Self-cleaning anti-dust-deposition glass and preparation method thereof

Abstract

The invention belongs to the field of self-cleaning coatings, and provides self-cleaning anti-dust-deposition glass and a preparation method thereof.According to the self-cleaning anti-dust-deposition glass and the preparation method thereof, hydroxyl is formed on the surface of the glass through pretreatment, the glass is better combined with a coating solution subsequently, TiO2 particles of a micro-nano structure (the micro-nano structure that nano TiO2 is loaded on micron TiO2) are prepared, and the self-cleaning anti-dust-deposition glass is obtained. The preparation method comprises the following steps: firstly, preparing TiO2 particles with a micro-nano structure, then carrying out super-hydrophobic modification on the TiO2 particles with the micro-nano structure, preparing a spraying solution from the super-hydrophobic TiO2 particles and PDMS, and finally, spraying the spraying solution onto glass with hydroxyl to obtain the self-cleaning anti-dust-deposition glass. The coating does not contain fluoride and is environmentally friendly; the binding force of glass pretreatment and the coating is improved; tiO2 has a photocatalytic self-cleaning effect and can degrade oil stains on the surface of the assembly; the super-hydrophobic TiO2 micro-nano particles have micron-scale and nano-scale structures at the same time, and the hydrophobic capacity is higher; and the leveling agent is added, so that the coating is more stable.

Description

Technical Field

[0001] This invention belongs to the field of self-cleaning coatings and relates to a self-cleaning anti-dust glass and its preparation method. Background Technology

[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] For long-term photovoltaic (PV) power generation systems, the deposition of fine particles such as dust and particulate matter, which are ubiquitous in the natural environment, on the surface of PV panels constitutes a significant external factor affecting the light-to-electricity conversion efficiency. Currently, manual cleaning dominates in PV power plants due to its wide applicability. However, this cleaning method suffers from low efficiency and high cost. Superhydrophobic self-cleaning coatings offer an excellent solution for addressing the problems of dust and oil accumulation on modules.

[0004] A study has disclosed a SiO2 / PDMS composite transparent superhydrophobic coating that can be used as a self-cleaning and anti-fouling coating for windshields or solar panels. However, the SiO2 / PDMS composite transparent superhydrophobic coating has low adhesion to the substrate.

[0005] A study has disclosed a nano-biomimetic waterproof material with a lotus leaf effect for use in the field of mesh fabrics. However, the preparation method is complex, requires high-end equipment, and causes significant solution pollution during the sizing process.

[0006] One study disclosed a polypropylene composite material that creates a lotus leaf effect on oil stains, but the preparation method requires a large amount of raw materials, which increases the cost accordingly. The preparation method also contains fluorides, which is not environmentally friendly.

[0007] In summary, traditional processes mainly only prepare hydrophobic coatings without considering the impact of oil stains on components. Furthermore, the glass is not pretreated, resulting in poor adhesion between the coating and the glass, and the use of fluorinated compounds is environmentally unfriendly. Summary of the Invention

[0008] To address the issue of dust and oil buildup on the glass surface of power modules after long-term use, which affects power generation, this invention provides a self-cleaning anti-dust-accumulation glass and its preparation method. This invention involves pretreatment to imbue the glass surface with hydroxyl groups, enabling better bonding with the subsequent coating solution. Next, micro / nano-structured TiO2 particles (micro / nano-structured TiO2 loaded with nano-TiO2 on micron-sized TiO2) are prepared. Then, the micro / nano-structured TiO2 particles are modified to be superhydrophobic. Finally, a spraying solution is prepared using the superhydrophobic TiO2 particles and PDMS. Finally, the spraying solution is sprayed onto the hydroxyl-containing glass to obtain the self-cleaning anti-dust-accumulation glass.

[0009] To achieve the above objectives, the present invention adopts the following technical solution: A first aspect of the present invention provides a method for preparing self-cleaning, dust-resistant glass, comprising: The glass is modified by hydroxylation to obtain pretreated glass; After uniformly mixing micron-sized TiO2 solution and catalyst, a titanium source is added, followed by hydrolysis and condensation reaction, aging reaction, solid-liquid separation, washing, drying, and calcination to obtain TiO2 with micro-nano structure. A dispersion of TiO2 with micro-nano structure was prepared, and a first silane coupling agent was added for hydrophobic modification. The mixture was then separated into solid and liquid phases, washed, dried, and calcined to obtain superhydrophobic TiO2 particles. A superhydrophobic TiO2 particle suspension was prepared, and a second silane coupling agent was added to react and obtain a superhydrophobic TiO2 particle mixture. Mix PDMS A and B components to obtain a PDMS mixture; The PDMS mixture was added to the superhydrophobic TiO2 particle mixture and mixed evenly to carry out the reaction. After the reaction was completed, a leveling agent was added and mixed evenly to obtain the spraying liquid. The coating liquid is applied to the pretreated glass to obtain the final product.

[0010] In a second aspect, the present invention provides a self-cleaning, dust-resistant glass prepared by the above-described method.

[0011] A third aspect of the present invention provides the application of the above-described self-cleaning, dust-resistant glass in the manufacture of photovoltaic power generation systems.

[0012] Beneficial effects of the present invention (1) The coating of the present invention does not contain fluorides and is environmentally friendly; the bonding force between glass pretreatment and coating is improved; TiO2 has photocatalytic self-cleaning effect and can degrade oil stains on the surface of components; the superhydrophobic TiO2 micro-nano particles have both micron-scale and nano-scale structures, and have stronger hydrophobicity; the addition of leveling agent makes the coating more stable.

