A deep ultraviolet transparent glass and its preparation method and application

Abstract

The present invention relates to a deep ultraviolet-transmitting glass, its preparation method, and application. The deep ultraviolet-transmitting glass comprises, by mass percentage, 30-40 wt% of phosphorus pentoxide; 35-50 wt% of silicon dioxide; 5-10 wt% of aluminum oxide; 10-15 wt% of boron trioxide; 1-3 wt% of tin oxide; 3-6 wt% of zinc oxide; 1-3 wt% of barium oxide; and 2-5 wt% of fluoride, the total content of which is 100 wt%. When the deep ultraviolet-transmitting glass of the present invention has a thickness of 1.0 mm, a light transmittance of greater than 78% at a wavelength of 200 nm, water resistance of HGB1 grade, and a refractive index of 1.480-1.490. The preparation method of the deep ultraviolet-transmitting glass is simple, without the need for a pretreatment step to remove impurities, and achieves the preparation of ultraviolet-transmitting glass with high ultraviolet transmission performance, chemical stability, and refractive index matching.

Description

Technical Field

[0001] The present invention belongs to the field of glass manufacturing, and in particular relates to deep ultraviolet transparent glass and a preparation method and application thereof. Background Art

[0002] Ultraviolet light is a ubiquitous electromagnetic wave in nature. Due to the effects of atmospheric molecules and particles, the deep ultraviolet region of the solar spectrum, approximately 200-280 nm, is strongly absorbed by the ozone layer in the atmosphere, providing protection for humans. This portion of the ultraviolet spectrum is also known as the "solar-blind zone." Detectors operating in this solar-blind region experience virtually no interference from the background environment. Leveraging this characteristic, they are widely used in applications such as missile early warning, power safety monitoring, and ultraviolet imaging. For example, while the intensity of corona discharges in the 200-280 nm band is much weaker, this band lies within the solar-blind zone. Corona discharges occurring in this band can be detected against the strong background of solar radiation. Therefore, the detection of deep ultraviolet light is of great significance.

[0003] Only a few glasses with special compositions have UV transmittance, but these glasses have disadvantages such as poor chemical stability, high refractive index, and low transmittance in the deep ultraviolet band. For example, when the refractive index is greater than 1.5, the transmittance at 200nm in the deep ultraviolet band is only 40%-50%, which greatly limits the possibility of using these glasses in UV-related technical equipment.

[0004] In addition to glass composition, harmful impurities within the glass also significantly impact deep UV transmittance. These impurities primarily originate from the transition metal Fe, which, due to its rich band structure, strongly absorbs deep UV light. Currently, these impurities are mitigated by pre-ferrification of raw materials or by increasing their purity. However, these methods are costly. Therefore, it is necessary to simplify the process and reduce the impact of these impurities during glass production to improve optical performance and reduce costs. Summary of the Invention

[0005] In view of this, the main purpose of the present invention is to provide a deep ultraviolet transparent glass and its preparation method and application. The technical problem to be solved is how to achieve the production of deep ultraviolet transparent glass with excellent ultraviolet transmission performance, chemical stability and adapted refractive index while simplifying the process steps and reducing costs, so as to meet the requirements of the development of ultraviolet detection and other fields for deep ultraviolet transparent glass materials.

[0006] The objectives of the present invention and the technical problems solved therein are achieved by the following technical solutions. A deep ultraviolet-transmitting glass according to the present invention comprises, by weight percentage, 30-40 wt% of phosphorus pentoxide; 35-50 wt% of silicon dioxide; 5-10 wt% of aluminum oxide; 10-15 wt% of boron trioxide; 1-3 wt% of tin oxide; 3-6 wt% of zinc oxide; 1-3 wt% of barium oxide; and 2-5 wt% of fluoride, the total content of which is 100 wt%.

[0007] The purpose of the present invention and the solution to its technical problems can be further achieved by adopting the following technical measures.

[0008] Preferably, in the aforementioned deep ultraviolet transparent glass, the fluoride is selected from at least one of sodium fluoride and potassium fluoride.

[0009] Preferably, in the aforementioned deep ultraviolet transparent glass, the mass ratio of zinc oxide to barium oxide is 1-4.

[0010] Preferably, the aforementioned deep ultraviolet transparent glass, when the thickness of the deep ultraviolet transparent glass is 1.0 mm, has a light transmittance of greater than 78% at a wavelength of 200 nm, a water resistance stability of HGB1 level, and a refractive index of 1.480-1.490.

[0011] The purpose of the present invention and the technical problem solved are also achieved by adopting the following technical solutions. According to the present invention, a method for preparing deep ultraviolet transparent glass includes the following steps:

[0012] 1) stirring raw materials comprising the following components: 30-40 wt% of phosphorus pentoxide, 35-50 wt% of silicon dioxide, 5-10 wt% of aluminum oxide, 10-15 wt% of boron trioxide, 1-3 wt% of tin oxide, 3-6 wt% of zinc oxide, 1-3 wt% of barium oxide, and 2-5 wt% of fluoride to obtain a raw material mixture;

[0013] 2) melting the raw material mixture obtained in step 1) under vacuum or negative pressure to obtain a glass melt;

[0014] 3) The glass melt obtained in step 2) is clarified, formed by leaking, and annealed to obtain the high ultraviolet transmittance glass.

[0015] The purpose of the present invention and the solution to its technical problems can be further achieved by adopting the following technical measures.

[0016] Preferably, in the aforementioned method for preparing deep ultraviolet transparent glass, in step 2), the vacuum degree of the melting is -0.07 MPa to -0.04 MPa.

