Silica sol-gel coating, preparation method and product

Abstract

The present invention relates to a silica sol-gel coating, a preparation method, and a product. Tetraethyl silicate, a saturated fatty alcohol, a dispersant, and water are uniformly mixed according to a ratio, the pH value is adjusted to 9-11 with a pH regulator, and the mixture is stirred and reacted at 20-60°C for 15-45 minutes to obtain a mixed solution; the mixed solution is subjected to a first microwave treatment and then cooled to obtain an intermediate solution; the intermediate solution is uniformly mixed with fluorosilane and glucomannan, and then subjected to a second microwave treatment. After cooling, the pH regulator is removed to obtain a silica sol-gel coating. The silica sol-gel coating of the present invention is applied to the surface of a substrate and then cured to form a coating having not only ultra-low reflectivity and ultra-high transmittance, but also good corrosion resistance and multifunctionality.

Description

Technical Field

[0001] The invention relates to a silicon dioxide sol-gel coating, a preparation method and a product, and belongs to the field of surface treatment. Background Art

[0002] Solar energy is currently the world's largest energy source. Photovoltaic power generation offers advantages such as environmental friendliness, versatility, and zero loss. However, low photoelectric conversion efficiency severely hinders the large-scale application of solar cells. Therefore, improving the transmittance of photovoltaic glass plays a vital role in enhancing solar photoelectric conversion efficiency. Currently, one of the most effective methods for increasing the transmittance of photovoltaic glass is to deposit an anti-reflective (AR) coating on the surface of the glass.

[0003] In recent years, AR coatings have been widely used in applications such as solar collectors, display devices, architectural glass, cathode ray tubes, filters, and photovoltaic modules due to their excellent heat resistance, hydrophobicity, ultra-low refractive index, and high transmittance. For AR coatings, the refractive index (RI) is a critical optical parameter, reflecting the light transmission loss at the interface between two different optical materials at a given wavelength. Reported results indicate that the RI of single-layer AR coatings can be as low as 1.23, approaching the RI (1.52) of many optical materials. However, for bulk materials, the RI is typically higher than 1.23. Therefore, to reduce the RI, researchers have developed methods and techniques that introduce air into the material to achieve a lower RI. Currently, oblique angle deposition (OAD) and nanoscale etching are considered two very effective methods for introducing air into bulk materials. However, both methods have significant disadvantages. For example, OAD methods typically require high vacuum conditions, while nanoscale etching techniques require highly corrosive reagents. These drawbacks have severely hindered their large-scale application. Therefore, there is a need to develop safer, cheaper, and more time-efficient methods to reduce the RI of coatings. Summary of the Invention

[0004] In view of the shortcomings of the prior art, one of the objects of the present invention is to provide a silica sol-gel coating, wherein the coating prepared by the silica sol-gel coating has low refractive index, high transmittance and excellent anti-corrosion effect; the second object of the present invention is to provide a method for preparing the silica sol-gel coating; the third object of the present invention is to provide a product having the above-mentioned coating.

[0005] In order to solve the above technical problems, the technical solutions of the present invention are as follows:

[0006] A silica sol-gel coating comprises, by weight, 10,000 parts of tetraethyl silicate, 30,000-60,000 parts of saturated fatty alcohol, 10-30 parts of a dispersant, 1,000-10,000 parts of water, 5,000-50,000 parts of fluorosilane, and 1-20 parts of glucomannan, wherein the dispersant is one or more of linoleic acid, linolenic acid, palmitic acid, and oleic acid.

[0007] Furthermore, the raw material composition includes, by weight, 10,000 parts of tetraethyl silicate, 40,000-50,000 parts of saturated fatty alcohol, 15-25 parts of dispersant, 2,000-9,000 parts of water, 10,000-40,000 parts of fluorosilane, and 3-15 parts of glucomannan.

[0008] Furthermore, the saturated fatty alcohol is one or more of methanol, ethanol, propanol, ethylene glycol, propylene glycol, and butanediol.

[0009] Furthermore, the fluorosilane is 1H,1H,2H,2H-perfluorododecyltriethoxysilane.

[0010] Furthermore, the average molecular weight of the glucomannan is 10,000-30,000.

[0011] The method for preparing the silica sol-gel coating as described above comprises the following steps:

[0012] S1. Mix tetraethyl silicate, saturated fatty alcohol, dispersant and water in a uniform ratio, adjust the pH value to 9-11 with a pH adjuster, and stir the mixture at 20-60° C. for 15-45 minutes to obtain a mixed solution.

[0013] S2, subjecting the mixed solution to a microwave treatment, and then cooling the mixed solution to obtain an intermediate solution;

[0014] S3. After uniformly mixing the intermediate solution with fluorosilane and glucomannan, the mixture is subjected to a second-stage microwave treatment. After cooling, the pH regulator is removed to obtain a silica sol-gel coating.

[0015] Furthermore, in S1, the pH adjuster is one or more of ammonia water, potassium hydroxide, and sodium hydroxide, preferably ammonia water.

[0016] Optionally, in S1, mechanical stirring is performed, preferably magnetic stirring.

