High-thermal-stability cut-off glass as well as preparation method and application thereof

Abstract

The invention relates to the field of special glass materials, and provides high-thermal-stability cut-off glass as well as a preparation method and application thereof. Elements in a network structure of the cut-off glass exist in the form of combined state ions, and the cut-off glass comprises Si < 4 + > (62.1 to 67.6 mol%), Al < 3 + > (0.1 to 1.1 mol%), Zn < 2 + > (6.0 to 8.2 mol%), K < + > (3.5 to 9.4 mol%), Ca < 2 + > (0.1 to 1.0 mol%), Mg < 2 + > (0.3 to 1.4 mol%), Na < + > (7.3 to 15.7 mol%), B < 3 + > (6.4 to 12.8 mol%), Se < 2-> (0.7 to 1.5 mol%) and Cd < 2 + > (0.1 to 0.5 mol%). The cut-off type glass has excellent comprehensive performance: the bending strength is greater than 110 MPa, the maximum optical transmittance of a 6mm glass sample is greater than or equal to 91.0%, the sag temperature Tf is greater than or equal to 670 DEG C, the thermal expansion coefficient alpha is less than or equal to 70 * 10 <-7 > / DEG C, the cut-off wavelength is 625 + / -15 nm, the gradient is greater than or equal to 1.0, and the cut-off type glass has I-grade acid-resistant stability and moisture-resistant stability. The glass can be applied to the fields of optical windows, optical lenses and the like for image surveying and mapping in a complex illumination environment, and is particularly suitable for optical elements in electronic digital products, aerospace or military environments.

Description

Technical Field

[0001] The present application relates to special glass materials, and in particular to a high thermal stability cut-off glass and its preparation method and application. Background Art

[0002] Any discussion of the prior art throughout the specification should not be considered as an admission that such prior art is widely known or forms part of the common general knowledge in the field.

[0003] Cutoff glass is a glass material with unique optical properties. It achieves high transmittance or high reflectance within a specific wavelength range, thereby achieving a cutoff or filtering effect. This type of glass material boasts exceptional properties such as pure color, high transmittance, and a steep light absorption curve. It can achieve a transmittance range from near zero to maximum within a very narrow wavelength band.

[0004] Over the past 20 years, artistic glass and electronic digital products have experienced rapid development. Cutoff glass has garnered widespread attention due to its pure color and excellent optical properties. In the field of electronic digital products, cutoff glass near the 630nm band has a particularly broad application, such as in mobile phone lenses, camera projectors, surveillance equipment lenses, and optical window glass for image mapping in complex lighting environments, such as aerospace, military, and other applications. In these applications, the 630nm band lies in the transition region between visible red light and near-infrared, a critical wavelength for common red lasers, red LEDs, and some fluorescent signals. By achieving precise cutoff in this band, interfering background light can be effectively filtered out, imaging contrast can be enhanced, and the incidence of non-target wavelengths can be suppressed, thereby enabling high-precision optical recognition, ranging, or sensing functions. Therefore, cutoff performance near 630nm is currently a hot topic in the field of optical glass materials.

[0005] However, the existing cutoff glass in practical applications still has some problems that need to be solved: (1) Insufficient thermal stability: In an environment with large temperature changes, the existing cutoff glass is prone to thermal expansion and contraction, resulting in dimensional instability and affecting optical performance. Especially under high temperature conditions, the glass material is prone to softening and deformation, and the sag temperature is generally low. (2) Limited mechanical strength: In mechanical stress environments such as vibration and impact, the existing cutoff glass has insufficient bending resistance and is prone to microcracks or even breakage, affecting service life and reliability. (3) Difficulty in controlling optical performance: It is difficult to accurately control the cutoff wavelength and steepness with existing technology, especially the cutoff characteristics near the 630nm band are more difficult to control, resulting in poor consistency between batches. (4) Insufficient chemical stability: In high humidity, acidic or alkaline environments, the glass surface is easily corroded, resulting in a decrease in transmittance and an increase in scattering, affecting the use effect of the optical window. (5) Poor processing performance: The existing cutoff glass is prone to defects such as deformation, bubbles, streaks, and crystallization during thermal processing, which increases manufacturing costs and scrap rates. The low annealing point and softening point make it difficult to control the precise processing dimensions.

[0006] Especially in complex environmental applications, more stringent requirements are placed on the thermal stability, mechanical strength, optical properties and processing precision of glass materials. Existing cut-off glass has obvious deficiencies in these key performance indicators, which limits its promotion and use in high-end applications. Summary of the Invention

[0007] The main purpose of the present invention is to provide a high thermal stability cutoff glass and its preparation method and application, in order to solve the technical problem that existing cutoff glass is difficult to meet the application requirements of complex lighting environments. In the present invention, a complex lighting environment refers to at least one of the following environments: an environment with large temperature fluctuations, an environment that requires precise spectral screening, an environment with mechanical stress, or an environment with chemical corrosion. Existing cutoff glass exhibits many shortcomings when facing these complex environments: it is easy to deform in an environment with drastic temperature changes, has poor impact resistance under mechanical stress, is difficult to accurately control the cutoff characteristics near the 630nm band, and has insufficient stability in harsh chemical environments. These problems seriously limit its application in high-end fields such as electronic digital products, aerospace, and military.

[0008] The present invention precisely controls Si 4+ 、Al 3+ 、Zn 2+ , K ＋ , Ca 2+ Mg 2+ 、Na ＋ 、B 3+ 、Se 2- and Cd 2+The composition and content of these ions, combined with an optimized preparation process, enable the glass material to possess at least one of a series of excellent properties. These properties include: mechanical properties with a bending strength greater than 110 MPa, high-quality optical properties with a maximum optical transmittance of greater than 91.0% for a 6 mm sample, a sag temperature Tf ≥ 670°C, and a thermal expansion coefficient ɑ ≤ 70 × 10 -7 The glass material of the present invention has thermal stability of 1000 nm / °C, precise spectral control with a cutoff wavelength of 625±15 nm and a steepness ≥1.0, and Class I acid and moisture resistance. In optimal circumstances, the glass material of the present invention can simultaneously possess all of the above excellent properties, but it is not required to meet these indicators simultaneously in all application scenarios.

[0009] This flexible and powerful combination of properties enables the cutoff glass of this invention to adapt to various complex lighting environments, leveraging its advantages based on specific application requirements. This not only addresses the shortcomings of existing technologies but also provides a new solution for the development of optical materials in demanding applications, particularly in high-end applications that require a balance of performance requirements.

[0010] Specifically, the present invention provides the following technical solutions.

[0011] In a first aspect of the present invention, a cut-off glass is provided, wherein the elements in the network structure of the glass exist in the form of bound ions, and the elements include or consist of the following in terms of molar percentage (mol%): Si 4+ 62.1-67.6mol%Al 3+ 0.1-1.1mol% Zn 2+ 6.0-8.2mol%; K ＋ 3.5-9.4mol%Ca 2+ 0.1-1.0mol%Mg 2+ 0.3-1.4mol%;Na ＋ 7.3-15.7mol%B 3+ 6.4-12.8mol%; Se 2- 0.7-1.5mol% Cd 2+ 0.1-0.5mol%.

[0012] In the present invention, the contents of all components are expressed in mole percentage (mol%), that is, each component is calculated in its ionic form and measured in mole percentage, which represents the relative molar amount of each ion in the glass network structure. These ions include Si 4+ 、Al 3+ 、Zn 2+ , K ＋ , Ca 2+ Mg2+ 、Na ＋ 、B 3+ 、Se 2- and Cd 2+ Regardless of whether the raw materials are added in the form of oxides, carbonates, sulfides, or other compounds, the component contents are converted to the final molar percentage of the ions in the glass network. The sum of the molar percentages of the various ions listed in the present invention is 100%.

[0013] The "bound ionic form" mentioned in the present invention refers to the existence of elements in the form of specific valence ions in the amorphous network structure of glass. These ions form a complex three-dimensional network structure with oxygen (or other non-metallic elements) through covalent bonds, ionic bonds or mixed bonds according to their functions and coordination characteristics, rather than existing as independent ions or molecules.

[0014] The high-thermal-stability cutoff glass of this invention achieves a functional distribution and synergistic effect of each element within the glass network through a specific component structure design. This structural design is based on a deep understanding of the mechanism of action of each element in the glass system and achieves overall performance optimization through precise ratio control.

[0015] Si 4+ As the main network former of glass, the content of Si in the present invention is 62.1-67.6 mol%, which is responsible for building the basic network skeleton of glass. 4+ Forming a silicon-oxygen tetrahedron network provides the basic skeleton of the glass, giving the glass good chemical stability and mechanical strength. 4+ The content effectively reduces the thermal expansion coefficient of the glass and significantly improves the heat resistance, chemical stability and softening temperature, which is one of the key factors to achieve high thermal stability. 4+ When the content is lower than 62.1 mol%, the structural strength and chemical stability of the glass will be significantly reduced; when it exceeds 67.6 mol%, the melting point will be too high, increasing the difficulty of preparation and processing.

