Skin glass composition, skin glass and method of preparation and use thereof

Abstract

The application provides a skin glass composition, the skin glass and a preparation method and application thereof. The composition comprises, in terms of mass percentage: 60-75% of quartz sand, 1.5-15% of boric acid, 1-5% of aluminum oxide, 1-10% of sodium carbonate, 1-8% of potassium bifluoride, 1-8% of calcium fluoride, 0-5% of basic magnesium carbonate, 0-8% of lithium carbonate, 0-5% of zinc oxide and 0-2% of cerium oxide; the total content of impurities Fe, Cu and Mn in the raw materials is less than or equal to 3ppm, and the total content of impurities Nd, Pr, U, Er, Eu, Tb and Dy is less than or equal to 2ppm. The technical problem to be solved is how to prepare the skin glass, so that the skin glass can simultaneously meet the requirements of wide spectrum response, radiation resistance and low refractive index, and the spectral transmittance is greater than or equal to 75% in the wavelength range of 330-2000nm under the thickness of 100mm; the skin glass is applied to the environment of high radiation and wide spectrum detection in the field of aerospace, so that the imaging clarity and service life of the glass can be effectively improved, and long-distance detection is realized.

Description

Technical Field

[0001] This invention relates to the field of glass manufacturing technology, and in particular to a glass composite, a glass preparation method thereof, and its application. Background Technology

[0002] Fiber optic image arrays are made of tens of millions of micron-sized fiber filaments tightly and regularly arranged and fused together. They can transmit images with high fidelity and have the characteristics of zero optical thickness, large numerical aperture, and high resolution. They include optical fiber panels, fiber optic image inverters, fiber optic tapers, fiber optic image bundles, etc., and can be applied to aerospace, low-light night vision, medical diagnostics and other fields. They are high-tech cutting-edge products in the optoelectronics industry.

[0003] Fiber optic image transmission arrays utilize high-refractive-index core glass and low-refractive-index sheath glass tubes, combined with rods and tubes to draw monofilaments for arrangement. Absorbing glass is drawn into filaments and inserted into the arranged monofilaments; the absorbing glass primarily absorbs stray light. These are then bundled into composite rods, drawn, arranged, and hot-melted into blank sections, and finally precision-processed. Primarily used for high-definition image transmission, this system solves the problems of low field image resolution and poor clarity, thus improving imaging clarity.

[0004] Currently, fiber optic imaging arrays are used for long-distance detection in radiation-exposed environments such as space. This requires glass with broad spectral transmittance for greater detection distances, while also being able to withstand radiation. Achieving both simultaneously is difficult. The sheath glass is a core component of the fiber optic imaging array, its main function being to form a total reflection layer at the core-skin interface. Because the sheath glass is smaller within the fiber panel, it is more prone to defects during manufacturing. Therefore, its radiation resistance and ultraviolet transmission performance must be superior to that of the core glass. However, current technology lacks a sheath glass that simultaneously meets the three conditions of broad spectral response, radiation resistance, and low refractive index, thus failing to meet the requirements for long-distance detection in radiation-exposed environments such as aerospace. Summary of the Invention

[0005] The main objective of this invention is to provide a glass composite, a glass composite, its preparation method, and its applications. The technical problem to be solved is how to prepare a glass composite that simultaneously meets the requirements of broad spectral response, radiation resistance, and low refractive index. Specifically, at a thickness of 100 mm, it exhibits a spectral transmittance ≥75% in the wavelength range of 330–2000 nm; after irradiation at a dose of 6.4 kGy for 500 h, the transmittance at 350 nm decreases by ≤3%; the refractive index is ≤1.50; and the average linear thermal expansion coefficient in the temperature range of 30–300 °C is 75 × 10⁻⁶. -7 / ℃~85×10 -7 / ℃; it does not crystallize when held at 910℃ for 5 hours. After melting, it has the advantages of no stones or bubbles inside the glass, good anti-crystallization performance, good moisture resistance and stability, and excellent chemical stability. Its thermal properties meet the requirements of fiber optic imaging array manufacturing process. When the glass is used in the aerospace field in environments with high radiation and wide spectrum detection, it can effectively improve the imaging clarity and service life of the glass, thus making it more suitable for practical use.

[0006] The objective of this invention and the technical problem it solves are achieved by the following technical solution. A glass composition for a protective layer, according to this invention, comprises, by weight percentage:

[0007]

[0008] The total content of impurities Fe, Cu and Mn in the above raw materials is ≤3ppm, and the total content of impurities Nd, Pr, U, Er, Eu, Tb and Dy is ≤2ppm.