[0017] Optionally, in S1, the reaction is stirred at 25-50°C for 20-40 min, and further, the reaction is stirred at 30-45°C for 25-35 min.

[0018] Furthermore, in S2, during the microwave treatment, the microwave power is controlled to be 100-600 W, further to 150-500 W, and further to 200-400 W; preferably, the microwave frequency is 20-100 Hz, further to 30-90 Hz, and further to 40-80 Hz; preferably, the reaction time is 20-90 min, further to 30-80 min, and further to 40-70 min.

[0019] Furthermore, in S3, during the second stage microwave treatment, the microwave power is controlled to be 100-600 W, further 150-500 W, further 200-400 W; preferably, the microwave frequency is 20-100 Hz, further 30-90 Hz, further 40-80 Hz; preferably, the reaction time is 20-90 min, further 30-80 min, further 40-70 min;

[0020] Preferably, the pH adjuster is aqueous ammonia, and the pH adjuster is removed by vacuum rotary evaporation.

[0021] Preferably, the mass concentration of the ammonia water is 20-50%, more preferably 25-40%.

[0022] Under the action of base catalysis and microwaves, tetraethyl silicate can rapidly undergo self-hydrolysis and self-polymerization. At the same time, under the action of a dispersant, a microwave treatment can first generate well-dispersed spherical nano-silica as a core. Subsequently, after being evenly mixed with fluorosilane and glucomannan, the fluorosilane is further accelerated to hydrolyze to generate hydroxyl groups under the action of base catalysis and microwaves, and the hydrolyzed 1H,1H,2H,2H-perfluorododecyltriethoxysilane is promoted to undergo self-polymerization reaction with the nano-silica generated in the early stage. At the same time, through the hydrogen bonding effect between glucomannan and nano-silica, the glucomannan is adsorbed on the surface of the nano-silica, and finally a silica sol-gel coating solution with a core-shell structure of varying sizes is obtained, which is conducive to obtaining a coating surface with a rough structure. This rough structure coating is not only conducive to light transmission, but also conducive to surface corrosion protection.

[0023] A product includes a substrate, the surface of which is provided with a coating formed by curing the silica sol-gel coating or the silica sol-gel coating prepared by the preparation method; preferably, the substrate is made of glass or aluminum alloy.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] (1) The silica sol-gel coating of the present invention contains silica particles with a core-shell structure of varying sizes, which is very beneficial for obtaining a coating surface with a rough structure. The coating with the rough structure is not only beneficial for light transmission, but also for surface corrosion protection. The coating formed by curing after being applied to the surface of a substrate not only has an ultra-low refractive index and an ultra-high transmittance, but also has good corrosion resistance, demonstrating multifunctionality.

[0026] (2) The preparation process of the present invention adopts microwave reaction. Compared with the traditional simple acid or base catalysis, the time required for synthesizing the silica sol-gel coating is greatly shortened, and the total reaction time is only about 1-2 hours.

[0027] (3) The preparation method of the silica sol-gel coating of the present invention has advantages such as simple operation.

[0028] (4) The preparation process of the present invention does not require high vacuum conditions or highly corrosive reagents, and has the advantages of safety, environmental protection, and low cost. Compared with existing technologies such as oblique angle deposition and nano-scale etching, it has a better prospect for large-scale promotion and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 Fourier transform infrared (FT-IR) spectra of PSP, PSPF-0.5, PSPF-1.5 and PSPF-2 samples.

[0030] Figure 2 These are the X-ray photoelectron energy (XPS) spectra of PSPF-0.5, PSPF-1.5 and PSPF-2 samples.

[0031] Figure 3 This is the transmission electron microscope (TEM) image of the PSPF-1.5 sample.

[0032] Figure 4 SEM images of PSPF-0.5, PSPF-1.0, PSPF-1.5 and PSPF-2 coatings, where a: PSPF-0.5, b: PSPF-1.0, c: PSPF-1.5, d: PSPF-2.0.

[0033] Figure 5 These are the refractive index diagrams of PSPF-0.5, PSPF-1.0, PSPF-1.5, and PSPF-2 coatings, where 1: PSPF-0.5, 2: PSPF-1.0, 3: PSPF-1.5, and 4: PSPF-2.0.

[0034] Figure 6These are the light transmittance graphs of PSPF-0.5, PSPF-1.0, PSPF-1.5 and PSPF-2 coatings, where 1: PSPF-0.5, 2: PSPF-1.0, 3: PSPF-1.5, and 4: PSPF-2.0.

[0035] Figure 7 These are the Nyquist plots of PSPF-0.5-C, PSPF-1.0-C, PSPF-1.5-C, and PSPF-2.0-C coatings, where 1: PSPF-0.5, 2: PSPF-1.0, 3: PSPF-1.5, and 4: PSPF-2.0.

[0036] Figure 8 is the Nyquist plot of the blank sample. DETAILED DESCRIPTION

[0037] The present invention will be described in detail below with reference to the embodiments. It should be noted that the embodiments and features of the embodiments of the present invention can be combined with each other without conflict.