[0017] Preferably, in the aforementioned method for preparing deep ultraviolet transparent glass, in step 2), the melting temperature is 1550-1600° C. and the melting time is 4-6 hours.

[0018] Preferably, in the aforementioned method for preparing deep ultraviolet transparent glass, in step 3), the annealing temperature is 540-590° C. and the time is 4-6 hours.

[0019] The objectives of the present invention and the technical problems solved therein are also achieved by the following technical solutions. According to the present invention, an optical device includes a high-UV-transmittance window, a lamp, or a camera lens, wherein the high-UV-transmittance window, lamp, or camera lens comprises deep-UV-transmitting glass; the deep-UV-transmitting glass comprises, by weight percentage, the following: 30-40 wt% phosphorus pentoxide; 35-50 wt% silicon dioxide; 5-10 wt% aluminum oxide; 10-15 wt% boron trioxide; 1-3 wt% tin oxide; 3-6 wt% zinc oxide; 1-3 wt% barium oxide; and 2-5 wt% fluoride, the total content of which is 100 wt%.

[0020] The purpose of the present invention and the solution to its technical problems can be further achieved by adopting the following technical measures.

[0021] Preferably, the aforementioned optical device is an ultraviolet imaging detector or an ultraviolet night vision device.

[0022] According to the above technical solution, the deep ultraviolet transparent glass of the present invention and its preparation method and application have at least the following beneficial effects:

[0023] The deep ultraviolet transparent glass and its preparation method described in the present invention are prepared by rationally designing the glass components and contents. When the glass has a thickness of 1.0 mm, the transmittance of light at a wavelength of 200 nm is greater than 78%, the water resistance stability is HGB1 level, and the refractive index is 1.480-1.490, which can meet the performance requirements of application fields such as ultraviolet detection.

[0024] The deep ultraviolet transparent glass and preparation method thereof of the present invention increase the acidic components and reducing components, increase the melting temperature, and introduce fluoride, eliminating the need for pre-iron removal treatment of the glass raw materials. This can reduce the number of glass preparation process steps, lower costs, and effectively improve the ultraviolet transmission performance of the glass. DETAILED DESCRIPTION

[0025] To further illustrate the technical means and effectiveness of the present invention in achieving its intended objectives, the following, in conjunction with preferred embodiments, provides a detailed description of a deep-UV-transmitting glass, its preparation method, and its specific implementation, structure, features, and effectiveness. In the following description, different references to "one embodiment" or "embodiment" do not necessarily refer to the same embodiment. Furthermore, specific features, structures, or characteristics of one or more embodiments may be combined in any suitable manner.

[0026] Unless otherwise specified, the materials and reagents mentioned below are commercially available products familiar to those skilled in the art. Unless otherwise specified, the methods described are all well-known methods in the art. Unless otherwise defined, technical or scientific terms used shall have the same meanings as those commonly understood by those skilled in the art.

[0027] According to some embodiments of the present invention, there is provided a deep ultraviolet transparent glass, which comprises, by mass percentage:

[0028] 30-40wt% of phosphorus pentoxide; 35-50wt% of silicon dioxide; 5-10wt% of aluminum oxide; 10-15wt% of boron trioxide; 1-3wt% of tin oxide; 3-6wt% of zinc oxide; 1-3wt% of barium oxide; and 2-5wt% of fluoride. The total content of the above components is 100wt%.

[0029] In the above technical solution, the present invention prepares high-performance ultraviolet-transmitting glass by rationally designing the glass components and eliminating the influence of impurities during the production process. The ultraviolet transmission cutoff wavelength of phosphorus pentoxide glass is 145nm, the ultraviolet transmittance is high, and the thermal expansion coefficient is large, but the chemical stability is poor, and pure phosphate glass does not have much practical value. Therefore, silicon dioxide with good chemical stability and high ultraviolet transmittance is introduced to prepare silicon phosphate glass. At the same time, in order to ensure the stability of the glass structure, aluminum oxide and boron oxide are introduced to regulate the glass structure, so that it has the advantages of good chemical stability, high deep ultraviolet transmittance (200-275nm band) and adapted refractive index. In addition to being related to the glass components, the actual deep ultraviolet transmittance of the glass is also affected by trace impurities, mainly variable valence ions of different valence states, including transition metal Fe, etc. These impurities may be introduced by raw materials or from pollution of melting technology. By increasing the content of acidic components in the glass components, such as silicon dioxide, boron trioxide, and phosphorus pentoxide, and adding the reducing component tin oxide, the impurity elements in the glass are more likely to transform into low-valent elements, forming low-valent Fe 2+ ions, and Fe 2+ Ions selectively absorb the near-infrared band with a longer wavelength and have no effect on the ultraviolet band. Iron has a high ionization energy and easily forms a complex [FeF6] after the introduction of fluoride. 2-, and its volatility can eliminate the effects of Fe. Increasing the melting temperature increases the tetrahedral low-coordination content in the glass, reducing short-wave absorption. By increasing the acidic and reducing components, raising the melting temperature, and introducing fluorides, the effects of trace impurities on the glass's UV transmission properties can be significantly reduced or even eliminated, thereby improving the glass's UV transmittance.

[0030] Optionally, the fluoride is selected from at least one of sodium fluoride and potassium fluoride; and the mass ratio of zinc oxide to barium oxide is 1-4.

[0031] According to tests, when the thickness of the deep ultraviolet transparent glass is 1.0 mm, the transmittance of light with a wavelength of 200 nm is greater than 78%, the water resistance stability is HGB1 level, and the refractive index is 1.480-1.490.

