Environment-friendly radiation-resistant glass, preparation method and application thereof

Abstract

The application provides an environment-friendly high-refractive radiation-resistant glass, which comprises the following components in percentage by mass: 8-18% of SiO2, 6-15% of B2O3, 20-35% of La2O3, 3-10% of Y2O3, 24-38% of BaO, 0-5% of SrO, 0.1-2% of CaO, 4.9-10% of Nb2O5, 1-7% of ZrO2, 0.1-1.3% of CeO2 and 0-1% of NaCl. The glass is lead-free and environment-friendly, has excellent spectral transmittance, high refractive index, stable thermodynamic and chemical properties, good X-ray radiation resistance and process forming adaptability, and has wide application prospects in the fields of digital X-ray imaging, pet medical treatment, security inspection, industrial nondestructive testing and food safety detection.

Description

Technical Field

[0001] This application relates to the field of glass technology, specifically to an environmentally friendly radiation-resistant glass, its preparation method, and its application. Background Technology

[0002] Any discussion of prior art throughout the specification should not be construed as an admission that such prior art is well-known or constitutes part of common general knowledge in the art.

[0003] X-ray detectors are the core of computed tomography (CT) imaging, converting invisible X-rays into digital signals that form an image. They are widely used in digital X-ray imaging, veterinary medicine, security inspection, industrial non-destructive testing, and food safety testing. Fiber optic panels, also known as optical fiber panels, are rigid panels made from many single or composite optical fibers through a hot-pressing process. The main advantages of these panels include low interstage coupling loss, high light transmission efficiency, and clear image transmission capabilities, making them a key component in optical imaging systems. In particular, radiation-resistant fiber optic panels with high X-ray absorption properties play a crucial role in digital radiographic imaging technology. These fiber optic panels not only serve as scintillator substrates in detector systems but also effectively reduce noise and protect sensors, thereby enhancing image contrast. This further enables users to acquire high-resolution images in real time while reducing the exposure of sensors such as charge-coupled devices (CCDs) and complementary metal-oxide-semiconductor (CMOS) devices to X-ray environments.

[0004] Currently, glass is commonly used in radiation-resistant fiber optic panels, but this raises several issues. First, regarding optical performance, the refractive index of glass is typically between 1.70 and 1.77. In fiber optics, light must enter the fiber at a specific cone angle to propagate; half of this cone angle is called the reception angle θ. The higher the glass's refractive index, the larger the reception angle θ, and the more light can enter the fiber. Therefore, the relatively low refractive index of glass limits its light-capturing efficiency. Second, to improve the refractive index and X-ray absorption performance of radiation-resistant fiber optic panels, high levels of lead oxide are often added to the glass. This leads to several important problems: environmental and health impacts—high-lead glass releases lead volatilization during the smelting process, which not only alters the glass's physicochemical properties and affects product quality but also pollutes the environment, seriously threatening the health of workers and surrounding residents. Economic costs—lead oxide is an expensive chemical raw material; its volatilization increases raw material consumption, resulting in economic losses for companies. Thermal stability and optical performance—excessive lead oxide reduces the glass's thermal stability, making it prone to crystallization during the fiber drawing process for radiation-resistant fiber optic panels, leading to low product yield. Meanwhile, high lead oxide content can give glass an orange-yellow tint, affecting its optical properties. In summary, while glass has certain advantages as a material for radiation-resistant fiber optic panels, issues related to its refractive index, environmental and health impacts, economic costs, thermal stability, and optical performance require further resolution.

[0005] The object of this invention is to overcome or improve at least one disadvantage of the prior art, or to provide a useful alternative. Unless the context clearly requires otherwise, the words “comprising” and “including” should be interpreted in an inclusive sense rather than an exclusive or exhaustive sense throughout the specification and claims; that is, in the sense of “including, but not limited to”. Summary of the Invention

[0006] This invention provides an environmentally friendly high-refractive-index radiation-resistant glass, its preparation method, and its applications. The glass is lead-free and environmentally friendly, possessing excellent spectral transmittance, high refractive index, stable thermodynamic and chemical properties, good resistance to X-ray radiation, and suitable thermal expansion coefficient and softening temperature. It exhibits good process adaptability during processing, wire drawing, and hot pressing. The glass has broad application prospects in fields such as digital X-ray imaging, pet medical care, security inspection, industrial non-destructive testing, and food safety testing.

[0007] Specifically, the present invention provides the following technical features, and the combination of one or more of the following technical features constitutes the technical solution of the present invention.

[0008] In one aspect of the present invention, an environmentally friendly high-refractive-index radiation-resistant glass is provided, the components of which, by mass percentage, comprise: 8%–18% SiO2, 6%–15% B2O3, 20%–35% La2O3, 3%–10% Y2O3, 24%–38% BaO, 0%–5% SrO, 0.1%–2% CaO, 4.9%–10% Nb2O5, 1%–7% ZrO2, 0.1%–1.3% CeO2, and 0%–1% NaCl.

[0009] In some embodiments of the present invention, the environmentally friendly high-refractive-index radiation-resistant glass is composed of the following components by mass percentage: 8%–18% SiO2, 6%–15% B2O3, 20%–35% La2O3, 3%–10% Y2O3, 24%–38% BaO, 0%–5% SrO, 0.1%–2% CaO, 4.9%–10% Nb2O5, 1%–7% ZrO2, 0.1%–1.3% CeO2, and 0%–1% NaCl. Unless otherwise specified, when the present invention refers to the composition of the following components by mass percentage, the sum of the mass percentages of each component mentioned is 100%.

[0010] The glass material described in this invention must contain specific amounts of SiO2, B2O3, La2O3, Y2O3, BaO, CaO, Nb2O5, ZrO2, and CeO2 in its basic composition. This is an important condition for the radiation-resistant glass described in this invention to have excellent spectral transmittance, high refractive index, stable thermodynamic and chemical properties, and good resistance to X-ray radiation.

[0011] In this invention, SiO2, as a glass-forming oxide, is the main component forming the glass framework network structure. In some embodiments of this invention, the environmentally friendly high-refractive-index radiation-resistant glass, by mass percentage, has SiO2 content ranging from 8% to 18%, 15.1% to 18%, 15.4% to 18%, 16% to 18%, 16.5% to 18%, 17% to 18%, 17.3% to 18%, 17.5% to 18%, 15.1% to 17.5%, 15.4% to 17.5%, 16% to 17.5%, 16.5% to 17.5%, 17% to 17.5%, 17.3% to 17.5%, 15.1% to 17.3%, 15.4% to 17.3%, 16% to 17.3%, and 16.5% to 17.3%. %, 17%–17.3%, 15.1%–17%, 15.4%–17%, 16%–17%, 16.5%–17%, 15.1%–16.5%, 15.4%–16.5%, 16%–16.5%, 15.1%–16%, 15.4%–16%, 8%–10%, 8%–13%, 8%–16.5%, 8%–17%, 8%–17.3%, 10%–13%, 10%–16.5%, 10%–17%, 10%–17.3%, 10%–18%, 13%–16.5%, 13%–17%, 13%–17.3%, 13%–18%, 16.5%–17%. In some preferred embodiments of the present invention, the SiO2 content is higher than 15%.

