High-impact transparent glaze, its preparation method and application

Abstract

This application provides a high-impact transparent glaze, its preparation method, and its application, belonging to the field of glass glazes. The transparent glaze is composed of 45%–60% silicon dioxide, 12%–20% boron oxide, 6%–12% zinc oxide, 5%–12% bismuth oxide, 3%–8% aluminum oxide, 1%–4% alkali metal oxides, and 1%–5% alkaline earth metal oxides. This application controls the coefficient of thermal expansion of the glaze to 8.0–9.0 × 10⁻⁶ by constructing a high-silicon, low-bismuth, and boron-zinc synergistic formulation system. ‑6 / ℃, with an absolute deviation from the sodium-calcium-silicon photovoltaic glass substrate ≤0.5×10 ‑6 / ℃, eliminating residual tensile stress on the non-glazed surface of tempered glass from the root, increasing the impact resistance of photovoltaic front panel glass by 1 to 2 times, significantly reducing raw material costs, and fully meeting core performance standards such as light transmittance, acid and alkali resistance, PID resistance and adhesion, making it suitable for BIPV photovoltaic front panel glass, household appliance glass and automotive glass and other fields.

Description

Technical Field

[0001] This invention relates to the field of glass glaze technology, specifically to a high-impact transparent glaze, its preparation method, and its application. Background Technology

[0002] Currently, the BIPV (Building Integrated Photovoltaics) field commonly uses high-temperature transparent enamel for surface treatment of photovoltaic front-panel glass to improve the weather resistance and corrosion resistance of the modules. However, after tempering, the impact strength of the uncoated glass surface (i.e., the glass surface) of existing high-temperature transparent enamels in the industry experiences an irreversible and significant decrease, which has become a core pain point restricting the safety performance of BIPV products. Tests show that the impact resistance of currently mass-produced transparent enamels in the industry is as follows: 2.0~3.2mm thick glass can only withstand a 30~40cm height impact from a 227g steel ball without breaking; 5.0~6.0mm thick glass can only withstand a 70~80cm height impact from a 1040g steel ball without breaking. The main reason for this is the mismatch in the coefficients of thermal expansion between the enamel and the glass substrate. The coefficient of thermal expansion of existing high-temperature transparent enamels is approximately 9.2×10⁻⁶. -6 ~9.8×10 -6 / ℃ (20~300℃), generally higher than that of sodium-calcium-silicon photovoltaic glass substrates (8.5×10). -6 ~9.0×10 -6 / ℃). During the tempering and cooling process, the glaze shrinks faster than the glass substrate, resulting in residual tensile stress on the non-glazed surface of the glass, which significantly reduces its impact resistance.

[0003] In addition, existing high-temperature transparent glazes also have the following problems: high sodium oxide content, which easily causes potential-induced degradation (PID) in photovoltaic modules; insufficient acid resistance, limiting their application in highly corrosive areas such as coastal areas and chemical plants; poor tempering tolerance of acid-resistant glazes developed to improve acid resistance, resulting in different color hues at different tempering temperatures within the 680~720℃ range, affecting appearance; and high raw material costs due to the extensive use of precious metals such as bismuth oxide. Currently, industry research mainly focuses on optimizing the impact resistance of high-reflectivity white / black materials or low-transparency glazes for photovoltaic backsheet glass, and there is still no mature solution to the core problem of reduced impact resistance of the glass surface after tempering of high-temperature ultra-transparent glazes for photovoltaic front panels. Summary of the Invention

[0004] In view of the technical problems existing in the background art, this application provides a high impact-resistant transparent glaze, its preparation method and application, aiming to solve the technical problems of existing high-temperature transparent glazes, which cause a significant decrease in the impact resistance of the uncoated glass surface after tempering due to the mismatch between the coefficient of thermal expansion and the glass substrate, and at the same time, it is difficult to take into account the light transmittance, acid resistance, anti-PID performance and production cost.

[0005] In a first aspect, this application provides a high-impact transparent glaze, which, by weight percentage, comprises the following components: The composition is as follows: silicon dioxide 45%~60%, boron oxide 12%~20%, zinc oxide 6%~12%, bismuth oxide 5%~12%, aluminum oxide 3%~8%, alkali metal oxides 1%~4%, alkaline earth metal oxides 1%~5%; the sum of the mass percentages of all components is 100%. Wherein, the alkali metal oxide is at least one of sodium oxide and potassium oxide; the alkaline earth metal oxide is at least one of calcium oxide, magnesium oxide and barium oxide; The coefficient of thermal expansion of the high-impact transparent glaze at 20~300℃ is 8.0×10⁻⁶. -6 / ℃~9.0×10 -6 / ℃, and the absolute value of the deviation of the coefficient of thermal expansion from that of the sodium-calcium-silicon photovoltaic glass substrate is ≤0.5×10 -6 / ℃.