[0013] (2) The preparation method of the present invention is simple, practical and easy to promote. Attached Figure Description

[0014] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. Exemplary embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0015] Figure 1 This is a test image of the coating contact angle prepared in Example 1 of the present invention. Detailed Implementation

[0016] It should be noted that the following detailed descriptions are exemplary and intended to provide further illustration of the invention. Unless otherwise specified, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0017] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of skill in the art. The reagents and raw materials used in this invention are readily available through conventional means, and unless otherwise specified, they are used in accordance with conventional methods in the art or product instructions. Similarly, unless otherwise specified, the test methods of this invention are performed in accordance with conventional methods in the art or industry-standard methods or practices. Furthermore, any methods and materials similar to or equivalent to those described herein may be applied to the methods of this invention. The preferred embodiments and materials described herein are for illustrative purposes only.

[0018] This invention provides a method for preparing self-cleaning, dust-resistant glass, comprising: The glass is modified by hydroxylation to obtain pretreated glass; After uniformly mixing micron-sized TiO2 solution and catalyst, a titanium source is added, followed by hydrolysis and condensation reaction, aging reaction, solid-liquid separation, washing, drying, and calcination to obtain TiO2 with micro-nano structure. A dispersion of TiO2 with micro-nano structure was prepared, and a first silane coupling agent was added for hydrophobic modification. The mixture was then separated into solid and liquid phases, washed, dried, and calcined to obtain superhydrophobic TiO2 particles. A superhydrophobic TiO2 particle suspension was prepared, and a second silane coupling agent was added to react and obtain a superhydrophobic TiO2 particle mixture. Mix PDMS A and B components to obtain a PDMS mixture; The PDMS mixture was added to the superhydrophobic TiO2 particle mixture and mixed evenly to carry out the reaction. After the reaction was completed, a leveling agent was added and mixed evenly to obtain the spraying liquid. The coating liquid is applied to the pretreated glass to obtain the final product.

[0019] The present invention does not impose any particular limitation on the method of hydroxylation modification, as long as it can make the glass surface have hydroxyl groups. Therefore, in some embodiments, the method of hydroxylation modification includes: oxygen plasma treatment, strong oxidizing acid cleaning, alkali treatment, ultraviolet ozone cleaning, and acid treatment.

[0020] In some embodiments, the oxygen plasma treatment conditions are: operating pressure 0.1-1 Torr, radio frequency power 50W-200W, and treatment time 1-10 minutes. High-energy oxygen plasma (containing O2) + O- (O*, free radicals, etc.) bombard the glass surface: efficiently removes organic pollutants (oxidized and decomposed into volatile gases such as CO2 and H2O). It breaks the Si-O-Si bonds on the surface, generating new Si-OH groups. This greatly enhances the surface's hydrophilicity.

[0021] In some embodiments, the catalyst is concentrated nitric acid or concentrated ammonia.

[0022] During the hydrolysis-condensation reaction, the titanium source is added at a rate of 1 drop per 5-10 seconds. The dropping rate is crucial for success; the slower the better. The goal is to allow sufficient time for the precursor molecules to diffuse to the surface of the micron-sized particles and be adsorbed, undergoing hydrolysis and condensation on their surface, rather than agglomerating in solution. Rapid addition inevitably leads to the formation of a large number of free nanoparticles.

[0023] In some embodiments, the aging reaction is carried out at 40-60°C for 5-6 hours, allowing the adsorbed titanium species on the surface to fully hydrolyze and condense to form nanoparticles.

[0024] In some embodiments, the calcination conditions are to hold at 350-450°C for 1.5-2 hours, or at 400°C for 2 hours, to completely remove organic matter such as PVP, to crystallize the newly generated titanium dioxide nanoparticles (usually anatase phase), and to enhance the bonding force between the nanoparticles and the micron substrate (formed by sintering).

[0025] The type and amount of coupling agent can affect the hydrophobic modification effect. Therefore, this invention studies the type and amount of silane coupling agent. In some embodiments, the first silane coupling agent is hexadecyltrimethoxysilane; in some embodiments, the mass ratio of the first silane coupling agent to TiO2 with micro / nano structure is 2-4:1; in some embodiments, the second silane coupling agent is KH-560; in some embodiments, the mass ratio of the second silane coupling agent to superhydrophobic TiO2 particles is 1-2:15 to obtain a better hydrophobic modification effect.

[0026] The curing and annealing temperatures and times affect the coating's microstructure, self-cleaning properties, etc. Therefore, this invention has studied the curing and annealing temperatures and times. In some embodiments, the spraying steps include: after spraying the first layer, spraying the second layer in a perpendicular cross direction, letting it stand, pre-curing at 80-90℃ for 4-6 hours, and annealing at 120-140℃ for 2-4 hours to obtain a better self-cleaning coating.

[0027] More specifically, including: (a) Glass pretreatment steps: Oxygen plasma treatment (O2Plasma): Equipment: Plasma cleaner. Procedure: Place the clean, dry photovoltaic glass into the plasma chamber. Evacuate to the baseline pressure. Introduce high-purity oxygen (O2) and maintain a certain operating pressure (e.g., 0.1 - 1 Torr). Apply radio frequency (RF) power (e.g., 50W - 200W) for 1-10 minutes. After treatment, remove the glass slide and use it immediately (surface activity will decay over time).

[0028] (II) Specific operational steps for micro / nano structures of micron-sized TiO2 loaded with nano-sized TiO2: 1. Prepare the substrate dispersion: Add the weighed 1μm titanium dioxide particles (0.5-1.0g) to a three-necked flask (or a round-bottom flask) equipped with a magnetic stir bar.

[0029] Add 80 ml of anhydrous ethanol. Add dispersant (e.g., 0.2 g PVP). Place the flask on a magnetic stirrer and stir vigorously. Ultrasonic dispersion: Place the flask in an ultrasonic water bath and sonicate for 30-60 minutes until the particles are uniformly dispersed without significant sedimentation or agglomeration. (Stirring can be paused during this process and resumed after ultrasonication). Connect the condenser (to prevent solvent evaporation, especially during subsequent heating). Connect the thermometer and heat to the set temperature (40°C-60°C).