[0016] Therefore, in the present invention, Si 4+ The content of Si is 62.1-67.6 mol%. In some embodiments of the present invention, Si 4 +The content of can be selected from the following ranges: 62.1-62.8 mol%, 62.1-63.1 mol%, 62.1-63.2 mol%, 62.1-64.0 mol%, 62.1-64.2 mol%, 62.1-64.4 mol%, 62.1-65.3 mol%, 62.1-67.6 mol%, 62.8-63.1 mol%, 62.8-63.2 mol%, 62.8-64.0 mol%, 62.8-64.2 mol%, 62.8-64.4 mol%, 62.8-65.3 mol%, 62.8-67.6 mol%, 63.1-63.2 mol%, 63.1-64.0 mol%, 63.1-64.2 mol%, 63.1-64.4 mol%, 63.1-65.3 mol%, 63.1-67.6 mol%, 63.2-64.0 mol%, 63.2-64.2 mol%, 63.2-64.4 mol%, 63.2-65.3 mol%, 63.2-67.6 mol%, 63.5-64.2 mol%, 64.0-64.2 mol%, 64.0-64.4 mol%, 64.0-65.3 mol%, 64.0-67.6 mol%, 64.2-64.4 mol%, 64.2-65.3 mol%, 64.2-67.6 mol%, 64.4-65.3 mol%, 64.4-67.6 mol%, 65.3-67.6 mol%. In some preferred embodiments, Si 4+ The content of may be selected from the following ranges: 64.2-65.3 mol%, 64.2-64.4 mol%, 64.4-67.6 mol%, 64.2-67.6 mol%, 64.0-65.0 mol%, 63.0-65.0 mol%. In some exemplary embodiments, Si 4+ The content can be selected from the endpoint values of any of the above ranges or any value within the range, for example, 64.2 mol%, 67.6 mol%, 64.4 mol%, 5.3 mol%, 63.1 mol%, 63.2 mol%, 62.1 mol%, 62.8 mol%, etc.

[0017] Al 3+ As an important network intermediate, the content of Al in the present invention is 0.1-1.1 mol%, playing multiple roles in the glass network. 3+ It is mainly used to improve the chemical stability of glass, effectively reduce the tendency of glass to crystallize, and at the same time improve the hardness, mechanical strength and tensile modulus of glass. 3+It can enter the glass network structure as a network former, and can also act as a network modifier to optimize the glass properties. 3+ The thermal expansion coefficient of the glass is reduced, and the thermal stability and softening temperature are significantly improved. However, when the content exceeds 1.1 mol%, the melting point is increased and the viscosity of the glass liquid is too high, which is not conducive to melting and processing. In addition, in the embodiment of the present invention, when Al 3+ When the content is extremely low (e.g., lower than the limit of the present invention or close to zero) or completely absent (e.g., no additional addition), the performance of the glass deteriorates, such as decreased chemical stability, significantly reduced acid resistance and moisture resistance; significantly reduced sag temperature; increased thermal expansion coefficient; and decreased bending strength.

[0018] Therefore, in the present invention, Al 3+ The content of Al is 0.1-1.1 mol%. In some embodiments of the present invention, 3+ The content of can be selected from the following ranges: 0.1-0.5 mol%, 0.1-0.6 mol%, 0.1-1.0 mol%, 0.1-1.1 mol%, 0.5-0.6 mol%, 0.5-1.0 mol%, 0.5-1.1 mol%, 0.6-1.0 mol%, 0.65-1.0 mol%, 0.6-1.1 mol%, 1.0-1.1 mol%. In some preferred embodiments, Al 3+ The content of may be selected from the following ranges: 0.1-1.0 mol%, 0.6-1.0 mol%, 0.1-0.6 mol%, 0.9-1.1 mol%, 0.5-1.0 mol%. In some exemplary embodiments, Al 3+ The content of can be selected from any endpoint value of the above range or any value within the range, for example, 1 mol%, 0.1 mol%, 0.6 mol%, 0.5 mol%, 1.1 mol%, etc.

[0019] In the present invention, Zn 2+ It is a key component with special functions. During the high temperature melting and cooling process of glass, Zn 2 + Can react reversibly with selenides and sulfides (such as ZnO + CdS ZnS + CdO, ZnO + CdSe ZnSe + CdO), significantly reducing the volatilization loss of colorants Se and Cd, ensuring that the spectral absorption performance of the cut-off glass is precisely controlled. 2+When the content is insufficient, the colorant is easy to volatilize and the optical properties are unstable; while when the content is too high, the transparency and melting characteristics of the glass may be affected. 2+ When the content is extremely low (e.g., below the limit of the present invention or close to zero) or completely absent (e.g., no additional addition), the optical properties of the glass tend to deteriorate. For example, the cutoff wavelength may lose stability and tend to shift significantly; the steepness value is significantly reduced, and the cutoff characteristics tend to deteriorate; and the transmittance and batch stability will be significantly affected.

[0020] Therefore, in the present invention, Zn 2+ The content of Zn is 6.0-8.2 mol%. In some embodiments of the present invention, Zn 2+ The content of Zn may be selected from the following ranges: 6.0-6.1 mol%, 6.0-6.7 mol%, 6.0-6.8 mol%, 6.0-6.9 mol%, 6.0-7.7 mol%, 6.0-8.2 mol%, 6.1-6.7 mol%, 6.1-6.8 mol%, 6.1-6.9 mol%, 6.1-7.7 mol%, 6.1-8.2 mol%, 6.7-6.8 mol%, 6.7-6.9 mol%, 6.7-7.7 mol%, 6.7-8.2 mol%, 6.8-6.9 mol%, 6.8-7.7 mol%, 6.8-8.2 mol%, 6.9-7.5 mol%, 6.9-7.7 mol%, 6.9-8.2 mol%, 7.7-8.2 mol%. In some preferred embodiments, Zn 2+ The content of Zn may be selected from the following ranges: 6.7-6.9 mol%, 6.9-7.7 mol%, 6.7-7.7 mol%, 6.8-7.0 mol%, 6.8-7.0 mol%, 6.7-7.0 mol%. In some exemplary embodiments, Zn 2+ The content can be selected from any endpoint value of the above range or any value within the range, for example, 6.9 mol%, 6.7 mol%, 7.7 mol%, 6.8 mol%, 6.1 mol%, 6.9 mol%, 6 mol%, 8.2 mol%, etc.

[0021] In the present invention, K ＋ and Na ＋ As alkali metal ions, the content is 3.5-9.4mol% and 7.3-15.7mol%, respectively, which belong to the network modifier in the glass. These alkali metal ions are easy to move and diffuse in the glass. Their main function is to reduce the viscosity of the glass during high temperature melting, promote the melting and homogenization of the glass, and are good fluxing agents. In the present invention, by precisely controlling K＋ and Na ＋ The content and ratio of Na can effectively balance the processing performance and thermal stability of the glass, avoiding the problem of increased thermal expansion coefficient, decreased chemical stability and mechanical strength caused by excessive alkali metal content. ＋ and K ＋ The specific ratio can also achieve the "mixed alkali effect", further improving the overall performance of the glass.

[0022] Therefore, in the present invention, K + The content is 3.5-9.4 mol%. In some embodiments of the present invention, K + The content may be selected from the following ranges: 3.5-3.6 mol%, 3.5-4.6 mol%, 3.5-5.9 mol%, 3.5-6.0 mol%, 3.5-6.6 mol%, 3.5-8.2 mol%, 3.5-9.0 mol%, 3.5-9.4 mol%, 3.6-4.6 mol%, 3.6-5.9 mol%, 3.6-6.0 mol%, 3.6-6.6 mol%, 3.6-8.2 mol%, 3.6-9.0 mol%, 3.6-9.4 mol%, 4.6-5.9 mol%, 4.6-6.0 mol%, 4.6-6.6 mol%, 4.6-8.2 mol%, 4.6-9.0 mol%, 4.6-9.4 mol%, 5.9-6.0 mol%, 5.9-6.6 mol%, 5.9-8.2 mol%, 5.9-9.0 mol%, 5.9-9.4 mol%, 6.0-6.6 mol%, 6.6-8 mol%, 6.0-8.2 mol%, 6.0-9.0 mol%, 6.0-9.4 mol%, 6.6-8.2 mol%, 6.6-9.0 mol%, 6.6-9.4 mol%, 8.2-9.0mol%, 8.2-9.4 mol%, 9.0-9.4 mol%. In some preferred embodiments, K + The content may be selected from the following ranges: 6.0-6.6 mol%, 6.6-9.0 mol%, 3.6-6.6 mol%, 3.6-9.0 mol%, 6.5-6.8 mol%, 6.0-7.0 mol%. In some exemplary embodiments, K + The content can be selected from any endpoint value of the above range or any value within the range, for example, 6.6 mol%, 6 mol%, 3.6 mol%, 9 mol%, 9.4 mol%, 8.2 mol%, 5.9 mol%, 4.6 mol%, 3.5 mol%, etc.