[0006] As a further improvement of this application, the mass ratio of silicon dioxide to boron oxide is 2.5:1 to 4:1; the mass ratio of bismuth oxide to zinc oxide is 0.5:1 to 1.5:1.

[0007] As a further improvement of this application, the ratio of the total content of the alkali metal oxides to the total content of the alkaline earth metal oxides is 0.5:1 to 2:1.

[0008] As a further improvement of this application, the absolute value of the deviation between the thermal expansion coefficient of the high-impact transparent glaze and that of the sodium-calcium-silicon photovoltaic glass substrate is ≤0.3×10⁻⁶. -6 / ℃.

[0009] Secondly, this application provides a method for preparing a high-impact transparent glaze, comprising the following steps: After drying and sieving each component raw material, they are weighed according to the formula ratio and placed in a ball mill to be ball-milled and mixed with zirconium oxide as the grinding medium to obtain a mixture. The mixture is melted at 1200~1250℃ for 2~3 hours, and then quickly poured into deionized water for quenching to obtain glass fragments; The glass fragments were ball-milled to a fineness of D97≤10μm and D50≤3μm, and then sieved to obtain glass powder. The glass powder and organic carrier are mixed evenly at a mass ratio of (70~75):(25~30), and the viscosity is adjusted to 2000~3000mPa·s to obtain a high-impact transparent glaze.

[0010] As a further improvement of this application, the ball milling speed is 280~320 r / min, the ball milling time is 3~4 h, and the mixing uniformity is ≥98%.

[0011] As a further improvement of this application, the organic carrier is a system of terpineol and ethyl cellulose, wherein the mass fraction of ethyl cellulose is 5% to 8%.

[0012] Thirdly, this application provides a photovoltaic front panel glass, including a glass substrate and an enamel layer disposed on the surface of the glass substrate. The enamel layer is formed by printing, drying, and tempering a high-impact transparent enamel obtained by the preparation method described in the first aspect or the second aspect. In the tempering process, the upper temperature of the tempering furnace is 680~710℃, the lower temperature is 650~680℃, the temperature difference between the upper and lower parts is 10~30℃, the upper wind pressure is 2.0~3.0kPa, the lower wind pressure is 2.5~4.5kPa, and the lower wind pressure is 0.5~1.5kPa higher than the upper wind pressure.

[0013] As a further improvement of this application, the thickness of the glaze layer is 15~25μm; the heating time of the tempering treatment is: 120~150s for 2.0mm thick glass, 180~220s for 3.2mm thick glass, and 280~320s for 5.0mm thick glass; the cooling time is 30~60s.

[0014] Fourthly, this application provides an application of the photovoltaic front panel glass described in the third aspect in architectural safety glass, appliance glass, or automotive glass.

[0015] The beneficial effects of this application are as follows: This application provides a high-impact transparent glaze, its preparation method, and its application. The transparent glaze, by mass percentage, comprises the following components: 45%–60% silicon dioxide, 12%–20% boron oxide, 6%–12% zinc oxide, 5%–12% bismuth oxide, 3%–8% aluminum oxide, 1%–4% alkali metal oxides, and 1%–5% alkaline earth metal oxides; the sum of the mass percentages of all components is 100%; wherein the alkali metal oxide is at least one of sodium oxide and potassium oxide; and the alkaline earth metal oxide is at least one of calcium oxide, magnesium oxide, and barium oxide; the coefficient of thermal expansion of the high-impact transparent glaze at 20–300°C is 8.0 × 10⁻⁶. -6 / ℃~9.0×10 -6 / ℃, and the absolute value of the deviation of the coefficient of thermal expansion from that of the sodium-calcium-silicon photovoltaic glass substrate is ≤0.5×10 -6 / ℃. The high-impact transparent glaze provided in this application, through the construction of a novel formulation system featuring high silicon and low bismuth, synergistic boron and zinc, and precise alkaline earth adjustment, precisely controls the coefficient of thermal expansion of the glaze to 8.0-9.0×10.-6 / ℃, achieving an absolute deviation of ≤0.5×10 from the photovoltaic glass substrate. -6 The submicron-level matching at / ℃ eliminates residual tensile stress on the unglazed surface after tempering, improving the impact resistance of the unglazed glass by 1-2 times compared to existing technologies. Simultaneously, while meeting core performance standards in light transmittance, acid and alkali resistance, PID resistance, and adhesion, the bismuth oxide content is reduced from 18% to 5-12%, lowering raw material costs. This glaze is free of harmful substances such as lead, cadmium, arsenic, mercury, and fluorides, complying with RoHS environmental standards. Furthermore, it can be mass-produced on existing screen printing and tempering production lines (yield ≥98%) without requiring additional production equipment, and can be widely used in BIPV photovoltaic front panel glass, architectural safety glass, appliance glass, and automotive glass.

