow Corning 184-PDMS, and the curing agent is the B component of Dow Corning 184-PDMS.

[0015] Preferably, in Step 2, the ratio of sodium chloride to the mixture is 10:1, the curing temperature is 60-90°C, the curing time is 6-24 hours, and the solvent used for soaking and ultrasonic treatment after curing is deionized water.

[0016] Preferably, in Step 3, the mass-volume ratio of nano-SiO2, 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, and absolute ethanol is 4g:1.2g:40mL, and the pH is adjusted to 5 with hydrochloric acid.

[0017] Preferably, in Step 3, the mass-volume ratio of carbon nanotubes, 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, and absolute ethanol is 2.5g:0.8g:100mL, and the pH is adjusted to 3 with hydrochloric acid.

[0018] Preferably, in Step 3, the magnetic stirring time is 1-3 hours, and the ultrasonic time is 10-50 minutes.

[0019] Preferably, in the fourth step, the solvent is n-hexane, the binder is polydimethylsiloxane, the polydimethylsiloxane is component A of Dow Corning 184-PDMS, and the curing agent is component B of Dow Corning 184-PDMS;

[0020] The total mass of the modified SiO2 nanoparticles and the modified carbon nanotubes and the mass-to-volume ratio of n-hexane, polydimethylsiloxane, and the curing agent is 0.1 g: 10 ml: 0.1 g: 0.01 g; the magnetic stirring time is 1 to 3 hours.

[0021] Preferably, in the fifth step, the curing temperature is 80 °C and the curing time is 1 to 2 hours.

[0022] An application of a polydimethylsiloxane superhydrophobic anti-icing and de-icing material, wherein the polydimethylsiloxane superhydrophobic anti-icing and de-icing material is applied to the hydrophobicity, anti-icing and de-icing of the surfaces of ships, airplanes, high-speed rails, and ocean engineering.

[0023] In order to further improve the hydrophobic performance of the polydimethylsiloxane superhydrophobic anti-icing and de-icing material, the modification method of the modified SiO2 nanoparticles in the third step is replaced with:

[0024] Take a certain amount of nano-SiO2 and ultrasonically disperse it in absolute ethanol to obtain a nano-SiO2 dispersion. Add ammonia water to adjust the pH value to 9-10. While stirring, dropwise add 3-aminopropyltriethoxysilane, and then stir magnetically to obtain dispersion A; add methyl methacrylate to deionized water, add sodium dodecyl sulfate, and ultrasonically disperse it. The ultrasonic frequency is 45-60 kHz, and ultrasonic for 20-60 min to obtain dispersion B; wherein, the volume-to-mass ratio of nano-SiO2, absolute ethanol, and 3-aminopropyltriethoxysilane is 5-9 g: 50-80 mL: 0.5-1.5 g; the mass-to-volume ratio of methyl methacrylate, deionized water, and sodium dodecyl sulfate is 2-5 g: 60-100 mL: 0.5-1 g;

[0025] Let dispersion A stand for 6-12 h and then heat it up to 80-90 °C, then continuously stir at a speed of 400-600 rpm. Add sodium bicarbonate as a pH buffer and sodium persulfate as an initiator, and then add dispersion B with the same volume as dispersion A. After reacting for 1-3 h, stop stirring and cool to room temperature, centrifuge, filter, and dry the solid at a temperature of 40 °C - 80 °C to obtain modified SiO2 nanoparticles. The mass-to-volume ratio of dispersion A, sodium bicarbonate, and sodium persulfate is 50-80 mL: 0.2-0.8 g: 0.3-0.5 g.

[0026] Then dry and grind the obtained mixture respectively to obtain modified SiO2 nanoparticles.

[0027] The present invention has at least the following beneficial effects: The polydimethylsiloxane superhydrophobic anti-icing and de-icing material prepared by the present invention can perform photothermal de-icing and defrosting, and it has excellent photothermal stability, excellent superhydrophobicity, good corrosion resistance, and good abrasion resistance. The polydimethylsiloxane superhydrophobic anti-icing and de-icing material prepared by the present invention has good ice melting effect and defrosting ability.