[0030] 2. Preparation of catalyst solution: In a small test tube or beaker, add 50 μl of concentrated nitric acid to 1 ml of anhydrous ethanol and mix thoroughly. (If using other catalysts such as concentrated ammonia, adjust the ratio accordingly). Label this solution A.

[0031] 3. Preparation of precursor solution: In a dry glass bottle or syringe, measure 1.0 ml of tetraisopropyl titanate (or tetra-n-butyl titanate) and add it to 10 ml of anhydrous ethanol. Mix well. Label this solution as Solution B. This solution should be prepared fresh and kept sealed before use.

[0032] 4. Introduction of a catalyst: Using a syringe pump or a constant-pressure dropping funnel, slowly add solution A (catalyst) dropwise (e.g., 1 drop / second or slower) to the vigorously stirred base dispersion. After the addition is complete, stir for another 10-15 minutes to allow the catalyst to distribute evenly in the system.

[0033] 5. Controlled hydrolysis (core step): Using a syringe pump or a constant-pressure dropping funnel, add solution B (precursor) very slowly (e.g., 1 drop / 5-10 seconds, or even slower; flow rate is critical) to the reaction system with continuous vigorous stirring.

[0034] Key points: The dropping rate is crucial to success. The slower the better. The goal is to allow precursor molecules sufficient time to diffuse to the surface of the micron-sized particles and be adsorbed, hydrolyzing and condensing on their surface, rather than agglomerating in solution. Rapid dropping inevitably leads to the formation of a large number of free nanoparticles.

[0035] Maintain good mixing: Ensure the entire system is mixed evenly to avoid localized excessive concentrations.

[0036] Observation: The solution should remain clear or slightly turbid (from micron-sized particles) and should not rapidly turn white or produce a large amount of precipitate (this is a sign of free nucleation). If turbidity occurs, stop adding the solution immediately, stir and observe for a few minutes. If the turbidity does not disappear or worsens, the reaction is out of control, and the experiment needs to be terminated and the parameters adjusted (reduce the precursor concentration, slow down the dropping rate, and lower the temperature).

[0037] The dripping process takes 1-2 hours or even longer (depending on the dripping rate and the total amount of precursor).

[0038] 6. Aging reaction: After the precursor solution is completely added, continue stirring and react at the set temperature (40-60℃) for 5-6 hours. This allows the titanium species adsorbed on the surface to fully hydrolyze and condense to form nanoparticles.

[0039] 7. Termination of reaction and dilution: Stop heating and allow the system to cool to room temperature. Add a large amount (at least 200 ml) of anhydrous ethanol to dilute the reaction system, significantly reducing the concentration of reactants and essentially terminating the reaction.

[0040] 8. Separation and washing: Transfer the reaction mixture into centrifuge tubes.

[0041] Centrifugal separation: Centrifuge at a relatively high speed (e.g., 8000-10000 rpm, 10-15 minutes) to precipitate the loaded micron particles.

[0042] Carefully discard the supernatant: The supernatant may contain unreacted precursors, byproducts (alcohols), dispersants, and most importantly, free titanium dioxide nanoparticles. Thorough removal of these free particles is one of the core objectives of this step.

[0043] Washing: Redisperse the precipitate with anhydrous ethanol, sonicate for 5 minutes to aid dispersion, and centrifuge again. Repeat this washing process at least 5-6 times until the supernatant is completely clear and transparent (indicating that free nanoparticles and soluble matter have been largely removed). A final wash with deionized water 1-2 times is recommended.

[0044] 9. Drying: Transfer the final precipitate to petri dishes or petri dishes and dry in an oven at 60-80°C overnight (12-24 hours).

[0045] 10. Calcination: Place the dried powder into a crucible. Calcinate in a muffle furnace under air atmosphere. Heating program: Increase the temperature to 350-450°C (e.g., 400°C) at a rate of 1-5°C / min, hold for 2 hours, and then cool to room temperature in the furnace.

[0046] Purpose of calcination: To completely remove organic matter such as PVP, to crystallize the newly generated titanium dioxide nanoparticles (usually anatase phase), and to enhance the bonding force between the nanoparticles and the micron substrate (through sintering neck formation).

[0047] (III) The superhydrophobic modification process of TiO2 with micro / nano structures; 1. Preparation process: By weight, 1 part of micro / nano TiO2 particles are placed in 100 parts of ethanol and sonicated for 1 hour to fully dissolve the TiO2 particles. After sonication, the particles are transferred to a three-necked flask equipped with a mechanical stirrer and a reflux condenser. The flask is heated to 80°C, and 2 parts of hexadecyltrimethoxysilane are added to modify the nanoparticles for hydrophobicity (reaction for 6-8 hours) to make the micro / nano TiO2 particles superhydrophobic.

[0048] 2. Separation and washing: Transfer the reaction mixture into centrifuge tubes.

[0049] Centrifugal separation: Centrifuge at a relatively high speed (e.g., 8000-10000 rpm, 10-15 minutes) to precipitate the loaded micron particles.

[0050] Carefully discard the supernatant: The supernatant may contain unreacted precursors, byproducts (alcohols), dispersants, and most importantly, free titanium dioxide nanoparticles.

[0051] 3. Washing: Redisperse the precipitate with anhydrous ethanol, sonicate for 5 minutes to aid dispersion, and centrifuge again. Repeat this washing process at least 5-6 times until the supernatant is completely clear and transparent (indicating that free nanoparticles and soluble matter have been largely removed). A final wash with deionized water 1-2 times is recommended.