[0009] The objective of this invention and the technical problem it solves are achieved by the following technical solution. A method for preparing a glass film according to this invention includes the following steps:

[0010] S21 raw material is metered to obtain a mixture; by mass percentage, the mixture includes: 60-75% quartz sand, 1.5-15% boric acid, 1-5% alumina, 1-10% sodium carbonate, 1-8% potassium hydrofluoric acid, 1-8% calcium fluoride, 0-5% basic magnesium carbonate, 0-8% lithium carbonate, 0-5% zinc oxide, and 0-2% cerium oxide; in the above raw materials, the total content of impurities Fe, Cu and Mn is ≤3ppm, and the total content of impurities Nd, Pr, U, Er, Eu, Tb and Dy is ≤2ppm;

[0011] S22 involves melting, clarifying, and stirring the mixture; oxygen is introduced into the molten glass during the melting, clarifying, and stirring steps; the apparatus for preparing and melting the mixture is made of non-metallic materials; the melting furnace used for melting and clarifying is made of refractory material with a heavy metal content ≤5ppm;

[0012] S23 molten glass is discharged, cast into shape, annealed, and then the resulting glass is a skin.

[0013] The objectives of this invention and the technical problems it addresses can be further achieved by the following technical measures.

[0014] Preferably, in the aforementioned preparation method, the container for melting the mixture is a quartz crucible; the surface of the crucible is coated with a silicon oxide coating.

[0015] Preferably, in the aforementioned preparation method, the refractory material is an erosion-resistant and high-temperature resistant material with a temperature resistance ≥1700℃.

[0016] Preferably, in the aforementioned preparation method, the melting furnace is dedicated to the preparation of the sheet glass.

[0017] Preferably, in the aforementioned preparation method, the mixture is melted by adding the mixture into a container in 3-5 portions, with each portion spaced 0.5-2 hours apart.

[0018] Preferably, in the aforementioned preparation method, the melting temperature of the mixture is 1350-1400℃; the clarification and stirring temperature is 1460-1530℃, and the clarification and stirring time is 1-2h; the discharge temperature is 1300-1350℃; the annealing temperature is 550-600℃, and the annealing time is 2-4h.

[0019] Preferably, in the aforementioned preparation method, the flow rate of oxygen introduced into the molten glass is 0.04-0.18 mol / L / min.

[0020] The objective of this invention and the technical problem it solves are achieved through the following technical solution. A type of glass according to this invention is characterized in that, at a thickness of 100 mm, its spectral transmittance in the wavelength range of 330–2000 nm is ≥75%; after irradiation at a dose of 6.4 kGy for 500 h, its transmittance at 350 nm exhibits a attenuation rate ≤3%; its refractive index is ≤1.50; and its average linear thermal expansion coefficient in the temperature range of 30–300 °C is 75 × 10⁻⁶. -7 / ℃~85×10 -7 / ℃; it does not crystallize when kept at 910℃ for 5 hours.

[0021] The objective of this invention and the technical problem it solves are achieved by the following technical solution: An application of the aforementioned sheath glass in a broadband-response radiation-resistant fiber optic imaging array, according to this invention.

[0022] By employing the above technical solutions, the glass-like composition, glass-like material, preparation method, and application proposed in this invention have at least the following advantages:

[0023] The glass composition, glass material, preparation method, and application proposed in this invention achieve good technical results through control of the composition, content, and purity of the raw materials. At a thickness of 100 mm, the spectral transmittance is ≥75% in the wavelength range of 330–2000 nm; after irradiation at a dose of 6.4 kGy for 500 h, the transmittance at 350 nm decreases by ≤3%; the refractive index is ≤1.50; and the average linear thermal expansion coefficient in the temperature range of 30–300 °C is 75 × 10⁻⁶. -7 / ℃~85×10 -7 / ℃; it does not crystallize when held at 910℃ for 5 hours. After melting, it has the advantages of no stones or bubbles inside the glass, good anti-crystallization performance, good moisture resistance and excellent chemical stability. Its thermal properties meet the requirements of fiber optic imaging array fabrication process. It can simultaneously meet the requirements of wide spectral response, radiation resistance and low refractive index, and has high ultraviolet transmittance. Specifically, this invention strictly controls the impurities and their content in raw materials. By using high-purity raw materials for formulation, it strictly controls the content of Fe, Cu, Mn, etc., ensuring that the content of coloring elements in all raw materials is below 3 ppm. When using rare earth oxides such as Ce, the introduction of impurity elements such as Nd, Pr, U, Er, Eu, Tb, and Dy is strictly prohibited, ensuring their total content is below 2 ppm. Because harmful impurities in glass, such as transition metal ions and heavy metal ions, have low electron transition energies, their electrons absorb energy and undergo transitions under high-energy radiation, resulting in significant ultraviolet absorption in the ultraviolet region. This invention, by strictly limiting their purity, ensures the ultraviolet transmittance of the glass material.