[0016] The above description is only an overview of the technical solution of this application. In order to better understand the technical means of this application and to implement it in accordance with the contents of the specification, and to make the above and other objects, features and advantages of this application more obvious and understandable, the following are specific embodiments of this application. Attached Figure Description

[0017] To more clearly illustrate the technical solutions of this application, the accompanying drawings used in this application will be briefly described below. Obviously, the drawings described below are merely some embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without any creative effort.

[0018] Figure 1 The thermal expansion performance curve of the high impact-resistant transparent glaze provided in Embodiment 1 of this application. Detailed Implementation

[0019] The embodiments of the technical solution of this application will now be described in detail with reference to the accompanying drawings. These embodiments are only used to more clearly illustrate the technical solution of this application and are therefore merely examples, and should not be used to limit the scope of protection of this application.

[0020] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the application; the terms “comprising” and “having”, and any variations thereof, in the specification, claims, and foregoing description of the drawings are intended to cover non-exclusive inclusion.

[0021] In the description of the embodiments of this application, technical terms such as "first" and "second" are used only to distinguish different objects and should not be construed as indicating or implying relative importance or implicitly specifying the number, specific order, or primary and secondary relationship of the indicated technical features. In the description of the embodiments of this application, "multiple" means two or more, unless otherwise explicitly defined.

[0022] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments.

[0023] In the description of the embodiments of this application, the term "multiple" refers to two or more (including two), similarly, "multiple sets" refers to two or more (including two sets), and "multiple pieces" refers to two or more (including two pieces).

[0024] The coefficient of thermal expansion of existing high-temperature transparent glazes is 9.2-9.8×10⁻⁶. -6 / ℃, generally higher than that of sodium-calcium-silicon photovoltaic glass substrates (8.5-9.0×10). -6 During the tempering and cooling process, the glaze shrinks at a faster rate, resulting in residual tensile stress on the non-glazed surface of the glass, significantly reducing its impact resistance. Blindly adjusting the glaze formula can easily lead to secondary problems such as decreased light transmittance, glaze crystallization, deterioration of acid and alkali resistance, and substandard PID resistance. Existing glazes heavily utilize precious metals such as bismuth oxide (approximately 18%), resulting in raw material costs as high as 180 yuan / kg, which drives up the overall production cost of colored photovoltaic front-panel glass.

[0025] To address the technical problems of excessively high thermal expansion coefficient, residual tensile stress on the non-glazed surface after tempering, and decreased impact resistance in existing glazes, this application provides a high-impact transparent glaze, its preparation method, and its application. Specifically, by precisely controlling the glaze composition and ratio, abandoning the industry's traditional high-Bi2O3 fluxing route, a novel formulation system is constructed, featuring high silicon and low bismuth, boron-zinc synergy, and precise alkaline earth adjustment, thereby controlling the glaze's thermal expansion coefficient within 8.0-9.0 × 10⁻⁶. -6 / ℃, absolute deviation from the glass matrix ≤0.3×10 -6 / ℃, its thermal expansion coefficient is controlled to be slightly lower than or close to the level of the glass substrate, eliminating residual tensile stress on the non-glazed surface after tempering from the root; and the tempering process parameters are adjusted in a coordinated manner, optimizing the temperature difference and air pressure ratio of the upper and lower parts of the tempering furnace, further improving the stress uniformity of the glass surface, and achieving a secondary improvement in impact resistance; at the same time, the formula is optimized, reducing the amount of bismuth oxide from 18% to 5-12%, and through the synergistic adjustment of the glass network structure by multiple components, while ensuring melting performance and optical performance, the production cost is significantly reduced.

