High-toughness silicate glass and methods of making and using the same

Abstract

The application discloses a kind of high tough silicate glass and its preparation method and application, by mass percentage, the high tough silicate glass includes: silicon dioxide 50~60%;Aluminum oxide 10~18%;Lithium oxide 3~8%;Sodium oxide 10~15%;Potassium oxide 1~3%;Magnesium oxide 0~4%;Zirconium oxide 0~3%;Cerium dioxide 0~6%;Boron trioxide 0~3%;Yttrium oxide 5~15%;Titanium dioxide 0.5~3%.The high tough silicate glass prepared in the application has the characteristics of high hardness (≥780 Hv), high bending strength (≥730 MPa) and good light transmittance in visible light region (≥90%), and is suitable for high reliability transparent structural parts, optical windows and protective glass and other fields.

Description

Technical Field

[0001] This invention relates to the field of special glass materials, specifically to a high-strength and tough silicate glass prepared by a composite strengthening process combining microcrystallization and chemical strengthening, as well as its preparation method and applications. Background Technology

[0002] Silicate glass possesses a low coefficient of thermal expansion, good chemical stability, and high mechanical strength, making it widely used in optical devices, communication substrates, and special windows. However, the inherent brittleness and surface micro-defects of glass result in actual strength far lower than theoretical values. To improve its mechanical properties, microcrystallization or chemical strengthening is commonly employed. Microcrystallization, by precipitating nanocrystals within the glass matrix, can inhibit crack propagation and improve toughness; chemical strengthening introduces a compressive stress layer on the glass surface through ion exchange, enhancing flexural strength and impact resistance. However, a single strengthening method often struggles to simultaneously achieve high hardness, high strength, and good light transmittance. Therefore, developing a composite strengthening process combining microcrystallization and chemical strengthening is of great significance.

[0003] Existing technology discloses a method for preparing high-strength aluminosilicate glass by adding oxides such as yttrium trioxide, niobium pentoxide, and tantalum pentoxide, combined with chemical tempering. However, this method does not involve microcrystallization treatment, and there is still room for improvement in bending strength. In addition, this type of glass is prone to problems such as bubbles and crystallization during high-temperature melting, affecting optical uniformity and mechanical reliability. Summary of the Invention

[0004] In view of this, the main objective of the present invention is to provide a high-strength and high-toughness silicate glass, its preparation method and application. The technical problem to be solved is to significantly improve the surface hardness and bending strength of the glass by means of specific component design and synergistic strengthening mechanism, while ensuring optical performance and environmental compatibility.

[0005] The objective of this invention and the technical problem it solves are achieved through the following technical solution. This invention provides a high-strength, high-toughness silicate glass, comprising, by mass percentage: Silicon dioxide 50-60%; aluminum oxide 10-18%; lithium oxide 3-8%; sodium oxide 10-15%; potassium oxide 1-3%; magnesium oxide 0-4%; zirconium oxide 0-3%; cerium dioxide 0-6%; yttrium oxide 5-15%; boron trioxide 0-3%; titanium dioxide 0.5-3%.

[0006] The objectives of this invention and the technical problems solved can be further achieved by the following technical measures.

[0007] Preferably, the aforementioned high-strength and high-toughness silicate glass has a Vickers hardness ≥780 Hv and a bending strength ≥730 MPa.

[0008] Preferably, the aforementioned high-strength and high-toughness silicate glass has an average transmittance of ≥90% in the visible light band when the thickness is 3 mm.

[0009] The objectives of this invention and the technical problems it solves can be further achieved by the following technical measures. The present invention provides a method for preparing high-strength and high-toughness silicate glass, comprising the following steps: S1 Batching and Melting: After mixing all raw materials evenly, melt them at 1550~1600 ℃ for 2~4 hours to obtain homogenized glass melt; S2 Forming and Annealing: The molten glass is poured into shape, then annealed at 450~550 ℃ for 12~24h, and cooled in the furnace to obtain the base glass; S3 Microcrystallization treatment: The base glass is subjected to microcrystallization treatment; S4 Chemical strengthening treatment: The microcrystallized glass is subjected to chemical strengthening treatment to obtain the high-strength and tough silicate glass.

[0010] The objectives of this invention and the technical problems solved can be further achieved by the following technical measures.

[0011] Preferably, in the aforementioned method for preparing high-strength and tough silicate glass, step S3, the microcrystallization treatment is a two-step heat treatment, including: a) Nucleation stage: Keep warm at 520~580 ℃ for 6~10h; b) Crystallization stage: Keep warm at 530~720 ℃ for 1~8h.

[0012] Preferably, in the aforementioned method for preparing high-strength and tough silicate glass, the chemical strengthening treatment in step S4 is a one-step or two-step ion exchange method.

[0013] Preferably, in the aforementioned method for preparing high-strength and tough silicate glass, step S4, the one-step ion exchange method includes: Microcrystalline glass is immersed in water at 400~430℃. Ion exchange in molten salt for 1-4 hours.

[0014] Preferably, in the aforementioned method for preparing high-strength and tough silicate glass, step S4, the two-step ion exchange method includes: a) First step of exchange: Immerse the microcrystalline glass in water at 400~450℃. Molten salt or and Treatment in mixed molten salt for 1-8 hours; b) Second step of exchange: After cleaning, immerse the glass in water at 380~430 ℃. Treat in molten salt for 1-4 hours.

[0015] Preferably, in the aforementioned method for preparing high-strength and tough silicate glass, in step S1, the melting is carried out in a platinum or platinum-rhodium alloy crucible.

[0016] The objectives of this invention and the technical problems it solves can also be achieved by the following technical measures. This invention proposes an optical window, which is made of the aforementioned high-strength and tough silicate glass.

[0017] The objectives of this invention and the technical problems it solves can also be achieved using the following technical measures. This invention proposes a special vehicle windshield, which is made of the aforementioned high-strength and tough silicate glass.

[0018] The objectives of this invention and the technical problems it solves can also be achieved by the following technical measures. This invention proposes an electronic device cover plate, which is made of the aforementioned high-strength and tough silicate glass.