[0032] It should be noted here that the above-mentioned deep ultraviolet transparent glass refers to glass with a thickness of 1.0 mm, a light transmittance of more than 78% at a wavelength of 200 nm, a water resistance stability of HGB1 level, and a refractive index of 1.480-1.490.

[0033] The functions of the above components are as follows:

[0034] Phosphorus pentoxide is a network-forming oxide with a short UV cutoff wavelength of only 145nm. It forms the backbone of glass and is the primary component for improving UV transmittance. Within the glass network, phosphorus pentoxide typically forms double-bonded [PO4] tetrahedrons, connected at their vertex angles. If the phosphorus pentoxide content is less than 30wt%, it is difficult to achieve high-transmittance deep UV glass. If the phosphorus pentoxide content exceeds 40wt%, the glass's refractive index decreases and its thermal expansion coefficient increases, while the chemical stability and anti-devitrification properties of the glass decrease.

[0035] The ultraviolet transmission cutoff wavelength of silicon dioxide is 160nm, and it has excellent ultraviolet transmission performance. It is also the main component of the glass skeleton and can form a unified network inside the glass. The vertices of the silicon oxide tetrahedron and the phosphorus oxide tetrahedron are connected, which shifts the ultraviolet transmission cutoff wavelength to a shorter wavelength. Introducing silicon dioxide into the glass can improve the strength, viscosity and thermal stability of the glass, and reduce the thermal expansion coefficient of the glass. If the silicon dioxide content is less than 35wt%, the overall performance of the glass will deteriorate, and it will be difficult to obtain glass with high transmittance. If the silicon dioxide content is higher than 50wt%, the temperature required for the glass melting process will be too high, and defects such as stones will be caused, thus affecting the final performance of the glass.

[0036] Aluminum oxide is an intermediate oxide that can form a network structure with SiO2, making the glass structure more compact and thus improving a series of glass properties. At the same time, aluminum oxide can capture free oxygen in the glass to form aluminum oxide tetrahedrons, which are similar to silicon oxide tetrahedrons in structure and can improve and strengthen the structure of phosphate glass, thereby increasing the ultraviolet transmittance and chemical stability of the glass. If the aluminum oxide content is less than 5wt%, the internal network structure of the glass will be low, and the properties such as strength, viscosity and ultraviolet transmittance will be poor, and the network gap will be small. If the aluminum oxide content is higher than 10wt%, the temperature required for glass melting will be too high, and defects such as stones will be caused. In addition, it will react with fluorides, making the glass prone to opacification, thereby affecting the final properties of the glass.

[0037] Boron trioxide has a UV cutoff wavelength of 170nm, which can effectively improve the UV transmittance of glass. Boron trioxide is one of the important components of glass. In addition, it is a good fluxing agent that can accelerate the dissolution and clarification of glass. Boron trioxide forms boron-oxygen tetrahedra in glass, making the structure more compact and increasing the viscosity of the glass. The introduction of boron trioxide can repair the broken network structure inside the glass, strengthen the three-dimensional skeleton structure of the glass, and promote the transmission of ultraviolet waves. If the content of boron trioxide is higher than 15wt%, the required temperature during the glass melting process will be too high. Boron trioxide appears in the glass structure as boron-oxygen triangles instead of boron-oxygen tetrahedra, which weakens the glass structure, leads to poor performance, and phase separation. If the content of boron trioxide is lower than 10wt%, insufficient boron-oxygen tetrahedra cannot be formed in the glass, causing the boron structure to transform from a layered structure to a framework structure. The broken network structure in the glass cannot be repaired, resulting in poor UV transmission performance.

[0038] Tin oxide reduces free oxygen in glass, increasing its transmittance. It also provides reducing melting conditions, reducing high-charge impurities in the glass to low-charge impurities, minimizing their impact on UV transmittance. Tin oxide also improves glass's high-temperature resistance and thermal shock resistance. If the tin oxide content is less than 1wt%, the reducing properties are insufficient, resulting in low UV transmittance. If the tin oxide content exceeds 3wt%, it will form dispersed suspended particles in the glass, causing the glass to become opaque.

[0039] Zinc oxide forms [ZnO4] and enters the glass's structural network, stabilizing the glass's structure and reducing its thermal expansion coefficient, thereby improving its chemical stability and refractive index. Furthermore, the zinc ions, with their high field strength, polarize the oxygen ions, weakening the oxygen ions' effective electric field on the central metal ion and reducing the splitting energy of the coordination field, thus facilitating deep ultraviolet light transmission. If the zinc oxide content is less than 3wt%, the improvement in the glass's chemical stability and UV transmittance is insignificant. If the zinc oxide content is above 6wt%, the glass's tendency to separate increases, making it prone to crystallization, while its UV transmittance decreases and its refractive index becomes excessively high.

[0040] Barium oxide is an oxide outside the glass structure network, which can increase the refractive index of the glass. At the same time, the barium ions with a strong electric field strength polarize the oxygen ions, weakening the effective electric field of the oxygen ions on the central metal ions and reducing the splitting energy of the coordination field, which is conducive to the transmission of deep ultraviolet light. If the barium oxide content is less than 1wt%, it will lower the transition temperature of the glass and have little effect on the improvement of ultraviolet transmittance. If the barium oxide content is higher than 3wt%, the barium oxide in the glass will cause the boron oxide in the glass to change from tetrahedron to triangular, making the glass structure less tight, resulting in poor ultraviolet transmittance and chemical stability of the glass, and further increasing the tendency of crystallization.