[0024] Furthermore, this invention controls the glass melting and forming process. On the one hand, it ensures that the materials used in the batching and melting process are all non-metallic, and for plastic products, colorless and transparent materials are used. This avoids the container material melting into the glass or impurities in the glass raw material entering the glass during direct contact between the glass raw material and the container, thus preventing adverse effects on the glass. On the other hand, by controlling the material of the melting furnace for heating the container / equipment to be refractory, and strictly controlling the heavy metal content to ≤5ppm, it avoids the refractory material affecting the glass composition through the container opening. At the same time, oxygen is continuously introduced into the molten glass during melting, clarifying, and stirring to create a strong oxidizing atmosphere, thereby enabling precise control of the valence distribution of variable valence elements and ensuring that the glass has high transmittance under radiation resistance.

[0025] The technical solution of this invention, through strict limitation of the types, contents, and purity of raw materials in the glass composition, enables the preparation of a skin glass with excellent comprehensive performance. Furthermore, through strict control of the glass melting and forming processes, it ensures that no new impurities are introduced into the glass during these processes, thereby guaranteeing that the final skin glass composition ratio remains essentially stable at the initial raw material composition ratio. This ensures an optimal balance among various properties, simultaneously satisfying broad spectral response, radiation resistance, and low refractive index, while also exhibiting high ultraviolet transmittance and high imaging clarity in radiation-exposed environments such as space. The glass has a long service life, ensuring that the glass material obtained by this invention can be used in fiber optic imaging arrays. At a thickness of 100 mm, the spectral transmittance is ≥75%; after irradiation at a dose of 6.4 kGy for 500 h, the transmittance at 350 nm decreases by ≤3%, improving the service life and stability of the glass material in X-ray irradiation environments; the refractive index is ≤1.50, ensuring better light-gathering capability of the fiber optic imaging array; after melting, the glass material of this invention has advantages such as no internal stones or bubbles, good anti-crystallization performance, good moisture resistance, and excellent chemical stability, and its thermal properties meet the requirements of fiber optic imaging array fabrication processes.

[0026] The above description is merely an overview of the technical solution of the present invention. In order to better understand the technical means of the present invention and to implement it in accordance with the contents of the specification, the preferred embodiments of the present invention are described in detail below. Detailed Implementation

[0027] To further illustrate the technical means and effects adopted by the present invention to achieve the intended purpose, the following detailed description, in conjunction with preferred embodiments, provides a detailed explanation of the specific implementation methods, structures, features, and effects of a glass composite, glass substrate, and its preparation method according to the present invention, as well as their application. In the following description, different "embodiments" or "embodiments" do not necessarily refer to the same embodiment. Furthermore, specific features, structures, or characteristics in one or more embodiments can be combined in any suitable manner.

[0028] This invention proposes a glass coating composition, which, by mass percentage, comprises: 60-75% quartz sand, 1.5-15% boric acid, 1-5% alumina, 1-10% sodium carbonate, 1-8% potassium hydrofluoric acid, 1-8% calcium fluoride, 0-5% basic magnesium carbonate, 0-8% lithium carbonate, 0-5% zinc oxide, and 0-2% cerium oxide; wherein the total content of impurities Fe, Cu, and Mn in the above raw materials is ≤3ppm, and the total content of impurities Nd, Pr, U, Er, Eu, Tb, and Dy is ≤2ppm.

[0029] The above-mentioned glass composition can be melted, clarified and stirred, shaped and annealed to obtain a glass with a coating. All components in the glass are in the form of oxides, that is, the glass contains SiO2, B2O3, Al2O3, Na2O, K2O, CaO, MgO, Li2O, ZnO and CeO2.

[0030] In the aforementioned glass cladding, SiO2 is introduced in the form of quartz sand, forming the main body of the glass skeleton and playing a major role in the glass skeleton. The weight percentage of quartz sand in the cladding glass is 60-75%. When the content of quartz sand raw material is below 60%, it is difficult to obtain glass with a low refractive index, and it also reduces the chemical stability of the glass; while when the content of quartz sand raw material is above 75%, the high-temperature viscosity of the glass increases, resulting in excessively high glass melting temperature, and the coefficient of thermal expansion of the glass also decreases.