[0019] Compared with existing technologies, the high-strength and high-toughness silicate glass, its preparation method, and its applications described in this invention have the following beneficial effects: 1. Synergistic strengthening mechanism of components: Yttrium oxide and titanium dioxide synergistically enhance mechanical properties: Yttrium oxide, as a high field strength component, can enhance the compactness of the glass network structure and significantly improve the elastic modulus and bending strength; Titanium dioxide, as a nucleating agent, can promote the formation of microcrystals in the glass after crystallization treatment, and inhibit the propagation of microcracks in the glass through dispersion strengthening, thus significantly improving the glass's resistance to crack propagation.

[0020] 2. Process optimization and performance enhancement: Through an optimized one-step or two-step chemical tempering process, ion exchange is carried out in pure potassium nitrate molten salt or in sodium nitrate and potassium nitrate molten salt respectively, so that a high compressive stress layer is formed on the glass surface. The bending strength after tempering is greater than or equal to 730 MPa, which is more than 5 times higher than that before tempering.

[0021] 3. Excellent overall performance and wide range of applications: The glass has an average light transmittance of ≥90% (3mm thickness) in the visible light band, good optical uniformity, and comprehensive characteristics of high strength, high modulus, and acid resistance grade 1; it is suitable for high-end transparent structural components with stringent requirements for mechanical strength, environmental durability and optical quality, such as aerospace windshields, deep-sea equipment windows, and bulletproof glass for special vehicles.

[0022] 4. Adjusting the melting process to improve glass quality: The melting temperature is controlled between 1450 and 1500℃, and mechanical stirring (30 to 50 rpm, 1 to 3 hours) is used to significantly improve the melting uniformity of high rare earth and refractory oxide content. The high-temperature viscosity of the glass is moderate, which is conducive to the elimination of bubbles and the improvement of optical uniformity.

[0023] This invention achieves a balanced improvement in the strength and chemical stability of silicate glass by combining composition design with process control, and has significant prospects for industrial application.

[0024] The above description is merely an overview of the technical solution of the present invention. In order to better understand the technical means of the present invention and to implement it in accordance with the contents of the specification, the preferred embodiments of the present invention are described in detail below. Attached Figure Description

[0025] Figure 1 The Raman spectra of titanium dioxide modified high-strength and high-toughness silicate glasses in Comparative Example 2 and Example 3 of this invention are shown. Figure 2 The DSC curves of the high-strength and high-toughness silicate glasses of Comparative Example 2 and Example 3 of this invention; Figure 3 The XRD patterns of the high-strength and high-toughness silicate glasses of Comparative Example 2 and Example 3 of this invention; Figure 4 The above diagrams show the surface Na and K element distribution of the high-strength and high-toughness silicate glass of Comparative Example 2 and Example 3 of this invention before and after ion exchange. Figure 5 The hardness and strength variation curves of the high-strength and tough silicate glass in Comparative Example 2 and Example 3 of the present invention are shown. Figure 6 This is a graph showing the relationship between the light transmittance and crystallization temperature of the high-strength and tough silicate glass in Comparative Example 2 and Example 3 of the present invention. Detailed Implementation

[0026] To further illustrate the technical means and effects adopted by the present invention to achieve the intended purpose, the following detailed description, in conjunction with preferred embodiments, provides a detailed explanation of the high-strength and tough silicate glass, its preparation method, and its application, as well as its structure, features, and effects. In the following description, different "embodiments" or "embodiments" do not necessarily refer to the same embodiment. Furthermore, specific features, structures, or characteristics in one or more embodiments can be combined in any suitable manner.

[0027] Unless otherwise specified, all materials and reagents mentioned below are commercially available products well-known to those skilled in the art; unless otherwise specified, all methods described are methods known in the art. Unless otherwise defined, the technical or scientific terms used should have the ordinary meaning understood by those skilled in the art. Where specific experimental steps or conditions are not specified below, they can be performed according to the conventional experimental steps or conditions described in the literature in this field.

[0028] According to some embodiments of the present invention, a high-strength and high-toughness silicate glass is provided, comprising, by weight percentage: Silicon dioxide 50-60%; aluminum oxide 10-18%; lithium oxide 3-8%; sodium oxide 10-15%; potassium oxide 1-3%; magnesium oxide 0-4%; zirconium oxide 0-3%; cerium dioxide 0-6%; yttrium oxide 5-15%; boron trioxide 0-3%; titanium dioxide 0.5-3%.

[0029] In the above technical solution, a composite strengthening process combining titanium dioxide-induced microcrystallization and two-step ion exchange is employed. The yttrium oxide content is adjusted to reduce the glass melting difficulty, and high surface compressive stress is achieved through two-step chemical strengthening. This process produces silicate microcrystalline glass with high hardness, high strength, and good light transmittance. During the microcrystallization process, care must be taken to avoid excessively long heat treatment times, otherwise, the transmittance will decrease due to excessively large crystals.

[0030] The functions and content selection of each component are as follows: Silica acts as a network forger in glass, forming the glass network framework. However, the inventors discovered that when the silica content is less than 50 wt%, the interconnectivity of silicon-oxygen tetrahedra decreases, leading to reduced glass stability. When the silica content exceeds 60 wt%, it increases the difficulty of glass melting. Therefore, this invention selects a silica content of 50-60 wt% in the high-strength and tough silicate glass.

[0031] Aluminum oxide (A₂O₃) acts as an intermediate in silicate glass, participating in the network structure and improving the glass's mechanical strength and chemical stability. In this high-strength and high-toughness silicate glass, when the A₂O₃ content is less than 10 wt%, the glass network structure is not dense enough, leading to a decrease in the glass's strength and chemical stability; when the A₂O₃ content is greater than 18 wt%, it increases the difficulty of glass melting and may lead to an increased tendency for crystallization. Therefore, this invention selects an A₂O₃ content between 10 and 18 wt% in the high-strength and high-toughness silicate glass.