[0023] In the present invention, Na + The content of Na is 7.3-15.7 mol%. In some embodiments, Na + The content of can be selected from the following ranges: 9.8-15.7 mol%, 9.8-12.6 mol%, 9.8-10.8 mol%, 9.8-10.9 mol%, 9.8-10.0 mol%, 9.1-9.8 mol%, 9.1-15.7 mol%, 9.1-12.6 mol%, 9.1-10.8 mol%, 9.1-10.9 mol%, 9.1-10.0 mol%, 7.3-9.8 mol%, 7.3-9.1 mol%, 7.3-15.7 mol%, 7.3-12.6 mol%, 7.3-10.8 mol%, 7.3-10.9 mol%, 7.3-10.0 mol%, 12.6-15.7 mol%, 10.8-15.7 mol%, 10.8-12.6 mol%, 10.9-15.7 mol%, 10.9-12.6 mol%, 10.9-10.8 mol%, 10.0-15.7 mol%, 10.0-12.6 mol%, 10.0-10.8 mol%, 10.0-10.9 mol%. In some preferred embodiments, Na + The content of can be selected from the following ranges: preferably, 7.3-9.1 mol%, 7.3-10.8 mol%, 9.1-10.8 mol%, 7.2-7.5 mol%, 7.3-9.1 mol%, 7.3-9 mol%, 7.3-8.0 mol%. In some exemplary embodiments, Na + The content can be selected from any endpoint value of the above range or any value within the range, for example, 7.3 mol%, 9.1 mol%, 10.8 mol%, 10.9 mol%, 9.8 mol%, 12.6 mol%, 15.7 mol%, 10 mol%, etc.

[0024] Ca 2+ and Mg 2+ As alkaline earth metal ions, the contents in the present invention are 0.1-1.0 mol% and 0.3-1.4 mol% respectively, and the total amount in the present invention does not exceed 2.4 mol%. The introduction of these two ions forms an exquisite balance system: Ca 2+ Increase the chemical stability and mechanical strength of glass, but it is easy to cause glass crystallization; Mg 2+ The thermal stability is improved and the thermal expansion coefficient is significantly reduced, but too much increases the viscosity of the glass and makes molding difficult. 2+ With Ca 2+The synergistic effect of Mg 2+ The addition of Ca 2+ The thermal expansion coefficient increases, and the two together improve the mechanical strength and chemical durability of the glass, forming a unique synergistic performance enhancement mechanism. In the embodiment of the present invention, when other alkaline earth metal ions (such as Ba 2+ ) replaces Ca 2+ Even with similar molar contents, glass properties often change: the thermal expansion coefficient generally tends to increase; the sag temperature may decrease; the cutoff wavelength often shifts slightly; the steepness value may decrease; and the flexural strength generally tends to decrease. These trends demonstrate the considerable specificity of the elemental composition of the present invention, and element substitution can lead to diverse changes in properties.

[0025] In the present invention, Ca 2+ The content of Ca is 0.1-1.0 mol%. In some embodiments, Ca 2+ The content of can be selected from the following ranges: 0.1-0.2 mol%, 0.1-0.3 mol%, 0.1-0.5 mol%, 0.1-1.0 mol%, 0.2-0.3 mol%, 0.2-0.5 mol%, 0.2-1.0 mol%, 0.3-0.5 mol%, 0.3-1.0 mol%, 0.35-0.5 mol%, 0.4-0.5 mol%, 0.5-1.0 mol%. In some preferred embodiments, Ca 2+ The content of may be selected from the following ranges: 0.5 mol%, 0.4-0.6 mol%, 0.3-0.7 mol%, 0.1-0.5 mol%. In some exemplary embodiments, Ca 2+ The content of can be selected from the endpoint value of any of the above ranges or any value within the range, for example, 0.5 mol%, 0.1 mol%, 0.3 mol%, 1 mol%, 0.2 mol%, etc.

[0026] In the present invention, Mg 2+ The content of Mg is 0.3-1.4 mol%. In some embodiments, Mg 2+ The content of Mg may be selected from the following ranges: 0.3-0.4 mol%, 0.3-0.7 mol%, 0.3-1.4 mol%, 0.4-0.7 mol%, 0.4-1.4 mol%, 0.7-1.4 mol%, 0.5-0.7 mol%, 0.7-1.3 mol%, 0.7-1.0 mol%. In some preferred embodiments, Mg 2+The content of Mg may be selected from the following ranges: 0.7 mol%, 0.6-0.8 mol%, 0.5-0.9 mol%, 0.4-0.7 mol%. In some exemplary embodiments, Mg 2+ The content of can be selected from any endpoint value of the above range or any value within the range, for example, 0.7 mol%, 0.4 mol%, 0.3 mol%, 1.4 mol%, etc.

[0027] B 3+ In the present invention, the content is 6.4-12.8 mol%, with unique dual structure characteristics. 3+ It can form [BO4] tetrahedrons into the glass network to increase the bridging oxygen content, and it can also form [BO3] triangles to play a chain breaking effect. This structural duality makes B 3+ The ability to flexibly adjust the connectivity of the glass network has a positive effect on reducing high-temperature viscosity, improving melting quality, and increasing chemical stability. 2- and Cd 2+ In glass of semiconductor materials such as B 3+ The ratio with alkali metal ions also directly affects the formation of colored microcrystals, and balance needs to be achieved through precise control.

[0028] B 3+ In the present invention, the content is 6.4-12.8 mol%, with unique dual structure characteristics. 3+ It can form [BO4] tetrahedrons into the glass network to increase the bridging oxygen content, and it can also form [BO3] triangles to play a chain breaking effect. This structural duality makes B 3+ The ability to flexibly adjust the connectivity of the glass network has a positive effect on reducing high-temperature viscosity, improving melting quality, and increasing chemical stability. 3+ The content of B is 6.4-12.8 mol%. In some embodiments, B 3+The content of can be selected from the following ranges: 9.6-12.8 mol%, 9.6-11.2 mol%, 9.6-10.5 mol%, 8.1-9.6 mol%, 8.1-12.8 mol%, 8.1-11.2 mol%, 8.1-10.5 mol%, 8.0-9.6 mol%, 8.0-8.1 mol%, 8.0-12.8 mol%, 8.0-11.2 mol%, 8.0-10.5 mol%, 6.4-9.6 mol%, 6.4-8.1 mol%, 6.4-8.0 mol%, 6.4-12.8 mol%, 6.4-11.2 mol%, 6.4-10.5 mol%, 11.2-12.8 mol%, 10.5-12.8 mol%, 10.5-11.2 mol%, 10.6-11.2 mol%, 11.2-12.5 mol%, 11.2-12.0 mol%. In some preferred embodiments, B 3+ The content of may be selected from the following ranges: preferably, 8.1-11.2 mol%, 10.5-11.2 mol%, 8.1-10.5 mol%, 8.1-11.2 mol%, 11.0-11.5 mol%, 8.0-11.2 mol%. In some exemplary embodiments, B 3+ The content can be selected from the endpoint values of any of the above ranges or any value within the range, for example, 11.2 mol%, 8.1 mol%, 10.5 mol%, 8.1 mol%, 8 mol%, 9.6 mol%, 6.4 mol%, 12.8 mol%, etc.

[0029] Se 2- and Cd 2+ Se is present in the present invention at a content of 0.7-1.5 mol% and 0.1-0.5 mol% respectively. These two elements are important components for achieving specific optical properties of the cut-off glass of the present invention. 2- and Cd 2+ The content of Se is 625±15nm, and the cut-off wavelength is controlled to be 625±15nm and the steepness is greater than 1.0, which meets the precise requirements for spectral screening under complex lighting environments. 2- and Cd 2+When both are missing (e.g., not added) or significantly reduced (e.g., below the limit of the present invention or close to zero), the cutoff characteristics of the glass will be greatly weakened. For example, the transmittance curve tends to be continuous transmission type, and the cutoff wavelength and steepness characteristics may be significantly deteriorated; the color tone usually tends from light yellow to colorless; the spectral selectivity function is significantly reduced, the infrared isolation effect is greatly weakened, and the visible light / near infrared separation ability tends to decrease. In the present invention, Se 2- The content of Se is 0.7-1.5 mol%. In some embodiments, Se 2- The content of can be selected from the following ranges: 0.7-0.8 mol%, 0.7-1.0 mol%, 0.7-1.2 mol%, 0.7-1.5 mol%, 0.8-1.0 mol%, 0.8-1.2 mol%, 0.8-1.5 mol%, 1.0-1.2 mol%, 1.0-1.5 mol%, 1.0-1.5 mol%, 1.2-1.5 mol%. In some preferred embodiments, Se 2- The content of may be selected from the following ranges: 1.0-1.5 mol%, 1.0-1.4 mol%, 1.0-1.3 mol%, 1.0-1.2 mol%, 1.0-1.1 mol%, 0.9-1.2 mol%, 1.2-1.5 mol%, 0.9-1.5 mol%, 1.1-1.3 mol%, 0.9-1.2 mol%, 1.2-1.45 mol%, 1.1-1.2 mol%. In some exemplary embodiments, Se 2- The content of Cd can be selected from any endpoint value of the above range or any value within the range, for example, 1.2 mol%, 1 mol%, 1.5 mol%, 0.8 mol%, 0.7 mol%, etc. In the present invention, Cd 2+ The content of Cd is 0.1-0.5 mol%. In some embodiments, Cd 2+ The content of Cd can be selected from the following ranges: 0.1-0.2 mol%, 0.1-0.3 mol%, 0.1-0.4 mol%, 0.1-0.5 mol%, 0.2-0.3 mol%, 0.2-0.4 mol%, 0.2-0.5 mol%, 0.3-0.4 mol%, 0.3-0.5 mol%, 0.4-0.5 mol%, 0.31-0.4 mol%, 0.4-0.49 mol%. In some preferred embodiments, Cd 2+The content of Cd may be selected from the following ranges: 0.2-0.5 mol%, 0.2-0.4 mol%, 0.1-0.4 mol%, 0.3-0.4 mol%, 0.4-0.5 mol%, 0.1-0.5 mol%, 0.3-0.5 mol%, 0.31-0.5 mol%, 0.2-0.4 mol%. In some exemplary embodiments, Cd 2+ The content of can be selected from any endpoint value of the above range or any value within the range, for example, 0.4 mol%, 0.2 mol%, 0.5 mol%, 0.1 mol%, 0.3 mol%, etc.