[0031] B₂O₃, introduced in the form of boric acid, is a glass-forming oxide and a component of the glass framework. It also acts as a flux to reduce the viscosity of the glass melt. Boron-oxygen trigonal [BO₃] and boron-oxygen tetrahedron [BO₄] are structural components. Under different conditions, boron may exist as trigonal [BO₃] or boron-oxygen tetrahedron [BO₄]. At high-temperature melting conditions, it is generally difficult to form boron-oxygen tetrahedra, and it can only exist as trihedrons. However, at low temperatures, under certain conditions, boron... 3+ It tends to capture free oxygen to form tetrahedrons, making the structure more compact and increasing the low-temperature viscosity of the glass. However, because it has the characteristic of decreasing glass viscosity at high temperatures and increasing it at low temperatures, and is also a major component in reducing the glass refractive index, its content range is relatively small. The preferred weight percentage of boric acid raw material in the aforementioned glass is 1.5-15%. When the content of boric acid raw material is greater than 15%, it will decrease the glass refractive index and also increase the glass's tendency to phase separation.

[0032] Al₂O₃, introduced as alumina, is an intermediate oxide in glass and can improve the radiation resistance of glass while reducing its tendency for phase separation. Replacing some SiO₂ with Al₂O₃... 3+ Preferentially, it captures free oxygen to form [AlO4], which then enters the glass network. 3+ Occupy Si 4+ The location. Due to Al 3+ and Si 4+Different valence states require alkali metal ions to fill and balance the valence state. Broken structural chains in the glass are reconnected, making the glass structure more compact and reducing the amount of non-bridging oxygen, thus improving the glass's radiation resistance. Therefore, within a certain content range, it can become a major component of the glass network, similar to SiO2. The alumina content is 1-5% by weight; when the alumina content exceeds 5%, it significantly increases the high-temperature viscosity of the glass and simultaneously raises the glass's melting temperature.

[0033] Na₂O, introduced in the form of sodium carbonate, is an alkali metal oxide and an outer oxide of the glass network structure. Na₂O repairs the break points between [SiO₄] and [BO₃], transforming the triangular layered structure of [BO₃] into a tetrahedron of [BO₄], thus strengthening the network connections, increasing the number of bridging oxygen atoms, and shifting the intrinsic ultraviolet absorption towards shorter wavelengths, thereby improving the glass's broadband transmittance. The preferred weight percentage of sodium carbonate is 1-10%. A sodium carbonate content greater than 10% increases the glass's refractive index and coefficient of thermal expansion, and also increases its tendency to crystallize.

[0034] K₂O, introduced in the form of potassium fluoride, is an alkali metal oxide and an outer oxide of the glass network structure. K₂O repairs the breakpoints between [SiO₄] and [BO₃], transforming the triangular layered structure of [BO₃] into a tetrahedron of [BO₄], thus strengthening the network connections, increasing the number of bridging oxygen atoms, and shifting the intrinsic ultraviolet absorption towards shorter wavelengths, thereby improving the glass's broadband transmittance. - The introduction of F can fill oxygen vacancies in the glass, thereby repairing structural defects and improving glass transmittance. Meanwhile, F... - To achieve a stable octet structure, the strong binding effect of potassium fluoride on outer electrons reduces the number of high-energy free electrons generated by irradiation, preventing the formation of color centers and improving the glass's radiation resistance. The preferred weight percentage of potassium fluoride is 1-8%. A potassium fluoride content greater than 8% increases the glass's refractive index and coefficient of thermal expansion, and also increases its tendency to crystallize.

[0035] CaO is introduced in the form of calcium fluoride to improve the glass's radiation resistance and broad spectral transmittance. - The introduction of F can fill oxygen vacancies in the glass, thereby repairing structural defects and improving glass transmittance. Meanwhile, F... - To achieve a stable octet structure, the strong binding effect of calcium fluoride on outer electrons reduces the number of high-energy free electrons generated by irradiation, preventing the formation of color centers and improving the glass's radiation resistance. The weight percentage of calcium fluoride raw material is 1-8%. A calcium fluoride content greater than 8% will reduce the glass's chemical stability and increase its tendency to crystallize.

[0036] MgO is introduced in the form of basic magnesium carbonate, which is an outer oxide of the glass structure network and is used to adjust the glass crystallization temperature. The weight percentage of basic magnesium carbonate raw material is 0-5%. If the content of basic magnesium carbonate raw material is greater than 5%, it will increase the tendency of glass to crystallize.

[0037] Li₂O, introduced in the form of lithium carbonate, is an external oxide of the glass network structure. Lithium oxide has a small ionic radius and high electronegativity, making it easy to enter the glass network structure and exert a strong attraction on surrounding molecules. This contributes to the densification of the glass structure, reduces internal defects and scattering centers, thereby improving the glass's transmittance. The weight percentage of lithium carbonate is 0-8%; a lithium carbonate content greater than 8% will increase the glass's coefficient of thermal expansion.

