High resistivity anti-fog conductive glass and method of making same

Abstract

The present application relates to the technical field of conductive glass, and particularly relates to a high-resistivity anti-fog conductive glass and a preparation method thereof. The glass is composed of a glass substrate, a tin dioxide conductive layer, an organic-inorganic network layer, tin oxide nano nodes and an amphiphilic ion polymer brush layer, and the like. The preparation process comprises the following steps: spray pyrolysis deposition of the tin dioxide layer, immersion to form an organic-inorganic hybrid layer, in-situ generation of tin oxide nano nodes, and covalent grafting of the amphiphilic ion polymer brush layer, while functionalized Janus nanoparticles are introduced to improve the interface bonding and the durability of the coating. The multi-layer synergistic structure gives the glass high surface resistivity, good light transmission, low haze and the like, and the glass has excellent passive anti-fog, self-cleaning and anti-static properties, significantly reduces energy consumption, improves long-term stability, and is suitable for use in the fields of automobiles and buildings.

Description

Technical Field

[0001] This invention relates to the field of conductive glass technology, and in particular to a high resistivity anti-fog conductive glass and its preparation method. Background Technology

[0002] With the increasing demands for energy conservation in buildings and the rapid development of intelligent building technologies, anti-fog conductive glass, as a new type of functional material, is widely used in automotive windshields, building curtain walls, electronic display devices, and other fields. Traditional anti-fog glass mainly relies on the principle of heating to remove fog. This is achieved by preparing a low-resistivity transparent conductive film, such as indium tin oxide (ITO) film, on the glass surface. When a voltage is applied, a Joule heating effect is generated, raising the surface temperature of the glass and thus evaporating surface droplets or preventing water vapor condensation.

[0003] However, existing low-resistivity heating defogging solutions face several technical bottlenecks. First, the fabrication of low-resistivity ITO films typically requires the expensive precious metal indium. With indium resources becoming increasingly scarce, material costs are constantly rising, limiting its large-scale industrial application. Second, low-resistivity conductive films generate significant Joule heat during operation, leading to high energy consumption, especially in continuous fogging environments where prolonged heating is required, making energy consumption a significant issue and inconsistent with current green and energy-saving development trends. Furthermore, low-resistivity surfaces are prone to electrostatic adsorption, allowing dust and pollutants from the air to easily adhere to the glass surface, affecting transparency and aesthetics, and increasing subsequent cleaning and maintenance costs.

[0004] More importantly, traditional heated defogging solutions are active anti-fogging technologies that rely on an external power supply to function, which presents significant limitations in certain applications. For example, they cannot provide continuous anti-fogging protection for car windshields when the car is parked or for building glass during a power outage. Furthermore, uneven temperature distribution on the glass surface during heated defogging can lead to thermal stress concentration, affecting the glass's mechanical strength and lifespan.

[0005] In recent years, researchers have begun to explore passive anti-fogging technologies based on surface wettability control. This involves constructing a superhydrophilic coating on the glass surface, allowing water vapor to condense and rapidly spread to form a uniform, transparent water film, rather than light-scattering droplets, thus achieving an anti-fogging effect. The advantage of this approach is that it requires no external energy input, making it energy-saving and environmentally friendly. However, most existing superhydrophilic anti-fogging coatings use purely organic or purely inorganic material systems, resulting in poor durability and susceptibility to failure. While organic polymer coatings possess good film-forming properties and hydrophilicity control capabilities, they are prone to aging and degradation under environmental factors such as ultraviolet light irradiation and temperature changes. Inorganic oxide coatings, although chemically stable, have a limited density of hydrophilic groups on their surface, often resulting in less than ideal anti-fogging effects.

[0006] Furthermore, existing technologies often struggle to simultaneously achieve both anti-fogging and antistatic functions. Purely superhydrophilic coatings are typically insulating materials and cannot provide antistatic properties; while materials with a certain degree of conductivity often fail to achieve ideal superhydrophilic performance. Achieving both excellent passive anti-fogging performance and necessary antistatic functionality while maintaining high resistivity (to avoid high energy consumption) is a significant challenge in this technological field.

[0007] Therefore, there is an urgent need to develop a new technical solution that can achieve passive anti-fogging function of conductive glass under high resistivity conditions. This solution avoids the high energy consumption problem of traditional low-resistivity solutions and provides durable and stable anti-fogging and antistatic performance, meeting the comprehensive requirements of modern applications for energy saving, environmental protection, and high performance. Summary of the Invention

[0008] In view of this, the purpose of this invention is to provide a high resistivity anti-fog conductive glass and its preparation method, so as to achieve the passive anti-fog function of conductive glass while maintaining high resistivity.

[0009] To achieve the above objectives, the present invention provides a high resistivity anti-fog conductive glass, comprising a glass substrate and a tin dioxide conductive layer disposed on the surface of the glass substrate.

[0010] Preferably, the glass substrate has a length and width of 50×50mm and a thickness of 1.1mm.

