High-transmittance high-acid-and-alkali-resistance double-layer glass colored glaze structure and preparation method thereof

Abstract

The invention relates to the technical field of photovoltaic glass, and provides a high-transmittance high-acid-and-alkali-resistance double-layer glass colored glaze structure and a preparation method thereof.The method comprises the steps that an ultra-white glass substrate with the thickness being 1.5-8 mm is provided; glass powder, a pigment and an organic carrier are mixed to form glass colored glaze ink, the glass powder is a SiO2, R2O and B2O3 system, and the pigment is an absorption type inorganic pigment or an interference type pearlescent pigment; the method comprises the following steps: applying glass colored glaze ink to the surface of an ultra-white glass substrate in a screen printing, roll printing or spraying manner, and tempering and sintering at 600-730 DEG C to form a glass colored glaze layer with the thickness of 10-20 microns; acid liquor containing one or more of sulfuric acid, hydrochloric acid, nitric acid and hydrofluoric acid is adopted for carrying out acid etching treatment on the glass colored glaze layer, and a nano glass film layer is formed on the surface of the glass colored glaze layer by controlling the concentration of the acid liquor, the acid etching time and the temperature; the glass substrate subjected to acid etching is sequentially subjected to ultrasonic cleaning with water, ethanol and deionized water and dried, and the high-transmittance and high-acid-and-alkali-resistance double-layer glass colored glaze structure is prepared.

Description

Technical Field

[0001] This application relates to the field of photovoltaic glass technology, and in particular to a high-transmittance, highly acid- and alkali-resistant double-layer glass glaze structure and its preparation method. Background Technology

[0002] In the field of building-integrated photovoltaics (BIPV), enamel glass, as a key material combining decoration and functionality, must simultaneously meet the requirements of high weather resistance, high light transmittance, and optical performance matching the efficiency of solar cells. Traditional enamel glass typically uses high-temperature ink printing on the inner side of the glass (surface 2). However, when applied to the outer side of building facades (surface 1), existing glass enamels exhibit significant defects: insufficient density under low-temperature short-time tempering (e.g., 600-730℃), and alkali metal ions are easily corroded by acids, resulting in insufficient acid resistance for long-term outdoor use. Increasing the silica content to enhance acid resistance leads to a higher glass softening point and a mismatch between the coefficient of thermal expansion and the ultra-clear glass substrate, causing film cracking. Furthermore, existing technologies improve acid resistance and light transmittance through surface coating or sol-gel methods, but these suffer from poor adhesion and high cost, hindering industrial application. Therefore, how to achieve high acid and alkali resistance, low softening point, thermal expansion matching and high light transmittance simultaneously through process innovation without changing the traditional low-cost glass powder system has become a technical challenge in the field of BIPV colored glaze glass.

[0003] Therefore, a preparation method is urgently needed to solve at least one of the above problems. Summary of the Invention

[0004] This application provides a high-transmittance, high-acid- and alkali-resistant double-layer glass glaze structure and its preparation method, aiming to solve the problem that traditional glaze glass usually prints high-temperature ink on the inner side of the glass (surface 2), but when applied to the outer side of the building facade (surface 1), the existing glass glaze has significant defects: insufficient density under low-temperature short-time tempering (such as 600-730℃), and alkali metal ions are easily corroded by acid, resulting in the inability to meet the acid resistance requirements for long-term outdoor use.

[0005] In a first aspect, this application provides a method for preparing a high-transmittance, highly acid- and alkali-resistant double-layer glass enamel structure, the method comprising: Provides ultra-white glass substrates with thicknesses ranging from 1.5 to 8 mm; Glass powder, pigments, and an organic carrier are mixed to form a glass enamel ink. The glass powder is a SiO2, R2O, B2O3 system, the pigments are absorption-type inorganic pigments or interference-type pearlescent pigments, and the organic carrier is a water-based acrylic resin system. The glass powder content is 50% to 75%, and the pigment content is ≤20%. The glass enamel ink is applied to the surface of the ultra-white glass substrate by screen printing, roller printing, or spraying, and tempered and sintered at 600 to 730°C to form a glass enamel layer with a thickness of 10 to 20 μm. The glass enamel layer is acid-etched using an acid solution containing one or more of sulfuric acid, hydrochloric acid, nitric acid, and hydrofluoric acid. By controlling the acid concentration, etching time, and temperature, a nano-glass film is formed on the surface of the glass enamel layer. The nano-glass film has a SiO2 content of more than 50%, a thickness of 100 to 200 nm, and a refractive index of 1.1 to 1.3. The acid-etched glass substrate was sequentially ultrasonically cleaned with water, ethanol, and deionized water, and then dried to obtain a high-transmittance, highly acid- and alkali-resistant double-layer glass enamel structure.

[0006] In some embodiments, the process of mixing glass powder, pigment, and organic carrier to form glass enamel ink includes: the glass powder being composed of 45-55% SiO2, 15-25% R2O, 5-12% B2O3, and the balance Al2O3 by mass percentage; the mixing is performed using a ball milling process with a ball-to-material ratio of 2:1, a rotation speed of 200-300 rpm, and a mixing time of 2-4 hours, so that the particle size D50 is ≤5μm; in R2O, R is Na or K.

[0007] In some embodiments, the etching treatment of the glass enamel layer with an acid solution containing one or more of sulfuric acid, hydrochloric acid, nitric acid, and hydrofluoric acid includes: when the acid solution contains hydrofluoric acid, the concentration is controlled at 0.5 to 3 vol%; if the acid solution is a hydrochloric acid single-liquid system, the concentration range is 5 to 15 wt%; the etching temperature is set at 25 to 50°C, the treatment time is 30 to 120 seconds, and the reaction is terminated when the refractive index of the film reaches 1.2 ± 0.05 by monitoring with an online spectrometer.

[0008] In some embodiments, forming a nano-glass film layer on the surface of the glass enamel layer by controlling the acid concentration, etching time, and temperature includes: employing a gradient acid etching process, wherein in the first stage, the surface layer is removed by treating with 5% hydrochloric acid for 60 seconds. + The second stage involves switching to a mixed acid treatment containing 1% hydrofluoric acid for 20 seconds to form a porous high-silicon layer with a porosity of 30 to 50%, resulting in a final film thickness of 120 to 180 nm.

[0009] In some embodiments, applying the glass enamel ink to the surface of the ultra-white glass substrate by screen printing, roller printing or spraying includes: using a 250 to 350 mesh nickel screen for screen printing, printing pressure of 0.2-0.4 MPa, printing in two stages, and preheating and drying at 80-120℃ for 5-10 minutes after each printing to ensure that the uniformity error of the enamel layer thickness is ≤±5%.

[0010] In some embodiments, the nanoglass film has a hierarchical porous structure, wherein the surface layer has a porosity of 40 to 60% and a pore size of 5 to 20 nm; the bottom layer has a porosity of 10 to 30% and a pore size of ≤ 5 nm; the porous structure is formed by alternating acid etching and deionized water rinsing cycles of 3 to 5 times.

[0011] In some embodiments, the glass glaze layer is composed of at least two layers of glaze of different colors, with the bottom layer being an absorptive dark blue inorganic pigment layer and the top layer being an interference-type light blue pearlescent pigment layer; the two layers are locally acid-etched to form a light-transmitting micropore array with a pore diameter of 10 to 50 μm and a pore spacing of 100 to 200 μm, so that the incident light undergoes secondary refraction at the micropores to improve the light absorption rate of the solar cell.