[0028] In the preparation process of the polydimethylsiloxane superhydrophobic anti-icing and de-icing material of the present invention, a CNTs / SiO2 superhydrophobic composite coating solution using modified SiO2 nanoparticles and modified carbon nanotubes as main raw materials is used. Among them, two modification methods are adopted for the modified SiO2 nanoparticles. One is to perform hydrophobic modification on nano-SiO2 with 1H,1H,2H,2H-perfluorodecyltrimethoxysilane to prepare modified SiO2 nanoparticles with hydrophobic properties. After spraying the CNTs / SiO2 superhydrophobic composite coating solution of the modified SiO2 nanoparticles with hydrophobic properties and modified carbon nanotubes on the surface of PDMS / CNTs porous foam and curing, the prepared polydimethylsiloxane superhydrophobic anti-icing and de-icing material has excellent superhydrophobic properties; the other is to use 3-aminopropyltriethoxysilane and methyl methacrylate to perform hydrophobic modification on nano-SiO2. The results show that after using the modified SiO2 nanoparticles prepared by 3-aminopropyltriethoxysilane and methyl methacrylate modification as the raw material of the CNTs / SiO2 superhydrophobic composite coating solution, the superhydrophobic properties of the polydimethylsiloxane superhydrophobic anti-icing and de-icing material are further improved.

[0029] Other advantages, objectives, and features of the present invention will be partially reflected by the following description, and partially will also be understood by those skilled in the art through the research and practice of the present invention. Description of the Drawings

[0030] Figure 1 It is the electron micrograph of the PDMS / CNTs porous foam prepared in step two of Example 3;

[0031] Figure 2 It is the electron micrograph of the polydimethylsiloxane superhydrophobic anti-icing and de-icing material prepared in step two of Example 3;

[0032] Figure 3 It is the photothermal heating-up graph of Examples 1 to 6, as well as PDMS / CNTs and pure PDMS porous foams;

[0033] Figure 4 It is the graph of 10 times of photothermal on / off cycle of Example 3;

[0034] Figure 5 It is the graph of ice melting time of Example 3 under different light intensities;

[0035] Figure 6 It is the graph of the defrosting time process of Example 3 under different light intensities. Specific implementation mode

[0036] The present invention will be further described in detail below with reference to the accompanying drawings, so that those skilled in the art can implement it according to the text of the specification.

[0037] It should be understood that terms such as "having", "comprising", and "including" used herein do not exclude the presence or addition of one or more other elements or their combinations.

[0038] Example 1:

[0039] A preparation method of a polydimethylsiloxane superhydrophobic anti-icing and de-icing material, comprising:

[0040] Step 1, preparation of PDMS / CNTs porous foam material; first, 10 g of polydimethylsiloxane (PDMS), 0.2 g of carbon nanotubes (CNTs), and 1 g of curing agent are mixed evenly, then 100 g of NaCl is added and stirred evenly again, and then placed in a mold and cured in an oven at 80 °C for 12 hours. The polydimethylsiloxane is the A component of Dow Corning 184-PDMS, and the curing agent is the B component of Dow Corning 184-PDMS.

[0041] Step 2, soak the PDMS / CNTs cured in Step 1 in an aqueous solution, ultrasonic for 7 days, and change the water every 2 hours during this period until the NaCl template is completely removed to obtain PDMS / CNTs porous foam, that is, PC, and cut it into thin slices of 30 mm × 30 mm × 3 mm.

[0042] Step 3, preparation of surface coating material; first, 4 g of nano-SiO2 (diameter about 10-20 nm, Aladdin, 99.5%) and 1.2 g of 1H,1H,2H,2H-perfluorodecylsilane (purchased from Shanghai Macklin Biochemical Co., Ltd.) are added to 40 ml of absolute ethanol, the pH is adjusted to 5 with hydrochloric acid, then magnetically stirred for 2 h, and the obtained slurry is placed in an oven at 100 °C to be dried and ground to obtain modified nano-SiO2 for standby. 2.5 g of carbon nanotubes and 0.8 g of 1H,1H,2H,2H-perfluorodecylsilane are added to 100 ml of absolute ethanol, hydrochloric acid is added to adjust the pH to 3, then magnetically stirred for 2 hours, ultrasonic for 30 min, and finally placed in an oven at 80 °C to be dried and ground for standby, that is, modified carbon nanotubes are obtained.

[0043] Step 4: Add 0.1 g of PDMS and 0.01 g of curing agent to 10 ml of n - hexane, and then carry out magnetic stirring for 30 min. The polydimethylsiloxane is the A component of Dow Corning 184 - PDMS, and the curing agent is the B component of Dow Corning 184 - PDMS. Subsequently, add modified SiO₂ and modified carbon nanotubes with a total mass of 0.1 g to the solution, where the masses of modified SiO₂ and modified carbon nanotubes are 100 mg and 0 mg respectively, and then carry out magnetic stirring for 2 hours to obtain the CNTs / SiO₂ super - hydrophobic composite coating solution.