[0052] 4. Drying: Transfer the final precipitate to petri dishes or petri dishes and dry in an oven at 60-80°C overnight (12-24 hours).

[0053] 5. Calcination: Place the dried powder into a crucible. Calcinate in a muffle furnace under air atmosphere. Heating program: Increase the temperature to 350-450°C (e.g., 400°C) at a rate of 1-5°C / min, hold for 2 hours, and then cool to room temperature in the furnace.

[0054] (iv) Preparation of spraying solution using superhydrophobic TiO2 particles and PDMS: 1. Dispersing TiO2: Add 1.2g of superhydrophobic nano TiO2 to 8ml of toluene, and sonicate in an ice bath (300W, 40kHz) for 30min to obtain a uniform suspension.

[0055] 2. Coupling treatment: Add 0.08g KH-560 and stir magnetically (500rpm) for 40min → silane reacts with TiO2 surface.

[0056] 3. Premix PDMS: In another container, mix PDMS-A glue and B glue at a ratio of 10:1, stir for 5 minutes, and let stand for 10 minutes to defoam.

[0057] 4. Mixed solution: Add the PDMS mixture to the TiO2 dispersion, add toluene to a total volume of 10 ml, and stir in the dark (60℃ water bath, 300 rpm) for 2 h.

[0058] 5. Add leveling agent: Add 0.01g BYK-333 and stir for 10 minutes → to obtain milky white spray liquid.

[0059] (V) Coating Preparation Spraying parameters: Spray gun type: Gravity spray gun (0.3mm nozzle) → SATA Minijet 4 recommended.

[0060] Spraying air pressure: 0.25 MPa → constant air supply pressure.

[0061] Spraying distance: 10-30 cm (distance from gun muzzle to glass surface) The gun moves at a constant speed of 5-15 cm / s. Coating thickness 20±10 μm (wet film) monitored by film thickness gauge Spraying process: First coat: Spray a thin single layer (wet film thickness ≈ 10μm), and immediately place in an 80℃ oven for pre-curing for 5 minutes after spraying.

[0062] Second coat: Spray another layer perpendicular to the cross direction (wet film thickness ≈ 10μm), let it air dry at room temperature for 3 minutes to evaporate the solvent, pre-cur at 80-90℃ for 4-6 hours, and then anneal at 120-140℃ (2-4 hours).

[0063] The present invention will be further described in detail below with reference to specific embodiments. It should be noted that the specific embodiments are explanations of the present invention and not limitations thereof.

[0064] Example 1 (a) Glass pretreatment steps: Oxygen plasma treatment (O2Plasma): Equipment: Plasma cleaner. Procedure: Place the clean and dry photovoltaic glass into the plasma chamber. Evacuate to the baseline pressure. Introduce high-purity oxygen (O2) and maintain a certain operating pressure (e.g., -0.5 Torr). Apply radio frequency (RF) power (125W) for 5 minutes. After treatment, remove the glass slide and use it immediately (surface activity will decay over time).

[0065] (II) Specific operational steps for micro / nano structures of micron-sized TiO2 loaded with nano-sized TiO2: 1. Prepare the substrate dispersion: Add the weighed 1μm titanium dioxide particles (0.75g) to a three-necked flask equipped with a magnetic stir bar.

[0066] Add 80 ml of anhydrous ethanol. Add dispersant (0.2 g PVP). Place the flask on a magnetic stirrer and stir vigorously. Ultrasonic dispersion: Place the flask in an ultrasonic water bath and sonicate for 45 minutes until the particles are uniformly dispersed without significant sedimentation or agglomeration. Connect the condenser. Connect the thermometer and heat to the set temperature (50°C).

[0067] 2. Preparation of catalyst solution: In a small beaker, add 50 μl of concentrated nitric acid to 1 ml of anhydrous ethanol and mix thoroughly. Label this solution A.

[0068] 3. Preparation of precursor solution: In a dry glass bottle, measure 1.0 ml of tetraisopropyl titanate and add it to 10 ml of anhydrous ethanol. Mix well. Label this solution B.

[0069] 4. Introduction of a catalyst: Using a syringe pump, slowly add solution A (catalyst) dropwise (1 drop / second) to the vigorously stirred base dispersion. After the addition is complete, stir for another 12 minutes to allow the catalyst to distribute evenly in the system.

[0070] 5. Controlled hydrolysis: Using a syringe pump or a constant-pressure dropping funnel, add solution B (precursor) very slowly (1 drop / 7.5 seconds) to the reaction system under continuous vigorous stirring.

[0071] 6. Aging reaction: After the precursor solution is added, continue stirring and react at the set temperature (50°C) for 5.5 hours.

[0072] 7. Termination of reaction and dilution: Stop heating and allow the system to cool to room temperature. Add a large amount (at least 200 ml) of anhydrous ethanol to dilute the reaction system, significantly reducing the concentration of reactants and essentially terminating the reaction.

[0073] 8. Separation and washing: Transfer the reaction mixture into centrifuge tubes.

[0074] Centrifugation: Centrifuge at a relatively high speed (e.g., 9000 rpm, 12.5 minutes) to precipitate the loaded micron particles.

[0075] Washing: Redisperse the precipitate with anhydrous ethanol, sonicate for 5 minutes to aid dispersion, and centrifuge again. Repeat this washing process at least 5 times until the supernatant is completely clear. A final wash with deionized water may be performed.

[0076] 9. Drying: The final precipitate was transferred to a petri dish and dried overnight (18 hours) in an oven at 70°C.

[0077] 10. Calcination: The dried powder is placed in a crucible. Calcination is carried out in a muffle furnace under an air atmosphere. Heating program: Heat to 400°C at a rate of 3°C / min, hold for 2 hours, and then cool to room temperature with the furnace.