[0012] In some embodiments, the pigment comprises a pearlescent pigment of titanium dioxide coated mica with a particle size D90≤15μm and a surface modified by a silane coupling agent; the pearlescent pigment is oriented in the glaze layer with the orientation direction forming an angle of 30 to 60° with the plane of the glass substrate to enhance the reflectivity of near-infrared light to ≥85%.

[0013] In some embodiments, the acid solution is hydrochloric acid with a concentration of 5% to 10%, or a corrosive acid solution containing hydrofluoric acid; wherein, acid etching removes acid-sensitive ions and B2O3 components from the surface of the glass enamel layer, thereby increasing the SiO2 content in the nano-glass film layer to more than 70%; the tempering sintering temperature is 650 to 700°C to form a dense glass enamel layer.

[0014] Secondly, this application provides a high-transmittance, highly acid- and alkali-resistant double-layer glass glaze structure, which is prepared by the preparation method provided in any embodiment of this application.

[0015] This application employs a 2-6mm ultra-white glass substrate to provide structural support and optical transmission. The glaze preparation and sintering process involves mixing glass powder (50-75%), absorbing / interfering pigments (≤20%), and a water-based acrylic carrier, then coating the mixture onto the substrate using screen printing / roll printing / spraying processes. The resulting glaze is then tempered and sintered at 600-730℃ to form a 10-20μm glass glaze layer. The surface of the glaze layer is etched using an acid solution containing sulfuric acid, hydrochloric acid, nitric acid, and hydrofluoric acid to remove acid-sensitive R-reactive materials. +The ions and B2O3 components form a nano-glass film with SiO2 content >50%, thickness 100-200nm, and refractive index 1.1-1.3, simultaneously achieving acid and alkali resistance enhancement and anti-reflection and anti-reflection; the post-treatment involves ultrasonic cleaning and drying with water, ethanol, and deionized water to obtain the target structure.

[0016] By removing acid-sensitive components from the glaze surface through acid etching, the SiO2 content is increased from 40-50% in the traditional system to over 50% (preferably 70%-90%), significantly enhancing the acid resistance of the outer side and meeting the long-term outdoor weathering requirements of BIPV. The thickness and refractive index of the nanofilm layer are precisely controlled (100-200nm, 1.1-1.3), achieving anti-reflection and anti-reflection in the 400-1100nm wavelength band, matching the absorption spectrum of silicon-based cells, and improving the power generation efficiency of the module. Based on the traditional SiO2, R2O, and B2O3 system, the acid etching process modifies the material without the need to replace expensive raw materials or complex coating equipment. It is compatible with existing tempering production lines, has low cost, and the film adhesion is superior to the spray sol method, resulting in high reliability. It retains the low softening point characteristics of the glass powder system (suitable for low-temperature tempering at 600-730℃), while strengthening the acid resistance through the surface nanolayer, thus resolving the contradiction between the softening point and thermal expansion coefficient of traditional high-silicon glass.

[0017] It should be understood that the above general description and the following detailed description are exemplary and explanatory only, and do not limit this application. Attached Figure Description

[0018] To more clearly illustrate the technical solutions of the embodiments of this application, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0019] Figure 1 This is a schematic flowchart illustrating the steps of a method for preparing a high-transmittance, highly acid- and alkali-resistant double-layer glass enamel structure according to an embodiment of this application. Figure 2 This is a schematic diagram of a high-transmittance, highly acid- and alkali-resistant double-layer glass enamel structure provided in an embodiment of this application.

[0020] It should be understood that the above general description and the following detailed description are exemplary and explanatory only, and do not limit this application. Detailed Implementation

[0021] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0022] The flowchart shown in the attached diagram is for illustrative purposes only and does not necessarily include all content and operations / steps, nor does it necessarily have to be performed in the order described. For example, some operations / steps can be broken down, combined, or partially merged, so the actual execution order may change depending on the actual situation.

[0023] It should be understood that, in order to clearly describe the technical solutions of the embodiments of the present invention, the terms "first" and "second" are used in the embodiments of the present invention to distinguish identical or similar items with essentially the same function and effect. Those skilled in the art will understand that the terms "first" and "second" do not limit the quantity or execution order, and the terms "first" and "second" are not necessarily different.

[0024] It should be understood that the terminology used in this specification is for the purpose of describing particular embodiments only and is not intended to limit the scope of the application. As used in this specification and the appended claims, the singular forms “a,” “an,” and “the” are intended to include the plural forms unless the context clearly indicates otherwise.

[0025] It should also be understood that the term “and / or” as used in this application specification and the appended claims means any combination of one or more of the associated listed items and all possible combinations, and includes such combinations.

[0026] The following detailed description of some embodiments of this application is provided in conjunction with the accompanying drawings. Unless otherwise specified, the following embodiments and features can be combined with each other.

[0027] In the field of building-integrated photovoltaics (BIPV), enamel glass, as a key material combining decoration and functionality, must simultaneously meet the requirements of high weather resistance, high light transmittance, and optical performance matching the efficiency of solar cells. Traditional enamel glass typically uses high-temperature ink printing on the inner side of the glass (surface 2). However, when applied to the outer side of building facades (surface 1), existing glass enamels exhibit significant defects: insufficient density under low-temperature short-time tempering (e.g., 600-730℃), and alkali metal ions are easily corroded by acids, resulting in insufficient acid resistance for long-term outdoor use. Increasing the silica content to enhance acid resistance leads to a higher glass softening point and a mismatch between the coefficient of thermal expansion and the ultra-clear glass substrate, causing film cracking. Furthermore, existing technologies improve acid resistance and light transmittance through surface coating or sol-gel methods, but these suffer from poor adhesion and high cost, hindering industrial application. Therefore, how to achieve high acid and alkali resistance, low softening point, thermal expansion matching and high light transmittance simultaneously through process innovation without changing the traditional low-cost glass powder system has become a technical challenge in the field of BIPV colored glaze glass.

[0028] Therefore, a preparation method is urgently needed to solve at least one of the above problems.

[0029] To resolve the above issues, please refer to [link / reference]. Figure 1 , Figure 1 This is a schematic flowchart illustrating a method for preparing a high-transmittance, highly acid- and alkali-resistant double-layer glass enamel structure according to an embodiment of this application. This method is used to prepare... Figure 2 The corresponding high acid and alkali resistant double-layer glass enamel structure includes an ultra-clear glass layer 2, which serves as the glass enamel substrate, providing structural support and optical transmission. A glass enamel layer 1-2 is printed, tempered, and sintered onto the ultra-clear glass layer 2. A nano-glass layer 1-1 is formed on top of the glass enamel layer 1-2 through acid etching. The glass enamel layer 1-2 and the nano-glass layer 1-1 together constitute glass layer 1.

[0030] Please refer to Figure 1 Specifically, such as Figure 1 As shown, the method for preparing the high-transmittance, high-acid- and alkali-resistant double-layer glass enamel structure includes steps S101 to S103. Details are as follows: Step S101. Provide an ultra-white glass substrate with a thickness of 1.5 to 8 mm.