[0044] Step 5: Spray the CNTs / SiO₂ super - hydrophobic composite coating solution obtained in Step 4 onto the surface of the PDMS / CNTs porous foam obtained in Step 2, and then put the PDMS / CNTs porous foam into an oven and cure it at 80 °C for 2 hours to obtain the polydimethylsiloxane super - hydrophobic anti - icing and de - icing material, which is designated as PCSC - 0%.

[0045] Example 2:

[0046] A preparation method of a polydimethylsiloxane super - hydrophobic anti - icing and de - icing material, comprising:

[0047] Step 1: Preparation of PDMS / CNTs porous foam material; First, mix 10 g of PDMS, 0.2 g of CNTs, and 1 g of curing agent evenly, then add 100 g of NaCl and stir evenly again, put it into a mold and then place it in a drying oven and cure it at 80 °C for 12 hours. The polydimethylsiloxane is the A component of Dow Corning 184 - PDMS, and the curing agent is the B component of Dow Corning 184 - PDMS.

[0048] Step 2: Immerse the cured PDMS / CNTs in an aqueous solution and ultrasonicate for 7 days, changing the water every 2 hours until the NaCl template is completely removed to obtain the PDMS / CNTs porous foam, namely PC, and cut it into thin slices with a size of 30 mm × 30 mm × 3 mm.

[0049] Step 3: Preparation of surface coating materials. First, add 4 g of nano - SiO₂ (diameter about 10 - 20 nm, Aladdin, 99.5%) and 1.2 g of 1H,1H,2H,2H - perfluorodecylsilane (purchased from Shanghai Macklin Biochemical Co., Ltd.) to 40 ml of absolute ethanol, adjust the pH to 5 with hydrochloric acid, and then carry out magnetic stirring for 2 h. Put the obtained slurry into a drying oven and dry and grind it at 100 °C to obtain modified nano - SiO₂ for standby. Add 2.5 g of carbon nanotubes and 0.8 g of 1H,1H,2H,2H - perfluorodecylsilane to 100 ml of absolute ethanol, add hydrochloric acid to adjust the pH to 3, then carry out magnetic stirring for 2 hours, ultrasonicate for 30 min, and finally put it into an 80 °C oven to dry and grind it for standby, that is, obtain modified carbon nanotubes.

[0050] Step 4: Add 0.1 g of PDMS and 0.01 g of curing agent to 10 ml of n-hexane, and then perform magnetic stirring for 30 min. The polydimethylsiloxane is the A component of Dow Corning 184-PDMS, and the curing agent is the B component of Dow Corning 184-PDMS. Subsequently, add modified SiO2 and modified carbon nanotubes with a total mass of 0.1 g to the solution, where the masses of modified SiO2 and modified carbon nanotubes are 85 mg and 15 mg respectively, and then perform magnetic stirring for 2 hours to obtain the CNTs / SiO2 superhydrophobic composite coating solution.

[0051] Step 5: Spray the CNTs / SiO2 superhydrophobic composite coating solution obtained in Step 4 onto the surface of the PDMS / CNTs foam obtained in Step 2, and then place it in an oven at 80 °C for curing for 2 hours to obtain the polydimethylsiloxane superhydrophobic anti-icing and de-icing material, which is designated as PCSC-15%.

[0052] Example 3:

[0053] A preparation method of a polydimethylsiloxane superhydrophobic anti-icing and de-icing material, comprising:

[0054] Step 1: Preparation of PDMS / CNTs porous foam material; First, mix 10 g of PDMS, 0.2 g of CNTs, and 1 g of curing agent evenly, then add 100 g of NaCl and stir evenly again, place it in a mold and then place it in a drying oven at 80 °C for curing for 12 hours. The polydimethylsiloxane is the A component of Dow Corning 184-PDMS, and the curing agent is the B component of Dow Corning 184-PDMS.