[0032] Lithium oxide, as a flux, can effectively reduce the melting temperature and coefficient of thermal expansion of glass, and improve its fluidity. In the high-strength and high-toughness silicate glass of this invention, when the lithium oxide content is less than 3 wt%, the fluxing effect is not obvious, and the glass melting temperature is relatively high; when the lithium oxide content is greater than 8 wt%, it will excessively reduce the chemical stability of the glass, resulting in poor weather resistance. Therefore, this invention selects a lithium oxide content between 3 and 8 wt%.

[0033] Sodium oxide is a commonly used flux that can significantly reduce the melting temperature of glass and improve its formability. When the sodium oxide content is less than 10 wt%, the melting temperature of the glass is too high, which is detrimental to energy saving and production efficiency; when the sodium oxide content is greater than 15 wt%, it reduces the chemical stability and mechanical strength of the glass, and makes it prone to crystallization. Therefore, this invention selects a sodium oxide content between 10 and 15 wt%.

[0034] Potassium oxide, as a flux, can improve the gloss and transparency of glass and reduce its tendency to crystallize. When the potassium oxide content in the glass is less than 1 wt%, the melting temperature is high, and the optical properties of the glass may be insufficient; when the potassium oxide content is greater than 3 wt%, it leads to a decrease in the chemical stability and a deterioration in water resistance of the glass. Therefore, this invention selects a potassium oxide content between 1 and 3 wt%.

[0035] Magnesium oxide, an alkaline earth metal oxide, improves the chemical stability and mechanical strength of glass and inhibits crystallization. However, when the magnesium oxide content exceeds 4 wt%, it increases the viscosity of the glass, making melting difficult and potentially causing crystallization. Therefore, this invention selects a magnesium oxide content between 0 and 4 wt%.

[0036] Zirconia can significantly improve the refractive index, chemical stability, and mechanical strength of glass. However, when the zirconium oxide content exceeds 3 wt%, it increases the difficulty of glass melting and easily leads to the formation of inhomogeneous phases. Therefore, this invention selects a zirconium oxide content between 0 and 3 wt%.

[0037] Cerium dioxide can be used as a clarifying and decolorizing agent, while also improving the chemical stability and radiation resistance of glass. However, when the cerium dioxide content exceeds 6 wt%, it can cause glass coloring and increase the difficulty of melting. Therefore, this invention selects a cerium dioxide content between 0 and 6 wt%.

[0038] Yttrium trioxide (YTO), as a rare earth oxide, can significantly improve the hardness, strength, and refractive index of glass, and enhance its chemical stability. When the YTO content is less than 5 wt%, its strengthening effect on glass is not significant; when the YTO content is greater than 15 wt%, it greatly increases the difficulty and cost of glass melting and may cause crystallization. Therefore, this invention selects a YTO content between 5 and 15 wt%.

[0039] Boron trioxide, as a network forger, can lower the melting temperature of glass, improve its thermal and chemical stability, and enhance its mechanical strength. However, when the boron trioxide content exceeds 3 wt%, it leads to an increased tendency for phase separation and a decrease in chemical homogeneity. Therefore, this invention selects a boron trioxide content between 0 and 3 wt%.

[0040] Titanium dioxide can improve the refractive index, chemical stability, and ultraviolet absorption capacity of glass. When the titanium dioxide content is less than 0.5 wt%, its effect on improving glass properties is weak; when the titanium dioxide content is greater than 3 wt%, it leads to glass coloration and increases the tendency for crystallization. Therefore, this invention selects a titanium dioxide content between 0.5 and 3 wt%.

[0041] Tests showed that the high-strength and tough silicate glass has a Vickers hardness ≥ 780 Hv, a bending strength ≥ 730 MPa, and an average light transmittance of ≥ 90% in the visible light band at 3mm.

[0042] Some embodiments of the present invention also provide a method for preparing high-strength and high-toughness silicate glass, comprising the following steps: S1 Batching and Melting: After mixing all raw materials evenly, melt them at 1550~1600 ℃ for 2~4 hours to obtain homogenized glass melt. When the melting temperature is below 1550 ℃ or the melting time is less than 2 hours, the glass melt cannot be completely melted. When the temperature is above 1600 ℃ or the melting time is more than 4 hours, some components in the glass melt will change due to volatilization. S2 Forming and Annealing: The molten glass is poured into shape and then annealed at 450~550 ℃ for 12~24 h, and cooled in the furnace to obtain the base glass. This process can eliminate the internal stress of the glass during the process of changing from high temperature to low temperature. When the annealing temperature is below 450 ℃ or less than 12 h, the internal stress of the glass cannot be completely released, and it is easy to crack during subsequent processing or use. When the annealing temperature is above 550 ℃ or more than 24 h, the glass will soften and deform or induce spontaneous crystallization, resulting in a decrease in optical performance and affecting the effect of subsequent microcrystallization treatment. S3 Microcrystallization treatment: The base glass is subjected to microcrystallization treatment to induce internal crystallization; S4 Chemical strengthening treatment: The microcrystallized glass is subjected to chemical strengthening treatment to obtain the high-strength and tough silicate glass.

[0043] In some optional embodiments, step S3, the microcrystallization process is a two-step heat treatment, including: a) Nucleation stage: The glass is held at 520~580 ℃ for 6~10 h. During this stage, TiO2 induces the formation of a large number of uniform and fine crystal nuclei inside the glass, providing sufficient nucleation sites for subsequent crystal growth. When the nucleation temperature is below 520 ℃ or the holding time is less than 6 h, the atomic migration ability is insufficient, and the crystal nuclei are difficult to form or are few in number, resulting in abnormal crystal growth during subsequent crystallization, causing glass devitrification or a decrease in mechanical properties. When the nucleation temperature is above 580 ℃ or the holding time is more than 10 h, the crystal nuclei grow excessively or coarsen spontaneously, the crystal nuclei size distribution is uneven, and some crystal nuclei enter the crystallization stage prematurely, destroying the uniformity of the microcrystalline structure and ultimately affecting the transparency and strengthening effect of the glass. b) Crystallization stage: The crystals are held at 530~720 ℃ for 1~8h. During this stage, the crystal nuclei formed in the nucleation stage are further grown into nanoscale crystal phases. Through dispersion strengthening, crack propagation is inhibited and the hardness and toughness of the glass are improved. When the crystallization temperature is below 530 ℃ or the holding time is less than 1h, the crystal growth driving force is insufficient, crystallization is incomplete, and the content of crystal phases in the glass matrix is ​​too low, so effective microcrystalline strengthening cannot be achieved. When the crystallization temperature is above 720 ℃ or the holding time is more than 8h, the crystals grow excessively, and the grain size exceeds the nanoscale range, resulting in severe light scattering and a sharp decrease in light transmittance. At the same time, the excessively high temperature may cause the glass matrix to soften and deform or undergo crystal phase transformation, which will damage the overall performance of the material.