[0031] Specifically, ultra-clear glass substrates with a thickness of 1.5 to 8 mm are selected as the substrate material. Ultra-clear glass is a high-transmittance glass with low iron content (Fe2O3 content ≤0.015%), and its light transmittance is usually ≥91.5%. It has excellent chemical stability and optical uniformity, and is a key substrate material for photovoltaic modules in building-integrated photovoltaics (BIPV).

[0032] Substrate Selection: The thickness is selected based on the building facade design requirements (such as load-bearing capacity, light transmittance, and safety). Common specifications are 3mm, 4mm, and 5mm. Double-sided polished substrates are preferred to ensure surface flatness. Pretreatment: The substrate surface is rinsed with deionized water to remove dust, grease, and other impurities. It is then further purified by ultrasonic cleaning (frequency 20-40kHz, time 5-10 minutes). Finally, it is dried (temperature 50-80℃, time 10-15 minutes) to ensure that the substrate surface is free of contaminants and to avoid affecting the adhesion of the subsequent colored enamel layer.

[0033] The low-iron properties of ultra-clear glass reduce light absorption loss, providing ample incident light for photovoltaic cells and improving photoelectric conversion efficiency. A thickness range of 2-6mm balances structural strength (such as the load-bearing requirements of curtain wall glass) with lightweight design, meeting the mechanical performance requirements of various BIPV applications (such as skylights, curtain walls, and shading components). The low alkali metal ion deposition characteristics of the ultra-clear glass substrate lay the foundation for thermal expansion matching of subsequent colored enamel layers, reducing the risk of film cracking.

[0034] Step S102. Glass powder, pigment and organic carrier are mixed to form glass enamel ink, wherein the glass powder is a SiO2, R2O, B2O3 system, the pigment is an absorption type inorganic pigment or an interference type pearlescent pigment, and the organic carrier is a water-based acrylic resin system, wherein the glass powder content is 50 to 75% and the pigment content is ≤20%; the glass enamel ink is applied to the surface of the ultra-white glass substrate by screen printing, roller printing or spraying, and tempered and sintered at 600 to 730°C to form a glass enamel layer with a thickness of 10 to 20 μm.

[0035] Specifically, glass powder based on the SiO2, R2O, and B2O3 system (R2O being alkali metal oxides such as Na2O and K2O), pigments (absorbent inorganic pigments or interference-type pearlescent pigments), and a water-based acrylic resin organic carrier are mixed to form a glass enamel ink. The ink is applied to the surface of an ultra-clear glass substrate using screen printing, roller printing, or spraying processes, and then sintered at a low temperature of 600-730℃ to form a glass enamel layer with a thickness of 10-20 μm.

[0036] Ink formulation: Glass powder (50-75wt%): The core components are SiO2 (50-65%), B2O3 (15-25%), and R2O (8-15%). Among them, B2O3 lowers the softening point of the system (to 600-650℃), and R2O adjusts the coefficient of thermal expansion (8-12×10^-7 / ℃) to match it with the ultra-white glass substrate (coefficient of thermal expansion of about 9×10^-7 / ℃) to avoid cracking of the film layer after sintering.

[0037] Pigments (≤20wt%): Absorbent pigments (such as Fe2O3, CoO) are used to control color depth, while interference-type pearlescent pigments (such as TiO2-coated mica) enhance the decorative effect through light scattering. The dosage of both is strictly controlled to ensure a light transmittance of ≥70% (meeting the spectral response requirements of photovoltaic cells). Organic carrier (10-30wt%): Water-based acrylic resin (solid content 30-50%) is used as the dispersion medium, and ethanol (5-10%) is added to adjust the viscosity (1000-3000 mPa*s) to ensure ink flow and edge clarity during printing.

[0038] Printing Process: Screen Printing: Use a 200-300 mesh stainless steel screen, squeegee pressure 5-10 N / mm, and pre-dry at 80-100℃ for 10-15 minutes after printing to remove moisture from the organic carrier. Roller Printing / Spraying: Roller printing roller speed 5-10 rpm, coating thickness controlled by roller gap; spraying uses air atomizing nozzles, pressure 0.2-0.4 MPa, to ensure film uniformity. Tempering and Sintering: Send the printed glass substrate into a tempering furnace, heat to 600-730℃ at 5-10℃ / min (holding time 10-20 minutes), then air-cool quench (air pressure 0.5-1 MPa), so that the enamel layer forms a chemical bond (Si-O bond connection) with the substrate, and the film hardness reaches 5-6H (Mohs hardness).

[0039] By using the traditional glass powder system and avoiding the introduction of high-cost components (such as ZrO2 and TiO2), raw material costs are reduced by 30%-50%. Through optimization of the B2O3 and R2O ratio, the coefficient of thermal expansion of the colored enamel layer is kept within 10% of the ultra-white glass substrate, solving the problem of film cracking caused by the increased softening point of traditional high-SiO2 enamels. The 10-20μm thick colored enamel layer provides decorative color (color coordinate error ΔE≤2) while retaining sufficient light transmittance (visible light transmittance ≥70%), meeting the incident light requirements of photovoltaic cells.

[0040] Step S103. The glass enamel layer is acid-etched using an acid solution containing one or more of sulfuric acid, hydrochloric acid, nitric acid, and hydrofluoric acid. By controlling the acid concentration, etching time, and temperature, a nano-glass film is formed on the surface of the glass enamel layer. The nano-glass film has a SiO2 content of more than 50%, a thickness of 100 to 200 nm, and a refractive index of 1.1 to 1.3.

[0041] Specifically, an acid solution containing one or more of sulfuric acid, hydrochloric acid, nitric acid, and hydrofluoric acid is used to selectively etch the surface of the sintered colored glaze layer. By controlling the acid concentration (5-20wt%), temperature (20-60℃), and time (30-120s), alkali metal ions (R) on the film surface are dissolved. +It contains some low-melting-point components (such as B2O3), leaving behind a dense nanostructure layer mainly composed of SiO2 (SiO2 content >50%, thickness 100-200nm, refractive index 1.1-1.3).

[0042] Acid formulation design: Single acid: hydrofluoric acid (5-10wt%) is used to etch the glass matrix, preferentially dissolving BO and RO bonds and enriching the SiO2 network; hydrochloric acid (10-20wt%) or sulfuric acid (15-25wt%) is used to remove free alkali metal ions; Mixed acid: hydrofluoric acid (3-5wt%) + nitric acid (10-15wt%), synergistic etching (hydrofluoric acid destroys the network structure, and nitric acid accelerates ion dissolution), suitable for complex composition films.

[0043] Etching process control: Temperature: Low temperature (20-30℃) has a slow etching rate, suitable for precise control of film thickness; High temperature (50-60℃) accelerates the reaction, requiring real-time monitoring to avoid over-etching; Time: Precisely controlled by a timing device (error ≤5s), combined with microscopic observation of film surface roughness (target Ra≤5nm); Operation method: Use dip coating or spraying method to ensure uniform contact of acid solution with film layer, spraying pressure 0.2-0.4MPa, to avoid local over-etching.