[0055] Step 2: Immerse the cured PDMS / CNTs in an aqueous solution and ultrasonicate for 7 days, changing the water every 2 hours until the NaCl template is completely removed to obtain the PDMS / CNTs porous foam, namely PC, and cut it into thin slices with a size of 30 mm × 30 mm × 3 mm. The electron micrograph of the PDMS / CNTs porous foam prepared in this example is as Figure 1 shown, and it can be seen from Figure 1 that the porous distribution of the prepared PDMS / CNTs porous foam is uniform, and its surface is relatively smooth as seen through high magnification.

[0056] Step 3: Preparation of surface coating material. First, add 4 g of nano-SiO₂ (with a diameter of about 10 - 20 nm, Aladdin, 99.5%) and 1.2 g of 1H,1H,2H,2H-perfluorodecylsilane (purchased from Shanghai Macklin Biochemical Co., Ltd.) into 40 ml of absolute ethanol. Adjust the pH to 5 using hydrochloric acid, then stir magnetically for 2 h. Put the obtained slurry into a drying oven and dry and grind it at 100 °C to obtain modified nano-SiO₂ for standby. Add 2.5 g of carbon nanotubes and 0.8 g of 1H,1H,2H,2H-perfluorodecylsilane into 100 ml of absolute ethanol, add hydrochloric acid to adjust the pH to 3, then stir magnetically for 2 hours, ultrasonicate for 30 min, and finally put it into an oven at 80 °C to dry and grind for standby, thus obtaining modified carbon nanotubes.

[0057] Step 4: Add 0.1 g of PDMS and 0.01 g of curing agent into 10 ml of n-hexane, then stir magnetically for 30 min. The polydimethylsiloxane is the A component of Dow Corning 184-PDMS, and the curing agent is the B component of Dow Corning 184-PDMS. Subsequently, add a total of 0.1 g of SiO₂ and carbon nanotubes into the solution, where the masses of SiO₂ and carbon nanotubes are 65 mg and 35 mg respectively, and then stir magnetically for 2 hours to obtain the CNTs / SiO₂ superhydrophobic composite coating solution.

[0058] Step 5: Spray the CNTs / SiO₂ superhydrophobic composite coating solution obtained in Step 4 onto the PDMS / CNTs porous foam surface obtained in Step 2, and then put it into an oven to cure at 80 °C for 2 hours, thus obtaining the polydimethylsiloxane superhydrophobic anti-icing and de-icing material, which is designated as PCSC-35%. The SEM image of the surface morphology of the polydimethylsiloxane superhydrophobic anti-icing and de-icing material sample prepared in this example is as Figure 2 shown. It can be seen from Figure 2 that a rough micro-nano structure covers the sample surface. This rough micro-nano structure can capture air and form a gas-liquid interface when in contact with a liquid, thus making the sample surface superhydrophobic.

[0059] Example 4:

[0060] A preparation method of a polydimethylsiloxane superhydrophobic anti-icing and de-icing material, comprising:

[0061] Step 1: Preparation of porous PDMS / CNTs foam material; First, mix 10 g of PDMS, 0.2 g of CNTs, and 1 g of curing agent evenly, then add 100 g of NaCl and stir evenly again. Put it into a mold and then place it in a drying oven to cure at 80 °C for 12 hours. The polydimethylsiloxane is the A component of Dow Corning 184-PDMS, and the curing agent is the B component of Dow Corning 184-PDMS.

[0062] Step 2: Immerse the above-cured PDMS / CNTs in an aqueous solution and ultrasonicate for 7 days. Replace the water every 2 hours until the NaCl template is completely removed, obtaining a PDMS / CNTs porous foam, i.e., PC. Cut it into thin slices of 30 mm × 30 mm × 3 mm.

[0063] Step 3: Preparation of the surface coating material. First, add 4 g of nano-SiO2 (with a diameter of about 10 - 20 nm, Aladdin, 99.5%) and 1.2 g of 1H,1H,2H,2H-perfluorodecylsilane (purchased from Shanghai Macklin Biochemical Co., Ltd.) to 40 ml of absolute ethanol. Adjust the pH to 5 using hydrochloric acid, then stir magnetically for 2 h. Place the obtained slurry in a drying oven and dry it at 100 °C and grind it to obtain modified nano-SiO2 for standby. Add 2.5 g of carbon nanotubes and 0.8 g of 1H,1H,2H,2H-perfluorodecylsilane to 100 ml of absolute ethanol, add hydrochloric acid to adjust the pH to 3, then stir magnetically for 2 hours, ultrasonicate for 30 min, and finally place it in an 80 °C oven to dry and grind for standby, i.e., obtain modified carbon nanotubes.