[0012] In this invention, B2O3, as a glass-forming oxide, can replace SiO2 in certain aspects. Furthermore, B2O3 acts as a flux in glass, reducing its high-temperature viscosity, thus saving costs and facilitating production. However, as the B2O3 content increases, the devitrification range of the glass expands, and B2O3's volatility may cause environmental pollution. Therefore, the dosage should be strictly controlled during production to balance its improvement on peeling performance and potential environmental impact. In some embodiments of the present invention, the environmentally friendly high-refractive-index radiation-resistant glass, by mass percentage, may have a B2O3 content selected from 6%–15%, 6%–14%, 6%–13.5%, 6%–13%, 6%–12%, 6%–10.2%, 6%–10%, 6%–8%, 8%–15%, 8%–14%, 8%–13.5%, 8%–13%, 8%–12%, 8%–10%, 8%–10.2%, 10%–15%, 10%–14%, 10%–1 3.5%, 10%–13%, 10%–12%, 10%–10.2%, 10.2%–15%, 10.2%–14%, 10.2%–13.5%, 10.2%–13%, 10.2%–12%, 10.4%–15%, 12%–15%, 12%–14%, 12%–13.5%, 12%–13%, 13%–15%, 13%–14%, 13%–13.5%, 13.5%–15%, 13.5%–14%, 14%–15%.

[0013] In some embodiments of the present invention, the sum of the contents of SiO2 and B2O3, by mass percentage, is 16% to 33%. In some embodiments, the sum of the contents of SiO2 and B2O3 may be selected from 16% to 18.2%, 16% to 28%, 16% to 29.5%, 16% to 30%, 16% to 30.8%, 16% to 31%, 16% to 31.5%, 18.2% to 28%, 18.2% to 29.5%, 18.2% to 30%, and 18.2% to 30%. 0.8%, 18.2%–31%, 18.2%–31.5%, 28%–29.5%, 28%–30%, 28%–30.8%, 28%–31%, 28%–31.5%, 29.5%–30%, 29.5%–30.8%, 29.5%–31%, 29.5%–31.5%, 30%–30.8%, 30%–31%, 30%–31.5%, 30.8%–31%, 30.8%–31.5%, 31%–31.5%. In some preferred embodiments of the invention, the sum of the contents of SiO2 and B2O3 is greater than 30%. For example, in some embodiments, the sum of the contents of SiO2 and B2O3 is 30.5%–33%, further 30.8%–31% or 31%–31.5%.

[0014] In this invention, La2O3, as a rare earth oxide, is a glass structure regulating oxide. Appropriate use can increase the softening temperature of the glass, improve its properties, increase the refractive index, and reduce dispersion. In some embodiments of this invention, the environmentally friendly high-refractive-index radiation-resistant glass, by mass percentage, may contain La2O3 content selected from 20%–35%, 22%–35%, 23%–35%, 28%–35%, 30%–35%, 20%–30%, 22%–30%, 23%–30%, 28%–30%, 20%–28%, 22%–28%, 23%–28%, 20%–23%, and 22%–23%.

[0015] In this invention, Y₂O₃, as a rare earth oxide, can effectively reduce the high-temperature viscosity and melting temperature of glass when used in appropriate amounts, making the glass easier to melt and process, and is a good flux. In some embodiments of this invention, the environmentally friendly high-refractive-index radiation-resistant glass, by mass percentage, may have the following Y₂O₃ content: 3%–10%, 3%–8%, 3%–6%, 3%–5.4%, 3%–5%, 3%–4%, 4%–10%, 4%–8%, 4%–6%, 4%–5.4%, 4%–5%, 5%–10%, 5%–8%, 5%–6%, 5%–5.4%, 5.1%–10%, 5.1%–8%, 5.1%–6%, 5.1%–5.4%, 5.4%–10%, 5.4%–8%, 5.4%–6%, 6%–10%, 6%–8%, 8%–10%. In some preferred embodiments of this invention, the Y₂O₃ content is greater than 5%.

[0016] In this invention, the appropriate use of Nb₂O₅ can improve light transmittance, increase refractive index, and enhance the high-temperature stability of the glass. Furthermore, Nb₂O₅ can effectively replace lead oxide, eliminating irregular localized scattering in the glass and improving optical quality. In some embodiments of this invention, the environmentally friendly high-refractive-index radiation-resistant glass, by mass percentage, may contain Nb₂O₅ content selected from 4.9%–10%, 5%–10%, 5.5%–10%, 6%–10%, 8%–10%, 4.9%–8%, 5%–8%, 5.5%–8%, 6%–8%, 4.9%–6%, 5%–6%, 5.5%–6%, 4.9%–5.5%, 5%–5.5%, and 4.9%–5%.

[0017] In this invention, La2O3, Y2O3, and Nb2O5, as rare earth oxides added to glass, each have unique effects on the physical and chemical properties of the glass. Simultaneously, these additives also exhibit synergistic effects under certain conditions, jointly improving and regulating the glass's performance, contributing to a balance of its physical, chemical, and optical properties, and achieving superior overall performance.In some embodiments of the present invention, the environmentally friendly high-refractive-index radiation-resistant glass, by mass percentage, has Y₂O₃ accounting for no less than 10% of the sum of the contents of La₂O₃, Y₂O₃, and Nb₂O₅. For example, in some embodiments, the proportion of Y₂O₃ to the sum of the contents of La₂O₃, Y₂O₃, and Nb₂O₅ can be selected from 10.5%–25%, 10.71%–25%, 13.07%–25%, 13.79%–25%, 14.06%–25%, 15.15%–25%, 17.39%–25%, 18%–25%, 19.05%–25%, 22.86%–25%, 23.26%–25%, 10.5%–23%. 0.6%, 10.71%–23.6%, 13.07%–23.6%, 13.79%–23.6%, 14.06%–23.6%, 15.15%–23.6%, 17.39%–23.6%, 18%–23.6%, 19.05%–23.6%, 22.86%–23.6%, 10.5%–22.86%, 10.71%–22.86%, 13.07%–22.86%, 13.79%–22.86%, 14.06%–22.86%, 15.15%–22.86%, 17.39%–22.86%, 18%–22.86%, 19.05%–22.86%, 10. 5%–19.05%, 10.71%–19.05%, 13.07%–19.05%, 13.79%–19.05%, 14.06%–19.05%, 15.15%–19.05%, 17.39%–19.05%, 18%–19.05%, 10.5%–18%, 10.71%–18%, 13.07%–18%, 13.79%–18%, 14.06%–18%, 15.15%–18%, 17.39%–18%, 10.5%–17.39%, 10.71%–17.39%, 13.07%–17.39%, 13.79%–17.39%, 14.06% ~17.39%, 15.15%~17.39%, 10.5%~15.15%, 10.71%~15.15%, 13.07%~15.15%, 13.79%~15.15%, 14.06%~15.15%, 10.5%~14.06%, 10.71%~14.06%, 13.07%~14.06%, 13.79%~14.06%, 10.5%~13.79%, 10.71%~13.79%, 13.07%~13.79%, 10.5%~13.07%, 10.71%~13.07%, 10.5%~13.71%, 15%~23%, 19%~23%.

[0018] In this invention, BaO and SrO are alkaline earth metal oxides. Appropriate use can significantly reduce the tendency of glass to separate into phases, i.e., reduce the tendency for different chemical components in the glass to separate into independent phases. This is crucial for maintaining the uniformity and transparency of the glass, especially in high-performance optical and specialty glasses. Simultaneously, Ba is the heavy metal element with the largest X-ray absorption cross-section among alkaline earth metals, strongly absorbing X-rays and gamma rays. Furthermore, Ba can significantly replace lead in this invention, improving the radiation resistance of the glass. In some embodiments of the present invention, the environmentally friendly high-refractive-index radiation-resistant glass, by mass percentage, may have a BaO content selected from 24%–38%, 25%–38%, 26%–38%, 27%–38%, 28%–38%, 28.3%–38%, 30%–38%, 37%–38%, 24%–37%, 25%–37%, 26%–37%, 27%–37%, 28%–37%, 28.3%–37%, 30%–37 ...28%–37%, 28%–37%, 28%–37%, 28%–37%, 28%–37%, 28%–37%, 28%–37%, 28%–37%, 28%–37%, 28%–37%, 28%–37%, 28%–37%, 28%–37%, 28%–37%, 28%–37%, 28%–37 0%, 25%–30%, 26%–30%, 27%–30%, 28%–30%, 28.3%–30%, 24%–28.3%, 25%–28.3%, 26%–28.3%, 27%–28.3%, 28%–28.3%, 24%–28%, 25%–28%, 26%–28%, 27%–28%, 24%–27%, 25%–27%, 26%–27%, 24%–26%, 25%–26%, 24%–25%. In some embodiments of the present invention, the environmentally friendly high-refractive-index radiation-resistant glass may have an SrO content selected from 0, 0-5%, 1%-5%, 1.5%-5%, 2%-5%, 4%-5%, 0-4%, 1%-4%, 1.5%-4%, 2%-4%, 0-2%, 1%-2%, 1.5%-2%, and 0-1% by mass percentage.