[0044] The SiO2 enriched layer on the surface forms a "chemical barrier," reducing the exposure of alkali metal ions and improving acid resistance (tested according to GB / T 15245) from ΔE≤5 in traditional processes to ΔE≤2 (immersion in 10% hydrochloric acid for 24 hours). The refractive index of the nanofilm layer (1.1-1.3) is lower than that of the glass substrate (≈1.52), forming a gradient refractive index interface, reducing light reflection (reflectivity decreases from 8% to below 3%) and improving light transmittance (measured light transmittance increases by 2-5%). The etching process removes the loose areas on the film surface, forming a nanoscale dense structure (porosity ≤5%), enhancing surface hardness (Mohs hardness increases from level 5 to level 6). The low-cost glass powder formula does not need to be changed from the underlying colored glaze; the acid resistance problem is solved only through surface modification, avoiding the increase in softening point and thermal expansion mismatch caused by increasing SiO2 content in traditional methods.

[0045] Step S104. The acid-etched glass substrate is ultrasonically cleaned with water, ethanol, and deionized water in sequence and then dried to obtain a high-transmittance, high-acid- and alkali-resistant double-layer glass enamel structure.

[0046] Specifically, the acid-etched substrate is sequentially ultrasonically cleaned with water, ethanol, and deionized water to remove residual acid and etching products from the surface, and finally dried (temperature 50-80℃, time 10-30min) to obtain a high acid and alkali resistant colored glaze glass with a double-layer structure (bottom colored glaze layer + surface nano glass film layer).

[0047] Multi-stage cleaning: Stage 1: Ultrasonic cleaning with tap water (frequency 40kHz, power 200W) for 5-10 minutes to remove large etching residues; Stage 2: Ultrasonic cleaning with anhydrous ethanol for 5 minutes to dissolve residual organic matter (such as unvolatile resin additives); Stage 3: Ultrasonic cleaning with deionized water for 10 minutes to remove ionic impurities (such as Cl-). - SO4² - To avoid residual acid causing a long-term decrease in weather resistance. Drying process: A hot air circulating oven is used, with temperature control accuracy of ±2℃ and humidity ≤20%RH to ensure complete evaporation of moisture and avoid water stains affecting light transmittance.

[0048] Multi-stage cleaning thoroughly removes acid residue and prevents secondary corrosion of the film by residual acid (such as Cl). - (Causes long-term corrosion); a dry environment prevents moisture from remaining in the pores of the membrane, improving the product's weather resistance in high humidity environments (damp heat resistance test ≥1000h, no membrane peeling or discoloration); a clean surface eliminates light scattering caused by pollutants, ensuring that the anti-reflection effect of the nano-membrane is fully utilized (measured transmittance fluctuation ≤1%).

[0049] Innovative Dual-Layer Structure: The bottom glaze layer retains the traditional low-cost formula, achieving thermal expansion matching and a low softening point through component design; the surface nano-glass film layer, modified by acid etching, solves the problems of acid resistance and light transmittance without altering the underlying composition, overcoming the contradiction between "acid resistance, thermal matching, and cost." Process Compatibility: The combination of low-temperature tempering, conventional printing processes, and acid etching treatment adapts to existing production lines, requiring no significant equipment modifications and lowering the industrialization threshold. Balanced Performance Improvement: Acid resistance, light transmittance, and thermal stability are simultaneously optimized to meet the long-term outdoor use requirements of BIPV exterior walls (weather resistance rating reaches GB / T14522-2008 Class VIII), while also considering decorative appeal and photovoltaic efficiency.

[0050] In some embodiments, the process of mixing glass powder, pigment, and organic carrier to form glass enamel ink includes: the glass powder being composed of 45-55% SiO2, 15-25% R2O, 5-12% B2O3, and the balance Al2O3 by mass percentage; the mixing is performed using a ball milling process with a ball-to-material ratio of 2:1, a rotation speed of 200-300 rpm, and a mixing time of 2-4 hours, so that the particle size D50 is ≤5μm; in R2O, R is Na or K.

[0051] The glass powder consists of 45-55% SiO2, 15-25% R2O (R being Na or K), 5-12% B2O3, and the balance Al2O3 by mass percentage. Among them, R2O is selected from Na2O or K2O (or a mixture of both), and Al2O3 is used as an auxiliary component to adjust the melt viscosity and chemical stability.

[0052] Mixing process: Colored enamel inks are prepared using ball milling with a ball-to-material ratio of 2:1. The rotation speed is controlled at 200-300 rpm, and the mixing time is 2-4 hours, ensuring a particle size (D50) ≤ 5μm (detected by a laser particle size analyzer). Zirconia balls (3-5mm in diameter) are used as the grinding media to avoid introducing impurities.

[0053] By limiting the R2O (Na2O / K2O) content (15-25%), the thermal expansion coefficient of the colored glaze layer is controlled at 8-12×10^-7 / ℃, with an error of ≤10% compared to the ultra-white glass substrate (approximately 9×10^-7 / ℃), thus solving the problem of film cracking caused by the increased softening point of traditional high-SiO2 glazes.

[0054] Melt performance optimization: The introduction of Al2O3 (5-10%) improves the chemical stability of glass powder and inhibits excessive precipitation of R2O. At the same time, B2O3 (5-12%) lowers the softening point to 600-650℃, making it suitable for low-temperature tempering processes (600-730℃).

[0055] Improved ink uniformity: The ball milling process refines pigment particles (D50≤5μm), reducing screen clogging during printing. At the same time, the nano-sized particles form a denser glaze layer after sintering, with a surface roughness Ra≤3μm, improving light transmission uniformity.

[0056] In some embodiments, the etching treatment of the glass enamel layer with an acid solution containing one or more of sulfuric acid, hydrochloric acid, nitric acid, and hydrofluoric acid includes: when the acid solution contains hydrofluoric acid, the concentration is controlled at 0.5 to 3 vol%; if the acid solution is a hydrochloric acid single-liquid system, the concentration range is 5 to 15 wt%; the etching temperature is set at 25 to 50°C, the treatment time is 30 to 120 seconds, and the reaction is terminated when the refractive index of the film reaches 1.2 ± 0.05 by monitoring with an online spectrometer.

[0057] Acid composition and concentration control: When the acid solution contains hydrofluoric acid (HF), the concentration should be controlled at 0.5-3 vol% (vol%) to avoid excessive etching of the SiO2 framework by high concentrations of HF; if a hydrochloric acid (HCl) single-liquid system is used, the concentration range is 5-15 wt% (mass percentage), and R is controlled by adjusting the hydrochloric acid concentration. + ions (Na) + / K + The dissolution rate of ).

[0058] Process parameters: The acid etching temperature is set to 25-50℃ (controlled by water bath heating, with an error of ±2℃), the processing time is 30-120 seconds, and the refractive index of the film is monitored in real time by an online spectrometer. The reaction is automatically terminated when the refractive index reaches 1.2±0.05 (spectrometer wavelength scanning range 200-1100nm).

[0059] The online spectrometer provides real-time feedback on the refractive index, preventing excessive acid etching that could reduce the film's transmittance (target transmittance ≥85%). Simultaneously, it ensures a low refractive index (1.1-1.3) for the nanofilm, minimizing light reflection loss (reflectivity ≤5%). Low-concentration HF (≤3 vol%) selectively dissolves surface R2O, preserving the SiO2 framework and increasing the SiO2 content in the film to 60-70%. After immersion in 5% hydrochloric acid solution for 24 hours, the mass loss rate is ≤0.5% (compared to ≥5% with traditional processes). Precise temperature and time control prevent uneven acid etching, resulting in a film thickness error ≤±10nm, suitable for continuous industrial production (e.g., roll coating etching lines).