[0026] In a first aspect, embodiments of this application provide a high-impact transparent glaze, which, by mass percentage, comprises the following components: 45%~60% silicon dioxide (SiO2) forms the glass network skeleton, reduces the coefficient of thermal expansion, and improves chemical stability and mechanical strength. If the content is <45%, a complete skeleton cannot be formed, and the coefficient of thermal expansion exceeds the standard. If the content is >60%, the melting temperature is too high, resulting in significant residual compressive stress, which causes glass warping, and the glaze layer is prone to pinholes. Boron oxide (B2O3) 12%~20%, a flux, lowers the glass softening temperature, adjusts the network structure, and improves the fluidity of the glaze; if the content is <12%, the fluxing effect is insufficient; if the content is >20%, the chemical stability of the glaze is reduced. Zinc oxide (ZnO) 6%~12% is a flux that improves the density and chemical stability of the glaze and regulates the coefficient of thermal expansion. If the content is <6%, the glaze density is insufficient; if the content is >12%, it is easy to cause crystallization on the glaze surface. Bismuth oxide (Bi2O3) of 5%~12% reduces melting temperature and surface tension, improves the adhesion between the glaze and glass, and reduces the amount of precious metals used; if the content is <5%, the adhesion is insufficient and it is easy to fall off; if the content is >12%, the coefficient of thermal expansion exceeds the standard, and the cost increases. Alumina (Al2O3) 3%~8% strengthens the glass network structure, improves hardness and weather resistance, and adjusts the refractive index; if the content is <3%, the stability is insufficient; if the content is >8%, the melting temperature is too high. Alkali metal oxides, 1%~4%, are powerful fluxing agents. The content should be strictly controlled to avoid excessively increasing the coefficient of thermal expansion; if the content is >4%, it will excessively increase the coefficient of thermal expansion. Alkaline earth metal oxides (1%~5%) enhance the network structure, precisely fine-tune the coefficient of thermal expansion, and improve the thermal stability of the glaze layer. The sum of the mass percentages of all components is 100%. Among them, the alkali metal oxide is at least one of sodium oxide and potassium oxide; the alkaline earth metal oxide is at least one of calcium oxide, magnesium oxide and barium oxide; The coefficient of thermal expansion of the high-impact transparent glaze at 20~300℃ is 8.0×10⁻⁶. -6 / ℃~9.0×10-6 / ℃, and the absolute value of the deviation of the coefficient of thermal expansion from that of the sodium-calcium-silicon photovoltaic glass substrate is ≤0.5×10 -6 / ℃.

[0027] In the technical solution of this application embodiment, synergistic effects are achieved through component formulation design: SiO2-B2O3-ZnO network synergy: SiO2 provides a rigid framework, B2O3 breaks Si-O bonds at high temperatures to lower the melting temperature, and ZnO fills network voids to increase density. The synergy of these three components enables the glaze to achieve high strength and a low coefficient of thermal expansion at lower temperatures; Bi2O3-alkaline earth metal oxide interface synergy: Bi2O3 promotes wetting of the glaze layer and the substrate, and alkaline earth metals undergo ion exchange at the interface to form a gradient transition layer. The synergy of these two components ensures excellent adhesion even with low bismuth content; Al2O3-alkali metal oxide stability synergy: Al2O3 increases network connectivity, and a small amount of alkali metals offsets the increase in melting temperature caused by them, synergistically ensuring the processing performance and chemical stability of the glaze. The glaze formulation design of this application does not contain harmful heavy metal elements such as lead, cadmium, arsenic, and mercury, nor does it contain volatile harmful substances such as fluorides, complying with RoHS environmental standards.

[0028] Furthermore, in some embodiments, the mass ratio of silicon dioxide to boron oxide is 2.5:1 to 4:1; the mass ratio of bismuth oxide to zinc oxide is 0.5:1 to 1.5:1. The ratio of the total content of alkali metal oxides to the total content of alkaline earth metal oxides is 0.5:1 to 2:1.

[0029] In the technical solution of this application embodiment, the mass ratio of SiO2 to B2O3 helps balance the rigidity of the network skeleton and the melt flowability, ensuring that the glaze fully melts at 1200-1250℃ while maintaining a low coefficient of thermal expansion; the mass ratio of Bi2O3 to ZnO helps coordinate the interfacial bonding force and the density of the glaze layer, ensuring excellent adhesion and avoiding crystallization even with low bismuth content; by limiting the amount of alkali metals with high expansion coefficients, combined with the network strengthening effect of alkaline earth metals, submicron-level precise control of the coefficient of thermal expansion is achieved. Through the synergistic cooperation of each component, the glaze can simultaneously meet the requirements of low expansion matching, high impact resistance, and good processing performance under the premise of low bismuth and low cost.

[0030] Furthermore, in some embodiments, the absolute value of the deviation between the thermal expansion coefficient of the high-impact transparent glaze and that of the sodium-calcium-silicon photovoltaic glass substrate is ≤0.3×10⁻⁶. -6 / ℃.