[0019] In this invention, CaO is an alkaline earth metal oxide, belonging to the network exooxide in the glass structure. An appropriate amount of CaO can reduce the mid-temperature viscosity of the glass, a property important for improving its processing performance, making it easier to form and process. Simultaneously, an appropriate amount of CaO not only helps improve the mechanical strength of the glass but also extends its material properties, resulting in better stability and controllability during processing. In some embodiments of this invention, the environmentally friendly high-refractive-index radiation-resistant glass, by mass percentage, may have CaO content selected from 0.1%–2%, 0.4%–2%, 0.8%–2%, 1%–2%, 0.1%–1%, 0.4%–1%, 0.8%–1%, 0.1%–0.8%, 0.4%–0.8%, and 0.1%–0.4%.

[0020] In this invention, CeO2 acts as a stabilizer in glass, significantly improving the material's radiation resistance. However, its addition must be controlled to avoid affecting the glass's transparency and transmittance, especially in the near-ultraviolet band. Specifically, CeO2 can absorb radiation energy from ultraviolet light and some visible light, preventing these energies from causing changes or damage to the glass's internal structure. This absorption reduces radiation-induced color center formation (color centers are microscopic regions that color the glass), thereby maintaining the glass's transparency and color stability, especially after prolonged exposure to radiation. Although CeO2 can improve the radiation resistance of glass, because CeO2 itself has strong ultraviolet absorption properties, excessive CeO2 will absorb too much light, reducing the amount of light passing through the glass, thus affecting its transparency and optical properties. In this invention, an appropriate amount of CeO2 is particularly important, as it can not only improve the glass's radiation resistance but also, to some extent, regulate the glass's optical properties. In some embodiments of the present invention, the environmentally friendly high-refractive-index radiation-resistant glass, by mass percentage, has a CeO2 content of 0.1%–1.3%, 0.5%–1.3%, 0.8%–1.3%, 1%–1.3%, 1.2%–1.3%, 0.1%–1.2%, 0.5%–1.2%, 0.8%–1.2%, 1%–1.2%, 0.1%–1%, 0.1%–0.9%, 0.5%–1%, 0.8%–1%, 0.1%–0.8%, 0.5%–0.8%, or 0.1%–0.5%.

[0021] In this invention, ZrO2 is a glass intermediate oxide. An appropriate amount of ZrO2 can enhance the stability of the glass network, improve chemical stability, and prevent the exposure of alkali metal and alkaline earth metal ions. In glass structures, alkali metal and alkaline earth metal ions typically exist as network modifiers, helping to regulate the physical and chemical properties of the glass. However, excessive accumulation of these ions on the glass surface can lead to changes in the glass surface properties. In this invention, ZrO2, through its unique chemical properties, can promote the uniform distribution of these ions in the glass network, reduce their accumulation on the surface, and thus reduce the negative impacts on the glass surface caused by ion exposure. In some embodiments of the present invention, the environmentally friendly high-refractive-index radiation-resistant glass, by mass percentage, may have a ZrO2 content selected from 1%–7%, 2.4%–7%, 3%–7%, 3.5%–7%, 5%–7%, 5.1%–7%, 5.4%–7%, 5.5%–7%, 5.8%–7%, 6%–7%, 1%–6%, 2.4%–6%, 3%–6%, 3.5%–6%, 5%–6%, 5.5%–6%, 5.8%–6%, 1%– 5.8%, 2.4%–5.8%, 3%–5.8%, 3.5%–5.8%, 5%–5.8%, 5.5%–5.8%, 1%–5.5%, 2.4%–5.5%, 3%–5.5%, 3.5%–5.5%, 5%–5.5%, 1%–5%, 2.4%–5%, 3%–5%, 3.5%–5%, 1%–3.5%, 2.4%–3.5%, 3%–3.5%, 1%–3%, 2.4%–3%, 1%–2.4%. In some preferred embodiments of the present invention, the ZrO2 content is greater than 5%.

[0022] In this invention, NaCl is a high-temperature volatile clarifying agent. NaCl volatilizes at high temperatures, a process that helps agitate the glass melt, promoting the rise and release of bubbles to the glass surface, thus improving the clarification effect of the molten glass and reducing bubbles and defects in the finished product. The chloride ions produced when NaCl decomposes in the molten glass can reduce the surface tension of the glass melt, reducing the resistance encountered by bubbles during their rise and collapse, allowing them to escape more easily from the melt. The presence of chloride ions can also affect the absorption behavior of gases by the molten glass. To some extent, this may reduce the amount of dissolved gas in the glass melt, further reducing bubbles in the finished product. By reducing surface tension, NaCl may also indirectly affect the fluidity of the glass melt, making it easier to handle and shape. In some embodiments of the present invention, the environmentally friendly high-refractive-index radiation-resistant glass, by mass percentage, may contain NaCl content selected from 0–1%, 0.1%–1%, 0.2%–1%, 0.5%–1%, 0.6%–1%, 0–0.6%, 0.1%–0.6%, 0.2%–0.6%, 0.5%–0.6%, 0–0.5%, 0.1%–0.5%, 0.2%–0.5%, 0–0.2%, 0.1%–0.2%, and 0–0.1%.

[0023] In some embodiments of the present invention, the environmentally friendly high-refractive-index radiation-resistant glass is composed of the following components by mass percentage: 15.1%–18% SiO2, 6%–15% B2O3, 20%–35% La2O3, 3%–10% Y2O3, 24%–38% BaO, 0–5% SrO, 0.1%–2% CaO, 4.9%–10% Nb2O5, 1%–7% ZrO2, 0.1%–1.3% CeO2, and 0–1% NaCl.

[0024] In some embodiments of the present invention, the environmentally friendly high-refractive-index radiation-resistant glass is composed of the following components by mass percentage: 8%–18% SiO2, 6%–15% B2O3, 20%–35% La2O3, 5.1%–10% Y2O3, 24%–38% BaO, 0%–5% SrO, 0.1%–2% CaO, 4.9%–10% Nb2O5, 1%–7% ZrO2, 0.1%–1.3% CeO2, and 0%–1% NaCl.

[0025] In some embodiments of the present invention, the environmentally friendly high-refractive-index radiation-resistant glass is composed of the following components by mass percentage: 8%–18% SiO2, 6%–15% B2O3, 20%–35% La2O3, 3%–10% Y2O3, 24%–38% BaO, 0%–5% SrO, 0.1%–2% CaO, 4.9%–10% Nb2O5, 5.1%–7% ZrO2, 0.1%–1.3% CeO2, and 0%–1% NaCl.

[0026] In some embodiments of the present invention, the environmentally friendly high-refractive-index radiation-resistant glass is composed of the following components by mass percentage: 8%–18% SiO2, 6%–15% B2O3, 20%–35% La2O3, 3%–10% Y2O3, 24%–38% BaO, 0%–5% SrO, 0.1%–2% CaO, 4.9%–10% Nb2O5, 1%–7% ZrO2, 0.1%–1.3% CeO2, and 0.1%–1% NaCl.