[0041] The fluoride is at least one of sodium fluoride and potassium fluoride. Fluoride can reduce the viscosity and surface tension of glass, promoting clarification and homogenization of the glass liquid. It fills the voids in the glass network structure in the form of small molecules, increasing the strength of the glass while also regulating the refractive index. It can also convert harmful impurities such as Fe into FeF3, which volatilizes, or form a complex [FeF6]. 2- , reducing the impact of impurities on UV transmittance. If the fluoride content is less than 2wt%, the effect of reducing viscosity and eliminating impurities at high temperatures is not obvious. If the fluoride content is higher than 5wt%, the volatility is high during glass melting, affecting the glass composition.

[0042] Barium oxide is a network exosome oxide that can release free oxygen, while zinc oxide is a network intermediate that can absorb free oxygen and enter the network as [ZnO4] tetrahedron, which is beneficial to reduce the concentration of free oxygen. By controlling the mass ratio of zinc oxide to barium oxide, the glass can have a high transmittance. 2+ The field strength is greater than Ba 2+ , which makes the polarizability of oxygen ions relatively decrease, resulting in a decrease in splitting energy. At the same time, the increase in the mass ratio of zinc oxide to barium oxide can reduce the alkalinity of the glass, which is conducive to the low valence of impurity ions. If the mass ratio of zinc oxide to barium oxide is less than 1, the relative content of zinc oxide is low, and there is more free oxygen in the glass. At the same time, the splitting energy increases, which is not conducive to improving the ultraviolet transmittance. If the mass ratio of zinc oxide to barium oxide is greater than 4, the relative content of zinc oxide is high, and the effect of barium oxide is not obvious, which will reduce the refractive index and ultraviolet transmittance. At the same time, the difficulty of glass melting increases and the glass is prone to crystallization.

[0043] According to some embodiments of the present invention, a method for preparing deep ultraviolet transparent glass is further provided, comprising the following steps:

[0044] 1) stirring raw materials comprising the following components: 30-40 wt% of phosphorus pentoxide, 35-50 wt% of silicon dioxide, 5-10 wt% of aluminum oxide, 10-15 wt% of boron trioxide, 1-3 wt% of tin oxide, 3-6 wt% of zinc oxide, 1-3 wt% of barium oxide, and 2-5 wt% of fluoride to obtain a raw material mixture;

[0045] 2) melting the raw material mixture obtained in step 1) under vacuum and negative pressure to obtain a glass melt; specifically, placing the raw material mixture in a melting furnace, evacuating the furnace, and melting the raw material mixture under negative pressure;

[0046] 3) The glass melt obtained in step 2) is clarified, formed by leaking, and annealed to obtain the high ultraviolet transmittance glass.

[0047] Furthermore, in step 2) of some embodiments, the vacuum degree of the melting furnace can be set to -0.07 MPa to -0.04 MPa. The purpose of maintaining a certain vacuum degree in the melting furnace during the glass melting process is to make the volatile substance FeF3 generated by the reaction more easily volatilize from the glass melt, which is conducive to promoting the reduction or removal of impurity iron in the glass melt, improving the degree and efficiency of iron separation, and maintaining the stability of the glass composition. If the vacuum degree is greater than -0.04 MPa, the volatilization promotion effect of the volatile product is not obvious; if the vacuum degree is less than -0.07 MPa, other substances in the glass melt will be volatilized, which is not conducive to controlling the glass composition. At the same time, it places high requirements on equipment, resulting in increased costs and reduced efficiency.

[0048] Furthermore, in step 3) of some embodiments, the melting temperature can be set to 1550-1600°C, and the melting time can be set to 4-6 hours. The glass components contain refractory components such as silicon oxide and aluminum oxide. High-temperature metal ions also favor the formation of low-coordinated tetrahedra, while as the melting temperature decreases, the high-coordinated octahedron content increases. If the melting temperature is lower than 1550°C, the glass viscosity is high, making it difficult to form a uniform molten glass. The resulting volatile substances are also difficult to completely remove. Furthermore, the high-coordinated octahedron content in the glass increases, and these high-coordinated octahedra absorb shorter ultraviolet wavelengths, hindering high UV transmittance. If the melting temperature is higher than 1600°C, the volatility of the glass components increases, affecting the final composition of the glass and increasing energy consumption. If the melting time is less than 4 hours, the glass is not fully homogenized, affecting its uniformity, and the low-coordinated tetrahedra in the glass are not fully formed. If the melting time is longer than 6 hours, the reaction is already complete, and further increases in melting time result in reduced efficiency.

[0049] Furthermore, in step 4) of some embodiments, the annealing temperature can be set to 540-590°C, and the time can be set to 4-6h. The purpose of annealing is to eliminate the internal stress in the glass. If the annealing temperature is lower than 540°C, it is difficult for atoms and ions in the glass to move, and there is no time to form a stable state, resulting in low efficiency; if the annealing temperature is higher than 590°C, the energy consumption is too high, and new internal stress will be generated in the glass. If the annealing time is less than 4h, the effect of eliminating internal stress cannot be achieved, the annealing is insufficient, and the ions in the glass may have high octahedral coordination; if the annealing time is greater than 6h, the effect of eliminating internal stress will no longer increase, and energy consumption will increase.

[0050] According to some embodiments of the present invention, an optical device is further provided, which includes a high UV transmittance window, a lamp tube or a camera lens, wherein the high UV transmittance window, the lamp tube or the camera lens is composed of any of the above-mentioned deep UV transparent glasses.

[0051] In some embodiments, the optical device may be a UV detector, a UV night vision device, or the like. The UV detector may be used in UV early warning applications such as day-blind UV missile warning systems, power grid security monitoring, and forest fire warnings; the UV night vision device may be used in nighttime detection and imaging.