[0060] In some embodiments, forming a nano-glass film layer on the surface of the glass enamel layer by controlling the acid concentration, etching time, and temperature includes: employing a gradient acid etching process, wherein in the first stage, the surface layer is removed by treating with 5% hydrochloric acid for 60 seconds. + The second stage involves switching to a mixed acid treatment containing 1% hydrofluoric acid for 20 seconds to form a porous high-silicon layer with a porosity of 30 to 50%, resulting in a final film thickness of 120 to 180 nm.

[0061] Gradient acid etching process: First stage: Treat with 5% hydrochloric acid (wt%) for 60 seconds to remove R-type deposits accumulated on the surface of the colored glaze layer. + ions (Na) + / K + This forms a preliminary porous structure (porosity 10-20%). Second stage: switch to a mixed acid (HCl 10% + HF 1%) containing 1% hydrofluoric acid (vol%) for 20 seconds to etch the SiO2 framework to form nanoscale pores, and finally form a porous high-silicon layer with a porosity of 30-50%, with the film thickness controlled at 120-180nm (measured by ellipsometer).

[0062] The first stage prioritizes the removal of easily etched R2O, while the second stage uses HF to lightly etch SiO2, creating a gradient porosity of "loose surface - dense bottom" (surface pore size 5-20nm, bottom pore size ≤5nm). This preserves the film's mechanical strength while increasing the specific surface area through the porous structure, improving acid resistance (making it difficult for acid to penetrate the underlying glaze layer). The porous structure reduces light scattering (haze ≤2%), and the high silicon content (SiO2 ≥65%) ensures that the film's transmittance decreases by ≤3% after 1000 hours of UV aging (compared to ≥15% in traditional processes). The gradient processing time is shortened to 80 seconds (compared to 120-180 seconds for traditional single-acid processing), and excessive film dissolution caused by prolonged HF etching is avoided, reducing the scrap rate to ≤2%. In some embodiments, applying the glass enamel ink to the surface of the ultra-white glass substrate by screen printing, roller printing or spraying includes: using a 250 to 350 mesh nickel screen for screen printing, printing pressure of 0.2-0.4 MPa, printing in two stages, and preheating and drying at 80-120℃ for 5-10 minutes after each printing to ensure that the uniformity error of the enamel layer thickness is ≤±5%.

[0063] Refined screen printing process: Select a 250-350 mesh nickel screen (mesh size 40-60μm), control the printing pressure at 0.2-0.4 MPa, and adopt a two-stage printing process: After the first printing, preheat and dry at 80-120℃ for 5-10 minutes (to remove 50-70% of the moisture), and then perform a second printing to ensure that the uniformity error of the glaze layer thickness is ≤±5% (detected online by a film thickness gauge).

[0064] Double printing avoids edge blurring and bubble defects caused by single-pass thick film printing, improving thickness uniformity to over 95%. After sintering, the surface flatness of the colored glaze layer (warpage ≤ 0.1 mm / m) meets the optical consistency requirements of curtain wall glass. Preheating and drying partially cross-link the acrylic resin in the organic carrier, forming a "bottom anchor - surface cover" structure. After sintering, the adhesion between the glaze layer and the substrate reaches 5B level (cross-cut test), which is superior to the 4B level of traditional single-pass printing. The high abrasion resistance of the nickel screen is suitable for high-speed printing lines (capacity ≥ 1000 pieces / hour), and the 250-350 mesh precision can achieve fine control of 10-20 μm thickness, meeting the printing requirements of complex patterns (such as light-transmitting micro-hole arrays).

[0065] In some embodiments, the nanoglass film has a hierarchical porous structure, wherein the surface layer has a porosity of 40 to 60% and a pore size of 5 to 20 nm; the bottom layer has a porosity of 10 to 30% and a pore size of ≤ 5 nm; the porous structure is formed by alternating acid etching and deionized water rinsing cycles of 3 to 5 times.

[0066] By alternating acid etching and deionized water rinsing cycles 3-5 times (each etching lasts 10-30 seconds, followed by rinsing for 5 seconds), a hierarchical structure is formed with a surface porosity of 40-60% and a pore size of 5-20 nm, and a bottom layer porosity of 10-30% and a pore size ≤5 nm. The acid solution uses alternating HCl (5%) and HF (0.5%). After each etching cycle, ultrasonic cleaning with deionized water (frequency 40 kHz, time 1 minute) removes corrosion products.

[0067] The high porosity of the surface layer allows for rapid adsorption of H₂ from acidic solutions. +The dense structure of the bottom layer prevents acid penetration, ensuring that after immersion in strong acid (pH=1) and strong alkali (pH=13) environments for 72 hours, the mass loss rate is ≤0.3% (compared to ≥2% in traditional processes), meeting the GB / T15252-2020 Class I acid resistance standard. The hierarchical porous structure forms a refractive index gradient similar to an "anti-reflective coating" (surface layer n=1.2, bottom layer n=1.45), reducing light reflection at the glaze-air interface (reflectivity decreases from 8% to 3%). Simultaneously, the small pore size of the bottom layer suppresses light scattering, increasing light transmittance to over 88% (compared to ≤80% in traditional processes). The low porosity of the bottom layer (10-30%) ensures a membrane hardness ≥5H (pencil hardness), exhibiting excellent impact resistance (50cm drop ball impact) without cracking, superior to traditional porous membranes (hardness 4H, prone to cracking).

[0068] In some embodiments, the glass glaze layer is composed of at least two layers of glaze of different colors, with the bottom layer being an absorptive dark blue inorganic pigment layer and the top layer being an interference-type light blue pearlescent pigment layer; the two layers are locally acid-etched to form a light-transmitting micropore array with a pore diameter of 10 to 50 μm and a pore spacing of 100 to 200 μm, so that the incident light undergoes secondary refraction at the micropores to improve the light absorption rate of the solar cell.

[0069] Multi-layer glaze structure design: Bottom layer: Printed absorption-type deep blue inorganic pigment layer (mainly composed of CoO-Fe2O3), 8-12μm thick, absorbing the 400-500nm blue light band, improving the photovoltaic cell's response to short-wavelength light; Surface layer: Printed interference-type light blue pearlescent pigment layer (TiO2 coated with mica, particle size D90≤15μm), 5-8μm thick, forming a decorative blue appearance through light interference; Micropore array preparation: After printing the two layers, acid etching is performed on local areas of the surface layer (pore size 10-50μm, pore spacing 100-200μm) to form light-transmitting micropores, with a micropore density of 50-100 pores / cm². 2 .

[0070] The bottom-layer absorptive pigments enhance the absorption rate of blue light in the solar cells (quantum efficiency improved by 5-8%), while the surface interference pigments increase the proportion of diffuse light through light scattering (diffuse light ratio ≥30%), reducing specular reflection and achieving color uniformity on the building facade (ΔE≤1.5). Secondary refraction at the micropores causes incident light to undergo multiple reflections on the cell surface (reflection count ≥3 times), increasing the equivalent optical path by 15-20%, especially at low incident angles (≤30°), resulting in a 3-5% increase in short-circuit current. The two glaze layers are chemically bonded through sintering (Si-O bond connection), and the micropore edges are strengthened through secondary sintering, ensuring wind pressure resistance (withstanding 2.5kPa pressure) meets the requirements of GB / T 21086-2007 for curtain wall glass.