[0078] (III) The superhydrophobic modification process of TiO2 with micro / nano structures; 1. Preparation process: By weight, 1 part of micro / nano TiO2 particles were placed in 100 parts of ethanol and sonicated for 1 hour to fully dissolve the TiO2 particles. After sonication, the particles were transferred to a three-necked flask equipped with a mechanical stirrer and a reflux condenser. The flask was heated to 80°C, and 2 parts of hexadecyltrimethoxysilane were added to modify the nanoparticles for hydrophobicity (reaction for 7 hours) to make the micro / nano TiO2 particles superhydrophobic.

[0079] 2. Separation and washing: Transfer the reaction mixture into centrifuge tubes.

[0080] Centrifugation: Centrifuge at a relatively high speed (e.g., 9000 rpm, 12.5 minutes) to precipitate the loaded micron-sized particles. Discard the supernatant.

[0081] 3. Washing: Redisperse the precipitate with anhydrous ethanol, sonicate for 5 minutes to aid dispersion, and centrifuge again. Repeat this washing process at least 5 times until the supernatant is completely clear and transparent (indicating that free nanoparticles and soluble matter have been largely removed). A final wash with deionized water is recommended.

[0082] 4. Drying: Transfer the final precipitate to petri dishes or petri dishes and dry in an oven at 70°C overnight (18 hours).

[0083] 5. Calcination: The dried powder is placed in a crucible. Calcination is carried out in a muffle furnace under an air atmosphere. Heating program: Heat to 400°C at a rate of 3°C / min, hold for 2 hours, and then cool to room temperature with the furnace.

[0084] (iv) Preparation of spraying solution using superhydrophobic TiO2 particles and PDMS: 1. Dispersing TiO2: Add 1.2g of superhydrophobic nano TiO2 to 8ml of toluene, and sonicate in an ice bath (300W, 40kHz) for 30min to obtain a uniform suspension.

[0085] 2. Coupling treatment: Add 0.08g KH-560 and stir magnetically (500rpm) for 40min → silane reacts with the TiO2 surface to obtain TiO2 dispersion.

[0086] 3. Premixed PDMS: In another container, mix PDMS-A glue and B glue at a ratio of 10:1, stir for 5 minutes, and let stand for 10 minutes to defoam, to obtain the PDMS mixture.

[0087] 4. Mixed solution: Add the PDMS mixture to the TiO2 dispersion, add toluene to a total volume of 10 ml, and stir in the dark (60℃ water bath, 300 rpm) for 2 h.

[0088] 5. Add leveling agent: Add 0.01g BYK-333 and stir for 10 minutes → to obtain milky white spray liquid.

[0089] (V) Coating Preparation Spraying parameters: Spray gun type: Gravity spray gun (0.3mm nozzle) → SATA Minijet 4.

[0090] Spraying air pressure: 0.25 MPa → constant air supply pressure.

[0091] Spraying distance: 10-30 cm (distance from gun muzzle to glass surface) Gun movement speed: 5-15 cm / s, constant speed movement Coating thickness: 20±10 μm (wet film), monitored by film thickness gauge Spraying process: First coat: Spray a thin single layer (wet film thickness ≈ 10μm), and immediately place in an 80℃ oven for pre-curing for 5 minutes after spraying.

[0092] Second coat: Spray another layer perpendicular to the cross direction (wet film thickness ≈ 10 μm), let it air dry at room temperature for 3 minutes to evaporate the solvent, pre-cure at 85℃ for 5 hours, and then anneal at 130℃ for 3 hours.

[0093] Example 2 (a) Glass pretreatment steps: Oxygen plasma treatment (O2Plasma): Equipment: Plasma cleaner. Procedure: Place the clean, dry photovoltaic glass into the plasma chamber. Evacuate to the baseline pressure. Introduce high-purity oxygen (O2) to maintain a certain operating pressure (e.g., 0.1 Torr). Apply radio frequency (RF) power (200W) for 1 minute. After treatment, remove the glass and use it immediately (surface activity will decay over time).

[0094] (II) Specific operational steps for micro / nano structures of micron-sized TiO2 loaded with nano-sized TiO2: 1. Prepare the substrate dispersion: Add the weighed 1μm titanium dioxide particles (0.5g) to a three-necked flask equipped with a magnetic stir bar.

[0095] Add 80 ml of anhydrous ethanol. Add dispersant (0.2 g PVP). Place the flask on a magnetic stirrer and stir vigorously. Ultrasonic dispersion: Place the flask in an ultrasonic water bath and sonicate for 30 minutes until the particles are uniformly dispersed without significant sedimentation or agglomeration. Connect the condenser. Connect the thermometer and heat to the set temperature (60°C).

[0096] 2. Preparation of catalyst solution: In a small beaker, add 50 μl of concentrated nitric acid to 1 ml of anhydrous ethanol and mix thoroughly. Label this solution A.

[0097] 3. Preparation of precursor solution: In a dry glass bottle, measure 1.0 ml of tetraisopropyl titanate (or tetrabutyl titanate) and add it to 10 ml of anhydrous ethanol. Mix well. Label this solution B.

[0098] 4. Introduction of a catalyst: Using a syringe pump, slowly add solution A (catalyst) dropwise (1 drop / second) to the vigorously stirred base dispersion. After the addition is complete, stir for another 10 minutes to allow the catalyst to distribute evenly in the system.

[0099] 5. Controlled hydrolysis: Using a syringe pump or a constant-pressure dropping funnel, add solution B (precursor) very slowly (1 drop / 5-10 seconds) to the reaction system under continuous vigorous stirring.

[0100] 6. Aging reaction: After the precursor solution is added dropwise, continue stirring and react for 6 hours at the set temperature (40°C).