[0011] An organic-inorganic network layer is formed by impregnation in an aqueous solution containing dopamine hydrochloride, methacrylate sulfobetaine monomer, copper sulfate pentahydrate and functionalized Janus nanoparticles, and the organic-inorganic network layer is disposed on the surface of the tin dioxide conductive layer.

[0012] Preferably, the weight ratio of dopamine hydrochloride, methacrylate sulfobetaine monomer, copper sulfate pentahydrate and functionalized Janus nanoparticles is 0.6-1.4:3-7:0.05-0.15:0.03-0.07.

[0013] Preferably, the organic-inorganic network layer is formed in an aqueous solution at pH 8.0-9.0 by dopamine oxidative self-polymerization in the presence of hydrogen peroxide.

[0014] Tin oxide nanonodes are generated in situ on the surface of the organic-inorganic network layer by sequentially immersing a substrate with the organic-inorganic network layer in an acidic solution and an alkaline solution containing tin tetrachloride.

[0015] Preferably, the acidic solution containing tin tetrachloride contains 0.3-0.7g of tin tetrachloride pentahydrate and 0.5-1.5mL of concentrated hydrochloric acid with a concentration of 37wt% per 100mL.

[0016] Preferably, the alkaline solution is ammonia water with a concentration of 28wt% and a content of 3-7mL per 100mL.

[0017] A zwitterionic polymer brush layer covalently grafted onto the surface of a glass substrate containing tin oxide nanonodes via surface-initiated atom transfer radical polymerization, the zwitterionic polymer brush layer being formed from a methacrylate sulfobetaine polymer.

[0018] Preferably, the surface-initiated atom transfer radical polymerization is carried out in an aqueous solution of methacrylate sulfobetaine monomer containing copper monobromide, copper dibromide and N,N,N',N',N'-pentamethyldiethylenetriamine.

[0019] The functionalized Janus nanoparticles were prepared by the following method:

[0020] S1: Alkenylated silica nanoparticles were obtained by grafting and modifying silica nanoparticles with vinyltriethoxysilane.

[0021] S2: Alkenylated silica nanoparticles are grafted with thiol-terminated polydimethylsiloxane in an oil-in-water system to obtain polydimethylsiloxane-modified silica nanoparticles.

[0022] S3: 3-Aminopropyltriethoxysilane grafted onto polydimethylsiloxane-modified silica nanoparticles and then reacted with 2-bromoisobutyryl bromide to obtain functionalized Janus nanoparticles.

[0023] Preferably, the average particle size of the silica nanoparticles in step S1 is 50 nm.

[0024] Preferably, in step S1, the weight ratio of silica nanoparticles to vinyltriethoxysilane is 5:1.5-2.5.

[0025] Preferably, in step S2, the weight ratio of alkenylated silica nanoparticles to mercapto-terminated polydimethylsiloxane is 5:0.6-1.4.

[0026] Preferably, in step S3, the weight ratio of polydimethylsiloxane-modified silica nanoparticles, 3-aminopropyltriethoxysilane, and 2-bromoisobutyryl bromide is 1:1.5-2.5:1.6-2.4.

[0027] Preferably, the surface resistivity of the high resistivity anti-fog conductive glass is 5.2 × 10⁻⁶. 8 Ω / sq up to 1.1×10 9 Ω / sq.

[0028] Preferably, the high resistivity anti-fog conductive glass has a light transmittance of not less than 89% and a haze of not more than 0.9%.

[0029] Furthermore, the present invention also provides a method for preparing high resistivity anti-fog conductive glass, comprising the following steps:

[0030] (1) A tin dioxide conductive layer was prepared on the surface of a glass substrate by spray pyrolysis deposition;

[0031] (2) An organic-inorganic network layer is formed by impregnating a glass substrate in an aqueous solution containing dopamine hydrochloride, methacrylate sulfobetaine monomer, copper sulfate pentahydrate and functionalized Janus nanoparticles.

[0032] (3) The glass substrate with the organic-inorganic network layer is immersed in acidic solution and alkaline solution containing tin tetrachloride in sequence to generate tin oxide nanonodes in situ on the surface.

[0033] (4) A zwitterionic polymer brush layer is grafted onto the surface of the glass substrate containing tin oxide nanonodes by surface-initiated atom transfer radical polymerization.

[0034] Preferably, the process conditions for spray pyrolysis deposition in step (1) are: substrate temperature 360-440℃, precursor solution atomization rate 1.5-2.5mL / min, deposition time 12-20min, and annealing temperature 380-420℃.

[0035] This invention achieves multiple technical advantages of high resistivity anti-fog conductive glass through the synergistic design of multi-level surface modification and interface engineering, resulting in the following significant beneficial effects:

[0036] Excellent passive anti-fogging effect: The synergistic design of the transparent conductive tin dioxide base layer prepared by spray pyrolysis process and the zwitterionic superhydrophilic coating gives the glass surface extremely strong hydration ability. The sulfonic acid groups and quaternary ammonium groups on the methacrylic acid sulfobetaine polymer molecular chain can form strong hydrogen bonds and electrostatic interactions with water molecules, promoting the rapid spread of condensate on the glass surface to form a uniform and transparent water film, effectively inhibiting the formation of light-scattering fog droplets, and achieving continuous anti-fogging function without external energy input.