[0038] Introducing zinc oxide (ZnO) results in a high bandgap and excitation binding energy, leading to a high absorption coefficient under certain radiation exposure conditions. A small amount of ZnO can improve the radiation resistance of glass. The weight percentage of zinc oxide is 0-5%. A zinc oxide content greater than 5% will reduce the chemical stability and thermal expansion coefficient of the glass, and increase its tendency to crystallize.

[0039] CeO2, introduced by cerium oxide, is a rare earth oxide. It utilizes the fact that cerium is a variable-valence element, and under radiation, it is in a high-valence state (Ce). 4+ It can first absorb high-energy electrons or free electrons induced by radiation, causing a change in the valence state of the ions without establishing color centers, thus achieving radiation resistance. After cerium changes its valence, the element in the new valence state absorbs ultraviolet and visible light, which also leads to a decrease in the transmittance of the fiber optic imaging array. Ce... 4+ It exhibits strong absorption in the visible light region, transforming into Ce. 3+ At this point, absorption in the spectral region above 300 nm is very small. By appropriately introducing a suitable amount of Ce and precisely controlling the valence state through an oxygen-enriched melting process, the amount of cerium with variable valence is minimized while still meeting radiation resistance requirements. This resolves the contradiction between ultraviolet transmission (avoiding as many variable valence elements as possible in the composition) and radiation resistance (introducing cerium with variable valence to absorb high-energy electrons generated by high-energy radiation and prevent color center formation). This achieves both radiation resistance and high transmittance in the ultraviolet region. The weight percentage of cerium oxide is 0-2%. A cerium oxide content greater than 2% increases the glass's tendency to crystallize and reduces its transmittance.

[0040] In the above technical solution, by controlling the composition and content of the glass coating composition, a glass coating with good technical performance is obtained after melting and forming. At a thickness of 100 mm, the spectral transmittance in the wavelength range of 330–2000 nm is ≥75%; after irradiation at a dose of 6.4 kGy for 500 h, the transmittance at 350 nm decreases by ≤3%; the refractive index is ≤1.50; and the average linear thermal expansion coefficient in the temperature range of 30–300 °C is 75 × 10⁻⁶. -7 / ℃~85×10 -7 / ℃; it does not crystallize when held at 910℃ for 5 hours. After melting, it has the advantages of no stones or bubbles inside the glass, good anti-crystallization performance, good moisture resistance and excellent chemical stability. Its thermal properties meet the requirements of fiber optic imaging array fabrication process. It can simultaneously meet the requirements of wide spectral response, radiation resistance and high refractive index, and has high ultraviolet transmittance. Specifically, this invention strictly controls the impurities and their content in raw materials. It uses high-purity raw materials for formulation and strictly controls the content of metals such as Fe, Cu, and Mn in the raw materials, ensuring that the content of coloring elements in all raw materials is below 3 ppm. When using rare earth oxides such as Ce in the formula, the introduction of impurity elements such as Nd, Pr, U, Er, Eu, Tb, and Dy is strictly prohibited, ensuring their total content is below 2 ppm. Because harmful impurities in glass, such as transition metal ions and heavy metal ions, have low electron transition energies, they may undergo transitions due to energy absorption under high-energy radiation, resulting in significant absorption of ultraviolet light in the ultraviolet region. This invention, by strictly limiting their purity, ensures the ultraviolet transmittance of the glass material, thus achieving a high transmittance.

[0041] This invention also proposes a method for preparing a glass cladding, which includes the following steps:

[0042] The first step is to measure the raw materials to obtain a mixture. By mass percentage, the mixture comprises: 60-75% quartz sand, 1.5-15% boric acid, 1-5% alumina, 1-10% sodium carbonate, 1-8% potassium hydrofluoric acid, 1-8% calcium fluoride, 0-5% basic magnesium carbonate, 0-8% lithium carbonate, 0-5% zinc oxide, and 0-2% cerium oxide. The total content of impurities Fe, Cu, and Mn in the above raw materials is ≤3 ppm, and the total content of impurities Nd, Pr, U, Er, Eu, Tb, and Dy is ≤2 ppm. This invention, through comprehensive design of the types, contents, and purity of raw materials, has formulated a glass composition with superior technical performance.