[0052] The present invention will be further described below with reference to specific embodiments, but these embodiments should not be construed as limiting the scope of protection of the present invention. Non-essential improvements and adjustments made by those skilled in the art based on the above-mentioned contents of the present invention still fall within the scope of protection of the present invention.

[0053] The test methods for various performance indicators in the embodiments of the present invention are as follows:

[0054] The refractive index is tested according to the method of GB / T 7962.1-2010 "Test methods for colorless optical glass Part 1: Refractive index and dispersion coefficient".

[0055] The transmittance is tested according to the method of GB / T 7962.12-2010 "Test methods for colorless optical glass Part 12: Spectral transmittance".

[0056] The water resistance stability is tested according to the method of GB / T 76582-2021 "Test method and classification of particles of glass at 98°C water resistance".

[0057] Example 1

[0058] According to the predetermined composition of deep UV-transmitting glass, the following raw materials were weighed and mixed uniformly: 40 wt% P2O5, 38 wt% SiO2, 10 wt% B2O3, 5 wt% Al2O3, 2 wt% sodium fluoride, 1 wt% SnO2, 3 wt% ZnO, and 1 wt% BaO. The P2O5 was weighed 200 g, and the remaining components were adjusted accordingly, with a ZnO to BaO mass ratio of 3. The mixed raw materials were then melted in a melting furnace at 1550°C for 4 hours, maintaining a vacuum of -0.07 MPa. The resulting glass melt was clarified, formed by sintering, and then annealed at 540°C for 34 hours to produce the deep UV-transmitting glass. Tests show that the prepared deep UV-transmitting glass has a transmittance of 78.2% at a wavelength of 200 nm at a thickness of 1.0 mm, a refractive index of 1.482, and water resistance of HGB1. The prepared deep UV-transmitting glass can be used for high-UV lenses in UV night vision devices.

[0059] Example 2

[0060] This embodiment differs from Example 1 in that the components are proportioned as shown in Table 1, with the P₂O₅ weighed 200g, and the remaining components corresponding thereto. The remaining steps and parameters are identical to those in Example 1. Testing showed that the prepared deep-UV-transmitting glass had a transmittance of 78.3% at a wavelength of 200nm at a thickness of 1.0mm, a refractive index of 1.483, and water resistance of HGB1. The deep-UV-transmitting glass prepared above can be used in high-UV lenses for UV night vision devices.

[0061] Example 3

[0062] This embodiment differs from Example 1 in that the components are proportioned as shown in Table 1, with the P₂O₅ weighed 200g, and the remaining components corresponding thereto. The remaining steps and parameters are identical to those in Example 1. Testing showed that the prepared deep-UV-transmitting glass had a transmittance of 78.1% at a wavelength of 200nm at a thickness of 1.0mm, a refractive index of 1.486, and water resistance of HGB1 grade. The deep-UV-transmitting glass prepared in this manner can be used in high-UV lenses for UV night vision devices.

[0063] Example 4

[0064] This embodiment differs from Example 1 in that the components are proportioned as shown in Table 1, with the P₂O₅ weighed 200g, and the remaining components corresponding thereto. The remaining steps and parameters are identical to those in Example 1. Testing showed that the prepared deep-UV-transmitting glass had a transmittance of 78.6% at a wavelength of 200nm at a thickness of 1.0mm, a refractive index of 1.486, and water resistance of HGB1. The deep-UV-transmitting glass prepared above can be used in high-UV lenses for UV night vision devices.

[0065] Example 5

[0066] This embodiment differs from Example 1 in that the components are proportioned as shown in Table 1, with the P₂O₅ weighed 200g, and the remaining components corresponding thereto. The remaining steps and parameters are identical to those in Example 1. Testing showed that the prepared deep-UV-transmitting glass had a transmittance of 78.3% at a wavelength of 200nm at a thickness of 1.0mm, a refractive index of 1.485, and water resistance of HGB1. The deep-UV-transmitting glass prepared above can be used in high-UV lenses for UV night vision devices.

[0067] Example 6

[0068] This embodiment differs from Example 1 in that the components are proportioned as shown in Table 1, with the P₂O₅ weighed 200g, and the remaining components corresponding thereto. The remaining steps and parameters are identical to those in Example 1. Testing showed that the prepared deep-UV-transmitting glass had a transmittance of 78.5% at a wavelength of 200nm at a thickness of 1.0mm, a refractive index of 1.487, and water resistance of HGB1 grade. The deep-UV-transmitting glass prepared in this manner can be used in high-UV lenses for UV night vision devices.

[0069] Example 7

[0070] This embodiment differs from Example 1 in that the components are proportioned as shown in Table 1, with the P₂O₅ weighed 200g, and the remaining components corresponding thereto. The remaining steps and parameters are identical to those in Example 1. Testing showed that the prepared deep-UV-transmitting glass had a transmittance of 78.9% at a wavelength of 200nm at a thickness of 1.0mm, a refractive index of 1.488, and water resistance of HGB1 grade. The deep-UV-transmitting glass prepared in this manner can be used in high-UV lenses for UV night vision devices.

[0071] Example 8

[0072] This embodiment differs from Example 1 in that the components are proportioned as shown in Table 1, with the P₂O₅ weighed 200g, and the remaining components corresponding thereto. The remaining steps and parameters are identical to those in Example 1. Testing showed that the prepared deep-UV-transmitting glass had a transmittance of 78.3% at a wavelength of 200nm at a thickness of 1.0mm, a refractive index of 1.488, and water resistance of HGB1. The deep-UV-transmitting glass prepared above can be used in high-UV lenses for UV night vision devices.