[0044] In some alternative embodiments, in step S4, the chemical enhancement treatment is a one-step or two-step ion exchange method, by transferring the molten salt... Ions and glass Ion exchange forms an effective stress layer on the glass surface, further improving the mechanical properties of the glass.

[0045] In some optional embodiments, step S4, the one-step ion exchange method includes: Microcrystalline glass is immersed in water at 400~430℃. Treatment in molten salt for 1-4 hours. This step allows for the treatment of large-radius... Replacement surface This creates high compressive stress on the surface, which occurs when the temperature is below 400 ℃ or for less than 1 hour. Insufficient diffusion depth and shallow stress layer; stress relaxation when the temperature is above 430 ℃ or for more than 4 hours leads to a decrease in surface compressive stress.

[0046] In some optional embodiments, step S4, the two-step ion exchange method includes: a) First step of exchange: Immerse the microcrystalline glass in water at 400~450℃. Molten salt or salt with a mass ratio of 7:3 and Treat in mixed molten salt for 1-8 hours; this step allows the molten salt to... With glass surface Exchange occurs, forming a preliminary compressive stress layer. When the temperature is below 400℃ or the exchange time is less than 1 hour, the strengthening effect is poor; when the temperature is above 450℃ or the exchange time is more than 8 hours, excessive expansion of the glass surface leads to microcracks. Choosing a single... Salt is used to introduce larger-sized [organisms]. , or to carry out The main gentle ion exchange; selection and Mixed salts utilize the unique physicochemical properties of mixed molten salts to achieve more complex or optimized surface modification; for example, they can simultaneously or competitively react with small ions in the glass. , Exchange, introduce a larger It can generate stronger surface compressive stress, and the strengthening effect may be more significant; b) Second step of exchange: After cleaning, immerse the glass in water at 380~430 ℃. Treatment in molten salt for 1-4 hours; this step allows for the treatment of large-radius... Replacement surface High compressive stress is formed on the surface, which occurs when the temperature is below 380 ℃ or for less than 1 hour. Insufficient diffusion depth and shallow stress layer; stress relaxation when the temperature is above 430 ℃ or for more than 4 hours leads to a decrease in surface compressive stress.

[0047] In some alternative embodiments, the melting in step S1 is carried out in a platinum or platinum-rhodium alloy crucible.

[0048] Some embodiments of the present invention also provide an optical window, which is made of the aforementioned high-strength and tough silicate glass. When used in optical windows, its spectral transmittance, refractive index uniformity, and environmental adaptability must be comprehensively considered; the crystallite size must be controllable to avoid light scattering, while balancing rare earth oxides (such as...) The absorption peak of the mirror is affected, and the requirements for radiation resistance, thermal shock resistance and thermal expansion matching with the mirror base material are met.

[0049] Some embodiments of the present invention also provide a special vehicle windshield, which is made of the above-mentioned high-strength and tough silicate glass. When used in a special vehicle windshield, its resistance to multiple shrapnel impacts and wind and sand erosion must be comprehensively considered; the depth of the surface compressive stress layer must be sufficient to suppress crack propagation, while balancing the bonding strength with the intermediate layer in the multi-layer composite structure, and meeting the requirements for thermal shock resistance and long-term weather resistance under extreme temperature differences.

[0050] Some embodiments of the present invention also provide an electronic device cover plate, which is made of the above-mentioned high-strength and tough silicate glass. When used as an electronic device cover plate, its surface scratch resistance and drop resistance must be comprehensively considered; the uniformity of the microcrystalline phase must be ensured to balance hardness and transmittance, while balancing the stress relaxation effect after ion exchange, and meeting the dielectric properties under ultra-thin form and the thermal expansion matching requirements with the touch module.

[0051] The present invention will be further described below with reference to specific embodiments, but this should not be construed as a limitation on the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention still fall within the scope of protection of the present invention.

[0052] The glass design composition of the embodiments and comparative examples of this invention is shown in Table 1. All raw materials used in this invention are commercially available. Vickers hardness is measured according to GB / T 37900-2019, "Test Method for Hardness and Fracture Toughness of Ultra-thin Glass - Small Load Vickers Hardness Indentation Method". Bending strength is measured according to GB / T 37781-2019, "Test Method for Bending Strength of Glass Materials". Transmittance testing is performed according to GB / T 2680-2021, "Determination of Visible Light Transmittance, Direct Solar Transmittance, Total Solar Transmittance, Ultraviolet Transmittance, and Related Parameters of Architectural Glass".