[0027] In some embodiments of the present invention, the environmentally friendly high-refractive-index radiation-resistant glass is composed of the following components by mass percentage: 8%–17% SiO2, 8%–15% B2O3, 20%–35% La2O3, 6%–8% Y2O3, 25%–28% BaO, 1–5% SrO, 0.1%–1% CaO, 4.9%–8% Nb2O5, 2.4%–7% ZrO2, 0.1%–1.3% CeO2, and 0–1% NaCl.

[0028] In some embodiments of the present invention, the environmentally friendly high-refractive-index radiation-resistant glass is composed of the following components by mass percentage: 16.5%–17% SiO2, 6%–15% B2O3, 20%–35% La2O3, 5.4%–10% Y2O3, 24%–38% BaO, 0–5% SrO, 0.1%–2% CaO, 4.9%–10% Nb2O5, 5.5%–7% ZrO2, 0.1%–1.3% CeO2, and 0.1%–1% NaCl.

[0029] In another aspect of the present invention, a method for preparing any of the above-mentioned environmentally friendly high-refractive-index radiation-resistant glasses is provided, comprising: mixing raw materials, melting at high temperature, clarifying with auxiliary stirring, cooling and molding, and precision annealing.

[0030] In some embodiments of the present invention, the high-temperature melting temperature is 1380–1490°C, the forming temperature is 1075–1160°C, and the annealing temperature is 535–650°C.

[0031] In some embodiments of the present invention, the raw materials may be selected from the following materials as needed: quartz sand, boron oxide (or boric acid), lanthanum oxide, yttrium trioxide, barium oxide (or barium carbonate), strontium oxide, calcium oxide (or calcium carbonate), niobium pentoxide, zirconium oxide, cerium oxide, and sodium chloride.

[0032] In some embodiments of the present invention, the molding method and the stirring and clarification method can be selected from conventional processing methods in the field as needed; for example, the molding method can be mechanical or manual casting molding, or others; for example, the auxiliary stirring and clarification can be mechanical stirring and auxiliary bubbling clarification.

[0033] The method of this invention possesses process stability; the glass material prepared using this method exhibits stable properties and does not experience significant fluctuations in glass performance due to increases or decreases in the process range. Of course, it is understood that within this process range, higher temperatures can shorten the preparation process compared to lower temperatures. If minimizing time and cost is required, those skilled in the art can select relatively higher temperatures within the temperature range disclosed in this invention.

[0034] In another aspect of the invention, an optical fiber panel is provided, which uses any of the environmentally friendly high-refractive-index radiation-resistant glass of the present invention as raw material.

[0035] For example, in one embodiment of the present invention, the fiber optic panel may be a fiber optic panel for an X-ray detector.

[0036] In another aspect of the invention, a radiation shielding material is provided, which is made of any of the environmentally friendly high-refractive-index radiation-resistant glasses of the present invention described above.

[0037] For example, in one embodiment of the present invention, the radiation shielding material is an X-ray radiation shielding material.

[0038] In addition, the present invention also provides an optical element comprising any of the environmentally friendly high-refractive-index radiation-resistant glass of the present invention described above.

[0039] For example, in one embodiment of the present invention, the optical element is an optical window element, such as a radiation-shielding optical window element, or further, an X-ray radiation-shielding optical window element.

[0040] In addition, the present invention also provides applications of any of the above-mentioned environmentally friendly high-refractive-index radiation-resistant glasses in radiation shielding, digital X-ray imaging, pet medical care, security inspection, industrial non-destructive testing and food safety testing.

[0041] For example, in fields such as radiation shielding, nuclear power plants, and radiotherapy rooms, the environmentally friendly high-refractive-index radiation-resistant glass described in this invention can be used as a protective window, providing a line of sight while preventing radiation leakage.

[0042] For example, in digital X-ray imaging equipment, a protective layer used as a display screen not only protects the equipment from physical damage but may also reduce the impact of radiation on operators.

[0043] For example, in security inspection and food safety testing equipment, this glass can be used as a component of detectors to improve the detector's responsiveness to radiation and image clarity.

[0044] For example, in industrial non-destructive testing, it serves as a window component of the testing equipment, ensuring a clear view while protecting the equipment from the effects of the industrial environment.

[0045] For example, in pet medical care and scientific research, they can be made into laboratory supplies such as test tubes and observation windows for observation and analysis, while ensuring that the samples are not affected by external radiation.

[0046] For example, in environments requiring radiation protection, such as areas handling radioactive materials, this glass can be used to create enclosures or protective barriers to protect workers and the environment.

[0047] The various specific technical features described in the above embodiments of the present invention can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0048] Unless otherwise specified, the numerical range described in this invention includes all values ​​within this range, and also includes the range value formed by any two values ​​within this range. For example, 0.1% to 1.3% includes all values ​​between 0.1% and 1.3%, and also includes the range value (0.2% to 1.1%) formed by any two values ​​within this range (e.g., 0.2% and 1.1%). Different values ​​of the same indicator appearing in all embodiments of this invention can be arbitrarily combined to form a range value.

[0049] The following beneficial effects can be achieved through one or more of the above-mentioned technical means:

[0050] This invention provides a lead-free, environmentally friendly glass with excellent spectral transmittance, high refractive index, stable thermodynamic and chemical properties, and good resistance to X-ray radiation. Specifically, the glass provided by this invention has a refractive index ≥1.88, a transition temperature ≥665℃, a sag temperature ≥718℃, and good thermal stability. Its coefficient of linear expansion from 30 to 300℃ is (92–105) × 10⁻⁶. -7The glass has good thermal processing properties, which is beneficial for the molding and preparation of large-size devices. The transmittance of the 2mm sample decreased by ≤1.32% after being irradiated with 10000Gy X-rays. Under the conditions of 160kV and 1 mA energy, the X-ray absorption rate of the 2mm sample is ≥94.6%. The glass composition does not contain lead compounds, which protects the health of operators and the surrounding population. Attached Figure Description

[0051] The accompanying drawings, which form part of this application, are used to provide a further understanding of this application. The illustrative embodiments and descriptions of this application are used to explain this application and do not constitute an undue limitation of this application. The embodiments of this application will be described in detail below with reference to the accompanying drawings, wherein:

[0052] Figure 1 The image shows a comparison of the transmittance (@560nm) of the glass material in Example 4 of the present invention before and after X-ray (10000Gy dose) irradiation.

[0053] Figure 2 The diagram shows a comparison of the absorption rate of glass materials in Examples 1-9 and Comparative Examples 1-9 of the present invention to X-rays (160 kV, 1 mA energy) and the transmittance (@560 nm) after X-ray (10000 Gy dose) irradiation. Detailed Implementation

[0054] The present application is further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the application. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions or as recommended by the manufacturer.

[0055] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of skill in the art. All reagents and materials used in this application are readily available through conventional means, and unless otherwise specified, they are used in accordance with conventional methods or product instructions. Furthermore, any methods and materials similar to or equivalent to those described herein may be applied to the methods of this application. The preferred embodiments and materials described herein are for illustrative purposes only. In this invention, weight percentage (wt%) and mass percentage (mass percentage) have the same meaning, indicating the proportion of a component in a mixture. This proportion is calculated by dividing the mass of the component by the total mass of the entire mixture and then multiplying by 100%, and can be expressed as wt%.

[0056] The testing methods for glass properties in the embodiments and comparative examples of this invention:

[0057] The refractive index of the glass samples was measured using a Metricon Model 2010 / M prism coupler. (GB / T 7962.1~2010)

[0058] The transmittance of glass samples was determined using a Shimadzu UV-Vis spectrophotometer (UV-3600Plus). The test wavelength range was 300 nm to 1500 nm. The glass samples were optically polished and 2 mm thick (GB / T7962.12-2010). The transmittance changes of the glass samples before and after X-ray irradiation with a dose of 10000 Gy were also compared. The X-ray generator used was an IXS160BP 200P387, and the X-ray dose rate was 5.654 mGy / s. The X-ray absorbance of the glass samples was also measured using this X-ray generator.