[0038] Example 1

[0039] Weigh 10 g of tetraethyl silicate, 45 g of ethylene glycol, 20 mg of linoleic acid and 5 g of deionized water, add them to a 200 mL beaker, adjust the pH to 10 with aqueous ammonia (NH3·H2O) (mass concentration 37%), control the reaction temperature to 30°C, and mechanically stir for 30 min. Subsequently, the mixed solution is transferred to an MCR-3A microwave reactor, and the microwave reaction parameters are adjusted as follows: reaction power 300 W, reaction time 30 min, and microwave frequency 30 Hz. After the reaction is completed, cool to room temperature to obtain a well-dispersed spherical nano-silica sol-gel solution, marked as PSP, for standby use.

[0040] 10 g of 1H,1H,2H,2H-perfluorododecyltriethoxysilane and 10 mg of glucomannan (average molecular weight of 15,000) were added to the above-mentioned PSP stand-by solution, and magnetic stirring was started until the 1H,1H,2H,2H-perfluorododecyltriethoxysilane and glucomannan were completely dissolved; further, the above-mentioned mixed solution was transferred to an MCR-3A model microwave reactor, and the microwave reaction parameters were adjusted: reaction power of 300 W, reaction time of 40 min, and microwave frequency of 30 Hz. After the reaction was completed, the solution was cooled to room temperature; then, the remaining ammonia in the solution was removed by vacuum rotary evaporation to obtain the final silica sol-gel coating solution of nano-silica particles with a core-shell structure, which was labeled PSPF-1.

[0041] Example 2

[0042] Weigh 10 g of tetraethyl silicate, 45 g of ethylene glycol, 20 mg of linoleic acid and 5 g of deionized water, add them to a 200 mL beaker, adjust the pH to 9.5 with aqueous ammonia (NH3·H2O) (mass concentration 37%), control the reaction temperature to 30°C, and mechanically stir for 30 min. Subsequently, the mixed solution is transferred to an MCR-3A microwave reactor, and the microwave reaction parameters are adjusted as follows: reaction power 400 W, reaction time 30 min, and microwave frequency 30 Hz. After the reaction is completed, cool to room temperature to obtain a well-dispersed spherical nano-silica sol-gel solution, marked as PSP, for standby use.

[0043] 5 g of 1H,1H,2H,2H-perfluorododecyltriethoxysilane and 5 mg of glucomannan were added to the PSP stand-by solution, and magnetic stirring was started until the 1H,1H,2H,2H-perfluorododecyltriethoxysilane and glucomannan were completely dissolved; further, the mixed solution was transferred to an MCR-3A microwave reactor, and the microwave reaction parameters were adjusted as follows: reaction power of 400 W, reaction time of 40 min, and microwave frequency of 30 Hz. After the reaction, the solution was cooled to room temperature; subsequently, the remaining NH3·H2O in the solution was removed by vacuum rotary evaporation to obtain a final silica sol-gel coating solution with a core-shell structure, which was labeled PSPF-0.5.

[0044] Example 3

[0045] Weigh 10 g of tetraethyl silicate, 45 g of ethylene glycol, 20 mg of linoleic acid and 5 g of deionized water, add them to a 200 mL beaker, adjust the pH to 10.8 with aqueous ammonia (NH3·H2O) (mass concentration 37%), control the reaction temperature to 30°C, and mechanically stir for 30 min. Subsequently, the mixed solution is transferred to an MCR-3A microwave reactor, and the microwave reaction parameters are adjusted as follows: reaction power is 300 W, reaction time is 30 min, and microwave frequency is 30 Hz. After the reaction is completed, cool to room temperature to obtain a well-dispersed spherical nano-silica sol-gel solution, marked as PSP, for standby use.

[0046] 15 g of 1H,1H,2H,2H-perfluorododecyltriethoxysilane and 10 mg of glucomannan were added to the PSP stand-by solution, and magnetic stirring was started until the 1H,1H,2H,2H-perfluorododecyltriethoxysilane and glucomannan were completely dissolved; further, the mixed solution was transferred to an MCR-3A microwave reactor, and the microwave reaction parameters were adjusted as follows: reaction power of 300 W, reaction time of 40 min, and microwave frequency of 30 Hz. After the reaction, the solution was cooled to room temperature; subsequently, the remaining NH3·H2O in the solution was removed by vacuum rotary evaporation to obtain a final silica sol-gel coating solution with a core-shell structure, which was labeled PSPF-1.5.

[0047] Example 4

[0048] Weigh 10 g of tetraethyl silicate, 45 g of ethylene glycol, 20 mg of linoleic acid and 5 g of deionized water, add them to a 200 mL beaker, adjust the pH to 10.5 with aqueous ammonia (NH3·H2O) (mass concentration 37%), control the reaction temperature to 30°C, and mechanically stir for 30 min. Subsequently, the mixed solution is transferred to an MCR-3A microwave reactor, and the microwave reaction parameters are adjusted as follows: reaction power is 300 W, reaction time is 30 min, and microwave frequency is 30 Hz. After the reaction is completed, cool to room temperature to obtain a well-dispersed spherical nano-silica sol-gel solution, marked as PSP, for standby use.