[0073] Example 9

[0074] This embodiment differs from Example 1 in that the vacuum level in this embodiment is -0.04 MPa. The remaining steps and parameters are the same as in Example 1. Testing shows that the deep-UV-transmitting glass prepared has a transmittance of 78.6% at a wavelength of 200 nm at a thickness of 1.0 mm, a refractive index of 1.482, and water resistance of HGB1. The deep-UV-transmitting glass prepared above can be used in high-UV lenses for UV night vision devices.

[0075] Example 10

[0076] This embodiment differs from Example 1 in that the melting temperature is 1600°C, while the remaining steps and parameters are identical to those of Example 1. Testing shows that the deep-UV-transmitting glass prepared has a transmittance of 78.7% at a wavelength of 200 nm at a thickness of 1.0 mm, a refractive index of 1.484, and water resistance of HGB1. The deep-UV-transmitting glass prepared above can be used for high-UV lenses in UV night vision devices.

[0077] Example 11

[0078] This embodiment differs from Example 1 in that the melting time is 6 hours, while the remaining steps and parameters are the same as in Example 1. Testing shows that the deep-UV-transmitting glass prepared has a transmittance of 78.2% at a wavelength of 200 nm at a thickness of 1.0 mm, a refractive index of 1.482, and water resistance of HGB1. The deep-UV-transmitting glass prepared above can be used in high-UV lenses for UV night vision devices.

[0079] Example 12

[0080] This embodiment differs from Example 1 in that the annealing temperature is 590°C. The remaining steps and parameters are the same as in Example 1. Testing shows that the deep-UV-transmitting glass prepared has a transmittance of 78.3% at a wavelength of 200 nm at a thickness of 1.0 mm, a refractive index of 1.482, and water resistance of HGB1. The deep-UV-transmitting glass prepared above can be used in high-UV lenses for UV night vision devices.

[0081] Example 13

[0082] This embodiment differs from Example 1 in that the annealing time is 6 hours. The remaining steps and parameters are the same as in Example 1. Testing shows that the deep-UV-transmitting glass prepared has a transmittance of 78.3% at a wavelength of 200 nm at a thickness of 1.0 mm, a refractive index of 1.483, and water resistance of HGB1. The deep-UV-transmitting glass prepared above can be used in high-UV lenses for UV night vision devices.

[0083] Example 14

[0084] This embodiment differs from Example 1 in that the components are proportioned as shown in Table 1, with the P₂O₅ weighed 200g, and the remaining components corresponding thereto. The remaining steps and parameters are identical to those in Example 1. Testing showed that the prepared deep-UV-transmitting glass had a transmittance of 78.9% at a wavelength of 200nm at a thickness of 1.0mm, a refractive index of 1.485, and water resistance of HGB1. The deep-UV-transmitting glass prepared above can be used in high-UV lenses for UV night vision devices.

[0085] Example 15

[0086] This embodiment differs from Example 1 in that the components are proportioned as shown in Table 1, with the P₂O₅ weighed 200g, and the remaining components corresponding thereto. The remaining steps and parameters are identical to those in Example 1. Testing showed that the prepared deep-UV-transmitting glass had a transmittance of 78.7% at a wavelength of 200nm at a thickness of 1.0mm, a refractive index of 1.484, and water resistance of HGB1 grade. The deep-UV-transmitting glass prepared in this manner can be used in high-UV lenses for UV night vision devices.

[0087] Example 16

[0088] This embodiment differs from Example 1 in that the components are proportioned as shown in Table 1, with the P₂O₅ weighed 200g, and the remaining components corresponding thereto. The remaining steps and parameters are identical to those in Example 1. Testing showed that the prepared deep-UV-transmitting glass had a transmittance of 78.3% at a wavelength of 200nm at a thickness of 1.0mm, a refractive index of 1.482, and water resistance of HGB1 grade. The deep-UV-transmitting glass prepared in this manner can be used in high-UV lenses for UV night vision devices.

[0089] Example 17

[0090] This embodiment differs from Example 1 in that the components are proportioned as shown in Table 1, with the P₂O₅ weighed 200g, and the remaining components corresponding thereto. The remaining steps and parameters are identical to those in Example 1. Testing showed that the prepared deep-UV-transmitting glass had a transmittance of 78.5% at a wavelength of 200nm at a thickness of 1.0mm, a refractive index of 1.485, and water resistance of HGB1. The deep-UV-transmitting glass prepared above can be used in high-UV lenses for UV night vision devices.

[0091] Example 18

[0092] This embodiment differs from Example 1 in that the components are proportioned as shown in Table 1, with the P₂O₅ weighed 200g, and the remaining components corresponding to the weight. The remaining steps and parameters are identical to those in Example 1. Testing showed that the prepared deep-UV-transmitting glass had a transmittance of 78.2% at a wavelength of 200nm at a thickness of 1.0mm, a refractive index of 1.486, and water resistance of HGB1. The deep-UV-transmitting glass prepared above can be used in high-UV lenses for UV night vision devices.

[0093] Example 19

[0094] This embodiment differs from Example 1 in that the components are proportioned as shown in Table 1, with the P₂O₅ weighed 200g, and the remaining components corresponding thereto. The remaining steps and parameters are identical to those in Example 1. Testing showed that the prepared deep-UV-transmitting glass had a transmittance of 78.4% at a wavelength of 200nm at a thickness of 1.0mm, a refractive index of 1.483, and water resistance of HGB1. The deep-UV-transmitting glass prepared above can be used in high-UV lenses for UV night vision devices.