[0059] The coefficient of thermal expansion of glass samples was tested using a Netzsch DIL 402 thermal expansion meter. Sample preparation involved grinding and polishing the glass sample into a cylindrical strip with a diameter of 6 × 50 mm, ensuring both ends were parallel. The heating rate was set to 5 °C / min, and the data acquisition period was 20 ms. The data were plotted as a temperature versus linear expansion curve, and the glass transition temperature (Tg), relaxation temperature (Tf), and coefficient of linear expansion were obtained using the tangent method (GB / T 7962.16~2010). The expression for calculating the coefficient of thermal expansion is shown below:

[0060]

[0061] In the formula, α is the coefficient of linear expansion of the glass sample; L1 and L2 are the lengths of the glass sample at temperatures T1 and T2, respectively.

[0062] Example 1

[0063] This embodiment provides an environmentally friendly high-refractive-index radiation-resistant glass, composed of the following components by mass percentage: 16.5% SiO2, 13% B2O3, 20% La2O3, 3% Y2O3, 38% BaO, 0.4% CaO, 5% Nb2O5, 3% ZrO2, 1% CeO2, and 0.1% NaCl.

[0064] Preparation method: Using quartz sand, boron oxide, lanthanum oxide, yttrium oxide, barium oxide, calcium carbonate, niobium pentoxide, zirconium oxide, cerium oxide and sodium chloride as raw materials, the glass raw materials are mixed in proportion, the batch is melted at 1490℃, clarified by auxiliary stirring, mechanically shaped at 1143℃, and annealed at 622℃ to obtain glass blank.

[0065] The glass properties were tested; its refractive index is 1.88, its transition temperature is 694℃, its relaxation temperature is 744℃, and its coefficient of linear expansion from 30 to 300℃ is 95.2 × 10⁻⁶. -7 At ℃, the transmittance of the 2mm sample after X-ray irradiation with a dose of 10000Gy was 82.02%, a decrease of 1.06%. Under the conditions of 160kV and 1 mA energy, the X-ray absorption rate of the 2mm sample was 95.8%.

[0066] Example 2

[0067] This embodiment provides an environmentally friendly high-refractive-index radiation-resistant glass, composed of the following components by mass percentage: 13% SiO2, 15% B2O3, 22% La2O3, 5% Y2O3, 30% BaO, 2% SrO, 2% CaO, 6% Nb2O5, 3.5% ZrO2, 0.5% CeO2, and 1% NaCl.

[0068] Preparation method: Using quartz sand, boric acid, lanthanum oxide, yttrium oxide, barium oxide, strontium oxide, calcium oxide, niobium pentoxide, zirconium oxide, cerium oxide and sodium chloride as raw materials, the glass raw materials are mixed in proportion, the batch is melted at 1462℃, clarified by auxiliary stirring, mechanically formed at 1160℃, and annealed at 650℃ to obtain glass blank.

[0069] The glass properties were tested; its refractive index is 1.887, its transition temperature is 688℃, its relaxation temperature is 738℃, and its coefficient of linear expansion from 30 to 300℃ is 98.4 × 10⁻⁶. -7 At ℃, the transmittance of the 2mm sample after X-ray irradiation with a dose of 10000Gy was 82%, a decrease of 1.32%. Under the conditions of 160kV and 1 mA energy, the X-ray absorption rate of the 2mm sample was 95%.

[0070] Example 3

[0071] This embodiment provides an environmentally friendly high-refractive-index radiation-resistant glass, composed of the following components by mass percentage: 8% SiO2, 8% B2O3, 35% La2O3, 6% Y2O3, 25% BaO, 5% SrO, 0.8% CaO, 4.9% Nb2O5, 7% ZrO2, 0.1% CeO2, and 0.2% NaCl.

[0072] Preparation method: Using quartz sand, boron oxide, lanthanum oxide, yttrium oxide, barium oxide, strontium oxide, calcium carbonate, niobium pentoxide, zirconium oxide, cerium oxide and sodium chloride as raw materials, the glass raw materials are mixed in proportion, the batch is melted at 1444℃, clarified by auxiliary stirring, mechanically shaped at 1119℃, and annealed at 589℃ to obtain glass blank.

[0073] The glass properties were tested; its refractive index is 1.895, its transition temperature is 672℃, its sag temperature is 725℃, and its coefficient of linear expansion from 30 to 300℃ is 99.1 × 10⁻⁶. -7 At ℃, the transmittance of the 2mm sample after X-ray irradiation with a dose of 10000Gy was 83.37%, a decrease of 0.85%. Under the conditions of 160kV and 1 mA energy, the X-ray absorption rate of the 2mm sample was 94.6%.

[0074] Example 4

[0075] This embodiment provides an environmentally friendly high-refractive-index radiation-resistant glass, composed of the following components by mass percentage: 8% SiO2, 10.2% B2O3, 30% La2O3, 8% Y2O3, 28% BaO, 4% SrO, 0.1% CaO, 8% Nb2O5, 2.4% ZrO2, and 1.3% CeO2.

[0076] Preparation method: Using quartz sand, boron oxide, lanthanum oxide, yttrium oxide, barium carbonate, strontium oxide, calcium carbonate, niobium pentoxide, zirconium oxide and cerium oxide as raw materials, the glass raw materials are mixed in proportion, the batch is melted at 1405℃, clarified by auxiliary stirring, mechanically shaped at 1075℃, and annealed at 535℃ to obtain glass blank.

[0077] The glass properties were tested; its refractive index is 1.896, its transition temperature is 675℃, its relaxation temperature is 730℃, and its coefficient of linear expansion from 30 to 300℃ is 104.2 × 10⁻⁶. -7 At ℃, the transmittance of the 2mm sample after X-ray irradiation with a dose of 10000Gy was 83.04%, a decrease of 0.42%. Under the conditions of 160kV and 1 mA energy, the X-ray absorption rate of the 2mm sample was 95%.

[0078] Example 5

[0079] This embodiment provides an environmentally friendly high-refractive-index radiation-resistant glass, composed of the following components by mass percentage: 10% SiO2, 6% B2O3, 23% La2O3, 10% Y2O3, 28.3% BaO, 5% SrO, 1% CaO, 10% Nb2O5, 5% ZrO2, 1.2% CeO2, and 0.5% NaCl.

[0080] Preparation method: Using quartz sand, boron oxide, lanthanum oxide, yttrium oxide, barium carbonate, strontium oxide, calcium oxide, niobium pentoxide, zirconium oxide, cerium oxide and sodium chloride as raw materials, the glass raw materials are mixed in proportion, the batch is melted at 1380℃, clarified by auxiliary stirring, mechanically formed at 1093℃, and annealed at 556℃ to obtain glass blank.

[0081] The glass properties were tested; its refractive index is 1.893, its transition temperature is 665℃, its relaxation temperature is 718℃, and its coefficient of linear expansion from 30 to 300℃ is 105.1 × 10⁻⁶. -7 At ℃, the transmittance of the 2mm sample after X-ray irradiation with a dose of 10000Gy was 82.65%, a decrease of 1%. Under the conditions of 160kV and 1 mA energy, the X-ray absorption rate of the 2mm sample was 94.8%.

[0082] Example 6

[0083] This embodiment provides an environmentally friendly high-refractive-index radiation-resistant glass, composed of the following components by mass percentage: 18% SiO2, 12% B2O3, 20% La2O3, 4% Y2O3, 37% BaO, 1.5% SrO, 0.1% CaO, 5% Nb2O5, 1% ZrO2, 0.8% CeO2, and 0.6% NaCl.