[0053] Table 1. Glass composition of Examples 1-6 and Comparative Examples 1-3 of the present invention. Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 silicon dioxide 50 54 52 50 54 58 45 55 65 Aluminum oxide 15 15 11 15 10 10 20 10 5 Lithium oxide 3 5 5 5 6 4 2 10 4 Sodium oxide 15 12 13 15 10 12 5 10 18 potassium oxide 2 2 3 1 2 2 0 4 2 magnesium oxide 2 0 0 1 2 0 2 4 1 Zirconia 1 1 0 1 1 1 4 2 2 Yttrium oxide 8 5 8 6 5 8 10 0 3 Cerium dioxide 2 5 6 5 5 0 0 5 0 Boron trioxide 0 0 0 0 3 3 10 0 0 Titanium dioxide 2 1 2 1 2 2 2 0 0 Example 1

[0054] Weigh and mix the raw materials according to the proportions required in Table 1. The glass composition (wt%) is: silicon dioxide 50, aluminum oxide 15, lithium oxide 3, sodium oxide 15, potassium oxide 2, magnesium oxide 2, zirconium oxide 1, yttrium oxide 10, cerium dioxide 2, boron oxide 0, titanium dioxide 2; The raw material ratio (g) is as follows: 500.0 g of quartz sand, 150.0 g of aluminum oxide, 63.5 g of lithium carbonate, 159.0 g of sodium carbonate, 21.5 g of potassium carbonate, 20.0 g of magnesium oxide, 10.0 g of zirconium oxide, 100.0 g of yttrium oxide, 20.0 g of cerium dioxide, and 20.0 g of titanium dioxide; The preparation method is as follows: The above raw materials are mixed evenly, placed in a Pt-10Rh crucible and transferred to a melting furnace. After pretreatment at 600℃ for 4 hours, the temperature is raised to 1560℃ for melting for 3 hours to obtain homogenized glass melt. During the melting process, the glass melt is subjected to regional ultrasonic vibration: the frequency of the lower 1 / 3 region is 100kHz, the frequency of the middle 1 / 3 region is 70kHz, and the frequency of the upper 1 / 3 region is 30kHz. At the same time, a double-blade Pt stirrer is used to stir upward at a speed of 60rpm for 3 hours. Then, the glass melt is formed by inverting the Pt-10Rh crucible onto a rolling table, annealed at 500℃ for 24 hours, and cooled in the furnace to obtain the base glass. Then, microcrystallization and ion exchange are performed: the base glass is heated to 560℃ at 3℃ / min and held for 8 hours for nucleation, and then heated to 700℃ at 2℃ / min and held for 2 hours for crystallization. Then, two-step ion exchange is performed: first, in pure ion exchange at 400℃... Ion exchange in molten salt for 2 hours, followed by washing and then immersion in pure molten salt at 380℃ Ion exchange in molten salt for 1 hour yields the silicate glass.

[0055] Performance: In this embodiment, the base glass has a Vickers hardness of 721 Hv, a bending strength of 118 MPa, and an average transmittance of 90% in the visible light band; the silicate glass obtained after microcrystallization and chemical strengthening has a Vickers hardness of 798 Hv, a bending strength of 765 MPa, and an average transmittance of 90% in the visible light band when the thickness is 3 mm. Example 2

[0056] Weigh and mix the raw materials according to the proportions required in Table 1. The glass composition (wt%) is: silicon dioxide 54, aluminum oxide 15, lithium oxide 5, sodium oxide 12, potassium oxide 3, magnesium oxide 0, zirconium oxide 1, yttrium oxide 5, CeO 25, B2O 30, TiO 21; The raw material ratio (g) is as follows: quartz sand 540.0, aluminum oxide 150.0, lithium carbonate 105.8, sodium carbonate 127.2, potassium carbonate 21.5, zirconium oxide 10.0, yttrium oxide 50.0, cerium dioxide 50.0, titanium oxide 10.0; The preparation method is as follows: The above raw materials are mixed evenly, placed in a Pt-10Rh crucible and transferred to a melting furnace. After pretreatment at 550℃ for 5 hours, the temperature is raised to 1540℃ for melting for 3 hours to obtain homogenized glass melt. During the melting process, the glass melt is subjected to regional ultrasonic vibration: the frequency of the lower 1 / 3 region is 100kHz, the frequency of the middle 1 / 3 region is 70kHz, and the frequency of the upper 1 / 3 region is 30kHz. At the same time, a double-blade stirrer is used to stir upward at a speed of 50rpm for 5 hours. Then, the glass melt is formed by inverting the Pt-10Rh crucible onto a rolling table, annealed at 500℃ for 24 hours, and then cooled in the furnace to obtain the base glass. Then, microcrystallization and ion exchange are performed: the base glass is heated to 520℃ at 3℃ / min and held for 8 hours for nucleation, and then heated to 720℃ at 2℃ / min and held for 2 hours for crystallization. Then, a one-step ion exchange is performed: pure ion exchange is carried out at 420℃. Ion exchange in molten salt for 4 hours yields the silicate glass.

[0057] Performance: In this embodiment, the base glass has a Vickers hardness of 760 Hv, a bending strength of 136 MPa, and an average transmittance of 90% in the visible light band; the silicate glass obtained after microcrystallization and chemical strengthening has a Vickers hardness of 812 Hv, a bending strength of 782 MPa, and an average transmittance of 91% in the visible light band when the thickness is 3 mm. Example 3

[0058] Weigh and mix the raw materials according to the proportions required in Table 1. Glass composition (wt%): silicon dioxide 52, aluminum oxide 11, lithium oxide 5, sodium oxide 13, potassium oxide 3, magnesium oxide 0, zirconium oxide 0, yttrium oxide 8, cerium dioxide 6, boron oxide 0, titanium dioxide 2; Raw material ratio (g): Quartz sand 520.0, aluminum oxide 110.0, lithium carbonate 105.8, sodium carbonate 137.8, potassium carbonate 32.3, yttrium oxide 80.0, cerium dioxide 60.0, titanium dioxide 20.0; The preparation method is as follows: The above raw materials are mixed evenly, placed in a Pt-10Rh crucible and transferred to a melting furnace. After pretreatment at 600℃ for 4 hours, the temperature is raised to 1550℃ and melted for 3 hours to obtain homogenized glass melt. During the melting process, the glass melt is subjected to regional ultrasonic vibration: the frequency of the lower 1 / 3 region is 100kHz, the frequency of the middle 1 / 3 region is 70kHz, and the frequency of the upper 1 / 3 region is 30kHz. At the same time, a double-blade Pt stirrer is used to stir upward at a speed of 70rpm for 3 hours. Then, the glass melt is formed by inverting the Pt-10Rh crucible onto a rolling table. After annealing at 500℃ for 24 hours, the base glass is obtained after furnace cooling. Then, microcrystallization and ion exchange are performed: the base glass is heated to 520℃ at 3℃ / min and held for 10 hours for nucleation, and then heated to 720℃ at 2℃ / min and held for 1 hour for crystallization. Then, two-step ion exchange is performed: first, pure ion exchange is carried out at 400℃. Ion exchange in molten salt for 8 hours, followed by washing and then ion exchange at 420℃ in pure water. Ion exchange in molten salt for 2 hours yields the silicate glass.