[0095] Comparative Example 1

[0096] This comparative example differs from Example 1 in that the mass ratio of ZnO / BaO in this comparative example is 6 (as shown in Table 2). The remaining steps and parameters are the same as those in Example 1. Testing shows that the prepared deep-UV transparent glass has a transmittance of 51.2% at a wavelength of 200 nm at a thickness of 1.0 mm, a refractive index of 1.498, and water resistance stability of HGB1.

[0097] Comparative Example 2

[0098] This comparative example differs from Example 1 in that the melting furnace in this comparative example was not vacuumed (as shown in Table 2). The remaining steps and parameters were the same as in Example 1. Testing showed that the prepared deep-UV-transmitting glass had a transmittance of 29.2% at a wavelength of 200 nm at a thickness of 1.0 mm, a refractive index of 1.498, and water resistance of HGB2.

[0099] Comparative Example 3

[0100] This comparative example differs from Example 1 in that no fluoride (as shown in Table 1) is added. The remaining steps and parameters are the same as those in Example 1. Testing shows that the prepared deep-UV transparent glass has a transmittance of 34.2% at a wavelength of 200 nm at a thickness of 1.0 mm, a refractive index of 1.45, and water resistance stability of HGB2.

[0101] Comparative Example 4

[0102] This comparative example differs from Example 1 in that the components of this example are proportioned as shown in Table 1, with the P₂O₅ weighed 200 g, and the remaining components corresponding thereto. The remaining steps and parameters are identical to those of Example 1. Testing shows that the prepared deep-UV-transmitting glass exhibits a transmittance of 48.7% at a wavelength of 200 nm at a thickness of 1.0 mm, a refractive index of 1.482, and water resistance of HGB2 grade.

[0103] Comparative Example 5

[0104] This comparative example differs from Example 1 in that the components of this example are as shown in Table 1, with the P₂O₅ weighed 200g, and the remaining components corresponding to the reference weight. The remaining steps and parameters are the same as those in Example 1. Testing shows that the prepared deep-UV-transmitting glass exhibits a transmittance of 15.2% at a wavelength of 200nm and a refractive index of 1.483 at a thickness of 1.0mm, and water resistance of HGB2.

[0105] Comparative Example 6

[0106] This comparative example differs from Example 1 in that the components of this example are as shown in Table 1, with the P₂O₅ weighed 200 g, and the remaining components corresponding thereto. The remaining steps and parameters are the same as in Example 1. Testing shows that the prepared deep-UV-transmitting glass has a transmittance of 37.1% at a wavelength of 200 nm and a refractive index of 1.495 at a thickness of 1.0 mm, and a water resistance stability of HGB2.

[0107] Comparative Example 7

[0108] This comparative example differs from Example 1 in that the components of this example are as shown in Table 1, with the P₂O₅ weighed 200 g, and the remaining components corresponding thereto. The remaining steps and parameters are the same as in Example 1. Testing shows that the prepared deep-UV-transmitting glass has a transmittance of 38.5% at a wavelength of 200 nm at a thickness of 1.0 mm, a refractive index of 1.512, and water resistance of HGB2 level.

[0109] The raw material composition ratios and preparation process conditions of Examples 1-19 and Comparative Examples 1-7 are summarized in Tables 1 and 2 below.

[0110] Table 1 Ratio of raw material components of Examples 1-19 and Comparative Examples 1-7

[0111]

[0112]

[0113] Table 2 Preparation process conditions of Examples 1-19 and Comparative Examples 1-7

[0114]

[0115]

[0116] The test data from Examples 1-19 above show that the deep UV-transmitting glass prepared by the method of the present invention, when having a thickness of 1.0 mm, has a light transmittance of greater than 78% at a wavelength of 200 nm, a water resistance of HGB1, and a refractive index of 1.480-1.490. Compared to Example 1, the fluoride content in Example 5 is increased from 2% to 5%, which can more effectively convert the harmful impurity Fe into FeF3 for volatilization or form a complex [FeF6]. 2- , in order to reduce the influence of impurities on the ultraviolet transmittance, thereby improving the ultraviolet transmittance of the glass. Compared with Example 1, the mass ratio of zinc oxide to barium oxide in Example 7 is increased, which means that the zinc oxide content is increased, and it can absorb more free oxygen into the network as [ZnO4] tetrahedron, thereby reducing the concentration of free oxygen and the alkalinity of the glass, which can lead to the low valence of impurity ions in the glass. At the same time, Zn 2+ The field strength is greater than Ba 2+ , resulting in a weakening of the effective electric field of oxygen ions on the central metal ions, a reduction in the splitting energy of the coordination field, and an increase in the ultraviolet transmittance of the glass; while in Example 8, the mass ratio of zinc oxide to barium oxide is reduced, so the effective electric field of oxygen ions on the central metal ions is enhanced, the splitting energy of the coordination field is increased, and the ultraviolet transmittance is reduced. Compared with Example 1, the melting temperature of Example 10 is increased from 1550°C to 1600°C. The high temperature is conducive to the formation of a low-coordination state of tetrahedrons, reducing the absorption of the ultraviolet band, and improving the ultraviolet transmittance of the glass. Compared with Example 1, the fluoride content in Examples 14-16 is varied. It can be seen that as the fluoride content increases, more harmful impurities Fe in the glass are converted into FeF3 and volatilized, or form complexes [FeF6]. 2- , reducing the impact of impurities on UV transmittance, thereby increasing the UV transmittance of the glass. Compared to Example 1, the tin oxide content in Examples 17-19 varies. As the tin oxide content increases, free oxygen in the glass, which is detrimental to transmittance, is further reduced. At the same time, as many impurities in the glass as possible are reduced to low-valent states. Low-valent impurity atoms have little impact on the UV transmittance of the glass, thereby increasing the UV transmittance of the glass.