[0030] In a preferred embodiment, the elements in the network structure of the high thermal stability cut-off glass exist in the form of bound ions, and the molar percentage includes: Si 4+ 64.0-67.6mol%Al 3+ 0.5-1.0mol% Zn 2+ 6.5-7.7mol%; K ＋ 5.5-9.4mol%Ca 2+ 0.3-0.7mol%Mg 2+ 0.5-0.8mol%;Na ＋ 7.3-11.0mol%B 3+ 8.0-11.5mol%; Se 2- 0.8-1.2mol% Cd 2+ 0.2-0.4mol%.

[0031] In another preferred embodiment, the elements in the network structure of the high thermal stability cut-off glass exist in the form of bound ions, and include or consist of the following by molar percentage: Si 4+ 63-67.6mol%Al 3+ 0.1-1mol% Zn 2+ 6.1-7.7mol%; K ＋ 3.6-9.4mol%Ca 2+ 0.3-1.0mol%Mg 2+ 0.5-1.4mol%Na ＋ 7.3-12.6mol%B 3+ 8-11.2mol% Se 2- 1-1.5mol%Cd 2+ 0.2-0.5mol%.

[0032] In a more preferred embodiment, the elements in the network structure of the high thermal stability cut-off glass exist in the form of bound ions, and include or consist of the following by molar percentage: Si 4+ 63.1-67.6mol%Al 3+ 0.1-1.0mol% Zn 2+ 6.7-7.0mol%; K ＋ 6.0-9.4mol%Ca 2+ 0.1-0.6mol%Mg 2+ 0.4-0.8mol%;Na ＋ 7.3-10.9mol%B 3+ 8.0-11.5mol%; Se 2- 0.7-1.2mol% Cd 2+ 0.1-0.4mol%.

[0033] In a more preferred embodiment, the elements in the network structure of the high thermal stability cut-off glass exist in the form of bound ions, and include or consist of the following in terms of molar percentage: Si 4+ 64.2-67.6mol%Al 3+ 0.6-1mol% Zn 2+ 6.7-7.7mol%; K ＋ 3.6-9mol%Ca 2+ 0.3-0.9mol%Mg 2+ 0.5-0.7mol%;Na ＋ 7.3-10.9mol%B 3+ 8.1-11.2 mol% Se 2- 1-1.2mol%Cd 2+ 0.2-0.4mol%.

[0034] In a more preferred embodiment, the elements in the network structure of the high thermal stability cut-off glass exist in the form of bound ions, and include or consist of the following in terms of molar percentage: Si 4+ 64.0-64.5mol%Al 3+ 0.9-1.0mol% Zn 2+ 6.8-7.0mol%; K ＋ 6.5-6.8mol%Ca 2+ 0.4-0.6mol%Mg 2+ 0.6-0.8mol%;Na ＋ 7.2-7.5mol%B 3+ 11.0-11.5mol%; Se2- 1.1-1.2mol%Cd 2+ 0.3-0.5mol%.

[0035] In a more preferred embodiment, the elements in the network structure of the high thermal stability cut-off glass exist in the form of bound ions, and include or consist of the following by molar percentage: include by molar percentage: Si 4+ 64.0-65.5mol%Al 3+ 0.5-1.0mol% Zn 2+ 6.7-7.0mol%; K ＋ 6.0-8.0mol%Ca 2+ 0.3-0.6mol%Mg 2+ 0.6-0.8mol%;Na ＋ 7.3-9.1mol%B 3+ 10.0-11.5mol%; Se 2- 1.0-1.2mol% Cd 2+ 0.3-0.4mol%.

[0036] The specific technical features described in the above embodiments of the present invention include the following: 4+ 、Al 3+ 、Zn 2+ , K ＋ , Ca 2+ Mg 2+ 、Na ＋ 、B 3+ 、Se 2- and Cd 2+ The content ranges of the present invention can be combined in various appropriate ways, provided there are no technical conflicts, to form other embodiments of the present invention. This means that each element can be selected at any value within its respective content range and combined with any appropriate content value of other elements to form a new effective formula. To avoid unnecessary redundancy, the present invention does not further describe these possible element content combinations in detail.

[0037] It should be noted that all numerical ranges mentioned in this invention should be understood to include all values within that range, as well as sub-ranges consisting of any two values within that range. For example, when expressed as "0.2-1," the range not only includes values such as 0.2, 0.3, 0.4, ..., and 1.0, but also includes a sub-range consisting of any two values within those ranges (i.e., 0.21-0.9). Furthermore, different numerical values or ranges involving the same technical indicator in various embodiments of the present invention may be cross-combined to form new valid ranges, and these combinations also fall within the scope of protection of this invention.

[0038] In addition to the individual effects of each component, the high-thermal-stability cutoff glass system provided by the present invention achieves synergistic optimization of the material's thermal stability, mechanical strength, optical properties, and chemical stability by optimizing and controlling the ratios between the components. The following describes typical component ratios and their effects within the present system.

[0039] In some embodiments, Mg 2+ , Ca 2+ With Al 3+ The three together play a role in regulating the glass structure. Through formula analysis and performance evaluation, it was found that when Mg 2+ / Ca 2+ When the molar ratio is controlled within the range of 1.0-4.0, preferably 1.4-4.0, the resulting glass generally exhibits relatively balanced properties in terms of thermal expansion coefficient and flexural strength. For example, in Example 5, the ratio is approximately 1.4, and the corresponding glass sample exhibits excellent thermal stability and mechanical strength. In an embodiment of the present invention, when the Mg content is changed, the glass sample exhibits relatively good thermal stability and mechanical strength. 2+ and Ca 2+ When the content ratio is, for example, Mg in the above range 2+ / Ca 2+ When the ratio is significantly reduced (for example, the molar ratio is lower than 1.0), the thermal expansion coefficient of the glass tends to increase; the sag temperature usually decreases; the cutoff wavelength may shift; and the steepness value tends to decrease. These trends indicate that Mg 2+ / Ca 2+ The ratio has an important influence on the thermal and optical properties of glass. Reasonable control of the ratio helps to achieve better comprehensive performance.

[0040] Furthermore, in the system, Al 3+ / (Mg 2+ +Ca 2+ When the ratio of Al to Zn is 0.08-2.2, preferably 0.08-1.0, and more preferably 0.08-0.85, a relatively stable glass network structure can be obtained. When the total amount of the above three elements is controlled at 1.0-3.5 mol%, preferably 1.0-2.2 mol%, and more preferably 1.3-2.2 mol%, it is generally beneficial to improve the overall mechanical and thermal properties while ensuring melt processability. In an embodiment of the present invention, when Al 3+ / (Mg 2+ +Ca 2+When the ratio of Al2O3 decreases to a lower level (e.g., below the limit of the present invention), the thermal stability of the glass tends to decrease, the sag temperature usually decreases; the thermal expansion coefficient may increase; the mechanical strength tends to decrease; the chemical stability tends to decrease; the anti-crystallization ability may weaken, and the crystal phase is more likely to appear after long-term high-temperature preservation. These trends indicate that Al2O3 is a kind of glass with a low thermal stability and a low thermal conductivity. 3+ The synergistic ratio between alkaline earth metal ions and the glass has an important influence on the comprehensive properties of the glass. Reasonable control of this ratio helps to achieve a better performance balance.