[0084] Preparation method: Using quartz sand, boron oxide, lanthanum oxide, yttrium oxide, barium oxide, strontium oxide, calcium oxide, niobium pentoxide, zirconium oxide, cerium oxide and sodium chloride as raw materials, the glass raw materials are mixed in proportion, the batch is melted at 1428℃, clarified by auxiliary stirring, mechanically shaped at 1105℃, and annealed at 574℃ to obtain glass blank.

[0085] The glass properties were tested; its refractive index is 1.889, its transition temperature is 699℃, its relaxation temperature is 747℃, and its coefficient of linear expansion from 30 to 300℃ is 92.8 × 10⁻⁶. -7 At ℃, the transmittance of the 2mm sample after X-ray irradiation with a dose of 10000Gy was 82.08%, a decrease of 1.28%. Under the conditions of 160kV and 1 mA energy, the X-ray absorption rate of the 2mm sample was 95.5%.

[0086] Example 7

[0087] This embodiment provides an environmentally friendly high-refractive-index radiation-resistant glass, composed of the following components by mass percentage: 17.3% SiO2, 13.5% B2O3, 28% La2O3, 5.4% Y2O3, 24% BaO, 0.4% CaO, 5% Nb2O5, 5.8% ZrO2, 0.5% CeO2, and 0.1% NaCl.

[0088] Preparation method: Using quartz sand, boron oxide, lanthanum oxide, yttrium oxide, barium carbonate, calcium carbonate, niobium pentoxide, zirconium oxide, cerium oxide and sodium chloride as raw materials, the glass raw materials are mixed in proportion, the batch is melted at 1465℃, clarified by auxiliary stirring, mechanically shaped at 1125℃, and annealed at 648℃ to obtain glass blank.

[0089] The glass properties were tested; its refractive index is 1.888, its transition temperature is 689℃, its relaxation temperature is 747℃, and its coefficient of linear expansion from 30 to 300℃ is 99.8 × 10⁻⁶. -7 At ℃, the transmittance of the 2mm sample after X-ray irradiation with a dose of 10000Gy was 82.33%, a decrease of 0.76%. Under the conditions of 160kV and 1 mA energy, the X-ray absorption rate of the 2mm sample was 95.2%.

[0090] Example 8

[0091] This embodiment provides an environmentally friendly high-refractive-index radiation-resistant glass, composed of the following components by mass percentage: 16.5% SiO2, 15% B2O3, 20% La2O3, 6% Y2O3, 27% BaO, 2% SrO, 1% CaO, 5.5% Nb2O5, 5.5% ZrO2, 0.5% CeO2, and 1% NaCl.

[0092] Preparation method: Using quartz sand, boron oxide, lanthanum oxide, yttrium oxide, barium carbonate, strontium oxide, calcium oxide, niobium pentoxide, zirconium oxide, cerium oxide and sodium chloride as raw materials, the glass raw materials are mixed in proportion, the batch is melted at 1471℃, clarified by auxiliary stirring, mechanically shaped at 1117℃, and annealed at 636℃ to obtain glass blank.

[0093] The glass properties were tested; its refractive index is 1.896, its transition temperature is 699℃, its relaxation temperature is 752℃, and its coefficient of linear expansion from 30 to 300℃ is 101.2 × 10⁻⁶. -7At ℃, the transmittance of the 2mm sample after X-ray irradiation with a dose of 10000Gy was 83.81%, a decrease of 0.42%. Under the conditions of 160kV and 1 mA energy, the X-ray absorption rate of the 2mm sample was 96.8%.

[0094] Example 9

[0095] This embodiment provides an environmentally friendly high-refractive-index radiation-resistant glass, composed of the following components by mass percentage: 17% SiO2, 14% B2O3, 22% La2O3, 8% Y2O3, 26% BaO, 1% SrO, 0.1% CaO, 5% Nb2O5, 6% ZrO2, 0.8% CeO2, and 0.1% NaCl.

[0096] Preparation method: Using quartz sand, boron oxide, lanthanum oxide, yttrium oxide, barium oxide, strontium oxide, calcium oxide, niobium pentoxide, zirconium oxide, cerium oxide and sodium chloride as raw materials, the glass raw materials are mixed in proportion, the batch is melted at 1468℃, clarified by auxiliary stirring, mechanically shaped at 1145℃, and annealed at 634℃ to obtain glass blank.

[0097] The glass properties were tested; its refractive index is 1.891, its transition temperature is 691℃, its relaxation temperature is 740℃, and its coefficient of linear expansion from 30 to 300℃ is 103.5 × 10⁻⁶. -7 At ℃, the transmittance of the 2mm sample after X-ray irradiation with a dose of 10000Gy was 83.09%, a decrease of 0.82%. Under the conditions of 160kV and 1 mA energy, the X-ray absorption rate of the 2mm sample was 95.7%.

[0098] Comparative Example 1

[0099] This comparative example provides a glass composed of the following components in weight percentages: 27.5% SiO2, 2% La2O3, 8% BaO, 5% CaO, 0.5% Nb2O5, 3% CeO2, 2% Al2O3, 50% PbO, 1% Ta2O5, 0.5% Rb2O, and 0.5% Cs2O.

[0100] Preparation method: Using quartz sand, lanthanum oxide, barium nitrate, calcium carbonate, niobium pentoxide, cerium oxide, aluminum hydroxide, lead silicate, tantalum pentoxide, rubidium carbonate and cesium carbonate as raw materials, the glass raw materials are mixed in proportion and glass blanks are obtained according to the method of Example 1.

[0101] The glass properties were tested; its refractive index is 1.830, its transition temperature is 574℃, its relaxation temperature is 680℃, and its coefficient of linear expansion from 30 to 300℃ is 86.2 × 10⁻⁶.-7 At ℃, the transmittance of the 2mm sample after X-ray irradiation with a dose of 10000Gy was 79.23%, a decrease of 2.78%. Under the conditions of 160kV and 1 mA energy, the X-ray absorption rate of the 2mm sample was 95.2%.

[0102] Comparative Example 2

[0103] This comparative example provides a glass composed of the following components in mass percentage: 50% SiO2, 15% Y2O3, 18% BaO, 5% SrO, 5% CaO, 2% Nb2O5, and 5% ZrO2.

[0104] Preparation method: Using quartz sand, yttrium oxide, barium oxide, strontium oxide, calcium carbonate, niobium pentoxide and zirconium oxide as raw materials, the glass raw materials are mixed in proportion and glass blanks are obtained according to the method of Example 1.

[0105] The glass properties were tested; its refractive index is 1.662, its transition temperature is 621℃, its relaxation temperature is 711℃, and its coefficient of linear expansion from 30 to 300℃ is 83 × 10⁻⁶. -7 At ℃, the transmittance of the 2mm sample after X-ray irradiation with a dose of 10000Gy was 58.2%, a decrease of 31.42%. Under the conditions of 160kV and 1 mA energy, the X-ray absorption rate of the 2mm sample was 81.2%.

[0106] Comparative Example 3

[0107] This comparative example provides a glass composed of the following components by mass percentage: 28% SiO2, 40% B2O3, 8% La2O3, 5% Y2O3, 5% BaO, 2% CaO, 5% Nb2O5, 2% ZrO2, and 5% CeO2. The glass material of this comparative example is prepared by mixing various glass raw materials—quartz sand, boron oxide, lanthanum oxide, yttrium oxide, barium carbonate, calcium carbonate, niobium pentoxide, zirconium oxide, and cerium oxide—in proportions according to the method of Example 1 to obtain a glass preform.

[0108] The glass properties were tested; its refractive index is 1.527, its transition temperature is 599℃, its relaxation temperature is 702℃, and its coefficient of linear expansion from 30 to 300℃ is 88.5 × 10⁻⁶. -7 At ℃, the transmittance of the 2mm sample after X-ray irradiation with a dose of 10000Gy was 75.43%, a decrease of 14.7%. Under the conditions of 160kV and 1 mA energy, the X-ray absorption rate of the 2mm sample was 83.5%.