[0049] 20 g of 1H,1H,2H,2H-perfluorododecyltriethoxysilane and 10 mg of glucomannan were added to the PSP stand-by solution, and magnetic stirring was started until the 1H,1H,2H,2H-perfluorododecyltriethoxysilane and glucomannan were completely dissolved; further, the mixed solution was transferred to an MCR-3A microwave reactor, and the microwave reaction parameters were adjusted as follows: reaction power of 300 W, reaction time of 40 min, and microwave frequency of 30 Hz. After the reaction, the solution was cooled to room temperature; then, the remaining NH3·H2O in the solution was removed by vacuum rotary evaporation to obtain the final silica sol-gel coating solution with a core-shell structure, which was labeled PSPF-2.

[0050] 10 mg of PSP, PSPF-0.5, PSPF-1.0, PSPF-1.5 and PSPF-2 samples were characterized by infrared spectrometer and UV-visible spectrometer respectively. The results are shown in the figure. Figure 1 As shown; 5 mg of PSP, PSPF-1.5 and PSPF-2 samples were taken respectively, and their chemical compositions were characterized by X-ray electron spectrometer. The results obtained are shown as follows Figure 2As shown; 5 mg of PSP, PSPF-1.5 and PSPF-2 samples were taken respectively, and the average particle size of nano-silica ions in the samples was characterized by a Nano-ZET dynamic light scattering instrument. The results obtained are shown in Table 1.

[0051] Figure 1 The Fourier transform infrared (FT-IR) spectra of PSP, PSPF-0.5, PSPF-1.0, PSPF-1.5 and PSPF-2 samples are shown in Figure 3400 cm -1 The absorption peaks near the 1251 and 1100 cm-1 are the stretching vibration peaks of Si-OH. -1 The absorption peaks at 1056 and 803 cm are the stretching vibration peaks of -CF2 and -CF3; -1 The absorption peaks of 1056 and 803 cm-1 in PSPF-0.5, PSPF-1.0, PSPF-1.5 and PSPF-2 samples are the vibration peaks of Si-O-Si. -1 The intensities of the two absorption peaks increase with the increase of 1H,1H,2H,2H-perfluorododecyltriethoxysilane.

[0052] Figure 2 The X-ray photoelectron (XPS) spectra of PSP, PSPF-0.5, PSPF-1.0, PSPF-1.5, and PSPF-2 samples are shown. The peaks at 104.5, 288.4, 536.6, and 688.8 eV in the figure are the absorption peaks of Si 2p, C 1s, O 1s, and F 1s, respectively.

[0053] Table 1 shows the average particle size of the nano-silica particles of PSP, PSPF-0.5, PSPF-1.5 and PSPF-2 samples. As can be seen from Table 1, the particle size distribution of PSP, PSPF-0.5, PSPF-1.5 and PSPF-2 samples is between 20-30 nm.

[0054] Table 1. Average particle size of PSP, PSPF-0.5, PSPF-1.5 and PSPF-2 samples

[0055] sample Average particle size (nm) PSPF-0.5 20.2±0.9 PSPF-1.0 23.3±1.1 PSPF-1.5 25.2±0.3 PSPF-2.0 26.3±1.3

[0056] Figure 3 This is a TEM image of the PSPF-1.5 sample. It can be seen that PSPF-1.5 has nano-silica particles with a core-shell structure.

[0057] Example 5

[0058] Four pieces of photovoltaic glass with a size of 25 mm × 25 mm × 1.0 mm were cut and cleaned with deionized water, anhydrous ethanol and acetone in sequence under the action of ultrasound, dried and set aside; the PSPF-0.5, PSPF-1.0, PSPF-1.5 and PSPF-2.0 sol-gels prepared above were respectively coated on the surface of the treated photovoltaic glass (area of ​​about 10 cm) by rotary spraying. 2 ), and then, after curing at 200°C for 10 minutes, the corresponding coatings were obtained, and the corresponding coatings were marked as PSPF-0.5, PSPF-1.0, PSPF-1.5 and PSPF-2.0 coatings, wherein the thickness of each coating was controlled to be 36.5±1.5μm.

[0059] The morphology of PSPF-0.5, PSPF-1.0, PSPF-1.5 and PSPF-2.0 coatings was observed using a SIGMA300 scanning electron microscope (SEM); the refractive index of the coating was tested using an EA350 spectroscopic ellipsometer; and the light transmittance of the coating was tested using an N6000 ultraviolet-visible (UV-vis) spectrometer.

[0060] Figure 4 Figure 2 shows the SEM images of PSPF-0.5, PSPF-1.0, PSPF-1.5, and PSPF-2 coatings. It can be seen that all coatings have a rough surface and exhibit large voids.

[0061] Figure 5 Figure 2 is the refractive index diagram of PSPF-0.5, PSPF-1.0, PSPF-1.5, and PSPF-2 coatings. It can be found that the refractive indices of PSPF-0.5, PSPF-1.0, PSPF-1.5, and PSPF-2 coatings are 1.06, 1.03, 1.02, and 1.01, respectively.

[0062] Figure 6 Figure 2 shows the light transmittance of PSPF-0.5, PSPF-1.0, PSPF-1.5, and PSPF-2 coatings. It can be found that the light transmittance of PSPF-0.5, PSPF-1.0, PSPF-1.5, and PSPF-2 coatings are 99.8%, 99.8%, 99.9%, and 99.9%, respectively.