[0041] In terms of optical performance construction, Se 2- 、Cd 2+ With Zn 2+ The ratio relationship between them also constitutes one of the control factors of the present invention. 2- / Cd 2+ When the molar ratio is controlled within the range of 2.0-8.0, preferably 3.0-5.0, different coloring effects can be obtained, and good cutoff characteristics in the 625±15 nm band can be achieved. In a typical embodiment, such as Example 5, when Se 2- / Cd 2+ When ≈3.0, the glass exhibits better optical filtering performance.

[0042] In addition, Zn 2+ / Se 2- The molar ratio is controlled between 4.6–10.25, preferably 5.75–6.7, or Zn 2+ / (Se 2- +Cd 2 + ) is controlled between 3.45-8.6, preferably between 4.3-5.6, which can help suppress Se in the glass system provided by the present invention. 2- The total content of the above three is controlled at 6.8-9.3 mol%, preferably 7.9-8.9 mol%, which further enhances the controllability of the cutoff wavelength and the steepness of the transmittance curve. In the embodiment of the present invention, when Zn 2+ / (Se 2- +Cd 2+ ) ratio is reduced to a lower level (for example, below the limit of 3.45 in the present invention), the transmittance of the glass tends to change; the cutoff wavelength usually shifts and may deviate from the target wavelength region; the batch-to-batch stability tends to decrease; and the color change during heat treatment may become more sensitive. These trends indicate that Zn 2+ with Se 2- 、Cd 2+ The synergistic ratio between them has an important influence on product performance, and reasonable control of their ratio helps to obtain more stable optical performance.

[0043] In terms of glass network skeleton construction, Si 4+ With B 3+ The ratio relationship between can be used to control the viscosity, structural stability and thermal expansion behavior of the glass. 4+ / B 3+ The molar ratio is 4.9-9.9, preferably 5.6-8.4; 3+ / Si 4+ When measured by angle, the ratio is more appropriately controlled within the range of 0.1–0.21. Controlling the total content of the two within the range of 69.6–75.7 mol%, preferably 74.9–75.7 mol%, and more preferably 75.5–75.7 mol%, helps achieve good skeleton continuity and structural density.

[0044] Na ＋ With K ＋ As a network modifying element, its proportion control is mainly used to adjust the melting processing performance and chemical stability of the glass in the present invention. ＋ / K ＋ When the molar ratio is between 0.81-3.42, preferably between 1.1-1.52, the prepared glass samples exhibit good molding fluidity and moisture and heat resistance; Na ＋ +K ＋ When the total content of Na is controlled at 13.5-20.3 mol%, preferably 13.9-16.3 mol%, it also contributes to the overall balance of performance. ＋ / K ＋ When the ratio deviates significantly from the optimal range (such as the limit range of the present invention), such as Na ＋ / K ＋ If the ratio is too high, the balance of the mixed alkali effect will be destroyed, and the acid resistance and moisture resistance of the glass will tend to decrease; the thermal expansion coefficient will generally tend to increase; the sag temperature may decrease; and the bending strength will tend to decrease. These trends indicate that Na ＋ and K ＋ The appropriate ratio of has an important influence on the performance of glass, and the rational use of mixed alkali effect helps to achieve better comprehensive performance.

[0045] In more complex network structure regulation, (Si 4+ +Al 3+ +B 3+ ) total amount is controlled at 70.7–76.8 mol%, preferably 75.5–76.5 mol%; (Si 4+ +Al 3+ +B 3+ ) / (Na ＋+K ＋ ) is controlled between 3.55–5.70, preferably 5.01–5.51, which is beneficial to the structural synergy between the network former and the modifier.

[0046] In the design that takes both structural regulation and spectral function into consideration, (Al 3+ +Mg 2+ +Ca 2+ ) / (Se 2- +Cd 2+ ) is controlled in the range of 0.90–2.34, preferably 1.08–1.375, or Zn 2+ / (Al 3+ +Mg 2+ +Ca 2+ ) is 1.9–6.8, preferably 3.1–5.2, which is generally more conducive to the matching between functional elements and the coordination of comprehensive performance.

[0047] The aforementioned ratios and their control methods are optimized within the multi-component architecture of the present invention, demonstrating the synergistic compatibility between the components. These parameters are not isolated control measures, but rather form part of the present invention's overall performance-building strategy, allowing for flexible combination and adjustment based on actual performance requirements.

[0048] This multi-element, multi-level overall balanced design is the key to the present invention's ability to achieve synergistic optimization of high thermal stability, excellent optical properties, and good mechanical properties, enabling it to meet stringent application requirements in complex lighting environments.

[0049] The present invention is to Si 4+ 、Al 3+ 、Zn 2+ , K ＋ , Ca 2+ Mg 2+ 、Na ＋ 、B 3+ 、Se 2- and Cd 2+ By optimizing and controlling the contents of the components and their mutual proportions, the prepared high thermal stability cut-off glass achieves synergistic improvements in multiple key performance indicators, specifically: In terms of optical performance: The glass of the present invention has a maximum transmittance of over 91% at a thickness of 6 mm, and in preferred embodiments can reach 92% or above; the cutoff wavelength is in the range of 625±15 nm; the steepness index is not less than 1.0, and in preferred embodiments can reach 1.5 or above, and in some embodiments can reach 1.6 or above, showing excellent narrowband cutoff capability and color purity.

[0050] Thermal stability: The sag temperature of the glass of the present invention is not less than 660°C, preferably 670°C or above, and in some embodiments can reach 683°C, showing excellent thermal processing adaptability; the thermal expansion coefficient is controlled within 70×10 -7 / ℃ and below, preferably 68×10 -7 / ℃ and below, which helps maintain dimensional stability in environments with drastic temperature differences.

[0051] In terms of mechanical properties: the glass generally has a bending strength of more than 110 MPa, preferably more than 125 MPa, and can reach 135 MPa in a preferred embodiment, which is significantly better than similar products in the prior art and is suitable for optical structural parts in high-load or impact-prone environments.

[0052] In terms of chemical stability: the glass of the present invention exhibits Class I acid and moisture resistance in both acidic and hot and humid environments, ensuring its service life and optical cleanliness under complex environmental conditions.

[0053] The synergistic realization of the above performance indicators is achieved through the coordinated control of the ratio of multiple glass formers, network regulators and optical functional elements. 2+ -Ca 2+ -Al 3+ The ratio of Zn helps to enhance the structural strength and thermal stability; controlling 2+ -Se 2- -Cd 2+ The ratio of Si 4+ -B 3+ 、Na ＋ -K ＋ The combination of and improves network stability and processing performance. The resulting high-performance glass system can be widely used in optical windows, image acquisition, monitoring equipment, and high-end lenses in complex lighting environments.

[0054] In a second aspect, the present invention provides a method for preparing the cutoff glass described in the first aspect. This method can be used to prepare the cutoff glass described in any of the preceding aspects. By rationally selecting raw material types and ratios, as well as melting, fining, and forming process parameters, this method ensures that the glass product maintains excellent coloring properties while achieving coordinated control of thermal stability, mechanical strength, and chemical stability.

[0055] The method comprises the following steps: Raw material mixing: take the 4+ 、Al 3+ 、Zn 2+ , K ＋ , Ca 2+ Mg 2+ 、Na＋ 、B 3+ 、Se 2- and Cd 2+ The raw materials are uniformly mixed within a predetermined molar percentage range. For example, in one embodiment, the raw materials corresponding to each element may be: quartz sand, aluminum hydroxide, zinc oxide, potassium carbonate, calcium carbonate, basic magnesium carbonate, sodium carbonate, boric acid, selenium powder, and cadmium sulfide. Nitrates are introduced to avoid an oxidizing melting atmosphere.

[0056] Melting and stirring: The mixed raw materials are melted in a temperature range of 1500-1600°C in a neutral or weakly reducing atmosphere for 8-16 hours to ensure that the components fully react and form a uniform melt. Mechanical or electromagnetic stirring methods can be used during the melting process, with a stirring speed of preferably 10-30 r / min and a stirring time of 3-12 hours to suppress crystallization, bubbles, and component segregation. Clarification: After melting is completed, the high temperature is maintained for a period of time to complete the clarification process and remove residual bubbles and impurities in the melt to obtain good optical uniformity. Clarification conditions can be adapted and optimized according to the specific melting system.

[0057] Molding: The clarified glass liquid is molded at 1400-1450°C for 5-25 minutes. Conventional processes such as molding, sheet casting, or continuous rolling can be used. The cooling rate must be controlled to avoid thermal stress or structural distortion.

[0058] Optionally, after forming, the glass can undergo further heat treatment to achieve annealing and secondary color development, release residual stress within the glass, and adjust the cutoff wavelength of the glass, thereby improving the mechanical stability, dimensional accuracy, and cutoff wavelength accuracy of the finished product. The heat treatment temperature is 640-670°C for 6-10 hours. After the heat treatment is completed, the power is turned off and the temperature is slowly lowered. In the present invention, by controlling the melting temperature in the range of 1500-1600°C, it is ensured that each component is fully melted and reacted, which is particularly beneficial for high-content Si 4+ The melting time is controlled within 8~16h to fully homogenize the glass liquid, ensure the uniform distribution of each component, avoid component segregation and streak defects. The melting atmosphere is neutral or weakly reducing atmosphere to avoid the formation of Se 4+ , resulting in the glass not being tinted.