[0037] High resistivity and antistatic properties coexist: The transparent conductive tin dioxide substrate and the in-situ generated tin oxide nanonodes form a special confined conductive network structure, providing a controllable charge conduction pathway while maintaining high sheet resistance. This conductivity mechanism near the penetration threshold avoids the high energy consumption problem of low-resistance solutions, effectively dissipates static charge accumulation, significantly reduces the electrostatic adsorption of dust and contaminants, and maintains the cleanliness and transparency of the glass surface.

[0038] The coating exhibits excellent stability and durability: the organic network formed by dopamine self-polymerization achieves strong adhesion to the glass substrate and oxide layer through coordination and π-π interactions, providing a stable interfacial bond for subsequent functional layers. The directional embedding of Janus silica nanoparticles provides microscopic support and interfacial bridging, significantly improving the coating's mechanical strength and peel resistance, and reducing the risk of failure under humid environments and mechanical stress.

[0039] Covalent grafting ensures long-term stability: The zwitterionic brush layer, constructed through surface-initiated atom transfer radical polymerization, forms covalent bonds with the substrate. Compared to physical adsorption or electrostatic assembly, it exhibits superior wash resistance, chemical corrosion resistance, and resistance to changes in ionic strength. This covalent grafting structure ensures the stability of anti-fogging performance during long-term use, effectively solving the technical problems of easy peeling and performance degradation of traditional coatings.

[0040] Multiple synergistic effects enhance overall performance: The interpenetrating hybrid structure of organic network and inorganic nodes achieves complementary advantages between the organic and inorganic phases, maintaining the flexibility and processing performance of the organic phase while obtaining the chemical stability and optical transparency of the inorganic phase. The amphiphilic nature of Janus nanoparticles enables them to be compatible with both hydrophilic and hydrophobic components, acting as an interfacial compatibilizer and optimizing the microstructure and macroscopic properties of the coating. Attached Figure Description

[0041] To more clearly illustrate the technical solutions in this invention or the prior art, the accompanying drawings used in the description of the embodiments or the prior art will be briefly introduced below.

[0042] Figure 1 The infrared spectra of silica nanoparticles, polydimethylsiloxane-modified silica nanoparticles, and functionalized Janus nanoparticles in Example 2 of this invention are shown.

[0043] Figure 2 The X-ray diffraction patterns of the glass surface coatings of the single-modified glass substrate, the double-modified glass substrate, and the triple-modified glass substrate in Embodiment 2 of the present invention are shown. Detailed Implementation

[0044] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments.

[0045] Example 1:

[0046] (1) Add 7g of tin tetrachloride pentahydrate and 1.5g of acetylacetone to a 500mL round-bottom flask, then add 200mL of anhydrous ethanol and 200mL of deionized water in sequence, and stir magnetically for 30min at room temperature to obtain a tin dioxide precursor solution.

[0047] (2) The glass substrate (Schott D263T eco thin glass, 50×50mm in length and width, and 1.1mm in thickness) was placed on the heating stage and heated to 360°C. The tin dioxide precursor solution was atomized at a rate of 1.5mL / min using an ultrasonic atomizer and transported to the substrate surface by a carrier gas (compressed air, flow rate 4L / min) for spray pyrolysis deposition. The deposition time was controlled to be 12min. Then, it was annealed at 380°C for 20min. After cooling to room temperature, a modified glass substrate was obtained.

[0048] (3) Disperse 5g of silica nanoparticles (average particle size 50nm) and 0.05mL of glacial acetic acid in 100mL of anhydrous ethanol and 1mL of deionized water, add 1.5g of vinyltriethoxysilane under nitrogen protection, stir and react at room temperature for 1.5h, centrifuge and wash, and vacuum dry to obtain alkenylated silica nanoparticles.

[0049] (4) Add 90 mL of n-hexadecane (oil phase) and 280 mL of deionized water to a separatory funnel, add 5 g of alkenylated silica nanoparticles, sonicate for 25 min, then add 0.6 g of mercapto-terminated polydimethylsiloxane (GelestDMS-SM21) and 0.03 g of photoinitiator 369 to the system, and carry out a sulfur-alkene click reaction for 20 min under 365 nm ultraviolet light irradiation to selectively graft polydimethylsiloxane onto the oil phase contact surface of the particles. After the reaction, the layers are separated, demulsified, washed with ethanol, and dried to obtain polydimethylsiloxane-modified silica nanoparticles.