[0109] Comparative Example 4

[0110] This comparative example provides a glass composed of the following components in mass percentage: 6% SiO2, 18% B2O3, 23% La2O3, 2% Y2O3, 28% BaO, 6% TiO2, 2% SrO, 5.2% Nb2O5, 5% ZrO2, 1.8% CeO2, 1% Na2O, and 2% K2O.

[0111] Preparation method: Using quartz sand, boron oxide, lanthanum oxide, yttrium oxide, barium nitrate, titanium dioxide, strontium oxide, niobium pentoxide, zirconium oxide, cerium oxide, sodium carbonate and potassium carbonate as raw materials, the glass raw materials are mixed in proportion and glass blanks are obtained according to the method of Example 1.

[0112] The glass properties were tested; its refractive index is 1.832, its transition temperature is 621℃, its relaxation temperature is 705℃, and its coefficient of linear expansion from 30 to 300℃ is 83.2 × 10⁻⁶. -7 At ℃, the transmittance of the 2mm sample after being irradiated with 10000Gy X-rays was 59.75%, a decrease of 0.8%. Under the conditions of 160kV and 1 mA energy, the X-ray absorption rate of the 2mm sample was 92.3%.

[0113] Comparative Example 5

[0114] This comparative example provides a glass composed of the following components in weight percentages: 9% SiO2, 15% B2O3, 30% La2O3, 3% Y2O3, 30% BaO, 1.5% SrO, 0.5% CaO, 9% Nb2O5, and 2% ZrO2.

[0115] Preparation method: Using quartz sand, boric acid, lanthanum trioxide, yttrium trioxide, barium carbonate, strontium carbonate, calcium carbonate, niobium pentoxide and zirconium oxide as raw materials, the glass raw materials are mixed in proportion and glass blanks are obtained according to the method of Example 1.

[0116] The glass properties were tested; its refractive index is 1.78, its transition temperature is 601℃, its relaxation temperature is 705℃, and its coefficient of linear expansion from 30 to 300℃ is 90 × 10⁻⁶. -7 At ℃, the transmittance of the 2mm sample after X-ray irradiation with a dose of 10000Gy was 66.23%, a decrease of 22.33%. Under the conditions of 160kV and 1 mA energy, the X-ray absorption rate of the 2mm sample was 76.2%.

[0117] Comparative Example 6

[0118] This comparative example provides a glass composed of the following components in weight percentages: 5% SiO2, 25% B2O3, 32% La2O3, 2% Y2O3, 28% BaO, 1% CaO, 6% Nb2O5, and 1% ZrO2.

[0119] Preparation method: Using quartz sand, boric acid, lanthanum trioxide, yttrium trioxide, barium carbonate, strontium carbonate, calcium carbonate, niobium pentoxide and zirconium oxide as raw materials, the glass raw materials are mixed in proportion and glass blanks are obtained according to the method of Example 1.

[0120] The glass properties were tested; its refractive index is 1.850, its transition temperature is 603℃, its relaxation temperature is 710℃, and its coefficient of linear expansion from 30 to 300℃ is 85×10⁻⁶. -7 At ℃, the transmittance of the 2mm sample after X-ray irradiation with a dose of 10000Gy was 59.88%, a decrease of 29.88%. Under the conditions of 160kV and 1 mA energy, the X-ray absorption rate of the 2mm sample was 69.8%.

[0121] Comparative Example 7

[0122] This comparative example provides a glass composed of the following components by mass percentage: 16.5% SiO2, 15% B2O3, 20% La2O3, 6% Y2O3, 24.5% BaO, 2% SrO, 1% CaO, 5.5% Nb2O5, 5.5% ZrO2, 3% CeO2, and 1% NaCl.

[0123] Preparation method: Using quartz sand, boron oxide, lanthanum oxide, yttrium trioxide, barium nitrate, strontium oxide, calcium carbonate, niobium pentoxide, zirconium oxide, cerium oxide and sodium chloride as raw materials, the glass raw materials are mixed in proportion and glass blanks are obtained according to the method of Example 1.

[0124] The glass properties were tested; its refractive index is 1.866, its transition temperature is 654℃, its relaxation temperature is 710℃, and its coefficient of linear expansion from 30 to 300℃ is 100×10⁻⁶. -7 At ℃, the transmittance of the 2mm sample after X-ray irradiation with a dose of 10000Gy was 79.99%, a decrease of 1.05%. Under the conditions of 160kV and 1 mA energy, the X-ray absorption rate of the 2mm sample was 94.2%.

[0125] Comparative Example 8

[0126] This comparative example provides a glass composed of the following components in mass percentage: 16.5% SiO2, 15% B2O3, 20% La2O3, 6% Y2O3, 25% BaO, 2% TiO2, 2% SrO, 1% CaO, 5.5% Nb2O5, 5.5% ZrO2, 0.5% CeO2, and 1% NaCl.

[0127] Preparation method: Using quartz sand, boron oxide, lanthanum oxide, yttrium oxide, barium nitrate, titanium dioxide, strontium oxide, calcium carbonate, niobium pentoxide, zirconium oxide, cerium oxide and sodium chloride as raw materials, the glass raw materials are mixed in proportion and glass blanks are obtained according to the method of Example 1.

[0128] The glass properties were tested; its refractive index is 1.861, its transition temperature is 664℃, its relaxation temperature is 716℃, and its coefficient of linear expansion from 30 to 300℃ is 106 × 10⁻⁶. -7 At ℃, the transmittance of the 2mm sample after X-ray irradiation with a dose of 10000Gy was 78.22%, a decrease of 5.74%. Under the conditions of 160kV and 1 mA energy, the X-ray absorption rate of the 2mm sample was 93.6%.

[0129] Comparative Example 9

[0130] This comparative example provides a glass composed of the following components in weight percentages: 16.5% SiO2, 15% B2O3, 20% La2O3, 6% Y2O3, 28% BaO, 2% SrO, 1% CaO, 5.5% Nb2O5, 5.5% ZrO2, and 0.5% CeO2.

[0131] Preparation method: Using quartz sand, boron oxide, lanthanum oxide, yttrium oxide, barium nitrate, strontium oxide, calcium carbonate, niobium pentoxide, zirconium oxide and cerium oxide as raw materials, the glass raw materials are mixed in proportion and glass blanks are obtained according to the method of Example 1.

[0132] The glass properties were tested; its refractive index is 1.857, its transition temperature is 660℃, its relaxation temperature is 711℃, and its coefficient of linear expansion from 30 to 300℃ is 107 × 10⁻⁶. -7 At ℃, the transmittance of the 2mm sample after X-ray irradiation with a dose of 10000Gy was 78.56%, a decrease of 4.71%. Under the conditions of 160kV and 1 mA energy, the X-ray absorption rate of the 2mm sample was 90.8%.

[0133] The composition and properties of the glass samples of Examples 1-9 and Comparative Examples 1-9 of the present invention are shown in Table 1 and Table 2, respectively.

[0134] Table 1. Composition of glass samples from Examples 1-9 and Comparative Examples 1-9

[0135]

[0136]

[0137] Table 2. Performance test results of glass samples from Examples 1-9 and Comparative Examples 1-9

[0138]

[0139]

[0140] As shown in Table 2, the high-refractive-index radiation-resistant glass in each embodiment has a refractive index ≥1.88, a transition temperature ≥665℃, and a relaxation temperature ≥718℃, exhibiting good thermal stability. Its coefficient of linear expansion from 30 to 300℃ is (92~105)×10⁻⁶. -7 The temperature is ℃, which has good thermal processing performance and is conducive to the molding and preparation of large-size devices. The transmittance of the 2mm sample decreased by ≤1.32% after being irradiated with 10000Gy X-rays. Under the conditions of 160kV and 1 mA energy, the X-ray absorption rate of the 2mm sample is ≥94.6%.