[0059] Performance: In this embodiment, the base glass has a Vickers hardness of 743 Hv, a bending strength of 153 MPa, and an average transmittance of 90% in the visible light band; the silicate glass obtained after microcrystallization and chemical strengthening has a Vickers hardness of 805 Hv, a bending strength of 795 MPa, and an average transmittance of 90% in the visible light band when the thickness is 3 mm. Example 4

[0060] Weigh and mix the raw materials according to the proportions required in Table 1. The glass composition (wt%) is: silicon dioxide 50, aluminum oxide 15, lithium oxide 5, sodium oxide 15, potassium oxide 1, magnesium oxide 1, zirconium oxide 1, yttrium oxide 6, cerium dioxide 5, boron oxide 0, and titanium dioxide 1. The raw material ratio (g) is as follows: quartz sand 500.0, aluminum oxide 150.0, lithium carbonate 105.8, sodium carbonate 159.0, potassium carbonate 10.8, magnesium oxide 10.0, zirconium oxide 10.0, yttrium oxide 60.0, cerium dioxide 50.0, titanium dioxide 10.0; The preparation method is as follows: The above raw materials are mixed evenly, placed in a Pt-10Rh crucible, and transferred to a melting furnace. After pretreatment at 650℃ for 3 hours, the mixture is transferred to a high-temperature melting furnace at 1570℃ to obtain homogenized glass melt. During the melting process, the glass melt is subjected to regional ultrasonic vibration: the frequency of the lower 1 / 3 region is 120kHz, the frequency of the middle 1 / 3 region is 60kHz, and the frequency of the upper 1 / 3 region is 20kHz. At the same time, a double-blade Pt stirrer is used to stir upward at a speed of 40rpm for 6 hours. Then, the temperature is lowered to 1360℃ for casting. After annealing at 500℃ for 24 hours, the base glass is obtained after furnace cooling. Then, microcrystallization and ion exchange are performed: the base glass is heated to 540℃ at 4℃ / min and held for 12 hours, and then heated to 680℃ at 2℃ / min and held for 4 hours to complete microcrystallization. Then, a one-step ion exchange is performed: the glass is heated to 400℃ in pure... Ion exchange in molten salt for 3 hours yields the silicate glass.

[0061] Performance: In this embodiment, the base glass has a Vickers hardness of 716 Hv, a bending strength of 128 MPa, and an average transmittance of 90% in the visible light band; the silicate glass obtained after microcrystallization and chemical strengthening has a Vickers hardness of 795 Hv, a bending strength of 740 MPa, and an average transmittance of 90% in the visible light band when the thickness is 3 mm. Example 5

[0062] Weigh and mix the raw materials according to the proportions required in Table 1. The glass composition (wt%) is: silicon dioxide 54, aluminum oxide 10, lithium oxide 6, sodium oxide 10, potassium oxide 2, magnesium oxide 2, zirconium oxide 1, yttrium oxide 5, cerium dioxide 5, boron oxide 3, titanium dioxide 2; The raw material ratio (g) is as follows: quartz sand 540.0, alumina 100.0, lithium carbonate 126.9, sodium carbonate 106.0, potassium carbonate 21.5, magnesium oxide 20.0, zirconium oxide 10.0, yttrium oxide 50.0, cerium dioxide 50.0, boric acid 53.7, titanium dioxide 20.0; The preparation method is as follows: The above raw materials are mixed evenly, placed in a Pt-10Rh crucible and transferred to a melting furnace. After pretreatment at 500℃ for 5 hours, the temperature is raised to 1580℃ for melting for 4 hours to obtain homogenized glass melt. During the melting process, the glass melt is subjected to regional ultrasonic vibration: the frequency of the lower 1 / 3 region is 120kHz, the frequency of the middle 1 / 3 region is 70kHz, and the frequency of the upper 1 / 3 region is 40kHz. At the same time, a double-blade Pt stirrer is used to stir upward at a speed of 60rpm for 4 hours. Then, the glass melt is formed by inverting the Pt-10Rh crucible onto a rolling table. After annealing at 500℃ for 24 hours, the base glass is obtained after furnace cooling. Microcrystallization and ion exchange: The base glass is nucleated at 570℃ for 6 hours at a rate of 3℃ / min, and then crystallized at 710℃ for 2 hours at a rate of 2℃ / min. Then, a step-by-step ion exchange is performed: first at 420℃... and Ion exchange in a mixed molten salt (mass ratio 7:3) for 5 hours, followed by washing and then ion exchange at 430℃. Ion exchange in molten salt for 2 hours yields the silicate glass.

[0063] Performance: In this embodiment, the Vickers hardness of the base glass is 740 Hv, the bending strength is 133 MPa, and the average transmittance in the visible light band is 90%; the silicate glass obtained after microcrystallization and chemical strengthening has a Vickers hardness of 790 Hv, a bending strength of 770 MPa, and an average transmittance in the visible light band of about 90% when the thickness is 3 mm. Example 6