[0050] (5) 1 g of polydimethylsiloxane-modified silica nanoparticles were dispersed in a mixed solution of 45 mL of anhydrous ethanol and 4 mL of deionized water. 1.5 g of 3-aminopropyltriethoxysilane was added and the mixture was refluxed at 55°C for 0.5 h to graft amino groups onto the hydrophilic side of the particles. After cooling, the particles were centrifuged, washed, and redispersed in 50 mL of dry dichloromethane. Then, 0.8 g of triethylamine and 1.6 g of 2-bromoisobutyryl bromide were added sequentially under ice bath conditions. The mixture was reacted for 30 min and washed with deionized water and ethanol, respectively, and dried to obtain functionalized Janus nanoparticles.

[0051] (6) Add 1000mL of deionized water to a 1L beaker, adjust the pH to 8.0 with ammonia (concentration 28wt%), then add 0.6g of dopamine hydrochloride, 3g of methacrylic acid sulfobetaine monomer and 0.05g of copper sulfate pentahydrate in sequence. After stirring and dissolving, add 0.5mL of hydrogen peroxide solution (concentration 30wt%) and 0.03g of functionalized Janus nanoparticles that can initiate polymerization. Sonicate for 20min, then completely immerse the first modified glass substrate in the solution and react for 8min. Remove, rinse with deionized water, and dry to obtain the second modified glass substrate.

[0052] (7) Immerse the double-modified glass substrate in a 100mL aqueous solution containing 0.3g tin tetrachloride pentahydrate and 0.5mL concentrated hydrochloric acid (concentration 37wt%) for 1.5min, then transfer it to a 100mL aqueous solution containing 3mL ammonia (concentration 28wt%) for 1.5min, remove it, rinse with deionized water, and dry it to obtain a triple-modified glass substrate;

[0053] (8) Dissolve 7g of methacrylic acid sulfobetaine monomer in 500mL of deionized water, add 0.15g of copper monobromide, 0.015g of copper dibromide and 0.3g of N,N,N',N',N''-pentamethyldiethylenetriamine, purge with nitrogen for 25min to remove oxygen, immerse the triple-modified glass substrate in it for 12min, take it out and soak it in 1000mL of aqueous solution containing 1g of disodium ethylenediaminetetraacetate dihydrate for 5min, then rinse with ethanol 3 times, and dry in an oven at 75°C for 50min to obtain high resistivity anti-fog conductive glass.

[0054] Example 2:

[0055] (1) Add 10g of tin tetrachloride pentahydrate and 2g of acetylacetone to a 500mL round-bottom flask, then add 200mL of anhydrous ethanol and 200mL of deionized water in sequence, and stir magnetically for 30min at room temperature to obtain a tin dioxide precursor solution.

[0056] (2) The glass substrate (Schott D263T eco thin glass, 50×50mm in length and width, and 1.1mm in thickness) was placed on the heating stage and heated to 400°C. The tin dioxide precursor solution was atomized at a rate of 2mL / min using an ultrasonic atomizer and transported to the substrate surface by a carrier gas (compressed air, flow rate 5L / min) for spray pyrolysis deposition. The deposition time was controlled to be 15min. Then, the substrate was annealed at 400°C for 30min. After cooling to room temperature, a modified glass substrate was obtained.

[0057] (3) Disperse 5g of silica nanoparticles (average particle size 50nm) and 0.1mL of glacial acetic acid in 100mL of anhydrous ethanol and 2mL of deionized water, add 2g of vinyltriethoxysilane under nitrogen protection, stir and react at room temperature for 2h, centrifuge and wash, and vacuum dry to obtain alkenylated silica nanoparticles.

[0058] (4) Add 100 mL of n-hexadecane (oil phase) and 300 mL of deionized water to a separatory funnel, add 5 g of alkenylated silica nanoparticles, sonicate for 30 min, then add 1 g of mercapto-terminated polydimethylsiloxane (GelestDMS-SM21) and 0.05 g of photoinitiator 369 to the system, and carry out a sulfur-alkene click reaction for 30 min under 365 nm ultraviolet light irradiation to selectively graft polydimethylsiloxane onto the oil phase contact surface of the particles. After the reaction, the layers are separated, demulsified, washed with ethanol, and dried to obtain polydimethylsiloxane-modified silica nanoparticles.

[0059] (5) 1g of polydimethylsiloxane-modified silica nanoparticles were dispersed in a mixed solution of 50mL anhydrous ethanol and 5mL deionized water. 2g of 3-aminopropyltriethoxysilane was added and the mixture was refluxed at 60°C for 1h to graft amino groups onto the hydrophilic side of the particles. After cooling, the particles were centrifuged, washed, and redispersed in 50mL of dry dichloromethane. Then, 1g of triethylamine and 2g of 2-bromoisobutyryl bromide were added sequentially under ice bath conditions. The mixture was reacted for 45min and washed with deionized water and ethanol, respectively, and dried to obtain functionalized Janus nanoparticles.