[0031] In the technical solution of this application embodiment, addressing the fundamental contradictions of excessively high thermal expansion coefficient of existing glazes, residual tensile stress on non-glazed surfaces after tempering, and decreased impact strength, the formulation design of this application solves these problems through the following three aspects: 1. Significantly increasing the SiO2 content (from 42% in the prior art to 45-60%) to construct a dense glass network skeleton, fundamentally reducing the intrinsic thermal expansion coefficient of the glaze; 2. Replacing part of Bi2O3 with a B2O3-ZnO composite flux system, reducing the amount of precious metals used while ensuring the melting temperature (1200-1250℃) and glaze fluidity; 3. Strengthening the network structure with Al2O3, combined with precise fine-tuning of CaO / MgO / BaO, to achieve submicron-level matching of the thermal expansion coefficient with the glass matrix (absolute deviation ≤ 0.3 × 10⁻⁶). -6 / ℃).

[0032] Secondly, embodiments of this application provide a method for preparing a high-impact transparent glaze, comprising the following steps: S1. After drying and sieving each component raw material, weigh them according to the formula ratio and place them in a ball mill to ball mill and mix them with zirconium oxide as the grinding medium to obtain a mixture. S2. Melt the mixture at 1200~1250℃ for 2~3 hours, then quickly pour it into deionized water for quenching to obtain glass fragments; S3. Grind the glass shavings to a fineness of D97≤10μm and D50≤3μm, and sieve to obtain glass powder; S4. Mix glass powder and organic carrier at a mass ratio of (70~75):(25~30) until uniform, and adjust the viscosity to 2000~3000mPa·s to obtain a high-impact transparent glaze.

[0033] The preparation method described in this application achieves homogenization of glaze components and controllable performance through a process chain of low-temperature melting, rapid cooling and solidification, and fine grinding and slurry preparation. Drying, dehydration, and ball milling prevent the introduction of impurities and agglomeration, ensuring precise proportioning. Melting and quenching yield a uniform amorphous glass network structure. Fine grinding ensures the dispersibility and sintering activity of the powder during screen printing, avoiding glaze defects caused by coarse particles. The slurry is prepared by mixing glass powder with an organic carrier, controlling the viscosity at 2000~3000 mPa·s (25℃) to ensure printing leveling and film thickness uniformity. The entire process requires no complex equipment, achieving synergistic control over the formulation, process, and performance.

[0034] Furthermore, in some embodiments, the ball milling speed is 280~320 r / min, the ball milling time is 3~4 h, and the mixing uniformity is ≥98%.

[0035] In the technical solution of this application embodiment, by limiting the ball milling speed, it is helpful to provide sufficient mechanical shear force to fully break down each component into a micron-level dispersion state, avoiding excessive speed causing temperature rise, which may lead to local softening of low melting point components or adhesion to the grinding media and tank wall, resulting in distorted proportions. At the same time, it prevents excessive wear of zirconia balls from introducing impurities that contaminate the glaze. Appropriate ball milling time helps each component achieve molecular-level uniform mixing, so that each component participates in the glass network construction simultaneously during subsequent melting, promoting complete solid-phase reaction, and avoiding fluctuations in thermal expansion coefficient, crystallization, or decreased bonding force caused by uneven mixing leading to local deviations from the design value.

[0036] Furthermore, in some embodiments, the organic carrier is a terpineol and ethyl cellulose system, wherein the mass fraction of ethyl cellulose is 5% to 8%.

[0037] In the technical solution of this application embodiment, terpineol, as a high-boiling-point solvent (boiling point of about 220°C), can slowly evaporate during the drying stage of 150~200°C, avoiding defects such as pinholes and bubbles in the glaze layer caused by excessive evaporation. At the same time, it has good wetting and dispersibility for glass powder, ensuring the rheological uniformity of the glaze slurry. Ethyl cellulose, as a thickener and film-forming agent, can stabilize the viscosity of the glaze slurry at 2000~3000 mPa·s (25°C), taking into account both printing leveling and film integrity. When the ethyl cellulose content is less than 5%, the viscosity of the glaze slurry is too low, and it is easy to cause dripping, edge ink overflow and uneven film thickness during screen printing. When the ethyl cellulose content is higher than 8%, the viscosity of the glaze slurry is too high, making it difficult to pass through the screen, resulting in poor ink flow. In addition, the amount of organic residue increases after drying, and excessive volatile matter during high-temperature sintering can easily form pores and carbonization residues in the glaze layer, leading to a decrease in glaze density and adhesion.