[0064] Weigh and mix the raw materials according to the proportions required in Table 1. The glass composition (wt%) is: silicon dioxide 58, aluminum oxide 10, lithium oxide 4, sodium oxide 12, potassium oxide 2, magnesium oxide 0, zirconium oxide 1, yttrium oxide 8, cerium dioxide 0, boron oxide 3, titanium dioxide 2; The raw material ratio (g) is as follows: quartz sand 580.0, alumina 100.0, lithium carbonate 84.6, sodium carbonate 127.2, potassium carbonate 21.5, zirconium dioxide 10.0, yttrium oxide 80.0, boric acid 53.7, titanium dioxide 20.0; The preparation method is as follows: The above raw materials are mixed evenly, placed in a Pt-10Rh crucible and transferred to a melting furnace. After pretreatment at 700℃ for 4 hours, the temperature is raised to 1560℃ for 3 hours to obtain homogenized glass melt. During the melting process, the glass melt is subjected to regional ultrasonic vibration: the frequency of the lower 1 / 3 region is 110kHz, the frequency of the middle 1 / 3 region is 80kHz, and the frequency of the upper 1 / 3 region is 30kHz. At the same time, a double-blade Pt stirrer is used to stir upward at a speed of 80rpm for 3 hours. Then, the glass melt is formed by inverting the Pt-10Rh crucible onto a rolling table. After annealing at 500℃ for 24 hours, the base glass is obtained after furnace cooling. Then, microcrystallization and ion exchange are performed: the base glass is heated to 530℃ at 3℃ / min and held for 8 hours for nucleation, and then heated to 690℃ at 2℃ / min and held for 3 hours for crystallization. Then, two-step ion exchange is performed: first, pure ion exchange is carried out at 410℃. The silicate glass is obtained by ion exchange in molten salt for 4 hours, followed by washing and then ion exchange in pure KNO3 molten salt at 420℃ for 2 hours.

[0065] Performance: In this embodiment, the Vickers hardness of the base glass is 756 Hv, the bending strength is 123 MPa, and the average transmittance in the visible light band is 91%; the silicate glass obtained after microcrystallization and chemical strengthening has a Vickers hardness of 820 Hv, a bending strength of 800 MPa, and an average transmittance in the visible light band of 90% when the thickness is 3 mm.

[0066] Comparative Example 1 The glass composition (wt%) is: silicon dioxide 45, aluminum oxide 20, lithium oxide 2, sodium oxide 5, potassium oxide 0, magnesium oxide 2, zirconium oxide 4, yttrium oxide 10, cerium dioxide 0, boron oxide 10, and titanium dioxide 2. The raw material ratio (g) is as follows: quartz sand 450.0, aluminum oxide 200.0, lithium carbonate 42.3, sodium carbonate 53.0, magnesium oxide 20.0, zirconium oxide 40.0, yttrium oxide 100.0, boric acid 179.0, titanium dioxide 20.0; The preparation method is as follows: The above raw materials are mixed evenly, placed in a Pt-10Rh crucible, and transferred to a melting furnace. After pretreatment at 600℃ for 4 hours, the temperature is raised to 1560℃ for high-temperature melting for 3 hours, using only conventional mechanical stirring at a speed of 60 rpm for 3 hours. Then, the glass melt is formed by inverting the Pt-10Rh crucible onto a rolling mill.

[0067] The glass in this comparative example has many air bubbles, poor uniformity, and poor resistance to thermal shock and temperature differences.

[0068] In this comparative example, an attempt at microcrystallization (heating at 3℃ / min to 580℃ / 10h + heating at 2℃ / min to 720℃ / 2h) resulted in abnormal crystallization and cracking due to internal bubbles and inhomogeneity. An attempt was made using ion exchange (pure...) at 400℃. After 6 hours of molten salt treatment, the strength improvement was limited and pitting corrosion appeared.

[0069] Performance: The glass in this comparative example has a hardness of only 620 Hv, a bending strength of 450 MPa, and an average transmittance of less than 70% in the visible light band with a thickness of 3 mm, and exhibits significant scattering.

[0070] Comparative Example 2 The glass composition (wt%) is: silicon dioxide 55%, aluminum oxide 10%, lithium oxide 10%, sodium oxide 10%, potassium oxide 4%, magnesium oxide 4%, zirconium oxide 2%, yttrium oxide 0%, cerium dioxide 5%, boron oxide 0%, titanium dioxide 0%. The raw material ratio (g) is: 550.0g of quartz sand, 100.0g of alumina, 211.5g of lithium carbonate, 106.0g of sodium carbonate, 43.0g of potassium carbonate, 40.0g of magnesium oxide, 20.0g of zirconium oxide, and 50.0g of cerium dioxide. The preparation method is as follows: the above raw materials are mixed evenly, placed in a Pt-10Rh crucible and transferred to a melting furnace. After pretreatment at 700℃ for 4 hours, the temperature is raised to 1560℃ for high-temperature melting for 4 hours, using a frame stirrer at a speed of 60 rpm for 4 hours. Subsequently, the glass melt is formed by inverting the Pt-10Rh crucible onto a rolling mill.

[0071] The comparative sample had a high alkali metal content, poor chemical stability, and the frame stirrer was severely deformed.

[0072] The base glass in this comparative example underwent microcrystallization (heating to 560℃ / 8h at 3℃ / min + heating to 700℃ / 2h at 2℃ / min). Due to excessive alkali metal content, crystal overgrowth occurred, resulting in a sharp decrease in light transmittance. Ion exchange (at 410℃) was then performed. After molten salt (4h), the chemical stability further deteriorated, and white spots appeared on the surface.

[0073] Performance: The glass in this comparative example has a hardness of 650 Hv and a bending strength of 500 MPa. Although the initial transmittance can reach 88% when the thickness is 3mm, the surface becomes fogged after ion exchange.

[0074] Comparative Example 3 The glass composition (wt%) is: silicon dioxide 65, aluminum oxide 5, lithium oxide 4, sodium oxide 18, potassium oxide 2, magnesium oxide 1, zirconium oxide 2, yttrium oxide 3, cerium dioxide 0, boron oxide 0, titanium dioxide 0; The raw material ratio (g) is as follows: 650.0 g of quartz sand, 50.0 g of aluminum oxide, 84.6 g of lithium carbonate, 190.8 g of sodium carbonate, 21.5 g of potassium carbonate, 10.0 g of magnesium oxide, 20.0 g of zirconium oxide, and 30.0 g of yttrium oxide; The preparation method is as follows: Mix the above raw materials evenly, place them in a Pt-10Rh crucible, transfer them to a melting furnace, pre-treat at 700℃ for 4 hours, then heat to 1580℃ for high-temperature melting for 4 hours, using the bubbling method (passing through...) Clarification was carried out at 0.8 L / min for 2 hours without ultrasonication or forced stirring; the glass melt was formed by an inverted rolling mill using a Pt-10Rh crucible.