[0060] (6) Add 1000mL of deionized water to a 1L beaker, adjust the pH to 8.5 with ammonia (concentration 28wt%), then add 1g of dopamine hydrochloride, 5g of methacrylic acid sulfobetaine monomer and 0.1g of copper sulfate pentahydrate in sequence, stir to dissolve, then add 1mL of hydrogen peroxide solution (concentration 30wt%) and 0.05g of functionalized Janus nanoparticles that can initiate polymerization, sonicate for 30min, then completely immerse the first modified glass substrate in the solution and react for 10min, take it out, rinse with deionized water, dry, and obtain the second modified glass substrate;

[0061] (7) Immerse the double-modified glass substrate in a 100mL aqueous solution containing 0.5g tin tetrachloride pentahydrate and 1mL concentrated hydrochloric acid (concentration 37wt%) for 2min, then transfer it to a 100mL aqueous solution containing 5mL ammonia (concentration 28wt%) for 2min, remove it, rinse with deionized water, and dry it to obtain a triple-modified glass substrate.

[0062] (8) Dissolve 10g of methacrylic acid sulfobetaine monomer in 500mL of deionized water, add 0.2g of copper monobromide, 0.02g of copper dibromide and 0.4g of N,N,N',N',N''-pentamethyldiethylenetriamine, purge with nitrogen for 30min to remove oxygen, immerse the triple-modified glass substrate in it for 15min, take it out and soak it in 1000mL of aqueous solution containing 2g of disodium ethylenediaminetetraacetate dihydrate for 5min, then rinse with ethanol 3 times, and dry in an oven at 80°C for 60min to obtain high resistivity anti-fog conductive glass.

[0063] Example 3:

[0064] (1) Add 13g of tin tetrachloride pentahydrate and 2.5g of acetylacetone to a 500mL round-bottom flask, then add 200mL of anhydrous ethanol and 200mL of deionized water in sequence, and stir magnetically for 40min at room temperature to obtain a tin dioxide precursor solution.

[0065] (2) The glass substrate (Schott D263T eco thin glass, 50×50mm in length and width, and 1.1mm in thickness) was placed on the heating stage and heated to 440°C. The tin dioxide precursor solution was atomized at a rate of 2.5mL / min using an ultrasonic atomizer and transported to the substrate surface by a carrier gas (compressed air, flow rate 6L / min) for spray pyrolysis deposition. The deposition time was controlled to be 20min. Then, it was annealed at 420°C for 40min. After cooling to room temperature, a modified glass substrate was obtained.

[0066] (3) Disperse 5g of silica nanoparticles (average particle size 50nm) and 0.2mL of glacial acetic acid in 100mL of anhydrous ethanol and 5mL of deionized water, add 2.5g of vinyltriethoxysilane under nitrogen protection, stir and react at room temperature for 3h, centrifuge and wash, and vacuum dry to obtain alkenylated silica nanoparticles.

[0067] (4) Add 110 mL of n-hexadecane (oil phase) and 320 mL of deionized water to a separatory funnel, add 5 g of alkenylated silica nanoparticles, sonicate for 40 min, then add 1.4 g of mercapto-terminated polydimethylsiloxane (GelestDMS-SM21) and 0.07 g of photoinitiator 369 to the system, and carry out a sulfur-alkene click reaction for 40 min under 365 nm ultraviolet light irradiation to selectively graft polydimethylsiloxane onto the oil phase contact surface of the particles. After the reaction, separate the layers, demulsify and separate the layers, wash with ethanol, and dry to obtain polydimethylsiloxane modified silica nanoparticles.

[0068] (5) 1g of polydimethylsiloxane-modified silica nanoparticles were dispersed in a mixed solution of 55mL anhydrous ethanol and 6mL deionized water. 2.5g of 3-aminopropyltriethoxysilane was added and the mixture was refluxed at 70°C for 1.5h to graft amino groups onto the hydrophilic side of the particles. After cooling, the particles were centrifuged, washed, and redispersed in 50mL of dry dichloromethane. Then, 1.2g of triethylamine and 2.4g of 2-bromoisobutyryl bromide were added sequentially under ice bath conditions. The mixture was reacted for 60min and washed with deionized water and ethanol, respectively, and dried to obtain functionalized Janus nanoparticles.

[0069] (6) Add 1000mL of deionized water to a 1L beaker, adjust the pH to 9.0 with ammonia (concentration 28wt%), then add 1.4g of dopamine hydrochloride, 7g of methacrylic acid sulfobetaine monomer and 0.15g of copper sulfate pentahydrate in sequence. After stirring and dissolving, add 1.5mL of hydrogen peroxide solution (concentration 30wt%) and 0.07g of functionalized Janus nanoparticles that can initiate polymerization. Sonicate for 40min, then completely immerse the first modified glass substrate in the solution and react for 15min. Remove, rinse with deionized water, and dry to obtain the second modified glass substrate.