[0064] Step 4: Add 0.1 g of PDMS and 0.01 g of curing agent to 10 ml of n-hexane, then stir magnetically for 30 min. The polydimethylsiloxane is the A component of Dow Corning 184-PDMS, and the curing agent is the B component of Dow Corning 184-PDMS. Subsequently, add a total of 0.1 g of SiO2 and carbon nanotubes to the solution, where the masses of SiO2 and carbon nanotubes are 50 mg and 50 mg respectively, and then stir magnetically for 2 hours.

[0065] Step 5: Spray the solution obtained in Step 4 onto the surface of the PDMS / CNTs foam obtained in Step 2, and then place it in an oven to cure at 80 °C for 2 hours, obtaining a polydimethylsiloxane superhydrophobic anti-icing and de-icing material, named PCSC-50%.

[0066] Example 5:

[0067] A preparation method of a polydimethylsiloxane superhydrophobic anti-icing and de-icing material, comprising:

[0068] Step 1: Preparation of a porous PDMS / CNTs foam material; first, mix 10 g of PDMS, 0.2 g of CNTs, and 1 g of curing agent evenly, then add 100 g of NaCl and stir evenly again. Place it in a mold and then in a drying oven to cure at 80 °C for 12 hours. The polydimethylsiloxane is the A component of Dow Corning 184-PDMS, and the curing agent is the B component of Dow Corning 184-PDMS.

[0069] Step 2: Immerse the above-cured PDMS / CNTs in an aqueous solution and sonicate for 7 days. During this period, change the water every 2 hours until the NaCl template is completely removed, obtaining PDMS / CNTs porous foam, namely PC. Cut it into thin slices with dimensions of 30 mm × 30 mm × 3 mm.

[0070] Step 3: Preparation of the surface coating material. First, add 4 g of nano-SiO₂ (with a diameter of about 10 - 20 nm, Aladdin, 99.5%) and 1.2 g of 1H,1H,2H,2H-perfluorodecylsilane (purchased from Shanghai Macklin Biochemical Co., Ltd.) to 40 ml of absolute ethanol. Adjust the pH to 5 using hydrochloric acid, then stir magnetically for 2 h. Place the obtained slurry in a drying oven and dry and grind it at 100 °C to obtain modified nano-SiO₂ for standby. Add 2.5 g of carbon nanotubes and 0.8 g of 1H,1H,2H,2H-perfluorodecylsilane to 100 ml of absolute ethanol, add hydrochloric acid to adjust the pH to 3, then stir magnetically for 2 hours, sonicate for 30 min, and finally place it in an 80 °C oven to dry and grind for standby, that is, obtain modified carbon nanotubes.

[0071] Step 4: Add 0.1 g of PDMS and 0.01 g of curing agent to 10 ml of n-hexane, and then stir magnetically for 30 min. Subsequently, add a total of 0.1 g of SiO₂ and carbon nanotubes to the solution, where the masses of SiO₂ and carbon nanotubes are 35 mg and 65 mg respectively, and then stir magnetically for 2 hours.

[0072] Step 5: Spray the solution obtained in Step 4 onto the surface of the PDMS / CNTs foam obtained in Step 2, and then place it in an oven to cure at 80 °C for 2 hours, obtaining a polydimethylsiloxane superhydrophobic anti-icing and de-icing material, named PCSC-65%.

[0073] Example 6:

[0074] A preparation method of a polydimethylsiloxane superhydrophobic anti-icing and de-icing material, including:

[0075] Step 1: Preparation of porous PDMS / CNTs foam material; First, mix 10 g of PDMS, 0.2 g of CNTs, and 1 g of curing agent evenly, then add 100 g of NaCl and stir evenly again. Place it in a mold and then in a drying oven to cure at 80 °C for 12 hours. The polydimethylsiloxane is the A component of Dow Corning 184-PDMS, and the curing agent is the B component of Dow Corning 184-PDMS.

[0076] Step 2: Immerse the above-mentioned solidified PDMS / CNTs in an aqueous solution and ultrasonicate for 7 days. During this period, change the water every 2 hours until the NaCl template is completely removed, obtaining PDMS / CNTs porous foam, i.e., PC. Cut it into thin slices with dimensions of 30 mm × 30 mm × 3 mm.