[0043] In this step, the purity control of raw materials is crucial because harmful impurities may be present in the raw materials, such as transition metal ions and heavy metal ions. These ions have low electron transition energies and absorb energy to undergo transitions under high-energy radiation, exhibiting significant absorption of ultraviolet light in the ultraviolet region. Therefore, to avoid their impact on the ultraviolet transmittance of the glass material, this invention strictly controls the content of harmful impurities such as oxides or salts in the formulation of the glass composition. All raw materials used in the formulation are high-purity, and the contents of Fe, Cu, Mn, etc., are strictly controlled to keep the content of coloring elements in all raw materials below 3 ppm. When using rare earth oxides such as Ce, the introduction of impurity elements such as Nd, Pr, U, Er, Eu, Tb, and Dy is strictly prohibited, and their total content is controlled below 2 ppm. This ensures that the glass formulated by this technical solution has excellent overall performance.

[0044] Furthermore, this step requires high purity of raw materials. Therefore, the containers and tools used in the mixing process also need to be strictly controlled. For example, the material of the mixing containers must be strictly controlled to be non-metallic; if plastic products are used, they should preferably be colorless and transparent. The reason for this is that since the containers, such as crucibles, are in direct contact with the glass, any impurities, whether from the crucible material or the crucible itself, if introduced into the mixture, may melt into the glass during the subsequent melting process, which will adversely affect the quality and performance of the glass. For example, if a platinum crucible is used, platinum particles or ions may enter the glass, leading to ultraviolet absorption and negatively impacting the glass's light transmittance. According to the composition of the glass material of the present invention, a quartz crucible is preferably used, and a high-purity silicon oxide coating is provided on the surface of the crucible to reduce the influence of the crucible composition on the glass composition and reduce the introduction of impurities.

[0045] The second step is to melt the prepared mixture and then clarify and stir it. The container for melting the mixture is also made of a non-metallic material; as mentioned above, the present invention preferably uses a quartz crucible as the melting container, and the surface of the crucible is coated with a high-purity silicon oxide coating.

[0046] In this step, the mixture can be directly added to the container for melting; however, in order to improve melting efficiency and the quality of the molten glass, the present invention preferably adds the mixture to the melting container in batches; in some specific embodiments of the present invention, it is preferred to add the mixture to the container in 3-5 batches, with an interval of 0.5-2 hours between each batch; adding the mixture in batches in this way can more efficiently complete the melting of the glass composition.

[0047] The melting process of the glass composition can be adjusted according to its specific ingredients. Under the composition formulation conditions designed in this invention, the preferred melting temperature is 1350-1400℃, so that the glass composition can be melted quickly.

[0048] After the glass composition is completely melted, the molten glass can be clarified and stirred. In this step, the preferred clarification and stirring temperature is 1460-1530℃, and the clarification and stirring time is 1-2 hours. It is preferable to stir the molten glass throughout the clarification process, and it is preferable to use a double-bladed agitator to improve the stirring effect. It is also preferable that the agitator is made of a non-metallic material to avoid contact with the molten glass and the introduction of harmful impurities.

[0049] To ensure high transmittance of the resulting glass substrate under irradiation conditions, this invention strictly limits the introduction of oxygen into the molten glass during the melting and refining stages to create a strongly oxidizing atmosphere. The amount of oxygen introduced adjusts the concentration of the oxidizing atmosphere in the molten glass, allowing variable-valence elements to melt in an oxygen-rich environment. This ensures that the molten glass contains sufficient high-valence variable elements to meet the glass's radiation resistance requirements, while preventing an excessive amount of high-valence variable elements that could absorb light and negatively impact the glass's transmittance. In some specific embodiments of this invention, the preferred oxygen flow rate into the molten glass is 0.04-0.18 mol / L / min. This allows for precise adjustment of the valence state of the radiation-resistant variable element cerium, ensuring high transmittance of the glass substrate under irradiation conditions.

[0050] Glass melting is generally carried out in an open crucible. Since the decomposition of raw materials in the glass composition may produce a large amount of volatile gases, and some components of the glass composition are also volatile, these volatile components can corrode the material of the melting furnace. This corroded material may also affect the glass itself through the crucible opening. Therefore, this invention preferably uses a refractory material for the melting and refining furnace. By strictly controlling the content of heavy metals, such as lead, cadmium, and mercury, to ≤5ppm, the adverse effects of the furnace material on the quality of the molten glass are directly reduced. Furthermore, by preferably using a corrosion-resistant and high-temperature-resistant refractory material, preferably with a temperature resistance ≥1700℃, the corrosion of the melting furnace by volatile glass components can be avoided or reduced, thereby indirectly reducing the adverse effects of the furnace material on the quality of the molten glass.