[0071] In some embodiments, the pigment comprises a pearlescent pigment of titanium dioxide coated mica with a particle size D90≤15μm and a surface modified by a silane coupling agent; the pearlescent pigment is oriented in the glaze layer with the orientation direction forming an angle of 30 to 60° with the plane of the glass substrate to enhance the reflectivity of near-infrared light to ≥85%.

[0072] Pearl pigment modification and alignment: Surface modification: Pearl pigments with titanium dioxide-coated mica (particle size D90≤15μm) are modified with silane coupling agent (γ-methacryloyloxypropyltrimethoxysilane). The modification process is as follows: the pigment and coupling agent (1-3% of the pigment mass) are stirred at 80℃ for 30 minutes to form a surface silanized layer. Orientation: During printing, the orientation of the pigment is controlled by the squeegee angle (45-60°) so that the angle between the pearl pigment and the substrate plane in the glaze layer is 30-60°. The alignment consistency is observed by polarizing microscope (orientation deviation ≤10°).

[0073] Oriented pearlescent pigments exhibit a reflectivity of ≥85% for near-infrared light (700-1100nm) compared to ≤70% for conventionally randomly arranged pigments, reducing heat absorption on building facades (lowering surface temperature by 5-8℃ in summer), reducing air conditioning load, and achieving building energy conservation. Silane coupling agent modification improves the compatibility between the pigment and glass powder, resulting in a ≤5% delamination rate after 24 hours of ink standing (≥30% for conventional unmodified pigments), and enhanced adhesion between the pigment and glaze layer after sintering (no peeling test). Oriented arrangement avoids the decrease in light transmittance caused by pigment agglomeration (visible light transmittance ≥75%), while enhancing color consistency across multiple angles (color difference ΔE ≤1.0 between front and side views), meeting the decorative requirements of high-end building facades.

[0074] In some embodiments, the acid solution is hydrochloric acid with a concentration of 5% to 10%, or a corrosive acid solution containing hydrofluoric acid; wherein, acid etching removes acid-sensitive ions and B2O3 components from the surface of the glass enamel layer, thereby increasing the SiO2 content in the nano-glass film layer to more than 70%; the tempering sintering temperature is 650 to 700°C to form a dense glass enamel layer.

[0075] Optimization of acid etching and tempering process: Acid selection: Use 5-10% hydrochloric acid (wt%) or corrosive acid containing HF (HF concentration ≤2 vol%) to remove acid-sensitive R2O ions and B2O3 components from the surface of the colored glaze layer through acid etching, thereby increasing the SiO2 content in the nanofilm layer to over 70% (EDS energy dispersive spectroscopy detection); sintering temperature is controlled at 650-700℃ (600-730℃ for traditional processes), and the holding time is 15-20 minutes to form a dense glass colored glaze layer (density ≥98%, porosity ≤2%).

[0076] After removing surface B2O3 (a component easily corroded by acid), the film layer loses ≤0.2% after immersing in 5% sulfuric acid solution for 48 hours (compared to ≥3% weight loss with B2O3 layer in traditional processes), achieving the highest acid resistance rating (A1 grade) of ISO 1515-1981 standard. Sintering at 650-700℃ ensures the glass powder fully melts without excessive flow, forming a uniform and dense glaze layer (hardness 6H, elastic modulus 70GPa). Simultaneously, the coefficient of thermal expansion is ≤5% of the substrate's tolerance, preventing film cracking (compared to ≥10% cracking rate in traditional high-temperature sintering). Utilizing a traditional glass powder system (without adding high-valence oxides), surface defects are removed through acid etching, improving acid resistance while reducing production costs by 60% compared to surface coating methods, making it suitable for large-scale industrial production (single-line capacity ≥500,000 m³). 2 / Year).

[0077] In some embodiments, a database containing over 500 historical glass powder compositions (SiO2, R2O, B2O3, Al2O3 percentages), coefficients of thermal expansion (CTE), softening points (SP), and acid resistance weight loss rates (AR) is constructed. A BP neural network is used to establish a composition-performance mapping model (4 nodes in the input layer, 20 nodes in the hidden layer, and 3 nodes in the output layer). The CTE is matched with the ultra-white glass substrate (9±0.9×10). -7 The optimal composition was determined by optimizing the model parameters using a genetic algorithm: SiO2 52%, Na2O 18%, K2O 3%, B2O3 10%, and Al2O3 17% (mass percentage) with a concentration of 5% hydrochloric acid, SP ≤ 650℃, and AR ≤ 0.5% (after soaking in 5% hydrochloric acid for 24 hours). When mixing the optimized glass powder with pigments and organic carriers, an online particle size analyzer (such as a Malvern Panaco Mastersizer 3000) was used to provide real-time feedback on the D50 particle size. The ball milling time was automatically adjusted via a PLC system (target D50 ≤ 4μm) with an error of ±0.5μm.

[0078] The error in the coefficient of thermal expansion is reduced to ±5% (compared to ≥10% with traditional trial-and-error methods), completely resolving the film cracking problem; the softening point is lowered to 630℃, making it compatible with low-temperature tempering furnaces (reducing energy consumption by 20%), while the acid resistance weight loss rate is reduced to 0.3% (10 times better than traditional processes). The composition optimization cycle is shortened from the traditional 3-6 months to 72 hours, reducing experimental trial-and-error costs by 90%, and supporting rapid response to the special performance requirements of personalized BIPV projects (such as glazes for high-altitude, high-UV environments). Online particle size monitoring enables dynamic closed-loop control of ink particle size, with density fluctuations in the sintered glaze layer ≤1% (compared to ≥5% with traditional processes), and film thickness uniformity improved to over 98%.

[0079] In some embodiments, a Raman spectrometer (sampling frequency 10Hz) and an electrochemical impedance spectroscopy (EIS) are integrated in the acid etching tank to monitor the changes in SiO2 content and porosity on the film surface in real time. The acid concentration (HCl 3-8% + HF 0.3-1.5%) and etching time (30-90 seconds per stage) are dynamically adjusted by a fuzzy control algorithm.

[0080] Phase 1: Etching with 5% HCl for 60 seconds to remove the surface R layer. + Ions, simultaneously activated by low-frequency plasma (13.56MHz, 50W), bombard the surface, breaking the Si-OB bonds and promoting the dissolution of B2O3. Second stage: Switch to mixed acid containing 1% HF, adjust the etching time according to real-time spectral data (target SiO2 content 75±2%), and immediately after completion, bombard with Ar plasma (power 100W) for 10 seconds to repair surface microcracks.

[0081] Through plasma-assisted acid etching, the SiO2 content in the film is increased to 78% (70% in traditional gradient acid etching), and the B2O2 residue is ≤1% (5-8% in traditional processes). The amount of ion precipitation is reduced by 60% in acid and alkali resistance tests. Plasma bombardment forms a nano-scale dense silicon oxide layer (5-10nm thick) on the film surface, increasing the hardness to 7H (pencil hardness). Its resistance to sand and dust impact (150m / s wind speed) is 3 times better than that of traditional films.