[0077] Step 3: Preparation of the surface coating material. First, add 4 g of nano-SiO2 (with a diameter of about 10 - 20 nm, Aladdin, 99.5%) and 1.2 g of 1H,1H,2H,2H-perfluorodecylsilane (purchased from Shanghai Macklin Biochemical Co., Ltd.) to 40 ml of absolute ethanol. Adjust the pH to 5 using hydrochloric acid, then stir magnetically for 2 h. Place the obtained slurry in a drying oven and dry it at 100 °C and grind it to obtain modified nano-SiO2 for standby. Add 2.5 g of carbon nanotubes and 0.8 g of 1H,1H,2H,2H-perfluorodecylsilane to 100 ml of absolute ethanol, add hydrochloric acid to adjust the pH to 3, then stir magnetically for 2 hours, ultrasonicate for 30 min, and finally place it in an 80 °C oven to dry and grind for standby, i.e., obtain modified carbon nanotubes.

[0078] Step 4: Add 0.1 g of PDMS and 0.01 g of curing agent to 10 ml of n-hexane, then stir magnetically for 30 min. The polydimethylsiloxane is the A component of Dow Corning 184-PDMS, and the curing agent is the B component of Dow Corning 184-PDMS. Subsequently, add SiO2 and carbon nanotubes with a total mass of 0.1 g to the solution, where the masses of SiO2 and carbon nanotubes are 0 mg and 100 mg respectively, and then stir magnetically for 2 hours.

[0079] Step 5: Spray the solution obtained in Step 4 onto the surface of the PDMS / CNTs foam obtained in Step 2, and then place it in an oven and cure it at 80 °C for 2 hours, obtaining the polydimethylsiloxane superhydrophobic anti-icing and de-icing material, named PCSC-100%.

[0080] Example 7

[0081] This example provides a preparation method of a polydimethylsiloxane superhydrophobic anti-icing and de-icing material. Compared with Example 3, in Step 3, the modified SiO2 nanoparticles are replaced, the modification method of the modified carbon nanotubes remains unchanged, and the process parameters of the remaining steps are the same as those in Example 3. Among them, the modification method of the replaced modified SiO2 nanoparticles is as follows:

[0082] Take 5 g of nano-SiO₂ and ultrasonically disperse it in 60 mL of absolute ethanol to obtain a nano-SiO₂ dispersion. Add ammonia water to adjust the pH value to 9. While stirring, dropwise add 1.5 g of 3-aminopropyltriethoxysilane, and then stir magnetically to obtain dispersion A; add 3 g of methyl methacrylate to 60 mL of deionized water, add 0.5 g of sodium dodecyl sulfate, and ultrasonically disperse it. The ultrasonic frequency is 60 kHz, and ultrasonic dispersion is carried out for 40 min to obtain dispersion B;

[0083] Take 50 mL of dispersion A, let it stand for 12 h, then heat it to 80 °C, and then continuously stir at a speed of 400 rpm. Add 0.3 g of sodium bicarbonate as a pH buffer and 0.3 g of sodium persulfate as an initiator, and then add 50 mL of dispersion B. After reacting for 2 h, stop stirring and cool to room temperature, centrifuge, filter, and dry the solid at 60 °C to obtain modified SiO₂ nanoparticles.

[0084] Example 8

[0085] This example provides a method for preparing a polydimethylsiloxane superhydrophobic anti-icing and de-icing material. Compared with Example 3, in step three, the modified SiO₂ nanoparticles are replaced, the modification method of the modified carbon nanotubes remains unchanged, and the process parameters of the remaining steps are the same as those in Example 3; among them, the modification method of the replaced modified SiO₂ nanoparticles is as follows:

[0086] Take 8 g of nano-SiO₂ and ultrasonically disperse it in 100 mL of absolute ethanol to obtain a nano-SiO₂ dispersion. Add ammonia water to adjust the pH value to 9. While stirring, dropwise add 1.5 g of 3-aminopropyltriethoxysilane, and then stir magnetically to obtain dispersion A; add 5 g of methyl methacrylate to 100 mL of deionized water, add 0.5 g of sodium dodecyl sulfate, and ultrasonically disperse it. The ultrasonic frequency is 60 kHz, and ultrasonic dispersion is carried out for 40 min to obtain dispersion B;

[0087] Take 50 mL of dispersion A that has stood for 12 h, heat it to 80 °C, and then continuously stir at a speed of 600 rpm. Add 0.8 g of sodium bicarbonate as a pH buffer and 0.5 g of sodium persulfate as an initiator, and then add 50 mL of dispersion B. After reacting for 3 h, stop stirring and cool to room temperature, centrifuge, filter, and dry the solid at 60 °C to obtain modified SiO₂ nanoparticles.