[0059] Mechanical stirring is an optional stirring method in the preparation method of the present invention. For example, by controlling the stirring speed between 10 and 30 r / min and the stirring time between 3 and 12 hours, it effectively promotes homogenization of the glass melt and the removal of bubbles. Appropriate stirring speed and time can significantly improve the optical uniformity of the glass, reduce defects such as streaks and bubbles, and prevent the introduction of new bubbles or impurities due to excessive stirring.

[0060] The molding temperature is controlled between 1400°C and 1450°C, and the molding time is 5 to 25 minutes. These process parameters were selected based on a systematic study of the glass's compositional characteristics and rheological properties. The appropriate molding temperature and time ensure that the glass has the appropriate viscosity for precise molding, while also avoiding the loss of volatile components caused by excessively high temperatures, or the molding difficulties and increased internal stress caused by excessively low temperatures.

[0061] By optimizing the aforementioned process parameters, the preparation method of the present invention achieves high-quality, controllable preparation of high-thermal-stability cutoff glass, providing high-quality glass blanks for subsequent processing steps such as cutting, grinding, and polishing, ensuring that the final product has excellent optical properties and physical stability.

[0062] In the present invention, by accurately controlling the key process parameters such as melting temperature, melting time, stirring parameters, clarification and molding conditions, combined with the above-mentioned first aspect of the Si 4+ 、Al 3+ 、Zn 2+ , K ＋ , Ca 2+ Mg 2+ 、Na ＋ 、B 3+ 、Se 2- and Cd 2+ Through systematic optimization of the ratios of various components, the resulting glass material maintains excellent molding adaptability while consistently achieving high transmittance, precisely controllable cutoff wavelength, high thermal stability, excellent mechanical strength, and Class I chemical durability. This preparation process, characterized by a mature process, a wide parameter window, and excellent batch-to-batch consistency, is widely applicable to the mass production of optical components in complex lighting environments. It is particularly well-suited for applications such as lens windows, filters, and projection imaging systems that require high spectral cutoff accuracy and structural stability.

[0063] The process parameter ranges provided in this disclosure are highly adaptable and can accommodate the differences in equipment and conditions commonly encountered in industrial production. For example, different-sized furnaces, different types of stirring devices, or different molding processes may require fine-tuning of specific parameters. However, as long as these parameters are kept within the ranges described in this disclosure, high-thermal-stability cutoff glass that meets performance requirements can generally be obtained.

[0064] A third aspect of the present invention provides the use of the cutoff glass described in any of the aforementioned aspects in optical elements, particularly in image acquisition or precision measurement scenarios under complex lighting environments.

[0065] The complex lighting environment includes but is not limited to the following situations: situations where there are significant temperature fluctuations (such as outdoor monitoring and vehicle-mounted imaging); situations where precise screening of specific wavelength bands is required (such as camera red light correction and night vision filtering); assembly structures that withstand mechanical stress or impact loads (such as aerial photography lenses and military observation windows); situations where the equipment is exposed to acidic, humid, hot or corrosive environments for long-term use (such as field terminals and equipment in humid and hot areas), etc.

[0066] The high thermal stability cutoff glass provided by the present invention has a narrow-band spectral cutoff (e.g., 625±15nm), high transmittance (≥91%), excellent flexural strength (>110 MPa), good thermal stability (sag temperature ≥670°C), and Class I chemical stability. Therefore, it is suitable for preparing various high-performance optical components, such as optical windows, filters, imaging lenses, window glass in cameras and projection systems, and red light cutoff filter components.

[0067] For example, in a typical embodiment, the cutoff glass is used to manufacture red light cutoff filters near the 630 nm wavelength band, effectively suppressing red light interference in image sensing systems while also exhibiting excellent durability and processing compatibility. Such products are particularly suitable for consumer electronics, surveillance equipment, aerospace, military surveying and mapping, and high-end optical instruments.

[0068] In a fourth aspect of the present invention, there is provided an optical element comprising the cut-off glass described in the first aspect; The optical element may be a stand-alone structure or a component of a larger optical system (e.g., an imaging module, a window assembly, a sensor module, etc.). In some embodiments, the optical element specifically includes, but is not limited to, the following forms: filters or optical lenses, such as cutoff filters, optical lenses in camera lenses, projector lenses or module windows, outer window glass of monitoring equipment, and optical cover plates used for image acquisition and spectral control.

[0069] For example, in one embodiment, the optical element is a red light cutoff filter used in an image system, or a window sheet installed in front of an image sensing component. It is made of the glass material of the present invention, can effectively block interfering light near the 630nm band, improve imaging clarity and color purity, and has excellent thermal stability and mechanical strength, and maintains stable performance when subjected to harsh environments such as high temperature, impact or humidity.

[0070] This type of optical component can be widely used in technical fields such as consumer electronics, optical instruments, precision projection, aerospace and military mapping, which have high requirements for spectral control and environmental adaptability.

[0071] Compared with the prior art, the advantages of the present invention include: Compared with the existing technology, the high thermal stability cut-off glass provided by the present invention has achieved systematic improvements and technological breakthroughs in many aspects such as component system construction, optical performance regulation, thermomechanical stability improvement and process adaptability, showing significant comprehensive performance advantages.

[0072] The present invention is constructed by Si 4+ 、Al 3+ 、Zn 2+ , K ＋ , Ca 2+ Mg 2+ 、Na ＋ 、B 3+ 、Se 2- and Cd 2+ This multi-component, synergistic system, with targeted control strategies for component ratios, results in a glass material that exhibits a well-balanced balance of structural density, tinting stability, and spectral cutoff characteristics. Compared to the single-component-dominated design common in existing cutoff glasses, this integrated formulation overcomes the issues of performance bias and mutually exclusive parameters, enabling the simultaneous optimization of optical, mechanical, and chemical properties, meeting the high demands for comprehensive material performance in complex applications.

[0073] In terms of optical performance, the cutoff glass provided by the present invention can achieve stable cutoff control in the 625±15 nm band, and obtain spectral filtering characteristics with a transmittance of not less than 91% and a steepness of not less than 1.0 under preferred formulation conditions. Some embodiments can achieve a high steepness value of 1.6, effectively solving the shortcomings of existing red light cutoff glass in cutoff accuracy, filtering edge stability and color consistency. It is particularly suitable for image system scenarios with high requirements for imaging clarity and color reproduction.

[0074] In terms of thermodynamic and mechanical properties, the present invention introduces Mg 2+ , Ca 2+ With Al 3+ The coordinated control structure improves the bending resistance and thermal stability of the glass, making the glass have a sag temperature of no less than 670°C and a thermal expansion coefficient controlled at 70×10 -7 The glass has a bending strength of no less than 110 MPa and a bending strength of up to 135 MPa in a preferred embodiment. These properties ensure that the glass maintains good dimensional stability and physical integrity even in outdoor applications with high temperatures, drastic temperature fluctuations, or complex structural stresses.

[0075] At the same time, the material system of the present invention avoids the use of highly toxic components such as TeO2 and As2O3, and has good environmental properties. It also has excellent melt processability, high clarification efficiency, and good bubble control effect. It is suitable for conventional industrial glass forming processes such as calendering, molding, rolling, float glass, etc., which facilitates the stable mass production of large-size glass products and has significant engineering implementation value.

[0076] Taking the aforementioned performance into consideration, the present invention not only overcomes the technical bottleneck of existing cutoff glass in achieving a balance between optical cutoff characteristics, thermomechanical properties, chemical stability, and environmentally friendly processes, but also provides a solid material foundation and preparation guarantee for the expanded application of high-end optical glass materials in aerospace, consumer electronics, surveillance imaging, precision mapping, and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0077] The drawings constituting part of the present application are provided to provide a further understanding of the present application. The illustrative embodiments and their descriptions of the present application are provided to explain the present application and do not constitute an undue limitation on the present application. The following describes the implementation scheme of the present application in detail in conjunction with the drawings, wherein: Figure 1 This is a comparative curve chart of the transmittance of 6 mm thick glass products of Comparative Example 2 and Example 5 in the wavelength range of 200-1000 nm. DETAILED DESCRIPTION

[0078] The present application will be further described in conjunction with specific examples. It should be understood that these examples are intended to illustrate the present application only and are not intended to limit the scope thereof. Experimental methods for which specific conditions are not specified in the examples are generally performed under conventional conditions or conditions recommended by the manufacturer.

[0079] Unless otherwise defined, all technical terms and scientific terms used in this application should have the meaning familiar to those skilled in the art. Unless otherwise specified, the reagents or raw materials used in this application can be obtained by conventional means and used in accordance with conventional methods or product specifications in this area. In addition, any content similar to or equivalent to the methods or materials described can be applied to the methods of this application. The preferred embodiments and materials described in this application are for illustrative purposes only.