[0082] The intelligent system automatically identifies the compositional fluctuations of different batches of colored glaze layers (such as R2O content ±2%) and dynamically adjusts the acid etching parameters to make the film refractive index consistency error ≤ ±0.02 (traditional process error ±0.08), increasing the yield from 85% to 97%.

[0083] Plasma treatment reduces HF usage by 30% (from 1% to 0.7%), while reducing the concentration of metal ions in etching wastewater by 40% and lowering wastewater treatment costs by 25%.

[0084] In some embodiments, a silica pillar array metasurface (duty cycle 0.6-0.8) with a period of 200-500 nm and a height of 50-100 nm is designed using FDTD (finite-difference time-domain method) simulation. This structure achieves a reflectivity of ≤1% and a transmittance of ≥95% in the 300-1200 nm wavelength band.

[0085] Step-by-step fabrication process: Step 1: A polymethyl methacrylate (PMMA) mold is prepared on an ultra-white glass substrate using nanoimprint lithography (NIL) at a pressure of 5 MPa and a temperature of 110°C to form a microstructure master. Step 2: Glass enamel ink (containing 5% nano-SiO2 particles with a particle size of 20 nm) is filled into the microstructure grooves. After sintering at 650°C, the PMMA mold undergoes pyrolysis and volatilization, leaving an enamel layer integrated with the metasurface structure. Step 3: The surface of the raised structure is treated with oxygen plasma (80 W power, 30 seconds) to improve hydrophilicity (contact angle ≤10°) and reduce dust adhesion.

[0086] The metasurface structure achieves a "zero-reflection" optical interface (reflectivity reduced from the traditional 8% to 0.8%), increasing the equivalent transmittance to over 95% (traditional processes ≤88%), and improving the short-circuit current of photovoltaic modules by 7-10%. The wide-angle diffuse effect (scattering angle ≥45°) increases light absorption efficiency by 25% at low incident angles (≤20°), solving the bottleneck of power generation efficiency in traditional planar colored glazes under low light conditions in the morning and evening. The nanopillar structure increases the specific surface area of ​​the film by 3 times. The porous layer formed after acid etching synergizes with the metasurface, improving acid resistance to GB / T 15252-2020 Grade I (the highest grade). Simultaneously, the hydrophilic surface enhances self-cleaning ability (dust residue ≤5% after rainwater washing). The nanoimprint mold has a lifespan of over 100,000 cycles, with a single imprint area ≥1㎡, reducing production costs by 80% compared to photolithography, making it suitable for large-area industrial production of architectural glass.

[0087] In some embodiments, a gradient composition glaze layer design is used: bottom layer (close to the glass substrate): high R2O content (Na2O+K2O=22%) formulation, CTE=9.2×10^-7 / ℃, thickness 8μm, to enhance thermal matching with the substrate; middle layer: medium R2O (15%) + high B2O3 (18%) formulation, softening point 620℃, thickness 6μm, as a stress buffer layer; top layer: low R2O (8%) + high SiO2 (65%) formulation, which forms a high silicon nanofilm layer after acid etching, with a thickness of 6μm; each layer is printed at a 5-minute interval and left to dry at room temperature, and the uniformity of each layer is monitored online using a thickness profiler (error ≤±3%).

[0088] Photovoltaic cell coupling optimization: In the grid line region corresponding to the gradient enamel layer of the solar cell, transparent micropores with a diameter of 50 μm are created by laser micromachining (wavelength 355 nm, power 10 W), with a pore density of 200 pores / cm². 2 This ensures that the current collection efficiency is not affected.

[0089] Thermal stress elimination in all dimensions: Gradient layer CTE from the bottom layer 9.2×10 -7 The temperature gradually transitions from 8.5 × 10 °C to 8.5 × 10 °C on the surface. -7 / ℃, with substrate (9×10 -7 The interfacial stress is reduced by 70% ( / ℃), and it does not crack after 500 cycles of hot and cold cycling from -40℃ to 85℃ (traditional single-layer will crack after 100 cycles).

[0090] After acid etching, the high-silica surface coating exhibits UV aging resistance (3000 hours) with a light transmittance decrease of ≤2% (compared to 15% for traditional single-layer coatings), and is resistant to salt spray corrosion (NSS test 1000 hours) with no peeling of the film layer, meeting the requirements for use in highly corrosive coastal environments.

[0091] The softening point of the gradient layer ranges from 620℃ at the bottom layer to 680℃ at the surface layer. During sintering, a "bottom layer melt anchoring - surface layer semi-melted and dense" structure is formed, which improves the light absorption matching degree between the cell and the colored glaze layer (spectral response matching degree ≥92%), and the module efficiency is 3.5% higher than that of the traditional structure.

[0092] In some embodiments, a multiphysics coupled simulation platform is established, which includes a glass substrate heat transfer model (ANSYS Fluent), a colored glaze layer sintering kinetic model (JMA equation), and an acid etching process mass transfer model (Fick's law). Real-time production data (such as furnace temperature fluctuation ±2℃ and acid concentration drift ±1%) is input for dynamic calibration.

[0093] Intelligent production control: An infrared thermal imager matrix (accuracy ±1℃) is arranged in the tempering furnace to capture the temperature distribution of the glass surface in real time. The digital twin system predicts the risk of film cracking and automatically adjusts the heating rate (±0.5℃ / min). The acid etching line integration uses a machine vision system (resolution 5μm / pixel) to identify film surface defects (such as pinholes and uneven thickness) and uses a model to back-calculate the optimal acid etching parameters for compensation (such as time ±5 seconds and concentration ±0.5%).

[0094] The digital twin system reduces the tempered glass cracking rate from the traditional 12% to 0.8%, the acid etching defect rate from 8% to 1.2%, and the overall yield to 98.5% (industry average ≤95%). It supports multi-variety, small-batch production (changeover time ≤30 minutes) and meets the personalized design needs of building-integrated photovoltaics (BIPV) systems (such as gradient color and artistic patterned enamel glass). Through optimized heat flow during sintering, energy consumption per square meter of glass is reduced by 15% (from 1.2 kWh / m²). 2 Reduced to 1.02 kWh / m 2 The automatic acid etching solution compensation system reduces chemical consumption by 20%, while the effective component recovery rate in waste acid solution reaches 30% (through membrane distillation technology), achieving green manufacturing.

[0095] Quality traceability and continuous optimization: Each batch of products generates an independent digital twin file, including ingredients, process parameters, and performance data, supporting full lifecycle quality traceability (traceability time ≤ 10 minutes), accumulating tens of millions of effective data for subsequent product iterations.

[0096] In some embodiments, the surface of the lotus leaf is observed by scanning electron microscopy to replicate its hierarchical structure of "micropapillae (5-10 μm) + nanowax crystals (100-200 nm)", and a composite structure of silica micropillars (15 μm in height and 8 μm in diameter) + titanium dioxide nanowires (200 nm in length) is prepared on the surface of the colored glaze layer.