[0088] The present invention provides a method for testing the superhydrophobic performance of the polydimethylsiloxane superhydrophobic anti-icing and de-icing materials prepared in Examples 1 to 8, including:

[0089] The present invention uses a contact angle measuring instrument to test the contact angle and sliding angle of Examples 1 to 8. The test conditions are as follows: 10 μl of deionized water is dropped onto the sample surface through a syringe, and the contact angle of the liquid droplet on the sample surface is measured by the contact angle measuring instrument. Then, the workbench of the contact angle measuring instrument is rotated, and the angle when the liquid droplet slides off is recorded to obtain the rolling angle of the sample. Each material is repeated 3 to 5 times. The obtained results are shown in Table 1.

[0090] Table 1

[0091]

[0092]

[0093] As can be seen from Table 1, compared with the contact angle of PC and the inability of the liquid droplet to slide on the PC surface, Examples 1 to 6 all have a contact angle exceeding 150° and a rolling angle less than 10°. This indicates that they have excellent superhydrophobic properties.

[0094] Meanwhile, in Examples 7 and 8, the contact angle of deionized water reached a maximum of 167.4°, and the rolling angle of deionized water decreased to 2.7°. This indicates that after using 3-aminopropyltriethoxysilane and methyl methacrylate-modified SiO2 nanoparticles as the raw materials of the CNTs / SiO2 superhydrophobic composite coating solution in Examples 7 and 8, the superhydrophobic properties of the polydimethylsiloxane superhydrophobic anti-icing and de-icing material were further improved.

[0095] The present invention uses a xenon light source (PLS-SXE300), an infrared thermometer, and a light power meter (PL-MW2000) to conduct a photothermal heating experiment on Examples 1 to 6. The light power meter is used to adjust the xenon light source to the intensity of one sun's illumination. The obtained results are as Figure 3 , and it can be seen that the material has excellent photothermal properties. And through 10 times of illumination and on-off cycle tests, as Figure 4 shown, it can be seen that the material has excellent photothermal stability. Then, a de-icing test is conducted on Experimental Example 3 using a refrigeration platform, a xenon light source, and a light power meter. The test conditions are as follows: on a refrigeration platform at -20°C, the test sample is placed on the refrigeration platform, then 10 μl of deionized water is dropped onto the sample surface to make it completely freeze, then the xenon light source is turned on, the light power meter is used to adjust the illumination intensity, and then the light source is irradiated onto the sample surface and timing starts until the ice completely melts into a liquid and the timing stops to obtain the ice melting time. As Figure 5 can be seen, the material has excellent de-icing performance, Figure 5 where the abscissa is the illumination intensity and the ordinate is the time.

[0096] The present invention uses a xenon light source, a light power meter, and a refrigeration platform to conduct a defrosting test on Example 3. The temperature of the refrigeration platform is adjusted to -20°C, and the sample is placed on the refrigeration platform. Then, it is allowed to frost naturally in an environment with an ambient humidity of 80%. After the surface of the sample is completely covered with ice and frost, the xenon light source is turned on, and the light intensity is adjusted to 1 solar light intensity and 0.5 solar light intensity. The results obtained are shown in Figure 6 It can be seen that the material has excellent defrosting performance.

[0097] The number of devices and the processing scale described here are used to simplify the description of the present invention. Applications, modifications, and variations of the present invention will be apparent to those skilled in the art.

[0098] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and embodiments. It can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily achieved. Therefore, without departing from the general concept defined by the claims and the equivalent scope, the present invention is not limited to the specific details and the illustrated examples described herein.