[0080] The performance parameters in the following examples were measured using the following methods: The thermal expansion coefficient α and sag temperature Tf of glass samples were measured using a DIL 402 dilatometer from NETZSCH, Germany. Sample preparation: Glass samples were polished into cylindrical strips measuring Φ6 × 50 mm, with the ends parallel. The heating rate was set at 5°C / min, and the data acquisition period was 20 ms. (GB / T 7962.16-2010) Transmittance testing is performed using an ultraviolet-visible-infrared spectrophotometer to obtain a transmittance curve and determine the maximum optical transmittance. The cutoff wavelength and steepness are then obtained or calculated based on the transmittance curve. The cutoff wavelength is the spectral transmittance τ(λ) measured at a specific thickness (6 mm in the present invention), measured using automatic scanning or manual spot measurement. τ(λ) represents the spectral transmittance (transmittance) at wavelength λ, and τ(700nm) represents the transmittance measured at a wavelength of 700nm. τ(λj) is calculated based on the measured high transmittance τ(700nm). τ(λj) represents the transmittance at the cutoff wavelength and is defined as 50% of τ(700nm), i.e., τ(λj) = 0.5τ(700nm). The cutoff wavelength λj is then determined from this τ(λj) value, representing the wavelength at which the transmittance drops to half of τ(700nm). Measure the spectral transmittance τ(λj-20nm) and calculate the steepness K (indicates the steepness of the spectral curve in the cutoff region; a larger K value indicates better cutoff characteristics) using the following formula: K = D(λj-20nm) - D(λj); where D(λj-20nm) = -lgτ(λj-20nm); and D(λj) = -lgτ(λj). In the above formula, λj-20nm represents a wavelength 20nm shorter than the cutoff wavelength; τ(λj-20nm) represents the transmittance 20nm before the cutoff wavelength; D(λj-20nm) represents the optical density 20nm before the cutoff wavelength; and D(λj) represents the optical density at the cutoff wavelength.

[0081] After the surface of a polished glass sample is corroded by a test medium with an acidity of pH 2.9, pH 4.6, or pH 6.0, the time it takes for the glass surface to develop a purple-blue interference color, or for the surface to become mottled or fall off, is observed under an incandescent lamp. The acid resistance stability of colorless optical glass is classified in descending order based on the time it takes. (GB / T 7962.14-2010) Polished glass samples are kept at a constant temperature and humidity of 50°C and 85% for 20 hours. The turbidity values of colorless optical glass are then compared with those of standard samples H (BaK7) and H (ZK9) to determine their moisture stability in descending order. (GB / T7962.15-2010) The three-point bending method is used to test the flexural strength of glass samples. The glass sample is machined to the required dimensions and then placed between two supports. A fixed load is applied perpendicular to the center of the sample. Different bending moments are then applied to measure the bending stress and strain of the glass under different conditions. The flexural strength of the glass is ultimately determined. (GB / T 37781-2019) The present invention will be further described below with reference to the embodiments.

[0082] Example 1 The components of the high thermal stability cut-off glass of this embodiment, the weight percentages of the components, and the physical properties of the produced glass are shown in Tables 1 and 4.

[0083] The preparation method for high thermal stability cutoff glass is as follows: quartz sand, aluminum hydroxide, zinc oxide, potassium carbonate, calcium carbonate, basic magnesium carbonate, sodium carbonate, boric acid, selenium powder, and cadmium sulfide are used as raw materials. After thorough mixing, the glass is melted at 1500°C for 8 hours in a neutral melting atmosphere, mechanically stirred at 15 rpm for 3 hours, supplemented with high-temperature clarification, and then formed by pouring or pressing at 1450°C for 5 minutes to produce a glass blank. The glass blank is then placed in a preheated annealing furnace for annealing and secondary color development at 670°C for 10 hours. After the heat is maintained, the glass is slowly cooled with the power off to eliminate internal stress and adjust the cutoff wavelength.

[0084] Example 2 The components of the high thermal stability cut-off glass of this embodiment, the weight percentage of each component, and the physical properties of the produced glass are shown in Tables 1 and 4.

[0085] The preparation method is the same as that of Example 1.

[0086] Example 3 The components of the high thermal stability cut-off glass of this embodiment, the weight percentage of each component, and the physical properties of the produced glass are shown in Tables 1 and 4.

[0087] The preparation method is the same as that of Example 1.

[0088] Example 4 The components of the high thermal stability cut-off glass of this embodiment, the weight percentage of each component, and the physical properties of the prepared glass are shown in Tables 1 and 4.

[0089] The preparation method is the same as that of Example 1.

[0090] Example 5 The components of the high thermal stability cut-off glass of this embodiment, the weight percentage of each component, and the physical properties of the prepared glass are shown in Tables 1 and 4.

[0091] The preparation method is the same as that of Example 1.

[0092] Example 6 The components of the high thermal stability cut-off glass of this embodiment, the weight percentage of each component, and the physical properties of the prepared glass are shown in Tables 1 and 4.

[0093] The preparation method is the same as that of Example 1.

[0094] Example 7 The components of the high thermal stability cut-off glass of this embodiment, the weight percentage of each component, and the physical properties of the prepared glass are shown in Tables 1 and 4.

[0095] The preparation method is the same as that of Example 1.

[0096] Example 8 The components of the high thermal stability cut-off glass of this embodiment, the weight percentage of each component, and the physical properties of the prepared glass are shown in Tables 1 and 4.

[0097] The preparation method is the same as that of Example 1.

[0098] Example 9 The components of the high thermal stability cut-off glass of this embodiment, the weight percentage of each component, and the physical properties of the prepared glass are shown in Tables 1 and 4.

[0099] The preparation method is the same as that of Example 1.

[0100] Comparative Examples 1-13 The components of the glasses of Comparative Examples 1-13, the weight percentage of each component, and the physical properties of the glasses obtained are shown in Tables 2, 3, and 5.

[0101] The glasses in Comparative Examples 1-13 were prepared according to the method described in Example 1.

[0102] Table 1 Components and contents of high thermal stability cut-off glasses of Examples 1-9 of the present invention

[0103] Table 2 Components and contents of the glasses of Comparative Examples 1-5 of the present invention

[0104] Table 3 Components and contents of the glasses of Comparative Examples 6-13 of the present invention

[0105] Table 4 Performance test results of glass samples of Examples 1 to 9

[0106] Table 5 Performance test results of glass samples of Comparative Examples 1 to 13

[0107] By rationally adding the corresponding components and controlling the ratios of the raw materials, Examples 1-9 achieve improved glass strength, thermal stability, transmittance, chemical stability, and acid and alkali corrosion resistance. As shown in Table 4, the optical transmittance of the high-thermal-stability cutoff glasses produced in Examples 1-9 is as follows: within the wavelength range of 200-1000 nm, the maximum transmittance is ≥ 91.0%. These overall performance characteristics surpass those of the glasses described in Comparative Examples 1-13. Furthermore, their excellent acid and moisture resistance ensures long-term stability of the glass's internal structure.

[0108] Figure 1 This is a comparative curve chart of the transmittance of 6 mm thick glass products of Comparative Example 2 and Example 5 in the wavelength range of 200-1000 nm.

[0109] As can be seen from the foregoing, the high thermal stability cutoff glasses provided in Examples 1-9 of the present invention exhibit excellent optical transmittance, heat resistance, high flexural strength, excellent cutoff wavelength, steepness, and good chemical stability. This is due to adjustments in the proportions of the various raw materials used in the preparation of the high thermal stability cutoff glasses in Examples 1-9 of the present invention, as well as appropriate stirring speeds and times. Therefore, the high thermal stability cutoff glasses of the present invention exhibit excellent optical transmittance, heat resistance, high flexural strength, excellent cutoff wavelength, steepness, and good chemical stability, and have broad application prospects.

[0110] The above description is merely a preferred embodiment of the present application and is not intended to limit the scope of the present application. Although the present application has been described in detail with reference to the above embodiments, those skilled in the art may, after reading this description, make various modifications to the technical solution or replace some of the technical features with equivalents. Any modification, equivalent replacement, or improvement made within the spirit and principles of the present application shall be deemed to fall within the scope of protection of the present application.

Claims

1. A cut-off glass, characterized in that: The elements in the network structure of the glass exist in the form of bound ions, and the molar percentage (mol%) includes: Yeah 4＋ 62.1-67.6mol%; Al 3+ 0.1-1.1mol%; Zn 2+ 6.0-8.2mol%; K ＋ 3.5-9.4mol%; That 2+ 0.1-1.0mol%; Mg 2+ 0.3-1.4mol%; On ＋ 7.3-15.7mol%; B 3+ 6.4-12.8mol%; With 2- 0.7-1.5mol%; CD 2+ 0.1-0.5 mol%.