[0051] Furthermore, to avoid cross-contamination of the glass due to the erosion of the refractory material in the melting furnace, the present invention preferably uses a melting furnace that heats the container specifically for melting the sheet glass, thereby avoiding or reducing cross-contamination caused by the furnace material. Furthermore, even if the melting furnace is dedicated, the present invention can preferably replace it periodically according to usage and erosion conditions, thereby preventing harmful impurities such as Fe and Ti in the refractory material from entering the glass, thus avoiding or reducing the influence of the melting furnace on the composition of the molten glass.

[0052] Finally, the molten glass is discharged and poured into a mold to cast the desired glass shape; annealing then yields the glass sheet. The discharge, forming, and annealing temperatures and times of the molten glass can be adjusted according to the actual composition of the glass composition. In some specific embodiments of the present invention, based on the composition of the glass composition, the preferred discharge temperature is 1300-1350℃, the annealing temperature is 550-600℃, and the annealing time is 2-4 hours.

[0053] This invention also proposes a type of glass with a thickness of 100 mm, exhibiting a spectral transmittance ≥75% in the wavelength range of 330–2000 nm; a transmittance attenuation rate ≤3% at 350 nm after irradiation at a dose of 6.4 kGy for 500 h; a refractive index ≤1.50; and an average linear thermal expansion coefficient of 75 × 10⁻⁶ in the temperature range of 30–300 °C. -7 / ℃~85×10 -7 / ℃; it does not crystallize when kept at 910℃ for 5 hours.

[0054] In some specific embodiments of the present invention, the glass sheet is preferably made from the glass composition described above; the glass is preferably melted and clarified using the preparation method described above. This description does not constitute an exclusion of other glass preparation methods that do not introduce harmful impurities.

[0055] The present invention also proposes an application of the aforementioned glass material in a broadband-response radiation-resistant fiber optic imaging array.

[0056] The present invention also proposes an application of the aforementioned glass material for long-distance detection in aerospace radiation environments.

[0057] The present invention will be further described below with reference to specific embodiments, but this should not be construed as a limitation on the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention still fall within the scope of protection of the present invention.

[0058] Unless otherwise specified, all materials and reagents mentioned below are commercially available products well known to those skilled in the art; unless otherwise specified, all methods described are methods known in the art. Unless otherwise defined, the technical or scientific terms used should have the ordinary meaning understood by those skilled in the art to which this invention pertains.

[0059] Raw material requirements: Quartz sand (4N, less than 5% of material on 160μm sieve and less than 5% of material under 40μm sieve), boric acid (analytical grade, less than 10% of material on 400μm sieve and less than 10% of material under 63μm sieve), zinc oxide (analytical grade), aluminum oxide (analytical grade, average particle size 50μm), sodium carbonate (analytical grade), potassium hydrofluoric acid (analytical grade), calcium fluoride (analytical grade), basic magnesium carbonate (chemically pure, average particle size 50μm), lithium carbonate (analytical grade), cerium oxide (4N). Impurities in high-purity raw materials must be strictly controlled. The total content of coloring elements Fe, Cu, and Mn must be <3ppm. When using rare earth cerium oxide, the introduction of impurity elements such as Nd, Pr, U, Er, Eu, Tb, and Dy must be strictly prohibited, and their total content must be controlled to <2ppm.

[0060] Example 1

[0061] Melting of the glass: Raw materials were selected according to the glass composition in Example 1 of Table 1. The raw materials were weighed according to the batching table, mixed evenly, and then placed in a quartz crucible with a high-purity silica coating. All containers and utensils used in the batching and melting process were made of non-metallic materials; plastic products were colorless and transparent. The lead, cadmium, and mercury content in the furnace roof refractory material was controlled below 5 ppm. It was corrosion-resistant and could withstand temperatures above 1700℃. The melting furnace must be dedicated to this purpose to avoid cross-contamination caused by refractory material corrosion. The furnace was replaced periodically according to usage and corrosion conditions to prevent harmful impurities such as Fe and Ti from entering the glass.

[0062] The mixture was added to the crucible in five batches every 0.5 hours and melted at a high temperature of 1360°C. After the raw material mixture melted, it was clarified and stirred at 1470°C for 2 hours using a double-bladed stirrer to improve the stirring effect. During this melting and clarification stage, the oxygen valve was opened to introduce oxygen into the glass melt at a flow rate of 0.044 mol / L / min, creating a strong oxidizing atmosphere. The molten and clarified glass melt was discharged at 1300°C and cast into a mold to form the desired glass. After the glass cooled and solidified, it was annealed at 550°C for 4 hours to obtain the skin glass of this invention.