[0101] 7. Termination of reaction and dilution: Stop heating and allow the system to cool to room temperature. Add a large amount (at least 200 ml) of anhydrous ethanol to dilute the reaction system, significantly reducing the concentration of reactants and essentially terminating the reaction.

[0102] 8. Separation and washing: Transfer the reaction mixture into centrifuge tubes.

[0103] Centrifugation: Centrifuge at a relatively high speed (e.g., 8000 rpm, 15 minutes) to precipitate the loaded micron particles.

[0104] Washing: Redisperse the precipitate with anhydrous ethanol, sonicate for 5 minutes to aid dispersion, and centrifuge again. Repeat this washing process at least 6 times until the supernatant is completely clear. The final wash can be performed twice with deionized water.

[0105] 9. Drying: The final precipitate was transferred to a petri dish and dried overnight (12 hours) in an oven at 60°C.

[0106] 10. Calcination: The dried powder is placed in a crucible. Calcination is carried out in a muffle furnace under an air atmosphere. Heating program: Heat to 350°C at a rate of 1°C / min, hold for 2 hours, and then cool to room temperature with the furnace.

[0107] (III) The superhydrophobic modification process of TiO2 with micro / nano structures; 1. Preparation process: By weight, 1 part of micro / nano TiO2 particles were placed in 100 parts of ethanol and sonicated for 1 hour to fully dissolve the TiO2 particles. After sonication, the particles were transferred to a three-necked flask equipped with a mechanical stirrer and a reflux condenser. The flask was heated to 80°C, and 2 parts of hexadecyltrimethoxysilane were added to modify the nanoparticles for hydrophobicity (reaction for 6 hours) to make the micro / nano TiO2 particles superhydrophobic.

[0108] 2. Separation and washing: Transfer the reaction mixture into centrifuge tubes.

[0109] Centrifugation: Centrifuge at a relatively high speed (e.g., 8000 rpm, 15 minutes) to precipitate the loaded micron-sized particles. Discard the supernatant.

[0110] 3. Washing: Redisperse the precipitate with anhydrous ethanol, sonicate for 5 minutes to aid dispersion, and centrifuge again. Repeat this washing process at least 5 times until the supernatant is completely clear and transparent (indicating that free nanoparticles and soluble matter have been largely removed). A final wash with deionized water can be performed twice.

[0111] 4. Drying: Transfer the final precipitate to petri dishes or petri dishes and dry in an oven at 60°C overnight (24 hours).

[0112] 5. Calcination: The dried powder is placed in a crucible. Calcination is carried out in a muffle furnace under an air atmosphere. Heating program: Heat to 350°C at a rate of 1°C / min, hold for 2 hours, and then cool to room temperature with the furnace.

[0113] (iv) Preparation of spraying solution using superhydrophobic TiO2 particles and PDMS: 1. Dispersing TiO2: Add 1.2g of superhydrophobic nano TiO2 to 8ml of toluene, and sonicate in an ice bath (300W, 40kHz) for 30min to obtain a uniform suspension.

[0114] 2. Coupling treatment: Add 0.08g KH-560 and stir magnetically (500rpm) for 40min → silane reacts with the TiO2 surface to obtain TiO2 dispersion.

[0115] 3. Premixed PDMS: In another container, mix PDMS-A glue and B glue at a ratio of 10:1, stir for 5 minutes, and let stand for 10 minutes to defoam, to obtain the PDMS mixture.

[0116] 4. Mixed solution: Add the PDMS mixture to the TiO2 dispersion, add toluene to a total volume of 10 ml, and stir in the dark (60℃ water bath, 300 rpm) for 2 h.

[0117] 5. Add leveling agent: Add 0.01g BYK-333 and stir for 10 minutes → to obtain milky white spray liquid.

[0118] (V) Coating Preparation Spraying parameters: Spray gun type: Gravity spray gun (0.3mm nozzle) → SATA Minijet 4.

[0119] Spraying air pressure: 0.25 MPa → constant air supply pressure.

[0120] Spraying distance: 10-30 cm (distance from gun muzzle to glass surface) Gun movement speed: 5-15 cm / s, constant speed movement Coating thickness: 20±10 μm (wet film), monitored by film thickness gauge Spraying process: First coat: Spray a thin single layer (wet film thickness ≈ 10μm), and immediately place in an 80℃ oven for pre-curing for 5 minutes after spraying.

[0121] Second coat: Spray another layer perpendicular to the cross direction (wet film thickness ≈ 10 μm), let it air dry at room temperature for 3 minutes to evaporate the solvent, pre-cure at 80℃ for 4 hours, and then anneal at 120℃ (4 hours).

[0122] Example 3 (a) Glass pretreatment steps: Oxygen plasma treatment (O2Plasma): Equipment: Plasma cleaner. Procedure: Place the clean and dry photovoltaic glass into the plasma chamber. Evacuate to the baseline pressure. Introduce high-purity oxygen (O2) and maintain a certain working pressure (1 Torr). Apply radio frequency (RF) power (200W) for 1 minute. After treatment, remove the glass slide and use it immediately (surface activity will decay over time).

[0123] (II) Specific operational steps for micro / nano structures of micron-sized TiO2 loaded with nano-sized TiO2: 1. Prepare the substrate dispersion: Add the weighed 1μm titanium dioxide particles (1.0g) to a three-necked flask equipped with a magnetic stir bar.

[0124] Add 80 ml of anhydrous ethanol. Add dispersant (0.2 g PVP). Place the flask on a magnetic stirrer and stir vigorously. Ultrasonic dispersion: Place the flask in an ultrasonic water bath and sonicate for 60 minutes until the particles are uniformly dispersed without significant sedimentation or agglomeration. Connect the condenser. Connect the thermometer and heat to the set temperature (40°C).