2. The high thermal stability cut-off glass according to claim 1, characterized in that: The elements in the network structure of the glass exist in the form of bound ions, and the molar percentages include: Yeah 4+ 64.0-67.6mol%; Al 3+ 0.5-1.0mol%; Zn 2+ 6.5-7.7mol%; K ＋ 5.5-9.4mol%; That 2+ 0.3-0.7mol%; Mg 2+ 0.5-0.8mol%; On ＋ 7.3-11.0mol%; B 3+ 8.0-11.5mol%; If 2- 0.8-1.2mol%; Cd 2+ 0.2-0.4mol%; Preferably, the molar percentage comprises: Yeah 4+ 63-67.6mol%; Al 3+ 0.1-1mol%; Zn 2+ 6.1-7.7mol%; K ＋ 3.6-9.4mol%; That 2+ 0.3-1.0mol%; Mg 2+ 0.5-1.4mol%; On ＋ 7.3-12.6mol%; B 3+ 8-11.2mol%; With 2- 1-1.5mol%; CD 2+ 0.2-0.5mol%; Preferably, the molar percentage comprises: Yeah 4+ 63.1-67.6mol%; Al 3+ 0.1-1.0mol%; Zn 2+ 6.7-7.0mol%; K ＋ 6.0-9.4mol%; AC 2+ 0.1-0.6mol%; Mg 2+ 0.4-0.8mol%; Na ＋ 7.3-10.9mol%; B 3+ 8.0-11.5mol%; If 2- 0.7-1.2mol%; Cd 2+ 0.1-0.4mol%; Preferably, the molar percentage comprises: Yeah 4+ 64.2-67.6mol%; Al 3+ 0.6-1mol%; Zn 2+ 6.7-7.7mol%; K ＋ 3.6-9mol%; Ca 2+ 0.3-0.9mol%; Mg 2+ 0.5-0.7mol%; Na ＋ 7.3-10.8mol%; B 3+ 8.1-11.2mol%; If 2- 1-1.2mol%; Cd 2+ 0.2-0.4mol%; Preferably, the molar percentage comprises: If 4+ 64.0-64.5mol%; Al 3+ 0.9-1.0mol%; Zn 2+ 6.8-7.0mol%; K ＋ 6.5-6.8mol%; AC 2+ 0.4-0.6mol%; Mg 2+ 0.6-0.8mol%; Na ＋ 7.2-7.5mol%; B 3+ 11.0-11.5mol%; If 2- 1.1-1.2mol%; CD 2+ 0.3-0.5mol%; Preferably, the molar percentage comprises: If 4+ 64.0-65.5mol%; Al 3+ 0.5-1.0mol%; Zn 2+ 6.7-7.0mol%; K ＋ 6.0-8.0mol%; AC 2+ 0.3-0.6mol%; Mg 2+ 0.6-0.8mol%; On ＋ 7.3-9.1mol%; B 3+ 10.0-11.5mol%; If 2- 1.0-1.2mol%; Cd 2+ 0.3-0.4mol%.

3. The cutoff glass according to claim 1, wherein: Based on molar percentage, Mg 2+ / Ca 2+ The ratio is 1.0-4.0, preferably 1.4-4.0; Preferably, based on molar percentage, Al 3+ / (Mg 2+ +Ca 2+ ) is 0.08-2.2, preferably 0.08-1.0, more preferably 0.08-0.85; Preferably, based on molar percentage, (Mg 2+ +Ca 2+ ) / Al 3+ 0.45-12.0, preferably 1.0-12.0, more preferably 1.2-12; Preferably, based on molar percentage, Mg 2+ +Ca 2+ +Al 3+ The sum is 1.0-3.5 mol%, preferably 1.0-2.2 mol%, more preferably 1.3-2.2 mol%; Preferably, based on molar percentage, Se 2- / Cd 2+ The ratio is 2.0-8.0, preferably 3.0-7.0, more preferably 3.0-5.0; Preferably, based on molar percentage, Zn 2+ / Se 2- The ratio is 4.6-10.25, preferably 4.6-9.75, more preferably 4.6-6.7, most preferably 5.75-6.7; Preferably, based on molar percentage, Zn 2+ / (Se 2- +Cd 2+ ) is 3.45-8.6, preferably 3.45-5.6, more preferably 4.3-5.6; Preferably, based on molar percentage, Zn 2+ +Se 2- +Cd 2+ The sum is 6.8-9.3 mol%, preferably 7.6-8.9 mol%, more preferably 7.9-8.9 mol%, most preferably 7.9-8.5 mol%; Preferably, based on molar percentage, Si 4+ / B 3+ The ratio is 4.9-9.9, preferably 5.6-8.4, more preferably 5.6-6.6 or 6.7-8.35; Preferably, based on molar percentage, B 3+ / Si 4+ The ratio is 0.1-0.21, preferably 0.11-0.18, more preferably 0.16-0.18 or 0.11-0.14; Preferably, based on molar percentage, Si 4+ +B 3+ The sum is 69.6-75.7 mol%, preferably 71.1-75.7 mol%, more preferably 74.9-75.7 mol%, most preferably 75.5-75.7 mol%; Preferably, based on molar percentage, Si 4+ / (Si 4+ +B 3+ ) is 0.83-0.91, preferably 0.85-0.9, more preferably 0.85-0.86 or 0.87-0.9; Preferably, based on molar percentage, Na ＋ / K ＋ The ratio is 0.81-3.42, preferably 0.81-3.1, more preferably 1.1-3.1, and most preferably 1.1-1.52; Preferably, based on molar percentage, K ＋ / Na ＋ The ratio is 0.29-1.24, preferably 0.33-1.24, more preferably 0.65-0.91; Preferably, based on molar percentage, Na ＋ +K ＋ The sum is 13.5-20.3 mol%, preferably 13.9-20.1 mol%, more preferably 13.9-16.3 mol%, most preferably 13.9-15.1 mol%; Preferably, based on molar percentage, (Na ＋ +K ＋ ) / B 3+ 1.05-2.9, preferably 1.23-2.52, more preferably 1.23-1.87; Preferably, based on molar percentage, Si 4+ +Al 3+ +B 3+ The sum is 70.7-76.8 mol%, preferably 71.6-76.5 mol%, more preferably 74-76.5 mol%, most preferably 75.5-76.5 mol%; Preferably, based on molar percentage, (Si 4+ +Al 3+ +B 3+ ) / (Na ＋ +K ＋ ) is 3.55-5.70, preferably 3.56-5.51, more preferably 4.53-5.51, and most preferably 5.01-5.51; Preferably, based on molar percentage, (Si 4+ +B 3+ ) / (Na ＋ +K ＋ +Ca 2+ +Mg 2+ ) is 3.33-5.41, preferably 3.45-5.0, more preferably 4.1-5, most preferably 4.6-5; Preferably, based on molar percentage, (Al 3+ +Mg 2+ +Ca 2+ ) / (Se 2- +Cd 2+ ) is 0.90-2.34, preferably 0.9-2.0, more preferably 1.0-2.0, most preferably 0.90-1.40, more preferably 1.08-1.375; Preferably, based on molar percentage, Zn 2+ / (Al 3+ +Mg 2+ +Ca 2+ ) is 1.9-6.8, preferably 3.1-6.8, more preferably 3.1-5.5, most preferably 3.1-5.

2.

4. The cutoff glass according to any one of claims 1 to 3, wherein: The maximum optical transmittance of a 6 mm sample of the glass at 200-1000 nm is ≥91.0%, the sag temperature is ≥670°C, and the thermal expansion coefficient in the temperature range of 20°C to 300°C is ≤70×10 -7 / ℃, cut-off wavelength is 625±15nm, and steepness is ≥1.

0.

5. The cutoff glass according to any one of claims 1 to 3, characterized in that: The bending strength of the glass is greater than 110 MPa, and both the acid resistance stability and the moisture resistance stability are Class 1.

6. A method for preparing the cutoff glass according to any one of claims 1 to 5, characterized in that: include: The raw materials containing silicon, aluminum, zinc, potassium, calcium, magnesium, sodium, boron, selenium and cadmium are mixed evenly; The obtained mixture is melted at 1500-1600°C in a neutral or weakly reducing atmosphere and stirred; Then it is clarified and formed.

7. The method according to claim 6, characterized in that: Melting time is 8 to 16 hours; Preferably, the stirring speed is 10-30 r / min, and the stirring time is 3-12 hours; Preferably, the molding temperature is 1400-1450°C and the molding time is 5-25 minutes; Preferably, after forming, heat treatment is further performed to achieve annealing and secondary color development, wherein the heat treatment temperature is 640-670° C. and the holding time is 6-10 hours.

8. Use of the cutoff glass according to any one of claims 1 to 5 in optical elements, and in optical window glass for image mapping in complex lighting environments.

9. The use according to claim 8, characterized in that The cutoff glass is used to prepare optical elements for use in complex lighting environments, wherein the complex lighting environment is at least one of an environment with large temperature fluctuations, an environment requiring precise spectral screening, an environment with mechanical stress, or an environment with chemical corrosion. The optical elements include optical windows, lenses, or filters.

10. An optical element, characterized in that: Comprising the cut-off glass according to any one of claims 1 to 5; Preferably, the optical element is a filter or an optical lens.

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