[0063] Example 6

[0064] Four N70 aluminum alloy plates with a size of 5 cm × 5 cm were cut and polished using 300-mesh, 500-mesh, 800-mesh, and 1200-mesh sandpaper, respectively. After polishing, the plates were cleaned with deionized water, anhydrous ethanol, and acetone under ultrasonic conditions, and then dried under vacuum for later use.

[0065] The PSPF-0.5, PSPF-1.0, PSPF-1.5 and PSPF-2.0 sol-gels prepared above were coated on the surface of the treated N70 aluminum alloy plate (area of ​​about 10 cm) in sequence by rotary spraying. 2 ), then cured at 200 ° C for 10 minutes, and then the corresponding coatings were obtained (the thickness of each coating was controlled to be 36.5 ± 1.5 μm), and the corresponding coatings were marked as PSPF-0.5-C, PSPF-1.0-C, PSPF-1.5-C and PSPF-2.0-C coatings. The measurement adopts a classic three-electrode system, with the coating electrode and the bare aluminum alloy plate as working electrodes, the Pt electrode as the auxiliary electrode, and the reference electrode as a saturated calomel electrode. The electrochemical impedance spectroscopy (EIS) of carbon steel in different concentrations of corrosion inhibitor solutions was tested respectively, and the results were as follows Figure 7 and Figure 8 shown.

[0066] Figure 7 and Figure 8 It is the Nyquist diagram. As can be seen from the figure, the Nyquist diagram is a semicircular arc compressed on the Y-axis, and the size of the X-axis arc radius can reflect the size of the sample's anti-corrosion efficiency. Generally, the larger the radius, the larger the transfer charge (Rct) between the solution and the aluminum alloy plate interface, and thus the higher the anti-corrosion efficiency; on the contrary, if the radius is smaller, the anti-corrosion efficiency is lower. Compared with the blank (bare aluminum alloy plate) sample, the X-axis arc radius of the PSPF-0.5-C, PSPF-1.0-C, PSPF-1.5-C and PSPF-2.0-C coatings is much larger. At the same time, the Rct values ​​of the PSPF-0.5-C, PSPF-1.0-C, PSPF-1.5-C and PSPF-2.0-C coatings are 35785.7Ωcm, respectively. 2 、35732.7Ωcm 2 、35778.9Ωcm 2 、35766.1Ωcm 2 , which is much higher than the Rct value of the blank sample (bare aluminum alloy plate) (321.8Ωcm 2 Using Rct, the corrosion inhibition efficiency (η R %):

[0067]

[0068] where R (inh) and R (0)The Rct values ​​are shown below: with and without corrosion inhibitors. After calculation, the anti-corrosion efficiencies of PSPF-0.5-C, PSPF-1.0-C, PSPF-1.5-C, and PSPF-2.0-C coatings are 99.1%, 99.2%, 99.1%, and 99.1%, respectively.

[0069] Comparative Example 1

[0070] Weigh 10 g of tetraethyl silicate, 45 g of ethylene glycol, 20 mg of linoleic acid and 5 g of deionized water, add them to a 200 mL beaker, adjust the pH to 10 with aqueous ammonia (NH3·H2O) (mass concentration 37%), control the reaction temperature to 30°C, and mechanically stir for 30 min. Subsequently, the mixed solution is transferred to an MCR-3A microwave reactor, and the microwave reaction parameters are adjusted as follows: reaction power 300 W, reaction time 30 min, and microwave frequency 30 Hz. After the reaction is completed, cool to room temperature to obtain a well-dispersed spherical nano-silica sol-gel solution, marked as PSP, for standby use.

[0071] 10 g of 1H,1H,2H,2H-perfluorododecyltriethoxysilane was added to the PSP stand-by solution, and magnetic stirring was started until the 1H,1H,2H,2H-perfluorododecyltriethoxysilane was completely dissolved. Furthermore, the mixed solution was transferred to an MCR-3A microwave reactor, and the microwave reaction parameters were adjusted to: reaction power of 300 W, reaction time of 40 min, and microwave frequency of 30 Hz. After the reaction, the solution was cooled to room temperature. Subsequently, the remaining NH3·H2O in the solution was removed by vacuum rotary evaporation to obtain a final silica sol-gel coating solution with a core-shell structure, labeled PSPF-8.

[0072] Through the above preparation and test characterization methods, the refractive index, transmittance and anti-corrosion efficiency of the coating prepared from PSPF-8 were obtained to be 1.36, 91.3% and 83.6%, respectively.

[0073] Example 7

[0074] Weigh 10 g of tetraethyl silicate, 45 g of ethylene glycol, 20 mg of linoleic acid and 5 g of deionized water, add them to a 200 mL beaker, adjust the pH to 11 with ammonia (NH3·H2O) (mass concentration 37%), control the reaction temperature to 30°C, and mechanically stir for 30 minutes. Subsequently, the mixed solution is transferred to an MCR-3A microwave reactor, and the microwave reaction parameters are adjusted as follows: reaction power is 300 W, reaction time is 30 minutes, and microwave frequency is 30 Hz. After the reaction is completed, cool to room temperature to obtain a well-dispersed spherical nano-silica sol-gel solution, marked as PSP, for standby use.