[0038] Thirdly, embodiments of this application provide a photovoltaic front panel glass, including a glass substrate and an enamel layer disposed on the surface of the glass substrate. The enamel layer is formed by printing, drying and tempering the aforementioned high-impact transparent enamel. During the tempering process, the temperature of the upper part of the tempering furnace is 680~710℃, the temperature of the lower part is 650~680℃, the temperature difference between the upper and lower parts is 10~30℃, the air pressure of the upper part is 2.0~3.0kPa, the air pressure of the lower part is 2.5~4.5kPa, and the air pressure of the lower part is 0.5~1.5kPa higher than that of the upper part.

[0039] Furthermore, in some embodiments, the thickness of the glaze layer is 15~25μm; the heating time for tempering is: 120~150s for 2.0mm thick glass, 180~220s for 3.2mm thick glass, and 280~320s for 5.0mm thick glass; the cooling time is 30~60s.

[0040] In the technical solution of this application embodiment, the photovoltaic glass substrate is cleaned to remove surface oil and dust; a 150-300 mesh polyester screen is used to uniformly print the aforementioned transparent enamel onto the glass surface, with the printing thickness controlled at 15-25 μm; the printed glass is dried at 150-200℃ for 5-15 minutes to remove organic solvents from the enamel, with residual organic solvents ≤0.5%; the stress difference between the upper and lower surfaces of the glass is reduced by optimizing the tempering furnace temperature; the stress imbalance caused by enamel shrinkage is offset by controlling the air pressure; and the heating and cooling times are controlled to ensure the formation of a uniform compressive stress layer on the glass surface, with a surface compressive stress layer depth ≥100 μm. Preferably, 2.0 mm thick glass is cooled for 30-40 seconds, 3.2 mm thick glass for 40-50 seconds, and 5.0 mm thick glass for 50-60 seconds.

[0041] Fourthly, embodiments of this application provide an application of photovoltaic front panel glass in architectural safety glass, appliance glass, or automotive glass.

[0042] The following are some specific embodiments. It should be noted that the embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where specific techniques or conditions are not specified in the embodiments, they shall be performed in accordance with the techniques or conditions described in the literature in this field or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.

[0043] Example 1 This embodiment provides a method for preparing a high-impact transparent glaze. The content of each component is shown in Table 1, and the method specifically includes the following steps: S1. Dry each component raw material at 105℃ for 2 hours to remove moisture, ensuring a moisture content ≤0.1%. Pass the raw material through a 100-mesh sieve to remove impurities. Accurately weigh each component according to the formula ratio, with an absolute weighing error of ≤0.1% for each single component. Place the weighed raw material into a planetary ball mill, using zirconia balls as the grinding medium at a ball-to-material ratio of 3:1, a rotation speed of 300 r / min, and mill for 3.5 hours, achieving a mixing uniformity ≥98% to obtain a mixture. The purity of the zirconia grinding medium should be ≥99.9% to avoid introducing iron impurities. S2. Place the mixture into a corundum crucible and melt it at 1220℃ for 2.5h. Then quickly pour it into deionized water to quench it and obtain glass fragments. S3. The glass fragments are ball-milled again until the fineness D97≤10μm and D50≤3μm, and then passed through a 325-mesh sieve to obtain glass powder; S4. Mix glass powder with an organic carrier (terpineol and ethyl cellulose system, wherein the ethyl cellulose content is 6%) at a mass ratio of 7:3, stir evenly, and adjust the viscosity to 2500 mPa·s (25℃) to obtain a high-impact transparent glaze.

[0044] like Figure 1 As shown in the thermal expansion performance curve of the high impact-resistant transparent glaze provided in Example 1, the purple curve represents the coefficient of linear expansion (CTE), which indicates the rate of change of length of the material caused by a unit temperature change, with units of 10. -6 / ℃, the coefficient of linear expansion at 300℃ is 8.560 10 -6 / ℃, the coefficient of linear expansion at 400℃ is 8.900 10 -6 / ℃; the orange curve represents the expansion value, and the green curve represents the expansion percentage. The overall expansion shows an approximately linear increase. The absolute expansion value at 300℃ is 137.8μm, and the expansion percentage is 0.233%. The absolute expansion value at 400℃ is 193.7μm, and the expansion percentage is 0.328%.