[0125] 2. Preparation of catalyst solution: In a small beaker, add 50 μl of concentrated nitric acid to 1 ml of anhydrous ethanol and mix thoroughly. Label this solution A.

[0126] 3. Preparation of precursor solution: In a dry glass bottle, measure 1.0 ml of tetraisopropyl titanate (or tetrabutyl titanate) and add it to 10 ml of anhydrous ethanol. Mix well. Label this solution B.

[0127] 4. Introduction of a catalyst: Using a syringe pump, slowly add solution A (catalyst) dropwise (1 drop / second) to the vigorously stirred base dispersion. After the addition is complete, stir for another 15 minutes to allow the catalyst to distribute evenly in the system.

[0128] 5. Controlled hydrolysis: Using a syringe pump or a constant-pressure dropping funnel, add solution B (precursor) very slowly (1 drop / 10 seconds) to the reaction system under continuous vigorous stirring.

[0129] 6. Aging reaction: After the precursor solution is added dropwise, continue stirring and react for 5 hours at the set temperature (60°C).

[0130] 7. Termination of reaction and dilution: Stop heating and allow the system to cool to room temperature. Add a large amount (at least 200 ml) of anhydrous ethanol to dilute the reaction system, significantly reducing the concentration of reactants and essentially terminating the reaction.

[0131] 8. Separation and washing: Transfer the reaction mixture into centrifuge tubes.

[0132] Centrifugation: Centrifuge at a relatively high speed (10,000 rpm, 10 minutes) to precipitate the loaded micron particles.

[0133] Washing: Redisperse the precipitate with anhydrous ethanol, sonicate for 5 minutes to aid dispersion, and centrifuge again. Repeat this washing process at least 6 times until the supernatant is completely clear. The final wash can be performed twice with deionized water.

[0134] 9. Drying: The final precipitate was transferred to a petri dish and dried overnight (12 hours) in an oven at 80°C.

[0135] 10. Calcination: The dried powder is placed in a crucible. Calcination is then carried out in a muffle furnace under an air atmosphere. Heating program: Heat to 450°C at a rate of 5°C / min, hold for 2 hours, then cool to room temperature with the furnace.

[0136] (III) The superhydrophobic modification process of TiO2 with micro / nano structures; 1. Preparation process: By weight, 1 part of micro / nano TiO2 particles were placed in 100 parts of ethanol and sonicated for 1 hour to fully dissolve the TiO2 particles. After sonication, the particles were transferred to a three-necked flask equipped with a mechanical stirrer and a reflux condenser. The flask was heated to 80°C, and 2 parts of hexadecyltrimethoxysilane were added to modify the nanoparticles for hydrophobicity (reaction for 8 hours) to make the micro / nano TiO2 particles superhydrophobic.

[0137] 2. Separation and washing: Transfer the reaction mixture into centrifuge tubes.

[0138] Centrifugation: Centrifuge at a relatively high speed (10,000 rpm, 10 minutes) to precipitate the loaded micron-sized particles. Discard the supernatant.

[0139] 3. Washing: Redisperse the precipitate with anhydrous ethanol, sonicate for 5 minutes to aid dispersion, and centrifuge again. Repeat this washing process at least 6 times until the supernatant is completely clear and transparent (indicating that free nanoparticles and soluble matter have been largely removed). A final wash with deionized water is recommended.

[0140] 4. Drying: Transfer the final precipitate to petri dishes or petri dishes and dry in an oven at 80°C overnight (12 hours).

[0141] 5. Calcination: The dried powder is placed in a crucible. Calcination is then carried out in a muffle furnace under an air atmosphere. Heating program: Heat to 450°C at a rate of 5°C / min, hold for 2 hours, then cool to room temperature with the furnace.

[0142] (iv) Preparation of spraying solution using superhydrophobic TiO2 particles and PDMS: 1. Dispersing TiO2: Add 1.2g of superhydrophobic nano TiO2 to 8ml of toluene, and sonicate in an ice bath (300W, 40kHz) for 30min to obtain a uniform suspension.

[0143] 2. Coupling treatment: Add 0.08g KH-560 and stir magnetically (500rpm) for 40min → silane reacts with the TiO2 surface to obtain TiO2 dispersion.

[0144] 3. Premixed PDMS: In another container, mix PDMS-A glue and B glue at a ratio of 10:1, stir for 5 minutes, and let stand for 10 minutes to defoam, to obtain the PDMS mixture.

[0145] 4. Mixed solution: Add the PDMS mixture to the TiO2 dispersion, add toluene to a total volume of 10 ml, and stir in the dark (60℃ water bath, 300 rpm) for 2 h.

[0146] 5. Add leveling agent: Add 0.01g BYK-333 and stir for 10 minutes → to obtain milky white spray liquid.

[0147] (V) Coating Preparation Spraying parameters: Spray gun type: Gravity spray gun (0.3mm nozzle) → SATA Minijet 4.

[0148] Spraying air pressure: 0.25 MPa → constant air supply pressure.

[0149] Spraying distance: 10-30 cm (distance from gun muzzle to glass surface) Gun movement speed: 5-15 cm / s, constant speed movement Coating thickness: 20±10 μm (wet film), monitored by film thickness gauge Spraying process: First coat: Spray a thin single layer (wet film thickness ≈ 10μm), and immediately place in an 80℃ oven for pre-curing for 5 minutes after spraying.

[0150] Second coat: Spray another layer perpendicular to the cross direction (wet film thickness ≈ 10μm), let it air dry at room temperature for 3 minutes to evaporate the solvent, pre-cur at 90℃ for 4 hours, and then anneal at 140℃ for 2 hours.

[0151] Comparative Example 1 The difference from Example 1 is that step (a) is omitted and the glass surface is not hydroxylated.

[0152] Comparative Example 2 The difference from Example 1 is that in step (iii), micron-sized TiO2 of equal mass is used instead of micro / nano TiO2 particles.