[0070] (7) Immerse the double-modified glass substrate in a 100mL aqueous solution containing 0.7g tin tetrachloride pentahydrate and 1.5mL concentrated hydrochloric acid (concentration 37wt%) for 3min, then transfer it to a 100mL aqueous solution containing 7mL ammonia (concentration 28wt%) for 3min, remove it, rinse with deionized water, and dry it to obtain a triple-modified glass substrate;

[0071] (8) Dissolve 13g of methacrylic acid sulfobetaine monomer in 500mL of deionized water, add 0.25g of copper monobromide, 0.025g of copper dibromide and 0.5g of N,N,N',N',N''-pentamethyldiethylenetriamine, purge with nitrogen for 40min to remove oxygen, immerse the triple-modified glass substrate in it for 20min, take it out and soak it in 1000mL of aqueous solution containing 3g of disodium ethylenediaminetetraacetate dihydrate for 10min, then rinse with ethanol 3 times, and dry in a 90°C oven for 80min to obtain high resistivity anti-fog conductive glass.

[0072] Comparative Example 1:

[0073] The difference between Comparative Example 1 and Example 2 is that: in step (6), no methacrylic acid sulfobetaine monomer is added, and only dopamine hydrochloride is used for surface modification; in step (8), the methacrylic acid sulfobetaine monomer is adjusted to 15g, and the other conditions are the same as in Example 2.

[0074] Comparative Example 2:

[0075] The difference between Comparative Example 2 and Example 2 is that the methacrylic acid sulfobetaine monomer in step (6) is adjusted to 15g, and the methacrylic acid sulfobetaine monomer is not added in step (8). The other conditions are the same as in Example 2.

[0076] Comparative Example 3:

[0077] The difference between Comparative Example 3 and Example 2 is that the functionalized Janus silica nanoparticles in step (6) are replaced with silica nanoparticles, while the other conditions are the same as in Example 2.

[0078] Comparative Example 4:

[0079] The difference between Comparative Example 4 and Example 2 is that step (7) is omitted, while the other conditions are the same as in Example 2.

[0080] Comparative Example 5:

[0081] The difference between Comparative Example 5 and Example 2 is that the surface-initiated atom transfer radical polymerization process in step (8) is omitted, and the methacrylic acid sulfobetaine polymer is coated on the substrate surface only by physical adsorption. The other conditions are the same as in Example 2.

[0082] Comparative Example 6:

[0083] The difference between Comparative Example 6 and Example 2 is that the polydimethylsiloxane-modified silica nanoparticles in step (5) are replaced with silica nanoparticles, while the other conditions are the same as in Example 2.

[0084] Performance testing:

[0085] Infrared spectral characterization: Fourier transform infrared spectrometer was used for scanning, and the results are shown in Table 1.

[0086] X-ray diffraction analysis: The glass surface coatings of the single-layer modified glass substrate, the double-layer modified glass substrate, and the triple-layer modified glass substrate of Example 2 were scraped off with a scraper, ground through a 250-mesh sieve, and scanned using an X-ray diffractometer. The results are as follows: Figure 2 As shown.

[0087] Surface resistivity testing: The test was conducted according to GB / T 1410-2006. A four-probe tester with a probe spacing of 1 mm and a test voltage of 10 V was used to measure the surface resistivity of the samples under standard conditions. Five different locations were selected for testing for each sample. The average value and standard deviation were calculated to evaluate the conductivity uniformity and antistatic properties of the coating. The results are shown in Table 1.

[0088] Transmittance and haze testing: Tests were conducted according to GB / T 30983-2014. Visible light transmittance was measured in the wavelength range of 380-780 nm using a spectrophotometer. Total transmittance and scattered transmittance were measured using the integrating sphere method. Haze value (the percentage of scattered transmittance to total transmittance) was calculated. The light source was a D65 standard illuminator. The results are shown in Table 1.

[0089] Anti-fogging performance test: A hot and cold cycle atomization test method was adopted. The sample was placed on a cold plate at 5°C, and atomization conditions were created by spraying water vapor at 60°C and 95% relative humidity upwards for 5 minutes. The formation of water droplets, the spread of water film, and the dissipation time of the droplets on the sample surface were observed and recorded. The percentage of droplet coverage area was calculated by digital image analysis to quantitatively evaluate the anti-fogging performance. The test was repeated 3 times, and the average value was taken. The results are shown in Table 1.

[0090] Table 1 Performance Test Results

[0091]

[0092] Data Analysis:

[0093] As can be seen from Examples 1-3 in Table 1, this invention, through multi-step gradient surface modification and hybrid interface construction, enables the resulting glass to possess comprehensive performance advantages such as high resistivity, anti-fogging, and antistatic properties. First, the tin dioxide layer deposited by spray pyrolysis introduces a stable and uniform high-resistivity conductive channel into the glass surface, effectively suppressing electrostatic accumulation. Subsequently, based on the dopamine self-polymerized organic network, zwitterionic monomers are co-deposited, achieving extremely strong surface hydration capabilities, allowing water vapor to rapidly spread on the glass surface and significantly suppressing droplet formation. Janus nanoparticles achieve a firm bond with the organic layer and inorganic substrate through interface bridging and mechanical anchoring, improving the stability and transparency of the coating structure. Further surface-initiated polymerization optimizes the density and durability of the zwitterionic brush layer through covalent grafting, significantly improving the long-term stability, water resistance, and resistance to ion interference in anti-fogging performance. It is precisely this multi-level synergy and structural interpenetration that effectively balances sheet resistance, light transmittance, haze, and anti-fogging performance, which is the core of improving the overall performance of the material.