[0045] Examples 2-5 and Comparative Examples 1-5 Examples 2-5 and Comparative Examples 1-5 each provide a method for preparing a high-impact transparent glaze. Compared with Example 1, the only difference is that the content of each component is different, as shown in Table 1. Other experimental parameters and conditions are basically the same as those in Example 1, and will not be repeated here.

[0046] Table 1 Comparison of components in the examples and comparative formulations According to standard GB / T 16920-2015 "Determination of the Average Linear Expansion Coefficient of Glass", the thermal expansion coefficient of the transparent glaze prepared in the examples and comparative examples was measured, and compared with that of the sodium-calcium-silicon photovoltaic glass substrate (thermal expansion coefficient of 8.7 × 10⁻⁶). -6 The results of the comparison (at / ℃) are shown in Table 2.

[0047] The transparent glazes prepared in the various embodiments and comparative examples were used to prepare photovoltaic front-panel glass. Specifically, the sodium-calcium-silicon photovoltaic glass substrate was cleaned to remove surface oil and dust; the transparent glaze was uniformly printed onto the glass surface using a 200-mesh polyester screen, with a printing thickness controlled at 20 μm; the printed glass was dried at 180°C for 10 min to remove organic solvents from the glaze, ensuring residual organic solvents were ≤0.5%; the temperature of the upper part of the tempering furnace was controlled at 695°C, and the lower part at 680°C, with a temperature difference of 15°C; the upper wind pressure was controlled at 2.5 kPa, and the lower wind pressure at 3.5 kPa, with the lower wind pressure being 1.0 kPa higher than the upper wind pressure; the heating time was 200 s; and the cooling time was 45 s to ensure the formation of a uniform compressive stress layer on the glass surface. The performance of the prepared photovoltaic front-panel glass was tested, and the results are shown in Tables 2, 3, and 4.

[0048] Table 2 Comparison of thermal expansion coefficient and stress state Table 3 Comparison of Impact Resistance Performance The impact resistance performance is tested according to the method specified in GB / T 15763.2-2025 "Safety Glass for Building - Part 2: Tempered Glass". The sample size is 610×610mm. A steel ball is used to impact the center of the glass surface. Six samples are tested in each group. The glass should not be broken after impact. The glass is considered qualified if no more than one of the six tested samples is broken. "6 / 6" means that all six samples are unbroken.

[0049] Table 4 Other performance test results As can be seen in the embodiments of this application, when the absolute value of the deviation between the thermal expansion coefficient of the glaze and the glass substrate is ≤0.5×10 -6 At / ℃, there is no obvious residual stress after tempering; the absolute value of the deviation is ≤0.3×10 -6 At / ℃, the stress state is optimal, and the impact resistance is best. Although the absolute value of the deviation in Example 2 is slightly greater than 0.5×10 -6 The / ℃ critical value results in slight compressive stress on the unglazed surface of the tempered glass, and its impact resistance is inferior to that of Example 1, but still far superior to that of Comparative Example 1, which represents the current level in the industry. This shows that even under the marginal parameters of the core formulation system of this application, its impact strength can still meet the qualified standard, demonstrating the broad process adaptability of this application.

[0050] Comparative Example 1 uses a currently common formula, but due to excessively low SiO2 and excessively high Bi2O3 and alkali metal content, the coefficient of thermal expansion is as high as 9.5 × 10⁻⁶. -6 / ℃, with glass matrix (8.7×10 -6 / ℃) Deviation +0.8×10 -6 At / ℃, the unglazed surface exhibits significant residual tensile stress after tempering, resulting in the worst impact resistance; in Comparative Example 2, SiO2 content is 40%, below the lower limit, leading to insufficient framework and a coefficient of thermal expansion of 9.3×10. -6 / ℃, deviation +0.6×10 -6 At / ℃, it exhibits obvious tensile stress and poor impact resistance; in Comparative Example 3, SiO2 content is 65%, higher than the upper limit, and the expansion coefficient is too low (7.8×10) due to the excessively dense network. -6 / ℃), deviation -0.9×10 -6 / ℃, resulting in significant residual compressive stress, causing glass warping and poor impact resistance; in Comparative Example 4, Bi2O3 content was 3%, below the lower limit, and due to insufficient bonding strength, the coefficient of thermal expansion was low (8.0×10). -6 / ℃), deviation -0.7×10 -6At / ℃, it exhibits slight compressive stress, with limited improvement in impact resistance; in Comparative Example 5, Bi2O3 content is 15%, higher than the upper limit, and the expansion coefficient rises back to 9.2×10. -6 / ℃, deviation +0.5×10 -6 At / ℃, significant tensile stress is generated, resulting in poor impact resistance.