[0075] The glass in this comparative example has severe air bubbles, making it difficult to form and impossible to obtain completely transparent glass, thus lacking application value.

[0076] This comparative example could not be effectively microcrystallized due to the presence of numerous bubbles and streaks in the glass (deformation occurred upon attempt at heat treatment at 550℃). Ion exchange (pure glass at 420℃) After molten salt treatment for 5 hours, surface cracks appeared and internal defects were exacerbated.

[0077] Performance: This comparative example could not obtain effective hardness and strength test values, the material is opaque, and has no transmittance of practical significance.

[0078] Figure 1 The Raman spectra of the high-strength and high-toughness silicate glasses of Comparative Example 2 and Example 3 are shown to illustrate the effect of titanium dioxide on the glass network structure, especially the glass network after the introduction of titanium dioxide. In the structure The number of structural units increases, and the degree of network connectivity is improved. Figure 2 The DSC curves of high-strength and tough silicate glasses with different titanium dioxide contents in Comparative Example 2 and Example 3 are shown at multiple heating rates to analyze crystallization behavior and activation energy. After the introduction of titanium dioxide, the types of crystal precipitation in the glass were reduced from two to one. Figure 3 The XRD patterns of the high-strength and high-toughness silicate glasses of Comparative Example 2 and Example 3 at different crystallization temperatures are shown, illustrating that the crystal phases are composed of... and Transform into . Figure 4 The SEM-EDS elemental distribution of the high-strength and high-toughness silicate glasses of Comparative Example 2 and Example 3 before and after ion exchange is shown, indicating that the introduction of titanium dioxide... - Improved ion exchange efficiency is beneficial to the ion exchange process. Figure 5 The changes in Vickers hardness and flexural strength of the high-strength and high-toughness silicate glasses of Comparative Example 2 and Example 3 before and after ion exchange are shown at different crystallization temperatures. The horizontal axis represents the crystallization temperature. The introduction of titanium dioxide significantly improved both the Vickers hardness and flexural strength of the glass. However, the flexural strength of the glass decreased at a crystallization temperature of 700°C, indicating that excessive crystals in the glass would reduce the flexural strength. Figure 6 The changes in visible light transmittance of the high-strength and tough silicate glasses of Comparative Example 2 and Example 3 at different crystallization temperatures are shown. The higher the crystallization temperature, the lower the transmittance of the glass.

[0079] While numerous specific technical details are described in this specification, those skilled in the art should understand that embodiments of the present invention can be implemented without these specific details. In some embodiments, to avoid confusion in understanding this specification, well-known methods, structures, and techniques are not shown in detail.

[0080] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0081] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

[0082] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention shall still fall within the scope of the technical solution of the present invention.

Claims

1. A high-strength and high-toughness silicate glass, characterized in that, By weight percentage, the high-strength and high-toughness silicate glass comprises: 50-60% silicon dioxide; 10-18% aluminum oxide; 3-8% lithium oxide; 10-15% sodium oxide; 1-3% potassium oxide; 0-4% magnesium oxide; 0-3% zirconium oxide; 0-6% cerium dioxide; 5-15% yttrium oxide; 0-3% boron oxide; and 0.5-3% titanium dioxide.

2. The high-strength and high-toughness silicate glass as described in claim 1, characterized in that, The high-strength and tough silicate glass has a Vickers hardness ≥ 780 Hv and a bending strength ≥ 730 MPa.

3. The high-strength and high-toughness silicate glass as described in claim 1, characterized in that, The high-strength and tough silicate glass has an average transmittance of ≥ 88% in the visible light band when the thickness is 3mm.

4. A method for preparing high-strength and high-toughness silicate glass, characterized in that, Includes the following steps: S1 Batching and Melting: After mixing all raw materials evenly, melt them at 1550~1600 ℃ for 2~4 hours to obtain homogenized glass melt; S2 Forming and Annealing: The molten glass is poured into shape, then annealed at 450~550 ℃ for 12~24h, and cooled in the furnace to obtain the base glass; S3 Microcrystallization treatment: The base glass is subjected to microcrystallization treatment; S4 Chemical strengthening treatment: The microcrystallized glass is subjected to chemical strengthening treatment to obtain the high-strength and tough silicate glass.

5. The method for preparing high-strength and high-toughness silicate glass as described in claim 4, characterized in that, In step S3, the microcrystallization treatment is a two-step heat treatment, including: a) Nucleation stage: Keep warm at 520~580 ℃ for 6~10h; b) Crystallization stage: Keep warm at 530~730 ℃ for 1~8 hours.

6. The method for preparing high-strength and high-toughness silicate glass as described in claim 4, characterized in that, In step S4, the chemical enhancement treatment is a one-step or two-step ion exchange method.

7. The method for preparing high-strength and high-toughness silicate glass as described in claim 6, characterized in that, In step S4, the one-step ion exchange method includes: Microcrystalline glass is immersed in water at 400~430℃. Ion exchange in molten salt for 1-4 hours; Or the two-step ion exchange method may include: a) First step of exchange: Immerse the microcrystalline glass in water at 400~450℃. Molten salt or and Ion exchange in mixed molten salt for 1-3 hours; b) Second step of exchange: After cleaning, immerse the glass in water at 380~430 ℃. Ion exchange in molten salt for 1-4 hours.

8. An optical window, characterized in that, The optical window includes a transparent structural component made of the high-strength and tough silicate glass as described in any one of claims 1-3.

9. A windshield for a special vehicle, characterized in that, The windshield of the special vehicle includes a transparent structural component, which is made of the high-strength and tough silicate glass as described in any one of claims 1-3.

10. A cover plate for an electronic device, characterized in that, The cover plate of the electronic device includes a transparent structural component, which is made of the high-strength and tough silicate glass as described in any one of claims 1-3.

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