[0063] Testing revealed that the glass flakes produced in this embodiment, at a thickness of 100 mm, exhibited a spectral transmittance of 75.8% in the wavelength range of 330–2000 nm; after irradiation at a dose of 6.4 kGy for 500 hours, the transmittance at 350 nm decreased by 2.3%; the refractive index was 1.4985; and the average linear thermal expansion coefficient in the temperature range of 30–300 °C was 82 × 10⁻⁶. -7 / ℃; it does not crystallize when kept at 910℃ for 5 hours.

[0064] Examples 2 to 5

[0065] The process is the same as in Example 1. The formulation, raw material purity and process parameters of the glass composition are shown in Table 1, and the test results are also shown in Table 1.

[0066] Table 1 Chemical composition, process parameters, and properties of the glass sheets in Examples 1-5

[0067]

[0068]

[0069] Notes: a represents the total content of coloring elements such as Fe, Cu, and Mn in high-purity reagent quartz sand and cerium oxide, in ppm; b represents the total content of impurities Nd, Pr, U, Er, Eu, Tb, and Dy in cerium oxide, in ppm; c represents the transmittance of the 330nm–2000nm spectrum, in %; d represents the transmittance attenuation rate (at 350nm after 500h irradiation at a dose of 6.4kGy), in %; e represents the refractive index; f represents the average linear thermal expansion coefficient in the range of 30–300℃, in ×10⁻¹⁰. -7 / ℃.

[0070] As can be seen from the test data shown in Table 1, the glass material prepared in the embodiments of the present invention has excellent comprehensive performance, and it simultaneously meets the requirements of wide spectral response, radiation resistance and low refractive index, and has high ultraviolet transmittance.

[0071] The technical features in the claims and / or specification of this invention can be combined, and the combination is not limited to the combinations obtained through reference in the claims. Technical solutions obtained by combining the technical features in the claims and / or specification are also within the scope of protection of this invention.

[0072] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention shall still fall within the scope of the technical solution of the present invention.

Claims

1. A method of producing a skin glass, characterized by, It comprises the following steps: S21 raw material metering to obtain a mixture; the mixture comprises, in mass percentage, 60-75% quartz sand, 1.5-15% boric acid, 1-5% aluminum oxide, 1-10% sodium carbonate, 1-8% potassium bifluoride, 1-8% calcium fluoride, 0.1-5% basic magnesium carbonate, 0.1-8% lithium carbonate, 0.1-5% zinc oxide, and 0.1-2% cerium oxide; the total content of impurities Fe, Cu and Mn in the above raw materials is ≤3ppm, and the total content of impurities Nd, Pr, U, Er, Eu, Tb and Dy is ≤2ppm; S22 melting and refining stirring of the mixture; oxygen is introduced into the glass liquid during the melting and refining stirring; the apparatus for preparing and melting the mixture is made of non-metallic material; the melting and refining furnace is made of refractory material, and the content of heavy metals is ≤5ppm; S23 discharging the glass liquid, casting forming and annealing to obtain the skin glass.

2. The production method according to claim 1, characterized by, The container for melting the mixture is a quartz crucible, and the surface of the crucible is provided with a silica coating.

3. The production method according to claim 2, characterized by, The refractory material is an erosion-resistant and high-temperature-resistant material, and the temperature resistance is ≥1700℃.

4. The preparation method according to claim 2, characterized in that, The melting furnace is specially used for preparing the skin glass.

5. The production method according to any one of claims 1 to 4, characterized by, The melting of the mixture is carried out by adding the mixture into the container for 3-5 times with an interval of 0.5-2 hours.

6. The production method according to any one of claims 1 to 4, characterized by, The melting temperature of the mixture is 1350-1400℃; the refining stirring temperature is 1460-1530℃, the refining stirring time is 1-2h; the discharging temperature is 1300-1350℃; the annealing temperature is 550-600℃, and the annealing time is 2-4h.

7. The production method according to any one of claims 1 to 4, characterized by, The flow rate of the oxygen introduced into the glass liquid is 0.04-0.18mol / L / min.

8. A skin glass produced according to the production process of any one of claims 1 to 7, characterized in that It has a spectral transmittance ≥ 75% at 100 mm thickness in the wavelength range 330-2000 nm, a transmittance decay rate ≤ 3% at 350 nm for 500 h of irradiation at 6.4 kGy irradiation dose, a refractive index ≤ 1.50, an average linear thermal expansion coefficient in the range 30-300 °C of 75 x 10 -7 / °C to 85 x 10 -7 / °C, and is non-crystallizing at 910 °C for 5 hours.

9. Use of the skin glass according to claim 8 in a wide-spectrum response radiation-resistant fiber image array.

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