[0153] Comparative Example 3 The difference from Example 1 is that in step (iii), nano-sized TiO2 of equal mass is used instead of micro-nano TiO2 particles.

[0154] Comparative Example 4 The difference from Example 1 is that, “micro-nano structured TiO2 particles” were prepared according to the method in Section 5.2.2 of the paper “Micro-nano structured TiO2 particles and functional research on superhydrophobic titanium-silicon composite surface - Jiang Qi”. In step (iii), the above-mentioned “micro-nano structured TiO2 particles” of equal mass were used to replace the micro-nano TiO2 particles. The specific preparation methods for "micro-nano structured TiO2 particles" include: (1) Take 0.75g of micron-sized TiO2 and disperse it in 100 mL of ethanol solution, and sonicate it for 15 min to obtain a suspension of microspheres; (2) Add 1.0 ml of tetraisopropyl titanate and dispersant PVP (0.2 g) to 100 mL of ethanol, mix well, and then use a peristaltic pump to add the mixture at a uniform drip rate (5 mL·min). -1 Add it to the suspension of microspheres and continue stirring; (3) Add 1.2 g of deionized water and react for 2 h in a water bath at 80°C.

[0155] (4) After the reaction is complete, the product is washed three times by centrifugation with ethanol and dried at 80°C to obtain a powder sample; (5) The obtained powder sample was calcined at 600℃ for 3 h.

[0156] The contact angle and interlayer adhesion of the coatings prepared in the above embodiments and comparative examples were tested, and the test results are shown in Table 1: Table 1. Performance test results of the examples and comparative examples.

[0157] As can be seen from the descriptions in Examples 1-3, the coating prepared by the present invention has superior superhydrophobic properties, which can meet the requirements of self-cleaning and dust prevention. At the same time, the interlayer bonding force between the glass and the coating is superior, which can meet the requirements of long-term use.

[0158] As can be seen from the comparison between Example 1 and Comparative Example 1, the interlayer bonding between the unhydroxylated glass and the coating is poor, and the superhydrophobicity of the coating is also slightly reduced.

[0159] As can be seen from the comparison of Example 1 and Comparative Examples 2 and 3, the coating prepared by the micro-nano TiO2 particles of the present invention has better superhydrophobic properties compared with nano-sized TiO2 or micron-sized TiO2, and the interlayer bonding force is also slightly improved.

[0160] As can be seen from the comparison between Example 1 and Comparative Example 4, different preparation methods will affect the hydrophobic modification effect of micro-nano TiO2 particles. Compared with the existing methods, the micro-nano TiO2 particles prepared by the present invention have better hydrophobic modification effect and better interlayer bonding force.

[0161] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing self-cleaning, dust-resistant glass, characterized in that, include: The glass is modified by hydroxylation to obtain pretreated glass; After uniformly mixing micron-sized TiO2 solution and catalyst, a titanium source is added, followed by hydrolysis and condensation reaction, aging reaction, solid-liquid separation, washing, drying, and calcination to obtain TiO2 with micro-nano structure. A dispersion of TiO2 with micro-nano structure was prepared, and a first silane coupling agent was added for hydrophobic modification. The mixture was then separated into solid and liquid phases, washed, dried, and calcined to obtain superhydrophobic TiO2 particles. A superhydrophobic TiO2 particle suspension was prepared, and a second silane coupling agent was added to react and obtain a superhydrophobic TiO2 particle mixture. Mix PDMS A and B components to obtain a PDMS mixture; The PDMS mixture was added to the superhydrophobic TiO2 particle mixture and mixed evenly to carry out the reaction. After the reaction was completed, a leveling agent was added and mixed evenly to obtain the spraying liquid. The coating liquid is applied to the pretreated glass to obtain the final product.

2. The method for preparing self-cleaning, dust-resistant glass as described in claim 1, characterized in that, The hydroxylation modification method includes: oxygen plasma treatment, strong oxidizing acid cleaning, alkali treatment, ultraviolet ozone cleaning, and acid treatment.

3. The method for preparing self-cleaning, dust-resistant glass as described in claim 1, characterized in that, The conditions for oxygen plasma treatment are: working pressure 0.1-1 Torr, radio frequency power 50W-200W, and treatment time 1-10 minutes.

4. The method for preparing self-cleaning, dust-resistant glass as described in claim 1, characterized in that, The catalyst is concentrated nitric acid or concentrated ammonia.

5. The method for preparing self-cleaning, dust-resistant glass as described in claim 1, characterized in that, The aging reaction is carried out at 40-60°C for 5-6 hours.

6. The method for preparing self-cleaning, dust-resistant glass as described in claim 1, characterized in that, The calcination conditions are to hold at 350-450℃ for 1.5-2 hours, or at 400℃ for 2 hours.

7. The method for preparing self-cleaning, dust-resistant glass as described in claim 1, characterized in that, The first silane coupling agent is hexadecyltrimethoxysilane; Alternatively, the mass ratio of the first silane coupling agent to TiO2 with micro / nano structures is 2-4:1; Alternatively, the second silane coupling agent is KH-560; Alternatively, the mass ratio of the second silane coupling agent to the superhydrophobic TiO2 particles is 1-2:

15.

8. The method for preparing self-cleaning, dust-resistant glass as described in claim 1, characterized in that, The spraying steps include: after spraying the first layer, spraying the second layer in a perpendicular and intersecting direction, letting it stand, pre-curing at 80-90℃ for 4-6 hours, and annealing at 120-140℃ for 2-4 hours.

9. The self-cleaning, dust-resistant glass prepared by the method according to any one of claims 1-8.

10. The application of the self-cleaning, dust-resistant glass according to claim 9 in the manufacture of a photovoltaic power generation system.

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