[0094] In Comparative Example 1, step (6) did not introduce zwitterionic monomers, resulting in only a dopamine network on the glass surface and a lack of an effective "strong hydration" layer. This significantly reduces the polarization spreading efficiency of water vapor, making it difficult to achieve excellent passive anti-fogging. Although more zwitterionic monomers were added at the end, the non-cooperative deposition and lack of covalent grafting on the surface layer made it difficult to obtain a dense and uniformly fixed superhydrophilic interface, resulting in an increased droplet coverage area and a significant deterioration in anti-fogging performance. Surface sheet resistance and light transmittance were not significantly affected, indicating that the zwitterionic layer is more crucial for passive anti-fogging.

[0095] Comparative Example 2 only initially co-deposited a large number of zwitterionic monomers, lacking subsequent brush layer growth and surface-initiated polymerization. This resulted in the zwitterionic components existing mainly in adsorbed or mixed forms, making them easily washed away and dissolved. Consequently, the antifogging effect was not durable, the antistatic capability was poor, and the droplet spreading was weak. The increased sheet resistance reflects damage to the surface conductive channels, and the light transmittance decreased slightly. This indicates that constructing a stable and dense zwitterionic interface requires considering the synergistic reaction of multiple steps before and after; adding only one step cannot achieve the ideal performance.

[0096] Comparative Example 3, which did not use functionalized Janus nanoparticles, lost its interfacial bridging and microscopic support functions, leading to a decrease in the bonding force between the organic network and the substrate. This resulted in compromised interfacial layer density, coating abrasion resistance, and hydrolysis resistance, ultimately manifesting as increased haze and droplet coverage area. The haze film exhibited poor spreadability, easily forming localized haze spots, and exhibiting poor coating transparency and uniformity. This highlights the crucial importance of the special Janus structure for superhydrophilicity and reducing the risk of anti-fogging failure.

[0097] Comparative Example 4 lacked in-situ generated tin oxide nanonodes, resulting in the absence of an organic-inorganic synergistic interpenetrating structure on the glass surface. The sheet resistance abruptly increased to extremely high levels, the conductive path broke, and the antistatic capability was completely lost. This indicates that tin oxide nodes play a dominant role in building high-resistance transparent conductive channels and synergistically dispersing electrostatic charges, while the zwitterionic layer cannot provide controllable surface resistance on its own.

[0098] Comparative Example 5, without surface-initiated covalent polymerization, involved applying zwitterionic polymers solely through physical adsorption. This resulted in a significant decrease in coating adhesion and density, and a decline in wash resistance. With variations in testing and application conditions, the active groups were easily stripped, leading to a substantial degradation in durable antifogging and antistatic properties, and a significant increase in droplet coverage. This demonstrates the necessity of surface-initiated polymerization for brush coating stability and long-term effectiveness.

[0099] In Comparative Example 6, the construction layer lost the directional support function of Janus particles, resulting in decreased uniformity of the surface microstructure, reduced effective apparent contact area, and significant deterioration in both anti-fogging and conductivity properties. In particular, the coating's wet durability and transparency could not be simultaneously achieved. This indicates that functionalized Janus particles are indispensable for achieving both transparency and performance enhancement in interlayer composites and interface assembly.

[0100] from Figure 1 It can be seen that silica nanoparticles have a size of ~1100 cm⁻¹ -1 Predominantly characterized by strong and wide Si-O-Si stretching, with a length of ~1200 cm⁻¹. -1 acromion, ~800cm -1 With ~460cm -1 Skeletal features, and ~3400 / 1635 cm due to adsorbed water. -1 Signal; after grafting polydimethylsiloxane via a sulfur-ene click reaction, the sample was at ~2962 / 2905 / 2860 cm⁻¹. -1 A -CH3 stretching peak appears, ~1260cm. -1 (Si-CH3) and ~864 cm -1 The (Si-(CH3)2) characteristic is obvious, and at the same time, ~950 cm -1 The weakening of the silanol peak indicates surface organication; further construction of the Janus structure and the introduction of initiators for acylation of the hydrophilic surface, in addition to retaining the PDMS and SiO2 framework peaks, a peak at ~1655 cm⁻¹ was observed. -1 With ~1545cm -1 Amine I and II showed paired absorption at ~1230 cm⁻¹. -1 CN stretching, ~650cm -1 The appearance of a weak C-Br peak comprehensively verifies the success of functionalization and the differences in interfacial chemistry.