[0075] 20 g of 1H,1H,2H,2H-perfluorododecyltriethoxysilane and 10 mg of glucomannan were added to the PSP stand-by solution, and magnetic stirring was started until the 1H,1H,2H,2H-perfluorododecyltriethoxysilane and glucomannan were completely dissolved; further, the mixed solution was transferred to an MCR-3A microwave reactor, and the microwave reaction parameters were adjusted as follows: reaction power of 300 W, reaction time of 50 min, and microwave frequency of 30 Hz. After the reaction, the solution was cooled to room temperature; then, the remaining NH3·H2O in the solution was removed by vacuum rotary evaporation to obtain a final silica sol-gel coating solution with a core-shell structure, labeled PSPF-9.

[0076] Through the above preparation and test characterization methods, the refractive index, transmittance and anti-corrosion efficiency of the coating prepared from PSPF-9 were obtained to be 1.09, 98.3% and 92%, respectively.

[0077] Example 8

[0078] Weigh 10 g of tetraethyl silicate, 45 g of ethylene glycol, 20 mg of linoleic acid and 5 g of deionized water, add them to a 200 mL beaker, adjust the pH to 10 with aqueous ammonia (NH3·H2O) (mass concentration 37%), control the reaction temperature to 30°C, and mechanically stir for 30 min. Subsequently, the mixed solution is transferred to an MCR-3A microwave reactor, and the microwave reaction parameters are adjusted as follows: reaction power is 600 W, reaction time is 30 min, and microwave frequency is 30 Hz. After the reaction is completed, cool to room temperature to obtain a well-dispersed spherical nano-silica sol-gel solution, marked as PSP, for standby use.

[0079] 10 g of 1H,1H,2H,2H-perfluorododecyltriethoxysilane and 10 mg of glucomannan were added to the PSP stand-by solution, and magnetic stirring was started until the 1H,1H,2H,2H-perfluorododecyltriethoxysilane and glucomannan were completely dissolved. Furthermore, the mixed solution was transferred into an MCR-3A microwave reactor, and the microwave reaction parameters were adjusted to: reaction power of 600 W, reaction time of 30 min, and microwave frequency of 30 Hz. After the reaction, the solution was cooled to room temperature. Subsequently, the remaining NH3·H2O in the solution was removed by vacuum rotary evaporation to obtain a final silica sol-gel coating solution with a core-shell structure, which was labeled PSPF-10.

[0080] Through the above preparation and test characterization methods, the refractive index, transmittance and anti-corrosion efficiency of the coating prepared from PSPF-10 were obtained to be 1.42, 92.3% and 91.6%, respectively.

[0081] Comparative Example 2

[0082] Example 8 was repeated, except that the microwave reaction power was 50 W. Through the above preparation and test characterization methods, the refractive index, transmittance and anti-corrosion efficiency of the prepared coating were obtained to be 1.51, 90.4% and 90.5% respectively.

[0083] Comparative Example 3

[0084] Example 8 was repeated, except that the microwave reaction power was 650 W. Through the above preparation and testing characterization methods, the refractive index, transmittance and anti-corrosion efficiency of the prepared coating were obtained to be 1.64, 88.2% and 87.6%, respectively.

[0085] Example 9

[0086] Weigh 10 g of tetraethyl silicate, 45 g of ethylene glycol, 20 mg of linoleic acid and 5 g of deionized water, add them to a 200 mL beaker, adjust the pH to 7.2 with ammonia (NH3·H2O) (mass concentration 37%), control the reaction temperature to 30°C, and mechanically stir for 30 min. Subsequently, the mixed solution is transferred to an MCR-3A microwave reactor, and the microwave reaction parameters are adjusted as follows: reaction power is 100 W, reaction time is 30 min, and microwave frequency is 30 Hz. After the reaction is completed, cool to room temperature to obtain a well-dispersed spherical nano-silica sol-gel solution, marked as PSP, for standby use.

[0087] 10 g of 1H,1H,2H,2H-perfluorododecyltriethoxysilane and 10 mg of glucomannan were added to the PSP stand-by solution, and magnetic stirring was started until the 1H,1H,2H,2H-perfluorododecyltriethoxysilane and glucomannan were completely dissolved; further, the mixed solution was transferred to an MCR-3A microwave reactor, and the microwave reaction parameters were adjusted as follows: reaction power of 100 W, reaction time of 30 min, and microwave frequency of 30 Hz. After the reaction, the solution was cooled to room temperature; then, the remaining NH3·H2O in the solution was removed by vacuum rotary evaporation to obtain the final silica sol-gel coating solution with a core-shell structure, which was labeled PSPF-11.

[0088] Through the above preparation and test characterization methods, the refractive index, transmittance and anti-corrosion efficiency of the coating prepared from PSPF-11 were obtained to be 1.36, 95.9% and 92.3%, respectively.