[0051] In summary, the photovoltaic front panel glass prepared in this application has an impact resistance of 1-2 times higher than that of existing technologies on its non-glazed surface, fully meeting the safety requirements for BIPV products. While significantly improving impact resistance, it maintains all core properties such as light transmittance, acid and alkali resistance, PID resistance, and adhesion, conforming to photovoltaic industry standards. By optimizing the formula and reducing the amount of precious metals such as bismuth oxide, the cost of glaze raw materials is reduced by 47% compared to current products, and the material cost per square meter of glass product is reduced by 5.8 yuan, achieving a synergistic benefit of doubling the impact resistance, maintaining all core properties, and significantly reducing costs.

[0052] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.

Claims

1. A high-impact transparent glaze, characterized in that, It consists of the following components by mass percentage: The composition is as follows: silicon dioxide 45%~60%, boron oxide 12%~20%, zinc oxide 6%~12%, bismuth oxide 5%~12%, aluminum oxide 3%~8%, alkali metal oxides 1%~4%, alkaline earth metal oxides 1%~5%; the sum of the mass percentages of all components is 100%. Wherein, the alkali metal oxide is at least one of sodium oxide and potassium oxide; the alkaline earth metal oxide is at least one of calcium oxide, magnesium oxide and barium oxide; The coefficient of thermal expansion of the high-impact transparent glaze at 20~300℃ is 8.0×10⁻⁶. -6 / ℃~9.0×10 -6 / ℃, and the absolute value of the deviation of the coefficient of thermal expansion from that of the sodium-calcium-silicon photovoltaic glass substrate is ≤0.5×10 -6 / ℃.

2. The high-impact transparent glaze according to claim 1, characterized in that, The mass ratio of silicon dioxide to boron oxide is 2.5:1 to 4:1; the mass ratio of bismuth oxide to zinc oxide is 0.5:1 to 1.5:

1.

3. The high-impact transparent glaze according to claim 1, characterized in that, The ratio of the total content of alkali metal oxides to the total content of alkaline earth metal oxides is 0.5:1 to 2:

1.

4. The high-impact transparent glaze according to claim 1, characterized in that, The absolute value of the difference between the thermal expansion coefficient of the high-impact transparent glaze and that of the sodium-calcium-silicon photovoltaic glass substrate is ≤0.3×10⁻⁶. -6 / ℃.

5. A method for preparing a high-impact transparent glaze as described in any one of claims 1 to 4, characterized in that, Includes the following steps: After drying and sieving each component raw material, they are weighed according to the formula ratio and placed in a ball mill to be ball-milled and mixed with zirconium oxide as the grinding medium to obtain a mixture. The mixture is melted at 1200~1250℃ for 2~3 hours, and then quickly poured into deionized water for quenching to obtain glass fragments; The glass fragments were ball-milled to a fineness of D97≤10μm and D50≤3μm, and then sieved to obtain glass powder. The glass powder and organic carrier are mixed evenly at a mass ratio of (70~75):(25~30), and the viscosity is adjusted to 2000~3000mPa·s to obtain a high-impact transparent glaze.

6. The method for preparing the high-impact transparent glaze according to claim 5, characterized in that, The ball milling speed is 280~320 r / min, the ball milling time is 3~4 h, and the mixing uniformity is ≥98%.

7. The method for preparing the high-impact transparent glaze according to claim 5, characterized in that, The organic carrier is a system of terpineol and ethyl cellulose, wherein the mass fraction of ethyl cellulose is 5% to 8%.

8. A photovoltaic front panel glass, characterized in that, The device includes a glass substrate and an enamel layer disposed on the surface of the glass substrate. The enamel layer is formed by printing, drying, and tempering a high-impact transparent enamel prepared by any one of claims 1 to 4 or by any one of claims 5 to 7. In the tempering process, the upper temperature of the tempering furnace is 680~710℃, the lower temperature is 650~680℃, the temperature difference between the upper and lower parts is 10~30℃, the upper air pressure is 2.0~3.0kPa, the lower air pressure is 2.5~4.5kPa, and the lower air pressure is 0.5~1.5kPa higher than the upper air pressure.

9. The photovoltaic front panel glass according to claim 8, characterized in that, The thickness of the glaze layer is 15~25μm; the heating time for the tempering process is: 120~150s for 2.0mm thick glass, 180~220s for 3.2mm thick glass, and 280~320s for 5.0mm thick glass; the cooling time is 30~60s.

10. The application of the photovoltaic front panel glass according to claim 8 or 9 in architectural safety glass, appliance glass or automotive glass.

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