[0141] The various specific technical features described in the above embodiments of the present invention can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0142] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. An environmentally friendly high-refractive-index radiation-resistant glass, comprising the following components by mass percentage: 8%~18% SiO2, 6%~15% B2O3, 20%~35% La2O3, 4%~10% Y2O3, 24%~38% BaO, 0~5% SrO, 0.1%~2% CaO, 4.9%~10% Nb2O5, 1%~7% ZrO2, 0.1%~0.9% CeO2, 0.1%~1% NaCl; Among them, Y2O3 accounts for 13.07% to 25% of the total content of La2O3, Y2O3 and Nb2O5.

2. The environmentally friendly high-refractive-index radiation-resistant glass according to claim 1, characterized in that, By mass percentage, it consists of the following components: 15.1%~18% SiO2, 6%~15% B2O3, 20%~35% La2O3, 4%~10% Y2O3, 24%~38% BaO, 0~5% SrO, 0.1%~2% CaO, 4.9%~10% Nb2O5, 1%~7% ZrO2, 0.1%~0.9% CeO2, and 0.1%~1% NaCl.

3. The environmentally friendly high-refractive-index radiation-resistant glass according to claim 1, characterized in that, By mass percentage, it consists of the following components: 8%~18% SiO2, 6%~15% B2O3, 20%~35% La2O3, 5.1%~10% Y2O3, 24%~38% BaO, 0~5% SrO, 0.1%~2% CaO, 4.9%~10% Nb2O5, 1%~7% ZrO2, 0.1%~0.9% CeO2, and 0.1%~1% NaCl.

4. The environmentally friendly high-refractive-index radiation-resistant glass according to claim 1, characterized in that, By mass percentage, it consists of the following components: 8%~18% SiO2, 6%~15% B2O3, 20%~35% La2O3, 4%~10% Y2O3, 24%~38% BaO, 0~5% SrO, 0.1%~2% CaO, 4.9%~10% Nb2O5, 5.1%~7% ZrO2, 0.1%~0.9% CeO2, and 0.1%~1% NaCl.

5. The environmentally friendly high-refractive-index radiation-resistant glass according to claim 1, characterized in that, By mass percentage, it consists of the following components: 8%~17% SiO2, 8%~15% B2O3, 20%~35% La2O3, 6%~8% Y2O3, 25%~28% BaO, 1~5% SrO, 0.1%~1% CaO, 4.9%~8% Nb2O5, 2.4%~7% ZrO2, 0.1%~0.9% CeO2, and 0.1%~1% NaCl.

6. The environmentally friendly high-refractive-index radiation-resistant glass according to claim 1, characterized in that, By mass percentage, it consists of the following components: 16.5%~17% SiO2, 6%~15% B2O3, 20%~35% La2O3, 5.4%~10% Y2O3, 24%~38% BaO, 0~5% SrO, 0.1%~2% CaO, 4.9%~10% Nb2O5, 5.5%~7% ZrO2, 0.1%~0.9% CeO2, and 0.1%~1% NaCl.

7. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1, 3, or 4, characterized in that, The combined content of SiO2 and B2O3, by mass percentage, is 16% to 33%.

8. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1, 3, 4 or 5, characterized in that, The combined content of SiO2 and B2O3, by mass percentage, is 18% to 32%.

9. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 6, characterized in that, The combined content of SiO2 and B2O3 by mass percentage is 30.5% to 32%.

10. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 6, characterized in that, By mass percentage, Y2O3 accounts for 15% to 23% of the total content of La2O3, Y2O3 and Nb2O5.

11. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 6, characterized in that, By mass percentage, Y2O3 accounts for 19% to 23% of the total content of La2O3, Y2O3 and Nb2O5.

12. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 4, characterized in that, The SiO2 content is 15.4%~18% by mass percentage.

13. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1, 3, or 4, characterized in that, The SiO2 content is 8%~17.3% by mass percentage.

14. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 4, characterized in that, The SiO2 content is 16.5%~18% by mass percentage.

15. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 4 or 6, characterized in that, The B2O3 content is 8%~15% by mass percentage.

16. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 6, characterized in that, The B2O3 content is 10%~15% by mass percentage.

17. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 6, characterized in that, The content of La2O3 is 20%~30% by mass percentage.

18. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 6, characterized in that, The content of La2O3 is 20%~28% by mass percentage.

19. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 6, characterized in that, The content of La2O3 is 30%~35% by mass percentage.

20. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 4, characterized in that, The Y2O3 content is 5.4%~10% by mass percentage.

21. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 4 or 6, characterized in that, The Y2O3 content is 5.4%~8% by mass percentage.

22. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 4 or 6, characterized in that, The Y2O3 content is 6%~8% by mass percentage.

23. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 4 or 6, characterized in that, The Nb2O5 content is 5%~10% by mass percentage.

24. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 4 or 6, characterized in that, The Nb2O5 content is 4.9%~8% by mass percentage.

25. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 6, characterized in that, The Nb2O5 content is 5%~5.5% by mass percentage.

26. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 4 or 6, characterized in that, The BaO content is 24%~28% by mass percentage.

27. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 6, characterized in that, The BaO content is 26%~28% by mass percentage.

28. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 4 or 6, characterized in that, The SrO content is 1% to 5% by mass percentage.

29. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 6, characterized in that, The SrO content is 1% to 2% by mass percentage.

30. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 6, characterized in that, The SrO content is 4% to 5% by mass percentage.

31. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 4 or 6, characterized in that, The CaO content is 0.1% to 1% by mass percentage.

32. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 6, characterized in that, The CaO content is 0.1% to 0.8% by mass percentage.

33. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 6, characterized in that, The CaO content is 0.8% to 1% by mass percentage.

34. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 6, characterized in that, The CeO2 content is 0.5% to 0.8% by mass percentage.

35. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 3, characterized in that, The ZrO2 content is 2.4% to 7% by mass percentage.

36. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 3 or 5, characterized in that, The ZrO2 content is 2.4% to 6% by mass percentage.

37. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 5, characterized in that, The ZrO2 content is 5.4% to 7% by mass percentage.

38. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 3 or 5, characterized in that, The ZrO2 content is 2.4% to 5.5% by mass percentage.

39. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 6, characterized in that, The ZrO2 content is 5.5% to 6% by mass percentage.

40. The environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 6, characterized in that, The NaCl content is 0.2% to 1% by mass percentage.

41. A method for preparing environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 40, comprising mixing raw materials, melting at high temperature, clarifying with auxiliary stirring, cooling and molding, and precision annealing to obtain the glass.

42. The method according to claim 41, characterized in that, The high-temperature melting temperature is 1380~1490 ℃, the forming temperature is 1075~1160 ℃, and the annealing temperature is 535~650 ℃.

43. An optical fiber panel, which uses the environmentally friendly high-refractive-index radiation-resistant glass as raw material as any one of claims 1 to 40.

44. The optical fiber panel according to claim 43, characterized in that, The fiber optic panel is a fiber optic panel for X-ray detectors.

45. A radiation shielding material made of any one of the environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 40.

46. ​​The radiation shielding material according to claim 45, characterized in that, The radiation shielding material is an X-ray radiation shielding material.

47. An optical element comprising the environmentally friendly, high-refractive-index radiation-resistant glass as claimed in any one of claims 1 to 40.

48. The optical element according to claim 47, characterized in that, The optical element is an optical window element.

49. The optical element according to claim 47, characterized in that, The optical element is a radiation-shielding optical window element.

50. The optical element according to claim 47, characterized in that, The optical element is an X-ray radiation shielding optical window element.

51. The application of the environmentally friendly high-refractive-index radiation-resistant glass according to any one of claims 1 to 40 in the fields of radiation shielding, digital X-ray imaging, pet medical care, security inspection, industrial non-destructive testing and food safety testing.

Images