[0117] Compared to Example 1, the mass ratio of zinc oxide to barium oxide in Comparative Example 1 is 6. The relative content of zinc oxide in the glass is large, and the effect of barium oxide is shielded, which will reduce the refractive index and ultraviolet transmittance of the glass. The high relative content of zinc oxide can easily cause the glass to delaminate. In Comparative Example 2, atmospheric pressure melting is used. The volatile impurities in the glass are not easy to volatilize, remaining in the glass and affecting the ultraviolet transmittance of the glass. In addition, the atmospheric pressure environment contains an oxidizing atmosphere, so the glass is melted under oxidizing conditions, resulting in the presence of high-valence impurities in the glass, which absorbs the ultraviolet band spectrum. In Comparative Example 3, no fluoride is added, and the harmful impurity iron in the glass cannot form volatile substances or form a complex [FeF6]. 2- , which remains in the glass and affects the ultraviolet transmittance. At the same time, it increases the viscosity of the glass and reduces the structural stability of the glass. In Comparative Example 4, the tin oxide content is 0.5%. The tin oxide content in the glass solution is not enough to reduce the impurity ions Fe in the glass, and the amount of free oxygen absorbed is limited, resulting in a decrease in the transmittance of the glass. In Comparative Example 5, the tin oxide content is 3.5%. The high content of tin oxide cannot be completely melted in the glass solution and will appear as suspended particles in the glass, resulting in a significant decrease in the transmittance of the glass. In Comparative Example 6, the fluoride content is 1%. Too little fluoride prevents the harmful impurity iron in the glass from forming volatile substances or forming complexes [FeF6]. 2- , remaining in the glass and affecting its UV transmittance; it also increases the viscosity of the glass, thereby reducing its structural stability. In Comparative Example 7, the fluoride content is 6%. Fluoride is volatile at high temperatures, and excessive fluoride volatilization causes changes in the composition of the glass, thereby affecting the transmittance of the glass.

[0118] In the description of the present invention, a large number of specific details are described. However, it is understood that embodiments of the present invention can be practiced without these specific details. In some embodiments, well-known methods, structures and techniques are not shown in detail so as not to obscure the understanding of this description.

[0119] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0120] In addition, the various embodiments of the present invention may be arbitrarily combined, and as long as they do not violate the concept of the present invention, they should also be regarded as the contents disclosed by the present invention.

[0121] The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Any simple modifications, equivalent changes and modifications made to the above embodiment based on the technical essence of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A deep ultraviolet transparent glass, characterized in that: The composition calculated based on the components in the raw materials is: 30-40 wt% of phosphorus pentoxide; 35-50 wt% of silicon dioxide; 5-10 wt% of aluminum oxide; 10-15 wt% of boron trioxide; 1-3 wt% of tin oxide; 3-6 wt% of zinc oxide; 1-3 wt% of barium oxide; and 2-5 wt% of fluoride, the sum of the contents of the above components being 100 wt%; the fluoride being selected from at least one of sodium fluoride and potassium fluoride; and the mass ratio of the zinc oxide to the barium oxide being 1-4.

2. The glass according to claim 1, wherein When the thickness of the deep ultraviolet transparent glass is 1.0 mm, the transmittance of light with a wavelength of 200 nm is greater than 78%, the water resistance stability is HGB1 level, and the refractive index is 1.480-1.

490.

3. A method for preparing deep ultraviolet transparent glass according to claim 1 or 2, characterized in that: The following steps are involved: 1) stirring raw materials comprising the following components: 30-40 wt% of phosphorus pentoxide, 35-50 wt% of silicon dioxide, 5-10 wt% of aluminum oxide, 10-15 wt% of boron trioxide, 1-3 wt% of tin oxide, 3-6 wt% of zinc oxide, 1-3 wt% of barium oxide, and 2-5 wt% of fluoride to obtain a raw material mixture; 2) melting the raw material mixture obtained in step 1) under vacuum or negative pressure to obtain a glass melt; 3) The glass melt obtained in step 2) is clarified, formed by leaking, and annealed to obtain the deep ultraviolet transparent glass.

4. The method for preparing deep ultraviolet transparent glass according to claim 3, characterized in that: In step 2), the melting vacuum degree is -0.07 MPa to -0.04 MPa.

5. The method for preparing deep ultraviolet transparent glass according to claim 3, characterized in that: In step 2), the melting temperature is 1550-1600° C. and the melting time is 4-6 h.

6. The method for preparing deep ultraviolet transparent glass according to claim 3, characterized in that: In step 3), the annealing temperature is 540-590° C. and the time is 4-6 h.

7. An optical device, characterized in that: The invention comprises a high-ultraviolet-transmittance window, a lamp tube or a camera lens, wherein the high-ultraviolet-transmittance window, lamp tube or camera lens comprises deep-ultraviolet-transmitting glass; the deep-ultraviolet-transmitting glass comprises, based on the components in the raw materials, 30-40 wt% of phosphorus pentoxide; 35-50 wt% of silicon dioxide; 5-10 wt% of aluminum oxide; 10-15 wt% of boron trioxide; 1-3 wt% of tin oxide; 3-6 wt% of zinc oxide; 1-3 wt% of barium oxide; and 2-5 wt% of fluoride, the sum of the contents of the above components being 100 wt%; the fluoride is selected from at least one of sodium fluoride and potassium fluoride; and the mass ratio of zinc oxide to barium oxide is 1-4.

8. The optical device according to claim 7, characterized in that The optical device is an ultraviolet imaging detector.

9. The optical device according to claim 7, wherein: The optical device is an ultraviolet night vision device.

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