[0089] Example 10

[0090] Weigh 10 g of tetraethyl silicate, 45 g of ethylene glycol, 20 mg of linoleic acid and 5 g of deionized water, add them to a 200 mL beaker, adjust the pH value to 10 with ammonia (NH3·H2O) (mass concentration 37%), control the reaction temperature to 30°C, and mechanically stir for 30 minutes. Subsequently, the mixed solution is transferred to an MCR-3A microwave reactor, and the microwave reaction parameters are adjusted as follows: reaction power is 150 W, reaction time is 30 minutes, and microwave frequency is 30 Hz. After the reaction is completed, cool to room temperature to obtain a well-dispersed spherical nano-silica sol-gel solution, marked as PSP, for standby use.

[0091] 10 g of 1H,1H,2H,2H-perfluorododecyltriethoxysilane and 10 mg of glucomannan were added to the PSP stand-by solution, and magnetic stirring was started until the 1H,1H,2H,2H-perfluorododecyltriethoxysilane and glucomannan were completely dissolved; further, the mixed solution was transferred to an MCR-3A microwave reactor, and the microwave reaction parameters were adjusted as follows: reaction power of 150 W, reaction time of 30 min, and microwave frequency of 30 Hz. After the reaction, the solution was cooled to room temperature; then, the remaining NH3·H2O in the solution was removed by vacuum rotary evaporation to obtain a final silica sol-gel coating solution with a core-shell structure, labeled as PSPF-12.

[0092] Through the above preparation and test characterization methods, the refractive index, transmittance and anti-corrosion efficiency of the coating prepared from PSPF-12 were obtained to be 1.26, 96.4% and 95.1%, respectively.

[0093] Example 11

[0094] Weigh 10 g of tetraethyl silicate, 45 g of ethylene glycol, 20 mg of linoleic acid and 5 g of deionized water, add them to a 200 mL beaker, adjust the pH to 10.5 with aqueous ammonia (NH3·H2O) (mass concentration 37%), control the reaction temperature to 30°C, and mechanically stir for 30 min. Subsequently, the mixed solution is transferred to an MCR-3A microwave reactor, and the microwave reaction parameters are adjusted as follows: reaction power is 200 W, reaction time is 30 min, and microwave frequency is 30 Hz. After the reaction is completed, cool to room temperature to obtain a well-dispersed spherical nano-silica sol-gel solution, marked as PSP, for standby use.

[0095] 10 g of 1H,1H,2H,2H-perfluorododecyltriethoxysilane and 10 mg of glucomannan were added to the PSP stand-by solution, and magnetic stirring was started until the 1H,1H,2H,2H-perfluorododecyltriethoxysilane and glucomannan were completely dissolved; further, the mixed solution was transferred to an MCR-3A microwave reactor, and the microwave reaction parameters were adjusted as follows: reaction power of 150 W, reaction time of 30 min, and microwave frequency of 30 Hz. After the reaction, the solution was cooled to room temperature; then, the remaining NH3·H2O in the solution was removed by vacuum rotary evaporation to obtain a final silica sol-gel coating solution with a core-shell structure, labeled PSPF-13.

[0096] Through the above preparation and test characterization methods, the refractive index, transmittance and anti-corrosion efficiency of the coating prepared from PSPF-13 were obtained to be 1.09, 98.1% and 95.6%, respectively.

[0097] Comparative Example 4

[0098] Weigh 10 g of tetraethyl silicate, 45 g of ethylene glycol and 5 g of deionized water, add them to a 200 mL beaker, adjust the pH value to 10 with ammonia (NH3·H2O) (mass concentration 37%), control the reaction temperature to 30°C, and mechanically stir for 30 minutes. Subsequently, the mixed solution is transferred to an MCR-3A microwave reactor, and the microwave reaction parameters are adjusted as follows: reaction power is 300 W, reaction time is 30 minutes, and microwave frequency is 30 Hz. After the reaction is completed, cool to room temperature to obtain a well-dispersed spherical nano-silica sol-gel solution, marked as PSP, for standby use.

[0099] 10 g of 1H,1H,2H,2H-perfluorododecyltriethoxysilane and 10 mg of glucomannan were added to the PSP stand-by solution, and magnetic stirring was started until the 1H,1H,2H,2H-perfluorododecyltriethoxysilane and glucomannan were completely dissolved. Furthermore, the mixed solution was transferred to an MCR-3A microwave reactor, and the microwave reaction parameters were adjusted to: reaction power of 300 W, reaction time of 40 min, and microwave frequency of 30 Hz. After the reaction, the solution was cooled to room temperature. Subsequently, the remaining NH3·H2O in the solution was removed by vacuum rotary evaporation to obtain a final silica sol-gel coating solution with a core-shell structure, labeled PSPF-14.

[0100] Through the above preparation and test characterization methods, the refractive index, transmittance and anti-corrosion efficiency of the coating prepared from PSPF-14 were obtained to be 1.28, 92.1% and 95.1%, respectively.

[0101] Comparative Example 5

[0102] Example 1 was repeated except that 0.5 mg of glucomannan was added. The relevant results are shown in Table 1.

[0103] Example 12

[0104] Example 1 was repeated except that 1 mg of glucomannan was added. The relevant results are shown in Table 1.