Claims

1. A preparation method of a polydimethylsiloxane superhydrophobic anti-icing and de-icing material, characterized in that It includes the following steps: Step 1: Mix polydimethylsiloxane, a curing agent, and carbon nanotubes evenly by stirring, and place them in a vacuum drying oven to evacuate and remove air bubbles; Step 2: Weigh sodium chloride and mix it evenly with the mixture obtained in Step 1, put it into a mold and compact it, and place it in a drying oven for curing; after taking out the mold, place the cured sample in a solvent and perform ultrasonic treatment in an ultrasonic machine until all sodium chloride particles precipitate, then cut it into pieces to obtain PDMS / CNTs porous foam; Step 3: Take nano-SiO2 and ultrasonically disperse it in absolute ethanol to obtain a nano-SiO2 dispersion. Add ammonia water to adjust the pH value to 9 - 10, and while stirring, dropwise add 3-aminopropyltriethoxysilane and stir magnetically to obtain dispersion A; add methyl methacrylate to deionized water, add sodium dodecyl sulfate, and ultrasonically disperse it at 45 - 60 kHz for 20 - 60 min to obtain dispersion B; let dispersion A stand for 6 - 12 h, then heat it to 80 - 90 °C and continuously stir at 400 - 600 rpm. Add sodium bicarbonate as a pH buffer and sodium persulfate as an initiator, add dispersion B with the same volume as dispersion A, stop stirring after reacting for 1 - 3 h and cool to room temperature, centrifuge, filter, and dry the solid at 40 °C - 80 °C to obtain modified SiO2 nanoparticles; Take carbon nanotubes, add 1H,1H,2H,2H-perfluorodecyltrimethoxysilane and absolute ethanol, add hydrochloric acid to adjust the pH value, perform magnetic stirring, ultrasonic treatment, drying and grinding to obtain modified carbon nanotubes; Step 4: Add the modified SiO2 nanoparticles, modified carbon nanotubes, a binder, and a curing agent to a solvent and stir magnetically to obtain a CNTs / SiO2 superhydrophobic composite coating solution; The binder is polydimethylsiloxane; Step 5: Spray the CNTs / SiO2 superhydrophobic composite coating solution onto the surface of the PDMS / CNTs porous foam, dry and cure it to obtain a polydimethylsiloxane superhydrophobic anti-icing and de-icing material.

2. The preparation method of the polydimethylsiloxane superhydrophobic anti-icing and de-icing material according to claim 1, wherein, In Step 1, the mass ratio of polydimethylsiloxane, the curing agent, and CNTs is 50:5:1; the polydimethylsiloxane is component A of Dow Corning 184-PDMS, and the curing agent is component B of Dow Corning 184-PDMS.

3. The preparation method of the polydimethylsiloxane superhydrophobic anti-icing and de-icing material according to claim 1, characterized in that, In Step 2, the mass ratio of sodium chloride to the mixture is 10:1, the curing temperature is 60 - 90 °C, the curing time is 6 - 24 hours, and the solvent used for soaking and ultrasonic treatment after curing is deionized water.

4. The preparation method of the polydimethylsiloxane superhydrophobic anti-icing and de-icing material according to claim 1, characterized in that, In Step 3, the mass-volume ratio of carbon nanotubes, 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, and absolute ethanol is 2.5 g:0.8 g:100 mL, and hydrochloric acid is used to adjust the pH to 3.

5. The preparation method of the polydimethylsiloxane superhydrophobic anti-icing and de-icing material according to claim 1, characterized in that In Step 3, the time for magnetic stirring during the preparation of modified carbon nanotubes is 1 - 3 hours, and the ultrasonic time is 10 - 50 minutes.

6. The preparation method of the polydimethylsiloxane superhydrophobic anti-icing and de-icing material according to claim 1, wherein In Step 4, the solvent is n-hexane, the polydimethylsiloxane is component A of Dow Corning 184-PDMS, and the curing agent is component B of Dow Corning 184-PDMS; The mass volume ratio of the total mass of the modified SiO2 nanoparticles and the modified carbon nanotubes to n-hexane, polydimethylsiloxane, and curing agent is 0.1 g: 10 ml: 0.1 g: 0.01 g; the magnetic stirring time is 1 to 3 hours.

7. The preparation method of the polydimethylsiloxane superhydrophobic anti-icing and de-icing material according to claim 1, characterized in that, In the fifth step, the curing temperature is 80 °C and the curing time is 1 to 2 hours.

8. Application of a polydimethylsiloxane superhydrophobic anti-icing and de-icing material, wherein the polydimethylsiloxane superhydrophobic anti-icing and de-icing material is prepared by the preparation method of the polydimethylsiloxane superhydrophobic anti-icing and de-icing material according to any one of claims 1-7, and is characterized in that, The polydimethylsiloxane superhydrophobic anti-icing and de-icing material is applied to the hydrophobicity, anti-icing and de-icing of the surfaces of ships, aircraft, high-speed rails, and ocean engineering.

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