[0101] from Figure 2 It can be seen that all three curves exhibit typical diffraction characteristics of rutile SnO2. The main peaks at 26.6° (110) and 33.9° (101) are clearly distinguishable in all stages. With the introduction of an organic-inorganic network layer through double modification, an amorphous bulge of ~22° appears in the low-angle region, and the overall peak intensity decreases slightly while the peak position remains basically unchanged. After triple modification, with the in-situ generation of tin oxide nanonodes on the surface of the network layer, the relative intensity ratio of (110) and (101) is slightly adjusted, and the half-width of (110) increases from ≈0.36° to ≈0.57° with a slight positive shift, which characterizes the SnO2 nascent grains with smaller scale / constrained strain.

[0102] Those skilled in the art should understand that the discussion of any of the above embodiments is merely exemplary and is not intended to imply that the scope of the invention is limited to these examples; within the framework of the invention, the technical features of the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.

Claims

1. A high resistivity, anti-fog conductive glass, characterized in that, comprise a glass substrate and a tin dioxide conductive layer disposed on the surface of the glass substrate; an organic-inorganic network layer formed by immersing in an aqueous solution containing dopamine hydrochloride, methacrylsulfobetaine monomer, copper sulfate pentahydrate and functionalized Janus nanoparticles, the organic-inorganic network layer being disposed on the surface of the tin dioxide conductive layer; the formation of the organic-inorganic network layer is achieved by self-polymerization of dopamine oxidation in an aqueous solution with pH of 8.0-9.0 in the presence of hydrogen peroxide; tin oxide nanonodes generated in situ on the surface of the organic-inorganic network layer by immersing the substrate with the organic-inorganic network layer in an acidic solution containing tin tetrachloride and then in an alkaline solution; an amphoteric polymer brush layer covalently grafted on the surface of the glass substrate containing tin oxide nanonodes by surface-initiated atom transfer radical polymerization, the amphoteric polymer brush layer being formed by methacrylsulfobetaine polymer; the functionalized Janus nanoparticles are prepared by the following method: S1: vinyltriethoxysilane is used to graft modify silica nanoparticles to obtain alkenylated silica nanoparticles; S2: the alkenylated silica nanoparticles are grafted with mercapto-terminated polydimethylsiloxane in an oil-in-water system to obtain polydimethylsiloxane-modified silica nanoparticles; S3: after 3-aminopropyltriethoxysilane is used to graft modify the polydimethylsiloxane-modified silica nanoparticles, the modified nanoparticles are reacted with 2-bromoisobutyryl bromide to obtain functionalized Janus nanoparticles.

2. The high resistivity, anti-fog conductive glass according to claim 1, wherein, The weight ratio of the dopamine hydrochloride, methacrylsulfobetaine monomer, copper sulfate pentahydrate and functionalized Janus nanoparticles is 0.6-1.4:3-7:0.05-0.15:0.03-0.

07.

3. The high resistivity, anti-fog conductive glass of claim 1, wherein, The acidic solution containing tin tetrachloride contains 0.3-0.7 g of tin tetrachloride pentahydrate and 0.5-1.5 mL of concentrated hydrochloric acid with a concentration of 37 wt% per 100 mL; the alkaline solution contains 3-7 mL of ammonia water with a concentration of 28 wt% per 100 mL.

4. The high resistivity, anti-fog conductive glass of claim 1, wherein, The surface-initiated atom transfer radical polymerization is carried out in an aqueous solution of methacrylsulfobetaine monomer containing cuprous bromide, cupric bromide and N,N,N',N',N''-pentamethyldiethylenetriamine.

5. The high resistivity, anti-fog conductive glass of claim 1, wherein, In step S1, the weight ratio of the silica nanoparticles and vinyltriethoxysilane is 5:1.5-2.5; in step S2, the weight ratio of the alkenylated silica nanoparticles and mercapto-terminated polydimethylsiloxane is 5:0.6-1.4; in step S3, the weight ratio of the polydimethylsiloxane-modified silica nanoparticles, 3-aminopropyltriethoxysilane and 2-bromoisobutyryl bromide is 1:1.5-2.5:1.6-2.

4.

6. The high resistivity, anti-fog conductive glass of claim 1, wherein, The high resistivity anti-fog conductive glass has a surface resistivity of 5.2 x 10 8 Ω / sq to 1.1 x 10 9 Ω / sq.

7. The high resistivity, anti-fog conductive glass of claim 1, wherein, The high-resistivity anti-fog conductive glass has a light transmittance of not less than 89% and a haze of not higher than 0.9%.

8. A method of making high resistivity, anti-fog conductive glass according to any one of claims 1-7, characterized in that, comprise the following steps: (1) preparing a tin dioxide conductive layer on the surface of a glass substrate by spray pyrolysis deposition; (2) immersing a glass substrate in an aqueous solution containing dopamine hydrochloride, methacrylate sulfobetaine monomer, copper sulfate pentahydrate and functionalized Janus nanoparticles to form an organic-inorganic network layer; (3) immersing the glass substrate with the organic-inorganic network layer in an acidic solution containing tin tetrachloride and then in an alkaline solution to generate tin oxide nanonodes in situ on the surface; (4) grafting an amphoteric polymer brush layer on the glass substrate surface containing tin oxide nanonodes by surface-initiated atom transfer radical polymerization.

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