[0097] Step-by-step preparation process: Step 1: Screen printing a glaze containing 5μm silica microspheres, which, after sintering, forms micron-sized protrusions (density 500 protrusions / cm²). 2 The second step involves growing titanium dioxide nanowires (50 nm thick) on the surface of the protrusions using atomic layer deposition (ALD) to create a nanoscale roughness (Ra = 80-100 nm). The third step involves preserving the protrusion structure during acid etching and etching only the concave areas to create a composite surface that is hydrophobic to the protrusions and porous and acid-resistant to the concave areas. Finally, a 0.1 μm thick hydrophobic fluorinated silane layer is coated (contact angle ≥ 150°, roll-off angle ≤ 5°).

[0098] The lotus leaf-inspired structure allows rainwater to carry away over 95% of dust particles (compared to only 60% on traditional surfaces), reducing manual cleaning frequency by 70%. The dense silica layer in the raised areas resists acid corrosion (weight loss ≤0.1%), while the porous structure in the recessed areas enhances overall acid resistance, achieving a balance between strong hydrophobicity and high corrosion resistance. Optical and electrical optimization is achieved through a hierarchical structure that reduces light reflection (overall reflectivity ≤4%), while titanium dioxide nanowires enhance ultraviolet light absorption (20% increase in absorption rate at 300-400nm), promoting the ultraviolet response of photovoltaic cells and increasing short-circuit current by 2-3%. The fluorinated silane coating chemically bonds with the high-silica film formed by acid etching; after 500 hours of ultraviolet aging, the contact angle decreases by ≤10% (compared to ≥30% for traditional coatings), extending the self-cleaning performance maintenance period to over 3 years.

[0099] It should be noted that those skilled in the art will clearly understand that, for the sake of convenience and brevity, the specific structure and connection process of the photovoltaic modules and each module described above can be referred to the corresponding process in the embodiments of the preparation method of the high transmittance and high acid and alkali resistant double-layer glass glaze structure described above, and will not be repeated here.

[0100] The above description is merely a specific embodiment of this application, but the scope of protection of this application is not limited thereto. Any person skilled in the art can easily conceive of various equivalent modifications or substitutions within the technical scope disclosed in this application, and these modifications or substitutions should all be covered within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. A method for preparing a high-transmittance, highly acid- and alkali-resistant double-layer glass enamel structure, characterized in that, include: Provides ultra-white glass substrates with thicknesses ranging from 1.5 to 8 mm; Glass powder, pigments, and an organic carrier are mixed to form a glass enamel ink. The glass powder is a SiO2, R2O, B2O3 system, the pigments are absorption-type inorganic pigments or interference-type pearlescent pigments, and the organic carrier is a water-based acrylic resin system. The glass powder content is 50% to 75%, and the pigment content is ≤20%. The glass enamel ink is applied to the surface of the ultra-white glass substrate by screen printing, roller printing, or spraying, and tempered and sintered at 600 to 730°C to form a glass enamel layer with a thickness of 10 to 20 μm. The glass enamel layer is acid-etched using an acid solution containing one or more of sulfuric acid, hydrochloric acid, nitric acid, and hydrofluoric acid. By controlling the acid concentration, etching time, and temperature, a nano-glass film is formed on the surface of the glass enamel layer. The nano-glass film has a SiO2 content of more than 50%, a thickness of 100 to 200 nm, and a refractive index of 1.1 to 1.

3. The acid-etched glass substrate was sequentially ultrasonically cleaned with water, ethanol, and deionized water, and then dried to obtain a high-transmittance, highly acid- and alkali-resistant double-layer glass enamel structure.

2. The method according to claim 1, characterized in that, The process of mixing glass powder, pigments, and organic carriers to form glass enamel ink includes: The glass powder is composed of 45 to 55% SiO2, 15 to 25% R2O, 5 to 12% B2O3 and the balance Al2O3 by mass percentage; ball milling is used for mixing, with a ball-to-material ratio of 2:1, a rotation speed of 200 to 300 rpm, and a mixing time of 2 to 4 hours, so that the particle size D50 is ≤5μm. In R₂O, R is either Na or K.

3. The method according to claim 1, characterized in that, The step of etching the glass enamel layer with an acid solution containing one or more of sulfuric acid, hydrochloric acid, nitric acid, and hydrofluoric acid includes: When the acid solution contains hydrofluoric acid, the concentration is controlled between 0.5 and 3 vol%; if the acid solution is a hydrochloric acid single-liquid system, the concentration range is 5 to 15 wt%; the acid etching temperature is set between 25 and 50°C, the treatment time is 30 to 120 seconds, and the reaction is terminated when the refractive index of the film reaches 1.2 ± 0.05 by monitoring with an online spectrometer.

4. The method according to claim 1, characterized in that, The process of forming a nano-glass film layer on the surface of the glass enamel layer by controlling the acid concentration, etching time, and temperature includes: A gradient acid etching process was employed. In the first stage, the surface R layer was removed by treating with 5% hydrochloric acid for 60 seconds. + The second stage involves switching to a mixed acid treatment containing 1% hydrofluoric acid for 20 seconds to form a porous high-silicon layer with a porosity of 30 to 50%, resulting in a final film thickness of 120 to 180 nm.

5. The method according to claim 1, characterized in that, The process of applying the glass enamel ink to the surface of the ultra-white glass substrate by screen printing, roller printing, or spraying includes: When screen printing, use a 250 to 350 mesh nickel screen, with a printing pressure of 0.2-0.4 MPa. Print in two stages, and after each printing, preheat and dry at 80-120℃ for 5-10 minutes to ensure that the uniformity of the glaze thickness is ≤±5%.

6. The method according to claim 1, characterized in that, The nanoglass film has a hierarchical porous structure, wherein the surface layer has a porosity of 40 to 60% and a pore size of 5 to 20 nm; the bottom layer has a porosity of 10 to 30% and a pore size of ≤ 5 nm; the porous structure is formed by alternating acid etching and deionized water rinsing cycles of 3 to 5 times.

7. The method according to claim 1, characterized in that, The glass glaze layer is composed of at least two layers of glaze of different colors. The bottom layer is an absorptive dark blue inorganic pigment layer, and the top layer is an interference-type light blue pearlescent pigment layer. The two layers are locally acid-etched to form a light-transmitting micropore array with a pore diameter of 10 to 50 μm and a pore spacing of 100 to 200 μm, so that the incident light undergoes secondary refraction at the micropores to improve the light absorption rate of the solar cell.

8. The method according to claim 1, characterized in that, The pigment comprises a pearlescent pigment of titanium dioxide coated with mica, with a particle size D90≤15μm and a surface modified by a silane coupling agent; the pearlescent pigment is oriented in the glaze layer, with the orientation direction forming an angle of 30 to 60° with the plane of the glass substrate to enhance the reflectivity of near-infrared light to ≥85%.

9. The method according to claim 1, characterized in that, The acid solution is hydrochloric acid with a concentration of 5% to 10%, or a corrosive acid solution containing hydrofluoric acid; In this process, acid etching is used to remove acid-sensitive ions and B2O3 components from the surface of the glass enamel layer, thereby increasing the SiO2 content in the nano glass film to over 70%. The tempering sintering temperature is 650 to 700°C to form a dense glass enamel layer.

10. A high-transmittance, highly acid- and alkali-resistant double-layer glass enamel structure, characterized in that, Prepared by the method according to any one of claims 1 to 9.

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