[0105] Example 13

[0106] Example 1 was repeated except that 20 mg of glucomannan was added. The relevant results are shown in Table 1.

[0107] Comparative Example 6

[0108] Example 1 was repeated except that 22 mg of glucomannan was added. The relevant results are shown in Table 1. Table 1 is a summary of the coating formulations of the examples and comparative examples and the relevant coating properties.

[0109] Table 1 Coating formulas of various examples and comparative examples and related coating performances

[0110]

[0111]

[0112] The contents illustrated in the above embodiments should be understood as these embodiments are only used to more clearly illustrate the present invention, and are not used to limit the scope of the present invention. After reading the present invention, various equivalent modifications of the present invention by those skilled in the art shall fall within the scope defined by the claims attached to this application.

Claims

1. A silica sol-gel coating, characterized in that: The raw material composition includes, by weight, 10,000 parts of tetraethyl silicate, 30,000-60,000 parts of saturated fatty alcohol, 10-30 parts of dispersant, 1,000-10,000 parts of water, 5,000-50,000 parts of fluorosilane, and 1-20 parts of glucomannan, wherein the dispersant is one or more of linoleic acid, linolenic acid, palmitic acid, and oleic acid, and the average molecular weight of the glucomannan is 10,000-30,000. The preparation method of the silica sol-gel coating comprises the following steps: S1. Mix tetraethyl silicate, saturated fatty alcohol, dispersant and water in a uniform ratio, adjust the pH value to 9-11 with a pH adjuster, and stir the mixture at 20-60° C. for 15-45 minutes to obtain a mixed solution. S2, subjecting the mixed solution to a microwave treatment, and then cooling the mixed solution to obtain an intermediate solution; During the first stage of microwave treatment, the microwave power is controlled to be 100-600W; the microwave frequency is 20-100Hz; and the reaction time is 20-90min. S3, after uniformly mixing the intermediate solution with fluorosilane and glucomannan, performing two-stage microwave treatment, cooling, and then removing the pH regulator to obtain a silica sol-gel coating; During the second-stage microwave treatment, the microwave power is controlled to be 100-600W; the microwave frequency is 20-100Hz; and the reaction time is 20-90min.

2. The silica sol-gel coating according to claim 1, characterized in that: The raw material composition includes, by weight, 10,000 parts of tetraethyl silicate, 40,000-50,000 parts of saturated fatty alcohol, 15-25 parts of dispersant, 2,000-9,000 parts of water, 10,000-40,000 parts of fluorosilane, and 3-15 parts of glucomannan.

3. The silica sol-gel coating according to claim 1, characterized in that: The saturated fatty alcohol is one or more of methanol, ethanol, propanol, ethylene glycol, propylene glycol, and butanediol.

4. The silica sol-gel coating according to claim 1, characterized in that: The fluorosilane is 1H,1H,2H,2H-perfluorododecyltriethoxysilane.

5. The silica sol-gel coating according to claim 1, characterized in that: In S1, the pH regulator is one or more of ammonia water, potassium hydroxide, and sodium hydroxide.

6. The silica sol-gel coating according to claim 1, characterized in that: In S2, during a microwave treatment, the microwave power is controlled to be 150-500W.

7. The silica sol-gel coating according to claim 6, characterized in that: In S2, during a microwave treatment, the microwave power is controlled to be 200-400W.

8. The silica sol-gel coating according to claim 1, characterized in that: In S2, during a microwave treatment, the microwave frequency is controlled to be 30-90 Hz.

9. The silica sol-gel coating according to claim 8, characterized in that: In S2, during a microwave treatment, the microwave frequency is controlled to be 40-80 Hz.

10. The silica sol-gel coating according to claim 1, characterized in that: In S2, during the microwave treatment, the reaction time is controlled to be 30-80 min.

11. The silica sol-gel coating according to claim 10, characterized in that: In S2, during the microwave treatment, the reaction time is controlled to be 40-70 min.

12. The silica sol-gel coating according to claim 1, characterized in that: In S3, during the second stage microwave treatment, the microwave power is controlled to be 150-500W.

13. The silica sol-gel coating according to claim 12, characterized in that: In S3, during the second stage microwave treatment, the microwave power is controlled to be 200-400W.

14. The silica sol-gel coating according to claim 1, characterized in that: In S3, during the second stage microwave treatment, the microwave frequency is controlled to be 30-90 Hz.

15. The silica sol-gel coating according to claim 14, characterized in that: In S3, during the second stage microwave treatment, the microwave frequency is controlled to be 40-80 Hz.

16. The silica sol-gel coating according to claim 1, characterized in that: In S3, during the second stage microwave treatment, the reaction time is controlled to be 30-80 min.

17. The silica sol-gel coating according to claim 16, characterized in that: In S3, during the second stage microwave treatment, the reaction time is controlled to be 40-70 min.

18. The silica sol-gel coating according to claim 1, characterized in that: The pH adjuster was ammonia water, which was removed by vacuum rotary evaporation.

19. An article comprising a substrate, characterized in that The surface of the base is provided with the silica sol-gel coating according to any one of claims 1 to 18; the material of the substrate is glass or aluminum alloy.

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